CN105315463B - Polymer, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element - Google Patents

Abstract

The present invention provide a kind of at least one and tetracarboxylic dianhydride comprising diamines represented by formula (1) react and the aligning agent for liquid crystal of the polymer that obtains, the liquid crystal orientation film that is formed using the aligning agent for liquid crystal and be a kind of liquid crystal display element with the liquid crystal orientation film.Even if liquid crystal display element of the invention, which has the characteristics that be exposed under strong light for a long time, shows that quality will not decline, and, when using aligning agent for liquid crystal of the invention, even if providing one kind is calcined the liquid crystal orientation film for being also able to achieve the performance of such liquid crystal display element with high temperature.In formula (1), R¹It is hydrogen or methyl；And R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

Description

Polymer, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element

Technical field

The present invention relates to a kind of polymer, liquid containing the polymer that diamines represented by formula (1) is used for raw material Brilliant alignment agent, liquid crystal orientation film, liquid crystal display element.

Background technique

Nowadays the mainstream of commercialization and the liquid crystal display element generally to circulate is the display element using nematic liquid crystal.To The display mode of column liquid crystal display element it is well-known be twisted nematic (Twisted Nematic, TN) mode, super twisted to (Super Twisted Nematic, the STN) mode of arranging.One of in recent years in order to improve these modes the problem of i.e. visual angle is narrow, It is proposed there is TN type liquid crystal display element using optical compensation films, and with the multizone of vertically oriented and protrusion structure technology The coplanar switching of vertically oriented (Multi-domain Vertical Alignment, MVA) mode or Transverse electric-field type (In-Plane Switching, IPS) mode, fringing field switch (Fringe Field Switching, FFS) mode, and Practical (referring to patent document 1~patent document 3).

The development of the technology of liquid crystal display element realizes not only by the improvement of these driving methods or component structure, But also it is realized by the improvement of member of formation used in element.Member of formation used in liquid crystal display element In, especially liquid crystal orientation film is one of the important materials for being related to display quality, with the high-quality of liquid crystal display element, Improving the performance of alignment films becomes important.

Currently, main liquid crystal orientation film to be used is that polyamic acid or the polyimides of solubility will be made to be dissolved in will be organic molten After solution made of in agent (varnish) is coated on substrate, the polyimides system liquid crystal to be formed a film by the methods of heating is taken To film.In general, implementing orientation using to polyimides system liquid crystal orientation film made of described be film-made in liquid crystal display element Processing.Known certain orientation process can easily carry out the rubbing manipulation of large area high speed processing by as taking in industrialness It is widely used to facture.Rubbing manipulation is using the cloth for having transplanted the fibers such as nylon, artificial silk, polyester, in one direction To the processing that the surface of liquid crystal orientation film rubs, the consistent orientation of liquid crystal molecule thus can get.

The purposes of liquid crystal display element bridge across personal computer (personal computer) monitor (monitor), The multiple fields of LCD TV, mobile phone, the display unit of smart phone, liquid crystal projection apparatus.In recent years, it is contemplated that display quality Raising or for outdoor, it may have the purposes increased before the brightness ratio of the backlight as light source, even if thus it requires a kind of It is exposed to the liquid crystal display element for showing that quality will not decline under strong light for a long time.

In order to cope with such requirement, various researchs also are carried out to liquid crystal orientation film, such as known there are as below methods: making raw material In containing the diamines with the structure of hindered amine or hindered phenol structure, the method (reference of the structure is imported in polyimides chain Patent document 4), or the method antioxidant with the structure of hindered amine or hindered phenol structure being added in aligning agent for liquid crystal (referring to patent document 5).However, even with these technologies, because of the difference of the manufacturing process of liquid crystal display element, wherein because making Liquid crystal orientation film is formed in the calcination temperature of the process on substrate and has the problems such as not showing required performance.

And the generation in order to inhibit in vertical alignment-type liquid crystal display device " burn mark ", it has carried out in side chain type diamine Side chain position imports the trial (referring to patent document 6) of the structure of hindered amine, but the Technological expression goes out the pre-tilt angle of liquid crystal molecule, It is not suitable as the IPS mode or FFS mode of lateral electric field mode.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 6-194646

[patent document 2] Japanese Patent Laid-Open 2001-117083

[patent document 3] Japanese Patent Laid-Open 6-160878

[patent document 4] Japanese Patent Laid-Open 2010-244015

[patent document 5] Japanese Patent Laid-Open 2012-194537

[patent document 6] International Publication 2008/078629

Summary of the invention

[problems to be solved by the invention]

Even if being exposed under strong light for a long time the issue of the present invention is to provide one kind and showing that quality will not decline Liquid crystal display element, even if while providing a kind of manufacturing process in liquid crystal display element, wherein forming liquid crystal orientation film High calcination temperature is selected in the process on substrate also can show the liquid crystal display element of required performance.In turn, this hair Bright project is to provide a kind of aligning agent for liquid crystal and liquid crystal orientation film for being capable of providing such display element.

[to solve the technological means of project]

The present inventor et al. carries out effort research, and as a result by using the compound of formula (1), completing one kind can be steadily Liquid crystal display element is provided without the calcination temperature of manufacturing process, particularly liquid crystal orientation film by the liquid crystal display element Different influences aligning agent for liquid crystal and liquid crystal orientation film, even if the liquid crystal display element is exposed to strong light for a long time Under, display quality will not decline.Especially in IPS mode and FFS mode, effect of the invention is further played.

The present invention includes composition below.

[1] a kind of polyamic acid or derivatives thereof is at least one and tetrabasic carboxylic acid two of diamines represented by formula (1) At least one of acid anhydride is reacted and is obtained:

In formula (1), R¹It is hydrogen or methyl；And

R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

[2] according to the polyamic acid or derivatives thereof of [1] Xiang Suoshu, wherein diamines represented by formula (1) is formula (1-1) institute At least one of the diamines of expression:

In formula (1-1), R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

[3] according to the polyamic acid or derivatives thereof of [1] Xiang Suoshu, wherein diamines represented by formula (1) is formula (1-2) institute At least one of the diamines of expression:

In formula (1-2), R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

[4] according to the polyamic acid or derivatives thereof of [2] Xiang Suoshu, wherein diamines represented by formula (1) is selected from formula (1- At least one of group of compound represented by 1-1)~formula (1-1-28):

[5] according to the polyamic acid or derivatives thereof of [3] Xiang Suoshu, wherein diamines represented by formula (1) is selected from formula (1- At least one of group of compound represented by 2-1)~formula (1-2-28):

[6] polyamic acid according to any one of [1] item to [5] item or derivatives thereof, be by formula (1) represented by Diamines at least one and other diamines at least one mixture reacted at least one of tetracarboxylic dianhydride and It obtains.

[7] polyamic acid according to any one of [1] item to [6] item or derivatives thereof, wherein tetracarboxylic dianhydride is At least one of group of tetracarboxylic dianhydride represented by following formula (AN-I)~formula (AN-VII):

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

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

In formula (AN-II)~formula (AN-IV), Y is stood alone as selected from following one of groups of base of trivalent,

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

In formula (AN-III)~formula (AN-V), ring A¹⁰For carbon number be 3~10 monocyclic hydrocarbon base or carbon number be 6~30 At least one hydrogen of the base of condensation polycyclic formula hydrocarbon, the base can be replaced by methyl, ethyl or phenyl, the associative key being connected on ring Link with the arbitrary carbon for constituting ring, 2 associative keys can link with the same carbon；

In formula (AN-VI), X¹⁰The alkylidene for being 2~6 for carbon number, Me indicate that methyl, Ph indicate phenyl,

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

[8] according to the polyamic acid or derivatives thereof of [7] Xiang Suoshu, wherein tetracarboxylic dianhydride is selected from following formula (AN-1- 1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN- 4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-11-3), at least one of formula (AN-16-3) and formula (AN-16-4):

In formula (AN-1-2) and formula (AN-4-17), m be 1~12 integer.

[9] according to the polyamic acid or derivatives thereof of [6] Xiang Suoshu, wherein other diamines are selected from by following formula (DI-1) At least one in group composed by~formula (DI-16), formula (DIH-1)~formula (DIH-3) and formula (DI-31)~formula (DI-35) Kind:

In formula (DI-1), G²⁰For-CH₂, at least one-CH₂It can be replaced by-NH- ,-O-, the integer that m is 1~12 is sub- At least one hydrogen of alkyl can be replaced by-OH；

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

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

In formula (DI-6) and formula (DI-7), G²²Stand alone as singly-bound ,-O- ,-S- ,-CO- ,-C (CH₃)₂-、-C(CF₃)₂Or carbon The alkylidene that number is 1~10；

In formula (DI-2)~formula (DI-7), at least one hydrogen of cyclohexane ring and phenyl ring can be 1~3 by-F ,-Cl, carbon number Alkyl ,-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl replace, in addition, in formula (DI-4), benzene At least one hydrogen of ring can by the base represented by following formula (DI-4-a)~formula (DI-4-e) group in a substitution；

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

The basis representation binding site on which ring that binding site is not fixed on the carbon atom for constituting ring be it is any ,- NH₂Binding site on cyclohexane ring or phenyl ring is except G²¹Or G²²Binding site other than arbitrary position；

In formula (DI-11), r is 0 or 1；

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

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

In formula (DI-13), R²³The alkoxy or-Cl that alkyl, carbon number that carbon number is 1~5 are 1~5 are stood alone as, p stands alone as 0 ~3 integer, the integer that q is 0~4；

In formula (DI-14), ring B is monocyclic heteroaromatic, R²⁴For hydrogen ,-F ,-Cl, carbon number be 1~6 alkyl, carbon number be The alkynyl that alkenyl that 1~6 alkoxy, carbon number are 2~6, carbon number are 1~6, q stand alone as 0~4 integer；

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

In formula (DI-16), G²⁴The alkylidene or Isosorbide-5-Nitrae-phenylene for being 2~6 for singly-bound, carbon number, r are 0 or 1；

In formula (DI-13)~formula (DI-16), binding site is not fixed to the basis representation on the carbon atom for constituting ring described Binding site on ring is any；

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

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

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

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

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、- CF₂O-、-OCF₂Or-(CH₂)_m', the integer that m' is 1~12, R²⁵For carbon number be 3~30 alkyl, phenyl, have steroids The base of skeleton or by the base represented by following formulas (DI-31-a), in the alkyl, at least one hydrogen can be replaced by-F, at least One-CH₂It can be replaced by-O- ,-CH=CH- or-C ≡ C-, the hydrogen of the phenyl can be by-F ,-CH₃、-OCH₃、-OCH₂F、- OCHF₂、-OCF₃, carbon number be 3~30 alkyl or carbon number be 3~30 alkoxy replace, be bonded-NH on phenyl ring₂Key Tying position indicates to be arbitrary position in the ring,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For bond base, they stand alone as the alkylene that singly-bound or carbon number are 1~12 Base, the more than one-CH of the alkylidene₂It can be replaced by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH-, ring B²¹, ring B²², ring B²³And ring B²⁴Stand alone as 1,4- phenylene, 1,4- cyclohexylidene, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- two Base, pyridine -2,5- diyl, naphthalene -1,5- diyl, naphthalene -2,7- diyl or anthracene -9,10- diyl, ring B²¹, ring B²², ring B²³And ring B²⁴ In, at least one hydrogen can be by-F or-CH₃Replace, s, t and u stand alone as 0~2 integer, they add up to 1~5, as s, t or When u is 2,2 bond bases in each bracket be may be the same or different, and 2 rings may be the same or different,

R²⁶For hydrogen ,-F ,-OH, carbon number be 1~30 alkyl, carbon number be 1~30 fluorine replace alkyl, carbon number to be 1~30 Alkoxy ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, at least one-CH for the alkyl that the carbon number is 1~30₂It can be by with following The base of divalent represented by formula (DI-31-b) replaces,

In formula (DI-31-b), R²⁷And R²⁸Stand alone as the alkyl that carbon number is 1~3, the integer that v is 1~6；

In formula (DI-32) and formula (DI-33), G³⁰Stand alone as singly-bound ,-CO- or-CH₂, R²⁹Stand alone as hydrogen or-CH₃, R³⁰For The alkenyl that the alkyl or carbon number that hydrogen, carbon number are 1~20 are 2~20；

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

In formula (DI-32) and formula (DI-33), binding site is not fixed to the basis representation on any one carbon atom for constituting ring Binding site on which ring is any；

In formula (DI-34) and formula (DI-35), G³¹Stand alone as the alkylidene that-O- or carbon number are 1~6, G³²For singly-bound or carbon The alkylidene that number is 1~3,

R³¹The alkyl for being 1~20 for hydrogen or carbon number, at least one-CH of the alkyl₂It can be by-O- ,-CH=CH- or-C ≡ C- replaces, R³²The alkyl for being 6~22 for carbon number, R³³The alkyl for being 1~22 for hydrogen or carbon number, ring B²⁵For 1,4- phenylene or 1 or 4 cyclohexylidene, r are 0 or 1, and, it is bonded-the NH on phenyl ring₂Indicate that binding site on which ring is any.

[10] according to the polyamic acid or derivatives thereof of [6] Xiang Suoshu, wherein other diamines are selected from by following formula (DI- 1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI-13- 1), at least one of group composed by formula (DI-16-1) and formula (DIH-2-1):

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

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

In formula (DI-7-3), n is 1 or 2.

[11] a kind of aligning agent for liquid crystal, containing polyamic acid described in good grounds [1] item to any one of [10] item or its Derivative.

[12] a kind of aligning agent for liquid crystal, containing polyamic acid described in good grounds [1] item to any one of [10] item or its Derivative and the polymer in addition to them.

[13] according to [11] item or the aligning agent for liquid crystal of [12] Xiang Suoshu, also contain selected from by alkenyl substitution nadik acyl Group with imine moiety, the compound with free-radical polymerised unsaturated double-bond, oxazines compound, oxazoline compound and epoxy At least one of heterogeneous compound group composed by compound.

[14] a kind of aligning agent for liquid crystal according to any one of [11] item to [13] item, is used for lateral electric-field type liquid Crystal display element.

[15] a kind of liquid crystal orientation film, the shape as the aligning agent for liquid crystal according to any one of [11] item to [14] item At.

[16] a kind of liquid crystal display element comprising according to the liquid crystal orientation film of [15] Xiang Suoshu.

[17] a kind of diamines, by formula (1-2) represented by:

In formula (1-2), R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

[The effect of invention]

Of the invention is formed by the excellent in reliability of liquid crystal orientation film by aligning agent for liquid crystal, and the aligning agent for liquid crystal contains Diamines represented by formula (1) is used for the polyamic acid or derivatives thereof of raw material.And the energy independent of the difference of manufacturing process Enough play certain performance.Even if the liquid crystal display element including the liquid crystal orientation film uses for a long time, show quality also not It can decline.Also, be intended to assign be further reduced image retention, improve to other characteristics such as printing of substrate in the case where, also can Enough pass through blends other polymers, or and the liquid crystal display element with required characteristic is provided with additive.

Specific embodiment

In diamines represented by formula (1), R¹It is hydrogen or methyl, R²It is alkyl that hydrogen ,-OH, carbon number are 1~6 or carbon number is 1 ~6 alkoxy.The position of substitution in the phenyl ring of 2 amino is not particularly limited, in order to be set as arranging liquid crystal point better Son aligning agent for liquid crystal, it is generally desirable to relative to amide groups the position of substitution and be 3,5 or 2,5.

Diamines represented by formula (1) is classified into R¹Diamines and R represented by formula (1-1) for hydrogen¹For the formula (1- of methyl 2) diamines represented by.

In formula (1-1) and formula (1-2), R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

, it is preferable to use the diamines of formula (1-1) in the case where dissolubility of the needs in solvent higher aligning agent for liquid crystal. Moreover, in the case where needing the higher liquid crystal orientation film of reliability, it is preferable to use R in formula (1-1) and formula (1-2)²For hydrogen or- The compound of OH.

The concrete example of diamines represented by formula (1-1) is compound represented by following formula (1-1-1)~formula (1-1-28).

The concrete example of diamines represented by formula (1-2) is compound represented by following formula (1-2-1)~formula (1-2-28).

It can be by the way that diamines represented by formula (1-1-1)~formula (1-1-4), formula (1-2-1) and formula (1-2-2) be used as structure At one of the raw material of polymer of aligning agent for liquid crystal of the invention, even if will not be declined using display quality for a long time to obtain The high liquid crystal orientation film of liquid crystal aligning.

The poly- of aligning agent for liquid crystal of the invention is constituted by the way that diamines represented by formula (1-2-1)~formula (1-2-6) to be used as Close object one of raw material, even and if other diamines other than the diamines represented by formula (1), can also press down in Macroscopic single crystal Gelation processed.Think that its reason is: the hydrogen of amide groups is replaced by methyl, so hydrogen bond is formed by intermolecular interaction It disappears.

The synthetic method > of diamines represented by < formula (1)

Diamines represented by formula (1) can be synthesized by process below.

The position of substitution of < amino is 3,5-, R¹For the compound > of hydrogen

In the presence of the alkali such as triethylamine, make 3,5- dinitrobenzoyl chloride and commercially available 4- amino -2,2,6,6- tetramethyls Piperidine derivative reaction carries out the reduction of nitro, under hydrogen environment then in the presence of palladium-carbon catalyst thus to obtain ammonia The position of substitution of base is 3,5-, R¹For the diamines of the formula (1) of hydrogen.

The position of substitution of < amino is 3,5-, R¹For the compound > of methyl

Make commercially available 4- amino-2,2,6,6-tetramethylpiperidine derivative and iodomethane reaction, obtain methylamino -2 4-, 2,6,6- tetramethyl piperidine derivative.The position of substitution according to amino is 3,5-, R¹Synthesis for the compound of hydrogen carries out it Reaction afterwards, the position of substitution thus to obtain amino are 3,5-, R¹Diamines represented by formula (1) for methyl.

The position of substitution of < amino is 2,5-, R¹For the compound > of hydrogen

The bromo- 5- nitrobenzoic acid of commercially available 2- is set to react with thionyl chloride and obtain the bromo- 5- nitro benzoyl chloride of 2-.In three second In the presence of the alkali such as amine, keep the bromo- 5- nitro benzoyl chloride of 2- obtained and commercially available 4- amino-2,2,6,6-tetramethylpiperidine derivative Object reaction, and obtain amide body.It is reacted using Buchwald (Buchwald) come described in obtaining and being replaced with benzophenone imine Compound made of the bromine of amide body.Benzophenone imine position is changed into amino with the acid such as hydrochloric acid, is then catalyzed in palladium carbon In the presence of agent, the reduction of nitro is carried out under hydrogen environment, the position of substitution thus to obtain amino is 2,5-, R¹For hydrogen Diamines represented by formula (1).

The position of substitution of < amino is 2,5-, R¹For the compound > of methyl

Make commercially available 4- amino-2,2,6,6-tetramethylpiperidine derivative and iodomethane reaction, obtain methylamino -2 4-, 2,6,6- tetramethyl piperidine derivative.The position of substitution according to amino is 2,5-, R¹Synthesis for the compound of hydrogen carries out it Reaction afterwards, the position of substitution thus to obtain amino are 2,5-, R¹Diamines represented by formula (1) for methyl.

Polyamic acid and its derivative of the invention are illustrated.

Polyamic acid and its derivative of the invention is tetracarboxylic dianhydride and the diamines containing diamines represented by formula (1) Reaction product.The derivative of the 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, the liquid using polyimides as principal component can be formed The ingredient of brilliant alignment films.As the derivative of such polyamic acid, for example, can enumerate soluble polyimide, poly amic acid ester, And more specifically polyamic acid amide etc. can be enumerated: 1) all amino of polyamic acid and carboxyl carry out dehydration closed-loop reaction Made of polyimides, 2) partly carry out dehydration closed-loop reaction made of part polyimides, 3) by the carboxyl of polyamic acid It is transformed into poly amic acid ester made of ester, 4) has been replaced to a part of acid dianhydride contained in tetracarboxylic dianhydride's compound Machine dicarboxylic acids is simultaneously reacted and polyamic acid-polyamide copolymer for obtaining and 5) makes the polyamic acid-copolyamide Part or all of object carries out polyamidoimide made of dehydration closed-loop reaction.The polyamic acid and its derivative can be A kind of compound can also be two or more.As long as and the polyamic acid and its derivative are with tetracarboxylic dianhydride and diamines Reaction product structure compound, it is possible to use other raw materials and other than reacting containing tetracarboxylic dianhydride and diamines Other reaction reaction products.

The tetracarboxylic dianhydride of polyamic acid for manufacturing the present invention and its derivative is illustrated.

Tetracarboxylic dianhydride used in the present invention can unlimitedly select from well known tetracarboxylic dianhydride.Such tetrabasic carboxylic acid Dianhydride can be to belong to the aromatic system (comprising miscellaneous aromatic ring) and dicarboxylic anhydride is not that dicarboxylic anhydride is directly bonded on aromatic rings Tetracarboxylic dianhydride directly in any group of fatty family (including heterocycle system) of the bond on aromatic rings.

Appearance as the suitable example of such tetracarboxylic dianhydride, when the easiness or polymer polymerizing that are obtained with regard to raw material Tetracarboxylic dianhydride for the viewpoint of the electrical characteristics of Yi Xing, film, represented by can enumerating by formula (AN-I)~formula (AN-VII).

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

In formula (AN-III)~formula (AN-V), ring A¹⁰For carbon number be 3~10 monocyclic hydrocarbon base or carbon number be 6~30 At least one hydrogen of the base of condensation polycyclic formula hydrocarbon, the base can be replaced by methyl, ethyl or phenyl, be connected to associative key on ring with The arbitrary carbon connection of ring is constituted, 2 associative keys can link with the same carbon.In formula (AN-VI), X¹⁰The Asia for being 2~6 for carbon number Alkyl, Me indicate that methyl, Ph indicate phenyl.In formula (AN-VII), G¹⁰- O- ,-COO- or-OCO- are stood alone as, r stands alone as 0 or 1.

More specifically, the tetrabasic carboxylic acid two represented by can enumerating by formula below (AN-1)~formula (AN-16-14) formula Acid anhydride.

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

In formula (AN-1), G¹¹Alkylidene, 1,4- phenylene or the 1,4- cyclohexylidene for being 1~12 for singly-bound, carbon number.X¹¹ Stand alone as singly-bound or-CH₂-。G¹²Stand alone as any of the base of following trivalents.

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。

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-1), represented by can enumerating by following formulas Object.

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), R¹²Stand alone as hydrogen ,-CH₃、-CH₂CH₃Or phenyl.

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-2), represented by can enumerating by following formulas Object.

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

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

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-3), represented by can enumerating by following formulas Object.

[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)₂Or By the base of the divalent represented by following formulas (G13-1), the integer that m is 1~12.Ring A¹¹It is each independently cyclohexane ring or benzene Ring.G¹³Ring A can be bonded to¹¹Arbitrary position.

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

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-4), represented by can enumerating by following formulas Object.

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

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

In formula (AN-5), R¹¹For hydrogen or-CH₃.Binding site is not fixed to the R on the carbon atom for constituting phenyl ring¹¹It indicates Binding site in phenyl ring is any.

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-5), represented by can enumerating by following formulas Object.

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

In formula (AN-6), X¹¹Stand alone as singly-bound or-CH₂-。X¹²For-CH₂-、-CH₂CH₂Or-CH=CH-.N is 1 or 2.

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-6), represented by can enumerating by following formulas Object.

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

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

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-7), represented by can enumerating by following formulas Object.

[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.

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-8), represented by can enumerating by following formulas Object.

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

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

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-9), represented by can enumerating by following formulas Object.

[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 A¹¹Stand alone as cyclohexane ring or phenyl ring.

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-11), represented by can enumerating by following formulas Object.

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

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

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-12), represented by can enumerating by following formulas Object.

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

In formula (AN-13), X¹³The alkylidene for being 2~6 for carbon number, Ph indicate phenyl.

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-13), represented by can enumerating by following formulas Object.

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

In formula (AN-14), G¹⁴- O- ,-COO- or-OCO- are stood alone as, r stands alone as 0 or 1.

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-14), represented by can enumerating by following formulas Object.

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

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

Chemical combination as the example by the tetracarboxylic dianhydride represented by formula (AN-15), represented by can enumerating by following formulas Object.

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

The appropriate materials that each characteristic is improved in the acid dianhydride are described.In the feelings for the orientation for paying attention to being promoted liquid crystal Under condition, preferably by the compound represented by formula (AN-1), formula (AN-3) and formula (AN-4), particularly preferably by formula (AN-1-2), formula (AN-1-13), compound represented by formula (AN-3-2), formula (AN-4-17) and formula (AN-4-29), wherein at formula (AN-1-2) In, preferably m=4 or 8, in formula (AN-4-17), preferably m=4 or 8, particularly preferably m=8.

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

Paying attention to the case where promoting voltage retention (voltage the holding ratio, VHR) of liquid crystal display element Under, in the acid dianhydride, preferably by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4- 17), compound represented by formula (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and formula (AN-16-4), Wherein in formula (AN-1-2), preferably m=4 or 8, in formula (AN-4-17), preferably m=4 or 8, particularly preferred m=8.

As one of the method for preventing burn mark, effectively make to take and reducing the volumetric resistivity value of liquid crystal orientation film The mitigation speed of residual charge (remnant dc electricity (Direct Current, DC)) into film improves.Paying attention to the purpose In the case of, in the acid dianhydride, preferably by 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 to polyamic acid for manufacturing the present invention and its derivative are illustrated.Manufacturing this hair When bright polyamic acid or derivatives thereof, diamines and two hydrazides can be unlimitedly selected from well known diamines and two hydrazides.

Diamines can be divided into 2 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 2 amino as main chain.The side chain radical is that have to increase The base of the effect of pre-tilt angle.Side chain radical with such effect must be that the base that carbon number is 3 or more can be enumerated as concrete example: The alkoxyalkyl and there is steroids bone that alkoxy that alkyl that carbon number is 3 or more, carbon number are 3 or more, carbon number are 3 or more The base of frame.Ring with 1 or more ring and its end has the alkoxy that the alkyl that carbon number is 1 or more, carbon number are 1 or more And either one or two of the alkoxyalkyl that carbon number is 2 or more also has the effect of as the base of substituent group as side chain radical.Following Explanation in, the diamines with such side chain radical is known as side chain type diamine sometimes.Moreover, will not have such side chain radical sometimes Diamines be known as non-side chain type diamine.

By the way that non-side chain type diamine is suitably used separately with side chain type diamine, pre-dumping required for can correspond to respectively 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 Diamines is preferably accepted or rejected for the purpose of being promoted for the vertical orientation of liquid crystal, voltage retention, burn mark characteristic and orientation Selection is to use.

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

In the formula (DI-1), G²⁰For-CH₂, at least one-CH₂Can be replaced by-NH- ,-O-, m be 1~12 it is whole Number, at least one hydrogen of alkylidene can be replaced by-OH.In formula (DI-3) and formula (DI-5)~formula (DI-7), G²¹Stand alone as list Key ,-NH- ,-NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C (CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂- CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH- (CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n- CO- or-S- (CH₂)_m- S-, m stand alone as 1~12 it is whole Number, the integer that k is 1~5, n are 1 or 2.In formula (DI-4), s stands alone as 0~2 integer.In formula (DI-6) and formula (DI-7), G²² Stand alone as singly-bound ,-O- ,-S- ,-CO- ,-C (CH₃)₂-、-C(CF₃)₂Or the alkylidene that carbon number is 1~10.Formula (DI-2)~formula (DI-7) at least one hydrogen of cyclohexane ring and phenyl ring in can be by-F ,-Cl, the alkyl that carbon number is 1~3 ,-OCH₃、-OH、- CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl replace, in addition, cyclohexane ring and phenyl ring are at least in formula (DI-4) One hydrogen can by the base represented by following formula (DI-4-a)~formula (DI-4-e) group in a substitution.Binding site It is any for being not fixed to binding site of the basis representation on the carbon atom for constituting ring on the ring.Moreover,-NH₂In cyclohexane ring Or the binding site on phenyl ring is except G²¹Or G²²Binding site other than arbitrary position.

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

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

In formula (DI-12), R²¹And R²²Stand alone as the alkyl or phenyl that carbon number is 1~3, G²³Standing alone as carbon number is 1~6 Alkylidene, phenylene or through alkyl-substituted phenylene, the integer that w is 1~10.In formula (DI-13), R²³Standing alone as carbon number is 1 ~5 alkyl, the alkoxy or-Cl that carbon number is 1~5, p stand alone as 0~3 integer, the integer that q is 0~4.Formula (DI-14) In, ring B is the hetero ring type aromatic series base of monocycle, R²⁴For hydrogen ,-F ,-Cl, carbon number be 1~6 alkyl, alkoxy, vinyl, alkynes Base, q stand alone as 0~4 integer.In formula (DI-15), ring C is hetero ring type aromatic series base or hetero ring type fatty group.Formula (DI- 16) in, G²⁴The alkylidene or Isosorbide-5-Nitrae-phenylene for being 2~6 for singly-bound, carbon number, r are 0 or 1.Moreover, binding site is not fixed to structure Binding site of the basis representation on the ring on the carbon atom of cyclization is any.In formula (DI-13)~formula (DI-16), bond exists - NH on ring₂Binding site be arbitrary position.

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

Example of the following presentation by the diamines represented by formula (DI-1).

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

Example of the following presentation by the diamines represented by formula (DI-2)~formula (DI-3).

Example of the following presentation by the diamines represented by formula (DI-4).

Example of the following presentation by the diamines represented by formula (DI-5).

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.

Example of the following presentation by the diamines represented by formula (DI-6).

Example of the following presentation by the diamines represented by formula (DI-7).

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

Example of the following presentation by the diamines represented by formula (DI-8).

Example of the following presentation by the diamines represented by formula (DI-9).

Example of the following presentation by the diamines represented by formula (DI-10).

Example of the following presentation by the diamines represented by formula (DI-11).

Example of the following presentation by the diamines represented by formula (DI-12).

Example of the following presentation by the diamines represented by formula (DI-13).

Example of the following presentation by the diamines represented by formula (DI-14).

Example of the following presentation by the diamines represented by formula (DI-15).

Example of the following presentation by the diamines represented by formula (DI-16).

Two hydrazides are illustrated.As known two hydrazides without side chain, can enumerate formula below (DIH-1)~ Formula (DIH-3).

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

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

Following presentation formula (DIH-1)~formula (DIH-3) example.

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

Such non-side chain type diamine and two hydrazides have the improvement electrical characteristics such as reduces the ion concentration of liquid crystal display element Effect.Use non-side chain type diamine and/or two hydrazides as to manufacture used in aligning agent for liquid crystal of the invention Polyamic acid or derivatives thereof diamines in the case where, its shared ratio is set as preferably in the total amount of diamines and two hydrazides 0mol% (molar percentage)~90mol%, is more preferably set as 0mol%~50mol%

Side chain type diamine is illustrated.As the side chain radical of side chain type diamine, base below can be enumerated.

It as side chain radical, can enumerate first: alkyl, alkoxy, alkoxyalkyl, alkyl-carbonyl, alkyl carbonyl oxy, alcoxyl Base carbonyl, alkyl amino-carbonyl, alkenyl, alkenyloxy group, alkenyl carbonyl, alkynyl carbonyloxy group, allyloxycarbonyl, alkenyl amino carbonyl, Alkynyl, alkynyloxy group, alkynylcarbonyl groups, alkynyl carbonyloxy group, alkynyloxycar bonyl, alkynylaminocarbonyl etc..Alkyl, alkenyl in these bases And alkynyl is the base that carbon number is 3 or more.But in alkoxyalkyl, as long as the carbon number of entire base is 3 or more.This A little bases can be straight-chain, be also possible to branched.

Secondly, alkoxy or carbon number that the alkyl for being 1 or more with carbon number with the ring of end, carbon number are 1 or more are 2 or more Alkoxyalkyl as substituent group be condition, can enumerate: phenyl, phenylalkyl, phenyl alkoxy, phenoxy group, phenylcarbonyl group, Phenyl carbonyloxy group, phenyloxycarbonyl, phenyl amino carbonyl, phenyl cyclohexyloxy, the naphthenic base that carbon number is 3 or more, cyclohexyl alkane Base, cyclohexyloxy, cyclohexyloxy carbonyl, cyclohexyl phenyl, cyclohexyl phenyl alkyl, cyclohexyl benzene oxygroup, bis- (cyclohexyl) oxygen Base, bis- (cyclohexyl) alkyl, bis- (cyclohexyl) phenyl, bis- (cyclohexyl) phenylalkyls, bis- (cyclohexyl) Epoxide carbonyls, bis- (rings Hexyl) ring structures such as phenyloxycarbonyl and bis- (phenyl) Epoxide carbonyls of cyclohexyl base.

In turn, the ring set base that can be listed below, for the base of the phenyl ring with 2 or more, with 2 or more hexamethylenes The base more than base of alkane ring or 2 rings comprising phenyl ring and cyclohexane ring, and bond base stand alone as singly-bound ,-O- ,-COO- ,- The alkylidene that OCO- ,-CONH- or carbon number are 1~3, the ring of end have the fluorine that alkyl, carbon number that carbon number is 1 or more are 1 or more Replace the alkoxy that alkyl, carbon number are 1 or more or the alkoxyalkyl that carbon number is 2 or more as substituent group.With steroids bone The base of frame is also effective as side chain radical.

Compound as the diamines with side chain, represented by can enumerating by formula below (DI-31)~formula (DI-35).

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、- CF₂O-、-OCF₂Or-(CH₂)_m', m' be 1~12 integer.G²⁶Preferred example be singly-bound ,-O- ,-COO- ,-OCO- ,- CH₂The alkylidene that O- and carbon number are 1~3, example particularly preferably are singly-bound ,-O- ,-COO- ,-OCO- ,-CH₂O-、-CH₂And- CH₂CH₂-。R²⁵For carbon number be 3~30 alkyl, phenyl, the base with steroid skeleton or by following formula (DI-31-a) institutes The base of expression.In the alkyl, at least one hydrogen can be replaced by-F, and at least one-CH₂It can be by-O- ,-CH=CH- or-C ≡ C- replaces.The hydrogen of the phenyl can be by-F ,-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃, carbon number be 3~30 alkyl or carbon Number replaces for 3~30 alkoxy.It is bonded-the NH on phenyl ring₂Binding site expression be arbitrary position in the ring, should The preferred meta or para position of binding site.That is, working as base " R²⁵-G²⁶" binding site when being set as 1,2 binding sites preferably 3 Position and 5 or 2 and 5.

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For bond base, they stand alone as the alkylene that singly-bound or carbon number are 1~12 Base, the more than one-CH of the alkylidene₂It can be replaced by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH-.Ring B²¹, ring B²², ring B²³And ring B²⁴Stand alone as 1,4- phenylene, 1,4- cyclohexylidene, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- two Base, pyridine -2,5- diyl, naphthalene -1,5- diyl, naphthalene -2,7- diyl or anthracene -9,10- diyl, ring B²¹, ring B²², ring B²³And ring B²⁴ In, at least one hydrogen can be by-F or-CH₃Replace, s, t and u stand alone as 0~2 integer, they add up to 1~5, as s, t or When u is 2,2 bond bases in each bracket be may be the same or different, moreover, 2 rings can be identical, it can also not Together.R²⁶For hydrogen ,-F ,-OH, carbon number be 1~30 alkyl, carbon number be 1~30 fluorine replace the alcoxyl that alkyl, carbon number are 1~30 Base ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, at least one-CH for the alkyl which is 1~30₂It can be by with following formula (DI- The base of divalent represented by 31-b) replaces.

In formula (DI-31-b), R²⁷And R²⁸Stand alone as the alkyl that carbon number is 1~3, the integer that v is 1~6.R²⁶It is preferred The alkoxy that example is the alkyl that carbon number is 1~30 and carbon number is 1~30.

In formula (DI-32) and formula (DI-33), G³⁰Stand alone as singly-bound ,-CO- or-CH₂, R²⁹Stand alone as hydrogen or-CH₃, R³⁰For The alkenyl that the alkyl or carbon number that hydrogen, carbon number are 1~20 are 2~20.At least one hydrogen of phenyl ring in formula (DI-33) can be by carbon Number replaces for 1~20 alkyl or phenyl.Moreover, binding site is not fixed to the basis representation on any one carbon atom for constituting ring Binding site in the ring is any.2 bases "-phenylene-G in preferred formula (DI-32)³⁰A bond of-O- " is in class 3 of sterol core, another bond is at 6 of steroids core.2 bases "-phenylene-G in formula (DI-33)³⁰- O- " is in phenyl ring On binding site preferably with respect to the binding site of steroids core, respectively meta or para position.Formula (DI-32) and formula (DI- 33) in, it is bonded-the NH on phenyl ring₂Indicate that the binding site in the ring is any.

In formula (DI-34) and formula (DI-35), G³¹Stand alone as the alkylidene that-O- or carbon number are 1~6, G³²For singly-bound or carbon The alkylidene that number is 1~3.R³¹The alkyl for being 1~20 for hydrogen or carbon number, at least one-CH of the alkyl₂It can be by-O- ,-CH= CH- or-C ≡ C- replaces.R³²The alkyl for being 6~22 for carbon number, R³³The alkyl for being 1~22 for hydrogen or carbon number.Ring B²⁵For the Asia 1,4- Phenyl or 1 or 4 cyclohexylidene, r are 0 or 1.Moreover,-NH of the bond on phenyl ring₂Indicate that the binding site on the ring is to appoint Meaning, but it is preferred independently and relative to G³¹Binding site be meta or para position.

The concrete example of side chain type diamine illustrated below.As two of the formula (DI-31)~formula (DI-35) with side chain Amine, the compound represented by can enumerating by following formulas (DI-31-1)~formula (DI-35-3).

Example of the following presentation by the compound represented by formula (DI-31).

In formula (DI-31-1)~formula (DI-31-11), R³⁴For carbon number be 1~30 alkyl or carbon number be 1~30 alcoxyl The alkoxy that the alkyl or carbon number that base, preferably carbon number are 5~25 are 5~25.R³⁵For carbon number be 1~30 alkyl or carbon number be 1 The alkoxy that the alkyl or carbon number that~30 alkoxy, preferably carbon number are 3~25 are 3~25.

In formula (DI-31-12)~formula (DI-31-17), R³⁶The alkyl for being 4~30 for carbon number, preferably carbon number are 6~25 Alkyl.R³⁷The alkyl that the alkyl for being 6~30 for carbon number, preferably carbon number are 8~25.

In formula (DI-31-18)~formula (DI-31-43), R³⁸For carbon number be 1~20 alkyl or carbon number be 1~20 alcoxyl The alkoxy that the alkyl or carbon number that base, preferably carbon number are 3~20 are 3~20.R³⁹For hydrogen ,-F, carbon number be 1~30 alkyl, carbon Alkoxy ,-CN ,-OCH of the number for 1~30₂F、-OCHF₂Or-OCF₃, preferably carbon number be 3~25 alkyl or carbon number be 3~25 Alkoxy.Moreover, G³³The alkylidene for being 1~20 for carbon number.

Example of the following presentation by the compound represented by formula (DI-32).

Example of the following presentation by the compound represented by formula (DI-33).

Example of the following presentation by the compound represented by formula (DI-34).

In formula (DI-34-1)~formula (DI-34-12), R⁴⁰The alkyl for being 1~20 for hydrogen or carbon number, preferably hydrogen or carbon number are 1 ~10 alkyl, moreover, R⁴¹The alkyl for being 1~12 for hydrogen or carbon number.

Example of the following presentation by the compound represented by formula (DI-35).

In formula (DI-35-1)~formula (DI-35-3), R³⁷The alkyl for being 6~30 for carbon number, R⁴¹It is 1~12 for hydrogen or carbon number Alkyl.

As the diamines in the present invention, also can be used by formula (DI-1-1)~formula (DI-16-1), formula (DIH-1-1)~ Diamines other than diamines represented by formula (DIH-3-6) and formula (DI-31-1)~formula (DI-35-3).As such diamines, such as Compound represented by can enumerating by following formula (DI-36-1)~formula (DI-36-13).

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

In formula (DI-36-9)~formula (DI-36-11), the integer that e is 2~10, in formula (DI-36-12), R⁴³Independently For hydrogen ,-NHBoc or-N (Boc)₂, R⁴³At least one be-NHBoc or-N (Boc)₂, in formula (DI-36-13), R⁴⁴For- NHBoc or-N (Boc)₂, moreover, the integer that m is 1~12.Herein, Boc is tert-butoxycarbonyl.

In the case where paying attention to further promoting the orientation of liquid crystal, it is preferable to use by formula in the diamines and two hydrazides (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), diamines represented by formula (DI-6-7), formula (DI-7-3) and formula (DI-11-2), wherein in formula (DI-5-1), preferably m =2,4 or 6, particularly preferably m=4, in formula (DI-5-12), preferred m=2~6, particularly preferably m=5, excellent in formula (DI-5-13) M=1 or 2 is selected, particularly preferably m=1.

In the case where paying attention to promoting transmitance, it is preferable to use by formula (DI-1-3), formula in the diamines and two hydrazides (DI-2-1), diamines represented by formula (DI-5-1), formula (DI-5-5), formula (DI-5-24) and formula (DI-7-3), particularly preferably by Diamines represented by formula (DI-2-1).In formula (DI-5-1), preferably m=2,4 or 6, particularly preferably m=4, at formula (DI-7-3) In, preferably m=2 or 3, n=1 or 2, particularly preferably m=1.

In the case where paying attention to promoting the VHR of liquid crystal display element, it is preferable to use by formula in the diamines and two hydrazides (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5- 28), diamines represented by formula (DI-5-30) and formula (DI-13-1), particularly preferably by formula (DI-2-1), formula (DI-5-1) and formula (DI-13-1) diamines represented by.Wherein in formula (DI-5-1), particularly preferably m=1, in formula (DI-5-30), particularly preferably k= 2。

As one of the method for preventing burn mark, effectively make to take and reducing the volumetric resistivity value of liquid crystal orientation film The mitigation speed of residual charge (residual DC) into film improves.In the case where paying attention to the purpose, the diamines and two hydrazides In, it is preferable to use by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI- 5-12), diamines represented by formula (DI-5-13), formula (DI-5-28) and formula (DI-16-1), particularly preferably by formula (DI-4-1), formula (DI-5-1) and diamines represented by formula (DI-5-13).Wherein in formula (DI-5-1), preferably m=2,4 or 6, particularly preferably m= 4, in formula (DI-5-12), preferred m=2~6, particularly preferably m=5, in formula (DI-5-13), preferably m=1 or 2, particularly preferably m =1.

It, can also be in the range that the ratio of the monoamine relative to diamines is 40mol% or less, by diamines in each diamines A part be replaced to monoamine.Such substitution can cause the termination of polymerization reaction when generating polyamic acid, and it is anti-to can inhibit polymerization The further progress answered.Therefore, by such substitution, can easily control polymer obtained (polyamic acid or its spread out Biology) molecular weight, such as can lossless effect of the invention and improve the coating characteristics of aligning agent for liquid crystal.As long as the lossless present invention Effect, then the diamines for being substituted into monoamine can be one kind, is also possible to two or more.As the monoamine, such as can arrange It lifts: aniline, 4- hydroxyanilines, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, just Undecylamine, n-dodecylamine, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, hexadecylamine, positive heptadecyl-amine, octadecyl amine and positive two Ten amine.

Polyamic acid of the invention or derivatives thereof can contain in turn monoisocyanate compound in monomer.By Contain monoisocyanate compound in monomer, the end of polyamic acid obtained or derivatives thereof is modified, and molecular weight obtains To adjusting.By using the polyamic acid or derivatives thereof of the end modified type, for example, can lossless effect of the invention and improve The coating characteristics of aligning agent for liquid crystal.For the viewpoint, relative to the total amount of diamines and tetracarboxylic dianhydride in monomer, monomer In monoisocyanate compound the preferred 1mol%~10mol% of content.As the monoisocyanate compound, such as can It enumerates: phenyl isocyanate and naphthyl isocyanate.

Polyamic acid and its derivative of the invention can be by carrying out the mixture of the acid anhydrides in a solvent with diamines It reacts and obtains.In the synthetic reaction, in addition to the selection of raw material, it is not necessarily to special condition, it can be directly using common poly- Condition in amic acid synthesis.Used solvent will be aftermentioned.

Aligning agent for liquid crystal of the invention can and then contain the other compositions other than polyamic acid or derivatives thereof.Other compositions It can be a kind, be also possible to two or more.As other compositions, such as aftermentioned other polymers or compound can be enumerated etc..

Aligning agent for liquid crystal of the invention can be in turn containing other polymerizations other than polyamic acid of the invention or derivatives thereof Object.It as other polymers, can enumerate: react tetracarboxylic dianhydride with the diamines comprising diamines of the invention and obtain Polymer other than polyamic acid or derivatives thereof, that is, carry out tetracarboxylic dianhydride with the diamines without diamines of the invention anti- Answer and the polyamic acid that obtains or derivatives thereof (hereinafter referred to as " other polyamic acids or derivatives thereof "), polyester, polyamide, Polysiloxanes, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenylmaleimide) are derivative Object, poly- (methyl) acrylate etc..It can be a kind, be also possible to two or more.In these polymer, preferred other polyamic acids Or derivatives thereof and polysiloxanes, other more preferable polyamic acids or derivatives thereof.

It is orientated made of blending polyamic acid of the invention or derivatives thereof and other polyamic acids or derivatives thereof In agent, then as described later the structure or molecular weight for controlling each polymer are coated on substrate, and carry out predrying, by Polyamic acid of the invention or derivatives thereof ingredient [A] can be separated into upper layer by this, by other polyamic acids or derivatives thereof at [B] is divided to be separated into lower layer.It can be by being controlled using following phenomenon: in the polymer being mixed, surface can be small Polymer is separated into upper layer, and energy big polymer in surface is separated into lower layer.Layer separation is approved really by being formed by alignment films Surface can confirm for the value same or similar with the surface energy by the film that is formed of aligning agent for liquid crystal for only containing [A] ingredient.

It, can be unlimitedly from as closing as the tetracarboxylic dianhydride for synthesizing other polyamic acids or derivatives thereof Tetrabasic carboxylic acid well known to the tetracarboxylic dianhydride of essential component, that is, polyamic acid at aligning agent for liquid crystal of the invention or derivatives thereof It selects, can enumerate identical with the tetracarboxylic dianhydride of the illustration in dianhydride.

Wherein, in the acid dianhydride, in the case where paying attention to promoting layer separation property, preferred formula (AN-3-2), formula (AN-1- And formula (AN-4-30) 13).

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

In the case where paying attention to promoting the VHR of liquid crystal display element, in the acid dianhydride, preferably by formula (AN-1-2), formula (AN-2-1), represented by formula (AN-7-2), formula (AN-10-1), formula (AN-10-2), formula (AN-16-3) and formula (AN-16-4) Compound, wherein in formula (AN-1-2), preferably m=4 or 8.

As one of the method for preventing burn mark, effectively make to take and reducing the volumetric resistivity value of liquid crystal orientation film The mitigation speed of residual charge (residual DC) into film improves.In the case where paying attention to the purpose, in the acid dianhydride, preferably By the compound represented by formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and formula (AN-11-3).

As the tetracarboxylic dianhydride for synthesizing other polyamic acids or derivatives thereof, preferably with respect to all tetrabasic carboxylic acids two Acid anhydride and aromatic tetracarboxylic dianhydride containing 10mol% or more, the aromatic tetracarboxylic acid two of further preferably 30mol% or more Acid anhydride.

As the diamines and two hydrazides for synthesizing other polyamic acids or derivatives thereof, can enumerate and above as available The diamines illustrated by other diamines for synthesizing essential component, that is, polyamic acid of aligning agent for liquid crystal of the invention or derivatives thereof And two hydrazides it is identical.

Wherein, in the case where paying attention to further promoting layer separation property, that is, liquid crystal orientation, the diamines and two hydrazides In, it is preferable to use by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-5-1), formula (DI-5-9), formula (DI-5- 28) and diamines represented by formula (DIH-2-1) and two hydrazides, wherein in formula (DI-5-1), preferably m=1,2 or 4 are special excellent Select m=1 or 2.

In the case where paying attention to promoting transmitance, it is preferable to use by formula (DI-1-2), formula in the diamines and two hydrazides (DI-2-1), diamines represented by formula (DI-5-1) and formula (DI-7-3), particularly preferably by the diamines represented by (DI-2-1).In In formula (DI-5-1), preferably m=1,2 or 4, particularly preferably m=1 or 2, in formula (DI-7-3), preferably m=2 or 3, n=1 or 2, Particularly preferably m=1.

In the case where paying attention to promoting the VHR of liquid crystal display element, it is preferable to use by formula in the diamines and two hydrazides (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5- 30) and diamines represented by formula (DI-13-1), particularly preferably by formula (DI-2-1), formula (DI-5-1) and formula (DI-13-1) institute table The diamines shown.Wherein, in (DI-5-1), particularly preferably m=1 or 2, in (DI-5-30), particularly preferably k=2.

As one of the method for preventing burn mark, effectively make to take and reducing the volumetric resistivity value of liquid crystal orientation film The mitigation speed of residual charge (residual DC) into film improves.In the case where paying attention to the purpose, the diamines and two hydrazides In, it is preferable to use by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI- 5-9), two represented by formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30) and formula (DI-16-1) Amine, particularly preferably by the diamines represented by formula (DI-4-1), formula (DI-5-1) and formula (DI-5-12).Wherein, at formula (DI-5-1) In, preferably m=1 or 2, in (DI-5-12), preferred m=2~6, particularly preferably m=5, in (DI-5-13), preferably m=1 or 2, particularly preferably m=1, in (DI-5-30), particularly preferably k=2.

As the diamines for synthesizing other polyamic acids or derivatives thereof, contain preferably with respect to all diamines The aromatic diamine of 30mol% or more, the further preferably aromatic diamine of 50mol% or more.

Other polyamic acids or derivatives thereof respectively can be according to the essential component below as aligning agent for liquid crystal of the invention That is method documented by the synthetic method of polyamic acid or derivatives thereof synthesizes.

As [A] ingredient relative to polyamic acid of the invention or derivatives thereof ([A] ingredient) and other polyamide The ratio of the total amount of acid or derivatives thereof ([B] ingredient), preferably 10wt% (weight percent)~100wt% are more excellent Select 20wt%~100wt%.

It is special that Japanese Patent Laid-Open 2009-036966, Japanese Patent Laid-Open 2010-185001, Japan Patent can be contained in turn Open 2011-102963, Japanese Patent Laid-Open 2011-253175, Japanese Patent Laid-Open 2012-159825, International Publication 2008/ 044644, International Publication 2009/148099, International Publication 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, the world Polysiloxanes disclosed in 2012/115157, International Publication 2012/165354 etc. is disclosed as the polysiloxanes.

< alkenyl replaces nadikimide compound >

For example, aligning agent for liquid crystal of the invention can for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term Further replace nadikimide compound containing alkenyl.Alkenyl replaces nadikimide compound to can be used a kind, can also To be used in combination of two or more.For the purpose, relative to polyamic acid or derivatives thereof, alkenyl replaces nadikimide Close content preferred 1wt%~100wt%, the more preferable 1wt%~70wt% of object, and then more preferably 1wt%~50wt%.

Nadikimide compound is specifically described below.

Alkenyl replace nadikimide compound preferably may be dissolved in dissolution the present invention used in polyamic acid or Compound in the solvent of its derivative.Such alkenyl replaces the example of nadikimide compound that can enumerate by following formulas (NA) compound represented by.

In formula (NA), L¹And L²Stand alone as hydrogen, the alkenyl that the alkyl that carbon number is 1~12, carbon number are 3~6, carbon number are 5~8 Naphthenic base, carbon number be 6~12 aryl or benzyl, n be 1 or 2.

In formula (NA), as n=1, W be carbon number be 1~12 alkyl, carbon number be 2~6 alkenyl, carbon number be 5~8 Naphthenic base, carbon number be 6~12 aryl, benzyl, by-Z¹-(O)_r-(Z²O)_k-Z³- H (herein, Z¹、Z²And Z³Standing alone as carbon number is 2 ~6 alkylidene, r be 0 or 1, moreover, k be 1~30 integer) represented by base, by-(Z⁴)_r-B-Z⁵- H (herein, Z⁴And Z⁵ The alkylidene that carbon number is 1~4 or the cycloalkylidene that carbon number is 5~8 are stood alone as, B is phenylene, moreover, r is 0 or 1) represented Base, by-B-T-B-H (herein, B is phenylene, moreover, T be-CH₂-、-C(CH₃)₂,-O- ,-CO- ,-S- or-SO₂) institute The base that 1 hydrogen~3 hydrogen warp-OH of the base of expression or these bases replaces.

At this point, preferred W be carbon number be 1~8 alkyl, carbon number be 3~4 alkenyl, cyclohexyl, phenyl, benzyl, carbon number For 4~10 poly- (inferior ethoxyl) ethyl, Phenoxyphenyl, phenyl methyl phenyl, phenyl isopropylidene phenyl and these bases The base that 1 hydrogen or 2 hydrogen warp-OH replace.

In formula (NA), as n=2, W be carbon number be 2~20 alkylidene, carbon number be 5~8 cycloalkylidene, carbon number 6 ~12 arlydene, by-Z¹-O-(Z²O)_k-Z³(herein, Z¹~Z³And k is as defined above) represented by base, by-Z⁴- B-Z⁵(herein, Z⁴、Z⁵And B is as defined above) represented by base, by-B- (O-B)_r-T-(B-O)_r(herein, B is Asia to-B- Phenyl, T are alkylidene ,-O- or the-SO that carbon number is 1~3₂, r is as defined above) represented by base or these bases 1 The base that a hydrogen~3 hydrogen warp-OH replaces.

At this point, preferred W be carbon number be 2~12 alkylidene, cyclohexylidene, phenylene, toluylene, benzene diformazan Base, by-C₃H₆-O-(Z²-O)_n-O-C₃H₆(herein, Z²The alkylidene for being 2~6 for carbon number, n be 1 or 2) represented by base, by- (herein, B is phenylene to B-T-B-, moreover, T is-CH₂,-O- or-SO₂) represented by base, by-B-O-B-C₃H₆-B-O-B- The base that 1 hydrogen or 2 hydrogen warp-OH of base represented by (herein, B is phenylene) and these bases replace.

Such alkenyl replaces nadikimide compound to can be used for example as remembered in No. 2729565 bulletins of Japan Patent Carry like that, by by alkenyl replaces carbic anhydride derivative and diamines 80 DEG C~220 DEG C at a temperature of holding 0.5 hour~ The compound or commercially available compound obtained to be synthesized for 20 hours.Replace nadikimide compound as alkenyl Concrete example, compound shown below can be enumerated.

Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of N- methyl-allyl, N- methyl allyl ylmethyl are double Ring [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- methyl-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two Carboxyl acid imide, N- methyl-methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- ethyl Hexyl)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide,

Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of N- (2- ethylhexyl)-allyl (methyl), N- allyl Base-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- allyl-allyl methyl bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximide, N- Allyl-methyl pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyl are sub- Amine, N- isopropenyl-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- isopropenyl-allyl (first Base) bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- isopropenyl-methacrylic bicyclic [2.2.1] hept- 5- Alkene -2,3- dicarboximide, N- cyclohexyl-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- hexamethylene Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base-allyl (methyl), N- Cyclohexyl-methyl pi-allyl bicyclic Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboxyl acyl of [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- Phenyl-allyl Imines,

Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of N- Phenyl-allyl (methyl), N- benzyl-allyl Bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- benzyl-allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- Dicarboximide, N- benzyl-methyl pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- hydroxyl second Base)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2- ethoxy)-allyl (methyl) be bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, alkene -2 N- (2- ethoxy)-methacrylic bicyclic [2.2.1] hept- 5-, 3- dicarboximide,

N- (2,2- dimethyl -3- hydroxypropyl)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of (2,2- dimethyl -3- hydroxypropyl)-allyl (methyl), N- (2,3- Dihydroxypropyl)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (2,3- dihydroxypropyl)-allyl (methyl) bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (3- hydroxyl -1- acrylic)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, bicyclic [2.2.1] the hept- 5- of N- (4- hydroxy-cyclohexyl)-allyl (methyl) Alkene -2,3- dicarboximide,

N- (4- hydroxyphenyl)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (4- hydroxyphenyl) - Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of allyl (methyl), N- (4- hydroxyphenyl)-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (4- hydroxyphenyl)-methacrylic methyl bicycle [2.2.1] hept- 5- Alkene -2,3- dicarboximide, N- (3- hydroxyphenyl)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of (3- hydroxyphenyl)-allyl (methyl), N- (to hydroxybenzyl)-alkene Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of propyl, N- { 2- (2- hydroxyl-oxethyl) ethyl }-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide,

Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboxyl acyl of N- { 2- (2- hydroxyl-oxethyl) ethyl }-allyl (methyl) Imines, N- { 2- (2- hydroxyl-oxethyl) ethyl }-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- { 2- (2- hydroxyl-oxethyl) ethyl }-methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- [2- { 2- (2- hydroxyl-oxethyl) ethyoxyl } ethyl]-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- [2- { 2- (2- hydroxyl-oxethyl) ethyoxyl } ethyl] bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyl of-allyl (methyl) Imines, N- [2- { 2- (2- hydroxyl-oxethyl) ethyoxyl } ethyl]-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl Base acid imide, N- { 4- (4- hydroxyphenyl isopropylidene) phenyl }-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyl are sub- Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboxyl acyl of amine, N- { 4- (4- hydroxyphenyl isopropylidene) phenyl }-allyl (methyl) is sub- Amine, N- { 4- (4- hydroxyphenyl isopropylidene) phenyl }-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyl are sub- Amine and their oligomer,

N, N'- ethylidene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, the Asia N'- second Base-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N'- ethylidene-bis- (methallyls Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base), N, N'- trimethylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- hexa-methylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyl Imines), N, N'- hexa-methylene-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- ten Dimethylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, ten dimethylene of N'--bis- (alkene Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of hydroxypropyl methyl), N, N'- cyclohexylidene-bis- (pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- cyclohexylidene-bis- (allyl methyl bicyclic [2.2.1] hept- 5- Alkene -2,3- dicarboximide),

1,2- bis- { 3'- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) propoxyl group } ethane, 1,2- Bis- { 3'- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) propoxyl group } ethane, the bis- { 3'- of 1,2- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) propoxyl group } ethane, bis- [2'- { 3'- (allyls Bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) propoxyl group } ethyl] ether, bis- [2'- { 3'- (allyl methyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximide) propoxyl group } ethyl] ether, the bis- { 3'- (pi-allyl bicyclics [2.2.1] of 1,4- Hept- 5- alkene -2,3- dicarboximide) propoxyl group } butane, bis- { 3'- (allyl methyl bicyclic [2.2.1] the hept- 5- alkene-of 1,4- 2,3- dicarboximide) propoxyl group } butane,

N, N'- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) bis- to phenylene -, N, N'- is to Asia Phenyl-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N'- metaphenylene-bis- (allyls Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base), N, N'- metaphenylene-bis- (allyl methyl bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximide), N, N'- { (1- methyl) -2,4- phenylene }-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- terephthaldehyde base-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl Acid imide), N, N'- terephthaldehyde base-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, Xyxylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N between N'-, xyxylene-between N'- Bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides),

Bis- [4- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] third of 2,2- Bis- [4- { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] third of alkane, 2,2- Bis- [4- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] third of alkane, 2,2- Alkane, bis- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (allyl methyls Bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane,

Bis- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl ether, it is bis- 4- (alkene -2 allyl methyl bicyclic [2.2.1] hept- 5-, 3- dicarboximide) phenyl } ether, bis- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) benzene Base } ether, bis- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } sulfones, bis- { 4- (allyl first Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base) phenyl } sulfone,

Bis- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } sulfones, the bis- (alkene of 1,6- Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of propyl) -3- hydroxy-hexane, the bis- (methacrylic bicyclics of 1,12- [2.2.1] hept- 5- alkene -2,3- dicarboximide) -3,6- dihydroxy-dodecane, the bis- (pi-allyl bicyclics [2.2.1] of 1,3- Hept- 5- alkene -2,3- dicarboximide) -5- hydroxy-cyclohexan alkane, bis- { 3'- (pi-allyl bicyclic [2.2.1] the hept- 5- alkene-of 1,5- 2,3- dicarboximide) propoxyl group } -3- hydroxyl-pentane, bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyls of 1,4- Base acid imide) -2- hydroxyl-benzene,

Bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) -2,5- dihydroxy-benzene of 1,4-, N, N'- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) bis- to (2- hydroxyl) xyxylene -, N, N'- pairs (2- hydroxyl) xyxylene-bis- (allyl methyl ring [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, (2- hydroxyl between N'- Base) xyxylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, (2- hydroxyl) benzene two between N'- Methyl-bis- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N'- is to (2,3- dihydroxy) benzene Dimethyl-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides),

Bis- [4- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) -2- hydroxyls-benzene oxygen of 2,2- Base } phenyl] propane, bis- { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) -2- hydroxyls-benzene Base } methane, bis- { 3- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) -4- hydroxy-pheny } ethers, bis- { 3- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) -5- hydroxy-pheny } sulfone, the { 4- (alkene of 1,1,1- tri- Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of hydroxypropyl methyl) } phenoxymethyl propane, N, (the ethylidene of N', N "-three Methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) fulminuric acid ester and their oligomer etc..

In turn, the alkenyl used in the present invention replaces nadikimide compound that can be to contain asymmetrical alkylene Base phenylene by the compound represented by following formulas.

Following presentation alkenyl replaces the preferred compound in nadikimide compound.

N, N'- ethylidene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, the Asia N'- second Base-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N'- ethylidene-bis- (methallyls Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base), N, N'- trimethylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- hexa-methylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyl Imines), N, N'- hexa-methylene-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- ten Dimethylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, ten dimethylene of N'--bis- (alkene Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of hydroxypropyl methyl), N, N'- cyclohexylidene-bis- (pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- cyclohexylidene-bis- (allyl methyl bicyclic [2.2.1] hept- 5- Alkene -2,3- dicarboximide),

N, N'- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) bis- to phenylene -, N, N'- is to Asia Phenyl-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N'- metaphenylene-bis- (allyls Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base), N, N'- metaphenylene-bis- (allyl methyl bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximide), N, N'- { (1- methyl) -2,4- phenylene }-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- terephthaldehyde base-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl Acid imide), N, N'- terephthaldehyde base-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, Xyxylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N between N'-, xyxylene-between N'- Bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), the bis- [4- { 4- (pi-allyl bicyclics of 2,2- [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] propane, the bis- [4- { 4- (allyl methyl bicyclics of 2,2- [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] propane, the bis- [4- { 4- (methacrylic bicyclics of 2,2- [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] propane, bis- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- Alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyls Imines) phenyl } methane.

Bis- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl ether, it is bis- 4- (alkene -2 allyl methyl bicyclic [2.2.1] hept- 5-, 3- dicarboximide) phenyl } ether, bis- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) benzene Base } ether, bis- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } sulfones, bis- { 4- (allyl first Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base) phenyl } sulfone, bis- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } sulfone.

The preferred alkenyl of following presentation replaces nadikimide compound.

N, N'- ethylidene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, the Asia N'- second Base-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N'- ethylidene-bis- (methallyls Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base), N, N'- trimethylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- hexa-methylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl acyl Imines), N, N'- hexa-methylene-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- ten Dimethylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, ten dimethylene of N'--bis- (alkene Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of hydroxypropyl methyl), N, N'- cyclohexylidene-bis- (pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- cyclohexylidene-bis- (allyl methyl bicyclic [2.2.1] hept- 5- Alkene -2,3- dicarboximide).

N, N'- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) bis- to phenylene -, N, N'- is to Asia Phenyl-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N'- metaphenylene-bis- (allyls Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximide of base), N, N'- metaphenylene-bis- (allyl methyl bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximide), N, N'- { (1- methyl) -2,4- phenylene }-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, N'- terephthaldehyde base-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxyl Acid imide), N, N'- terephthaldehyde base-bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N, Xyxylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N between N'-, xyxylene-between N'- Bis- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides).

Bis- [4- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] third of 2,2- Bis- [4- { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] third of alkane, 2,2- Bis- [4- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenoxy group } phenyl] third of alkane, 2,2- Alkane, bis- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (allyl methyls Bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane, bis- { 4- (methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- two Carboxyl acid imide) phenyl } methane.

Moreover, replacing nadikimide compound as alkenyl particularly preferably, can enumerate: by following formula (NA-1) institute table Bis- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } methane for showing, by formula (NA-2) institute table Xyxylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) and by formula (NA- between the N shown, N'- 3) N represented by, N'- hexa-methylene-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, aligning agent for liquid crystal of the invention can for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term Further 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, be also possible to compound of more than two kinds.Furthermore with free-radical polymerised unsaturated double-bond Replace nadikimide compound without alkenyl in compound.For the purpose, relative to polyamic acid or its derivative Object, with free-radical polymerised unsaturated double-bond compound content preferred 1wt%~100wt%, more preferable 1wt%~ 70wt%, and then more preferably 1wt%~50wt%.

Furthermore there is free-radical polymerised unsaturated double-bond about relative to alkenyl substitution nadikimide compound Compound ratio, in order to reduce liquid crystal display element ion concentration, inhibit ion concentration through when increase, and then press down The generation of image retention processed, with free-radical polymerised unsaturated double-bond compound/alkenyl replace nadikimide compound with Weight ratio meter preferably 0.1~10, more preferable 0.5~5.

The compound with free-radical polymerised unsaturated double-bond is specifically described below.

It as the compound with free-radical polymerised unsaturated double-bond, can enumerate: (methyl) acrylate, (methyl) third (methyl) acrylic acid derivative such as acrylamide and double maleimides.Change with free-radical polymerised unsaturated double-bond Closing object more preferably has 2 or more (methyl) acrylic acid derivative of free-radical polymerised unsaturated double-bond.

It as the concrete example of (methyl) acrylate, such as can enumerate: (methyl) cyclohexyl acrylate, (methyl) propylene Acid -2- methyl cyclohexyl, (methyl) dicyclopentanyl acrylate, two cyclopentyloxy ethyl ester of (methyl) acrylic acid, (methyl) acrylic acid Isobornyl thiocyanoacetate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate and (methyl) third Olefin(e) acid -2- hydroxy propyl ester.

As the concrete example of two functions (methyl) acrylate, such as can enumerate: ethylenebis acrylate, as East Asia Sieve's Ah Knicks M-210 (Aronix M-210), the Aronix M-240 and Aronix of the product of synthetic chemical industry (share) M-6200, the card Ya De HDDA (KAYARAD HDDA) of the product as Japanese chemical drug (share), KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, V260, V312 of the product as Osaka Organic Chemical Industry (share) and V335HP, and the light acrylate BA-4EA (Light of the product as common prosperity society oil chemical industry (share) Acrylate BA-4EA), Light Acrylate BP-4PA and Light Acrylate BP-2PA.

It as the concrete example of multifunctional (methyl) acrylate more than trifunctional, such as can enumerate: 4,4'- di-2-ethylhexylphosphine oxides (N, N- N-dihydroxy ethylidene acrylate aniline), the Aronix M- of the product as East Asia synthetic chemical industry (share) 400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, as KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, the KAYARAD of the product of Japanese chemical drug (share) DPCA-60, KAYARAD DPCA-120, and the VGPT of the product as Osaka Organic Chemical Industry (share).

It as the concrete example of (methyl) acrylamide derivative, such as can enumerate: n-isopropyl acrylamide, N- isopropyl Methacrylamide, N- propyl Methacrylamide, N- n-propyl Methacrylamide, N- cyclopropyl acrylamide, N- cyclopropyl Methacrylamide, N- ethoxyethyl group acrylamide, N- ethoxyethyl group Methacrylamide, N- tetrahydrofurfuryl acryloyl Amine, N- tetrahydrofurfuryl Methacrylamide, N- ethyl acrylamide, N- ethyl-N-methyl acrylamide, N, N- diethyl propylene Amide, N- methyl-N-n-propyl acrylamide, N- methyl-N-isopropyl acrylamide, N- acryloylpiperidine, N- acryloyl Base pyrrolidines, N, N'- methylene-bisacrylamide, N,N' ethylene bis acrylamide, N, the double propylene of N'- dihydroxy ethylidene Amide, N- (4- hydroxyphenyl) Methacrylamide, N- phenyl methacrylamide, N- butyl methyl acrylamide, N- (isobutyl oxygen Ylmethyl) Methacrylamide, N- [2- (N, N- dimethylamino) ethyl] Methacrylamide, N, N- dimethyl methacryl Amine, N- [3- (dimethylamino) propyl] Methacrylamide, N- (methoxy) Methacrylamide, N- (methylol) -2- Methacrylamide, N- benzyl -2- Methacrylamide and N, N'- methylenebismethacrylamide.

Among (methyl) acrylic acid derivative, particularly preferably N, N'- methylene-bisacrylamide, N, N'- dihydroxy are sub- Ethyl-bisacrylamide, ethylenebis acrylate and 4,4' methylene bis (N, N- dihydroxy ethylidene acrylate benzene Amine).

As double maleimides, such as can enumerate: KI be melted into (share) manufacture BMI-70 and BMI-80 and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000 of big and chemical conversion industry (share) manufacture.

< oxazines compound >

For example, aligning agent for liquid crystal of the invention can for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term Further contain oxazines compound.Oxazines compound can be a kind of compound, be also possible to compound of more than two kinds.It is just described For purpose, relative to polyamic acid or derivatives thereof, the preferred 0.1wt%~50wt% of the content of oxazines compound, more preferably 1wt%~40wt%, and then more preferably 1wt%~20wt%.

Oxazines compound is specifically described below.

Oxazines compound is preferably soluble in the solvent for dissolving polyamic acid or derivatives thereof and has ring-opening polymerization Oxazines compound.

In addition, the quantity of the oxazines structure in oxazines compound is not particularly limited.

It has been known that there is various structures for the structure of oxazines.In the present invention, the structure of oxazines is not particularly limited, in oxazines compound In oxazines structure in, benzoxazine or naphtho- oxazines etc. can be enumerated with the aromatic series base containing fused-ring aromatic base The structure of oxazines.

As oxazines compound, such as following formula (OX-1)~formula (OX-6) compound represented can be enumerated.Furthermore under It states in formula, key represented by the center towards ring indicates bond on any one carbon for constituting ring and being bonded substituent group.

In formula (OX-1)~formula (OX-3), L³And L⁴The organic group for being 1~30 for carbon number, in formula (OX-1)~formula (OX-6), L⁵~L⁸The alkyl for being 1~6 for hydrogen or carbon number, in formula (OX-3), formula (OX-4) and formula (OX-6), Q¹For singly-bound ,-O- ,-S- ,- S-S-、-SO₂-、-CO-、-CONH-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_v-、-O-(CH₂)_v-O-、-S- (CH₂)_v- S-, herein, the integer that v is 1~6, in formula (OX-5) and formula (OX-6), Q²Stand alone as singly-bound ,-O- ,-S- ,-CO- ,-C (CH₃)₂-、-C(CF₃)₂Or the alkylidene that carbon number is 1~3, Q²In phenyl ring, the hydrogen that is bonded on naphthalene nucleus it is independent and can by-F ,- CH₃、-OH、-COOH、-SO₃H、-PO₃H₂Replace.

In addition, oxazines compound includes having oxazines in oligomer or polymer, main chain on side chain with oxazines structure The oligomer or polymer of structure.

As by the oxazines compound represented by formula (OX-1), such as oxazines compound below can be enumerated.

In formula (OX-1-2), L³It is preferred that the alkyl that carbon number is 1~30, the alkyl that more preferable carbon number is 1~20.

As by the oxazines compound represented by formula (OX-2), such as oxazines compound below can be enumerated.

In formula, L³It is preferred that the alkyl that carbon number is 1~30, the alkyl that more preferable carbon number is 1~20.

As the oxazines by the oxazines compound represented by formula (OX-3), represented by can enumerating by following formula (OX-3-I) Close object.

In formula (OX-3-I), L³And L⁴The organic group for being 1~30 for carbon number, L⁵~L⁸The alkyl for being 1~6 for hydrogen or carbon number, Q¹For singly-bound ,-CH₂-、-C(CH₃)₂-、-CO-、-O-、-SO₂-、-C(CH₃)₂Or-C (CF₃)₂-.As by formula (OX-3-I) institute The oxazines compound of expression, such as oxazines compound below can be enumerated.

In formula, L³And L⁴It is preferred that the alkyl that carbon number is 1~30, the alkyl that more preferable carbon number is 1~20.

As by the oxazines compound represented by formula (OX-4), such as oxazines compound below can be enumerated.

As by the oxazines compound represented by formula (OX-5), such as oxazines compound below can be enumerated.

As by the oxazines compound represented by formula (OX-6), such as oxazines compound below can be enumerated.

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

Oxazines compound can by with International Publication 2004/009708, Japanese Patent Laid-Open 11-12258, Japan Patent Documented method identical method manufactures in special open 2004-352670.

It can be by obtaining phenolic compounds and reaction with level-one amine and aldehyde by the oxazines compound represented by formula (OX-1) It obtains (referring to International Publication 2004/009708).

It can be obtained in the following way by the oxazines compound represented by formula (OX-2): by slowly being added into formaldehyde After the method for level-one amine is reacted, adding, there is the compound of naphthols system hydroxyl to be reacted (referring to International Publication 2004/ 009708)。

It can be obtained in the following way by the oxazines compound represented by formula (OX-3): in secondary fatty race amine, three-level rouge In the presence of fat race amine or alkaline nitrogen-containing heterocycle compound, make 1 mole of phenolic compounds, 1 phenol relative to the phenolic compounds Hydroxyl is at least 2 moles or more of aldehyde and 1 mole of level-one amine is reacted in organic solvent (referring to International Publication 2004/009708 and Japanese Patent Laid-Open 11-12258).

It can be obtained in the following way by the oxazines compound represented by formula (OX-4)~formula (OX-6): at 90 DEG C or more At a temperature of, make 4,4'- diaminodiphenyl-methane etc. that there is the diamines of multiple phenyl ring and the organic group being bonded with these phenyl ring, first The aldehyde such as aldehyde and phenol carry out dehydration condensation in n-butanol (referring to Japanese Patent Laid-Open 2004-352670).

< oxazoline compound >

For example, aligning agent for liquid crystal of the invention can for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term Further contain oxazoline compound.Oxazoline compound is the compound with oxazoline structure.Oxazoline compound can be with It is a kind of compound, is also possible to compound of more than two kinds.For the purpose, relative to polyamic acid or derivatives thereof, The content of oxazoline compound preferred 0.1wt%~50wt%, more preferable 1wt%~40wt%, and then more preferably 1wt%~ 20wt%.Alternatively, when the oxazoline structure in oxazoline compound is converted into oxazoline, for the purpose, relatively In polyamic acid or derivatives thereof, the preferred 0.1wt%~40wt% of the content of oxazoline compound.

Oxazoline compound is specifically described below.

Oxazoline compound can only have a kind of oxazoline structure in a kind of compound, it is possible to have two or more.Separately Outside, as long as oxazoline compound has 1 oxazoline structure in a kind of compound, but preferably there are 2 or more.In addition, Oxazoline compound can be the polymer on side chain with oxazoline structure, be also possible to copolymer.There is oxazole on side chain The polymer of quinoline structure can be the homopolymer of the monomer on side chain with oxazoline structure, be also possible to have oxazole on side chain The copolymer of the monomer of quinoline structure and the monomer for not having oxazoline structure.Copolymer on side chain with oxazoline structure can be with It is the copolymer of the monomer of more than two kinds on side chain with oxazoline structure, is also possible to 2 with oxazoline structure on side chain Kind or more monomer with do not have oxazoline structure monomer copolymer.

Oxazoline structure preferably can be into one or two carbonyl with polyamic acid of the oxygen and nitrogen in oxazoline structure The mode of row reaction is present in the structure in oxazoline compound.

It as oxazoline compound, such as can enumerate: 2,2'- bis- (2- oxazolines), 1,2,4- tri--(2- oxazoline group- 2)-benzene, 4- furans -2- methylene -2- phenyl -4H- oxazole -5- ketone, 1,4- bis- (4,5- dihydro -2- oxazolyl) benzene, 1,3- Bis- (4,5- dihydro -2- oxazolyl) benzene, 2,3- bis- (4- isopropenyl -2- oxazoline -2- base) butane, the bis- -4- benzyls-of 2,2'- Bis- (isopropyl -2- oxazoline -2- base) pyridines of 2- oxazoline, 2,6-, bis- (the 4- third butyl -2- oxazoles of 2,2'- isopropylidene Quinoline), 2,2'- isopropylidene bis- (4- phenyl -2- oxazolines), 2,2' methylene bis (4- third butyl -2- oxazoline) and 2, 2'- di-2-ethylhexylphosphine oxide (4- phenyl -2- oxazoline).In addition to these oxazoline compounds, it can also enumerate such as Ai Bo Kroes (Epocros) (trade name, Japanese catalyst (share) manufacture) such polymer or oligomer with oxazolyl.These oxazoles Among quinoline compound, bis- (4, the 5- dihydro -2- oxazolyl) benzene of 1,3- can be more preferably enumerated.

< epoxide >

For example, aligning agent for liquid crystal of the invention can for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term Further contain epoxide.Epoxide can be a kind of compound, be also possible to compound of more than two kinds.It is just described For purpose, relative to polyamic acid or derivatives thereof, the preferred 0.1wt%~50wt% of the content of epoxide, more preferably 1wt%~40wt%, and then more preferably 1wt%~20wt%.

Epoxide is specifically described below.

As epoxide, various compounds of the intramolecular with 1 or 2 or more epoxide ring can be enumerated.As Intramolecular has the compound of 1 epoxide ring, such as can enumerate: phenyl glycidyl ether, butyl glycidyl ether, 3, and 3,3- tri- Methyl fluoride propylene oxide, styrene oxide, hexafluoropropylene oxide, 7-oxa-bicyclo[4.1.0 (cyclohexane oxide), 3- shrink sweet Oily oxygroup propyl trimethoxy silicane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, N- glycidyl neighbour's benzene Dicarboximide, (nine fluoro- N- butyl) epoxides, perfluoro-ethyl glycidol ether, epichlorohydrin, epibromohydrin, N, N- bis- shrink Glyceryl aniline and 3- [2- (perfluoro hexyl) ethyoxyl] -1,2- epoxy group propane.

There is the compound of 2 epoxide rings as intramolecular, such as can enumerate: ethylene glycol diglycidylether, poly- second two Alcohol diglycidyl ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol (N, N- bis- shrinks sweet by diglycidyl ether, 3,4- epoxycyclohexyethylSiOi enylmethyl -3', 4'- epoxycyclohexyethylSiOi olefinic carboxylic acid ester and 3- Oil base) TSL 8330.

There is the compound of 3 epoxide rings as intramolecular, such as can enumerate: 2- [4- (2,3- epoxy group propoxyl group) benzene Base] -2- [4- [bis- [4- ([2,3- epoxy group propoxyl group] the phenyl)] ethyls of 1,1-] phenyl] propane (trade name " iron Ke Moya VG3101L (Techmore VG3101L) ", (Mitsui Chemicals (share) manufacture)).

There is the compound of 4 epoxide rings as intramolecular, such as can enumerate: 1,3,5,6- four glycidyl group -2,4- Hexylene glycol, N, N, N', bis- (N, the N- diglycidyl amino methyl) hexamethylenes of N'- four glycidyl group-m-xylene diamine, 1,3- Alkane, N, N, N', N'- four glycidyl group -4,4'- diaminodiphenyl-methane and 3- (N- allyl-N- glycidyl) ammonia Base propyl trimethoxy silicane.

In addition to described, can also enumerate oligomer or polymer with epoxide ring has epoxide ring as intramolecular The example of compound.It as the monomer with epoxide ring, such as can enumerate: (methyl) glycidyl acrylate, (methyl) third Olefin(e) acid 3,4- epoxycyclohexyethylSiOi ester and (methyl) acrylic acid methylglycidyl esters.

It as the other monomers being copolymerized with the monomer with epoxide ring, such as can enumerate: (methyl) acrylic acid, (first Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) propylene Sour isobutyl ester, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, styrene, methyl styrene, 1-chloro-4-methyl-benzene, (methyl) acrylic acid (3- ethyl -3- oxetanylmethoxy) methyl esters, N- cyclohexylmaleimide and N- phenylmaleimide.

The preferred concrete example of polymer as the monomer with epoxide ring, can enumerate polymethyl acid glycidyl Ester etc..In addition, the preferred concrete example of the copolymer as monomer and other monomers with epoxide ring, can enumerate: N- phenyl Maleimide-glycidyl methacrylate copolymer, N- cyclohexylmaleimide-methacrylic acid contracting Water glycerol ester copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-methyl Glycidyl acrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, methyl-prop Olefin(e) acid (3- ethyl -3- oxetanylmethoxy) methyl esters-glycidyl methacrylate copolymer and styrene-t Glycidyl ester copolymer.

Among these examples, particularly preferably N, N, N', N'- four glycidyl group-m-xylene diamine, 1,3- are bis-, and (N, N- bis- shrinks Glyceryl amino methyl) hexamethylene, N, N, N', N'- four glycidyl group -4,4'- diaminodiphenyl-methane, trade name " Techmore VG3101L ", 3,4- epoxycyclohexyethylSiOi enylmethyl -3', 4'- epoxycyclohexyethylSiOi olefinic carboxylic acid ester, N- phenyl are along fourth Alkene imidodicarbonic diamide-glycidyl methacrylate copolymer and 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane.

It more systematically says, as epoxide, such as can enumerate: glycidol ether, ethylene oxidic ester, glycidol Amine, the acrylic resin containing epoxy group, glycidyl amide, fulminuric acid glycidol rouge, chain fatty race type Epoxide and annular aliphatic type ring oxygen compound.Furthermore epoxide refers to the compound with epoxy group, ring Oxygen resin refers to the resin with epoxy group.

As epoxide, such as can enumerate: glycidol ether, glycidyl amine, contains epoxy group at glycidol rouge Acrylic resin, glycidyl amide, fulminuric acid ethylene oxidic ester, chain fatty race type ring oxygen compound and Annular aliphatic type ring oxygen compound.

It as glycidol ether, such as can enumerate: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type Epoxide, biphenol type epoxy compound, A Hydrogenated Bisphenol A-A type ring oxygen compound, A Hydrogenated Bisphenol A-F type ring oxygen compound, hydrogen Change bis-phenol-S type ring oxygen compound, A Hydrogenated Bisphenol A type ring oxygen compound, brominated bisphenol-A type ring oxygen compound, brominated bisphenol-F type Epoxide, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolaks Type ring oxygen compound, bisphenol A novolac type ring oxygen compound, contains naphthalene bone at bromination cresol novolak type epoxy compound Epoxide, aromatic series poly epihydric alcohol ether compound, dicyclopentadiene phenol epoxide, the ester ring type two of frame contract Water glycerol ether compound, aliphatic polyglycidyl ether compound, polysulfide type 2-glycidyl ether compound and xenol Type ring oxygen compound.

It as ethylene oxidic ester, such as can enumerate: 2-glycidyl ester compounds and glycidyl ester epoxy compound.

It as glycidyl amine, such as can enumerate: poly epihydric alcohol amines and glycidyl amine type epoxy resin.

As the acrylic compounds containing epoxy group, such as can enumerate: with Oxyranyle (oxiranyl) The homopolymer and copolymer of monomer.

It as glycidyl amide, such as can enumerate: glycidyl acid amide type epoxide.

It as chain fatty race type ring oxygen compound, such as can enumerate: the carbon-to-carbon double bond of olefin(e) compound being aoxidized and is obtained The compound containing epoxy group obtained.

It as annular aliphatic type ring oxygen compound, such as can enumerate: by the carbon-to-carbon double bond oxidation of cyclic olefins The compound containing epoxy group obtained.

As bisphenol A type epoxy compound, such as can enumerate: jER828, jER1001, jER1002, jER1003, JER1004, jER1007, jER1010 (being trade name, Mitsubishi Chemical's (share) manufacture), the appropriate YD-128 of Ai Putuo (Epotohto YD-128) (Dongdu is melted into (share) manufacture), DER-331, DER-332, DER-324 (are DOW Chemical public affairs Take charge of (The Dow Chemical Company) manufacture), Chinese mugwort clone 840 (Epiclon840), Epiclon850, Epiclon1050 (being trade name, DIC (DIC) (share) manufacture), Epomik R-140 (Epomik R-140), Epomik R-301 and Epomik R-304 (being trade name, Mitsui Chemicals (company) manufacture).

As bisphenol F type epoxy compound, such as can enumerate: jER806, jER807, jER4004P (are trade name, three Water chestnut chemistry (share) manufacture), Epotohto YDF-170, Epotohto YDF-175S, Epotohto YDF-2001 (are quotient The name of an article, Dongdu chemical conversion (share) manufacture), DER-354 (trade name, Dow Chemical manufacture), Epiclon830 and Epiclon835 (being trade name, DIC (share) manufacture).

It as biphenol type epoxy compound, such as can enumerate: 2,2- bis- (4- hydroxyphenyls) -1,1,1,3,3,3- hexafluoropropane Epoxides.

As A Hydrogenated Bisphenol A-A type ring oxygen compound, such as can enumerate: quotient holds in the palm appropriate ST-3000 (Suntohto ST-3000) (trade name, Dongdu chemical conversion (share) manufacture), Li Kaleixin HBE-100 (Rikaresin HBE-100) (trade name, new Japan Physical and chemical (share) manufacture) and Dai Nakeer EX-252 (Denacol EX-252) (trade name, long rapids chemical conversion (Nagase ChemteX) (share) manufactures).

It as A Hydrogenated Bisphenol A type ring oxygen compound, such as can enumerate: hydrogenation bis- (the 4- hydroxyphenyls) -1,1,1,3,3,3- of 2,2- The epoxides of hexafluoropropane.

As brominated bisphenol-A type ring oxygen compound, such as can enumerate: jER5050, jER5051 (are trade name, Mitsubishi Chemical (share) manufacture), Epotohto YDB-360, Epotohto YDB-400 (are trade name, Dongdu chemical conversion (share) system Make), DER-530, DER-538 (being trade name, Dow Chemical's manufacture), Epiclon152 and Epiclon153 (are Trade name, DIC (share) manufacture).

As phenol novolak-type epoxy compound, such as can enumerate: jER152, jER154 (are trade name, Mitsubishi Chemical (share) manufacture), YDPN-638 (trade name, the manufacture of Dongdu chemical conversion company), DEN431, DEN438 (are trade name, pottery The manufacture of family name chemical company), Epiclon N-770 (trade name, DIC (share) manufacture), EPPN-201 and EPPN-202 are ( It is manufactured for trade name, Japanese chemical drug (share)).

It as cresol novolak type epoxy compound, such as can enumerate: jER180S75 (trade name, Mitsubishi Chemical's (stock Part) manufacture), YDCN-701, YDCN-702 (being trade name, the manufacture of Dongdu chemical conversion company), Epiclon N-665, Epiclon N-695 (be trade name, DIC (share) manufacture), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (being trade name, Japanese chemical drug (share) manufacture).

It as bisphenol A novolac type ring oxygen compound, such as can enumerate: jER157S70 (trade name, Mitsubishi Chemical's (stock Part) manufacture) and Epiclon N-880 (trade name, DIC (share) manufacture).

It as the epoxide containing naphthalene skeleton, such as can enumerate: Epiclon HP-4032, Epiclon HP- 4700, (trade name, Japanese chemical drug are public by Epiclon HP-4770 (being trade name, DIC (share) manufacture) and NC-7000 Department's manufacture).

It as aromatic series poly epihydric alcohol ether compound, such as can enumerate: hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2), resorcinolformaldehyde resin (following formula EP-3), 2- [4- (2,3- epoxy group propoxyl group) phenyl] -2- [4- [bis- [4- ([2,3- epoxy group propoxyl group] the phenyl)] ethyls of 1,1-] phenyl] third Alkane (following formula EP-4), three (4- glycidoxypropyl phenyl) methane (following formula EP-5), jER1031S, jER1032H60 are ( Manufactured for trade name, Mitsubishi Chemical's (share)), Plutarch replaces Ke Si -742 (TACTIX-742) (trade name, Dow Chemical's system Make), Denacol EX-201 (trade name, long rapids chemical conversion (share) manufacture), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (being trade name, Japanese chemical drug (share) manufacture), Techmore VG3101L (trade name, Mitsui Chemicals (share) Manufacture), by the compound represented by following formula EP-6, and by the compound represented by following formula EP-7.

It as dicyclopentadiene phenol epoxide, such as can enumerate: TACTIX-556 (trade name, DOW Chemical Company's manufacture) and Epiclon HP-7200 (trade name, DIC (share) manufacture).

It as ester ring type 2-glycidyl ether compound, such as can enumerate: cyclohexanedimethanodiglycidyl diglycidyl ether chemical combination Object and Rikaresin DME-100 (trade name, new Japan Chemical (share) manufacture).

It as aliphatic polyglycidyl ether compound, such as can enumerate: ethylene glycol diglycidylether (following formula EP- 8), diethylene glycol diglycidyl glycerin ether (following formula EP-9), polyethyleneglycol diglycidylether, propylene glycol diglycidylether (following formula EP-10), tripropyleneglycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol Diglycidyl ether (following formula EP-12), 1,4-butanediol diglycidyl ether (following formula EP-13), the contracting of 1,6- hexylene glycol two Water glycerin ether (following formula EP-14), dibromoneopentyl glycol diglycidyl ether (following formula EP-15), Denacol EX-810, Denacol EX-851、Denacol EX-8301、Denacol EX-911、Denacol EX-920、Denacol EX-931、 Denacol EX-211, Denacol EX-212, Denacol EX-313 (being trade name, long rapids chemical conversion (share) manufacture), DD-503 (trade name, Ai Dike (ADEKA) (share) manufacture), Rikaresin W-100 (trade name, new Japan Chemical (stock Part) manufacture), 1,3,5,6- four glycidyl group -2,4- hexylene glycol (following formula EP-16), glycerine polyglycidyl ether, sorbierite Polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythrite polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321 and Denacol EX-411 (are trade name, long rapids chemical conversion (share) system It makes).

As polysulfide type 2-glycidyl ether compound, such as can enumerate: FLDP-50 and FLDP-60 (is quotient The name of an article, beautiful skilful solid happy (Toray Thiokol) (share) manufacture in east).

As biphenyl phenolic epoxide, such as can enumerate: YX-4000, YL-6121H (are trade name, Mitsubishi Learn (share) manufacture), NC-3000P and NC-3000S (being trade name, Japanese chemical drug (share) manufacture).

It as 2-glycidyl ester compounds, such as can enumerate: terephthalic acid diglycidyl ester (following formula EP- 17), bis- (the 2- methyl oxirane ylmethyl) esters of o-phthalic acid diglycidyl ester (following formula EP-18), phthalic acid (following formula EP-19), hexahydrophthalic acid 2-glycidyl ester (following formula EP-20), by the change represented by following formula EP-21 Close object, by the compound represented by following formula EP-22 and by the compound represented by following formula EP-23.

As glycidyl ester epoxy compound, such as can enumerate: jER871, jER872 (are trade name, Mitsubishi Chemical (share) manufacture), Epiclon 200, Epiclon 400 (being trade name, DIC (share) manufacture), Denacol EX- 711 and Denacol EX-721 (being trade name, long rapids chemical conversion (share) manufacture).

As poly epihydric alcohol amines, such as can enumerate: N, N- diglycidylaniline (following formula EP-24), N, N- diglycidyl-ortho-aminotoluene (following formula EP-25), N, N- diglycidyl-meta-aminotoluene (following formula EP- 26), N, N- diglycidyl -2,4,6- tribromaniline (following formula EP-27), 3- (N, N- diglycidyl) aminopropyl Trimethoxy silane (following formula EP-28), N, N, O- triglycidyl group-para-aminophenol (following formula EP-29), N, N, O- tri- Glycidyl-m-aminophenol (following formula EP-30), N, N, N', N'- four glycidyl group -4,4'- diamino-diphenyl first Alkane (following formula EP-31), N, N, N', N'- four glycidyl group-m-xylene diamine (iron Te Lade-X (TETRAD-X) (commodity Name, Mitsubishi gas chemical (share) manufacture), following formula EP-32), bis- (N, the N- diglycidyl amino methyl) hexamethylenes of 1,3- Alkane (TETRAD-C (trade name, Mitsubishi's gas chemical (share) manufacture), following formula EP-33), bis- (N, the N- 2-glycidyls of Isosorbide-5-Nitrae- Base amino methyl) hexamethylene (following formula EP-34), bis- (N, N- diglycidyl amino) hexamethylene (the following formula EP- of 1,3- 35), bis- (N, the N- diglycidyl amino) hexamethylenes (following formula EP-36) of 1,4-, bis- (N, N- the diglycidyl ammonia of 1,3- Base) benzene (following formula EP-37), bis- (N, the N- diglycidyl amino) benzene (following formula EP-38) of 1,4-, bis- (N, the N- bis- of 2,6- Glycidyl-amino methyl) bicyclic [2.2.1] heptane (following formula EP-39), N, N, N', N'- four glycidyl group -4,4'- Diamino-dicyclohexyl methane (following formula EP-40), 2,2'- dimethyl-(N, N, N', N'- four glycidyl group) -4,4'- two Aminobphenyl (following formula EP-41), N, N, N', N'- four glycidyl group -4,4'- diaminodiphenyl ether (following formula EP-42), (N, N- bis- shrinks by 1,3,5- tri- (4- (N, N- diglycidyl) amino-benzene oxygen) benzene (following formula EP-43), 2,4,4'- tri- Glyceryl amino) diphenyl ether (following formula EP-44), three (4- (N, N- diglycidyl) aminophenyl) methane (following formula EP- 45), 3,4,3', 4'- tetra- (N, N- diglycidyl amino) biphenyl (following formula EP-46), 3,4,3', (N, N-'s 4'- tetra- bis- contracts Water glyceryl amino) diphenyl ether (following formula EP-47), by the compound represented by following formula EP-48 and by following formula EP-49 Represented compound.

As the homopolymer of the monomer with Oxyranyle, such as poly (glycidyl methacrylate) can be enumerated.Make It for the copolymer of the monomer with Oxyranyle, such as can enumerate: N- phenylmaleimide-Glycidyl methacrylate Glycerol ester copolymer, N- cyclohexylmaleimide-methyl propenoic acid glycidyl resin copolymer, methacrylic acid benzyl Ester-glycidyl methacrylate copolymer, butyl methacrylate glycidyl ester copolymer, methyl Acrylic acid 2- hydroxy methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3- ethyl -3- oxetanylmethoxy) first Ester-methyl propenoic acid glycidyl resin copolymer and styrene-t glycidol resin copolymer.

It as the monomer with Oxyranyle, such as can enumerate: (methyl) glycidyl acrylate, (methyl) propylene Sour 3,4- epoxycyclohexyethylSiOi ester and (methyl) acrylic acid methylglycidyl esters.

As other lists other than the monomer with Oxyranyle in the copolymer of the monomer with Oxyranyle Body, such as can enumerate: (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid isopropyl Ester, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, styrene, methylbenzene Ethylene, 1-chloro-4-methyl-benzene, (methyl) acrylic acid (3- ethyl -3- oxetanylmethoxy) methyl esters, N- cyclohexyl maleoyl- are sub- Amine and N- phenylmaleimide.

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

It as chain fatty race type ring oxygen compound, such as can enumerate: epoxidized polybutadiene, Ji Aibo Reed PB3600 (Epolead PB3600) (trade name, Daicel (Daicel) (share) manufacture).

It as annular aliphatic type ring oxygen compound, such as can enumerate: 3,4- epoxycyclohexyethylSiOi enylmethyl -3', 4'- rings Oxygroup cyclohexene carboxylate ester (silicon Luo Ji Saden 2021 (Celloxide2021) (Daicel (share) manufacture), following formula EP- 52), 2- methyl -3,4- epoxycyclohexylmethyl -2'- methyl -3', 4'- expoxycyclohexyl carboxylate (following formula EP- 53), 2,3- epoxy cyclopentane -2', 3'- epoxy cyclopentane ether (following formula EP-54), 6-caprolactone modify 3,4- epoxy group Cyclohexyl methyl -3', 4'- epoxycyclohexane carboxylate, 1,2:8,9- bicyclic oxygen limonene (Celloxide3000 (commodity Name, Daicel (share) manufacture), following formula EP-55), by the compound represented by following formula EP-56, CY-175, CY-177, CY-179 (be trade name, Ciba-Geigy Chemical Company (The Ciba-Geigy Chemical Corp.) manufacture (can be from day Ben Hengsimai (HuntsmanJapan) (share) is obtained)), EHPD-3150 (trade name, Daicel (share) manufacture) and ring Shape aliphatic type epoxy resin.

The preferred poly epihydric alcohol amines of epoxide, bisphenol A novolac type ring oxygen compound, cresol novolac are clear More than one of paint shaped epoxide and annular aliphatic type ring oxygen compound, more preferable N, N, tetra- glycidol of N', N'- Base-m-xylene diamine, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N', N'- four glycidyl group- 4,4'- diaminodiphenyl-methane, trade name " Techmore VG3101L ", 3,4- epoxycyclohexyethylSiOi enylmethyl -3', 4'- EpoxycyclohexyethylSiOi olefinic carboxylic acid ester, N- phenylmaleimide-glycidyl methacrylate copolymer, N, N, O- tri- contract The one of water glyceryl-para-aminophenol, bisphenol A novolac type ring oxygen compound and cresol novolak type epoxy compound Kind or more.

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

For example, the high-molecular compound for dissolving in organic solvent can be enumerated as the high-molecular compound.With regard to control institute For the electrical characteristics of the liquid crystal orientation film of formation or the viewpoint of orientation, such high-molecular compound is preferably added to the present invention Aligning agent for liquid crystal in.As the high-molecular compound, such as can enumerate: polyamide, polyureas, polyester, gathers polyurethanes Epoxides, polyester polyol, silicone modification polyurethanes and silicone modify polyester.

In addition, as the low molecular compound, such as 1) can be enumerated when expectation promotes coating and meet the purpose Surfactant, 2) antistatic agent can be enumerated when needing to promote antistatic, 3) it can when expectation promotes the adhesion with substrate The coupling agent of silane coupling agent or titanium system is enumerated, is urged in addition, 4) imidizate can be enumerated when carrying out imidizate at low temperature Agent.

It as silane coupling agent, such as can enumerate: vinyltrimethoxysilane, vinyltriethoxysilane, N- (2- Amino-ethyl) -3- aminopropylmethyldimethoxysilane, N- (2- amino-ethyl) -3- amino propyl methyl trimethoxy silicon Alkane, p-aminophenyl trimethoxy silane, p-aminophenyl triethoxysilane, m-aminophenyl base trimethoxy silane, ammonia Base phenyl triethoxysilane, 3- TSL 8330,3-aminopropyltriethoxysilane, 3- glycidol oxygen Base propyl trimethoxy silicane, 3- glycidoxypropyl dimethoxysilane, 3- chloropropyl dimethoxy silicon Alkane, 3- r-chloropropyl trimethoxyl silane, 3- methacryloxypropyl trimethoxy silane, 3- mercaptopropyi trimethoxy silicon Alkane, N- (1,3- dimethylbutylene) -3- (triethoxysilicane alkyl) -1- propylamine and the bis- [3- (trimethoxy silanes of N, N'- Base) propyl] ethylenediamine.Preferred silane coupling agent is 3-aminopropyltriethoxysilane.

It as imidization catalyst, such as can enumerate: the aliphatic amines such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine Class；N, accelerine, N, the aromatic amines such as N- diethylaniline, methyl-substituted aniline, hydroxy-substituted aniline；Pyridine, Methyl substituted pyridines, hydroxyl substituted pyridines, quinoline, methyl substd quinolines, hydroxyl substd quinolines, isoquinolin, methyl replace isoquinoline The ring types amines such as quinoline, hydroxyl substituted isoquinoline, imidazoles, methyl substituted imidazole, hydroxyl substituted imidazole.The imidization catalyst It is preferably selected from N, accelerine, ortho-aminophenol, hydroxyanilines, para hydroxybenzene amine, adjacent pyridone, hydroxyl pyrrole Pyridine, to one kind or two or more in pyridone and isoquinolin.

The additive amount of silane coupling agent is usually 0wt%~20wt% of the total weight of polyamic acid or derivatives thereof, excellent Select 0.1wt%~10wt%.

Relative to the carbonyl of polyamic acid or derivatives thereof, the additive amount of imidization catalyst be usually 0.01 equivalent~ 5 equivalents, preferably 0.05 equivalent~3 equivalents.

The additive amount of other additives is different according to its purposes, but the usually total weight of polyamic acid or derivatives thereof 0wt%~100wt%, preferably 0.1wt%~50wt%.

Polyamic acid of the invention or derivatives thereof can be with the well known polyamic acid of the formation of the film for polyimides Or derivatives thereof similarly manufacture.The total addition level of tetracarboxylic dianhydride is preferably set to and the total mole number of diamines substantially equimolar (molar ratio is 0.9~1.1 or so).

The weight average molecular weight (Mw) that the molecular weight of polyamic acid of the invention or derivatives thereof is converted with polystyrene Meter, preferably 7,000~500,000, more preferable 10,000~200,000.The molecular weight of the polyamic acid or derivatives thereof can It is found out by the measurement using gel permeation chromatography (Gel Permeation Chromatography, GPC) method.

Polyamic acid of the invention or derivatives thereof can confirm its presence in the following way: utilize infrared ray (Infrared, IR), nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) to make polyamic acid of the invention or The solid component that its derivative is precipitated in a large amount of poor solvent and obtained is analyzed.In addition, can come in the following way Monomer used in confirming: gas chromatography (Gas Chromatography, GC), high performance liquid chromatography (High are utilized Performance Liquid Chromatography, HPLC) or gas chromatography mass spectrometry (Gas Chromatography- Mass Spectrometry, GC-MS) to use the aqueous solution of the highly basic such as KOH or NaOH by described polyamic acid or derivatives thereof After decomposition, analyzed using the extract that organic solvent is extracted from its decomposition product.

In addition, for example with regard to the coating of aligning agent for liquid crystal or the polyamic acid or derivatives thereof concentration adjustment sight For point, aligning agent for liquid crystal of the invention can further contain solvent.As long as the solvent has dissolution macromolecule component The solvent of ability can then be applied with no particular limitation.The solvent includes sub- commonly used in polyamic acid, soluble polyamides extensively The manufacturing step or the solvent in terms of purposes of the macromolecule components such as amine can be suitable for selection according to purpose is used.The solvent can To be a kind, it is also possible to mixed solvent of more than two kinds.

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- N-methyl-2-2-pyrrolidone N, methylimidazole alkanone (dimethylimidazolidinone), N- methyl caprolactam, N- methyl Propionamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N,N-dimethylformamide, N, N- diethylformamide, diethyl second The lactones such as amide, gamma-butyrolacton.

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

Among these solvents, the solvent particularly preferably n-methyl-2-pyrrolidone, methylimidazole alkanone, γ-Ding Nei Ester, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether.

Preferred 0.1wt%~the 40wt% of the concentration of polyamic acid in alignment agent of the invention.It is coated with when by the alignment agent When on substrate, in order to adjust film thickness, it is sometimes desirable to the operation being diluted in advance using solvent to contained polyamic acid.

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

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

Liquid crystal orientation film of the invention is described in detail.Liquid crystal orientation film of the invention is by the present invention Aligning agent for liquid crystal film carry out heating be formed by film.Liquid crystal orientation film of the invention can be by making from aligning agent for liquid crystal The usual way of liquid crystal orientation film and obtain.For example, liquid crystal orientation film of the invention can be by by forming liquid of the invention The step of film of brilliant alignment agent, the step of of being thermally dried and carry out heating and calcining the step of and obtain.For the present invention Liquid crystal orientation film can optionally be carried out as described later to by heat-drying step, heating and calcining step film obtained Friction treatment assigns anisotropy.Alternatively, optionally, can after film-coating procedures, heat-drying step irradiation light, or heating Irradiation light assigns anisotropy after calcining step.Alternatively, it is also possible to be used as the vertical orientation without friction treatment (Vertical Alignment, VA) uses liquid crystal orientation film.

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 may be provided with tin indium oxide (Indium Tin Oxide, ITO), Indium zinc oxide (In₂O₃- ZnO, IZO), indium gallium zinc (In-Ga-ZnO₄, IGZO) electrodes such as electrode or colored filter etc. The substrate of glass system.

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 excellent Be selected in relative to the temperature in heating and calcining step be it is relatively low at a temperature of implement.Specifically, heat drying temperature is preferred 30 DEG C~150 DEG C of range, more preferable 50 DEG C~120 DEG C of range.

The heating and calcining step can be presented required for dehydration closed-loop reaction in described polyamic acid or derivatives thereof Under the conditions of carry out.The calcining of the film is commonly known to be had the method heated in baking oven or infra-red furnace, is heating The method etc. heated on plate.These methods can also be equally applicable in the present invention.Generally preferably 100 DEG C~ Carry out 1 minute~3 hours at a temperature of 300 DEG C or so, more preferable 120 DEG C~280 DEG C, and then more preferable 150~250 DEG C.

In the forming method of liquid crystal orientation film of the invention, in order to make liquid crystal relative to horizontal direction and/or Vertical Square To being orientated in one direction, forming method well known to rubbing manipulation or optical alignment method etc. can be properly used and be used as to orientation Film assigns anisotropic method.

It can be formed by following step using the liquid crystal orientation film of the invention of rubbing manipulation: liquid crystal of the invention is taken Step from substrate to agent that be coated on, heats the film at the step of being thermally dried to the substrate for being coated with alignment agent The step of calcining and to film carry out friction treatment the step of.

Friction treatment can be carried out similarly with the friction treatment of the common orientation process for liquid crystal orientation film, as long as The condition adequately postponed can be obtained in liquid crystal orientation film of the invention.Preferred condition is that mao intrusion is 0.2mm ~0.8mm, platform movement speed are 5mm/sec~250mm/sec, and roller rotation speed is 500rpm~2,000rpm.

Liquid crystal orientation film of the invention can by the method comprising other steps other than the step 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 used as required step, but cleaning step can be arranged according to the case where other steps.

It as the cleaning method using cleaning solution, can enumerate: scrub, spraying, steam purge or ultrasonic cleaning etc..These Method can be carried out individually, also can be used together.As cleaning solution, can be used: the various alcohol such as pure water or methanol, ethyl alcohol, isopropanol Class, benzene,toluene,xylene etc. is aromatic hydrocarbon, the halogen-based solvents such as methylene chloride, the ketones such as acetone, methyl ethyl ketone, but simultaneously It is not limited to these cleaning solutions.Certainly, the cleaning solution that these cleaning solutions can be used the impurity through sufficiently refining few.Such cleaning side In cleaning step when method also can be applied to be formed liquid crystal orientation film of the invention.

It, can be before and after heating and calcining step, friction in order to improve the liquid crystal aligning performance of liquid crystal orientation film of the invention The annealing using heat or light is applied in the front and back of the front and back of step or polarisation or the radioactive ray irradiation without polarisation.It moves back at this In fire processing, annealing temperature is 30 DEG C~180 DEG C, preferably 50 DEG C~150 DEG C, the time preferably 1 minute~2 hours.In addition, with In the annealing light of annealing, UV lamp, fluorescent lamp, LED light etc. can be enumerated.The preferred 0.3J/cm of the exposure of light²~10J/ cm²。

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

The characteristics of liquid crystal orientation film of the invention, is the anisotropy with king-sized orientation.It is such anisotropic Size can be evaluated by documented in Japanese Patent Laid-Open 2005-275364 etc. using the method for polarisation IR.In addition, such as with Under embodiment shown in like that, can also be evaluated by using the method for ellipsometry (ellipsometry).In detail and Light splitting ellipsometer can be used to measure the length of delay of liquid crystal orientation film in speech.The degree of orientation of the length of delay of film and main polymer chain at Increase to ratio.That is, the film with big length of delay have the big degree of orientation, when by alignment films of the invention be used as liquid crystal aligning When film, it is believed that there is big orientation restraint for liquid-crystal composition with bigger anisotropic alignment films.

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 is more got higher, and contrast more improves.Preferably 0.1 ° or less of the angle Pt.

In addition to the orientation purposes of the liquid-crystal composition of liquid crystal display, liquid crystal orientation film of the invention can be used for optics The tropism control of compensating material or other all liquid crystal materials.In addition, alignment films of the invention are due to big anisotropy, Therefore optical compensation material applications can be individually used for.

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 is formed in the pair of base Electrode in one or two of the respective opposite surface of plate, the liquid crystal aligning being formed in the respective opposite surface of the pair of substrate Film and the liquid crystal layer being formed between the pair of substrate, and the liquid crystal orientation film is alignment films of the invention.

As long as the electrode is formed in the electrode 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 may be formed in the entire surface in a face of substrate, can also be formed as Such as patterned desired shape.The desired shape of electrode can for example enumerate combed or broached-tooth design etc.. Electrode may be formed in a pair of of substrate substrate, can also be formed on two substrates.The formation form of electrode according to The type of liquid crystal display element and it is different, such as in the case where IPS type liquid crystal display element, by electrode configuration the pair of On one of substrate, in the case where other liquid crystal display elements, by electrode configuration on the pair of substrate two.Described The liquid crystal orientation film is formed on substrate or electrode.

The liquid crystal layer be with by 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.In the forming process of liquid crystal layer, optionally it can be used particulate or resin sheet etc. between the pair of Between substrate and form the spacer at interval appropriate.

There is no particular restriction for liquid-crystal composition, and it is positive or negative various liquid crystal combinations that dielectric constant anisotropy, which can be used, Object.The preferred liquid-crystal composition that dielectric constant anisotropy is positive can be enumerated: Japan Patent 3086228, Japan Patent 2635435, the flat 5-501735 of Japanese patent special table, 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), Japan are specially Sharp Japanese Laid-Open Patent Publication 8-199168 (EP722998A1), Japanese Patent Laid-Open 9-235552, Japanese Patent Laid-Open 9-255956, day This patent Japanese Laid-Open Patent Publication 9-241643 (EP885271A1), Japanese Patent Laid-Open 10-204016 (EP844229A1), Japan Patent Japanese Laid-Open Patent Publication 10-204436, Japanese Patent Laid-Open 10-231482, Japanese Patent Laid-Open 2000-087040, Japanese Patent Laid-Open Liquid-crystal composition disclosed in 2001-48822 etc..

Even if to dielectric constant anisotropy being the optical activity chemical combination of a kind of addition or more in positive or negative liquid-crystal composition Object comes using also having no effect.

The liquid-crystal composition being negative to the dielectric constant anisotropy is illustrated.Negative dielectric constant anisotropy Liquid-crystal composition can for example enumerate at least one liquid containing the group for being selected from liquid-crystal compounds represented by following formula (NL-1) Composition of the brilliant compound as the 1st ingredient.

Herein, R^1aAnd R^2aStanding alone as alkoxy, carbon number that alkyl, carbon number that carbon number is 1~12 are 1~12 is 2~12 The alkenyl that alkenyl or at least one hydrogen are 2~12 by fluorine-substituted carbon number, ring A²And ring B²Stand alone as 1,4- cyclohexylidene, tetrahydro Pyrans (tetrahydropyran) -2,5- diyl, 1,3- dioxanes -2,5- diyl, 1,4- phenylene, the fluoro- Asia the 1,4- benzene of 2- Base, the fluoro- 1,4- phenylene of 2,5- bis-, the fluoro- 1,4- phenylene of 2,3- bis-, the chloro- 1,4- phenylene of the fluoro- 3- of 2-, the fluoro- 6- first of 2,3- bis- Base-Isosorbide-5-Nitrae-phenylene, 2,6- naphthalene-diyl or 7,8- difluoro chroman (chromane) -2,6- diyl, herein, ring A²And ring B²Extremely Few one is the fluoro- 1,4- phenylene of 2,3- bis-, the chloro- 1,4- phenylene of the fluoro- 3- of 2-, the fluoro- 6- methyl-1 of 2,3- bis-, 4- phenylene, Or 7,8- difluoro chroman -2,6- diyl, Z¹Stand alone as singly-bound ,-(CH₂)₂-、-CH₂O- ,-COO- or-CF₂O-, j 1,2 or 3, When j is 2 or 3, any two ring A²It may be the same or different, any two Z¹It may be the same or different.

In order to improve dielectric constant anisotropy, preferred ring A²And ring B²Respectively the fluoro- 1,4- phenylene of 2,3- bis- or Oxinane -2,5- diyl, in order to reduce viscosity, preferred ring A²And ring B²Respectively 1,4- cyclohexylidene.

In order to improve dielectric constant anisotropy, preferred Z¹For-CH₂O-, in order to reduce viscosity, preferred Z¹For Singly-bound.

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

The concrete example of the liquid-crystal compounds of the formula (NL-1) can enumerate following formula (NL-1-1)~formula (NL-1-32) institute table The compound shown.

Herein, R^1aAnd R^2aStanding alone as alkoxy, carbon number that alkyl, carbon number that carbon number is 1~12 are 1~12 is 2~12 The alkenyl that alkenyl or at least one hydrogen are 2~12 by fluorine-substituted carbon number, ring A²¹, ring A²², ring A²³, ring B²¹And ring B²²It is independent For 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene, Z¹¹And Z¹²Stand alone as singly-bound ,-(CH₂)₂-、-CH₂O- or-COO-.

In order to make that stability of ultraviolet light or heat etc. is improved, preferred R^1aAnd R^2aIt is the alkyl that carbon number is 1~12, Or in order to improve the absolute value of dielectric constant anisotropy, preferred R^1aAnd R^2aIt is the alkoxy that carbon number is 1~12.

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

Preferred alkoxy is methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy or oxygroup in heptan.In order to Reduce viscosity, and then preferred alkoxy is methoxy or ethoxy.

Preferred alkenyl is vinyl, 1- acrylic, 2- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- penta Alkenyl, 2- pentenyl, 3- pentenyl, 4- pentenyl, 1- hexenyl, 2- hexenyl, 3- hexenyl, 4- hexenyl or 5- hexene Base.In order to reduce viscosity, and then preferred alkenyl is vinyl, 1- acrylic, 3- cyclobutenyl or 3- pentenyl.These The preferred spatial configuration of-CH=CH- (steric configuration) in alkenyl depends on the position of double bond.It is personal so that Viscosity reduction etc. considers, in such as 1- acrylic, 1- cyclobutenyl, 1- pentenyl, 1- hexenyl, 3- pentenyl, 3- hexenyl It is preferably trans- in such alkenyl.As 2- cyclobutenyl, 2- pentenyl, 2- hexenyl in alkenyl it is preferably cis-. It is in comparison preferably the alkenyl of straight chain with branch in these alkenyls.

At least one hydrogen is 2,2- difluoroethylene base, the fluoro- 2- propylene of 3,3- bis- by the preferred example of fluorine-substituted alkenyl Base, the fluoro- 3- cyclobutenyl of 4,4- bis-, the fluoro- 4- pentenyl of 5,5- bis- and the fluoro- 5- hexenyl of 6,6- bis-.In order to reduce viscosity, into And preferred example is 2,2- difluoroethylene base and the fluoro- 3- cyclobutenyl of 4,4- bis-.

In order to reduce viscosity, preferred ring A²¹, ring A²², ring A²³, ring B²¹And ring B²²Respectively 1,4- cyclohexylidene.

In order to improve dielectric constant anisotropy, preferred Z¹¹And Z¹²It is-CH₂O-, in order to reduce viscosity, preferably Z¹¹And Z¹²It is singly-bound.

In the liquid-crystal composition that there is negative dielectric constant anisotropy, the preferred compound as the 1st ingredient It (NL-1) is compound (NL-1-1), compound (NL-1-4), compound (NL-1-7) or compound (NL-1-32).

The preferred example of the liquid-crystal composition for having negative dielectric constant anisotropy can be enumerated in Japan Patent Tekiaki 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..

Moreover, for example from from the viewpoint of making orientation raising, such as liquid crystal combination used in element of the invention Object can also further add additive.Such additive is photopolymerization monomer, optically active compound, antioxidant, purple Ultraviolet absorbers, pigment, defoaming agent, polymerization initiator, polymerization inhibitor etc..

In order to improve the orientation of liquid crystal, the most preferred structure of photopolymerization monomer or oligomer can enumerate formula (PM-1- 1) structure of~formula (PM-1-6).

In order to show determine polymerization after liquid crystal inclined direction effect, photopolymerization monomer or oligomer are ideal It is 0.01 weight % or more.Moreover, in order to keep the orientation effect of the polymer after polymerization suitable, or in order to avoid in ultraviolet light After irradiation, unreacted monomer or oligomer are dissolved out into liquid crystal, it is generally desirable to 30 weight % or less.

Torsion angle is assigned in order to cause the helical structure of liquid crystal, in the composition hybrid optical reactive compound.It is such The example of compound is compound (PAC-1-1) to compound (PAC-1-4).

Optically active compound is preferably in a proportion of 5 weight % or less.And then preferred ratio is 0.01 weight % to 2 The range of weight %.

In order to prevent as heat in an atmosphere and caused by specific resistance (specific resistance) reduce, or In order to using after element, not only big voltage be maintained to keep at room temperature and at a temperature of high in long-time Rate mixes antioxidant in a liquid crystal composition.

The preferred example of antioxidant is the compound (AO-1) etc. that w is integer of 1 to 10.At compound (AO-1) In, preferred w is 1,3,5,7 or 9.And then preferred w is 1 or 7.The volatility for the compound (AO-1) that w is 1 is big, therefore Prevent as heat in an atmosphere and caused by specific resistance reduce when it is effective.The volatility for the compound (AO-1) that w is 7 is small, Therefore in long-time using after element, big voltage can also effectively not only be maintained at room temperature and at a temperature of high Conservation rate.In order to obtain its effect, the preferred ratio of antioxidant is 50ppm or more, in order not to reducing ceiling temperature or Person improves lower limit temperature, and the preferred ratio of antioxidant is 600ppm or less.And then preferred ratio is 100ppm To the range of 300ppm.

The preferred example of ultraviolet absorbing agent is benzophenone derivates, benzoate derivatives, triazole derivative etc.. Moreover, as with steric hindrance (steric hindrance) amine light stabilizer it is also preferred that.In order to obtain its effect, these The preferred ratio of absorbent or stabilizer is 50ppm or more, in order not to reduce ceiling temperature or mention lower limit temperature The preferred ratio of height, these absorbents or stabilizer is 10000ppm or less.And then preferred ratio be 100ppm extremely The range of 10000ppm.

In order to be suitble to the element of host and guest (Guest host, GH) mode, mixing such as azo system pigmen, anthraquinone in the composition It is dichroism pigment as pigment etc. (dichroic dye).The preferred ratio of pigment is 0.01 weight % to 10 weight % Range.

It blisters in order to prevent, mixes the defoaming agents such as dimethicone, methyl phenyl silicone oil in the composition.In order to obtain it Effect, the preferred ratio of defoaming agent are 1ppm or more, show in order to prevent bad, and the preferred ratio of defoaming agent is 1000ppm or less.And then the range that preferred ratio is 1ppm to 500ppm.

It, can in order to be suitble to the element of polymer stabilizing orientation (Polymer sustained alignment, PSA) mode Polymerizable compound is mixed in the composition.The preferred example of polymerizable compound is acrylate, methacrylic acid Ester, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxide (oxirane, oxetanes), second Alkenyl ketone etc. has the compound of polymerizable base.Example particularly preferably is the derivative of acrylate or methacrylate. The example of such compound is compound (PM-2-1) to compound (PM-2-9).In order to obtain its effect, polymerizable chemical combination The preferred ratio of object is about 0.05 weight % or more, shows the preferred ratio of bad, polymerizable compound in order to prevent It is about 10 weight % or less.And then preferred ratio is range of the about 0.1 weight % to about 2 weight %.

Herein, R^3a、R^4a、R^5aAnd R^6aStand alone as acryloyl group or methylacryloyl, R^7aAnd R^8aStand alone as hydrogen, halogen, Or the alkyl that carbon number is 1 to 10, Z¹³、Z¹⁴、Z¹⁵And Z¹⁶The alkylidene that singly-bound or carbon number are 1 to 12 is stood alone as, at least one- CH₂It can also be replaced by-O- or-CH=CH-, s, t and u are each independently 0,1 or 2.

As free radical or ion is easy to produce, cause substance required for chain polymerization reacts, it can mixed polymerization initiator. For example, as Photoepolymerizationinitiater initiater gorgeous good solid (Irgacure) 651 (registered trademark), Irgacure184 (registered trademark) or Da Luoka (Darocure) 1173 (registered trademark) (Japanese Qi Ba limited liability company (Ciba Japan K.K.)) is for freedom It is suitable for for base polymerization.Polymerizable compound preferably causes in the range of 0.1 weight % to 5 weight % comprising photopolymerization Agent.Particularly preferably be in the range of 1 weight % to 3 weight % comprising Photoepolymerizationinitiater initiater.

In free radical polymerization system, the mixed polymerization inhibitor using following purpose: with by polymerization initiator or list Free radical caused by body promptly reacts and changes the compound for stable free radical or neutrality, and result makes polymerization reaction Stop.Polymerization inhibitor can be classified as several in structure.One of them is such as three-p-nitrophenyl ylmethyls, two-p-fluorophenyls Its own stable free radical as amine etc., another kind are easily to react and become with the free radical in the presence of paradigmatic system For stable free radical, representative is nitro, nitroso, amino, polyol etc..The representative of the latter can be enumerated to benzene Diphenol, dimethoxy benzene etc..In order to obtain its effect, the preferred ratio of polymerization inhibitor is 5ppm or more, is shown in order to prevent Show bad, the preferred ratio of polymerization inhibitor is 1000ppm or less.And then the model that preferred ratio is 5ppm to 500ppm It encloses.

Using the liquid-crystal composition with negative dielectric constant anisotropy in liquid crystal display element of the invention, thus may be used There is provided that image retention characteristic is excellent and the good liquid crystal display element of orientation stability.

[embodiment]

Hereinafter, illustrating the present invention by embodiment.In addition, evaluation assessment used in embodiment and compound are as follows It is described.

< evaluation assessment >

1. weight average molecular weight (Mw)

The weight average molecular weight of polyamic acid is found out in the following way: showing difference using 2695 separation modules 2414 Refractometer (water generation (Waters) manufacture) is simultaneously measured using GPC method, and polystyrene conversion is then carried out.Utilize phosphoric acid-two Methylformamide (Dimethylformamide, DMF) mixed solution (phosphoric acid/DMF=0.6/100: weight ratio), with polyamide The mode that acid concentration becomes about 2wt% is diluted polyamic acid obtained.Tubing string uses HSPgel RT MB-M (water Generation manufacture), using the mixed solution as solvent, under conditions of tubing string temperature is 50 DEG C, flow velocity is 0.40mL/min into Row measurement.The TSK standard polystyren that standard polystyren uses Tosoh (Tosoh) (share) to manufacture.

2. pre-tilt angle measures

It is measured according to crystal rotation method (Crystal rotation method).

3. voltage retention

Utilize " water Shima et al., the 14th liquid crystal Proceedings of Symposium page 78 (1988) " in documented method and into Row.The rectangular wave of wave height (wave height) ± 5V is applied to unit (cell) and is measured.It is measured at 60 DEG C. The value is to indicate that applied voltage keeps the index of which kind of degree in the frame period (frame period) afterwards, the value if 100% indicates to keep all charges.When being 99.5% or more in the unit equipped with positive type liquid crystal, equipped with minus When being 97.5% or more in the unit of liquid crystal, become the second best in quality liquid crystal display element of display.

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

According to documented method in " Applied Physics ", volume 65, No. 10,1065 (1996), Dongyang technology public affairs are used It takes charge of 6254 type of liquid crystal physical property measurement system of manufacture and is measured.Frequency of use is the triangular wave of 0.01Hz, in the electricity of ± 10V Pressure range is measured that (area of electrode is 1cm at a temperature of 60 DEG C²).If ion concentration is big, it is easy to produce due to ion A problem that burn mark caused by property impurity.That is, ion concentration is the physics value of the index generated as prediction burn mark.When this When value is 40pC or less, become the second best in quality liquid crystal display element of display.

< tetracarboxylic dianhydride >

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

(AN-1-13): ethylenediamine tetra-acetic acid dianhydride

(AN-2-1): 1,2,3,4- cyclobutane tetracarboxylic dianhydride

(AN-3-2): equal benzene tertacarbonic acid's dianhydride

(AN-4-30): N, N'- (1,4- phenylene) bis- (1,3- dioxo octahydro isobenzofuran -5- formamides)

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

(AN-10-1): octahydro pentalene -1,3,4,6- tetrabasic carboxylic acid -1,3,4,6- dianhydride

< diamines >

(DI-5-1, m=1): 4,4'- diaminodiphenyl-methanes

(DI-5-1, m=4): 4,4'- diamino-diphenyl butane

(DI-5-9): 4,4'- diamino-diphenyl ether

(DI-5-12, m=3): 1,3- bis- (4- amino-benzene oxygen) pentanes

(DI-5-30, k=2): bis- (4- the aminophenyl)-N of N, N'-, N'- dimethyl-ethylenediamine

(DI-7-3, m=3, n=1): 1,3- bis- (4- ((4- aminophenyl) methyl) phenyl) propane

(DI-13-1): bis- (4- aminophenyl) piperazines of 4,4'-N, N'-

(DI-34-6, R⁴¹=n-C₅H₁₁): 4', 4'- (4- (2- (4- aminophenyl) ethyl) phenyl) -4- amyl it is bicyclic oneself Alkane

(DI-31-44): 3,5- diaminobenzoic acid cholesteryl ester

< solvent >

Tetrahydrofuran: THF

N-methyl-2-pyrrolidone: NMP

Gamma-butyrolacton: GBL

Butyl cellosolve (ethylene glycol monobutyl ether): BC

[synthesis example 1]

Compound represented by synthesis formula (1-1-1).

The synthesis of < the 1st stage > amide body

Into the three-necked flask for the 300mL for being equipped with thermometer and return pipe, 4- amino -2,2,6,6- tetramethyl piperazines are added Pyridine (15.0g, 96.0mmol) and potassium carbonate (19.9g, 144.0mmol), and add tetrahydrofuran (THF) 100mL.It on one side will be molten Liquid remains 5 DEG C hereinafter, one side is slowly added is dissolved in 3,5- dinitrobenzoyl chloride (24.3g, 105.6mmol) thereto Solution made of in THF 100mL.Stop cooling reaction solution, and then is stirred at room temperature 3 hours.Reaction solution is poured into pure water In 500mL, filtering obtains crystallization be precipitated, and dries 6 hours at 80 DEG C and obtains following compounds.Yield is 32.0g, is produced Rate is 95%.

The reduction of < the 2nd stage > nitro

The compound (32.0g, 91.3mmol) and 5wt% obtained in the 1st stage is added in 1L autoclave reactor Palladium carbon powder (3.2g), and add tetrahydrofuran 300mL.Under the hydrogen environment of 0.5mPa, it is stirred with 50 DEG C until hydrogen The absorption of gas stops.After placing cooling, using palladium carbon powder is filtered to remove, solvent under reduced pressure is evaporated and obtains coarse crystallization.From second Coarse crystallization is recrystallized and obtains compound represented by formula (1-1-1) in alcohol 50mL.Yield is 25.0g, and yield is 70%.

[synthesis example 2]

Compound represented by synthesis formula (1-1-2).

The synthesis of < the 1st stage > acyl chlorides

The bromo- 5- nitrobenzoic acid (25.0g, 101.6mmol) of 2- is added in the eggplant type flask of 300mL, and adds sulfurous Acyl chlorides 100mL.Be heated to reflux within 6 hours, evaporate thionyl chloride decompression after placing cooling and obtains the bromo- 5- nitro benzoyl of 2- Chlorine.Yield is 23.5g, yield 87%.

The synthesis of < the 2nd stage > amide body

Into the three-necked flask for the 300mL for being equipped with thermometer and return pipe, 4- amino -2,2,6,6- tetramethyl piperazines are added Pyridine (13.6g, 87.0mmol) and potassium carbonate (14.4g, 104.4mmol), and add THF 100mL.Solution is remained 5 on one side DEG C hereinafter, one side is slowly added thereto the 1st stage compound obtained (23.0g, 87.0mmol) being dissolved in THF Solution made of in 100mL.Stop cooling reaction solution, and then is stirred at room temperature 3 hours.Reaction solution is poured into pure water In 500mL, filtering obtains crystallization be precipitated, and dries 6 hours at 80 DEG C and obtains following compounds.Yield is 29.0g, is produced Rate is 87%.

The 3rd stage > of <

Into the three-necked flask for the 500mL for being equipped with thermometer and return pipe, compound obtained in the 2nd stage is added (29.0g, 75.5mmol), benzophenone imine (15.0g, 83.0mmol), [1,3- bis- (2,6- diisopropyl phenyl) imidazoles- 2- subunit] (the chloro- pyridyl group of 3-) palladium chloride (II) (2.1g, 3.0mmol) and potassium t-butoxide (12.7g, 113.2mmol), And add toluene 200mL.It is heated to reflux in a nitrogen environment 8 hours, utilizes filtering removal insoluble matter after placing cooling, then will Filtrate is poured into pure water (500mL), is extracted with ethyl acetate (500mL).3 are carried out to organic layer using pure water (500mL) Secondary cleaning.After keeping organic layer dry with anhydrous magnesium sulfate, solvent under reduced pressure is evaporated and obtains coarse crystallization.Pass through silica gel column chromatography Method (dissolution fluid；Toluene: ethyl acetate=6:4) coarse crystallization is isolated and purified and obtains following compounds.Yield is 22.4g, yield 62%.

Transformation of the 4th stage > of < to amino

The compound (22.0g, 45.3mmol) obtained in the 3rd stage is added in the eggplant type flask of 500mL, and thereto Add 6N hydrochloric acid 50mL and THF 200mL.After being stirred at room temperature 12 hours, solvent under reduced pressure is evaporated.It is added in residue pure Water 100mL adds 20% sodium hydrate aqueous solution when stirring until its fluidity becomes pH > 7, and then in room temperature Lower stirring 2 hours.Filtering obtains crystallization be precipitated, with pure water cleans crystallization and obtains following compounds.Yield is 12.3g, yield 85%.

The reduction of < the 5th stage > nitro

The compound (12.0g, 37.5mmol) and 5wt% obtained in the 4th stage is added in 1L autoclave reactor Palladium carbon powder (1.2g), and add THF 100mL.Under the hydrogen environment of 0.5mPa, it is stirred with 50 DEG C up to hydrogen It absorbs and stops.After placing cooling, using palladium carbon powder is filtered to remove, solvent under reduced pressure is evaporated and obtains coarse crystallization.From ethyl alcohol Coarse crystallization is recrystallized in 20mL and obtains compound represented by formula (1-1-2).Yield is 9.4g, yield 86%.

[synthesis example 3]

Compound represented by synthesis formula (C1).

The synthesis of < the 1st stage > ester body

Into the three-necked flask for the 300mL for being equipped with thermometer and return pipe, 4- amino -2,2,6,6- tetramethyl piperazines are added Pyridine (15.0g, 95.4mmol) and potassium carbonate (19.8g, 143.1mmol), and add THF 100mL.Solution is remained 5 on one side DEG C hereinafter, one side is slowly added thereto 3,5- dinitrobenzoyl chloride (24.2g, 105.0mmol) is dissolved in THF 100mL Made of solution.Stop cooling reaction solution, and then is stirred at room temperature 3 hours.Reaction solution is poured into pure water 500mL, mistake Filter obtains crystallization be precipitated, and dries 6 hours at 80 DEG C and obtains following compounds.Yield is 30.3g, yield 90%.

The reduction of < the 2nd stage > nitro

The compound (30.0g, 85.4mmol) and 5wt% obtained in the 1st stage is added in 1L autoclave reactor Palladium carbon powder (3.0g), and add THF 300mL.Under the hydrogen environment of 0.5mPa, it is stirred with 50 DEG C up to hydrogen It absorbs and stops.After placing cooling, using palladium carbon powder is filtered to remove, solvent under reduced pressure is evaporated and obtains coarse crystallization.From ethyl alcohol Coarse crystallization is recrystallized in 40mL and obtains compound represented by formula (C1).Yield is 17.6g, yield 71%.

[synthesis example 4]

Compound represented by synthesis formula (C2).

The 1st stage > of < is esterified

Into the three-necked flask for the 300mL for being equipped with thermometer and return pipe, addition 3,5- binitro bromobenzene (20.0g, 81.0mmol), 4- hydroxyl -2,2,6,6- tetramethyl piperidines (14.0g, 89.1mmol), potassium carbonate (13.4g, 97.2mmol) and Potassium iodide (1.3g, 8.1mmol), and add n,N-Dimethylformamide 200mL.In a nitrogen environment, small with 80 DEG C of stirrings 8 When, reaction solution is poured into pure water 500mL after placing cooling, filtering obtains crystallization be precipitated, 6 hours dry at 80 DEG C And obtain following compounds.Yield is 18.9g, yield 72%.

The reduction of < the 2nd stage > nitro

The compound (18.0g, 55.7mmol) and 5wt% obtained in the 1st stage is added in 1L autoclave reactor Palladium carbon powder (1.8g), and add THF 200mL.Under the hydrogen environment of 0.5mPa, it is stirred with 50 DEG C up to hydrogen It absorbs and stops.After placing cooling, using palladium carbon powder is filtered to remove, solvent under reduced pressure is evaporated and obtains coarse crystallization.From toluene/second Coarse crystallization is recrystallized and obtains compound represented by formula (C2) in the mixed solvent 30mL of alcohol=5/1.Yield is 11.9g, yield 81%.

The preparation of [embodiment 1] varnish

Into the eggplant type flask for the 200mL for being equipped with thermometer, nitrogen purging mouth and stirring rod, compound DI-7-3 is added (m=3, n=1) 2.5874g, compound (1-1-1) 0.610g, and add n-methyl-2-pyrrolidone (NMP) 59.0g and γ- Butyrolactone (GBL) 15.0g.Solution is cooled to 5 DEG C hereinafter, compound (AN-3-1) 0.5553g, compound are added thereto (AN-2-1) 0.9152g and compound (AN-1-13) 0.3261g, and then be stirred at room temperature 6 hours.Butyl is added thereto Cellosolve (BC) 20.0g carries out heating stirring until the viscosity of solution is about 35.0cP, to obtain solid at 70 DEG C Ingredient is the varnish 1 of 6wt%.The weight average molecular weight (Mw) of the varnish 1 is 68,000.

The varnish that following solid component is 6wt% is obtained according to documented method in embodiment 1.By the varnish of acquisition Composition, weight average molecular weight (Mw) it is shown in table 1.Also embodiment 1 is disclosed again.[] interior expression tetracarboxylic compound group, Respective molar ratio in diamine compound group.

Table 1

1 (Continued) of table

[embodiment 35]

The preparation of < aligning agent for liquid crystal, the production method of FFS unit, voltage retention and ion concentration measurement >

1 10g of varnish is weighed in 50mL eggplant type flask, and n-methyl-2-pyrrolidone 10g is added thereto and butyl is molten Fine agent 10g vibrates 2 hours and obtains the aligning agent for liquid crystal 1 that solid component is 3wt%.

Coating obtained is coated on FFS unit glass substrate with varnish using rotator.Application conditions are 2300rpm, 15 seconds.After carrying out precalcining in about 5 minutes after film with 80 DEG C, formed with 200 DEG C of 30 minutes calcination processings of progress The film thickness substantially liquid crystal orientation film of 100nm.Limited liability company, institute system is made using meal natural pond meter (Iinuma Gauge) The friction treatment device made is 0.40mm, platform movement speed in the hair intrusion of friction cloth (staple length 1.9mm: artificial silk) For 60mm/sec, under conditions of roller rotation speed is 1000rpm, friction treatment is carried out to polyimide film obtained.In second After carrying out 5 minutes ultrasonic cleanings to substrate obtained in alcohol, using ultrapure water clean the surface then in an oven with 120 DEG C It is 30 minutes dry.Make the formation of 2 substrates that alignment films are formed on substrate have alignment films in face of to respective orientation The frictional direction of film becomes parallel mode, and then is formed to towards after injecting the gap of liquid-crystal composition between opposite alignment films Fitting, to be assembled into the empty FFS unit that element thickness is 4 μm.The following eurymerics of vacuum injection into made empty FFS unit Liquid-crystal composition A, and inlet is sealed with photo-hardening agent.Then, heat treatment in 30 minutes is carried out at 110 DEG C and makes electricity spy Property evaluation use FFS liquid crystal display element (FFS unit) 1-1.

< positive type liquid crystal composition A >

Physics value: 100.1 DEG C of NI；Δε5.1；Δn 0.093；η25.6mPa·s.

The voltage retention of measurement unit obtained is 99.8% at 5V, 30Hz, ion concentration 10pC.It should Unit is placed in backlight testing machine (Fujiphoto (share) manufacture, Fuji color LED viewer (FujiCOLOR through lighting LED Viewer)Pro HR-2；Brightness 2,700cd/m²) on 1,000 hours and carry out reliability test.After reliability test Measurement with the voltage retention of unit be 99.7%, ion concentration 10pC.

[36~embodiment of embodiment 68 and 5~comparative example of comparative example 7]

According to documented method in embodiment 35, are prepared by liquid crystal and is taken for 2~varnish of varnish 34 and varnish C1~varnish C3 To agent, production FFS unit and measurement voltage retention, ion concentration.Show the result in table 2.Also embodiment 35 is disclosed again As a result.

Table 2

About all units other than the display element for the alignment films for including the alignment agent containing C3, in the early stage, reliability examination It is good result after testing.

[69~embodiment of embodiment 102 and 8~comparative example of comparative example 10]

When electrical characteristics evaluation FFS unit is made, calcination temperature when liquid crystal orientation film is formed is set as 230 DEG C, removes Other than this, according to method production electrical characteristics evaluation FFS unit documented in embodiment 35, thus measure voltage retention and Ion concentration.Show the result in table 3.

Table 3

About unit 1-2~unit 34-2, show in the early stage, after reliability test good as a result, but in unit C1- It is confirmed in 2~unit C3-2: in the early stage, it is seen that voltage retention and ion concentration reduce, after reliability test further Deterioration.

[103~embodiment of embodiment 136 and 11~comparative example of comparative example 13]

The liquid-crystal composition of injection is replaced with into negative type liquid crystal composition B from positive type liquid crystal composition A, in addition to this, according to According to method documented in embodiment 35 production electrical characteristics evaluation FFS unit, to measure the voltage retention of these units And ion concentration.Show the result in table 4.

< negative type liquid crystal composition B >

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

Table 4

About all units in embodiment, good result is obtained.

[137~embodiment of embodiment 170 and 14~comparative example of comparative example 16]

The liquid-crystal composition of injection is replaced with into negative type liquid crystal composition B from positive type liquid crystal composition A, and by liquid crystal aligning Calcination temperature when film formation is set as 230 DEG C, in addition to this, according to method production electrical characteristics evaluation documented in embodiment 35 With FFS unit, to measure the voltage retention and ion concentration of these units.Show the result in table 5.

Table 5

About unit 1-4~unit 34-4, show in the early stage, after reliability test good as a result, but in unit C1- It is confirmed in 4~unit C3-4: in the early stage, it is seen that voltage retention and ion concentration reduce, after reliability test further Deterioration.

Known to according to the above embodiments: of the invention includes the liquid crystal of the liquid crystal orientation film formed by aligning agent for liquid crystal Show that element shows always certain performance independent of the difference of manufacturing process, even if also keeping after long-time good Show quality.

[171~embodiment of embodiment 177] utilizes the confirmation of the effect of polymer blend system alignment agent

The varnish that following solid component is 6wt% is obtained according to documented method in embodiment 1.It will be obtained clear The composition of paint, weight average molecular weight (Mw) are shown in table 6.In [] interior expression tetracarboxylic compound group, diamine compound group Respective molar ratio.

Table 6

The preparation of [embodiment 178] polymer blend system alignment agent

39 0.8g of 1 0.2g of weighing varnish and varnish in sample bottle, add NMP/BC=1/1 (weight ratio) 1.67g and Obtain alignment agent B1.

[179~embodiment of embodiment 207]

The polymer blend system alignment agent being prepared as is shown in table 7.Also embodiment 178 is disclosed again.In table 7 in [] Digital representation weight %.

Table 7

Embodiment	Aligning agent for liquid crystal	Varnish 1	Varnish 2
				178	B1	1[20]	39[80]
179	B2	1[50]	39[50]
				180	B3	1[80]	39[20]
181	B4	1[20]	40[80]
				182	B5	1[50]	40[50]
183	B6	1[80]	40[20]
				184	B7	35[20]	39[80]
185	B8	35[50]	39[50]
				186	B9	35[80]	39[20]
187	B10	35[20]	40[80]
				188	B11	35[50]	40[50]
189	B12	35[80]	40[20]
				190	B13	36[20]	39[80]
191	B14	36[50]	39[50]
				192	B15	36[80]	39[20]
193	B16	36[20]	40[80]
				194	B17	36[50]	40[50]
195	B18	36[80]	40[20]
				196	B19	37[20]	39[80]
197	B20	37[50]	39[50]
				198	B21	37[80]	39[20]
199	B22	37[20]	40[80]
				200	B23	37[50]	40[50]
201	B24	37[80]	40[20]
				202	B25	41[20]	37[80]
203	B26	41[50]	37[50]
				204	B27	41[80]	37[20]
205	B28	41[20]	38[80]
				206	B29	41[50]	38[50]
207	B30	41[80]	38[20]
				Comparative example 17	C1-B	C1[20]	39[80]
Comparative example 18	C2-B	C1[50]	39[50]
				Comparative example 19	C3-B	C1[80]	39[20]
Comparative example 20	C4-B	C1[20]	40[80]
				Comparative example 21	C5-B	C1[50]	40[50]
Comparative example 22	C6-B	C1[80]	40[20]

[embodiment 208] includes the electrical characteristics evaluation of the alignment films of polymer blend system alignment agent

Using prepared polymer blend system alignment agent B1, the temperature of calcination processing is replaced with 230 DEG C from 200 DEG C, In addition to this, electrical characteristics evaluation is made according to method documented by embodiment 35 with FFS liquid crystal display element (FFS unit) B1C。

The voltage retention of measurement unit B 1C obtained is 99.7% at 5V, 30Hz, ion concentration 10pC. The unit is placed in backlight testing machine (Fujiphoto (share) manufacture, FujiCOLOR LED Viewer Pro through lighting HR-2；Brightness 2,700cd/m²) on 1,000 hours and carry out reliability test.Measurement unit after reliability test Voltage retention is 99.7%, ion concentration 10pC.

[209~embodiment of embodiment 237,23~comparative example of comparative example 28]

According to documented method in embodiment 208, also polymer blend system alignment agent B2~polymer blend system is taken FFS unit is made to agent B30 and polymer blend system alignment agent C1-B to polymer blend system alignment agent C6-B, measurement voltage is protected Holdup, ion concentration and progress reliability test.Show the result in table 8.Also the result of embodiment 208 is disclosed again.

Table 8

[embodiment 238]

Using prepared polymer blend system alignment agent B1, the temperature of calcination processing is replaced with 230 DEG C from 200 DEG C, And the liquid-crystal composition of injection is replaced with into negative type liquid crystal composition B, in addition to this, according to method documented by embodiment 35 Make electrical characteristics evaluation FFS liquid crystal display element (FFS unit) B1C-N.

The voltage retention of measurement unit B 1C-N obtained is 98.0% at 5V, 30Hz, and ion concentration is 15pC.The unit is placed in backlight testing machine (Fujiphoto (share) manufacture, FujiCOLOR LED Viewer through lighting Pro HR-2；Brightness 2,700cd/m²) on 1,000 hours and carry out reliability test.Measurement after reliability test is single The voltage retention of member is 97.9%, ion concentration 15pC.

[239~embodiment of embodiment 267,29~comparative example of comparative example 34]

According to documented method in embodiment 238, also polymer blend system alignment agent B2~polymer blend system is taken It is protected to agent B30 and polymer blend system alignment agent C1-B~polymer blend system alignment agent C6-B production FFS unit, measurement voltage Holdup, ion concentration and progress reliability test.Show the result in table 9.Also the result of embodiment 238 is disclosed again.

Table 9

Recognized according to result above: the alignment films comprising aligning agent for liquid crystal of the invention are in polymer blend system Play The effect of invention.And the liquid crystal of clamping plays The effect of invention in eurymeric and minus.

[comparative example 35]

Synthesized 41 1.0g of varnish in weighing embodiment 177, adds amine antioxidant (Ai Dike thereto (ADEKA) limited liability company manufactures, Ai Di Coase tower wave (Adekastab) LA-72) 0.18mg, and add NMP/BC=1/1 (weight ratio) 1.67g vibrates 1 hour at room temperature and obtains alignment agent R3HA.

Using prepared alignment agent R3HA, the liquid-crystal composition of injection is replaced with into negative type liquid crystal composition B, except this with Outside, according to method production electrical characteristics evaluation FFS liquid crystal display element (FFS unit) R3HAC documented in embodiment 35.

The voltage retention of measurement unit R 3HAC obtained is 97.5% at 5V, 30Hz, and ion concentration is 20pC.The unit is placed in backlight testing machine (Fujiphoto (share) manufacture, FujiCOLOR LED Viewer through lighting Pro HR-2；Brightness 2,700cd/m²) on 1,000 hours and carry out reliability test.Measurement after reliability test is single The voltage retention of member is 83.2%, ion concentration 195pC.

[comparative example 36]

The additive amount of Adekastab LA-72 is replaced with into 1.8mg, in addition to this, documented by example 35 Method prepares alignment agent R3HB, to make electrical characteristics FFS liquid crystal display element R3HBC.

The voltage retention of measurement unit R 3HBC obtained is 97.8% at 5V, 30Hz, and ion concentration is 25pC.The unit is placed in backlight testing machine (Fujiphoto (share) manufacture, FujiCOLOR LED Viewer through lighting Pro HR-2；Brightness 2,700cd/m²) on 1,000 hours and carry out reliability test.Measurement after reliability test is single The voltage retention of member is 91.1%, ion concentration 105pC.Drawn however, being confirmed in unit R 3HBC from initial stage by spot The display risen is bad.Think the display it is bad be that added JF-90 is segregated in most surface when preparing alignment films, thus generate Spot is bad.

[comparative example 37]

The additive amount of Adekastab LA-72 is replaced with into 18.0mg, in addition to this, documented by example 35 Method prepares alignment agent R3HC, to make electrical characteristics FFS liquid crystal display element R3HCC.

The voltage retention of measurement unit R 3HCC obtained is 97.6% at 5V, 30Hz, and ion concentration is 25pC.The unit is placed in backlight testing machine (Fujiphoto (share) manufacture, FujiCOLOR LED Viewer through lighting Pro HR-2；Brightness 2,700cd/m²) on 1,000 hours and carry out reliability test.Measurement after reliability test is single The voltage retention of member is 91.9%, ion concentration 95pC.Drawn however, being confirmed in unit R 3HCC from initial stage by spot The display risen is bad.

[industrial availability]

By using the liquid crystal orientation film of the invention formed by aligning agent for liquid crystal, can get by display quality for a long time The excellent liquid crystal display element that will not decline.It is characteristically played in the liquid crystal display element of IPS mode and FFS mode The effect.

Claims (16)

1. a kind of polymer is selected from polyamic acid, polyimides, part polyimides, poly amic acid ester, polyamic acid- At least one of polyamide copolymer and polyamidoimide, the polymer are at least one of diamines represented by formula (1) Kind is reacted at least one of tetracarboxylic dianhydride and is obtained, wherein the part polyimides is that partly progress dehydration closed-loop is anti- It answers and is formed:

In formula (1), R¹It is hydrogen or methyl；And

R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

2. polymer according to claim 1, wherein diamines represented by formula (1) is diamines represented by formula (1-1) It is at least one:

In formula (1-1), R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

3. polymer according to claim 1, wherein diamines represented by formula (1) is diamines represented by formula (1-2) It is at least one:

In formula (1-2), R²It is the alkyl that hydrogen ,-OH, carbon number are 1~6 or the alkoxy that carbon number is 1~6.

4. polymer according to claim 2, wherein diamines represented by formula (1) is selected from formula (1-1-1)~formula (1-1- 28) at least one of group of compound represented by:

5. polymer according to claim 3, wherein diamines represented by formula (1) is selected from formula (1-2-1)~formula (1-2- 28) at least one of group of compound represented by:

6. polymer according to any one of claim 1 to 5, be by formula (1) represented by diamines at least one It reacts and obtains at least one of tetracarboxylic dianhydride at least one mixture of other diamines.

7. polymer according to claim 6, wherein tetracarboxylic dianhydride is selected from following formula (AN-I)~formula (AN-VII) At least one of represented group of tetracarboxylic dianhydride:

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

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

In formula (AN-II)~formula (AN-IV), Y is stood alone as selected from following one of groups of base of trivalent,

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

In formula (AN-III)~formula (AN-V), ring A¹⁰For carbon number be 3~10 monocyclic hydrocarbon base or carbon number be 6~30 condensation At least one hydrogen of the base of polycycle hydrocarbon, the base can be replaced by methyl, ethyl or phenyl, the associative key and structure being connected on ring The arbitrary carbon connection of cyclization, 2 associative keys can link with the same carbon；

In formula (AN-VI), X¹⁰The alkylidene for being 2~6 for carbon number, Me indicate that methyl, Ph indicate phenyl,

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

8. polymer according to claim 7, wherein tetracarboxylic dianhydride is selected from following formula (AN-1-1), formula (AN-1- 2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN- 4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-11-3), formula (AN-16-3) and at least one of formula (AN-16-4):

In formula (AN-1-2) and formula (AN-4-17), m be 1~12 integer.

9. polymer according to claim 6, wherein other diamines be selected from by following formula (DI-1)~formula (DI-16), At least one of group composed by formula (DIH-1)~formula (DIH-3) and formula (DI-31)~formula (DI-35):

In formula (DI-1), G²⁰For-CH₂, at least one-CH₂It can be replaced by-NH- ,-O-, the integer that m is 1~12, alkylidene At least one hydrogen can be replaced by-OH；

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

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

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

In formula (DI-2)~formula (DI-7), at least one hydrogen of cyclohexane ring and phenyl ring can be by-F ,-Cl, the alkane that carbon number is 1~3 Base ,-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl replace, in addition, in formula (DI-4), phenyl ring At least one hydrogen can by the base represented by following formula (DI-4-a)~formula (DI-4-e) group in a substitution；

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

It is any ,-NH that binding site, which is not fixed to the binding site of basis representation on which ring on the carbon atom for constituting ring,₂In Binding site on cyclohexane ring or phenyl ring is except G²¹Or G²²Binding site other than arbitrary position；

In formula (DI-11), r is 0 or 1；

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

In formula (DI-12), R²¹And R²²Stand alone as the alkyl or phenyl that carbon number is 1~3, G²³Stand alone as the alkylene that carbon number is 1~6 Base, phenylene or through alkyl-substituted phenylene, the integer that w is 1~10；

In formula (DI-13), R²³The alkoxy or-Cl that alkyl, carbon number that carbon number is 1~5 are 1~5 are stood alone as, p stands alone as 0~3 Integer, q be 0~4 integer；

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

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

In formula (DI-16), G²⁴The alkylidene or Isosorbide-5-Nitrae-phenylene for being 2~6 for singly-bound, carbon number, r are 0 or 1；

In formula (DI-13)~formula (DI-16), binding site is not fixed to the basis representation on the carbon atom for constituting ring on which ring Binding site be any；

In formula (DIH-1), G²⁵For singly-bound, carbon number be 1~20 alkylidene ,-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 ring can be by methyl, ethyl or benzene Base replaces；

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

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

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、-CF₂O-、- OCF₂Or-(CH₂)_m', the integer that m' is 1~12, R²⁵For carbon number be 3~30 alkyl, phenyl, with steroid skeleton Base or by the base represented by following formulas (DI-31-a), in the alkyl, at least one hydrogen can be replaced by-F, at least one- CH₂It can be replaced by-O- ,-CH=CH- or-C ≡ C-, the hydrogen of the phenyl can be by-F ,-CH₃、-OCH₃、-OCH₂F、-OCHF₂、- OCF₃, carbon number be 3~30 alkyl or carbon number be 3~30 alkoxy replace, be bonded-NH on phenyl ring₂Binding site table Show to be arbitrary position in the ring,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For bond base, they stand alone as the alkylidene that singly-bound or carbon number are 1~12, institute State the more than one-CH of alkylidene₂It can be replaced by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH-, ring B²¹, ring B²², ring B²³And ring B²⁴Stand alone as 1,4- phenylene, 1,4- cyclohexylidene, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl, pyrrole 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, until Few hydrogen can be by-F or-CH₃Replace, s, t and u stand alone as 0~2 integer, they add up to 1~5, when s, t or u are 2 When, 2 bond bases in each bracket may be the same or different, and 2 rings may be the same or different,

R²⁶For hydrogen ,-F ,-OH, carbon number be 1~30 alkyl, carbon number be 1~30 fluorine replace the alcoxyl that alkyl, carbon number are 1~30 Base ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, at least one-CH for the alkyl that the carbon number is 1~30₂It can be by with following formula (DI-31-b) base of the divalent represented by replaces,

In formula (DI-31-b), R²⁷And R²⁸Stand alone as the alkyl that carbon number is 1~3, the integer that v is 1~6；

In formula (DI-32) and formula (DI-33), G³⁰Stand alone as singly-bound ,-CO- or-CH₂, R²⁹Stand alone as hydrogen or-CH₃, R³⁰For hydrogen, The alkenyl that the alkyl or carbon number that carbon number is 1~20 are 2~20；

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

In formula (DI-32) and formula (DI-33), binding site is not fixed to the basis representation on any one carbon atom for constituting ring in institute It is any for stating the binding site on ring；

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

R³¹The alkyl for being 1~20 for hydrogen or carbon number, at least one-CH of the alkyl₂It can be by-O- ,-CH=CH- or-C ≡ C- Replace, R³²The alkyl for being 6~22 for carbon number, R³³The alkyl for being 1~22 for hydrogen or carbon number, ring B²⁵For 1,4- phenylene or 1,4- Cyclohexylidene, r are 0 or 1, and, it is bonded-the NH on phenyl ring₂Indicate that binding site on which ring is any.

10. polymer according to claim 6, wherein other diamines are selected from by following formula (DI-1-3), formula (DI-2- 1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI- 5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI-13-1), formula (DI-16-1), And at least one of group composed by formula (DIH-2-1):

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

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

In formula (DI-7-3), n is 1 or 2.

11. a kind of aligning agent for liquid crystal contains polymer according to any one of claim 1 to 10.

12. a kind of aligning agent for liquid crystal, containing polymer according to any one of claim 1 to 10 and in addition to them Polymer.

13. aligning agent for liquid crystal according to claim 11 or 12, also contain selected from replacing nadikimide by alkenyl Compound, the compound with free-radical polymerised unsaturated double-bond, oxazines compound, oxazoline compound and epoxy compound At least one of heterogeneous compound group composed by object.

14. aligning agent for liquid crystal according to claim 11 or 12 is used for lateral electric-field type liquid crystal display element.

15. a kind of liquid crystal orientation film, the aligning agent for liquid crystal as described according to claim 1 any one of 1 to 14 and formed.

16. a kind of liquid crystal display element comprising liquid crystal orientation film according to claim 15.