CN107089956A

CN107089956A - Diamines, polyamic acid or derivatives thereof, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Info

Publication number: CN107089956A
Application number: CN201710087164.6A
Authority: CN
Inventors: 伊泽启介
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2016-02-18
Filing date: 2017-02-17
Publication date: 2017-08-25
Also published as: JP2017145346A; JP6565730B2

Abstract

The present invention relates to diamines, polyamic acid or derivatives thereof, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells.The present invention relates to the aligning agent for liquid crystal containing polyamic acid or derivatives thereof, described polyamic acid or derivatives thereof is to make tetracarboxylic dianhydride and comprising obtained from the diamine reactant of compound shown in formula (1).By using the aligning agent for liquid crystal of the present invention, the liquid crystal orientation film for the liquid crystal display cells that can be achieved will not also to be reduced exposed to strong light its display quality even if long-time can be formed.

Description

Diamines, polyamic acid or derivatives thereof, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal Display element

Technical field

The present invention relates to the diamines shown in formula (1) is used for the polyamic acid and its derivative of raw material, contains the polyamide Aligning agent for liquid crystal, the liquid crystal display cells of acid and its derivative.

Background technology

It is current with the liquid crystal display cells generally circulated in the form of product, used the display element of nematic crystal into For main flow.For the display mode of nematic crystal display element, sufficiently known is TN (twisted nematic, Twisted Nematic) pattern, STN (STN Super TN, Super Twisted Nematic) pattern.In recent years, it is used as this to improve The visual angle of one of a little pattern the problem of points is narrow, it is proposed that used the TN types liquid crystal display cells of optical compensation films, by vertically MVA (multidomain vertical orientation, Multi-domain Vertical that orientation and the technical combinations of raised structures thing are used Alignment) IPS (in-plane switching, In-Plane Switching) pattern of pattern or Transverse electric-field type, FFS (sides Edge switching, Fringe Field Switching) pattern, and put into practical (with reference to patent document 1~3.).

The technology development of liquid crystal display cells is not only realized by improveing these type of drive, component structure, is also passed through Member of formation used in element is improved to realize.Among member of formation used in liquid crystal display cells, especially, liquid crystal takes It is one of important materials related to display quality to film, with the high-quality of liquid crystal display cells, improves the property of alignment films It can gradually become important.

The liquid crystal orientation film primarily now used is that polyamic acid or the polyimides of solubility will be made to be dissolved in organic solvent Obtained from solution (varnish) be coated on after substrate, by the polyimides system liquid crystal orientation film for means and the film forming such as heating.

In industrial aspect, it can easily realize that the brushing method of the high speed processing of large area is widely used as orientation process Method.Brushing method is the cloth for making the fibers such as nylon, artificial silk, polyester hold up seta, and the surface of liquid crystal orientation film is entered Processing of the row along a direction friction, thus, it is possible to obtain being uniformly directed for liquid crystal molecule.

In addition, as the orientation position logos for substituting brushing method, irradiation light can be used and implement the light orientation of orientation process Facture.For light orientation position logos, it is proposed that a variety of orientations such as light decomposition method, photoisomerization method, photodimerization method, optical cross-linking method Mechanism (for example, referring to non-patent literature 1, patent document 4 and 5).Optical alignment method has the following advantages that：Compared with brushing method, take It is high to uniformity, and because it is non-contacting orientation position logos, therefore film will not be damaged, dust, electrostatic etc. can be reduced Liquid crystal display cells can be made to occur the reason for display is bad etc..

, to the key property of liquid crystal orientation film requirement, it can be enumerated as in order to improve the display quality of liquid crystal display cells Go out ion concentration.If ion concentration is high, the voltage reduction of liquid crystal is put in a frame period, as a result, luminance-reduction sometimes And normal gray scale is shown and counteracted.In addition, even if such as initial ion concentration is low but hot test after ion it is close It is undesirable to spend increased situation.It is used as the trial for solving the problem, it is known that：For example make to include in raw material and there is piperazine Etc cyclic secondary amine structure diamines, mutually isostructural method (reference patent document 6,7) is imported into polyimides chain.

And then, the purposes of liquid crystal display cells is throughout personal computer display, liquid crystal TV set, mobile phone, intelligent hand The multiple fields such as display part, the liquid crystal projection apparatus of machine.In recent years, it is contemplated that the improvement of display quality, the use in outdoor, also deposit It is higher than conventional purposes in the brightness for becoming the backlight of light source, even if seeking not to be only exposed to heat, being exposed to strong light for a long time Its ion concentration also will not increased liquid crystal orientation film.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 6-194646

Patent document 2：Japanese Unexamined Patent Publication 2001-117083

Patent document 3：Japanese Unexamined Patent Publication 6-160878

Patent document 4：Japanese Unexamined Patent Publication 9-297313

Patent document 5：Japanese Unexamined Patent Publication 10-251646

Patent document 6：Japanese Unexamined Patent Publication 2009-175684

Patent document 7：Japanese Unexamined Patent Publication 2011-028223

Non-patent literature

Non-patent literature 1：Liquid crystal, volume 3, No. 4, page 262,1999 years

The content of the invention

Problems to be solved by the invention

The problem of the present invention is that there is provided the liquid crystal that will not be also reduced exposed to strong light its display quality even if long-time Show element.And there is provided the aligning agent for liquid crystal and liquid crystal orientation film that can provide this display element.

The solution used to solve the problem

The present inventor etc. has made intensive studies, as a result by using the diamines of following formula (1), and completing can provide i.e. Make the aligning agent for liquid crystal and liquid crystal orientation film of liquid crystal display cells that will not be also reduced exposed to strong light its display quality for a long time. It is used for the liquid crystal display cells of the Transverse electric-field types such as IPS patterns and FFS mode with being particularly suitable for.

The present invention includes following technical proposals.

[1] a kind of polyamic acid or derivatives thereof, it is to make tetracarboxylic dianhydride and include the diamines of compound shown in formula (1) Obtained from reaction.

[2] polyamic acid according to [1] or derivatives thereof, wherein, tetracarboxylic dianhydride is selected from following formula (AN-I) It is at least one kind of in the group of tetracarboxylic dianhydride shown in~formula (AN-VII),

It is selected from by following formula (DI-1)~formula (DI-16), formula with other diamines that the diamines shown in formula (1) is used together (DIH-1) it is at least one kind of in~formula (DIH-3) and the group of formula (DI-31)~formula (DI-35) composition.

In formula (AN-I), formula (AN-IV) and formula (AN-V), X independently is singly-bound or-CH₂-；

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

In formula (AN-II)~formula (AN-IV), Y independently is a kind in the group selected from following trivalent groups,

At least one hydrogen on these groups is optionally replaced by methyl, ethyl or phenyl；

In formula (AN-III)~formula (AN-V), ring A¹⁰For the monocyclic alkyl or carbon number 6~30 of carbon number 3~10 Fused polycyclic alkyl, at least one hydrogen on the group optionally replaces by methyl, ethyl or phenyl, and the key being connected with ring connects Any carbon for constituting ring is connected to, 2 key options are connected to same carbon；

In formula (AN-VI), X¹⁰For the alkylidene of carbon number 2~6, Me represents methyl, and Ph represents phenyl,

In formula (AN-VII), G¹⁰It independently is-O- ,-COO- or-OCO-；Also, r independently is 0 or 1；

In formula (DI-1), G²⁰For-CH₂-, at least one-CH₂- optionally replaced by-NH- ,-O-, m is 1~12 integer, sub- At least one hydrogen on alkyl is optionally replaced by-OH；

In formula (DI-3) and formula (DI-5)~formula (DI-7), G²¹It independently is 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 ' independently be 1~12 integer, k is 1~5 integer, n be 1 or 2；

In formula (DI-4), s independently is 0~2 integer；

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

In formula (DI-2)~formula (DI-7), at least one hydrogen on cyclohexane ring and phenyl ring is optionally by-F ,-Cl, carbon number 1~3 alkyl ,-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl substitution, also, in formula (DI-4), Optionally be selected from the group of the group shown in following formula (DI-4-a)~formula (DI-4-e) a kind of at least one hydrogen on phenyl ring takes Generation；

In formula (DI-4-a) and formula (DI-4-b), R²⁰It independently is hydrogen or-CH₃；

The loose group of bonding position on the carbon atom for constituting ring represents that the bonding position on the ring is any ,-NH₂Bonding position on cyclohexane ring or phenyl ring is except G²¹Or G²²Bonding position outside optional position；

In formula (DI-11), r is 0 or 1；

In formula (DI-8)~formula (DI-11) ,-NH being bonded on ring₂Bonding position be optional position；

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

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

In formula (DI-14), ring B is monocyclic heteroaromatic, R²⁴It is former for hydrogen ,-F ,-Cl, the alkyl of carbon number 1~6, carbon Alkoxy, the alkenyl of carbon number 2~6, the alkynyl of carbon number 2~6 of subnumber 1~6, q independently are 0~4 integer；

In formula (DI-15), ring C is comprising heteroatomic monocyclic；

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

In formula (DI-13)~formula (DI-16), the loose group of bonding position on the carbon atom for constituting ring is represented Bonding position on the ring is arbitrary；

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

In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen on these rings is optionally by methyl, second Base or phenyl substitution；

In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen on these rings is optionally by first Base, ethyl or phenyl substitution, Y is singly-bound, the alkylidene of carbon number 1~20 ,-CO- ,-O- ,-S- ,-SO₂-、-C(CH₃)₂- Or-C (CF₃)₂-；

In formula (DIH-2) and formula (DIH-3) ,-CONHNH being bonded on ring₂Bonding position be optional position；

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、- CF₂O-、-OCF₂- or-(CH₂)_m’-, m ' is 1~12 integer, R²⁵Consolidate for the alkyl of carbon number 3~30, phenyl, with class In base shown in the group or following formula (DI-31-a) of ol skeleton, the alkyl, at least one hydrogen is optionally replaced by-F, and at least 1 Individual-CH₂- optionally replaced by-O- ,-CH=CH- or-C ≡ C-, the hydrogen on the phenyl is optionally by-F ,-CH₃、-OCH₃、-OCH₂F、- OCHF₂、-OCF₃, carbon number 3~30 alkyl or carbon number 3~30 alkoxy substitution ,-the NH being bonded on phenyl ring₂ Bonding position represent the optional position on the ring,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For linking group, they independently are singly-bound or carbon number 1~12 More than 1-CH in alkylidene, the alkylidene₂- optionally replaced by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH-, ring B²¹, ring B²², ring B²³With ring B²⁴Independently be 1,4- phenylenes, 1,4- cyclohexylenes, 1,3- dioxane -2,5- diyls, pyrimidine - 2,5- diyls, pyridine -2,5- diyl, piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -2,7- diyl or anthracene -9,10- diyl, ring B²¹, ring B²², ring B²³With ring B²⁴In, at least one hydrogen is optionally by-F or-CH₃Substitution, s, t and u independently are 0~2 integer, it Add up to 1~5, when s, t or u are 2,2 linking groups in each parantheses can be the same or different, and 2 rings can be with It is identical can also be different,

R²⁶For fluorine substitution alkyl, the carbon number 1 of hydrogen ,-F ,-OH, the alkyl of carbon number 1~30, carbon number 1~30 ~30 alkoxy ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, at least one-CH in the alkyl of the carbon number 1~30₂- appoint Select by the divalent group displacement shown in following formula (DI-31-b),

In formula (DI-31-b), R²⁷And R²⁸The alkyl of carbon number 1~3 independently is, v is 1~6 integer；

In formula (DI-32) and formula (DI-33), G³⁰It independently is singly-bound ,-CO- or-CH₂-, R²⁹It independently is hydrogen or-CH₃, R³⁰For the alkenyl of hydrogen, the alkyl of carbon number 1~20 or carbon number 2~20；

1 hydrogen on phenyl ring in formula (DI-33) is optionally replaced by the alkyl or phenyl of carbon number 1~20, also,

In formula (DI-32) and formula (DI-33), the loose group table of bonding position on any carbon atom for constituting ring It is arbitrary to show the bonding position on the ring；

In formula (DI-34) and formula (DI-35), G³¹It independently is the alkylidene of-O- ,-NH- or carbon number 1~6, G³²For The alkylidene of singly-bound or carbon number 1~3,

R³¹For hydrogen or the alkyl of carbon number 1~20, at least one-CH in the alkyl₂- optionally by-O- ,-CH=CH- Or-C ≡ C- displacements, R³²For the alkyl of carbon number 6~22, R³³For hydrogen or the alkyl of carbon number 1~22, ring B²⁵For 1,4- Phenylene or Isosorbide-5-Nitrae-cyclohexylene, r are 0 or 1, also ,-the NH being bonded on phenyl ring₂Representing the bonding position on the ring is Arbitrarily.

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

The other diamines being used together with the diamines shown in formula (1) be 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-5-5), formula (DI-5- 9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1) and formula (DI-31-56) are constituted It is at least one kind of in group.

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

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

In formula (DI-5-30), k is 1~5 integer；Also,

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

[4] polyamic acid according to any one of [1]~[3] or derivatives thereof, wherein, tetracarboxylic dianhydride and diamines In at least 1 include with photoreactivity structure compound.

[5] polyamic acid according to [4] or derivatives thereof, wherein, photoreactivity structure is selected from by following formula (P- 1) it is at least one kind of in the group of the structure composition shown in~formula (P-7).

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

[6] polyamic acid according to [4] or derivatives thereof, wherein, the compound with photoreactivity structure is choosing Free following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1)~formula (V-3) it is at least one kind of and in formula (VI-1), the group of formula (VI-2) composition.

It is above-mentioned it is various in, constitute ring any carbon atom on the loose group of bonding position represent on the ring Bonding position is arbitrary, in formula (V-2), R⁶It independently is-CH₃、-OCH₃、-CF₃Or-COOCH₃, a is each independently 0~2 Integer, in formula (V-3), ring A and ring B are each independently at least 1 in monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle Kind, R¹¹For the straight-chain alkyl-sub of carbon number 1~20 ,-COO- ,-OCO- ,-NHCO- or-N (CH₃) CO-, R¹²For carbon number 1 ~20 straight-chain alkyl-sub ,-COO- ,-OCO- ,-NHCO- or-N (CH₃) CO-, R¹¹And R¹²In, 1 or 2 on straight-chain alkyl-sub Individual-CH₂- optionally replaced by-O-, R⁷~R¹⁰It is each independently-F ,-CH₃、-OCH₃、-CF₃Or-OH, also, b~e is each only On the spot be 0~4 integer.

[7] polyamic acid according to [4] or derivatives thereof, wherein, under the compound with photoreactivity structure is State the diamines shown in formula (PDI-7).

In formula (PDI-7), R⁵¹It is each independently-CH₃、-OCH₃、-CF₃Or-COOCH₃, s is each independently 0~2 Integer.

[8] a kind of aligning agent for liquid crystal, it contains polyamic acid any one of [1]~[7] or derivatives thereof.

[9] aligning agent for liquid crystal according to [8], it, which also contains, is selected from You oxazine compounds, oxazoline compounds, epoxy It is at least one kind of in compound and the compound group of silane coupler composition.

[10] a kind of liquid crystal orientation film, it is formed as the aligning agent for liquid crystal described in [8] or [9].

[11] the driving liquid crystal orientation film used for liquid crystal display element of a kind of transverse electric field, it is as the liquid described in [8] or [9] Brilliant alignment agent formation.

[12] a kind of liquid crystal display cells, it has the liquid crystal orientation film described in [10] or [11].

[13] a kind of light orientation aligning agent for liquid crystal, its include polymer [A] and polymer [B], the polymer [A] and Polymer [B] is polyamic acid or derivatives thereof,

At least 1 in the starting monomer of aforementioned polymer have photoreactivity structure, and the raw material list of aforementioned polymer Body includes the compound shown in following formula (1).

[14] according to the light orientation aligning agent for liquid crystal described in [13], it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

The polymer [A] is the tetracarboxylic acid obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines At least 1 in acid dianhydride and diamines include the compound with photoreactivity structure,

The polymer [B] is the tetracarboxylic acid obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines Acid dianhydride and diamines do not have photoreactivity structure and diamines is comprising at least one kind of in compound shown in formula (1).

[15] according to the light orientation aligning agent for liquid crystal described in [13], it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

The polymer [A] is the tetracarboxylic acid obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines At least 1 in acid dianhydride and diamines, which include compound and diamines with photoreactivity structure, includes chemical combination shown in formula (1) Thing,

The polymer [B] is the tetracarboxylic acid obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines Acid dianhydride and diamines do not have photoreactivity structure.

[16] according to the light orientation aligning agent for liquid crystal described in [13], it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

[17] according to the light orientation aligning agent for liquid crystal described in [13], it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

The polymer [B] is the tetracarboxylic acid obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines At least 1 in acid dianhydride and diamines, which include compound and diamines with photoreactivity structure, includes compound shown in formula (1)

[18] the light orientation aligning agent for liquid crystal according to any one of [13]~[17], wherein, with photoreactivity The compound of structure has at least one kind of in following formula (P-1)~structure shown in formula (P-7).

[19] the light orientation aligning agent for liquid crystal according to any one of [13]~[17], wherein, with photoreactivity The compound of structure is selected from by following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV- 2) it is, at least one kind of in formula (V-1)~formula (V-3) and formula (VI-1), the group of formula (VI-2) composition.

[20] the light reaction aligning agent for liquid crystal according to any one of [13]~[17], wherein, with photoreactivity The compound of structure is the diamines shown in following formula (PDI-7).

[21] the light orientation aligning agent for liquid crystal according to any one of [13]~[20], wherein, without light reaction Property structure tetracarboxylic dianhydride be the group selected from the tetracarboxylic dianhydride shown in following formula (AN-I)~formula (AN-VII) at least 1 Kind；

Diamines without photoreactivity structure is selected from by following formula (DI-1)~formula (DI-16), formula (DIH-1)~formula (DIH-3) it is at least one kind of and in the group of formula (DI-31)~formula (DI-35) composition.

In formula (AN-VII), G¹⁰- O- ,-COO- or-OCO- independently are, r independently is 0 or 1；

In formula (DI-4), s independently is 0~2 integer；

In formula (DI-11), r is 0 or 1；

In formula (DI-15), ring C is comprising heteroatomic monocyclic；

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、- CF₂O-、-OCF₂- or-(CH₂)_m’-, m ' is 1~12 integer, R²⁵Consolidate for the alkyl of carbon number 3~30, phenyl, with class In group shown in the group or following formula (DI-31-a) of ol skeleton, the alkyl, at least one hydrogen is optionally replaced by-F, extremely Few 1-CH₂- optionally replaced by-O- ,-CH=CH- or-C ≡ C-, the hydrogen on the phenyl is optionally by-F ,-CH₃、-OCH₃、- OCH₂F、-OCHF₂、-OCF₃, carbon number 3~30 alkyl or carbon number 3~30 alkoxy substitution, on phenyl ring be bonded - NH₂Bonding position represent the optional position on the ring,

[22] the light orientation aligning agent for liquid crystal according to [21], wherein, the tetrabasic carboxylic acid without photoreactivity structure Dianhydride is selected from following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-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), in formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4) at least 1 kind；

Diamines without photoreactivity structure be 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-5-5), formula (DI-5-9), formula (DI-5- 12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), at least 1 in the group of formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1) and formula (DI-31-56) composition Kind.

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

In formula (DI-5-30), k is 1~5 integer；Also,

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

[23] according to the aligning agent for liquid crystal any one of [13]~[22], its also contain selected from You oxazine compounds, It is at least one kind of in the compound group of oxazoline compound, epoxide and silane coupler composition.

[24] a kind of liquid crystal orientation film, it is formed as the aligning agent for liquid crystal any one of [13]~[23].

[25] a kind of transverse electric field liquid crystal orientation film, it is as the aligning agent for liquid crystal any one of [13]~[23] Formed.

[26] a kind of liquid crystal display cells, it has the liquid crystal orientation film described in [24] or [25].

" at least 1 in tetracarboxylic dianhydride and diamines include the compound with photoreactivity structure " described in above Refer to " among tetracarboxylic dianhydride and diamines, at least one compound has photoreactivity structure ", specifically refer to, tetracarboxylic acid Acid dianhydride can use it is one kind or two or more, diamines can use it is one kind or two or more, among these all compounds, extremely A few compound has photoreactivity structure, i.e., including following form：At least one only in tetracarboxylic dianhydride has light At least one in the form of reactive structure, only diamines has in the form of photoreactivity structure, tetracarboxylic dianhydride at least One at least one having in photoreactivity structure and diamines has the form of photoreactivity structure.

The effect of invention

The liquid crystal of the polyamic acid as being used for raw material containing the compound shown in by formula (1) of the present invention or derivatives thereof takes To dosage form into liquid crystal orientation film will not also be reduced exposed to strong light its display quality even if long-time, long-term reliability is excellent. Possesses the image retention excellent of the liquid crystal display cells of the Transverse electric-field type of the liquid crystal orientation film formed by optical alignment method.Think When assigning other characteristics such as the printing that raising is printed on substrate, by being blended with other polymer, or by with adding Plus agent is applied in combination, the liquid crystal orientation film for possessing desired characteristic can be provided.

Embodiment

By the way that the compound shown in formula (1) is used as to constitute one of raw material of polymer of aligning agent for liquid crystal of the invention, Result in will not also be reduced exposed to strong light its display quality even if long-time, the liquid crystal orientation film that liquid crystal aligning is high.

Illustrated for the polyamic acid and its derivative of the present invention.The polyamic acid and its derivative of the present invention is four Carboxylic acid dianhydride and the reaction product for including the diamines of compound shown in formula (1)." diamines for including compound shown in formula (1) " is specific Refer to the mixing of the compound and at least one in other diamines in addition to the compound shown in formula (1) shown in formula (1) Thing.Make in addition, aftermentioned " other diamines " is additionally included in play in the polyamic acid of the present invention and its derivative with diamines identical Two hydrazides.In this specification, there is the statement that two hydrazides are regarded as to diamines.That is, the feelings of " diamines " in this specification, are denoted as Condition is sometimes what is used with the meaning including two hydrazides.

The derivative of foregoing polyamides acid refers to：Be dissolved in when the aftermentioned aligning agent for liquid crystal containing solvent is made solvent into Point, it can form the liquid crystal orientation film using polyimides as principal component when being and the aligning agent for liquid crystal being made into liquid crystal orientation film Composition.As the derivative of this polyamic acid, such as soluble polyimide, poly amic acid ester and polyamide can be included Sour acid amides etc., more specifically, can include 1) all amino of polyamic acid and occur dehydration closed-loop reaction with carboxyl and obtain Polyimides；2) partly occurs part polyimides obtained from dehydration closed-loop reaction；3) converting carboxylate groups of polyamic acid Poly amic acid ester obtained from into ester；4) a part of acid dianhydride included in tetracarboxylic dianhydride's compound is replaced as organic dicarboxyl Acid simultaneously makes polyamic acid-polyamide copolymer obtained from its reaction；And 5) the one of the polyamic acid-polyamide copolymer is made Partly or entirely occurs polyamidoimide obtained from dehydration closed-loop reaction.Foregoing polyamides are sour and its derivative can be 1 Kind of compound or two or more.In addition, foregoing polyamides acid and its derivative can be with tetracarboxylic dianhydride and two The compound of the structure of the reaction product of amine, can also contain passed through using other raw materials it is anti-except tetracarboxylic dianhydride and diamines Reaction product obtained from other reactions outside answering.

Illustrated for the tetracarboxylic dianhydride used to manufacture the polyamic acid and its derivative of the present invention.This hair The bright middle tetracarboxylic dianhydride used can unrestrictedly be selected from known tetracarboxylic dianhydride.This tetracarboxylic dianhydride can Have not direct in the fragrant family (including miscellaneous aromatic ring) and aromatic rings of dicarboxylic anhydride to belong to Direct Bonding on aromatic rings It is bonded with any group in the fatty family of dicarboxylic anhydride (including heterocycle system).

As the suitable example of this tetracarboxylic dianhydride, easness when obtaining easness, manufacture polymer from raw material, From the viewpoint of the electrical characteristics of film, the tetracarboxylic dianhydride shown in formula (AN-I)~formula (AN-VII) can be included.

In formula (AN-I), formula (AN-IV) and formula (AN-V), X independently is singly-bound or-CH₂-.In formula (AN-II), G is single Key, the alkylidene of carbon number 1~20 ,-CO- ,-O- ,-S- ,-SO₂-、-C(CH₃)₂- or-C (CF₃)₂-.Formula (AN-II)~formula (AN-IV) in, Y independently is a kind in the group selected from following trivalent groups, and key is connected to any carbon, and at least 1 on the group Individual hydrogen is optionally replaced by methyl, ethyl or phenyl.

In formula (AN-III)~formula (AN-V), ring A¹⁰For the monocyclic alkyl or carbon number 6~30 of carbon number 3~10 Fused polycyclic alkyl, at least one hydrogen on the group optionally replaces by methyl, ethyl or phenyl, and the key being connected with ring connects Any carbon for constituting ring is connected to, 2 key options are connected to same carbon.In formula (AN-VI), X¹⁰For the alkylene of carbon number 2~6 Base, Me represents methyl, and Ph represents phenyl.In formula (AN-VII), G¹⁰Independently be-O- ,-COO- or-OCO-, r independently be 0 or 1。

More specifically, the tetracarboxylic dianhydride shown in following formula (AN-1)~formula (AN-16-14) can be included.

[tetracarboxylic dianhydride shown in formula (AN-1)]

In formula (AN-1), G¹¹For singly-bound, the alkylidene of carbon number 1~12,1,4- phenylenes or 1,4- cyclohexylenes. X¹¹It independently is singly-bound or-CH₂-。G¹²It independently is any one of following trivalent groups.

G¹²For>During CH-,>Hydrogen on CH- is optionally by-CH₃Substitution.G¹²For>During N-, G¹¹It is not singly-bound and-CH₂-、X¹¹No It is singly-bound.And R¹¹For hydrogen or-CH₃。

As the example of the tetracarboxylic dianhydride shown in formula (AN-1), the compound shown in following formula can be included.

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

[tetracarboxylic dianhydride shown in formula (AN-3)]

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

As the example of the tetracarboxylic dianhydride shown in formula (AN-3), the compound shown in following formulas can be included.

[tetracarboxylic dianhydride shown in formula (AN-4)]

In formula (AN-4), G¹³For singly-bound ,-(CH₂)_m-、-O-、-S-、-C(CH₃)₂-、-SO₂-、-CO-、-C(CF₃)₂- or Divalent group shown in person's following formula (G13-1), m is 1~12 integer.Ring A¹¹It is each independently cyclohexane ring or phenyl ring. G¹³Optionally it is bonded to ring A¹¹Optional position.

In formula (G13-1), G^13aAnd G^13bIt is each independently the divalent group shown in singly-bound ,-O- or-NHCO-.Phenylene Preferably 1,4- phenylenes and 1,3- phenylenes.

As the example of the tetracarboxylic dianhydride shown in formula (AN-4), the compound shown in following formula can be included.

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

[tetracarboxylic dianhydride shown in formula (AN-5)]

In formula (AN-5), R¹¹For hydrogen or-CH₃.The loose R of bonding position on the carbon atom for constituting phenyl ring¹¹Represent Bonding position on phenyl ring is arbitrary.

As the example of the tetracarboxylic dianhydride shown in formula (AN-5), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-6)]

In formula (AN-6), X¹¹It independently is singly-bound or-CH₂-。X¹²For-CH₂-、-CH₂CH₂- or-CH=CH-.N is 1 or 2.

As the example of the tetracarboxylic dianhydride shown in formula (AN-6), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-7)]

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

As the example of the tetracarboxylic dianhydride shown in formula (AN-7), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-8)]

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

As the example of the tetracarboxylic dianhydride shown in formula (AN-8), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-9)]

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

As the example of the tetracarboxylic dianhydride shown in formula (AN-9), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-10-1) and formula (AN-10-2)]

[tetracarboxylic dianhydride shown in formula (AN-11)]

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

As the example of the tetracarboxylic dianhydride shown in formula (AN-11), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-12)]

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

As the example of the tetracarboxylic dianhydride shown in formula (AN-12), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-13)]

In formula (AN-13), X¹³For the alkylidene of carbon number 2~6, Ph represents phenyl.

As the example of the tetracarboxylic dianhydride shown in formula (AN-13), the compound shown in following formula can be included.

In formula (AN-13), Ph represents phenyl.

[tetracarboxylic dianhydride shown in formula (AN-14)]

In formula (AN-14), G¹⁴- O- ,-COO- or-OCO- independently are, r independently is 0 or 1.

As the example of the tetracarboxylic dianhydride shown in formula (AN-14), the compound shown in following formula can be included.

[tetracarboxylic dianhydride shown in formula (AN-15)]

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

As the example of the tetracarboxylic dianhydride shown in formula (AN-15), the compound shown in following formula can be included.

As tetracarboxylic dianhydride other than the above, following compounds can be included.

In above-mentioned tetracarboxylic dianhydride, described for the material suitable for improving each characteristic.Paying attention to making the orientation of liquid crystal Property improve in the case of, the compound preferably shown in formula (AN-1), formula (AN-3) and formula (AN-4), particularly preferably formula (AN- 1-2), the compound shown in formula (AN-1-13), formula (AN-3-2), formula (AN-4-17) and formula (AN-4-29), wherein, formula (AN- It is preferably m=4 or 8 in 1-2), is preferably m=4 or 8, more preferably m=8 in formula (AN-4-17).

Pay attention to making in the case that the transmissivity of liquid crystal display cells improves, preferably formula (AN-1-1), formula (AN-1-2), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-16- 3) with the compound shown in formula (AN-16-4), wherein, in formula (AN-1-2) in preferably m=4 or 8, formula (AN-4-17) preferably For m=4 or 8, more preferably m=8.

Pay attention to making in the case that the VHR of liquid crystal display cells improves, preferably formula (AN-1-1), formula (AN-1-2), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10-1), formula (AN-16-3) and formula (AN- Compound shown in 16-4), wherein, it is preferably preferably m=4 or 8 in m=4 or 8, formula (AN-4-17) in formula (AN-1-2), Particularly preferably m=8.

The residual charge in alignment films (remaining DC) mitigation is improved by reducing the volumetric resistivity value of liquid crystal orientation film Speed is effective as a method of ghost is prevented.In the case of paying attention to the purpose, preferably formula (AN-1-13), formula (AN-3-2), the compound shown in formula (AN-4-21), formula (AN-4-29) and formula (AN-11-3).

Illustrated for the diamines and two hydrazides used to manufacture the polyamic acid and its derivative of the present invention.System When making polyamic acid of the present invention or derivatives thereof, can unrestrictedly it be selected from known diamines and two hydrazides.

Diamines can be divided into 2 kinds according to its structure.Refer to：When the skeleton for connecting 2 amino is regarded as into main chain, with from master The group that chain component the goes out i.e. diamines of side-chain radical and the diamines without side-chain radical.The side-chain radical is that have increase The group of the effect of pre-tilt angle.Side-chain radical with this effect need be carbon number more than 3 group, as specific Example, can include the alkoxy alkane of the alkyl, the alkoxy of carbon number more than 3, carbon number more than 3 of carbon number more than 3 Base and the group with steroid skeleton.There is carbon number 1 as the ring of the group with more than 1 ring and its end Any one of alkoxyalkyl of alkyl above, the alkoxy of carbon number more than 1 and carbon number more than 2 is used as substitution The group of base also has the effect as side-chain radical.In the following description, the diamines with this side-chain radical is claimed sometimes For side chain type diamine.Also, the diamines without this side-chain radical is referred to as non-side chain type diamine sometimes.

By suitably flexibly using non-side chain type diamine and side chain type diamine, each required pre-tilt angle is coped with. Side chain type diamine is preferably applied in combination with the degree for not damaging characteristic of the present invention.In addition, for side chain type diamine and non-side chain type Diamines, it is preferred that according to the purpose improved for the vertical orientated property of liquid crystal, voltage retention, ghost characteristic and orientation Select and use to accept or reject.

Illustrated for non-side chain type diamine.As the known diamines without side chain, following formula can be included (DI-1) diamines of~formula (DI-16).

In above-mentioned formula (DI-1), G²⁰For-CH₂-, at least one-CH₂- optionally by-NH- ,-O- replace, m for 1~12 it is whole At least one hydrogen on number, alkylidene is optionally replaced by-OH.In formula (DI-3) and formula (DI-5)~formula (DI-7), G²¹It independently is Singly-bound ,-NH- ,-NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C (CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂- CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH- (CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n- CO- or-S- (CH₂)_m- S-, m independently are 1~12 Integer, k is 1~5 integer, and n is 1 or 2.In formula (DI-4), s independently is 0~2 integer.Formula (DI-6) and formula (DI-7) In, G²²It independently is singly-bound ,-O- ,-S- ,-CO- ,-C (CH₃)₂-、-C(CF₃)₂-, the alkylene of-NH- or carbon number 1~10 Base.At least one hydrogen of cyclohexane ring and phenyl ring in formula (DI-2)~formula (DI-7) is optionally by-F ,-Cl, carbon number 1~3 Alkyl ,-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl substitution, also, in formula (DI-4), hexamethylene At least one hydrogen on ring and phenyl ring is optionally selected from 1 in the group of the group shown in following formula (DI-4-a)~formula (DI-4-e) Plant substitution.The loose group of bonding position on the carbon atom for constituting ring represents that the bonding position on the ring is any 's.Also ,-NH₂Bonding position on cyclohexane ring or phenyl ring is except G²¹Or G²²Bonding position outside optional position.

In formula (DI-4-a) and formula (DI-4-b), R²⁰It independently is hydrogen or-CH₃。

In formula (DI-11), r is 0 or 1.In formula (DI-8)~formula (DI-11) ,-NH being bonded on ring₂Bonding position It is optional position.

In formula (DI-12), R²¹And R²²It independently is the alkyl or phenyl of carbon number 1~3, G²³It independently is carbon atom The alkylidene of number 1~6, phenylene or by alkyl-substituted phenylene, w is 1~10 integer.In formula (DI-13), R²³It is independent Ground independently is 0~3 integer for the alkyl, the alkoxy of carbon number 1~5 or-Cl, p of carbon number 1~5, and q is 0~4 Integer.In formula (DI-14), ring B is monocyclic hetero ring type aromatic group, R²⁴For hydrogen ,-F ,-Cl, carbon number 1~6 alkane Base, alkoxy, alkenyl, alkynyl, q independently are 0~4 integer.In formula (DI-15), ring C is hetero ring type aromatic group or miscellaneous Ring type aliphatic group.In formula (DI-16), G²⁴For singly-bound, the alkylidene of carbon number 2~6 or Isosorbide-5-Nitrae-phenylene, r is 0 or 1. Also, the loose group of bonding position on the carbon atom for constituting ring represents that the bonding position on the ring is arbitrary. In formula (DI-13)~formula (DI-16) ,-NH being bonded on ring₂Bonding position be optional position.

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

The example of diamines shown in formula (DI-1) described below.

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

The example of formula (DI-2) described below~diamines shown in formula (DI-3).

The example of diamines shown in formula (DI-4) described below.

The example of diamines shown in formula (DI-5) described below.

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

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

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

In formula (DI-5-30), k is 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), k is 1~5 integer, in formula (DI-5-40), and n is 1 or 2 integer.

The example of diamines shown in formula (DI-6) described below.

The example of diamines shown in formula (DI-7) described below.

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

In formula (DI-7-12), m is 1~12 integer.

The example of diamines shown in formula (DI-8) described below.

The example of diamines shown in formula (DI-9) described below.

The example of diamines shown in formula (DI-10) described below.

The example of diamines shown in formula (DI-11) described below.

The example of diamines shown in formula (DI-12) described below.

The example of diamines shown in formula (DI-13) described below.

The example of diamines shown in formula (DI-14) described below.

The example of diamines shown in formula (DI-15) described below.

The example of diamines shown in formula (DI-16) described below.

Illustrated for two hydrazides.As known two hydrazides without side chain, following formula (DIH-1) can be included ~formula (DIH-3).

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

In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen on the group is optionally by methyl, second Base or phenyl substitution.In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen on the group is appointed Choosing is replaced by methyl, ethyl or phenyl, and Y is singly-bound, the alkylidene of carbon number 1~20 ,-CO- ,-O- ,-S- ,-SO₂-、-C (CH₃)₂- or-C (CF₃)₂-.In formula (DIH-2) and formula (DIH-3) ,-CONHNH being bonded on ring₂Bonding position be any Position.

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

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

There is the ion concentration for making liquid crystal display cells the improvement electrical characteristics such as reduce for this non-side chain type diamine and two hydrazides Effect.Used non-as the diamines of the polyamic acid used in the aligning agent for liquid crystal for manufacturing the present invention or derivatives thereof When side chain type diamine and/or two hydrazides, its shared ratio in total amount of the diamines with two hydrazides is preferably set to 0~90 and rubbed Your %, more preferably it is set to 0~50 mole of %.

Illustrated for side chain type diamine.As the side-chain radical of side chain type diamine, following radicals can be included.

As side-chain radical, can include first alkyl, alkoxy, alkoxyalkyl, alkyl-carbonyl, alkyl carbonyl oxy, Alkoxy carbonyl, alkyl amino-carbonyl, alkenyl, alkenyloxy group, alkenyl carbonyl, alkynyl carbonyloxy group, allyloxycarbonyl, alkenyl amino carbonyl Base, alkynyl, alkynyloxy group, alkynylcarbonyl groups, alkynyl carbonyloxy group, alkynyloxycar bonyl, alkynylaminocarbonyl etc..Alkane in these groups Base, alkenyl and alkynyl are the groups of carbon number more than 3.Wherein, for alkoxyalkyl, the overall carbon atom of group Number is more than 3.These groups can be straight-chain or branched.

Then, the ring in end has the alkyl of carbon number more than 1, the alkoxy of carbon number more than 1 or carbon former Under conditions of the alkoxyalkyl of subnumber more than 2 is as substituent, phenyl, phenylalkyl, phenyl alkoxy, benzene oxygen can be included Base, phenylcarbonyl group, phenyl carbonyloxy group, phenyloxycarbonyl, phenyl amino carbonyl, phenyl cyclohexyloxy, the ring of carbon number more than 3 Alkyl, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxy carbonyl, cyclohexyl phenyl, cyclohexyl phenyl alkyl, cyclohexyl benzene epoxide, Double (cyclohexyl) epoxides, double (cyclohexyl) alkyl, double (cyclohexyl) phenyl, double (cyclohexyl) phenylalkyls, double (cyclohexyl) oxygen The group of the ring structures such as double (phenyl) Epoxide carbonyls of base carbonyl, double (cyclohexyl) phenyloxycarbonyls and cyclohexyl.

And then, the group with more than 2 phenyl ring, the group with more than 2 cyclohexane rings can be included or by benzene The group more than 2 rings that ring and cyclohexane ring are constituted, and linking group independently be singly-bound ,-O- ,-COO- ,-OCO- ,- CONH- or carbon number 1~3 alkylidene, the ring of end have the alkyl of carbon number more than 1, the fluorine of carbon number more than 1 Replace the alkoxyalkyl of alkyl, the alkoxy of carbon number more than 1 or carbon number more than 2 as many ring groups of substituent Group.Group with steroid skeleton is also effective as side-chain radical.

As the diamines with side chain, the compound shown in following formula (DI-31)~formula (DI-35) can be included.

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、- CF₂O-、-OCF₂- or-(CH₂)_m’-, m ' is 1~12 integer.G²⁶Preference be singly-bound ,-O- ,-COO- ,-OCO- ,-CH₂O- With the alkylidene of carbon number 1~3, particularly preferred example is singly-bound ,-O- ,-COO- ,-OCO- ,-CH₂O-、-CH₂- and- CH₂CH₂-。R²⁵For the alkyl of carbon number 3~30, phenyl, the group with steroid skeleton or following formula (DI-31-a) Shown group.In the alkyl, at least one hydrogen is optionally replaced by-F, also, at least one-CH₂- optionally by-O- ,-CH=CH- Or-C ≡ C- displacements.Hydrogen on the phenyl is optionally by-F ,-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃, carbon number 3~30 Alkyl or carbon number 3~30 alkoxy substitution.- the NH being bonded on phenyl ring₂Bonding position represent be on the ring Optional position, its bonding position is preferably meta or para position.That is, by group " R²⁵-G²⁶- " bonding position when being set to 1,2 Bonding position is preferably 3 and 5 or 2 and 5.

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For linking group, they independently are singly-bound or carbon number 1~12 More than 1-CH in alkylidene, the alkylidene₂- optionally replaced by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH-.Ring B²¹, ring B²², ring B²³With ring B²⁴Independently be 1,4- phenylenes, 1,4- cyclohexylenes, 1,3- dioxane -2,5- diyls, pyrimidine - 2,5- diyls, pyridine -2,5- diyl, piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -2,7- diyl or anthracene -9,10- diyl, ring B²¹, ring B²², ring B²³With ring B²⁴In, at least one hydrogen is optionally by-F or-CH₃Displacement, s, t and u independently are 0~2 integer, it Add up to 1~5, when s, t or u are 2,2 linking groups in each parantheses can be the same or different, also, 2 rings It can be the same or different.R²⁶Replace alkane for the fluorine of hydrogen ,-F ,-OH, the alkyl of carbon number 1~30, carbon number 1~30 Base, the alkoxy of carbon number 1~30 ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, in the alkyl of the carbon number 1~30 extremely Few 1-CH₂- optionally by the divalent group displacement shown in following formula (DI-31-b).

In formula (DI-31-b), R²⁷And R²⁸The alkyl of carbon number 1~3 independently is, v is 1~6 integer.R²⁶It is excellent It is the alkyl of carbon number 1~30 and the alkoxy of carbon number 1~30 to select example.

In formula (DI-32) and formula (DI-33), G³⁰It independently is singly-bound ,-CO- or-CH₂-, R²⁹It independently is hydrogen or-CH₃, R³⁰For the alkenyl of hydrogen, the alkyl of carbon number 1~20 or carbon number 2~20.At least 1 on phenyl ring in formula (DI-33) Individual hydrogen is optionally replaced by the alkyl or phenyl of carbon number 1~20.Also, the bonding position on any carbon atom for constituting ring Loose group represents that the bonding position on the ring is arbitrary.Preferably, in formula (DI-32) 2 groups "-Asia Phenyl-G³⁰One of-O- " be bonded to 3 of steroids core, another one be bonded to 6 of steroids core.In formula (DI-33) 2 group "-phenylene-G³⁰Bonding positions of-the O- " on phenyl ring be respectively preferably with respect to the bonding position of steroids core Meta or para position.In formula (DI-32) and formula (DI-33) ,-NH being bonded on phenyl ring₂Representing the bonding position on the ring is Arbitrarily.

In formula (DI-34) and formula (DI-35), G³¹It independently is the alkylidene of-O- ,-NH- or carbon number 1~6, G³²For The alkylidene of singly-bound or carbon number 1~3.R³¹For hydrogen or the alkyl of carbon number 1~20, at least one-CH in the alkyl₂- Optionally replaced by-O- ,-CH=CH- or-C ≡ C-.R³²For the alkyl of carbon number 6~22, R³³For hydrogen or carbon number 1~22 Alkyl.Ring B²⁵For Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylene, r is 0 or 1.Also ,-the NH being bonded on phenyl ring₂Represent at this Bonding position on ring is arbitrary, preferably with respect to G³¹Bonding position be respectively meta or para position.

It is illustrated below go out side chain type diamine concrete example.There is side chain as above-mentioned formula (DI-31)~formula (DI-35) Diamines, can include the compound shown in following formula (DI-31-1)~formula (DI-35-3).

The example of compound shown in formula (DI-31) described below.

In formula (DI-31-1)~formula (DI-31-11), R³⁴Alkyl or carbon number 1~30 for carbon number 1~30 The alkoxy of alkoxy, the preferably alkyl of carbon number 5~25 or carbon number 5~25.R³⁵For the alkane of carbon number 1~30 The alkoxy of the alkoxy of base or carbon number 1~30, the preferably alkyl of carbon number 3~25 or carbon number 3~25.

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

In formula (DI-31-18)~formula (DI-31-43), R³⁸Alkyl or carbon number 1~20 for carbon number 1~20 The alkoxy of alkoxy, the preferably alkyl of carbon number 3~20 or carbon number 3~20.R³⁹For hydrogen ,-F, carbon number 1~ 30 alkyl, the alkoxy of carbon number 1~30 ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, preferably carbon number 3~25 The alkoxy of alkyl or carbon number 3~25.Also, G³³For the alkylidene of carbon number 1~20.

The example of compound shown in formula (DI-32) described below.

The example of compound shown in formula (DI-33) described below.

The example of compound shown in formula (DI-34) described below.

In formula (DI-34-1)~formula (DI-34-14), R⁴⁰For hydrogen or the alkyl of carbon number 1~20, preferably hydrogen or carbon The alkyl of atomicity 1~10, also, R⁴¹For hydrogen or the alkyl of carbon number 1~12.

The example of compound shown in formula (DI-35) described below.

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

As the diamines in the present invention, it can also use except formula (DI-1-1)~formula (DI-16-1), formula (DIH-1-1) The diamines beyond diamines shown in~formula (DIH-3-6) and formula (DI-31-1)~formula (DI-35-3).As this diamines, it can arrange Enumerate the compound for example shown in following formula (DI-36-1)~formula (DI-36-14).

In formula (DI-36-1)~formula (DI-36-8), R⁴²The alkyl of carbon number 3~30 is represented independently of one another.

In formula (DI-36-9)~formula (DI-36-11), e is 2~10 integer, in formula (DI-36-12), R⁴³It is each independent Ground is hydrogen ,-NHBoc or-N (Boc)₂, at least one R⁴³For-NHBoc or-N (Boc)₂, in formula (DI-36-13), R⁴⁴For-NHBoc Or-N (Boc)₂, m is 1~12 integer, also, in formula (DI-36-14), n is 1~6 integer.Herein, Boc is tertiary fourth oxygen Base carbonyl.

In above-mentioned diamines and two hydrazides, described for the material suitable for improving each characteristic.Paying attention to making taking for liquid crystal In the case that tropism is further improved, formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula are preferably used (DI-5-12), the change shown in formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3) and formula (DI-11-2) Compound.In formula (DI-5-1), preferably m=2,4 or 6, more preferably m=4.In formula (DI-5-12), preferably m=2~6, more Preferably m=5.In formula (DI-5-13), preferably m=1 or 2, more preferably m=1.

Pay attention to make transmissivity improve in the case of, preferably use formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), Diamines shown in formula (DI-5-5), formula (DI-5-24), formula (DI-7-3) and formula (DI-36-14), more preferably formula (DI-2-1) Shown compound.In formula (DI-5-1), preferably m=2,4 or 6, more preferably m=4.In formula (DI-7-3), preferably m= 2 or 3, n=1 or 2, more preferably m=3, n=1.In formula (DI-36-14), preferably n=3.

Pay attention to make liquid crystal display cells VHR improve in the case of, preferably use formula (DI-2-1), formula (DI-4-1), Formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-28), formula (DI-5-30), formula (DI-13-1) and formula (DI-36-14) compound shown in, more preferably formula (DI-2-1), formula (DI-5-1), formula (DI-13-1) and formula (DI-36- 14) diamines shown in.In formula (DI-5-1), preferably m=1.In formula (DI-5-30), preferably k=2.Formula (DI-36-14) In, preferably n=3.

The mitigation speed of the residual charge (remaining DC) of alignment films is improved by reducing the volumetric resistivity value of liquid crystal orientation film It is effective to spend as a method of ghost is prevented.In the case of paying attention to the purpose, formula (DI-4-1), formula (DI- are preferably used 4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), Compound shown in formula (DI-7-12) and formula (DI-16-1), more preferably formula (DI-4-1), formula (DI-5-1) and formula (DI-5- 13) compound shown in.In formula (DI-5-1), preferably m=2,4 or 6, more preferably m=4.In formula (DI-5-12), preferably For m=2~6, more preferably m=5.In formula (DI-5-13), preferably m=1 or 2, more preferably m=1.Formula (DI-7-12) In, preferably m=3 or 4, more preferably m=4.

In each diamines, in scope of ratio of the monoamine relative to diamines for 40 moles of below %, a part for diamines is appointed Choosing is replaced as monoamine.This displacement can cause polymerisation to terminate when generating polyamic acid, can suppress polymerisation Carry out again.Therefore, by this displacement, the molecule of resulting polymers (polyamic acid or derivatives thereof) can easily be controlled Amount, for example, can improve effect of the coating characteristics of aligning agent for liquid crystal without damaging the present invention.It is replaced as the diamines of monoamine only Otherwise the effect of the present invention is damaged, then it can also be two or more that can be a kind.As foregoing monoamine, such as benzene can be included Amine, 4- hydroxyanilines, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive 11 Alkylamine, dodecyl amine, n-tridecane base amine, n-tetradecane base amine, n-pentadecane base amine, n-hexadecyl amine, positive ten Seven alkylamines, n-octadecane base amine and n-eicosane base amine.

Polyamic acid of the present invention or derivatives thereof can also include monoisocyanate compound in monomer.By Comprising monoisocyanate compound in monomer, the end of gained polyamic acid or derivatives thereof is modified, and molecular weight is adjusted. Polyamic acid by using the end modified type or derivatives thereof, can for example improve the coating characteristics of aligning agent for liquid crystal without Damage the effect of the present invention.Content from the monoisocyanate compound in foregoing viewpoint, monomer is relative in monomer The total amount of diamines and tetracarboxylic dianhydride are preferably 1~10 mole of %.As foregoing monoisocyanate compound, it can include for example Phenyl isocyanate and naphthyl isocyanate.

Polyamic acid using the present invention or derivatives thereof assigns liquid crystal as being irradiated by light irradiation, such as ultraviolet During the optical alignment film of alignment capability, as polyamic acid and its raw material of derivative, can compatibly use has photoreactivity knot The monomer of structure.By using the monomer with photoreactivity structure, can synthesize polyamic acid with photoreactivity structure and Its derivative.Photoreactivity structure refers to that the light shown in the following formula (P-1) for example irradiated and decomposed by ultraviolet divides Photoisomerization structure, formula (P-5)~formula of generation dimerization shown in solution structure, formula (P-2)~formula (P-4) of generation isomerization (P-7) photodimerization structure shown in etc..

As the compound with the light decomposition texture shown in formula (P-1), following formula (PA-1)~formula (PA- can be included 3) compound shown in.

, can be compatibly using the compound shown in above-mentioned formula (PA-1) and formula (PA-2) among these compounds.

It should be noted that the compound shown in formula (PA-1)~formula (PA-3) is used as make use of by photoisomerization reaction zone Come liquid crystal aligning ability aligning agent for liquid crystal, make use of the liquid crystal aligning ability brought by photodimerization aligning agent for liquid crystal or When person's brushing is with the starting monomer of the polymer used in aligning agent for liquid crystal, the tetrabasic carboxylic acid two without photoreactivity structure is regarded as Acid anhydride.

As the compound with the photoisomerization structure shown in formula (P-2)~formula (P-4), photonasty is preferably selected from good At least one kind of, the compound more preferably shown in formula (V) in the group of compound shown in good following formula (II)~formulas (VI).

R²-C≡C-R³ (II)

R²-C≡C-C≡C-R³ (III)

R²-C≡C-R⁴-C≡C-R³ (IV)

R²- N=N-R³ (V)

R⁵- CH=CH-R⁵ (VI)

In formula (II)~formula (V), R²And R³For with-NH₂1 valency organic group or 1 valency with-CO-O-CO- have In machine group, formula (IV), R⁴For divalent organic group, in formula (VI), R⁵For with-NH₂Or-CO-O-CO- aromatic rings.

Photoisomerization structure can be set into times in the main chain of the polyamic acid of the present invention or derivatives thereof or side chain One, by being set into main chain, can be suitably employed in the liquid crystal display cells of Transverse electric-field type.

As the material with foregoing photoisomerization structure, can be suitably employed in selected from following formula (II-1), formula (II-2), Shown in formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1)~formula (V-3), formula (VI-1) and formula (VI-2) Compound group at least 1.

It is above-mentioned it is various in, constitute ring any carbon atom on the loose group of bonding position represent on the ring Bonding position is arbitrary, in formula (V-2), R⁶It independently is-CH₃、-OCH₃、-CF₃Or-COOCH₃, a is 0~2 integer, formula (V-3) in, ring A and ring B are each independently at least 1, R in monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle¹¹For carbon Straight-chain alkyl-sub ,-COO- ,-OCO- ,-NHCO- or the-N (CH of atomicity 1~20₃) CO-, R¹²For the straight of carbon number 1~20 Chain alkylidene ,-COO- ,-OCO- ,-NHCO- or-N (CH₃) CO-, R¹¹And R¹²In, 1 in straight-chain alkyl-sub or 2-CH₂- Optionally replaced by-O-, R⁷~R¹⁰It is each independently-F ,-CH₃、-OCH₃、-CF₃Or-OH, also, b~e is each independently 0 ~4 integer.

Compound shown in above-mentioned formula (V-1), formula (V-2) and formula (VI-2) can be fitted especially from the viewpoint of its photonasty Use with closing.In formula (V-2) and formula (VI-2), the bonding position of amino is the a=0 in the compound and then formula (V-2) of contraposition Compound can more suitably be used from the viewpoint of its orientation.

Having shown in formula (II-1)~formula (VI-2) can be irradiated by ultraviolet and occur the acid of the structure of isomerization Dianhydride or diamines can specifically be represented with following formula (II-1-1)~formula (VI-2-3).

Among these, by the way that formula (VI-1-1)~formula (V-3-8) is occurred as comprising that can be irradiated by ultraviolet The compound of the structure of isomerization, is resulted in for the higher light orientation aligning agent for liquid crystal of the sensitivity of ultraviolet irradiation. By using formula (V-1-1), formula (V-2-1), formula (V-2-4)~formula (V-2-11) and formula (V-3-1)~formula (V-3-8) as comprising It can be irradiated by ultraviolet and occur the compound of the structure of isomerization, resulting in can be such that liquid crystal molecule is more uniformly orientated Light orientation aligning agent for liquid crystal.By the way that formula (V-2-4)~formula (V-3-8) is sent out as comprising that can be irradiated by ultraviolet The compound of the structure of raw isomerization, results in the less light orientation aligning agent for liquid crystal of the coloring of formed alignment films.

, can be by four with photoreactivity structure when synthesis has the polyamic acid and its derivative of photoreactivity structure Carboxylic acid dianhydride (hereinafter sometimes referred to photonasty tetracarboxylic dianhydride) or the above-mentioned diamines with photoreactivity structure is (below sometimes Referred to as photonasty diamines) it is used for raw material.Diamines with photoreactivity structure and the tetracarboxylic dianhydride with photoreactivity structure It can be applied in combination.

When synthesis has the polyamic acid and its derivative of photoreactivity structure, photonasty tetracarboxylic dianhydride is used for raw material In the case of, tetracarboxylic dianhydride's (hereinafter sometimes referred to non-photosensitive four without photoreactivity structure can also be applied in combination Carboxylic acid dianhydride.).Now, in order to prevent alignment films to the sensitivity decrease of light, the sense in tetracarboxylic dianhydride's total amount as raw material The ratio of photosensitiveness tetracarboxylic dianhydride is preferably 20 moles of more than %, more preferably 50 moles of more than %.In addition, in order to improve for The foregoing various characteristics such as sensitivity, the image retention characteristic of light, can also be applied in combination photonasty tetracarboxylic dianhydride of more than two kinds.

When synthesis has the polyamic acid and its derivative of photoreactivity structure, photonasty diamines is used for the situation of raw material Under, the diamines shown in the formula (1) of the present invention is applied in combination with photonasty diamines.Diamines shown in formula (1) does not have light reaction Property structure.It can also be further combined (following using the diamines without photoreactivity structure beyond the diamines shown in formula (1) Sometimes referred to as non-photosensitive diamines.).Now, in order to prevent alignment films to the sensitivity decrease of light, the diamines total amount as raw material In photonasty diamines ratio be preferably 20 moles of more than %, more preferably 50 moles of more than %.In addition, in order to improve for The foregoing various characteristics such as sensitivity, the image retention characteristic of light, can also be applied in combination photonasty diamines of more than two kinds.

When synthesis has the polyamic acid and its derivative of photoreactivity structure, by photonasty tetracarboxylic dianhydride and photonasty When diamines is applied in combination and is used for raw material, can also be applied in combination non-photosensitive tetracarboxylic dianhydride and diamines shown in Shi (1) with Outer non-photosensitive diamines.Now, in order to prevent alignment films to the sensitivity decrease of light, the tetracarboxylic dianhydride as raw material and two The toatl proportion of photonasty tetracarboxylic dianhydride and photonasty diamines in amine total amount are preferably 20 moles of more than %, more preferably 50 rubbed You are more than %.In addition, in order to improve the foregoing various characteristics such as sensitivity, image retention characteristic for light, can also be by photonasty four Two or more is applied in combination in carboxylic acid dianhydride or/and photonasty diamines.

Illustrated for the aligning agent for liquid crystal of the present invention.The aligning agent for liquid crystal of the present invention can also further contain formula (1) other compositions that the diamines shown in is used for outside polyamic acid of raw material or derivatives thereof.Other compositions can be a kind and also may be used To be two or more.As other compositions, it can include such as other polymer described later, compound.

Other polymer be instigate tetracarboxylic dianhydride and polyamic acid obtained from the diamine reactant comprising formula (1) diamines or Polymer outside its derivative.Specifically, so that obtained from diamines and tetracarboxylic dianhydride's reaction without formula (1) diamines Polyamic acid or derivatives thereof (hereinafter sometimes referred to other polyamic acids or derivatives thereof.) it is representative, polyester can be included, gathered Acid amides, polysiloxanes, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenyl maleimide) spread out Biological, poly- (methyl) acrylate etc..Among these, preferably other polyamic acids or derivatives thereof and polysiloxanes are more excellent Elect other polyamic acids or derivatives thereof as.

As in order to synthesize other polyamic acids or derivatives thereof and the tetracarboxylic dianhydride used and diamines, can be from above-mentioned example The known tetracarboxylic dianhydride shown and unrestrictedly selected in diamines.

In the present invention, polyamic acid that can will be used the diamines comprising formula (1) diamines and synthesize or derivatives thereof and its It is used for alignment agent after its polyamic acid or derivatives thereof blending.Using this pair of composition polymer when, such as in the presence of such as lower section Formula：Polymer of the one of which selection with the excellent performance of liquid crystal aligning ability, another one selection is for improving liquid crystal display There is the polymer of excellent properties for the electrical characteristics of element.Now, by controlling structure, the molecular weight of each polymer, To make these polymer be dissolved in solvent obtained from aligning agent for liquid crystal be coated on as described later substrate and carry out it is predrying and During forming film, the polymer with the excellent performance of liquid crystal aligning ability can be made to be segregated to the upper strata of film, and It can make to be segregated under film with the polymer that there are excellent properties for improving the electrical characteristics of liquid crystal display cells Layer.In this regard, can apply in the polymer being mixed, the small polymer of surface energy separates big to upper strata, surface energy Polymer separate to the phenomenon of lower floor.Confirmations of this layer separation can pass through formed alignment films surface energy and by The surface energy of the film of aligning agent for liquid crystal formation only containing the polymer for being intended to be segregated to upper strata is identical numerical value or close number Value confirms.

The aligning agent for liquid crystal of the present invention divides for the layer that in the mode of light orientation aligning agent for liquid crystal, can not be considered in film It is liftoff to use polyamic acid with photoreactivity structure of the present invention or derivatives thereof.In addition it is also possible to will have light reaction Property structure aligning agent for liquid crystal be used as being segregated to the polymer on aforementioned film upper strata.Now, it is segregated to the polymer of film lower floor Polyamic acid without photoreactivity structure or derivatives thereof, which can be used, but be segregated to the polymer of film lower floor to be Polyamic acid with photoreactivity structure or derivatives thereof.

Diamines shown in the formula (1) of the present invention may be used as being segregated to the starting monomer of the polymer on aforementioned film upper strata, It is also used as being segregated to the starting monomer of the polymer of film lower floor.Diamines shown in formula (1) may be used as in two polymer The starting monomer of any one, be also used as the starting monomer of two polymer.

As in order to synthesize the non-photosensitive four for being segregated to the polyamic acid or derivatives thereof on aforementioned film upper strata and using Carboxylic acid dianhydride, can unrestrictedly be selected from the above-mentioned known tetracarboxylic dianhydride exemplified.

Wherein, in the case where paying attention to improving layer separation property, preferably formula (AN-1-1), formula (AN-4-17) and formula (PA-1) compound shown in.It is preferably m=4 or 8, more preferably m=8 in formula (AN-4-17).

Pay attention to make liquid crystal display cells transmissivity improve in the case of, preferably formula (AN-1-1), formula (AN-1-2), Formula (PA-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10- 1), the compound shown in formula (AN-10-2), formula (AN-16-3) and formula (AN-16-4), wherein, it is preferably m in formula (AN-1-2) =4 or 8, it is preferably m=4 or 8, more preferably m=8 in formula (AN-4-17).

In the case where the VHR for paying attention to making liquid crystal display cells is improved, preferably formula (PA-1), formula (AN-7-2), formula (AN-10-1), the compound shown in formula (AN-10-2), formula (AN-16-3) and formula (AN-16-4), wherein, in formula (AN-1-2) Preferably m=4 or 8.

The mitigation speed of the residual charge (remaining DC) of alignment films is improved by reducing the volumetric resistivity value of liquid crystal orientation film It is effective to spend as a method of ghost is prevented.In the case of paying attention to the purpose, preferably formula (AN-1-13), formula (AN- 3-2), the compound shown in formula (AN-4-21), formula (AN-4-29) and formula (AN-11-3).

In order to synthesize the tetracarboxylic dianhydride for being segregated to the polyamic acid or derivatives thereof on film upper strata and using preferably four 10 moles of more than % aromatic tetracarboxylic acid's dianhydride is included in the total amount of carboxylic acid dianhydride, more than 30% is more preferably included.

As in order to synthesize the non-photosensitive diamines that is segregated to the polyamic acid or derivatives thereof on film upper strata and uses and Two hydrazides, can unrestrictedly be selected from the above-mentioned known diamines exemplified.

Wherein, in the case where paying attention to making a layer separation property, the in other words further raising of the orientation of liquid crystal, formula is preferably used (DI-4-1), formula (DI-5-1) and the compound shown in formula (DI-7-3).Wherein, in formula (DI-5-1) be preferably m=1,2 or 4, More preferably m=4.It is preferably m=3, n=1 in formula (DI-7-3).

In the case where paying attention to improving transmissivity, formula (PA-1), formula (DI-5-1) and formula (DI-7-3) institute are preferably used Compound shown in the diamines shown, particularly preferably formula (PA-1).It is preferably m=1,2 or 4, more preferably m in formula (DI-5-1) =1 or 2.

Pay attention to make liquid crystal display cells VHR improve in the case of, preferably use formula (DI-4-1), formula (DI-4-2), Shown in formula (DI-4-15), formula (DI-5-1), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30) and formula (DI-13-1) Compound shown in compound, more preferably formula (DI-5-1) and formula (DI-13-1).Wherein, further preferred formula (DI-5-1) K=2 compound in middle m=1 or 2 compound and formula (DI-5-30).

The mitigation speed of the residual charge (remaining DC) of alignment films is improved by reducing the volumetric resistivity value of liquid crystal orientation film It is effective to spend as a method of ghost is prevented.In the case of paying attention to the purpose, formula (DI-4-1), formula (DI- are preferably used 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) and the compound shown in formula (DI-16-1), more preferably formula (DI-4-1), formula (DI-5-1) With the compound shown in formula (DI-5-12).It is preferably m=1 or 2 in formula (DI-5-1).In formula (DI-5-12) be preferably m=2~ 6th, it is more preferably m=5.It is preferably m=1 or 2, more preferably m=1 in formula (DI-5-13).It is preferably k=in formula (DI-5-30) 2。

Preferably exist to synthesize the non-photosensitive diamines for being segregated to the polyamic acid or derivatives thereof on film upper strata and using 30 moles of more than % aromatic diamine is included in the total amount of diamines, more than 50% is more preferably included.

, can be with as in order to synthesize the tetracarboxylic dianhydride for being segregated to the polyamic acid or derivatives thereof of film lower floor and using Unrestrictedly selected from the above-mentioned known tetracarboxylic dianhydride exemplified.

Wherein, in the case where paying attention to improving layer separation property, preferably formula (AN-3-2), formula (AN-1-13), formula (AN- 1-1) with the compound shown in formula (AN-4-21).

Pay attention to make liquid crystal display cells transmissivity improve in the case of, preferably formula (AN-1-1), formula (AN-1-2), Formula (PA-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10- 1), the compound shown in formula (AN-10-2), formula (AN-16-3) and formula (AN-16-4).In formula (AN-1-2) be preferably m=4 or 8, it is preferably m=4 or 8, more preferably m=8 in formula (AN-4-17).

In order to synthesize the tetracarboxylic dianhydride for being segregated to the polyamic acid or derivatives thereof of film lower floor and using in tetrabasic carboxylic acid 10 moles of more than % aromatic tetracarboxylic acid's dianhydride is preferably comprised in the total amount of dianhydride, more preferably comprising more than 30%.

As in order to synthesize the non-photosensitive diamines that is segregated to the polyamic acid or derivatives thereof of film lower floor and uses and Two hydrazides, can unrestrictedly be selected from the above-mentioned known diamines exemplified.

Wherein, in the case where paying attention to making a layer separation property, in other words the orientation of liquid crystal further being improved, preferably formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-5-9), formula (DI-5-28), formula (DI-5-30) and formula (DIH-2- 1) compound shown in.Wherein, preferably in formula (DI-5-30) k=2 diamines.

In the case where paying attention to improving transmissivity, preferably shown in formula (PA-1), formula (DI-5-1) and formula (DI-7-3) Compound, the more preferably compound shown in formula (PA-1).In formula (DI-5-1), preferably m=1,2 or 4, more preferably m =1 or 2.

In the case where the VHR for paying attention to making liquid crystal display cells is improved, preferably formula (DI-4-1), formula (DI-4-2), formula (DI-4-15), the change shown in formula (DI-5-1), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30) and formula (DI-13-1) Compound shown in compound, more preferably formula (DI-5-1) and formula (DI-13-1).Wherein, m is particularly preferably in formula (DI-5-1) =1 or 2, particularly preferably k=2 in formula (DI-5-30).

The mitigation speed of the residual charge (remaining DC) of alignment films is improved by reducing the volumetric resistivity value of liquid crystal orientation film It is effective to spend as a method of ghost is prevented.In the case of paying attention to the purpose, preferably 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) and the compound shown in formula (DI-16-1), more preferably formula (DI-4-1), formula (DI-5-1) With the compound shown in formula (DI-5-12).Wherein, it is preferably m=1 or 2 in formula (DI-5-1).It is preferably m in formula (DI-5-12) =2~6, it is more preferably m=5.It is preferably m=1 or 2, more preferably m=1 in formula (DI-5-13).In formula (DI-5-30) preferably For k=2.

Preferably wrapped to synthesize the non-photosensitive diamines for being segregated to the polyamic acid or derivatives thereof of film lower floor and using Containing relative to the aromatic diamine that whole diamines are 30 moles of more than %, more preferably comprising more than 50%.

Be segregated to the polyamic acid on film upper strata or derivatives thereof and be segregated to film lower floor polyamic acid or its spread out Biological can be respectively the synthesis side of polyamic acid or derivatives thereof according to the essential component of the aligning agent for liquid crystal as the present invention Method and the content hereinafter recorded are synthesized.

Relative to polyamic acid for being segregated to film upper strata or derivatives thereof and it is segregated to the polyamic acid of film lower floor Or derivatives thereof total amount, the ratio for being segregated to the polyamic acid on film upper strata or derivatives thereof is preferably the weight of 5 weight %~50 Measure %, more preferably the weight % of 10 weight %~40.

As polysiloxanes, it can further contain Japanese Unexamined Patent Publication 2009-036966, Japanese Unexamined Patent Publication 2010-185001, day This JP 2011-102963, Japanese Unexamined Patent Publication 2011-253175, Japanese Unexamined Patent Publication 2012-159825, International Publication 2008/ 044644th, International Publication 2009/148099, International Publication 2010/074261, International Publication 2010/074264, International Publication 2010/126108th, 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.

For example, in the aligning agent for liquid crystal of the present invention, from making the electrical characteristics of liquid crystal display cells purpose steady in a long-term, Further Na Dike imide compounds can also be replaced containing alkenyl.Alkenyl substitution Na Dike imide compounds can be used 1 kind, two or more can also be applied in combination.The content of alkenyl substitution Na Dike imide compounds is from above-mentioned purpose, relatively It is preferably 1~100 weight %, more preferably 1~70 weight %, is more preferably 1~50 in polyamic acid or derivatives thereof Weight %.

Hereinafter, specifically illustrated for Na Dike imide compounds.

Alkenyl substitution Na Dike imide compounds are preferably the polyamic acid or its for dissolving in and being used in the dissolving present invention The compound of the solvent of derivative.The example of this alkenyl substitution Na Dike imide compounds can include following formula (NA) institute The compound shown.

In formula (NA), L¹And L²It independently is hydrogen, the alkyl of carbon number 1~12, the alkenyl of carbon number 3~6, carbon former The cycloalkyl of subnumber 5~8, the aryl or benzyl of carbon number 6~12, n are 1 or 2.

In formula (NA), during n=1, W is the alkyl of carbon number 1~12, the alkenyl of carbon number 2~6, carbon number 5~ 8 cycloalkyl, the aryl of carbon number 6~12, benzyl ,-Z¹-(O)_r-(Z²O)_k-Z³- H (herein, Z¹、Z²And Z³It independently is carbon The alkylidene of atomicity 2~6, r is 0 or 1, also, k is 1~30 integer.) shown in group ,-(Z⁴)_r-B-Z⁵- H is (herein, Z⁴And Z⁵The alkylidene of carbon number 1~4 or the ring alkylidene of carbon number 5~8 independently are, B is phenylene, also, r is 0 Or 1.) shown in group, (herein, B is phenylene to-B-T-B-H, also, T is-CH₂-、-C(CH₃)₂-、-O-、-CO-、-S- Or-SO₂-.) shown in group or these groups 1~3 hydrogen by-OH replace group.

Now, W preferably be the alkyl of carbon number 1~8, the alkenyl of carbon number 3~4, cyclohexyl, phenyl, benzyl, Poly- (oxygen ethene) ethyl of carbon number 4~10, Phenoxyphenyl, phenyl methyl phenyl, propyloxy phenyl fork base phenyl and this The group that 1 of a little groups or 2 hydrogen are replaced by-OH.

In formula (NA), during n=2, W is former for the alkylidene, the ring alkylidene of carbon number 5~8, carbon of carbon number 2~20 The arlydene ,-Z of subnumber 6~12¹-O-(Z²O)_k-Z³- (herein, Z¹~Z³With k is as defined above state n=1 when definition shown in.) Shown group ,-Z⁴-B-Z⁵- (herein, Z⁴、Z⁵With B is as defined above state n=1 when definition shown in.) shown in group ,-B- (O-B)_r-T-(B-O)_r(herein, B is phenylene to-B-, and T is alkylidene ,-O- or the-SO of carbon number 1~3₂-, r definition is such as Shown in definition during foregoing n=1.) shown in group or these groups 1~3 hydrogen by-OH replace group.

Now, W preferably is alkylidene, cyclohexylene, phenylene, xylene, the methylene of benzene two of carbon number 2~12 Base ,-C₃H₆-O-(Z²-O)_n-O-C₃H₆- (herein, Z²For the alkylidene of carbon number 2~6, n is 1 or 2.) shown in group ,- (herein, B is phenylene to B-T-B-, also, T is-CH₂- ,-O- or-SO₂-.) shown in group ,-B-O-B-C₃H₆-B-O-B- (herein, B is phenylene.) shown in group and the group that is replaced by-OH of 1 of these groups or 2 hydrogen.

This alkenyl substitution Na Dike imide compounds can be for example used as Japanese Patent 2729565 is recorded By replacing carbic anhydride derivative to be kept for 0.5~20 hour and synthesized at a temperature of 80~220 DEG C with diamines alkenyl Obtained compound, commercially available compound.Replace the concrete example of Na Dike imide compounds as alkenyl, can include following The compound shown.

N- methacrylic bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- methacrylic methyl bicycles [2.2.1] hept- 5- alkene -2,3- dicarboximides, the formyls of N- methyls pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two are sub- Amine, N- methyl-methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (2- ethylhexyls) allyl Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of base,

Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of N- (2- ethylhexyls) pi-allyls (methyl), N- pi-allyls Pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- pi-allyls allyl methyl bicyclic [2.2.1] hept- 5- alkene - 2,3- dicarboximides, N- Allyl-methyls pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- isopropyl alkene Base pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- isopropenyls pi-allyl (methyl) are bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximides, N- isopropenyls-formyls of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two are sub- Amine, N- cyclohexyl pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- cyclohexyl pi-allyl (methyl) are bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- Cyclohexyl-methyls pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- diformazans Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of acid imide, N- phenyl allyls,

Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of N- phenyl allyls (methyl), N- benzyl allyls are bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, the formyls of N- benzyl allyls methyl bicycle [2.2.1] hept- 5- alkene -2,3- two are sub- Amine, N- benzyl-methyls pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (2- hydroxyethyls) pi-allyl are double Ring [2.2.1] hept- 5- alkene -2,3- dicarboximides, bicyclic [2.2.1] the hept- 5- alkene of N- (2- hydroxyethyls) pi-allyls (methyl) - 2,3- dicarboximides, N- (2- hydroxyethyls)-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides,

N- (2,2- dimethyl -3- hydroxypropyls) pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of (2,2- dimethyl -3- hydroxypropyls) pi-allyl (methyl), N- (2,3- Dihydroxypropyl) pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (2,3- dihydroxypropyls) pi-allyl (methyl) bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (3- hydroxyl -1- acrylic) pi-allyl bicyclic [2.2.1] Hept- 5- alkene -2,3- dicarboximides, bicyclic [2.2.1] the hept- 5- alkene -2,3- two of N- (4- hydroxy-cyclohexyls) pi-allyls (methyl) Carboximide,

N- (4- hydroxy phenyls) pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (4- hydroxy phenyls) Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of pi-allyl (methyl), N- (4- hydroxy phenyls)-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (4- hydroxy phenyls)-methacrylic methyl bicycle [2.2.1] hept- 5- Alkene -2,3- dicarboximides, N- (3- hydroxy phenyls) pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (3- Hydroxy phenyl) bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of pi-allyl (methyl), N- (to hydroxybenzyl) pi-allyl be double Ring [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- { 2- (2- hydroxyl-oxethyls) ethyl } pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides,

The bicyclic formyls of [2.2.1] hept- 5- alkene -2,3- two of N- { 2- (2- hydroxyl-oxethyls) ethyl }-pi-allyl (methyl) are sub- Amine, N- { 2- (2- hydroxyl-oxethyls) ethyl }-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- { 2- (2- hydroxyl-oxethyls) ethyl }-methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (2- { 2- (2- hydroxyl-oxethyls) ethyoxyl } ethyl)-pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- (2- { 2- (2- hydroxyl-oxethyls) ethyoxyl } ethyl) bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of-pi-allyl (methyl), N- (2- { 2- (2- hydroxyl-oxethyls) ethyoxyl } ethyl) methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- { 4- (4- hydroxy phenyls isopropylidene) phenyl } pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides, N- { 4- (4- hydroxy phenyls isopropylidene) phenyl } bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of pi-allyl (methyl), N- { 4- (4- hydroxy phenyls isopropylidene) phenyl } methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides and they Oligomer,

N, N '-ethylenebis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-ethylenebis (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-ethylenebis (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, double (pi-allyl bicyclic [2.2.1] the hept- 5- alkene -2,3- of N '-trimethylene Dicarboximide), N, N '-hexamethylene bis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-six Di-2-ethylhexylphosphine oxide (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, the double (allyls of the dimethylenes of N '-ten Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of base), N, the double (allyl methyl bicyclics [2.2.1] of N '-ten dimethylenes Hept- 5- alkene -2,3- dicarboximides), N, N '-cyclohexylene is double, and (formyls of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two are sub- Amine), N, N '-cyclohexylene double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides),

Double { 3 '-(pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) propoxyl group } ethane of 1,2-, 1,2- are double Double { 3 '-(the methyl of { 3 '-(allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) propoxyl group } ethane, 1,2- Pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) propoxyl group ethane, double (2 '-{ 3 '-(pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides) propoxyl group ethyl) ether, double (2 '-{ 3 '-(allyl methyl bicyclics [2.2.1] Hept- 5- alkene -2,3- dicarboximides) propoxyl group ethyl) ether, 1,4- it is double 3 '-(pi-allyl bicyclic [2.2.1] hept- 5- alkene -2, 3- dicarboximides) propoxyl group butane, 1,4- it is double 3 '-(formyls of allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- two are sub- Amine) propoxyl group } butane,

N, N '-TOPOT 2,2′ p phenylenebis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-to sub- benzene Base double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, the double (pi-allyl bicyclics of N '-metaphenylene [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-metaphenylene it is double (allyl methyl bicyclic [2.2.1] hept- 5- alkene - 2,3- dicarboximides), N, N '-{ (1- methyl) -2,4- phenylenes }-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two Carboximide), N, N '-terephthalylidene double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N ' - Terephthalylidene double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-m-phenylenedimethylim- Double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-m-phenylenedimethylim- is double, and (allyl methyl is double Ring [2.2.1] hept- 5- alkene -2,3- dicarboximides),

Double (4- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenoxy group } phenyl) third of 2,2- Alkane, 2,2- pairs (4- { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenoxy group } phenyl propane, 2,2- is double (4- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenoxy group } phenyl propane, double { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } methane, double { 4- (allyl methyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } methane,

Double { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } methane, double { 4- (first Base allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl methane, double { 4- (pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl ether, double { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- Dicarboximide) phenyl ether, double { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } ethers, Double { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } sulfones, double { 4- (allyl methyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } sulfone,

Double (the allyls of double { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } sulfones, 1,6- Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of base) -3- hydroxyhexanes, the double (methacrylic bicyclics [2.2.1] of 1,12- Hept- 5- alkene -2,3- dicarboximides) -3,6- dihydroxy dodecane, double (pi-allyl bicyclic [2.2.1] the hept- 5- alkene -2,3- of 1,3- Dicarboximide) -5- hydroxycyclohexans, double { 3 '-(pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) of 1,5- Propoxyl group } -3- hydroxyls pentane, double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) -2- hydroxy benzenes of 1,4-,

1,4- double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) -2,5- dihydroxy benzenes, N, N '-(pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide), N double to (2- hydroxyls) phenylenedimethylidyne, N '-to (2- Hydroxyl) phenylenedimethylidyne double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, a N '-(2- hydroxyl Base) phenylenedimethylidyne double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-(2- hydroxyls) benzene two Di-2-ethylhexylphosphine oxide (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-to (2,3- dihydroxy) benzene two Di-2-ethylhexylphosphine oxide (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides),

Double (4- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) -2- hydroxyphenoxies } benzene of 2,2- Base) it is propane, double { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) -2- hydroxy phenyls } methane, double { 3- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) -4- hydroxy phenyls } ether, double { 3- (methacrylics pair Ring [2.2.1] hept- 5- alkene -2,3- dicarboximides) -5- hydroxy phenyls sulfone, the { 4- (allyl methyl bicyclics of 1,1,1- tri- [2.2.1] hept- 5- alkene -2,3- dicarboximides) } phenoxymethyl propane, N, N ', (the ethylidene methacrylic bicyclics of N "-three [2.2.1] hept- 5- alkene -2,3- dicarboximides) isocyanuric acid ester and their oligomer etc..

And then, the alkenyl substitution Na Dike imide compounds used in the present invention can be had comprising alkylidene and Asia Compound shown in the following formula of the asymmetric group of phenyl.

Among alkenyl substitution Na Dike imide compounds, compound preferably is as follows.

N, N '-TOPOT 2,2′ p phenylenebis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-to sub- benzene Base double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, the double (pi-allyl bicyclics of N '-metaphenylene [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-metaphenylene it is double (allyl methyl bicyclic [2.2.1] hept- 5- alkene - 2,3- dicarboximides), N, N '-{ (1- methyl) -2,4- phenylenes }-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two Carboximide), N, N '-terephthalylidene double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N ' - Terephthalylidene double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-m-phenylenedimethylim- Double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-m-phenylenedimethylim- is double, and (allyl methyl is double Ring [2.2.1] hept- 5- alkene -2,3- dicarboximides), double (4- { 4- (pi-allyl bicyclic [2.2.1] the hept- 5- alkene -2,3- two of 2,2- Carboximide) phenoxy group phenyl propane, double (4- { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- diformazans of 2,2- Acid imide) phenoxy group phenyl propane, the double (4- { 4- (formyls of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two of 2,2- Imines) phenoxy group phenyl propane, double { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } first Alkane, double { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } methane.

Double { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } methane, double { 4- (first Base allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl methane, double { 4- (pi-allyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl ether, double { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- Dicarboximide) phenyl ether, double { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } ethers, Double { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } sulfones, double { 4- (allyl methyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl sulfone, double { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- Dicarboximide) phenyl } sulfone.

Preferred alkenyl substitution Na Dike imide compounds are as follows.

N, N '-ethylenebis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-ethylenebis (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-ethylenebis (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, double (pi-allyl bicyclic [2.2.1] the hept- 5- alkene -2,3- of N '-trimethylene Dicarboximide), N, N '-hexamethylene bis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-six Di-2-ethylhexylphosphine oxide (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, the double (allyls of the dimethylenes of N '-ten Bicyclic [2.2.1] the hept- 5- alkene -2,3- dicarboximides of base), N, the double (allyl methyl bicyclics [2.2.1] of N '-ten dimethylenes Hept- 5- alkene -2,3- dicarboximides), N, N '-cyclohexylene is double, and (formyls of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two are sub- Amine), N, N '-cyclohexylene is double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides).

N, N '-TOPOT 2,2′ p phenylenebis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-to sub- benzene Base double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, the double (pi-allyl bicyclics of N '-metaphenylene [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-metaphenylene it is double (allyl methyl bicyclic [2.2.1] hept- 5- alkene - 2,3- dicarboximides), N, N '-{ (1- methyl) -2,4- phenylenes }-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two Carboximide), N, N '-terephthalylidene double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N ' - Terephthalylidene double (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-m-phenylenedimethylim- Double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N, N '-m-phenylenedimethylim- is double, and (allyl methyl is double Ring [2.2.1] hept- 5- alkene -2,3- dicarboximides).

Double (4- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenoxy group } phenyl) third of 2,2- Alkane, 2,2- pairs (4- { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenoxy group } phenyl propane, 2,2- is double (4- { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenoxy group } phenyl propane, double { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } methane, double { 4- (allyl methyl bicyclics [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl methane, it is double 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2, 3- dicarboximides) phenyl methane, double { 4- (methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- dicarboximides) Phenyl } methane.

Also, replace Na Dike imide compounds as particularly preferred alkenyl, following formula (NA-1) institute can be included N shown in double { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) phenyl } methane for showing, formula (NA-2), N shown in N '-m-phenylenedimethylim- double (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides) and formula (NA-3), N '-hexamethylene bis (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides).

For example, in the aligning agent for liquid crystal of the present invention, from making the electrical characteristics of liquid crystal display cells purpose steady in a long-term, The compound with free-radical polymerised unsaturated double-bond can also be included.Chemical combination with free-radical polymerised unsaturated double-bond Thing can be a kind of compound, or compound of more than two kinds.It should be noted that with free-radical polymerised unsaturation The compound of double bond does not include alkenyl and replaces Na Dike imide compounds.From above-mentioned purpose, with free-radical polymerised The content of the compound of unsaturated double-bond is preferably 1~100 weight %, more preferably 1 relative to polyamic acid or derivatives thereof ~70 weight %, more preferably 1~50 weight %.

It should be noted that receiving enlightening for alkenyl substitution on the compound phase with free-radical polymerised unsaturated double-bond The ratio of gram imide compound, in order to reduce the ion concentration of liquid crystal display cells, suppress ion concentration through when increase, enter And suppress the generation of image retention, the compound with free-radical polymerised unsaturated double-bond/alkenyl substitution Na Dike acid imide chemical combination Thing is preferably 0.1~10, more preferably 0.5~5 with weight ratio meter.

Hereinafter, it is specifically described for the compound with free-radical polymerised unsaturated double-bond.

As the compound with free-radical polymerised unsaturated double-bond, (methyl) acrylate, (methyl) can be included (methyl) acrylic acid derivative such as acrylamide and BMI.Compound with free-radical polymerised unsaturated double-bond More preferably there is (methyl) acrylic acid derivative of more than 2 free-radical polymerised unsaturated double-bonds.

As the concrete example of (methyl) acrylate, such as (methyl) cyclohexyl acrylate, (methyl) propylene can be included Acid -2- methyl cyclohexyls, the ring pentyl ester of (methyl) acrylic acid two, the cyclopentyloxy ethyl ester of (methyl) acrylic acid two, (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 esters.

As the concrete example of 2 functions (methyl) acrylate, such as ethylenebis acrylate, East Asia synthesis can be included The product ARONIX M-210, ARONIX M-240 and ARONIX M-6200 of chemical industry Co., Ltd., Japanese chemical drug strain formula meeting Product K AYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684 of society, Osaka Organic Chemical Industry Product V260, V312 and V335HP of Co., Ltd. and the product Light of oil chemical industry Co., Ltd. of common prosperity society Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA.

As the concrete example of multifunctional (methyl) acrylate more than 3 functions, such as 4,4 '-di-2-ethylhexylphosphine oxide can be included The product ARONIX M-400 of (N, N- N-dihydroxy ethylidene acrylate aniline), East Asia synthetic chemical industry Co., Ltd., ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, Japanese chemical drug The product K AYARADTMPTA of Co., Ltd., KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, The KAYARADDPCA-120 and product VGPT of Osaka Organic Chemical Industry Co., Ltd..

As the concrete example of (methyl) acrylamide derivative, such as NIPA, N- isopropyls can be included Butylmethacrylamide, N- propyl Methacrylamides, N- n-propyls Methacrylamide, N- cyclopropyl acrylamide, N- rings third Butylmethacrylamide, N- ethoxyethyl groups acrylamide, N- ethoxyethyl groups Methacrylamide, N- tetrahydrofurfuryl acryloyls Amine, N- tetrahydrofurfuryls Methacrylamide, N- ethyl acrylamides, N- ethyl-N-methyls acrylamide, N, N- diethyl propylene Acid amides, N- methyl-N-n-propyls acrylamide, N- methyl-N-isopropyls acrylamide, N- acryloylpiperidines, N- acryloyls Base pyrrolidines, N, N '-methylene-bisacrylamide, N, N '-ethylenebisacrylamide, N, the double propylene of N '-dihydroxy ethylidene Acid amides, N- (4- hydroxy phenyls) Methacrylamide, N- phenyl methacrylamides, N- butyl methyls acrylamide, N- (isobutyls Epoxide methyl) Methacrylamide, N- [2- (N, N- dimethylamino) ethyl] Methacrylamide, N, N- dimethyl methyl-props Acrylamide, N- [3- (dimethylamino) propyl group] Methacrylamide, N- (methoxy) Methacrylamide, N- (hydroxyls Methyl) -2- Methacrylamides, N- benzyl -2- Methacrylamides and N, N '-methylenebismethacrylamide.

Among above-mentioned (methyl) acrylic acid derivative, particularly preferably N, N '-methylene-bisacrylamide, N, N '-dihydroxy Base ethylenebisacrylamide, ethylenebis acrylate and 4,4 '-di-2-ethylhexylphosphine oxide (N, N- dihydroxy ethylidene acrylic acid Ester aniline).

As BMI, such as KI Chemical Industry Co. can be included, LTD. manufactures BMI-70 and BMI-80 and BMI-1000, BMI-3000, BMI-4000, BMI- of Daiwa Kasei Industry Co., Ltd.'s manufacture 5000 and BMI-7000.

For example, in the aligning agent for liquid crystal of the present invention, from making the electrical characteristics of liquid crystal display cells purpose steady in a long-term, Can also further Han You oxazine compounds.Oxazine compounds can be a kind of compound, or compound of more than two kinds. Relative to polyamic acid or derivatives thereof it is preferably 0.1~50 weight %, more from the contents of above-mentioned purpose , oxazine compounds Preferably 1~40 weight %, more preferably 1~20 weight %.

Following Zhen paroxazines compound is specifically described.

Oxazine compounds are preferably to dissolve in the solvent that dissolves polyamic acid or derivatives thereof and with ring-opening polymerization Oxazine compounds.

The number of Ling Wai , oxazine compounds Zhong oxazine structures is not particularly limited.

There are various structures known to the structure of oxazine.The structure of Zhong , oxazines of the present invention is not particularly limited in , oxazine compounds Oxazines structure, which can include benzoxazine, Nai Bing oxazines etc., has the aromatic group Evil of the group containing condensed polycyclc aromatic Piperazine structure.

Zuo Wei oxazine compounds, can include the compound for example shown in following formula (OX-1)~formula (OX-6).Need It is bright, in following formula, represent to be bonded to composition ring towards the key shown in ring center and any carbon of substituent can be bonded.

In formula (OX-1)~formula (OX-3), L³And L⁴For the organic group of carbon number 1~30, formula (OX-1)~formula (OX- 6) in, L⁵~L⁸For hydrogen or the alkyl of carbon number 1~6, in formula (OX-3), formula (OX-4) and formula (OX-6), Q¹For singly-bound ,- O-、-S-、-S-S-、-SO₂-、-CO-、-CONH-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_v-、-O-(CH₂)_v- O-、-S-(CH₂)_v- S-, herein, v are 1~6 integer, in formula (OX-5) and formula (OX-6), Q²Independently be singly-bound ,-O- ,- S-、-CO-、-C(CH₃)₂-、-C(CF₃)₂- or carbon number 1~3 alkylidene, being bonded in formula (OX-1)~formula (OX-6) Phenyl ring, the hydrogen of naphthalene nucleus are optionally independently by-F ,-CH₃、-OH、-COOH、-SO₃H、-PO₃H₂Substitution.

In addition , oxazine compounds include：In oligomer, the polymer of side chain Ju You oxazine structures；The Ju You Evil in main chain Oligomer, the polymer of piperazine structure.

As oxazine compounds shown in formula (OX-1), oxazine compounds Xia such as Yi can be included.

In formula (OX-1-2), L³The preferably alkyl of carbon number 1~30, more preferably carbon number 1~20 Alkyl.

As oxazine compounds shown in formula (OX-2), oxazine compounds Xia such as Yi can be included.

In formula, L³The preferably alkyl of the alkyl of carbon number 1~30, more preferably carbon number 1~20.

As oxazine compounds shown in formula (OX-3), oxazine compounds shown in following formula (OX-3-I) can be included.

In formula (OX-3-I), L³And L⁴For the organic group of carbon number 1~30, L⁵~L⁸For hydrogen or carbon number 1~6 Alkyl, Q¹For singly-bound ,-CH₂-、-C(CH₃)₂-、-CO-、-O-、-SO₂-、-C(CH₃)₂- or-C (CF₃)₂-.It is used as formula (OX-3- I oxazine compounds shown in), can include oxazine compounds Xia such as Yi.

In formula, L³And L⁴The preferably alkyl of the alkyl of carbon number 1~30, more preferably carbon number 1~20.

As oxazine compounds shown in formula (OX-4), oxazine compounds Xia such as Yi can be included.

As oxazine compounds shown in formula (OX-5), oxazine compounds Xia such as Yi can be included.

As oxazine compounds shown in formula (OX-6), oxazine compounds Xia such as Yi can be included.

Among these, more preferably formula (OX-2-1), formula (OX-3-1), formula (OX-3-3), formula (OX-3-5), formula (OX-3- 7), formula (OX-3-9), formula (OX-4-1)~formula (OX-4-6), formula (OX-5-3), formula (OX-5-4) and formula (OX-6-2)~formula (OX-6-4) oxazine compounds shown in.

Oxazine compounds can be utilized and International Publication 2004/009708, Japanese Unexamined Patent Publication 11-12258, Japanese Unexamined Patent Publication The method identical method that 2004-352670 is recorded is manufactured.

Oxazine compounds shown in formula (OX-1) can obtain (ginseng by making oxybenzene compound be reacted with primary amine and aldehyde According to International Publication 2004/009708.).

Oxazine compounds shown in formula (OX-2) can be obtained as below：By by primary amine gently be added to formaldehyde method and Make after its reaction, compound of the addition with naphthols system hydroxyl simultaneously makes its reaction (with reference to International Publication 2004/009708.).

Oxazine compounds shown in formula (OX-3) can be by making 1 mole of oxybenzene compound, relative to it in organic solvent The aldehyde and 1 mole of primary amine that phenolic hydroxyl group 1 is at least more than 2 moles are nitrogenous in secondary aliphatic amine, aliphatic tertiary amine or alkalescence React to obtain (with reference to International Publication 2004/009708 and Japanese Unexamined Patent Publication 11- in the presence of heterocyclic compound 12258。)。

Formula (OX-4)~oxazine compounds shown in formula (OX-6) can be by having 4,4 '-diaminodiphenyl-methane etc. The aldehyde such as diamines, the formaldehyde of their organic group of multiple phenyl ring and bonding and phenol are sent out in n-butanol with more than 90 DEG C of temperature Dehydration condensation is given birth to obtain (with reference to Japanese Unexamined Patent Publication 2004-352670.).

For example, in the aligning agent for liquid crystal of the present invention, from making the electrical characteristics of liquid crystal display cells purpose steady in a long-term, Can also further Han You oxazoline compounds.Oxazoline compound is the compound of Ju You oxazoline structures.Oxazoline chemical combination Thing can be a kind of compound, or compound of more than two kinds.From the content phase of above-mentioned purpose , oxazoline compounds It is preferably 0.1~50 weight %, more preferably 1~40 weight % for polyamic acid or derivatives thereof, is preferably 1~20 weight Measure %.In addition, the content , of Guan Yu oxazoline compounds is when oxazoline compound Zhong oxazoline structure Huan Suan oxazolines, It is preferably 0.1~40 weight % relative to polyamic acid or derivatives thereof from above-mentioned purpose.

Hereinafter, Zhen Dui oxazoline compounds are specifically described.

Oxazoline compound can only have 1 Zhong oxazoline structures in 1 compound, it is possible to have two or more.Separately Wai , oxazoline compounds have 1 Ge oxazoline structures in 1 compound, preferably with more than 2.Ling Wai , oxazolines Compound can be the polymer or copolymer of side chain Ju You oxazoline structures.Side chain Ju You oxazoline structures it is poly- Compound can be the monomer of side chain Ju You oxazoline structures homopolymer or side chain Ju You oxazoline structures monomer with The copolymer of the monomer of Bu Ju You oxazoline structures.The copolymer of side chain Ju You oxazoline structures can be side chain Ju You oxazolines The copolymer of two or more monomer of structure or two or more monomer of side chain Ju You oxazoline structures and Bu Ju You oxazoles The copolymer of the monomer of quinoline structure.

One or both of oxygen and nitrogen in oxazoline structure You Xuan Yi oxazoline structures can be with polyamic acid carbonyl In the mode Cun Yu oxazoline compounds of base reaction.

Zuo Wei oxazoline compounds, can include such as 2,2 '-bis- (2- oxazolines), 1,2,4- tri- (2- oxazolinyls- 2)-benzene, 4- furans -2- methylene -2- phenyl -4H- oxazole -5- ketone, 1,4- double (4,5- dihydro -2- oxazolinyls) benzene, 1, Double (4- isopropenyl -2- oxazoline -2- bases) butane of double (4,5- dihydro -2- oxazolinyls) benzene of 3-, 2,3-, 2,2 '-bis- -4- benzyls Double (isopropyl -2- oxazoline -2- bases) pyridines of base -2- oxazolines, 2,6-, the double (the 4- tert-butyl group -2- oxazoles of 2,2 '-isopropylidene Quinoline), 2,2 '-isopropylidene double (4- phenyl -2- oxazolines), 2,2 '-di-2-ethylhexylphosphine oxide (the 4- tert-butyl group -2- oxazolines) and 2,2 ' - Di-2-ethylhexylphosphine oxide (4- phenyl -2- oxazolines).Outside these, EPOCROS (trade name, Nippon Shokubai Co., Ltd can be also included System) as Ju You oxazolinyls polymer, oligomer.Among these, it may be more preferable to which ground includes 1,3- double (4,5- bis- Hydrogen -2- oxazolinyls) benzene.

For example, in the aligning agent for liquid crystal of the present invention, from making the electrical characteristics of liquid crystal display cells purpose steady in a long-term, Epoxide can also further be contained.Epoxide can be a kind of compound, or compound of more than two kinds. From above-mentioned purpose, the content of epoxide is preferably 0.1~50 weight %, more relative to polyamic acid or derivatives thereof Preferably 1~40 weight %, more preferably 1~20 weight %.

Hereinafter, it is specifically described for epoxide.

As epoxide, various compounds of the intramolecular with 1 or more than 2 epoxide ring can be included.As Intramolecular has the compound of 1 epoxide ring, can include such as phenyl glycidyl ether, butyl glycidyl ether, 3,3,3- Trifluoromethyl expoxy propane, styrene oxide, HFPO, cyclohexene oxide, 3- glycidoxypropyl group trimethoxies Silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, N- glycidyls phthalimide, (the positive fourth of nine fluorine Base) epoxides, perfluoro-ethyl glycidol ether, epichlorohydrin, epibromohydrin, N, N- diglycidylanilines and 3- [2- (perfluoro hexyl) ethyoxyl] -1,2 epoxy prapane.

There is the compound of 2 epoxide rings as intramolecular, such as ethylene glycol diglycidylether, poly- second two can be included 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 glycols Diglycidyl ether, 3,4- epoxy hexanes ylmethyl -3 ', 4 '-epoxy hexane carboxylate and 3- (N, N- 2-glycidyls Base) TSL 8330.

There is the compound of 3 epoxide rings as intramolecular, such as 2- [4- (2,3- glycidoxy) benzene can be included Base] -2- [4- [double [4- ([2,3- glycidoxies] the phenyl)] ethyls of 1,1-] phenyl] propane (trade name " Techmore VG3101L ", (Mitsui Chemicals, Inc's system)).

There is the compound of 4 epoxide rings as intramolecular, such as 1,3,5,6- four glycidyl groups -2,4- can be included Hexylene glycol, N, N, N ', double (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- pi-allyl-N- glycidyls) TSL 8330.

In addition to that mentioned above, there is the example of the compound of epoxide ring as intramolecular, can also include with epoxide ring Oligomer, polymer.As the monomer with epoxide ring, such as (methyl) glycidyl acrylate, (first can be included Base) acrylic acid 3,4- epoxies cyclohexyl and (methyl) acrylic acid methylglycidyl esters.

As other monomers that copolymerization is carried out with the monomer with epoxide ring, such as (methyl) acrylic acid, (first can be included Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) third Olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) propylene Sour 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, styrene, methyl styrene, 1-chloro-4-methyl-benzene, (methyl) propylene Sour (3- ethyl -3- oxetanylmethoxies) methyl esters, N- N-cyclohexylmaleimides and N-phenylmaleimide.

As the preferred concrete example of the polymer of the monomer with epoxide ring, polymethyl acid glycidyl can be included Ester etc..In addition, as the preferred concrete example of the monomer with epoxide ring and the copolymer of other monomers, N- phenyl horses can be included Come acid imide-glycidyl methacrylate copolymer, N- N-cyclohexylmaleimides-GMA common Polymers, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate shrink Glycerine ester copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3- second Base -3- oxetanylmethoxies) methyl esters-glycidyl methacrylate copolymer and styrene-t glycidol Ester copolymer.

Among these examples, particularly preferably N, N, N ', double (N, the N- bis- of N '-four glycidyl group m-xylene diamine, 1,3- Glycidyl-amino methyl) hexamethylene, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl-methane, trade name " Techmore VG3101L ", 3,4- epoxy hexanes ylmethyl -3 ', 4 '-epoxy hexane carboxylate, N- benzyl maleimides Amine-glycidyl methacrylate copolymer and 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane.

For more system, as epoxide, such as glycidol ether, ethylene oxidic ester, glycidol can be included Amine, the acrylic resin containing epoxy radicals, glycidyl acid amides, isocyanuric acid glycidyl esters, chain fatty race type ring Oxygen compound and annular aliphatic type epoxide.It should be noted that epoxide refers to the chemical combination with epoxy radicals Thing, epoxy resin refers to the resin with epoxy radicals.

As epoxide, can include for example glycidol ether, ethylene oxidic ester, glycidyl amine, containing epoxy radicals Acrylic resin, glycidyl acid amides, isocyanuric acid glycidyl esters, chain fatty race type epoxide and ring Shape aliphatic type epoxide.

As glycidol ether, such as bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S can be included Type epoxide, biphenol type epoxy compound, hydrogenated bisphenol A type epoxide, A Hydrogenated Bisphenol A F types epoxide, hydrogen Change bisphenol S type epoxy compound, A Hydrogenated Bisphenol A type epoxide, bmminated bisphenol-A type epoxide, brominated bisphenol F type rings Oxygen compound, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, brominated phenol phenolic varnish type Epoxide, bromination cresol novolak type epoxy compound, bisphenol A novolac type epoxide, containing naphthalene skeleton Epoxide, aromatic series poly epihydric alcohol ether compound, dicyclopentadiene phenol epoxide, ester ring type two shrink sweet Oily ether compound, aliphatic polyglycidyl ether compound, polysulfide ether type 2-glycidyl ether compound and biphenyl type epoxy Compound.

As ethylene oxidic ester, such as 2-glycidyl ester compounds and glycidyl ester epoxy compound can be included.

As glycidyl amine, such as poly epihydric alcohol amines and glycidyl amine type epoxy resin can be included.

As the acrylic compounds containing epoxy radicals, the homopolymerization of such as monomer with Oxyranyle can be included Thing and copolymer.

As glycidyl acid amides, such as glycidyl acid amide type epoxide can be included.

As chain fatty race type epoxide, it can include the carbon-to-carbon double bond oxidation of olefin(e) compound for example The obtained compound containing epoxy radicals.

As annular aliphatic type epoxide, it can include and for example aoxidize the carbon-to-carbon double bond of cyclic olefins Obtained from the compound containing epoxy radicals.

As bisphenol A type epoxy compound, can include such as jER828, jER1001, jER1002, jER1003, JER1004, jER1007, jER1010 (being trade name, Mitsubishi chemical Co., Ltd's system), Epotohto YD-128 (Dongdu Into Co. Ltd. system), DER-331, DER-332, DER-324 (being The Dow Chemical Company systems), EPICLON 840th, EPICLON 850, EPICLON 1050 (being trade name, Dainippon Ink Chemicals's system), EPOMIC R-140, EPOMIC R- 301 and EPOMIC R-304 (being trade name, Mitsui Chemicals, Inc's system).

As bisphenol F type epoxy compound, can include such as jER806, jER807, jER4004P (be trade name, Mitsubishi chemical Co., Ltd's system), Epotohto YDF-170, Epotohto YDF-175S, Epotohto YDF-2001 (be Trade name, Toto Kasei KK's system), DER-354 (trade name, The Dow Chemical Company systems), EPICLON 830 and EPICLON 835 (being trade name, Dainippon Ink Chemicals's system).

As biphenol type epoxy compound, double (the 4- hydroxy phenyls) -1 of such as 2,2-, 1,1,3,3,3- hexafluoro can be included The epoxides of propane.

As hydrogenated bisphenol A type epoxide, such as Santohto ST-3000 (trade name, Dongdu can be included Into Co. Ltd. system), RIKARESIN HBE-100 (trade name, New Japan Chem Co., Ltd's system) and DENACOL EX- 252 (trade name, Nagase ChemteX Corporation systems).

As A Hydrogenated Bisphenol A type epoxide, it can include and for example hydrogenate double (the 4- hydroxy phenyls) -1 of 2,2-, 1,1,3, The epoxides of 3,3- HFC-236fas.

As bmminated bisphenol-A type epoxide, it (is trade name, Mitsubishi that can include such as jER5050, jER5051 KCC's system), Epotohto YDB-360, Epotohto YDB-400 (be trade name, Toto Kasei KK System), DER-530, DER-538 (being trade name, The Dow Chemical Company systems), the and of EPICLON 152 EPICLON 153 (being trade name, Dainippon Ink Chemicals's system).

As phenol novolak-type epoxy compound, it (is trade name, three that can include such as jER152, jER154 Water chestnut KCC system), YDPN-638 (trade name, Dongdu chemical conversion society system), DEN431, DEN438 (be trade name, The Dow Chemical Company systems), EPICLON N-770 (trade name, Dainippon Ink Chemicals's system), EPPN-201 and EPPN- 202 (being trade name, Nippon Kayaku K. K's system).

As cresol novolak type epoxy compound, such as jER180S75 (trade name, Mitsubishi Chemical's strain can be included Formula commercial firm system), YDCN-701, YDCN-702 (being trade name, Dongdu chemical conversion society system), EPICLON N-665, EPICLON N- 695 (being trade name, Dainippon Ink Chemicals's system), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN- 1025 and EOCN-1027 (being trade name, Nippon Kayaku K. K's system).

As bisphenol A novolac type epoxide, such as jER157S70 (trade name, Mitsubishi Chemical's strain can be included Formula commercial firm system) and EPICLON N-880 (trade name, Dainippon Ink Chemicals's system).

As the epoxide containing naphthalene skeleton, such as EPICLON HP-4032, EPICLON HP- can be included 4700th, EPICLON HP-4770 (being trade name, Dainippon Ink Chemicals's system) and NC-7000 (trade name, Japanese chemical drug strain formula Commercial firm's system).

As aromatic series poly epihydric alcohol ether compound, such as quinhydrones diglycidyl ether (following formula EP- can be included 1), catechol diglycidyl ether (following formula EP-2), resorcinolformaldehyde resin (following formula EP-3), 2- [4- (2,3- Glycidoxy) phenyl] -2- [4- [double [4- ([2,3- glycidoxies] the phenyl)] ethyls of 1,1-] phenyl] propane (following formula EP-4), three (4- glycidyloxyphenyls) methane (following formula EP-5), jER1031S, jER1032H60 (are commodity Name, Mitsubishi chemical Co., Ltd's system), TACTIX-742 (trade name, The Dow Chemical Company systems), DENACOL EX-201 (trade name, Nagase ChemteX Corporation systems), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (being trade name, Nippon Kayaku K. K's system), Techmore VG3101L (trade name, Mitsui Chemicals, Inc Society's system), the compound shown in following formula EP-6 and the compound shown in following formula EP-7.

As dicyclopentadiene phenol epoxide, such as TACTIX-556 (trade name, The Dow can be included Chemical Company systems) and EPICLON HP-7200 (trade name, Dainippon Ink Chemicals's system).

As ester ring type 2-glycidyl ether compound, such as cyclohexanedimethanodiglycidyl diglycidyl ether chemical combination can be included Thing and RIKARESIN DME-100 (trade name, New Japan Chem Co., Ltd's system).

As aliphatic polyglycidyl ether compound, such as ethylene glycol diglycidylether (following formula EP- can be included 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 ethers (following formula EP-13), 1,6-HD two contract 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 (are trade name, Nagase ChemteX Corporation systems), DD-503 (trade name, ADEKA CORPORATION systems), RIKARESIN W-100 (trade name, new day This physics and chemistry Co. Ltd. system), 1,3,5,6- four glycidyl group -2,4- hexylene glycols (following formula EP-16), glycerine poly epihydric alcohol Ether, d-sorbite polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythrite polyglycidyl ether, DENACOL EX-313, DENACOL EX-611, DENACOL EX-321 and DENACOL EX-411 (are trade name, Nagase ChemteX Corporation systems).

As polysulfide ether type 2-glycidyl ether compound, it (is commodity that can include such as FLDP-50 and FLDP-60 Name, Toray Thiokol Co., Ltd. system).

As biphenol type epoxy compound, it (is trade name, Mitsubishi Chemical that can include such as YX-4000, YL-6121H Co. Ltd. system), NC-3000P and NC-3000S (being trade name, Nippon Kayaku K. K's system).

As 2-glycidyl ester compounds, such as terephthalic acid diglycidyl ester (following formula EP- can be included 17), o-phthalic acid diglycidyl ester (following formula EP-18), double (2- methyl oxiranes ylmethyl) phthalic acid esters Chemical combination shown in (following formula EP-19), hexahydrophthalic acid 2-glycidyl ester (following formula EP-20), following formula EP-21 The compound shown in compound and following formula EP-23 shown in thing, following formula EP-22.

As glycidyl ester epoxy compound, it (is trade name, Mitsubishi that can include such as jER871, jER872 Learn Co. Ltd. system), EPICLON 200, EPICLON 400 (being trade name, Dainippon Ink Chemicals's system), DENACOL EX- 711 and DENACOL EX-721 (being trade name, Nagase ChemteX Corporation systems).

As poly epihydric alcohol amines, such as N can be included, N- diglycidylanilines (following formula EP-24), N, N- diglycidyl ortho-aminotoluene (following formula EP-25), N, N- diglycidyl meta-aminotoluenes (following formula EP-26), N, N- diglycidyl -2,4,6- tribromanilines (following formula EP-27), 3- (N, N- diglycidyl) aminopropyl front three TMOS (following formula EP-28), N, N, O- triglycidyl group para-aminophenol (following formula EP-29), N, N, O- tri- shrink Glyceryl m-aminophenol (following formula EP-30), N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl-methane (under State formula EP-31), N, N, N ', N '-four glycidyl group m-xylene diamine (TETRAD-X (the chemical strain formulas of trade name, Mitsubishi gas Commercial firm's system), following formula EP-32), double (N, the N- diglycidyl amino methyl) hexamethylenes of 1,3- (TETRAD-C (trade name, Mitsubishi Gas Chemical Co., Ltd's system), following formula EP-33), double (N, the N- diglycidyl amino methyl) hexamethylenes of 1,4- Double (N, the N- diglycidyl amino) hexamethylenes (following formula EP-35) of (following formula EP-34), 1,3-, 1,4- are double, and (N, N- bis- contracts Water glyceryl amino) hexamethylene (following formula EP-36), double (N, the N- diglycidyl amino) benzene (following formula EP-37) of 1,3-, Double (N, the N- diglycidyl amino) benzene (following formula EP-38) of 1,4-, 2,6- are double (N, N- diglycidyl 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 '-benzidine (following formula EP- 41), N, N, N ', N '-four glycidyl group -4,4 '-diamino-diphenyl ether (following formula EP-42), 1,3,5- tri- (4- (N, N- Diglycidyl) amino-benzene oxygen) benzene (following formula EP-43), 2,4,4 '-three (N, N- diglycidyl amino) diphenyl Ether (following formula EP-44), three (4- (N, N- diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3 ', 4 '- Four (N, N- diglycidyl amino) biphenyl (following formula EP-46), 3,4,3 ', 4 '-four (N, N- diglycidyl amino) The compound shown in compound and following formula EP-49 shown in diphenyl ether (following formula EP-47), following formula EP-48.

As the homopolymer of the monomer with Oxyranyle, such as poly (glycidyl methacrylate) can be included. As the copolymer of the monomer with Oxyranyle, such as N-phenylmaleimide-Glycidyl methacrylate can be included Glycerine ester copolymer, N- N-cyclohexylmaleimides-glycidyl methacrylate copolymer, benzyl methacrylate-first Base glycidyl acrylate copolymer, butyl methacrylate glycidyl ester copolymer, methacrylic acid 2- hydroxy methacrylates-glycidyl methacrylate copolymer, methacrylic acid (3- ethyl -3- oxetanylmethoxies) methyl esters-first Base glycidyl acrylate copolymer and styrene-t glycidyl ester copolymer.

As the monomer with Oxyranyle, such as (methyl) glycidyl acrylate, (methyl) third can be included Olefin(e) acid 3,4- epoxies cyclohexyl and (methyl) acrylic acid methylglycidyl esters.

As other in addition to the monomer with Oxyranyle in the copolymer of the monomer with Oxyranyle Monomer, can include such as (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid Isopropyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid Cyclohexyl, (methyl) benzyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, styrene, Methyl styrene, 1-chloro-4-methyl-benzene, (methyl) acrylic acid (3- ethyl -3- oxetanylmethoxies) methyl esters, N- cyclohexyl Malaysia acyl Imines and N-phenylmaleimide.

As isocyanuric acid ethylene oxidic ester, such as 1 can be included, 3,5- triglycidyl groups -1,3,5-triazines -2,4, 6- (1H, 3H, 5H)-triketone (following formula EP-50), 1,3- diglycidyl -5- pi-allyl -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone (following formula EP-51) and isocyanuric acid glycidyl ester type epoxy resin.

As chain fatty race type epoxide, such as epoxidized polybutadiene and EPOLEAD PB3600 can be included (trade name, Daicel Corporation. systems).

As annular aliphatic type epoxide, such as 3,4- epoxy hexanes methyl -3 ', 4 '-epoxy can be included Cyclohexene carboxylate ester (CELLOXIDE 2021 (Daicel Corporation. systems), following formula EP-52), 2- methyl -3,4- rings - 2 '-methyl of oxygen cyclohexyl methyl -3 ', 4 '-epoxycyclohexylcarboxylate (following formula EP-53), 2,3- cyclopentane epoxides -2 ', 3 '-cyclopentane epoxide ether (following formula EP-54), 6-caprolactone are modified 3,4- epoxycyclohexyl-methyls -3 ', 4 ' -7-oxa-bicyclo[4.1.0 Carboxylate, 1,2:8,9- bicyclic oxygens limonene (CELLOXIDE 3000 (trade name, Daicel Corporation. systems), under It (is trade name, The Ciba- to state the compound shown in formula EP-55, following formula EP-56, CY-175, CY-177, CY-179 Geigy Chemical Corp. systems (can be obtained from Huntsman Japan KK)), EHPD-3150 (trade name, Daicel Corporation. make) and annular aliphatic type epoxy resin.

Epoxide is preferably poly epihydric alcohol amines, bisphenol A novolac type epoxide, cresol novolac One or more of type epoxy compound and annular aliphatic type epoxide, preferably N, N, N ', N '-four shrinks sweet Oil base m-xylene diamine, 1,3- double (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N '-four glycidyl group- 4,4 '-diaminodiphenyl-methane, trade name " Techmore VG3101L ", 3,4- epoxy hexanes methyl -3 ', 4 '-epoxy Cyclohexene carboxylate ester, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O- triglycidyl groups pair More than a kind in amino-phenol, bisphenol A novolac type epoxide and cresol novolak type epoxy compound.

In addition, aligning agent for liquid crystal of the invention can also further contain various additives.As various additives, The high-molecular compound and low molecular compound beyond such as polyamic acid and its derivative can be included, can be according to respective Purpose select and use.

For example, as foregoing high-molecular compound, it is soluble high-molecular compound that can include to organic solvent.From From the viewpoint of the electrical characteristics of the formed liquid crystal orientation film of control, orientation, preferably this high-molecular compound is added to In the aligning agent for liquid crystal of the present invention.As the high-molecular compound, can include for example polyamide, polyurethane, polyureas, polyester, Polyepoxide, PEPA, organic silicon modified polyurethane and organosilicon modified polyester.

In addition, as foregoing low molecular compound, can include for example：1) purpose is met when expecting to improve coating Surfactant；2) antistatic additive when needing to improve antistatic；3) silicon when expecting to improve the adaptation closely sealed with substrate Alkane coupling agent, titanium system coupling agent；In addition, 4) imidization catalyst when carrying out imidizate at low temperature.

As silane coupler, such as vinyltrimethoxy silane, VTES, N- can be included (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, N- (2- amino-ethyls) -3- amino propyl methyl trimethoxies Silane, p-aminophenyl trimethoxy silane, p-aminophenyl triethoxysilane, m-aminophenyl base trimethoxy silane, Aminophenyl triethoxysilane, 3- TSL 8330s, APTES, the oxygen of 3- epoxies third Base propyl trimethoxy silicane, 3- glycidoxypropyls dimethoxysilane, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyl silanes, 3- methacryloxypropyl trimethoxy silanes, 3-mercaptopropyi trimethoxy silane, N- (1,3- dimethyl butane) -3- (triethoxysilyl) -1- propylamine and N, N '-bis- [3- (trimethyoxysilanes Base) propyl group] ethylenediamine.Silane coupler is preferably APTES.

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

The addition of silane coupler is usually 0~20 weight %, preferably of the gross weight of polyamic acid or derivatives thereof For 0.1~10 weight %.

The addition of imidization catalyst is commonly angled relative to the carbonyl of polyamic acid or derivatives thereof and worked as 0.01~5 Amount, preferably 0.05~3 equivalent.

The addition of other additives is different because of its purposes, usually the 0 of the gross weight of polyamic acid or derivatives thereof~ 100 weight %, preferably 0.1~50 weight %.

Polyamic acid or derivatives thereof of the present invention can with for formed polyimide film known polyamic acid or its Derivative is similarly manufactured.The total amount of feeding of tetracarboxylic dianhydride is preferably set to the molal quantity roughly equal with the total mole number of diamines (mol ratio is 0.9~1.1 or so).

It is excellent in terms of the weight average molecular weight (Mw) that the molecular weight of the polyamic acid of the present invention or derivatives thereof is converted by polystyrene Elect 7000~500000, more preferably 10000~200000 as.The molecular weight of foregoing polyamides acid or derivatives thereof can utilize base Obtained in the measure of gel permeation chromatography (GPC) method.

Polyamic acid of the present invention or derivatives thereof can be obtained by using IR, NMR to precipitating it with a large amount of lean solvents To solid constituent analyzed confirm its exist.In addition, by using GC, HPLC or GC-MS to strong with KOH, NaOH etc. The extract obtained with organic solvent of the analyte of the foregoing polyamides acid that the aqueous solution of alkali is obtained or derivatives thereof is divided Analysis, so as to confirm the monomer used.

In addition, for example, in the aligning agent for liquid crystal of the present invention, the coating, foregoing polyamides from adjustment aligning agent for liquid crystal are sour Or derivatives thereof concentration from the viewpoint of, can also further contain solvent.As long as aforementioned solvents possess make macromolecule into Divide the solvent of the ability of dissolving, so that it may apply without particular limitation.Aforementioned solvents are included in polyamic acid, soluble poly extensively The usually used solvent of the manufacturing step of the macromolecule components such as acid imide, purposes aspect, can suitably be selected according to application target. It can also be mixed solvent of more than two kinds that aforementioned solvents, which can be a kind,.

As solvent, the good solvent of foregoing polyamides acid or derivatives thereof can be included, for improving the other of coating Solvent.

As for the aprotic polar organic solvent that polyamic acid or derivatives thereof is good solvent, N- first can be included Base -2-Pyrrolidone, dimethyl-imidazolinone, N- methylcaprolactones, N- methyl propanamides, DMAC N,N' dimethyl acetamide, diformazan Base sulfoxide, N,N-dimethylformamide, N, the lactone such as N- diethyl acetamides, diethyl acetamide, gamma-butyrolacton.

As the example of other solvents for improving coating etc., lactic acid alkyl ester, 3- methyl -3- methoxies can be included The diethylene glycols such as the ethylene glycol monoalkyl ethers such as base butanol, naphthane, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether Monoalky lether, glycol monoalkyl acetic acid esters or ethylene glycol phenyl yl acetate, triethylene glycol monoalky lether, propylene glycol monomethyl ether, The dialkyl malonates such as the propylene-glycol monoalky lethers such as propylene glycol monobutyl ether, diethyl malonate, dipropylene glycol monomethyl ether etc. two The ester compounds such as propylene-glycol monoalky lether, their acetate esters.

Among these, aforementioned solvents are particularly preferably METHYLPYRROLIDONE, dimethyl-imidazolinone, 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.

The concentration of polyamic acid in the alignment agent of the present invention is preferably 0.1~40 weight %.The alignment agent is coated on During substrate, in order to adjust thickness, it is sometimes desirable to by containing the polyamic acid operation that is diluted with solvent in advance.

Solid component concentration in the alignment agent of the present invention is not particularly limited, and is combined with following various coating method selections Optimum value.Generally, it is preferably 0.1~30 weight relative to varnish weight in order to suppress inequality, pin hole during coating etc. Measure %, more preferably 1~10 weight %.

The preferred scope of the viscosity of the aligning agent for liquid crystal of the present invention is dense because coating method, polyamic acid or derivatives thereof Species, the species of solvent and the ratio of degree, polyamic acid used or derivatives thereof and it is different.For example, utilizing printing machine coating When, it is 5~100mPas (more preferably 10~80mPas).During less than 5mPas, it is difficult to obtain sufficient thickness, exceed During 100mPas, uneven become greatly is printed sometimes.During using spin coating to be coated with, be suitably for 5~200mPas (more preferably 10~ 100mPa·s).When being coated using ink-jet coating apparatus, 5~50mPas (more preferably 5~20mPas) is suitably for. The viscosity of aligning agent for liquid crystal is determined using rotational viscometry, such as using rotation viscometer (Toki Sangyo Co., Ltd. The TVE-20L types of manufacture) it is measured (measure temperature：25℃).

It is described in detail for the liquid crystal orientation film of the present invention.The liquid crystal orientation film of the present invention is by heating foregoing Film formed by the film of the aligning agent for liquid crystal of invention.The liquid crystal orientation film of the present invention can be by making liquid crystal by aligning agent for liquid crystal The usual methods of alignment films is obtained.For example, the liquid crystal orientation film of the present invention can be by via the liquid crystal aligning for forming the present invention The step of film of agent, the step of of being thermally dried and carry out heating the step of burn till to obtain.Liquid on the present invention Brilliant alignment films, as needed as will be shown later, can also be to burning till the film that step obtains and brushing via heat-drying step, heating Mill handles to assign anisotropy.In addition, as needed, can also after film-coating procedures, heat-drying step irradiation light or Person's irradiation light after step is burnt till in heating assigns anisotropy.Furthermore it is also possible to not carry out the VA liquid of brushing processing The forms of brilliant alignment films is used.

The making of film and common liquid crystal orientation film is likewise by base plate coating this hair in liquid crystal display cells Bright aligning agent for liquid crystal is formed.Substrate, which can be included, is optionally provided with ITO (tin indium oxide, Indium Tin Oxide), IZO (In₂O₃-ZnO)、IGZO(In-Ga-ZnO₄) electrode, the colour filter such as electrode etc. glass substrate of electrode.

It is commonly known to have spinner method, print process, infusion process, drop as the method that aligning agent for liquid crystal is coated on to substrate Addition, ink-jet method etc..These methods can also be equally applicable to the present invention.

Foregoing heat-drying step it is commonly known that：The method that is heated in baking oven or infra-red furnace, in heat Method heated on plate etc..Heat-drying step preferably can in the range of evaporation solvent at a temperature of implement, More preferably implement at relatively low temperature compared with the temperature that step is burnt till in heating.Specifically, heat drying temperature is excellent Elect 30 DEG C~150 DEG C of scope, more preferably 50 DEG C~120 DEG C of scope as.

Step is burnt till in foregoing heating can be for occurring dehydration/ring-closure reaction for foregoing polyamides acid or derivatives thereof Carried out under the conditions of necessary.Foregoing film burn till it is commonly known that：The side heated in baking oven or infra-red furnace Method, the method heated on hot plate etc..These methods can also be applied similarly in the present invention.Generally preferably exist Progress 1 minute~3 hours at a temperature of 100~300 DEG C or so, more preferably 120~280 DEG C, more preferably 150~ 250℃.Burnt till furthermore, it is possible to carry out heating for multiple times at different temperatures.Setting can be used to multiple heating of different temperatures Device, can also use 1 heater to change to different temperatures successively on one side while carrying out.2 are carried out at different temperature Secondary heating is when burning till, and is carried out with 90~140 DEG C, the 2nd time with more than 180 DEG C of temperature for preferably the 1st time.

In the forming method of the liquid crystal orientation film of the present invention, in order that liquid crystalline phase is for horizontal and/or vertical folk prescription It is orientated to ground, anisotropic means is assigned as to alignment films, can be compatibly using shape known to brushing method, optical alignment method etc. Into method.

Substrate can be coated on via by the aligning agent for liquid crystal of the present invention by having used the liquid crystal orientation film of the invention of brushing method The step of, the step of be coated with the step of substrate of alignment agent is thermally dried, burn till film progress heating and will The step of film progress brushing processing, is formed.

Carried out in the same manner as the brushing processing that brushing processing can be for the purpose of the common orientation process by liquid crystal orientation film, As long as the liquid crystal orientation film of the present invention results in the condition of abundant retardation.Optimum condition is：Bristle lengths are pressed into Amount is that 0.2~0.8mm, pedestal translational speed are that 5~250mm/sec, roller rotary speed are 500~2000rpm.

The method of liquid crystal orientation film for being formed the present invention using optical alignment method is described in detail.Light orientation is used The liquid crystal orientation film of the invention of method is formed as follows：By after heat drying film, the rectilinearly polarized light of illumination radiation line or Unpolarized light and to film assign anisotropy, by the film progress heating burn till, so as to be formed.Furthermore it is possible to dry by heating After dry film and heating is burnt till, the rectilinearly polarized light of illumination radiation line or unpolarized light are formed.From the viewpoint of orientation, The irradiating step of radiation is carried out preferably before step is burnt till in heating.

And then, in order to improve the liquid crystal aligning ability of liquid crystal orientation film, film can also be heated while illumination radiation The rectilinearly polarized light of line or unpolarized light.The irradiation of radiation can by the step of heat drying film or heating burn till film The step of carry out, can also be carried out between heat-drying step and heating burn till step.Heat drying temperature in the step Degree is preferably 30 DEG C~150 DEG C of scope, is more preferably 50 DEG C~120 DEG C of scope.In addition, the heating in the step is burnt It is preferably 30 DEG C~300 DEG C of scope, is more preferably 50 DEG C~250 DEG C of scope into temperature.

As radiation, the ultraviolet or visible ray of the light for example comprising 150~800nm wavelength can be used, is preferably The ultraviolet of light comprising 300~400nm.In addition it is possible to use rectilinearly polarized light or unpolarized light.As long as these light can The light that foregoing film assigns liquid crystal aligning ability is just not particularly limited, it is desirable to strong orientation regulation power is shown for liquid crystal When, preferably rectilinearly polarized light.

The liquid crystal orientation film of the present invention can also show high liquid crystal aligning ability under the light irradiation of low energy. The exposure of rectilinearly polarized light in aforementioned radiation line irradiating step is preferably 0.05~20J/cm², more preferably 0.5~10J/ cm².In addition, the wavelength of rectilinearly polarized light is preferably 200~400nm, more preferably 300~400nm.Rectilinearly polarized light is for film The irradiating angle on surface is not particularly limited, it is desirable to when showing strong orientation regulation power for liquid crystal, from shortening orientation process From the viewpoint of time, preferably as far as possible perpendicular to film surface.In addition, the liquid crystal orientation film of the present invention is by irradiating linear polarization Light and liquid crystal can be made to be orientated along the direction vertical with the polarization direction of rectilinearly polarized light.

The light source used in the rectilinearly polarized light of radiation or the irradiating step of unpolarized light can unrestrictedly use super High-pressure sodium lamp, high-pressure sodium lamp, low pressure mercury lamp, deep UV (Deep UV) lamp, Halogen lamp LED, metal halide lamp, high-power metal Halide lamp, xenon lamp, mercury xenon lamp, Excimer lamp, KrF PRKs, fluorescent lamp, LED, sodium vapor lamp, microwave-excitation without Electrod lamp etc..

The liquid crystal orientation film of the present invention can be fitted by further comprising the method for other steps outside abovementioned steps Locality is obtained.For example, in the liquid crystal orientation film of the present invention, with cleaning fluid to burn till or irradiation with radiation after film cleaned Step is not essential, and can set cleaning step according to the situation of other steps.

As the method cleaned using cleaning fluid, scrub, injection, steam purge or ultrasonic wave cleaning can be included Deng.These methods can be carried out individually, can also be applied in combination.As cleaning fluid, pure water or methanol can be used, ethanol, different Halogen-based solvent, acetone, the MEKs such as the aromatic hydrocarbon, dichloromethane such as the various alcohols such as propyl alcohol, benzene,toluene,xylene etc. Ketone, but it is not limited to them.Certainly, these cleaning fluids can use the few material of the impurity fully purified.This cleaning side Method can also be applied in the foregoing cleaning step when forming the liquid crystal orientation film of the present invention.

In order to improve the liquid crystal aligning ability of liquid crystal orientation film of the invention, before and after step is burnt till in heating, brushing step Rapid front and rear or polarised light or the irradiation with radiation of unpolarized light it is front and rear, can use based on heat, the annealing of light. In the annealing, annealing temperature is 30~180 DEG C, is preferably 50~150 DEG C, and the time is preferably 1 minute~2 hours.This Outside, the annealing light used in annealing can include UV lamp, fluorescent lamp, LED etc..The exposure of light is preferably 0.3~ 10J/cm²。

The thickness of liquid crystal orientation film of the present invention is not particularly limited, and preferably 10~300nm, more preferably 30~ 150nm.The thickness of the liquid crystal orientation film of the present invention can be surveyed using film thickness measuring device known to difference of height meter, ellipsometer etc. It is fixed.

The liquid crystal orientation film of the present invention is characterised by, with king-sized oriented anisotropic.It is this anisotropic The use polarised light IR that big I passes through the records such as Japanese Unexamined Patent Publication 2005-275364 method is evaluated.In addition, implementing as following Shown in example like that, it can also be evaluated by using the method for ellipsometer.Specifically, it can be determined by light splitting ellipsometer The length of delay of liquid crystal orientation film.The length of delay of film and the degree of orientation of main polymer chain proportionally increase.I.e. it is considered that：Have Big length of delay refers to the big degree of orientation, during as liquid crystal orientation film, and the alignment films with more large anisotropy are for liquid Crystal composite has big orientation regulation power.

The liquid crystal orientation film of the present invention can be suitably employed in the liquid crystal display cells of Transverse electric-field type.For transverse electric field During the liquid crystal display cells of mode, Pt angles are smaller or liquid crystal aligning ability is higher, then black display water in the dark state It is flat uprise, contrast is improved.Pt angles are preferably less than 0.1 °.

The liquid crystal orientation film of the present invention may be used also in addition to the orientation purposes available for liquid crystal display liquid-crystal composition For the orientation of control optical compensation material, other all liquid crystal materials.In addition, the alignment films of the present invention have it is big it is each to The opposite sex, therefore optical compensation material applications can be individually used for.

For the liquid crystal display cells of the present invention, it is described in detail.

The present invention provides a kind of liquid crystal display cells, and it possesses：It is oppositely disposed a pair of substrates, each in foregoing a pair of substrates From it is respective to being taken to the liquid crystal formed on face to the upper electrode formed to one or both of face, in foregoing a pair of substrates Foregoing liquid crystal alignment films in the liquid crystal layer formed to film and between foregoing a pair of substrates, the liquid crystal display cells are this The alignment films of invention.

As long as the electrode that former electrodes are formed in the one side of substrate is just not particularly limited.This electrode can be included Such as ITO, metal deposition film.In addition, electrode can be formed at the whole face in a face of substrate, it can also be formed as example scheming The intended shape of case.The foregoing intended shape of electrode can be included such as combed or broached-tooth design.Electrode can be formed at A substrate among a pair of substrates, can also be formed at two substrates.The generation type of electrode is because of the kind of liquid crystal display cells Class and it is different, such as in the case of IPS type liquid crystal display cells, electrode is configured on one of foregoing a pair of substrates, at it In the case of its liquid crystal display cells, foregoing a pair of substrates both on configure electrode.Formed on aforesaid base plate or electrode Foregoing liquid crystal alignment films.

Liquid crystal display layer is to utilize relative foregoing a pair of substrate clampings liquid-crystal composition in face for being formed with liquid crystal orientation film Form formed.For the formation of liquid crystal layer, particulate, resin sheet etc. can be used to be clamped in as needed foregoing a pair The sept of appropriate intervals is formed between substrate.

Liquid-crystal composition is not particularly limited, and it is positive or negative various liquid crystal combinations that can use dielectric constant anisotropy Thing.Dielectric constant anisotropy is that positive preferred liquid-crystal composition can include Japanese Patent 3086228, Japanese Patent 2635435th, Japanese Kohyo 5-501735, Japanese Unexamined Patent Publication 8-157826, Japanese Unexamined Patent Publication 8-231960, Japanese Unexamined Patent Publication 9- 241644 (EP885272A1), Japanese Unexamined Patent Publication 9-302346 (EP806466A1), Japanese Unexamined Patent Publication 8-199168 (EP722998A1), Japanese Unexamined Patent Publication 9-235552, Japanese Unexamined Patent Publication 9-255956, Japanese Unexamined Patent Publication 9-241643 (EP885271A1), Japanese Unexamined Patent Publication 10-204016 (EP844229A1), Japanese Unexamined Patent Publication 10-204436, Japanese Unexamined Patent Publication Liquid-crystal composition disclosed in 10-231482, Japanese Unexamined Patent Publication 2000-087040, Japanese Unexamined Patent Publication 2001-48822 etc..

Dielectric constant anisotropy makes to add more than a kind of optically active compound in positive or negative liquid-crystal composition Even.

Illustrated for foregoing dielectric constant anisotropy for negative liquid-crystal composition.As negative dielectric constant it is each to The liquid-crystal composition of the opposite sex, can include and for example contain the LCD compound selected from shown in following formula (NL-1) as the 1st composition The composition of at least one kind of liquid-crystal compounds in the group of thing.

Herein, R^1aAnd R^2aIt independently is the alkyl, the alkoxy of carbon number 1~12, carbon atom of carbon number 1~12 The alkenyl for the carbon number 2~12 that the alkenyl or at least one hydrogen of number 2~12 are replaced by fluorine, ring A²With ring B²It independently is 1, 4- cyclohexylenes, tetrahydrofuran -2,5- diyls, 1,3- dioxane -2,5- diyls, 1,4- phenylenes, the fluoro- 1,4- phenylenes of 2-, The fluoro- 1,4- phenylenes of 2,5- bis-, the fluoro- 1,4- phenylenes of 2,3- bis-, the chloro- 1,4- phenylenes of the fluoro- 3- of 2-, the fluoro- 6- methyl of 2,3- bis-- Isosorbide-5-Nitrae-phenylene, 2,6- naphthalene-diyls or 7,8- difluoro chromogen alkane -2,6- diyl, herein, ring A²With ring B²In at least 1 be 2, The fluoro- 1,4- phenylenes of 3- bis-, the chloro- 1,4- phenylenes of the fluoro- 3- of 2-, the fluoro- 6- methyl isophthalic acids of 2,3- bis-, 4- phenylenes or 7,8- difluoro colors Former alkane -2,6- diyl, Z¹It independently is singly-bound ,-(CH₂)₂-、-CH₂O- ,-COO- or-CF₂When O-, j are 1,2 or 3, j are 2 or 3, Any 2 ring A²It can be the same or different, any 2 Z¹It can be the same or different.

In order to improve dielectric constant anisotropy, ring A²With ring B²It is preferred that being respectively the fluoro- 1,4- phenylenes of 2,3- bis- or tetrahydrochysene Furans -2,5- diyl, in order to reduce viscosity, ring A²With ring B²It is preferred that being respectively 1,4- cyclohexylenes.

In order to improve dielectric constant anisotropy, Z¹Preferably-CH₂O-, in order to reduce viscosity, Z¹Preferably singly-bound.

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

As the concrete example of the liquid-crystal compounds shown in above-mentioned formula (NL-1), following formula (NL-1-1)~formula can be included (NL-1-32) compound shown in.

Herein, R^1aAnd R^2aIt independently is the alkyl, the alkoxy of carbon number 1~12, carbon atom of carbon number 1~12 The alkenyl for the carbon number 2~12 that the alkenyl or at least one hydrogen of number 2~12 are replaced by fluorine, ring A²¹, ring A²², ring A²³, ring B²¹ With ring B²²It independently is Isosorbide-5-Nitrae-cyclohexylene or Isosorbide-5-Nitrae-phenylene, Z¹¹And Z¹²It independently is singly-bound ,-(CH₂)₂-、-CH₂O- or- COO-。

In order to improve to stability of ultraviolet or heat etc., R^1aAnd R^2aThe preferably alkyl of carbon number 1~12, in addition, In order to improve the absolute value of dielectric constant anisotropy, R^1aAnd R^2aThe preferably alkoxy of carbon number 1~12.

Alkyl is preferably methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group.In order to reduce viscosity, alkyl More preferably ethyl, propyl group, butyl, amyl group or heptyl.

Alkoxy is preferably methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy or epoxide in heptan.In order to drop Low viscosity, alkoxy is more preferably methoxy or ethoxy.

Alkenyl is preferably vinyl, 1- acrylic, 2- acrylic, 1- cyclobutenyls, 2- cyclobutenyls, 3- cyclobutenyls, 1- amylenes Base, 2- pentenyls, 3- pentenyls, 4- pentenyls, 1- hexenyls, 2- hexenyls, 3- hexenyls, 4- hexenyls or 5- hexenyls. In order to reduce viscosity, alkenyl is more preferably vinyl, 1- acrylic, 3- cyclobutenyls or 3- pentenyls.In these alkenyls- CH=CH- preferably vertical structure configuration depends on the position of double bond.In order to reduce viscosity etc., for 1- acrylic, 1- cyclobutenyls, 1- It is preferably trans for the alkenyl of pentenyl, 1- hexenyls, 3- pentenyls, 3- hexenyls etc.For 2- cyclobutenyls, 2- amylenes It is preferably cis for the alkenyl of base, 2- hexenyls etc.In these alkenyls, compared with branched-chain alkenyl, preferably straight-chain alkenyl.

The preference for the alkenyl that at least one hydrogen is replaced by fluorine is 2,2- difluoroethylenes base, the fluoro- 2- propylene of 3,3- bis- The fluoro- 3- cyclobutenyls of base, 4,4- bis-, the fluoro- 4- pentenyls of 5,5- bis- and the fluoro- 5- hexenyls of 6,6- bis-.In order to reduce viscosity, further It is preferred that example be 2,2- difluoroethylenes base and the fluoro- 3- cyclobutenyls of 4,4- bis-.

In order to reduce viscosity, ring A²¹, ring A²², ring A²³, ring B²¹With ring B²²It is preferred that being respectively 1,4- cyclohexylenes.

In order to improve dielectric constant anisotropy, Z¹¹And Z¹²Preferably-CH₂O-, in order to reduce viscosity, Z¹¹And Z¹²It is preferred that For singly-bound.

In the foregoing liquid-crystal composition with negative dielectric constant anisotropy, as the 1st composition it is preferred that formula (NL- 1) compound shown in is the compound shown in formula (NL-1-1), formula (NL-1-4), formula (NL-1-7) and formula (NL-1-32).

As the preference of the liquid-crystal composition of the foregoing dielectric constant anisotropy for having and bearing, Japanese Unexamined Patent Publication can be included Clear 57-114532, Japanese Unexamined Patent Publication 2-4725, Japanese Unexamined Patent Publication 4-224885, Japanese Unexamined Patent Publication 8-40953, Japanese Unexamined Patent Publication 8-104869, Japanese Unexamined Patent Publication 10-168076, Japanese Unexamined Patent Publication 10-168453, Japanese Unexamined Patent Publication 10-236989, Japanese Unexamined Patent Publication Flat 10-236990, Japanese Unexamined Patent Publication 10-236992, Japanese Unexamined Patent Publication 10-236993, Japanese Unexamined Patent Publication 10-236994, Japan Unexamined Patent 10-237000, Japanese Unexamined Patent Publication 10-237004, Japanese Unexamined Patent Publication 10-237024, Japanese Unexamined Patent Publication 10-237035, Japanese Unexamined Patent Publication 10-237075, Japanese Unexamined Patent Publication 10-237076, Japanese Unexamined Patent Publication 10-237448 (EP967261A1), Japan Unexamined Patent 10-287874, Japanese Unexamined Patent Publication 10-287875, Japanese Unexamined Patent Publication 10-291945, Japanese Unexamined Patent Publication 11-029581, Japanese Unexamined Patent Publication 11-080049, Japanese Unexamined Patent Publication 2000-256307, Japanese Unexamined Patent Publication 2001-019965, Japanese Unexamined Patent Publication 2001- 072626th, Japanese Unexamined Patent Publication 2001-192657, Japanese Unexamined Patent Publication 2010-037428, International Publication 2011/024666, International Publication 2010/072370th, disclosed in special table 2010-537010, Japanese Unexamined Patent Publication 2012-077201, Japanese Unexamined Patent Publication 2009-084362 etc. Liquid-crystal composition.

In addition, for example, in liquid-crystal composition for element of the present invention, such as, can from the viewpoint of orientation is improved Further to add additive.This additive is photopolymerization monomer, optically active compound, antioxidant, ultraviolet Absorbent, pigment, defoamer, polymerization initiator, polymerization inhibitor etc..

In order to improve the orientation of liquid crystal, as the most preferred configuration of photopolymerization monomer or oligomer, formula can be included (PM-1-1) structure shown in~formula (PM-1-6).

On photopolymerization monomer or oligomer, in order that they show to determine the effect of liquid crystal tilt direction after polymerisation Really, it is desired for more than 0.01 weight %.In addition, in order to they polymerize after make polymer orientation effect become it is appropriate or In order to avoid unreacted monomer or oligomer dissolution to liquid crystal after uv irradiation, it is desired for below 30 weight %.

Assign torsion angle in order to induce the helical structure of liquid crystal and into composition hybrid optical activity compound.This It is the compound shown in formula (PAC-1-1)~formula (PAC-1-4) to plant the example of compound.

Optically active compound is preferably in a proportion of below 5 weight %.Further preferred ratio is 0.01 weight % ~2 weight % scope.

In order to prevent that resistivity is reduced caused by the heating in air, or in order to be used for a long time after element in room temperature Big voltage retention is maintained under lower and high temperature and antioxidant is mixed into liquid-crystal composition.

The preference of antioxidant is compound shown in the formula (AO-1) for the integer that w is 1~10 etc..In formula (AO-1), w Preferably 1,3,5,7 or 9.W is more preferably 1 or 7.W is big for the volatility of the compound shown in 1 formula (AO-1), therefore, Prevent that when resistivity is reduced caused by the heating in air be effective.W is the volatilization of the compound shown in 7 formula (AO-1) Property it is small, therefore, for be used for a long time element after at room temperature be effective for the voltage retention for remaining big under high temperature 's.On the preferred proportion of antioxidant, be more than 50ppm to obtain its effect, in order to do not reduce ceiling temperature or Do not improve lower limit temperature and be below 600ppm.Further preferred ratio is 100ppm~300ppm scope.

The preference of ultra-violet absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc..Have The light stabilizer of sterically hindered amine etc is also preferred.On these absorbents, the preferred proportion of stabilizer, in order to obtain Its effect and be more than 50ppm, be below 10000ppm to do not reduce ceiling temperature or not improve lower limit temperature.Enter one The scope that the preferred ratio of step is 100ppm~10000ppm.

In order to meet GH (hosts and guests；Guest host) pattern element, in the composition mix azo system pigmen, anthraquinone system The dichroism pigment (dichroic dye) of pigment or the like.The model for being preferably in a proportion of the weight % of 0.01 weight %~10 of pigment Enclose.

In order to prevent foaming, the defoamers such as dimethicone, methyl phenyl silicone oil are mixed in the composition.On defoamer Preferred proportion, be more than 1ppm to obtain its effect, in order to prevent display bad and be below 1000ppm.Further It is preferred that ratio be 1ppm~500ppm scope.

In order to meet PSA, (polymer stabilizing is orientated；Polymer sustained alignment) pattern element, can The compound that can polymerize is mixed in the composition.The preferred example for the compound that can polymerize is acrylate, metering system Acid esters, vinyl compound, ethyleneoxy compounds, propylene ether, epoxide (oxirane, oxetanes), ethene Base ketone etc. has the compound for the group that can polymerize.More preferred example is the derivative of acrylate or methacrylate Thing.The example of this compound is the compound shown in formula (PM-2-1)~formula (PM-2-9).On the compound that can polymerize Preferred proportion, in order to obtain its effect and about more than 0.05 weight %, in order to prevent display bad and about 10 weight % Below.Further preferred ratio is the weight % of about 0.1 weight %~about 2 scope.

Herein, R^3a、R^4a、R^5aAnd R^6aIt independently is acryloyl group or methylacryloyl, R^7aAnd R^8aIt independently is hydrogen, halogen The alkyl of element or carbon number 1~10, Z¹³、Z¹⁴、Z¹⁵And Z¹⁶The alkylidene of singly-bound or carbon number 1~12 independently is, at least 1-CH₂- optionally replaced by-O- or-CH=CH-, s, t and u are each independently 0,1 or 2.

Free radical or ion are produced come necessary material for triggering chain polymerization to react as easy, can be mixed poly- Close initiator.For example, as the Irgacure651 (registration mark) of Photoepolymerizationinitiater initiater, Irgacure184 (registration mark) or Darocure1173 (registration mark) (Ciba Japan K.K.) is suitable for radical polymerization.It can polymerize Compound preferably includes Photoepolymerizationinitiater initiater with the weight % of 0.1 weight %~5 scope.Particularly preferably with the weight of 1 weight %~3 The scope for measuring % includes Photoepolymerizationinitiater initiater.

For radical polymerization system, in order to being reacted rapidly by the free radical of polymerization initiator or monomer generation And be transformed into the free radical or neutral compound of stabilization to terminate polymerisation, polymerization inhibitor can be mixed.Polymerization inhibitor is in structure On be classified as it is several.One of which is oneself of its own stabilization of three p-nitrophenyl ylmethyls, two p-fluorophenyl amine or the like By base, it is another be easily with the radical reaction that exists in polymerization system and be converted into the material of stabilized radical, it is represented For nitro, nitroso, amino, polyol etc..As the representative of the latter, quinhydrones, dimethoxy benzene etc. can be included.Close In the preferred proportion of polymerization inhibitor, be more than 5ppm to obtain its effect, in order to prevent display bad and be 1000ppm with Under.Further preferred ratio is 5ppm~500ppm scope.

The liquid crystal display cells of the present invention, can by using the liquid-crystal composition for possessing negative dielectric constant anisotropy Image retention excellent and the good liquid crystal display cells of orientation stability are provided.

Embodiment

Hereinafter, the present invention is illustrated by embodiment.It should illustrate, the evaluation method used in embodiment is as follows.

1. weight average molecular weight (Mw)

The weight average molecular weight of polyamic acid uses 2695Separations Module2414 differential refractometers (Waters Company system) it is measured by GPC method, obtained by polystyrene conversion.Gained polyamic acid is mixed with phosphoric acid-DMF Solution (phosphoric acid/DMF=0.6/100：Weight ratio) it is diluted, so that polyamic acid concentration reaches about 2 weight %.Post is used HSPgel RT MB-M (Waters company systems), using foregoing mixed solution as eluant, eluent, in 50 DEG C of column temperature, flow velocity 0.40mL/ It is measured under conditions of min.Polystyrene standard has used the TSK polystyrene standards that TOSOH Co., Ltd manufactures.

2. voltage retention

Carried out according to the method for " water island and other people, the pre- original text collection p78 (1988) of the 14th liquid crystal discussion " record.Survey It is fixed to be carried out by applying wave height ± 5V square wave to unit.Determine and carried out at 60 DEG C.The value is to represent applied electricity The index of which kind of degree can be kept by being pressed in after the frame period, represent that all electric charges are maintained if the numerical value is 100%. If more than 99.5%, then as the good liquid crystal display cells of display quality.

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

The method recorded according to Applied Physics the 65th volume No. 10 page 1065 (1996), uses TOYO Corporation The type of liquid crystal physical property measurement system 6254 of manufacture is measured.Frequency of use is 0.05Hz triangular wave, in ± 2V voltage model Enclose, be measured that (area of electrode is 1cm under temperature 60 C²).If ion concentration is big, easily produced because of ionic impurity A problem that ghost.That is, ion concentration is to turn into the physics value for the index that prediction ghost occurs.If the value is below 40pC, Then turn into the good liquid crystal display cells of display quality.

METHYLPYRROLIDONE：NMP

Gamma-butyrolacton：GBL

Butyl cellosolve (ethylene glycol monobutyl ether)：BC

The preparation of [embodiment 1] varnish

Compound DI-5-1 (m are put into the 200mL eggplant type flasks for be provided with thermometer, nitrogen blow valve port and stirring rod =1) 1.2698g, using Japanese Unexamined Patent Application 50-19897 record method synthesis formula (1) shown in compound 2.0774g, add Plus NMP 59.0g and GBL 15.0g.Solution is cooled to less than 5 DEG C, thereto the compound shown in throw-in type (AN-3-2) Compound 1.2560g shown in 1.3969g, formula (PA-1), is further stirred at room temperature 6 hours.Addition butyl is molten thereto Fine agent (BC) 20.0g, heating stirring is carried out with 70 DEG C untill the viscosity of solution reaches about 35.0mPas, so as to be consolidated Body composition is 6wt% varnish 1.The weight average molecular weight (Mw) of the varnish is 67000.

[2~embodiment of embodiment 23 and comparative example 1~5]

According to the method described in embodiment 1, the varnish that following solid constituents are 6wt% is obtained.By the composition of gained varnish, Weight average molecular weight (Mw) is shown in table 1-1 and table 1-2.Embodiment 1 is recorded again.[] interior each comfortable tetracarboxylic compound group of expression, Mol ratio in diamine compound group.

[table 1-1]

[table 1-2]

[embodiment 24]

10g varnish 1 is weighed into 50mL eggplant type flasks, 10g METHYLPYRROLIDONE and 10g is thereto added Butyl cellosolve, vibrates 2 hours and obtains the aligning agent for liquid crystal 1 that solid constituent is 3wt%.Using spin-coating method by the alignment agent 1 It is coated on the glass substrate of subsidiary ITO electrode and the glass substrate (2000rpm, 15 seconds) of subsidiary intercolumniation parting/ITO electrode.Apply After film with 80 DEG C of pre-fireds about 5 minutes after, carry out burning till processing in 30 minutes with 200 DEG C, so that it is about 100nm's to form thickness Liquid crystal orientation film.The brushing processing unit manufactured using Iinuma Gauge Manufacturing Co., Ltd.s, in brushing cloth (bristle lengths are 1.9mm：Artificial silk) bristle lengths intrusion be that 0.40mm, pedestal translational speed are 60mm/sec, roller rotation Rotary speed be 1000rpm under conditions of, to gained polyimide film carry out brushing processing.By gained substrate ultrasonic wave in ethanol After cleaning 5 minutes, surface is cleaned with ultra-pure water, is then dried 30 minutes with 120 DEG C in an oven.Taken for being formed with substrate To 2 plate bases of film, make the face for being formed with alignment films relative, glued in the mode that the brushing direction of respective alignment films is parallel Patch, so as to be assembled into the dummy cell that element thickness is 4 μm.The following positive type liquid crystal combinations of vacuum injection into made dummy cell Thing A, inlet is sealed with light curing agent.Then, with the heating of 110 DEG C of progress 30 minutes, so as to make measure liquid crystal Unit.

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

The voltage retention of gained measure unit is 99.8% under 5V, 30Hz, and ion concentration is 10pC.By the unit In backlight testing machine (electric flux industry Co. Ltd. system, the high-brightness LED panel transmission illuminator LPM-S-A4H lighted；Brightness For 12000cd/m²) on load 500 hours, carry out reliability test.The voltage of measure unit after reliability test is kept Rate is 99.7%, and ion concentration is 20pC.

[embodiment 25~46 and comparative example 6~8]

For varnish 2~23 and varnish C1~C3, the method also recorded according to embodiment 24 carries out the system of aligning agent for liquid crystal Standby, unit making and voltage retention, the measure of ion concentration.Show the result in table 2.The knot of embodiment 24 is recorded again Really.

[table 2]

In the whole results of liquid crystal display cells for having used aligning agent for liquid crystal 1~23, it is after initial, reliability test Good result.In the liquid crystal display cells for having used aligning agent for liquid crystal C1~C3, voltage retention and ion concentration it is initial Value is that bad result is presented after good result, but 500 hours.

[embodiment 47~89 and comparative example 9~13]

In addition to change tetracarboxylic dianhydride and diamines, it is 6 weights to prepare polymer solids constituent concentration according to embodiment 1 Measure % 24~varnish of varnish 66 and varnish C6~10.On weight average molecular weight, the raw material with photoisomerization structure is used Polymer adjusted to about 11000~13000, adjust to 40000 without using the polymer of the raw material with photoisomerization structure~ 50000.The weight average molecular weight of the tetracarboxylic dianhydride used and diamines and resulting polymers are shown in table 3-1~table 3-4.

[table 3-1]

[table 3-2]

[table 3-3]

[table 3-4]

The preparation, the making of electrical characteristics determining unit and electrical characteristics determining of [embodiment 90] single-layer type alignment agent

Synthesized to weighing 10.0g in the 50mL eggplant type flasks of stirring vane, nitrogen ingress pipe is provided with by embodiment 47 Varnish 24, thereto add METHYLPYRROLIDONE 5.0g and butyl cellosolve 5.0g, be stirred at room temperature 1 hour, from And obtain the alignment agent 24 that resin component concentration is 3 weight %.The alignment agent is coated on subsidiary ITO electrode using spin-coating method Glass substrate and the glass substrate of subsidiary intercolumniation parting/ITO electrode (2000rpm, 15 seconds).After coating, substrate is added with 80 DEG C Heat 3 minutes and make solvent evaporate after, the Multi-Light ML-501C/B manufactured using USHIO INC., from perpendicular to substrate Direction across polarizer irradiation ultraviolet radiation rectilinearly polarized light.Exposure energy now using USHIO INC. manufacture it is ultraviolet Line accumulated light meter UIT-150 (light-receiving devices：UVD-S365 light quantity) is determined, 1.3 are reached with the energy under wavelength 365nm ± 0.1J/cm²Mode adjust the time for exposure.Then, with 230 DEG C in dustless baking oven (ESPEC Co., Ltd.s, PVHC-231) Heat 15 minutes, so as to form the alignment films that thickness is 100 ± 10nm.By 2 plate bases for being formed with these alignment films with The face for being formed with alignment films is relative, and module units thickness is 4 μm of dummy cell.Into made dummy cell, vacuum injection is following Positive type liquid crystal composition A, inlet is sealed with light curing agent.Then, with the heating of 110 DEG C of progress 30 minutes, so as to make As measure liquid crystal cells.

The voltage retention of the liquid crystal cells is 99.8% under 5V-30Hz, and ion concentration is 10pC.By the unit in point Bright backlight testing machine (electric flux industry Co. Ltd. system, high-brightness LED panel transmission illuminator LPM-S-A4H；Brightness is 12000cd/m²) on load 500 hours, carry out reliability test.The voltage retention of measure unit after reliability test For 99.7%, ion concentration is 30pC.

[embodiment 91~102 and comparative example 14~16]

In addition to varnish used in change, liquid crystal cells are made according to embodiment 90, are carried out before reliability test Voltage retention, the measure of ion concentration afterwards.Measurement result and embodiment 90 are shown in table 4 in the lump.

[table 4]

For all units of embodiment 91~102, the value after initial value, reliability test can be obtained well Result.Herein, initial value refers to determine obtained result with not being placed in above-mentioned backlight testing machine after production unit.For than For unit compared with example 14~16, the initial value of voltage retention ion concentration can obtain good result, but voltage is protected The result of difference is presented in value of the holdup ion concentration after reliability test.

The preparation, the making of electrical characteristics determining unit and electrical characteristics determining of [embodiment 103] blending type alignment agent

Weigh what 2.0g was synthesized by embodiment 47 to being provided with the 50mL eggplant type flasks of stirring vane, nitrogen ingress pipe The varnish 58 that varnish 24 and 8.0g are synthesized by embodiment 81, adds METHYLPYRROLIDONE 5.0g thereto and butyl is molten Fine agent 5.0g, is stirred at room temperature 1 hour, so as to obtain the alignment agent 46 that resin component concentration is 3 weight %.According to embodiment 90 methods recorded make liquid crystal cells.The voltage retention of the liquid crystal cells is 99.8% under 5V-30Hz, and ion concentration is 10pC.The voltage retention of measure unit after reliability test is 99.7%, and ion concentration is 15pC.

[embodiment 104~150 and comparative example 17~19]

In addition to varnish used in change, liquid crystal cells are made according to embodiment 103, are carried out before reliability test Voltage retention, the measure of ion concentration afterwards.Used varnish and measurement result are shown in table 5- in the lump with embodiment 103 1 and table 5-2.It should illustrate, the varnish A in table is represented containing the clear of the polymer using the raw material with photoisomerization structure Paint, varnish B represents the varnish containing the polymer without using the raw material with photoisomerization structure.

[table 5-1]

[table 5-2]

In all units of embodiment 103~150, the value after initial value, reliability test can obtain good knot Really.Herein, initial value refers to determine obtained result with not being placed in above-mentioned backlight testing machine after production unit.For comparative example For 17~19 unit, the initial value of voltage retention ion concentration can obtain good result, but voltage is kept Bad result is presented in value of the rate ion concentration after reliability test.

It can be seen from above-described embodiment：Possesses the liquid crystal display of the liquid crystal orientation film formed by the aligning agent for liquid crystal of the present invention Element turns into can also keep the liquid crystal display cells of good display quality in backlight after long-time.

Industrial applicability

The liquid crystal orientation film formed by using the aligning agent for liquid crystal by the present invention, it is used even if resulting in for a long time The excellent liquid crystal display cells that display quality will not also be reduced.Especially, it is applicable to the liquid crystal as Transverse electric-field type Show IPS patterns, the FFS mode of element.

Claims

1. a kind of polyamic acid or derivatives thereof, it is to make tetracarboxylic dianhydride and include the diamine reactant of compound shown in formula (1) Obtained from,

2. polyamic acid according to claim 1 or derivatives thereof, wherein, tetracarboxylic dianhydride is selected from following formula (AN-I) It is at least one kind of in the group of tetracarboxylic dianhydride shown in~formula (AN-VII),

It is selected from by following formula (DI-1)~formula (DI-16), formula with other diamines that the diamines shown in formula (1) is used together It is (DIH-1) at least one kind of in~formula (DIH-3) and the group of formula (DI-31)~formula (DI-35) composition,

In formula (AN-III)~formula (AN-V), ring A¹⁰Monocyclic alkyl or carbon number 6~30 for carbon number 3~10 it is thick At least one hydrogen closed on polycycle alkyl, the group is optionally replaced by methyl, ethyl or phenyl, and the key being connected with ring is connected to Any carbon of ring is constituted, 2 key options are connected to same carbon；

In formula (DI-1), G²⁰For-CH₂-, at least one-CH₂- optionally replaced by-NH- ,-O-, m is 1~12 integer, alkylidene On at least one hydrogen optionally by-OH replace；

In formula (DI-3) and formula (DI-5)~formula (DI-7), G²¹It independently is 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 ' 1~12 integer independently is, k is 1~5 integer, and n is 1 or 2；

In formula (DI-4), s independently is 0~2 integer；

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

In formula (DI-2)~formula (DI-7), at least one hydrogen on cyclohexane ring and phenyl ring is optionally by-F ,-Cl, carbon number 1~3 Alkyl ,-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl substitution, also, in formula (DI-4), phenyl ring On at least one hydrogen be optionally selected from a kind in the group of the group shown in following formula (DI-4-a)~formula (DI-4-e) substitution；

The bonding position that the loose group of bonding position on the carbon atom for constituting ring represents on the ring be it is arbitrary ,- NH₂Bonding position on cyclohexane ring or phenyl ring is except G²¹Or G²²Bonding position outside optional position；

In formula (DI-11), r is 0 or 1；

In formula (DI-12), R²¹And R²²It independently is the alkyl or phenyl of carbon number 1~3, G²³Independently be carbon number 1~ 6 alkylidene, phenylene or by alkyl-substituted phenylene, w is 1~10 integer；

In formula (DI-13), R²³The alkyl, the alkoxy of carbon number 1~5 or-Cl, p for independently being carbon number 1~5 are independent Ground is 0~3 integer, and q is 0~4 integer；

In formula (DI-14), ring B is monocyclic heteroaromatic, R²⁴For hydrogen ,-F ,-Cl, the alkyl of carbon number 1~6, carbon number 1~6 alkoxy, the alkenyl of carbon number 2~6, the alkynyl of carbon number 2~6, q independently are 0~4 integer；

In formula (DI-15), ring C is comprising heteroatomic monocyclic；

In formula (DI-13)~formula (DI-16), the loose group of bonding position on the carbon atom for constituting ring is represented in the ring On bonding position be arbitrary；

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

In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, at least one hydrogen on these rings optionally by methyl, ethyl or Phenyl replaces；

In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, at least one hydrogen on these rings optionally by methyl, Ethyl or phenyl substitution, Y is singly-bound, the alkylidene of carbon number 1~20 ,-CO- ,-O- ,-S- ,-SO₂-、-C(CH₃)₂- or-C (CF₃)₂-；

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、-CF₂O-、- OCF₂- or-(CH₂)_m’-, m ' is 1~12 integer, R²⁵For the alkyl of carbon number 3~30, phenyl, with steroid skeleton In group shown in group or following formula (DI-31-a), the alkyl, at least one hydrogen is optionally replaced by-F, and at least one- CH₂- optionally replaced by-O- ,-CH=CH- or-C ≡ C-, the hydrogen on the phenyl is optionally by-F ,-CH₃、-OCH₃、-OCH₂F、- OCHF₂、-OCF₃, carbon number 3~30 alkyl or carbon number 3~30 alkoxy substitution ,-the NH being bonded on phenyl ring₂ Bonding position represent the optional position on the ring,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For linking group, they independently are the alkylene of singly-bound or carbon number 1~12 More than 1-CH in base, the alkylidene₂- optionally replaced by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH-, ring B²¹, ring B²², ring B²³With ring B²⁴It independently is 1,4- phenylenes, 1,4- cyclohexylenes, 1,3- dioxane -2,5- diyls, pyrimidine -2,5- two Base, pyridine -2,5- diyl, piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -2,7- diyl or anthracene -9,10- diyl, ring B²¹, ring B²², ring B²³With ring B²⁴In, at least one hydrogen is optionally by-F or-CH₃Substitution, s, t and u independently are 0~2 integer, and they are closed 1~5, when s, t or u are 2 is calculated as, 2 linking groups in each parantheses can be the same or different, and 2 rings can be with identical Can also be different,

R²⁶For fluorine substitution alkyl, the carbon number 1~30 of hydrogen ,-F ,-OH, the alkyl of carbon number 1~30, carbon number 1~30 Alkoxy ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, at least one-CH in the alkyl of the carbon number 1~30₂- optional quilt Divalent group displacement shown in following formula (DI-31-b),

In formula (DI-32) and formula (DI-33), the loose group of bonding position on any carbon atom for constituting ring is represented Bonding position on the ring is arbitrary；

In formula (DI-34) and formula (DI-35), G³¹It independently is the alkylidene of-O- ,-NH- or carbon number 1~6, G³²For singly-bound Or the alkylidene of carbon number 1~3,

R³¹For hydrogen or the alkyl of carbon number 1~20, at least one-CH in the alkyl₂- optionally by-O- ,-CH=CH- or-C ≡ C- are replaced, R³²For the alkyl of carbon number 6~22, R³³For hydrogen or the alkyl of carbon number 1~22, ring B²⁵For the sub- benzene of 1,4- Base or Isosorbide-5-Nitrae-cyclohexylene, r are 0 or 1, also ,-the NH being bonded on phenyl ring₂Represent that the bonding position on the ring is any 's.

3. polyamic acid according to claim 2 or derivatives thereof, wherein, tetracarboxylic dianhydride is selected from following formula (AN-1- 1), formula (AN-1-2), formula (AN-1-13), formula (PA-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4- 17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3) it is, at least one kind of in formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4)；

It is selected from by following formula (DI-1-3), formula (DI-2-1), formula with other diamines that the diamines shown in formula (1) is used together (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), Formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI- 7-3), in the group of formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1) and formula (DI-31-56) composition It is at least one kind of,

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

In formula (DI-5-30), k is 1~5 integer；Also,

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

4. according to polyamic acid according to any one of claims 1 to 3 or derivatives thereof, wherein, tetracarboxylic dianhydride and diamines In at least 1 include with photoreactivity structure compound.

5. polyamic acid according to claim 4 or derivatives thereof, wherein, photoreactivity structure is selected from by following formula It is (P-1) at least one kind of in the group of the structure composition shown in~formula (P-7),

6. polyamic acid according to claim 4 or derivatives thereof, wherein, the compound with photoreactivity structure is choosing Free following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1)~formula It is (V-3) at least one kind of and in formula (VI-1), the group of formula (VI-2) composition,

It is above-mentioned it is various in, constitute ring any carbon atom on the loose group of bonding position represent the bonding on the ring Position is arbitrary, in formula (V-2), R⁶It independently is-CH₃、-OCH₃、-CF₃Or-COOCH₃, a be each independently 0~2 it is whole Number, in formula (V-3), ring A and ring B be each independently it is at least one kind of in monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle, R¹¹For the straight-chain alkyl-sub of carbon number 1~20 ,-COO- ,-OCO- ,-NHCO- or-N (CH₃) CO-, R¹²For carbon number 1~ 20 straight-chain alkyl-sub ,-COO- ,-OCO- ,-NHCO- or-N (CH₃) CO-, R¹¹And R¹²In, 1 or 2 on straight-chain alkyl-sub Individual-CH₂- optionally replaced by-O-, R⁷~R¹⁰It is each independently-F ,-CH₃、-OCH₃、-CF₃Or-OH, also, b~e is each only On the spot be 0~4 integer.

7. polyamic acid according to claim 4 or derivatives thereof, wherein, under the compound with photoreactivity structure is The diamines shown in formula (PDI-7) is stated,

In formula (PDI-7), R⁵¹It is each independently-CH₃、-OCH₃、-CF₃Or-COOCH₃, s be each independently 0~2 it is whole Number.

8. a kind of aligning agent for liquid crystal, it contains polyamic acid according to any one of claims 1 to 7 or derivatives thereof.

9. aligning agent for liquid crystal according to claim 8, it, which also contains, is selected from You oxazine compounds, oxazoline compounds, ring It is at least one kind of in the compound group of oxygen compound and silane coupler composition.

10. a kind of liquid crystal orientation film, it is formed as the aligning agent for liquid crystal described in claim 8 or 9.

11. a kind of driving liquid crystal orientation film used for liquid crystal display element of transverse electric field, it is as the liquid described in claim 8 or 9 Brilliant alignment agent formation.

12. a kind of liquid crystal display cells, it has the liquid crystal orientation film described in claim 10 or 11.

13. a kind of light orientation aligning agent for liquid crystal, it includes polymer [A] and polymer [B], the polymer [A] and polymerization Thing [B] is polyamic acid or derivatives thereof,

At least 1 in the starting monomer of the polymer have photoreactivity structure, and the starting monomer bag of the polymer Containing the compound shown in following formula (1),

14. light orientation aligning agent for liquid crystal according to claim 13, it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

The polymer [A] is the tetrabasic carboxylic acid two obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines At least 1 in acid anhydride and diamines include the compound with photoreactivity structure,

The polymer [B] is the tetrabasic carboxylic acid two obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines Acid anhydride and diamines do not have photoreactivity structure and diamines is comprising at least one kind of in compound shown in formula (1).

15. light orientation aligning agent for liquid crystal according to claim 13, it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

The polymer [A] is the tetrabasic carboxylic acid two obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines At least 1 in acid anhydride and diamines, which include compound and diamines with photoreactivity structure, includes compound shown in formula (1),

The polymer [B] is the tetrabasic carboxylic acid two obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines Acid anhydride and diamines do not have photoreactivity structure.

16. light orientation aligning agent for liquid crystal according to claim 13, it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

The polymer [B] is the tetrabasic carboxylic acid two obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines Acid anhydride and diamines are without photoreactivity structure and diamines includes compound shown in formula (1).

17. light orientation aligning agent for liquid crystal according to claim 13, it includes at least one kind of polymer [A] and at least one kind of Polymer [B],

The polymer [B] is the tetrabasic carboxylic acid two obtained from making the starting monomer reaction comprising tetracarboxylic dianhydride and diamines At least 1 in acid anhydride and diamines, which include compound and diamines with photoreactivity structure, includes compound shown in formula (1).

18. the light orientation aligning agent for liquid crystal according to any one of claim 13~17, wherein, with photoreactivity knot The compound of structure have it is at least one kind of in following formula (P-1)~structure shown in formula (P-7),

19. the light orientation aligning agent for liquid crystal according to any one of claim 13~17, wherein, with photoreactivity knot The compound of structure is selected from by following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV- It is 2), at least one kind of in formula (V-1)~formula (V-3) and formula (VI-1), the group of formula (VI-2) composition,

20. the light reaction aligning agent for liquid crystal according to any one of claim 13~17, wherein, with photoreactivity knot The compound of structure is the diamines shown in following formula (PDI-7),

21. the light orientation aligning agent for liquid crystal according to any one of claim 13~20, wherein, without photoreactivity The tetracarboxylic dianhydride of structure is at least 1 in the group selected from the tetracarboxylic dianhydride shown in following formula (AN-I)~formula (AN-VII) Kind,

Diamines without photoreactivity structure is selected from by following formula (DI-1)~formula (DI-16), formula (DIH-1)~formula It is (DIH-3) at least one kind of and in the group of formula (DI-31)~formula (DI-35) composition,

In formula (DI-4), s independently is 0~2 integer；

In formula (DI-11), r is 0 or 1；

In formula (DI-15), ring C is comprising heteroatomic monocyclic；

22. light orientation aligning agent for liquid crystal according to claim 21, wherein, the tetrabasic carboxylic acid without photoreactivity structure Dianhydride is selected from following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-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), in formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4) at least 1 kind；

Diamines without photoreactivity structure is 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-5-5), formula (DI-5-9), formula (DI-5- 12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), at least 1 in the group of formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1) and formula (DI-31-56) composition Kind,

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

In formula (DI-5-30), k is 1~5 integer；Also,

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

23. the aligning agent for liquid crystal according to any one of claim 13~22, it, which also contains, is selected from You oxazine compounds, Evil It is at least one kind of in the compound group of isoxazoline compound, epoxide and silane coupler composition.

24. a kind of liquid crystal orientation film, it is formed as the aligning agent for liquid crystal any one of claim 13~23.

25. a kind of driving liquid crystal orientation film used for liquid crystal display element of transverse electric field, it is any in claim 13~23 What the aligning agent for liquid crystal described in was formed.

26. a kind of liquid crystal display cells, it has the liquid crystal orientation film described in claim 24 or 25.