CN106916307A

CN106916307A - Diamines, polyamic acid or derivatives thereof, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Info

Publication number: CN106916307A
Application number: CN201611008166.3A
Authority: CN
Inventors: 塚田裕以智; 藤马大亮; 瓜生阳; 瓜生阳一; 伊泽启介
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: Changsha Dao'anjie New Materials Co ltd
Priority date: 2015-11-16
Filing date: 2016-11-16
Publication date: 2017-07-04
Anticipated expiration: 2036-11-16
Also published as: JP6520657B2; CN106916307B; JP2017088801A

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 make polyamic acid or derivatives thereof obtained from least a kind in tetracarboxylic dianhydride and diamines shown in contained (1) of diamine reactant.Possesses following feature with the liquid crystal display cells of the liquid crystal orientation film formed containing the aligning agent for liquid crystal of aforementioned polymer are used：Viewing angle characteristic is excellent, even if exposed to high light, its display quality will not also be reduced for a long time.In formula (1), R is the alkoxy of hydrogen, OH, the alkyl of carbon number 1~6 or carbon number 1~6, X¹And X²It is each independently the divalent organic group of alkylidene and/or phenylene with carbon number 1~8.

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) being used for the polyamic acid and its derivative of raw material, containing the polyamide Acid and its aligning agent for liquid crystal, the liquid crystal display cells of derivative.

Background technology

In the current liquid crystal display cells generally circulated in the form of the product, used the display element of nematic crystal into It is 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, in order to improve as this The visual angle of one of problem points of a little patterns is narrow, it is proposed that used the TN types liquid crystal display cells of optical compensation films, incited somebody to action vertical MVA (multidomain vertical orientation, Multi-domain Vertical that orientation is used with the technical combinations of raised structures thing Alignment) IPS (in-plane switching, In-Plane Switching) pattern, the FFS (sides of pattern or Transverse electric-field type 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, also passed through The improvement element member of formation that is used is realized.Among the member of formation that liquid crystal display cells are used, 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 Can gradually become important.

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

In industrial aspect, 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 to liquid crystal orientation film is entered The treatment that row rubs along a direction, thus, it is possible to obtain being uniformly directed for liquid crystal molecule.

Additionally, orientation position logos of brushing method as an alternative, it is possible to use irradiation light and implement the light orientation of orientation process Facture.For light orientation position logos, it is proposed that various 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 Can make liquid crystal display cells that the reason for showing bad etc. occurs.

The purposes of liquid crystal display cells throughout personal computer display, liquid crystal TV set, mobile phone, smart mobile phone it is aobvious Show the multiple fields such as portion, liquid crystal projection apparatus.In recent years, it is contemplated that the improvement of display quality, the use in outdoor, also existing makes into For the brightness of the backlight of light source is higher than conventional purposes, even if seeking for a long time, exposed to high light, its display quality will not also be reduced Liquid crystal display cells.

In response to this requirement, liquid crystal orientation film has been also carried out it is various study intensively, such as known following methods：Make raw material Comprising the diamines with the structure of hindered amine, hindered phenol structure, to the mutually isostructural method of importing in polyimides chain (with reference to patent Document 6.)；By the antioxidant with the structure of hindered amine, hindered phenol structure added to the method in aligning agent for liquid crystal (with reference to specially Sharp document 7.)；To method (the reference patent document 8 that the structure of hindered amine is imported in the side chain position of side chain type diamine.).However, For the influence that the above method is caused to viewing angle characteristic, image retention characteristic, not yet studied in detail.

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 2010-244015

Patent document 7：Japanese Unexamined Patent Publication 2013-127597

Patent document 8：International Publication 2008/078629

Non-patent literature

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

The content of the invention

Problems to be solved by the invention

Problem of the invention is, there is provided even if the liquid crystal that will not be also reduced exposed to high light its display quality for a long time Show element, viewing angle characteristic, the liquid crystal display cells of image retention excellent are provided in the lump.And, there is provided this display can be provided The aligning agent for liquid crystal and liquid crystal orientation film of element.

The scheme for solving problem

The present inventor etc. is furtherd investigate, and as a result completes the diamines by using following formula (1) so as to provide Even if viewing angle characteristic and/or image retention excellent, the liquid crystal display that will not be also reduced exposed to high light its display quality for a long time The aligning agent for liquid crystal and liquid crystal orientation film of element.Can be particularly suitable for for Transverse electric-field types such as IPS patterns and FFS modes Liquid crystal display cells.

The present invention includes following technical scheme.

[1] a kind of polyamic acid or derivatives thereof, it is to make in tetracarboxylic dianhydride and diamines shown in contained (1) at least Obtained from a kind of diamine reactant.

In formula (1), R is the alkoxy of hydrogen ,-OH, the alkyl of carbon number 1~6 or carbon number 1~6；Also,

X¹And X²It is each independently the divalent organic group of alkylidene and/or phenylene with carbon number 1~8.

[2] polyamic acid according to [1] or derivatives thereof, wherein, the diamines shown in formula (1) is for shown in formula (1 ') Diamines.

In formula (1 '), R is the alkoxy of hydrogen ,-OH, the alkyl of carbon number 1~6 or carbon number 1~6；

A¹And A²It is each independently the alkylidene of singly-bound or carbon number 1~6；Also,

- the NH being bonded on ring₂Bonding position be optional position.

[3] polyamic acid according to [1] item or described in [2] item or derivatives thereof, wherein, in the diamines shown in formula (1), R It is hydrogen or-OH.

[4] polyamic acid according to [1] item or described in [2] item or derivatives thereof, wherein, under the diamines shown in formula (1) is State formula (1-15) or the compound shown in formula (1-29).

[5] according to polyamic acid any one of [1]~[4] or derivatives thereof, wherein, tetracarboxylic dianhydride be selected from At least a kind in the group of the tetracarboxylic dianhydride shown in following formula (AN-I)~formula (AN-VII)；

Other diamines being used together with the diamines shown in formula (1) are selected from by following formula (DI-1)~formula (DI-16), formula (DIH-1) at least a kind in the group of~formula (DIH-3) and 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, alkylidene ,-CO- ,-O- ,-the S- ,-SO of carbon number 1~20₂-、-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 A¹⁰It is 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 what is be connected with ring is bonded Any carbon for constituting ring is connected to, 2 key options are connected to same carbon；

In formula (AN-VI), X¹⁰It is 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-、- The alkylidene of NH- or 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), 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, R²⁴For hydrogen ,-F ,-Cl, the alkyl of carbon number 1~6, carbon are former The alkoxy of subnumber 1~6, 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-16), G²⁴It is 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), G²⁵It is singly-bound, alkylidene ,-CO- ,-O- ,-the S- ,-SO of carbon number 1~20₂-、-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 ring is optionally by methyl, ethyl Or phenyl substitution；

In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen on the ring is optionally by first Base, ethyl or phenyl substitution, Y are singly-bound, alkylidene ,-CO- ,-O- ,-the S- ,-SO of carbon number 1~20₂-、-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), G²⁶It is 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, solid with class Group shown in the group or following formula (DI-31-a) of ol skeleton, in 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,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹It is linking group, they independently are singly-bound or carbon number 1~12 Alkylidene, more than 1-CH in the alkylidene₂- optionally by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH- displacements, ring B²¹, ring B²², ring B²³With ring B²⁴Independently be 1,4- phenylenes, 1,4- cyclohexylenes, 1,3- diox -2,5- diyls, pyrimidine - 2,5- diyls, pyridine -2,5- diyls, piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyls, naphthalene -2,7- diyls or anthracene -9,10- diyls, 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, 2 rings can be with It is identical can also be different,

R²⁶It is 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 The divalent group displacement shown in following formula (DI-31-b) is selected,

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, R³⁰It is 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 Show that the 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 The alkylidene of singly-bound or carbon number 1~3,

R³¹It is 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, R³²It is the alkyl of carbon number 6~22, R³³It is hydrogen or the alkyl of carbon number 1~22, ring B²⁵It is 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.

[6] polyamic acid according to [5] 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), at least a kind in formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4)；

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 At least a kind 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.

[7] polyamic acid according to any one of [1]~[6] or derivatives thereof, in tetracarboxylic dianhydride and diamines At least 1 include the compound with photoreactivity structure.

[8] polyamic acid according to [7] or derivatives thereof, wherein, photoreactivity structure is selected from by following formula (P- 1) at least a kind 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.

[9] polyamic acid according to [7] 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) at least a kind 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 key on the ring It is arbitrary to close position, 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 is each independently selected from least 1 in monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle Kind, R¹¹It is straight-chain alkyl-sub ,-COO- ,-the OCO- ,-NHCO- or-N (CH of carbon number 1~20₃) CO-, R¹²It is 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 It is on the spot 0~4 integer.

[10] polyamic acid according to [7] 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.

[11] a kind of aligning agent for liquid crystal, it contains polyamic acid any one of [1]~[10] or derivatives thereof.

[12] a kind of light orientation aligning agent for liquid crystal, it includes polymer [A] and polymer [B], the polymer [A] and Polymer [B] is polyamic acid or derivatives thereof；

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

[13] the light orientation aligning agent for liquid crystal according to [12], it includes at least a kind polymer [A] and at least a kind Polymer [B],

The polymer [A] is the tetracarboxylic acid obtained from reacting the starting monomer comprising tetracarboxylic dianhydride and diamines In acid dianhydride and diamines at least 1 include the compound with photoreactivity structure,

The polymer [B] is to make tetracarboxylic dianhydride and diamines without photoreactivity structure and diamines is contained (1) At least a kind in shown compound of starting monomer reaction and obtain.

[14] the light orientation aligning agent for liquid crystal according to [12], it includes at least a kind polymer [A] and at least a kind Polymer [B],

The polymer [A] is the tetracarboxylic acid obtained from reacting the starting monomer comprising tetracarboxylic dianhydride and diamines In acid dianhydride and diamines at least 1 include the compound with photoreactivity structure and compound shown in diamines contained (1) In at least a kind,

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

[15] the light orientation aligning agent for liquid crystal according to [12], it includes at least a kind polymer [A] and at least a kind Polymer [B],

The polymer [B] is the tetracarboxylic acid obtained from reacting the starting monomer comprising tetracarboxylic dianhydride and diamines Acid dianhydride and diamines are without at least a kind in photoreactivity structure and compound shown in diamines contained (1).

[16] the light orientation aligning agent for liquid crystal according to [12], it includes at least a kind polymer [A] and at least a kind Polymer [B],

The polymer [B] is the tetracarboxylic acid obtained from reacting the starting monomer comprising tetracarboxylic dianhydride and diamines In acid dianhydride and diamines at least 1 include the compound with photoreactivity structure and compound shown in diamines contained (1) In at least a kind.

[17] the light orientation aligning agent for liquid crystal according to any one of [12]~[16], wherein, shown in formula (1) two Amine is the diamines shown in formula (1 ').

- the NH being bonded on ring₂Bonding position be optional position.

[18] the light orientation aligning agent for liquid crystal according to any one of [12]~[17], wherein, shown in formula (1) two In amine, R is hydrogen or-OH.

[19] the light orientation aligning agent for liquid crystal according to any one of [12]~[18], wherein, shown in formula (1) two Compound of the amine shown in following formula (1-15) or formula (1-29).

[20] the light orientation aligning agent for liquid crystal according to any one of [12]~[19], wherein, with photoreactivity The compound of structure has at least a kind in following formula (P-1)~structure shown in formula (P-7).

[21] the light orientation aligning agent for liquid crystal according to any one of [12]~[19], 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), at least a kind in formula (V-1)~formula (V-3) and 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 be each independently selected from monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle at least 1 kind, R¹¹It is straight-chain alkyl-sub ,-COO- ,-the OCO- ,-NHCO- or-N (CH of carbon number 1~20₃) CO-, R¹²It is carbon number 1~20 straight-chain alkyl-sub ,-COO- ,-OCO- ,-NHCO- or-N (CH₃) CO-, R¹¹And R¹²In, 1 on 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 It independently is 0~4 integer.

[22] the light reaction aligning agent for liquid crystal according to any one of [12]~[19], wherein, with photoreactivity The compound of structure is the diamines shown in following formula (PDI-7).

[23] the light orientation aligning agent for liquid crystal according to any one of [12]~[22], wherein, without light reaction The tetracarboxylic dianhydride of property 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 (DIH-3) at least a kind 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；

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 optional position outside；

In formula (DI-11), r is 0 or 1；

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

In formula (DI-31-a), G²⁷、G²⁸And G²⁹It is linking group, they independently are singly-bound or carbon number 1~12 Alkylidene, more than 1-CH in the alkylidene₂- optionally by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH- displacements, ring B²¹, ring B²², ring B²³With ring B²⁴Independently be 1,4- phenylenes, 1,4- cyclohexylenes, 1,3- diox -2,5- diyls, pyrimidine - 2,5- diyls, pyridine -2,5- diyls, piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyls, naphthalene -2,7- diyls or anthracene -9,10- diyls, 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,

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

[24] the light orientation aligning agent for liquid crystal according to [23], 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.

[25] according to the aligning agent for liquid crystal any one of [11]~[24], its also containing selected from You oxazine compounds, At least a kind in the compound group of oxazoline compound, epoxide and silane coupler composition.

[26] a kind of liquid crystal orientation film, it is that aligning agent for liquid crystal as any one of [11]~[25] is formed.

[27] a kind of transverse electric field liquid crystal orientation film, it is the aligning agent for liquid crystal as any one of [11]~[25] Formed.

[28] a kind of liquid crystal display cells, it has [26] item or the liquid crystal orientation film described in [27] item.

[29] a kind of diamines, it uses formula (1 ') to represent.

- the NH being bonded on ring₂Bonding position be optional position.

[30] diamines according to [29], it uses following formula (1-15) or formula (1-29) to represent.

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

The effect of invention

The liquid crystal aligning of the polyamic acid as being used for raw material containing the diamines shown in by formula (1) of the invention or derivatives thereof Dosage form into liquid crystal orientation film long-term reliability it is excellent.Additionally, possessing the transverse direction of the liquid crystal orientation film formed by brushing method The liquid crystal display cells of Electric Field Mode can suppress tilt angle relatively low, therefore viewing angle characteristic is excellent.Possess by light orientation The image retention excellent of the liquid crystal display cells of the Transverse electric-field type of the liquid crystal orientation film that method is formed.Want to assign and improve in base During other characteristics such as the printing printed on plate, it is blended by with other polymer, or be applied in combination by with additive, energy It is enough that the liquid crystal orientation film for possessing desired characteristic is provided.

Specific embodiment

In diamines shown in formula (1), R is the alkoxy of hydrogen ,-OH, the alkyl of carbon number 1~6 or carbon number 1~6； X¹And X²It is each independently the divalent organic group of the alkylidene with carbon number 1~8, the divalent organic group with phenylene Group or the divalent organic group of the alkylidene with carbon number 1~8 and phenylene.

When expecting dissolubility in a solvent aligning agent for liquid crystal higher, R is the two of alkoxy in preferably using formula (1) Amine.Additionally, it is desirable to during reliability liquid crystal orientation film higher, in formula (1), it is hydrogen or the compound of-OH to preferably use R.

The concrete example of the diamines shown in formula (1) is the compound shown in formula (the 1-1)~formula (1-84) being exemplified below out.

By the way that the diamines shown in formula (1-1)~formula (1-84) is used as to constitute the polymer of aligning agent for liquid crystal of the invention One of raw material, though be obtained in that for a long time will not also be reduced using its display quality, the liquid crystal orientation film that liquid crystal aligning is high.

When expecting dissolubility in a solvent aligning agent for liquid crystal higher, the two of formula (1-23) and formula (1-37) are preferably used Amine.Additionally, it is desirable to during reliability liquid crystal orientation film higher, preferably use formula (1-1), formula (1-15), formula (1-29) and formula (1- 43), the more preferably diamines of formula (1-15) and formula (1-29).

Illustrated for polyamic acid of the invention and its derivative.Polyamic acid of the invention and its derivative are four Product between carboxylic acid dianhydride and the diamines of the diamines shown in contained (1)." diamines of the diamines shown in contained (1) " Specifically refer to the diamines shown in a kind of formula (1), the mixture of the diamines shown in formula of more than two kinds (1) and at least a kind formula (1) Shown diamines and the mixture of at least a kind other diamines in addition to the diamines shown in formula (1).Additionally, aftermentioned, " other two Amine " plays two hydrazides acted on diamines identical in being additionally included in polyamic acid of the invention and its derivative.This specification In, there is the statement that two hydrazides are regarded as diamines.That is, the situation in this specification, being denoted as " diamines " is sometimes with including two acyls What the meaning of hydrazine was used.

Foregoing polyamides acid derivative refer to：Be dissolved in when being made the aftermentioned aligning agent for liquid crystal containing solvent solvent into Point, it is that the liquid crystal orientation film using polyimides as principal component can be formed when the aligning agent for liquid crystal is 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 dehydration closed-loop reaction occur with carboxyl and obtains Polyimides；2) partly there is 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 its polyamic acid-polyamide copolymer obtained from reaction；And 5) the one of the polyamic acid-polyamide copolymer is made Partly or entirely there is polyamidoimide obtained from dehydration closed-loop reaction.Foregoing polyamides acid 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 product of amine, it is also possible to containing using other raw materials by except tetracarboxylic dianhydride it is anti-with diamines Other product obtained from reaction outside answering.

Illustrated for the tetracarboxylic dianhydride used to manufacture polyamic acid of the invention and its derivative.This hair The bright middle tetracarboxylic dianhydride for using can unrestrictedly be selected from known tetracarboxylic dianhydride.This tetracarboxylic dianhydride can Have not direct in the fragrant family (comprising 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 (comprising 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 Alkylidene ,-CO- ,-O- ,-the S- ,-SO of key, carbon number 1~20₂-、-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, is bonded and is connected to any carbon, and on the group at least 1 Individual hydrogen is optionally replaced by methyl, ethyl or phenyl.

In formula (AN-III)~formula (AN-V), ring A¹⁰It is 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 what is be connected with ring is bonded Any carbon for constituting ring is connected to, 2 key options are connected to same carbon.In formula (AN-VI), X¹⁰It is 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), G¹¹It is 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 R¹¹It is 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 A¹¹It is 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), G¹³It is 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), R¹¹It is 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), X¹¹It is 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), X¹¹It is singly-bound or-CH₂-。R¹²It is 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), X¹³It is 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 for being suitable to improve 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- M=4 or 8 is preferably in 1-2), m=4 or 8, more preferably m=8 are preferably in formula (AN-4-17).

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

In the case that attention improves the VHR of liquid crystal display cells, 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, m=4 or 8 is preferably in formula (AN-1-2), m=4 or 8 is preferably in formula (AN-4-17), Particularly preferably m=8.

The mitigation of the residual charge (remaining DC) in alignment films 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 polyamic acid of the invention and its derivative.System When making polyamic acid of the invention or derivatives thereof, can unrestrictedly be selected from known diamines and two hydrazides.

Diamines can be divided into 2 kinds according to its structure.Refer to：When the skeleton that 2 amino will be connected is regarded as 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 tilt angle.Side-chain radical with this effect need be carbon number more than 3 group, as specific Example, can include alkyl, the alkoxy of carbon number more than 3, the alkoxy alkane of 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 with more than 1 group of ring and its end Any one of alkoxyalkyl of alkyl, the alkoxy of carbon number more than 1 and carbon number more than 2 above is used as substitution The group of base also has as the effect of side-chain radical.In the following description, the diamines with this side-chain radical is claimed sometimes It is 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, the tilt angle needed for coping with each. Side chain type diamine is preferably applied in combination with not damaging the degree of characteristic of the present invention.In addition, being directed to side chain type diamine and non-side chain type Diamines, it is preferred that according to the purpose of vertical orientated property, voltage retention, ghost characteristic and the orientation improved for liquid crystal 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 be 1~12 it is whole Number, at least one hydrogen on 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 is the alkyl of carbon number 1~5, the alkoxy of carbon number 1~5 or-Cl, p independently be 0~3 integer, 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), G²⁴It is 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 is 1~12 integer, formula (DI-5-38) and In formula (DI-5-39), k is 1~5 integer, and in formula (DI-5-40), 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), G²⁵It is singly-bound, alkylidene ,-CO- ,-O- ,-the S- ,-SO of carbon number 1~20₂-、-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 replace.In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen on the group is appointed Select by the substitution of methyl, ethyl or phenyl, alkylidene ,-CO- ,-O- ,-the S- ,-SO that Y is singly-bound, carbon number 1~20₂-、-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 to reduce for this non-side chain type diamine and two hydrazides Effect.Used non-as manufacturing the diamines of the polyamic acid used in aligning agent for liquid crystal of the 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 rubs 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 substitution base, 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, can include with more than 2 groups of phenyl ring, the group with more than 2 cyclohexane rings 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- ,- The alkylidene of CONH- or carbon number 1~3, the ring of end has the alkyl of carbon number more than 1, the fluorine of carbon number more than 1 The alkoxyalkyl of substitution alkyl, the alkoxy of carbon number more than 1 or carbon number more than 2 is used as many ring groups for replacing base 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), G²⁶It is 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-。R²⁵It is 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 on the ring and be 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 G²⁹It is linking group, they independently are singly-bound or carbon number 1~12 Alkylidene, more than 1-CH in the alkylidene₂- optionally by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH- displacements.Ring B²¹, ring B²², ring B²³With ring B²⁴Independently be 1,4- phenylenes, 1,4- cyclohexylenes, 1,3- diox -2,5- diyls, pyrimidine - 2,5- diyls, pyridine -2,5- diyls, piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyls, naphthalene -2,7- diyls or anthracene -9,10- diyls, 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 Can be the same or different.R²⁶For the fluorine of hydrogen ,-F ,-OH, the alkyl of carbon number 1~30, carbon number 1~30 replaces alkane Alkoxy ,-the CN ,-OCH of base, carbon number 1~30₂F、-OCHF₂Or-OCF₃, in the alkyl of the carbon number 1~30 extremely Few 1-CH₂- divalent the group displacement optionally 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, R³⁰It is the alkenyl of hydrogen, the alkyl of carbon number 1~20 or carbon number 2~20.In formula (DI-33) on phenyl ring at least 1 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 is 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.R³¹It is 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-.R³²It is the alkyl of carbon number 6~22, R³³It is hydrogen or carbon number 1~22 Alkyl.Ring B²⁵It is 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.As above-mentioned formula (DI-31)~formula (DI-35) with side chain Diamines, can include the compound shown in following formula (DI-31-1)~formula (DI-35-3).

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

In formula (DI-31-1)~formula (DI-31-11), R³⁴It is the alkyl or carbon number 1~30 of carbon number 1~30 Alkoxy, the preferably alkoxy of the alkyl of carbon number 5~25 or carbon number 5~25.R³⁵It is the alkane of carbon number 1~30 The alkoxy of base or carbon number 1~30, the preferably alkoxy of the alkyl of carbon number 3~25 or carbon number 3~25.

In formula (DI-31-12)~formula (DI-31-17), R³⁶It is the alkyl of carbon number 4~30, preferably carbon number 6 ~25 alkyl.R³⁷It is the alkyl of carbon number 6~30, the preferably alkyl of carbon number 8~25.

In formula (DI-31-18)~formula (DI-31-43), R³⁸It is the alkyl or carbon number 1~20 of carbon number 1~20 Alkoxy, the preferably alkoxy of the alkyl of carbon number 3~20 or carbon number 3~20.R³⁹For hydrogen ,-F, carbon number 1~ 30 alkyl, alkoxy ,-the CN ,-OCH of carbon number 1~30₂F、-OCHF₂Or-OCF₃, preferably carbon number 3~25 The alkoxy of alkyl or carbon number 3~25.Also, G³³It is the alkylidene of carbon number 1~20.

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

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

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

In formula (DI-34-1)~formula (DI-34-14), R⁴⁰It is hydrogen or the alkyl of carbon number 1~20, preferably hydrogen or carbon The alkyl of atomicity 1~10, also, R⁴¹It is hydrogen or the alkyl of carbon number 1~12.

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

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

As the diamines in the present invention, it is also possible to using 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, can arrange Enumerate the compound for example shown in following formula (DI-36-1)~formula (DI-36-13).

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 R⁴³It is-NHBoc or-N (Boc)₂, in formula (DI-36-13), R⁴⁴For-NHBoc Or-N (Boc)₂, also, m is 1~12 integer.Herein, Boc is tert-butoxycarbonyl.

In above-mentioned diamines and two hydrazides, described for the material for being suitable to improve 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) and formula (DI-7-3), the more preferably compound shown in formula (DI-2-1). 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.

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

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 It is 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.

It is that in 40 moles of scopes of below %, a part for diamines is appointed relative to the ratio of diamines in monoamine in each diamines Choosing is replaced as monoamine.This displacement can cause polymerisation to terminate when polyamic acid is generated, and 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 the coating characteristics of aligning agent for liquid crystal without damaging effect of the invention.It is replaced as the diamines of monoamine only Otherwise effect of the 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 invention or derivatives thereof can also include monoisocyanate compound in monomer.By The end for including monoisocyanate compound, gained polyamic acid or derivatives thereof in monomer 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 effect of the invention.Content from the monoisocyanate compound in foregoing viewpoint, monomer is relative in monomer The total amount of diamines and tetracarboxylic dianhydride is preferably 1~10 mole of %.As foregoing monoisocyanate compound, can include for example Phenyl isocyanate and naphthyl isocyanate.

Using polyamic acid of the invention or derivatives thereof liquid crystal is assigned 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 using with 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 the light point shown in the following formula (P-1) for example decomposed by ultraviolet irradiation Photoisomerization structure, formula (the P-5)~formula of generation dimerization shown in solution structure, formula (the 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.

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

It should be noted that the compound shown in formula (PA-1)~formula (PA-3) is used as to 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 During the starting monomer of the polymer used in person's brushing 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 a kind in the group of the compound shown in good following formula (II)~formulas (VI), the more preferably compound shown in formula (V).

R²-C≡C-R³ (II)

R²-C≡C-C≡C-R³ (III)

R²-C≡C-R⁴-C≡C-R³ (IV)

R²- N=N-R³ (V)

R⁵- CH=CH-R⁵ (VI)

In formula (II)~formula (V), R²And R³It is with-NH₂1 valency organic group or 1 valency with-CO-O-CO- have Machine group, in formula (IV), R⁴It is divalent organic group, in formula (VI), R⁵It is with-NH₂Or the aromatic rings of-CO-O-CO-.

Photoisomerization structure can be set into appointing in the main chain of polyamic acid of the 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 is each independently selected from least 1, R in monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle¹¹It is carbon The straight-chain alkyl-sub of atomicity 1~20 ,-COO- ,-OCO- ,-NHCO- or-N (CH₃) CO-, R¹²It is straight for 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 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 from the viewpoint of its orientation.

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

Among these, occur as comprising that can be irradiated by ultraviolet by using formula (VI-1-1)~formula (V-3-8) The compound of the structure of isomerization, is obtained in that the light orientation aligning agent for liquid crystal higher for 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 Can be irradiated by ultraviolet and the compound of the structure of isomerization occurs, being obtained in that can be such that liquid crystal molecule is more uniformly orientated Light orientation aligning agent for liquid crystal.Sent out as comprising that can be irradiated by ultraviolet by using formula (V-2-4)~formula (V-3-8) The compound of the structure of raw isomerization, is obtained in that the less light orientation aligning agent for liquid crystal of the coloring of formed alignment films.

When synthesis has the polyamic acid and its derivative of photoreactivity structure, can be by with photoreactivity structure four 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 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, it is also possible to it is applied in combination tetracarboxylic dianhydride's (the hereinafter sometimes referred to non-photosensitive four without photoreactivity structure Carboxylic acid dianhydride.).Now, in order to prevent alignment films to the sensitivity decrease of light, the sense in the 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 %.Additionally, in order to improve for The foregoing various characteristics such as sensitivity, the image retention characteristic of light, it is also possible to 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 to be used for the situation of raw material Under, the diamines shown in formula of the invention (1) and photonasty diamines are applied in combination.Diamines shown in formula (1) does not have light reaction Property structure.Can also be further combined using the diamines without photoreactivity structure beyond the diamines shown in formula (1) (below 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 %.Additionally, in order to improve for The foregoing various characteristics such as sensitivity, the image retention characteristic of light, it is also possible to 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, it is also possible to be applied in combination non-photosensitive tetracarboxylic dianhydride and the 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 is preferably 20 moles of more than %, more preferably 50 rubs You are more than %.Additionally, in order to improve the foregoing various characteristics such as sensitivity, image retention characteristic for light, it is also possible to by photonasty four Carboxylic acid dianhydride or/and photonasty diamines are applied in combination two or more.

Illustrated for aligning agent for liquid crystal of the invention.Aligning agent for liquid crystal of the invention can also further contain formula (1) other compositions that at least a kind diamines shown in is used for outside polyamic acid of raw material or derivatives thereof.Other compositions can be 1 kind can also be two or more.As other compositions, other polymer for example described later, compound etc. can be included.

Other polymer be instigate tetracarboxylic dianhydride and polyamic acid obtained from the diamine reactant of contained (1) diamines or Polymer outside its derivative.Specifically, so that obtained from the diamines without formula (1) diamines reacts with tetracarboxylic dianhydride 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 the tetracarboxylic dianhydride and diamines that are used to synthesize other polyamic acids or derivatives thereof, can be from above-mentioned example The known tetracarboxylic dianhydride for showing and unrestrictedly selected in diamines.

In the present invention, polyamic acid that will can be synthesized using the diamines of contained (1) diamines 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：One of which polymer of the selection with the excellent performance of liquid crystal aligning ability, another one selection is for improving liquid crystal display Polymer with 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 aligning agent for liquid crystal obtained from solvent coat 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 Can make that there is the polymer for having excellent properties for improving the electrical characteristics of liquid crystal display cells to be segregated under film 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 that this layer is separate can pass through formed alignment films surface energy and by The surface energy of the film that the aligning agent for liquid crystal only containing the polymer for being intended to be segregated to upper strata is formed is identical numerical value or close number Value confirms.

During aligning agent for liquid crystal of the invention is for the mode of light orientation aligning agent for liquid crystal, the layer point in film can not be considered It is liftoff to use polyamic acid with photoreactivity structure of the invention or derivatives thereof.In addition it is also possible to will be with light reaction Property structure aligning agent for liquid crystal be used as to be 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 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 formula (1) of the invention can serve as the starting monomer of the polymer for being segregated to aforementioned film upper strata, The starting monomer of the polymer for being also used as being segregated to film lower floor.Diamines shown in formula (1) can serve as in two polymer The starting monomer of any one, it is also possible to the starting monomer as two polymer.

The non-photosensitive four used as the polyamic acid on aforementioned film upper strata or derivatives thereof is segregated in order to synthesize Carboxylic acid dianhydride, can unrestrictedly be selected from the above-mentioned known tetracarboxylic dianhydride for exemplifying.

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.M=4 or 8, more preferably m=8 are preferably 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, m is preferably in formula (AN-1-2) =4 or 8, m=4 or 8, more preferably m=8 are preferably 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).

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

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

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.M=3, n=1 are preferably 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 for showing, particularly preferably formula (PA-1).M=1,2 or 4, more preferably m are preferably 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) The compound of k=2 in the compound and formula (DI-5-30) of middle m=1 or 2.

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).M=1 or 2 is preferably in formula (DI-5-1).In formula (DI-5-12) be preferably m=2~ 6th, it is more preferably m=5.M=1 or 2, more preferably m=1 are preferably in formula (DI-5-13).K=is preferably in formula (DI-5-30) 2。

The non-photosensitive diamines for the polyamic acid on film upper strata or derivatives thereof being segregated to synthesize and being used preferably exists In the total amount of diamines comprising 30 moles of aromatic diamines of more than %, more preferably comprising more than 50%.

The tetracarboxylic dianhydride used as polyamic acid of film lower floor or derivatives thereof is segregated in order to synthesize, can be with Unrestrictedly selected from the above-mentioned known tetracarboxylic dianhydride for exemplifying.

Wherein, in the case where paying attention to improving layer separation property, preferably formula (AN-3-2), formula (AN-1-13), formula (AN- Compound 1-1) and 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, m=4 or 8, more preferably m=8 are preferably in formula (AN-4-17).

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

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

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, k=2 is particularly preferably 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, m=1 or 2 is preferably in formula (DI-5-1).M is preferably in formula (DI-5-12) =2~6, it is more preferably m=5.M=1 or 2, more preferably m=1 are preferably in formula (DI-5-13).In formula (DI-5-30) preferably It is k=2.

The non-photosensitive diamines for polyamic acid of film lower floor or derivatives thereof being segregated to synthesize and being used preferably is wrapped Containing be 30 moles of aromatic diamines of more than % relative to whole diamines, 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 Biology can be respectively the synthesis side of polyamic acid or derivatives thereof according to the essential component as aligning agent for liquid crystal of the 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 5 weight %~50 weights Amount %, more preferably 10 weight %~40 weight %.

As polysiloxanes, 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 aligning agent for liquid crystal of the invention, from the purpose for making the electrical characteristics of liquid crystal display cells 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, it is also possible to be applied in combination two or more.The content of alkenyl substitution Na Dike imide compounds from above-mentioned purpose, relatively 1~100 weight %, more preferably 1~70 weight %, more preferably 1~50 are preferably 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 for showing.

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 substitution group.

Now, preferred W 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 alkylidene, the ring alkylidene of carbon number 5~8, the carbon original of carbon number 2~20 The arlydene ,-Z of subnumber 6~12¹-O-(Z²O)_k-Z³- (herein, Z¹~Z³Shown in definition when stating n=1 as defined above with k.) Shown group ,-Z⁴-B-Z⁵- (herein, Z⁴、Z⁵Shown in definition when stating n=1 as defined above with B.) shown in group ,-B- (O-B)_r-T-(B-O)_r(herein, B is phenylene to-B-, and T is the alkylidene ,-O- or-SO of carbon number 1~3₂-, the definition of r is such as Shown in definition during foregoing n=1.) shown in group or these groups 1~3 hydrogen by-OH substitution group.

Now, preferred W is alkylidene, cyclohexylene, phenylene, xylene, the methylene of benzene two of carbon number 2~12 Base ,-C₃H₆-O-(Z²-O)_n-O-C₃H₆- (herein, Z²It is 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 1 of these groups or 2 hydrogen by the group of-OH substitutions.

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

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

The bicyclic carbodiimides of [2.2.1] hept- 5- alkene -2,3- two of N- (2- ethylhexyls) pi-allyl (methyl), N- pi-allyls The carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two, N- pi-allyls allyl methyl bicyclic [2.2.1] hept- 5- alkene - The carbodiimides of 2,3- bis-, the carbodiimides of N- Allyl-methyls pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two, N- isopropyl alkene The carbodiimides of base pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two, N- isopropenyls pi-allyl (methyl) are bicyclic [2.2.1] The carbodiimides of hept- 5- alkene -2,3- two, N- isopropenyls-two carbon of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two are sub- Amine, the carbodiimides of N- cyclohexyl pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two, N- cyclohexyl pi-allyl (methyl) are bicyclic The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two, the carbon of N- Cyclohexyl-methyls pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two The bicyclic carbodiimides of [2.2.1] hept- 5- alkene -2,3- two of diimine, N- phenyl allyls,

The bicyclic carbodiimides of [2.2.1] hept- 5- alkene -2,3- two of N- phenyl allyls (methyl), N- benzyl allyls are bicyclic The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two, two carbon of N- benzyl allyls methyl bicycle [2.2.1] hept- 5- alkene -2,3- two are sub- Amine, the carbodiimides of N- benzyl-methyls pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two, N- (2- hydroxyethyls) pi-allyl are double The carbodiimides of ring [2.2.1] hept- 5- alkene -2,3- two, bicyclic [2.2.1] the hept- 5- alkene of N- (2- hydroxyethyls) pi-allyl (methyl) - The carbodiimides of 2,3- bis-, the carbodiimides of N- (2- hydroxyethyls)-methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two,

The carbodiimides of N- (2,2- dimethyl -3- hydroxypropyls) pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two, N- The bicyclic carbodiimides of [2.2.1] hept- 5- alkene -2,3- two of (2,2- dimethyl -3- hydroxypropyls) pi-allyl (methyl), N- (2,3- Dihydroxypropyl) carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two, N- (2,3- dihydroxypropyls) pi-allyl (methyl) bicyclic carbodiimides of [2.2.1] hept- 5- alkene -2,3- two, N- (3- hydroxyl -1- acrylic) pi-allyl bicyclic [2.2.1] The carbodiimides of hept- 5- alkene -2,3- two, bicyclic [2.2.1] the hept- 5- alkene -2,3- two of N- (4- hydroxy-cyclohexyls) pi-allyl (methyl) Carbodiimide,

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

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

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

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

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

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

Double { 4- (carbodiimides of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } methane, double { 4- (first The carbodiimides of base allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl methane, double { 4- (pi-allyl bicyclics The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two) phenyl ether, double { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- Two carbodiimides) phenyl ether, double { 4- (carbodiimides of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } ethers, Double { 4- (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } sulfones, double { 4- (allyl methyl bicyclics The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two) phenyl } sulfone,

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

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

Double (4- { 4- (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) -2- hydroxyphenoxies } benzene of 2,2- Base) it is propane, double { 4- (carbodiimides of allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) -2- hydroxy phenyls } methane, double { 3- (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) -4- hydroxy phenyls } ether, double { 3- (methacrylics pair The carbodiimides of ring [2.2.1] hept- 5- alkene -2,3- two) -5- hydroxy phenyls sulfone, the { 4- (allyl methyl bicyclics of 1,1,1- tri- The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two) } phenoxymethyl propane, N, N ', N "-three (ethylidene methacrylic bicyclics The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two) 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, preferred compound is as follows.

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

Double { 4- (carbodiimides of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } methane, double { 4- (first The carbodiimides of base allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl methane, double { 4- (pi-allyl bicyclics The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two) phenyl ether, double { 4- (allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- Two carbodiimides) phenyl ether, double { 4- (carbodiimides of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } ethers, Double { 4- (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } sulfones, double { 4- (allyl methyl bicyclics The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two) phenyl sulfone, double { 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- Two carbodiimides) phenyl } sulfone.

Preferred alkenyl substitution Na Dike imide compounds are as follows.

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

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

Double (4- { 4- (carbodiimides of pi-allyl bicyclic [2.2.1] the hept- 5- alkene -2,3- two) phenoxy group } phenyl) third of 2,2- Alkane, 2,2- pair (4- { 4- (carbodiimides of allyl methyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenoxy group } phenyl propane, 2,2- is double (4- { 4- (carbodiimides of methacrylic bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenoxy group } phenyl propane, double { 4- (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } methane, double { 4- (allyl methyl bicyclics The carbodiimides of [2.2.1] hept- 5- alkene -2,3- two) phenyl methane, it is double 4- (methacrylic bicyclic [2.2.1] hept- 5- alkene -2, The carbodiimides of 3- bis-) phenyl methane, double { 4- (carbodiimides of methacrylic methyl bicycle [2.2.1] hept- 5- alkene -2,3- two) 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- (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) phenyl } methane for showing, formula (NA-2), N shown in N '-m-phenylenedimethylim- double (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two) and formula (NA-3), N '-hexamethylene bis (carbodiimides of pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- two).

For example, in aligning agent for liquid crystal of the invention, from the purpose for making the electrical characteristics of liquid crystal display cells 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 having free-radical polymerised unsaturation The compound of double bond does not include that alkenyl 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 liquid crystal display cells ion concentration, 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 are more than 2 (methyl) acrylic acid derivatives of free-radical polymerised unsaturated double-bond.

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 of society, KAYARADR-604 and KAYARADR-684, 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 Product K AYARADTMPTA, KAYARADDPCA-20 of Co., Ltd., 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 aligning agent for liquid crystal of the invention, from the purpose for making the electrical characteristics of liquid crystal display cells 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. From the content of above-mentioned purpose , oxazine compounds 0.1~50 weight %, more is preferably relative to polyamic acid or derivatives thereof Preferably 1~40 weight %, more preferably 1~20 weight %.

Following Zhen paroxazines compound is specifically described.

Oxazine compounds be preferably dissolve in make polyamic acid or derivatives thereof dissolve solvent 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 can include benzoxazine, Nai Bing oxazines etc. with the aromatic group Evil containing condensed polycyclc aromatic group Piperazine structure.

Zuo Wei oxazine compounds, can include the compound for example shown in following formula (OX-1)~formula (OX-6).Need Bright, in following formula, the key shown in ring center represents any carbon for being bonded to and constituting ring and can be bonded substitution base.

In formula (OX-1)~formula (OX-3), L³And L⁴It is the organic group of carbon number 1~30, formula (OX-1)~formula (OX- 6) in, L⁵~L⁸It is 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 is 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 The oligomer of piperazine structure, polymer.

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 carbon number 1~30, the more preferably alkyl of 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 L⁴It is the organic group of carbon number 1~30, L⁵~L⁸It is hydrogen or carbon number 1~6 Alkyl, Q¹It is singly-bound ,-CH₂-、-C(CH₃)₂-、-CO-、-O-、-SO₂-、-C(CH₃)₂- or-C (CF₃)₂-.As formula (OX-3- I oxazine compounds shown in), can include oxazine compounds Xia such as Yi.

In formula, L³And L⁴The preferably alkyl of carbon number 1~30, the more preferably alkyl of 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 added to formaldehyde method and After reacting it, 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 1 aldehyde for being at least more than 2 moles of phenolic hydroxyl group and 1 mole of primary amine 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 have by making 4,4 '-diaminodiphenyl-methane etc. Multiple phenyl ring and the aldehyde such as diamines, formaldehyde and phenol of their organic group are bonded in n-butanol with more than 90 DEG C of temperature hair Dehydration condensation is given birth to obtain (with reference to Japanese Unexamined Patent Publication 2004-352670.).

For example, in aligning agent for liquid crystal of the invention, from the purpose for making the electrical characteristics of liquid crystal display cells 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 0.1~50 weight %, more preferably 1~40 weight % is preferably for polyamic acid or derivatives thereof, be preferably 1~20 weight Amount %.In addition, the content , of Guan Yu oxazoline compounds is when oxazoline compound Zhong oxazoline structure Huan Suan oxazolines, From above-mentioned purpose, 0.1~40 weight % is preferably relative to polyamic acid or derivatives thereof.

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 homopolymers, 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 of oxygen and nitrogen in oxazoline structure You Xuan Yi oxazoline structures or both can be with the carbonyls of polyamic acid 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 (4,5- dihydro -2- oxazolinyls) benzene of 3-, 2,3- double (4- isopropenyl -2- oxazoline -2- bases) butane, 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 aligning agent for liquid crystal of the invention, from the purpose for making the electrical characteristics of liquid crystal display cells 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, intramolecular can be included with 1 or more than the 2 various compounds of epoxide ring.As Intramolecular has 1 compound of 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 are 2 compounds of epoxide ring 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 are 3 compounds of epoxide ring 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 are 4 compounds of epoxide ring as intramolecular, such as 1,3,5,6- four glycidyl group -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 includes 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 for carrying out with the monomer with epoxide ring copolymerization, 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..Additionally, as the monomer with epoxide ring and the preferred concrete example of 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, can include for example by the carbon-to-carbon double bond oxidation of olefin(e) compound The compound containing epoxy radicals for obtaining.

As annular aliphatic type epoxide, 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 (are 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 (is 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, 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, such as jER5050, jER5051 can be included and (be trade name, Mitsubishi 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 (is trade name, Dainippon Ink Chemicals's system).

As phenol novolak-type epoxy compound, such as jER152, jER154 can be included and (be trade name, three 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 (is 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), DGEC (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 groups -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, such as FLDP-50 and FLDP-60 can be included and (be commodity Name, Toray Thiokol Co., Ltd. system).

As biphenol type epoxy compound, such as YX-4000, YL-6121H can be included and (be trade name, Mitsubishi Chemical 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, such as jER871, jER872 can be included and (be trade name, Mitsubishi Learn Co. Ltd. system), EPICLON 200, EPICLON 400 (being trade name, Dainippon Ink Chemicals's system), DENACOL EX- 711 and DENACOL EX-721 (are 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- diglycidyls meta-aminotoluene (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 (trade name, Mitsubishi gas chemistry strain formula 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 homopolymers 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 the copolymer of the monomer with Oxyranyle in addition to 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 ', The modified 3,4- epoxycyclohexyl-methyls -3 ' of 3 '-cyclopentane epoxide ether (following formula EP-54), 6-caprolactone, 4 ' -7-oxa-bicyclo[4.1.0 Carboxylate, 1,2:8,9- bicyclic oxygens limonene (CELLOXIDE 3000 (trade name, Daicel Corporation. systems), under State the compound shown in formula EP-55, following formula EP-56, CY-175, CY-177, CY-179 and (be trade name, The Ciba- 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 group 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 macromolecular 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, used as foregoing macromolecular compound, it is soluble macromolecular compound that can include to organic solvent.From From the viewpoint of electrical characteristics, the orientation of the formed liquid crystal orientation film of control, preferably this macromolecular compound is added to In aligning agent for liquid crystal of the invention.As the macromolecular compound, can include for example polyamide, polyurethane, polyureas, polyester, Polyepoxide, PEPA, organic silicon modified polyurethane and organosilicon modified polyester.

Additionally, 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；Additionally, 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, such as aliphatic amine such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine can be included Class；The aromatic amines such as N, accelerine, N, 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 pyridone and isoquinolin in it is one kind or two or more.

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

The addition of imidization catalyst is commonly angled relative to the carbonyl of polyamic acid or derivatives thereof for 0.01~5 works as 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 of the invention or derivatives thereof 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).

The molecular weight of polyamic acid of the invention or derivatives thereof is excellent in terms of the weight average molecular weight (Mw) of polystyrene conversion 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 invention or derivatives thereof can be obtained by using IR, NMR to precipitating it with a large amount of lean solvents To solid constituent be 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 such that it is able to confirm the monomer for having used.

In addition, for example, in aligning agent for liquid crystal of the 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 select according to application target. Aforementioned solvents can for a kind can also be mixed solvent of more than two kinds.

As solvent, can include foregoing polyamides acid or derivatives thereof good solvent, for improve coating other Solvent.

It is the aprotic polar organic solvent of good solvent as polyamic acid or derivatives thereof, N- first can be included Base -2-Pyrrolidone, dimethyl-imidazolinone, N- methylcaprolactones, N- methyl propanamides, DMAC N,N' dimethyl acetamide, diformazan The lactones such as base sulfoxide, N,N-dimethylformamide, N, 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 the polyamic acid in alignment agent of the invention is preferably 0.1~40 weight %.The alignment agent is coated During substrate, in order to adjust thickness, it is sometimes desirable to the operation that the polyamic acid that will contain is diluted with solvent in advance.

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

The preferred scope of the viscosity of aligning agent for liquid crystal of the invention is dense because coating method, polyamic acid or derivatives thereof The species of degree, polyamic acid used or derivatives thereof, the species of solvent and ratio and it is different.For example, using 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 change 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, for example, use rotation viscometer (Toki Sangyo Co., Ltd. The TVE-20L types of manufacture) it is measured (temperature of the measurement：25℃).

It is described in detail for liquid crystal orientation film of the invention.Liquid crystal orientation film of the invention is by heating foregoing The film of the aligning agent for liquid crystal of invention and the film that is formed.Liquid crystal orientation film of the invention can make liquid crystal by by aligning agent for liquid crystal The usual method of alignment films is obtained.For example, liquid crystal orientation film of the invention can be by via formation liquid crystal aligning of the invention The step of film of agent, the step of of being thermally dried and obtained the step of heating is burnt till.On liquid of the invention Brilliant alignment films, as needed as will be shown later, it is also possible to burning till the film that step obtains and brushing via heat-drying step, heating Mill processes to assign anisotropy.In addition, as needed, it is also possible to 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 treatment The form 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 can be included and optionally be 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.

Method as aligning agent for liquid crystal to be coated substrate, it is commonly known to have spinner method, print process, infusion process, drop 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 it there is 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 Carry out 1 minute~3 hours at a temperature of 100~300 DEG C or so, more preferably 120~280 DEG C, more preferably 150~ 250℃.Furthermore, it is possible to carry out heating for multiple times at different temperatures burn till.The multiple heating of setting to different temperatures can be used Device, it is also possible to change to different temperatures successively while carrying out on one side using 1 heater.2 are carried out at different temperature Secondary heating is when burning till, and is carried out with more than 180 DEG C of temperature with 90~140 DEG C, the 2nd time for preferably the 1st time.

In the forming method of liquid crystal orientation film of the 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 compatibly uses the known shapes such as brushing method, optical alignment method Into method.

Having used the liquid crystal orientation film of the invention of brushing method can coat substrate via by aligning agent for liquid crystal of the invention The step of, be coated with the substrate of alignment agent the step of be thermally dried, carry out the film the step of heating is burnt till and will Film formed the step of brushing is processed.

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

It is described in detail for the method that liquid crystal orientation film of the invention is formed using optical alignment method.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, the film is carried out into heating burns till, so as to be formed.Furthermore it is possible to it is dry to pass through heating After dry film and heating burns till, the rectilinearly polarized light of illumination radiation line or unpolarized light are formed.From from the viewpoint of orientation, The irradiating step of radiation is preferably carried out before step is burnt till in heating.

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

As radiation, it is possible to use the ultraviolet or visible ray of the light for example comprising 150~800nm wavelength, preferably The ultraviolet of the 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 show strong orientation regulation power for liquid crystal When, preferably rectilinearly polarized light.

Even if liquid crystal orientation film of the invention can also show liquid crystal aligning ability high under the light irradiation of low energy. The exposure of the 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.Additionally, liquid crystal orientation film of the 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..

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

Method as being cleaned using cleaning fluid, can include the cleaning of scrub, injection, steam purge or ultrasonic wave Deng.These methods can be carried out individually, it is also possible to be applied in combination.As cleaning fluid, it is possible to use pure water or methyl alcohol, 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 of fully purifying.This cleaning side Method can also be applied in the foregoing cleaning step when liquid crystal orientation film of the invention is formed.

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, it is possible to 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 Outward, the annealing light for being 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 invention is not particularly limited, preferably 10~300nm, more preferably 30~ 150nm.The thickness of liquid crystal orientation film of the invention can be surveyed using the known film thickness measuring device such as difference of height meter, ellipsometer It is fixed.

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

Liquid crystal orientation film of the 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 °.

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

For liquid crystal display cells of the 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 to the upper electrode for being formed in one of face or both, respective to being taken to the liquid crystal formed on face in foregoing a pair of substrates The liquid crystal layer formed to film and between foregoing a pair of substrates, the foregoing liquid crystal alignment films in 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 etc..In addition, electrode can be formed at the whole face in a face of substrate, it is also possible to be formed as example scheming The intended shape of case.The foregoing intended shape of electrode can include such as combed or broached-tooth design etc..Electrode can be formed at A substrate among a pair of substrates, it is also possible to 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 with using relative foregoing a pair of substrate clampings liquid-crystal composition in the face for being formed with liquid crystal orientation film Form formed.For the formation of liquid crystal layer, can be clamped in foregoing a pair using particulate, resin sheet etc. as needed The sept of appropriate intervals is formed between substrate.

Liquid-crystal composition is not particularly limited, it is possible to use dielectric constant anisotropy is positive or negative various liquid crystal combinations 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 is that the optically active compound of more than a kind of addition in positive or negative liquid-crystal composition makes Even.

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

Herein, R^1aAnd R^2aIt independently is alkyl, the alkoxy of carbon number 1~12, the carbon atom of carbon number 1~12 The alkenyl of 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- diox -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- diyls, 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- diyls, 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 A²Can be the same or different, any 2 Z¹Can 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- diyls, 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 alkyl, the alkoxy of carbon number 1~12, the carbon atom of carbon number 1~12 The alkenyl of 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 stability to 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- The preferably vertical structure configuration of CH=CH- 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 of 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 Preferred example is 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 It is singly-bound.

In the foregoing liquid-crystal composition with negative dielectric constant anisotropy, the preferred formula (NL- as the 1st composition 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 foregoing liquid-crystal composition with negative dielectric constant anisotropy, 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 for the liquid-crystal composition of element of the present invention, such as from from the viewpoint of improving orientation, can 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 photopolymerization monomer or the most preferred configuration of 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 %.Additionally, in order to they be polymerized 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 to the compound of hybrid optical activity in composition.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 % The scope of~2 weight %.

In order to prevent being reduced by resistivity caused by the heating in air, or in order to after long-term use element in room temperature Maintain big voltage retention under lower and high temperature and to mixing antioxidant in liquid-crystal composition.

The preference of antioxidant is compound shown in the formula (AO-1) of 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 that the volatility of the compound shown in 1 formula (AO-1) is big, therefore, It is effective when preventing from being reduced by resistivity caused by the heating in air.W is the volatilization of the compound shown in 7 formula (AO-1) Property is small, therefore, for after long-term use element at room temperature with high temperature under maintain big voltage retention for be effective 's.Preferred proportion on antioxidant, is 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 the scope of 100ppm~300ppm.

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.Preferred proportion on these absorbents, stabilizer, in order to obtain Its effect and be more than 50ppm, be below 10000ppm to not reducing ceiling temperature or not improve lower limit temperature.Enter one Walk the scope that preferred ratio 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 0.01 weight %~10 weight % 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 Preferred ratio is the scope of 1ppm~500ppm.

In order to meet PSA, (polymer stabilizing is orientated；Polymer sustained alignment) pattern element, can Mix the compound that can be polymerized in the composition.The preferred example of the compound that can be polymerized is acrylate, metering system Acid esters, vinyl compound, ethyleneoxy compounds, propylene ether, epoxide (oxirane, oxetanes), ethene The compound with the group that can be polymerized such as base ketone.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 be polymerized 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 for about the scope of 0.1 weight %~about 2 weight %.

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.

, come necessary material for triggering chain polymerization to react, can mix poly- as easily producing free radical or ion 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.Can be polymerized Compound preferably includes Photoepolymerizationinitiater initiater with the scope of 0.1 weight %~5 weight %.Particularly preferably with 1 weight %~3 weight The scope for measuring % includes Photoepolymerizationinitiater initiater.

For radical polymerization system, in order to be reacted rapidly with the free radical generated by polymerization initiator or monomer And it is transformed into the free radical or neutral compound of stabilization so as 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, another kind be easily with the radical reaction that exists in polymerization system and be converted into the material of stabilized radical, its representative It is 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 be 1000ppm with Under.Further preferred ratio is the scope of 5ppm~500ppm.

Liquid crystal display cells of the 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 be noted that the evaluation method used in embodiment and chemical combination Thing 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.The TSK polystyrene standards that polystyrene standard is manufactured using TOSOH Co., Ltd.

2. tilt angle is determined

It is measured according to Crystal Rotation (crystal rotation) method.Tilt angle is the finger for turning into prediction viewing angle characteristic Target physics value, if the value is less than 2.0, as in the good liquid crystal display unit of IPS patterns and FFS mode downwards angle of visibility characteristic Part.

3. 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 the square wave of wave height ± 5V to unit.Measure is carried out at 60 DEG C.The value is to represent applied electricity Being pressed in after the frame period can keep the index of which kind of degree, represent that all of electric charge is maintained if the numerical value is 100%. If being more than 97.5% in being more than 99.5% in being equipped with the unit of positive type liquid crystal, being equipped with the unit of negative type liquid crystal, into It is the good liquid crystal display cells of display quality.

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

According to the method that Applied Physics the 65th volume No. 10 page 1065 (1996) is recorded, TOYO Corporation are used The type of liquid crystal physical property measurement system 6254 of manufacture is measured.Frequency of use is the triangular wave of 0.01Hz, in the voltage model of ± 10V 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 the physics value for turning into the index that prediction ghost occurs.If the value is below 40pC, Then turn into the good liquid crystal display cells of display quality.

5. flow orientation

By liquid crystal cells be configured to crossed nicols 2 polarizers clamp, when being observed by visual observation, liquid crystal along It is referred to as flow orientation from the phenomenon of the direction arrangement of inlet flowing.Flow orientation is the index of the orientation of alignment films, is not sent out The alignment films of raw flow orientation possess good orientation.

N,N-dimethylformamide：DMF

Tetrahydrofuran：THF

METHYLPYRROLIDONE：NMP

Gamma-butyrolacton：GBL

Butyl cellosolve (ethylene glycol monobutyl ether)：BC

[embodiment 1]

The synthesis of the diamines shown in formula (1-15).

<1st stage>The synthesis of dinitro matrix

4- amino -2,2,6,6- tetramethyl piperidines are put into being provided with the 500mL there-necked flasks of thermometer and return duct (20.0g, 128.0mmol) and potassium carbonate (44.2g, 320.0mmol), adds the DMF of 200mL.By solution be maintained at 5 DEG C with Under, and 4- fluoronitrobenzenes (39.7g, 281.6mmol) are slowly added thereto.Stop the cooling of reaction solution, enter at room temperature One step is stirred 24 hours.Reaction solution is put into pure water 500mL, is extracted with ethyl acetate.By organic layer sulfuric acid Sodium anhydride is dried, and after filtering removal drier, vacuum distillation removes solvent and obtains crude product.Gained crude product is used Ethanol (50mL) is recrystallized and is obtained following compounds.Yield is 26.3g, yield is 52%.

<2nd stage>The reduction of nitro

To compound (26.3g, 66.0mmol) and 5wt% that input in 1L autoclave reactors is obtained by the 1st stage Palladium carbon powder (2.6g), adds the THF of 250mL.Stopped with the absorption of 50 DEG C of stirrings to hydrogen under the hydrogen atmosphere of 0.5mPa Untill.After letting cool, filtering removal palladium carbon powder, vacuum distillation removes solvent and obtains crude product.By crude product ethanol 40mL Recrystallized, obtained the compound shown in formula (1-15).Yield is 19.3g, yield is 86%.

[embodiment 2]

The synthesis of the diamines shown in formula (1-29)

<1st stage>The synthesis of dinitro matrix

4- amino -2,2,6,6- tetramethyl piperidines are put into being provided with the 500mL there-necked flasks of thermometer and return duct (20.0g, 128.0mmol) and potassium carbonate (44.2g, 320.0mmol), adds the DMF of 200mL.By solution be maintained at 5 DEG C with Under, and be slowly added makes 4- nitrobenzyl bromides (60.8g, 281.6mmol) be dissolved in obtained from DMF (50mL) thereto Solution.Stop the cooling of reaction solution, be further stirred at room temperature 5 hours.Reaction solution is put into pure water 500mL, is used Ethyl acetate is extracted.Organic layer sodium sulphate anhydride is dried, after filtering removal drier, vacuum distillation removal Solvent and obtain crude product.Gained crude product is recrystallized with ethanol (50mL) and following compounds are obtained.Yield is 46.2g, yield are 85%.

<2nd stage>The reduction of nitro

To being provided with the compound that input is obtained by the 1st stage in the 1000mL there-necked flasks of thermometer and return duct (46.2g, 108.3mmol), adds ethanol 300mL and water 50mL.Solution is maintained at less than 25 DEG C, and is slowly added vulcanization Sodium nonahydrate (295.4g, 649.9mmol).Be heated to reflux in a nitrogen atmosphere 8 hours, after letting cool, by reaction solution put into In pure water (500mL), extracted with ethyl acetate (500mL), organic layer is cleaned 3 times with pure water (500mL).By organic layer It is dried with sodium sulphate anhydride, after filtering removal drier, vacuum distillation removes solvent and obtains crude product.Gained is thick Product is recrystallized with ethanol (50mL), so as to obtain the compound shown in formula (1-29).Yield is 27.3g, yield is 69%.

[embodiment 3]

The synthesis of the diamines shown in formula (1-1)

<1st stage>Mesylation

To be provided with the 2000mL there-necked flasks of thermometer and return duct put into 2- nitroethyl alcohols (30.0g, 329.4mmol) with triethylamine (50.0g, 494.2mmol), the THF of 600mL is added.Solution is maintained at less than 5 DEG C, and to Wherein it is slowly added mesyl chloride (45.3g, 395.3mmol).Stop the cooling of reaction solution, be further stirred at room temperature 24 small When.Reaction solution is put into pure water 500mL, is extracted with ethyl acetate.Organic layer is dried with sodium sulphate anhydride, After filtering removal drier, vacuum distillation removes solvent and obtains following compounds.Yield is 53.2g, yield is 95%.

<2nd stage>The synthesis of dinitro matrix

4- amino -2,2,6,6- tetramethyl piperidines are put into being provided with the 2000mL there-necked flasks of thermometer and return duct (13.5g, 86.5mmol) and potassium carbonate (27.5g, 199.0mmol), adds the DMF of 200mL.Solution is maintained at less than 5 DEG C, And be slowly added makes the compound (30.0g, 177.4mmol) obtained by the 1st stage be dissolved in DMF (50mL) and obtain thereto The solution for arriving.Stop the cooling of reaction solution, be further stirred at room temperature 5 hours.Reaction solution is put into pure water 500mL In, extracted with ethyl acetate.Organic layer sodium sulphate anhydride is dried, after filtering removal drier, decompression is steamed Evaporate and crude product is obtained except solvent.Gained crude product is recrystallized with ethanol (50mL) and following compounds are obtained.Produce Measure as 19.2g, yield are 73%.

<3rd stage>The reduction of nitro

To being provided with the compound that addition is obtained by the 2nd stage in the 1000mL there-necked flasks of thermometer and return duct (15.0g, 49.6mmol) and methyl alcohol 50mL.Solution is maintained at -10 DEG C, and is slowly added 10% Pd/C (1.5g) and first Sour ammonium (30.8g, 496.1mmol), stirs 8 hours at the same temperature.Filter off catalyst.Then vacuum distillation removes solvent, Addition ethyl acetate and saturated aqueous sodium carbonate, pH is adjusted to more than 7.Organic layer is done with sodium sulphate anhydride Dry, after filtering removal drier, vacuum distillation removes solvent and obtains crude product.Gained crude product is carried out with ethanol (50mL) Recrystallization, so as to obtain the compound shown in formula (1-1).Yield is 9.6g, yield is 80%.

The preparation of [embodiment 4] varnish

Compound DI-7-3 (m are put into being provided with the 200mL eggplant type flasks of thermometer, nitrogen blow valve port and stirring rod =3, n=1) 2.5874g, the compound 0.610g shown in formula (1-1-1), addition 59.0g NMP and 15.0g GBL.By solution Less than 5 DEG C are cooled to, the compound shown in compound 0.5553g thereto shown in throw-in type (AN-3-1), formula (PA-1) Compound 0.3261g shown in 0.9152g and formula (AN-1-13), is further stirred at room temperature 6 hours.It is added to fourth Base cellosolve (BC) 20.0g, reaching about 35.0cP to the viscosity of solution with 70 DEG C of heating stirrings, so as to obtain solid constituent It is the varnish 1 of 6wt%.The weight average molecular weight (Mw) of the varnish is 68000.

[5~embodiment of embodiment 35 and comparative example 1~3]

According to the method described in embodiment 4, 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 4 is recorded again.[] interior each comfortable tetracarboxylic compound group of expression, Mol ratio in diamine compound group.

[table 1-1]

[table 1-2]

[embodiment 36]

To weighing 10g varnish 1 in 50mL eggplant type flasks, the METHYLPYRROLIDONE and 10g of 10g are added to 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 the glass substrate of subsidiary FFS electrodes and subsidiary glass partition thing (2000rpm, 15 seconds).After film After with 80 DEG C of pre-fireds about 5 minutes, carry out burning till treatment in 30 minutes with 200 DEG C, so as to form the thickness about liquid crystal of 100nm Alignment films.The brushing processing unit manufactured using Iinuma Gauge Manufacturing Co., Ltd.s, in brushing cloth (brush Staple length is 1.9mm：Artificial silk) bristle lengths intrusion for 0.40mm, pedestal translational speed be 60mm/sec, roller rotation speed Under conditions of spending for 1000rpm, brushing treatment is carried out to gained polyimide film.By the ultrasonic wave cleaning in ethanol of gained substrate After 5 minutes, surface is cleaned with ultra-pure water, then in an oven with 120 DEG C of dryings 30 minutes.For being formed with alignment films on substrate 2 plate bases, the face for making to be formed with alignment films is relative, in the parallel mode in the brushing direction of respective alignment films, further sets Put for the space to injection liquid-crystal composition between relative alignment films, and pasted, be 4 so as to be assembled into element thickness μm empty FFS units.To the following positive type liquid crystal composition A of vacuum injection in made empty FFS units, sealed with light curing agent Inlet.Then, the heating of 30 minutes is carried out with 110 DEG C, so as to make measure liquid crystal cells.

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, tilt angle is 1.3°.By the unit in backlight testing machine (Fuji film Co. Ltd. system, the FujiCOLOR LED Viewer Pro for lighting HR-2；Brightness is 2700cd/m²) on load 1000 hours, carry out reliability test.Measure unit after reliability test Voltage retention is 99.7%, and ion concentration is 10pC, tilt angle is 1.3 °.

[embodiment 37~67 and comparative example 4~6]

For varnish 2~32 and varnish C1~C3, the method also recorded according to embodiment 36 carries out the system of aligning agent for liquid crystal The standby, making of FFS units and voltage retention, ion concentration, the measure of tilt angle.Show the result in table 2.Record again and implement The result of example 36.

[table 2]

Use in whole results of liquid crystal display cells of aligning agent for liquid crystal 1~32, be after initial, reliability test Good result.Use in the liquid crystal display cells of aligning agent for liquid crystal C1~C2, voltage retention and ion concentration are good Result, but tilt angle is big, viewing angle characteristic is poor result is presented.In having used the liquid crystal display cells of aligning agent for liquid crystal C3, in advance Inclination angle is good result, but is presented that ion concentration is big, the result of poor reliability.

[embodiment 68~110 and comparative example 7~9]

In addition to change tetracarboxylic dianhydride and diamines, it is 6 weights to prepare polymer solids constituent concentration according to embodiment 4 Measure 33~varnish of varnish 75 and varnish C4~6 of %.On weight average molecular weight, the poly- of the raw material with photoisomerization structure is used The polymer that compound adjusted to about 12000~13000, do not use the raw material with photoisomerization structure adjusted to 40000~ 50000.The weight average molecular weight of the tetracarboxylic dianhydride that will be used and diamines and resulting polymers is shown in table 3-1~table 3-4.

[table 3-1]

[table 3-2]

[table 3-3]

[table 3-4]

The preparation of [embodiment 111] single-layer type alignment agent, the making of electrical characteristics determining unit and electrical characteristics determining

Synthesized by embodiment 68 to weighing 10.0g in being provided with the 50mL eggplant type flasks of stirring vane, nitrogen ingress pipe Varnish 33, be added to METHYLPYRROLIDONE 5.0g and butyl cellosolve 5.0g, be stirred at room temperature 1 hour, from And obtain the alignment agent 33 that resinous principle concentration is 3 weight %.The alignment agent is coated on subsidiary FFS electrodes using spin-coating method The glass substrate (2000rpm, 15 seconds) of glass substrate and subsidiary glass partition thing.After coating, substrate is heated 3 minutes with 80 DEG C And make solvent evaporate after, the Multi-Light ML-501C/B manufactured using USHIO INC., from perpendicular to the direction of substrate every The rectilinearly polarized light of polarizer irradiation ultraviolet radiation.The ultraviolet accumulation light that exposure energy now is manufactured using USHIO INC. Gauge UIT-150 (light-receiving devices：UVD-S365 light quantity) is determined, 1.3 ± 0.1J/cm is reached with the energy under wavelength 365nm²Side Formula adjusts the time for exposure.Then, 15 points are heated with 230 DEG C in dustless baking oven (ESPEC Co., Ltd.s, PVHC-231) Clock, so as to form the alignment films that thickness is 100 ± 10nm.2 plate bases of these alignment films will be formed with to be formed with alignment films Face it is relative and be provided for being pasted to the mode in the space for injecting liquid-crystal composition between relative alignment films.Now, photograph is made Be incident upon the rectilinearly polarized light of each alignment films direction of polarized light reach it is parallel.To injection positive type liquid crystal composition in these units A, production unit thickness is 7 μm of liquid crystal cells (liquid crystal display cells).

Above-mentioned such liquid crystal cells for making are clamped with 2 polarizers for being configured to crossed nicols, is carried out by visual observation Observation.As a result, not observing the so-called flow orientation that liquid crystal is arranged along the direction flowed from inlet completely.Additionally, should The voltage retention of liquid crystal cells is 99.8% under 5V-30Hz, and ion concentration is 10pC.By the unit in the backlight examination lighted Test machine (Fuji film Co. Ltd. system, FujiCOLOR LED Viewer Pro HR-2；Brightness is 2700cd/m²) on load 1000 hours, carry out reliability test.The voltage retention of the measure unit after reliability test is 99.7%, ion concentration It is 10pC.

[embodiment 112~123 and comparative example 10~12]

In addition to changing used varnish, liquid crystal cells are made according to embodiment 111, carry out the sight of flow orientation Examine and reliability test before and after voltage retention, the measure of ion concentration.Measurement result is shown in the lump with embodiment 111 Table 4.

[table 4]

For all units of embodiment 111~123, the value after initial value, reliability test can obtain good Good result.Herein, initial value refers to determine the result for obtaining with not being placed in above-mentioned backlight testing machine after production unit.For For the unit of comparative example 10~11, in the value after initial value, reliability test, voltage retention/ion concentration can be obtained Good result, but flow orientation is observed, the result of the poor orientation of liquid crystal is presented.In comparative example 12, flowing is not observed Orientation, can obtain good liquid crystal aligning, but be presented that the value of ion concentration is big, the result of poor reliability.

The preparation of [embodiment 124] blending type alignment agent, the making of electrical characteristics determining unit and electrical characteristics determining

Weigh what 2.0g was synthesized by embodiment 73 to being provided with the 50mL eggplant type flasks of stirring vane, nitrogen ingress pipe The varnish 67 that varnish 38 and 8.0g are synthesized by embodiment 102, is added to METHYLPYRROLIDONE 5.0g and butyl is molten Fine agent 5.0g, is stirred at room temperature 1 hour, so as to obtain the alignment agent 46 that resinous principle concentration is 3 weight %.According to embodiment 111 methods recorded make liquid crystal cells.The liquid crystal cells are clamped with 2 polarizers for being configured to crossed nicols, by mesh Depending on being observed, the so-called flowing that as a result do not observe completely carries out liquid crystal arrangement along the direction that liquid crystal flows from inlet takes To.Additionally, the voltage retention of the liquid crystal cells is 99.8% under 5V-30Hz, ion concentration is 10pC.After reliability test Measure unit voltage retention be 99.7%, ion concentration is 10pC.

[embodiment 125~172 and comparative example 13-15]

In addition to changing used varnish, liquid crystal cells are made according to embodiment 124, carry out the sight of flow orientation Examine and reliability test before and after voltage retention, the measure of ion concentration.The varnish and measurement result and reality that will be used Apply example 124 and be shown in table 5-1 and table 5-2 in the lump.It should be noted that in table, varnish A is represented containing using with photoisomerization knot The varnish of the polymer of the raw material of structure, varnish B is represented and is contained the clear of the polymer for not using the raw material with photoisomerization structure Paint.

[table 5-1]

[table 5-2]

In all units of embodiment 124~172, the value after initial value, reliability test can obtain good knot Really.Herein, initial value refers to determine the result for obtaining with not being placed in above-mentioned backlight testing machine after production unit.For comparative example For 13~14 unit, in the value after initial value, reliability test, voltage retention/ion concentration can obtain good As a result, but observe flow orientation, present liquid crystal aligning difference result.In comparative example 15, flow orientation is not observed, can be with Obtain good liquid crystal aligning, but be presented that the value of ion concentration is big, the result of poor reliability.

It can be seen from above-described embodiment：Possesses the liquid crystal display of the liquid crystal orientation film formed by aligning agent for liquid crystal of the invention Element turn into viewing angle characteristic it is excellent, even across the liquid crystal display cells that good display quality is also kept after long-time.

Industrial applicability

By using the liquid crystal orientation film formed by aligning agent for liquid crystal of the invention, it is obtained in that viewing angle characteristic, image retention are special Even if property is excellent, excellent liquid crystal display cells that are will not also being reduced using its display quality for a long time.It is especially adapted for use in work It is IPS patterns, the FFS mode of the liquid crystal display cells of Transverse electric-field type.

Claims

1. a kind of polyamic acid or derivatives thereof, it is to make at least a kind in tetracarboxylic dianhydride and diamines shown in contained (1) Obtained from diamine reactant,

2. polyamic acid according to claim 1 or derivatives thereof, wherein, the diamines shown in formula (1) is for shown in formula (1 ') Diamines,

- the NH being bonded on ring₂Bonding position be optional position.

3. polyamic acid according to claim 1 or derivatives thereof, wherein, in the diamines shown in formula (1), R be hydrogen or- OH。

4. polyamic acid according to claim 1 or derivatives thereof, wherein, the diamines shown in formula (1) is following formula (1- 15) compound or shown in formula (1-29),

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

Other diamines being used together with the diamines shown in formula (1) are selected from by following formula (DI-1)~formula (DI-16), formula (DIH-1) at least a kind in the group of~formula (DIH-3) and formula (DI-31)~formula (DI-35) composition,

In formula (AN-III)~formula (AN-V), ring A¹⁰For carbon number 3~10 monocyclic alkyl or carbon number 6~30 it is thick Polycycle alkyl is closed, at least one hydrogen on the group is optionally replaced by methyl, ethyl or phenyl, and being bonded for 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), R²³It independently is alkyl, the alkoxy of carbon number 1~5 or-Cl, the p independence of carbon number 1~5 Ground is 0~3 integer, and q is 0~4 integer；

In formula (DI-14), ring B is monocyclic heteroaromatic, R²⁴It is 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 is 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), G²⁵It is singly-bound, alkylidene ,-CO- ,-O- ,-the S- ,-SO of carbon number 1~20₂-、-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 ring is optionally by methyl, ethyl or benzene Base replaces；

In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen on the ring is optionally by methyl, second Base or phenyl replace, and Y is singly-bound, alkylidene ,-CO- ,-O- ,-the S- ,-SO of carbon number 1~20₂-、-C(CH₃)₂- or-C (CF₃)₂-；

In formula (DI-31), G²⁶It is 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 Group shown in group or following formula (DI-31-a), in the alkyl, at least one hydrogen is optionally replaced by-F, 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, on phenyl ring be bonded-NH₂ Bonding position represent the optional position on the ring,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹It is linking group, they independently are the alkylene of singly-bound or carbon number 1~12 Base, more than 1-CH in the alkylidene₂- optionally by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH- displacements, ring B²¹, ring B²², ring B²³With ring B²⁴It independently is 1,4- phenylenes, 1,4- cyclohexylenes, 1,3- diox -2,5- diyls, pyrimidine -2,5- two Base, pyridine -2,5- diyls, piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyls, naphthalene -2,7- diyls or anthracene -9,10- diyls, 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 is calculated as, 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 identical Can also be different,

R²⁶It is 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), 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；

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, G³²It is singly-bound Or the alkylidene of carbon number 1~3,

R³¹It is 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, R³²It is the alkyl of carbon number 6~22, R³³It is hydrogen or the alkyl of carbon number 1~22, ring B²⁵It is 1,4- Asias benzene 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.

6. polyamic acid according to claim 5 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), at least a kind in formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4)；

Other diamines being used together with the diamines shown in formula (1) are selected from by following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), 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 At least a 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 1 or 2.

7. polyamic acid according to claim 1 or derivatives thereof, wherein, in tetracarboxylic dianhydride and diamines at least 1 Comprising the compound with photoreactivity structure.

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

9. polyamic acid according to claim 7 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) at least a kind 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 is each independently 0~2 Integer, in formula (V-3), ring A and ring B is each independently selected from least 1 in monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle Kind, R¹¹It is straight-chain alkyl-sub ,-COO- ,-the OCO- ,-NHCO- or-N (CH of carbon number 1~20₃) CO-, R¹²It is 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 It is on the spot 0~4 integer.

10. polyamic acid according to claim 7 or derivatives thereof, wherein, the compound with photoreactivity structure is Diamines shown in following formula (PDI-7),

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

A kind of 11. aligning agent for liquid crystal, it contains polyamic acid any one of claim 1~10 or derivatives thereof.

A kind of 12. 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,

In the starting monomer of the polymer at least 1 have a photoreactivity structure, and the polymer starting monomer bag At least a kind in containing the compound shown in following formula (1),

13. light orientation aligning agent for liquid crystal according to claim 12, it includes at least a kind polymer [A] and at least a kind Polymer [B],

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

The polymer [B] is the tetrabasic carboxylic acid two obtained from reacting the starting monomer comprising tetracarboxylic dianhydride and diamines Acid anhydride and diamines are without at least a kind in photoreactivity structure and compound shown in diamines contained (1).

14. light orientation aligning agent for liquid crystal according to claim 12, it includes at least a kind polymer [A] and at least a kind Polymer [B],

The polymer [A] is the tetrabasic carboxylic acid two obtained from reacting the starting monomer comprising tetracarboxylic dianhydride and diamines In acid anhydride and diamines at least 1 comprising with photoreactivity structure compound and compound shown in diamines contained (1) in At least a kind,

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

15. light orientation aligning agent for liquid crystal according to claim 12, it includes at least a kind polymer [A] and at least a kind Polymer [B],

16. light orientation aligning agent for liquid crystal according to claim 12, it includes at least a kind polymer [A] and at least a kind Polymer [B],

The polymer [B] is the tetrabasic carboxylic acid two obtained from reacting the starting monomer comprising tetracarboxylic dianhydride and diamines In acid anhydride and diamines at least 1 comprising with photoreactivity structure compound and compound shown in diamines contained (1) in At least a kind.

17. light orientation aligning agent for liquid crystal according to claim 12, wherein, the diamines shown in formula (1) is formula (1 ') institute The diamines for showing,

- the NH being bonded on ring₂Bonding position be optional position.

18. light orientation aligning agent for liquid crystal according to claim 12, wherein, in the diamines shown in formula (1), R be hydrogen or- OH。

19. light orientation aligning agent for liquid crystal according to claim 12, wherein, the diamines shown in formula (1) is following formula (1- 15) compound or shown in formula (1-29),

20. light orientation aligning agent for liquid crystal according to claim 12, wherein, the compound tool with photoreactivity structure There is at least a kind in following formula (P-1)~structure shown in formula (P-7),

21. light orientation aligning agent for liquid crystal according to claim 12, wherein, the compound with photoreactivity structure is Selected from by following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1)~formula (V-3) at least a kind and in formula (VI-1), the group of formula (VI-2) composition,

22. light reaction aligning agent for liquid crystal according to claim 12, wherein, the compound with photoreactivity structure is Diamines shown in following formula (PDI-7),

23. light orientation aligning agent for liquid crystal according to claim 12, wherein, the tetrabasic carboxylic acid without photoreactivity structure Dianhydride is at least a kind in the group selected from the tetracarboxylic dianhydride shown in following formula (AN-I)~formula (AN-VII),

Diamines without photoreactivity structure is selected from by following formula (DI-1)~formula (DI-16), formula (DIH-1)~formula (DIH-3) at least a kind 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；

24. light orientation aligning agent for liquid crystal according to claim 23, 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.

25. aligning agent for liquid crystal according to claim 12, its also containing selected from You oxazine compounds, oxazoline compounds, At least a kind in the compound group of epoxide and silane coupler composition.

A kind of 26. liquid crystal orientation films, it is formed as the aligning agent for liquid crystal any one of claim 11~25.

A kind of 27. transverse electric field liquid crystal orientation films, it is as the aligning agent for liquid crystal any one of claim 11~25 Formed.

A kind of 28. liquid crystal display cells, it has the liquid crystal orientation film described in claim 26.

A kind of 29. diamines, it uses formula (1 ') to represent,

- the NH being bonded on ring₂Bonding position be optional position.

30. diamines according to claim 29, it uses following formula (1-15) or formula (1-29) to represent,