CN105505407B - Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display element, polymer, diamines and tetracarboxylic dianhydride - Google Patents

Abstract

The present invention provides a kind of favorable solubility containing ingredient of aligning agent for liquid crystal and can obtain the aligning agent for liquid crystal for showing the liquid crystal display element of good image retention characteristic, liquid crystal orientation film, liquid crystal display element, polymer, diamines and tetracarboxylic dianhydride.Contain the compound (P) with part-structure represented by following formula (1) in the aligning agent for liquid crystal.(in formula (1), Y¹For protecting group；" * " indicates associative key).

Description

Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display element, polymer, diamines and four Carboxylic acid dianhydride

Technical field

The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display element, polymer, diamines and tetracarboxylic acids Acid dianhydride.

Background technique

In the past, as liquid crystal display element, physical property, the manufacture step of electrode structure or used liquid crystal molecule have been developed Different a variety of driving methods such as rapid, such as known twisted nematic (Twisted Nematic, TN) type or STN Super TN (Super Twisted Nematic, STN) type, vertical orientation (Vertical Alignment, VA) type, coplanar switching (In- Plane Switching, IPS) type, the various liquid crystal displays of fringing field switching (fringe field switching, FFS) type etc. Element.These liquid crystal display elements have the liquid crystal orientation film to make liquid crystal molecular orientation.As the material of liquid crystal orientation film, For the good aspects of various characteristics such as the compatibility of heat resistance, mechanical strength and liquid crystal, usually using polyamic acid or gather Acid imide.

In recent years, in order to realize that the display performance of liquid crystal display element further increases, plurality of liquid crystals orientation is proposed Agent.For example, proposing for the purpose for reducing image retention using the polyimides comprising also having nitrogen-atoms in addition to imide Or the aligning agent for liquid crystal of its predecessor forms liquid crystal orientation film (referring for example to patent document 1).

Itd is proposed in patent document 1: make the tetracarboxylic dianhydride comprising 1,2,3,4- cyclobutane tetracarboxylic dianhydrides with comprising having The diamines of the diamines of amido bond (- NH-CO-) reacted and the polyamic acid that obtains and make tetracarboxylic dianhydride and diamines into Row reacts and the imide amination polymer of the polyamic acid of acquisition contains in aligning agent for liquid crystal；And it will be in aligning agent for liquid crystal The ratio of the quantity of imide ring possessed by imide amination polymer is set as particular range.In patent document 1, by using institute Aligning agent for liquid crystal is stated to realize the improvement of voltage retention property and image retention characteristic.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2009-294274 bulletin

Summary of the invention

[problem to be solved by the invention]

However, since amido bond polarity is high, and aligning agent for liquid crystal is less good to the dissolubility of solvent composition, so deposit The tendency of storage stability in aligning agent for liquid crystal or the coating to substrate (printing) being wanting in, there are further improvement Leeway.

An object of the present invention is to provide a kind of favorable solubility containing ingredient of aligning agent for liquid crystal and can obtain It must show the aligning agent for liquid crystal of the liquid crystal display element of good image retention characteristic.

[technical means to solve problem]

The artificial realization problem of the prior art as described above of the inventors of the present invention and actively studied, discovery by with Protecting group protects amido bond, is able to solve described problem.Specifically, provide aligning agent for liquid crystal below, liquid crystal orientation film, Liquid crystal display element, polymer and compound.

An aspect of of the present present invention is to provide a kind of aligning agent for liquid crystal, contains and ties with part represented by following formula (1) The compound (P) of structure.

[changing 1]

(in formula (1), Y¹For protecting group；" * " indicates associative key)

In addition, being on the other hand to provide the liquid crystal orientation film formed using the aligning agent for liquid crystal.Additionally, it is provided including The liquid crystal display element of the liquid crystal orientation film.

In addition, on the other hand to provide using polyamic acid, poly amic acid ester, polyimides or polyamide as main framing, And the polymer with part-structure represented by the formula (1).Additionally, it is provided having the knot of part represented by the formula (1) The diamines of structure and the tetracarboxylic dianhydride with part-structure represented by the formula (1).

[The effect of invention]

By being protected the amido bond in the compound with amido bond (- NH-CO-) with protecting group containing in liquid In brilliant alignment agent, the favorable solubility to solvent can be made.Thereby, it is possible to obtain storage stability or the excellent liquid crystal of printing to take To agent.In addition, the condition or light of heating, acid or alkali when the protecting group being directed into amido bond is for example, by film are irradiated Deng and be detached from, the high structure of liquid crystal aligning is thus regenerated after film, as a result can obtain the good liquid crystal of image retention characteristic Display element.

Detailed description of the invention

Fig. 1 is in the liquid crystal cells with patterned transparent conductive film for indicating to be manufactured by Examples and Comparative Examples Transparent conductive film pattern explanatory diagram.

[explanation of symbol]

A, B: electrode

ITO: tin indium oxide

Specific embodiment

Hereinafter, the other compositions to each ingredient contained in aligning agent for liquid crystal of the invention and optionally arbitrarily deployed It is illustrated.

<compound (P)>

Aligning agent for liquid crystal of the invention contains the compound (P) with part-structure represented by following formula (1).

[changing 2]

(in formula (1), Y¹For protecting group；" * " indicates associative key)

Y in the formula (1)¹As long as the guarantor that amide groups, imide, urea groups, carbamate groups are protected Protect base, be then not particularly limited, for example, can enumerate using heat, light, acid and alkali at least any one come any monovalent organic radical that is detached from Deng.Y¹Any monovalent organic radical being detached from preferably at least is utilized heat to, as its concrete example, such as can be enumerated: carbamate system Protecting group, amide system protecting group, imide series protecting group, sulphonyl amine system protecting group etc..In these groups, preferably carbamic acid Ester system protecting group as its concrete example, such as can be enumerated: tert-butoxycarbonyl, benzyloxycarbonyl, 1,1- dimethyl -2- halogen For ethyloxycarbonyl, 1,1- dimethyl -2- cyano ethyl Epoxide carbonyl, 9- fluorenylmethyloxycarbonyl, allyl oxygroup carbonyl Base, 2- (trimethylsilyl) ethoxy carbonyl etc..As Y¹Concrete example, and then following formula (7-1)~formula (7-5) can be enumerated Represented group etc. respectively.

[changing 3]

(in formula (7-1)~formula (7-5), Ar¹For the monovalence fragrance ring group of carbon number 6~10, R¹⁴For the alkyl of carbon number 1~12, R¹⁵For any monovalent organic radical；" * " indicates the associative key being bonded on nitrogen-atoms)

The Ar of the formula (7-2)¹To remove group made of a hydrogen atom from the aromatic rings of carbon number 6~10, as Concrete example, such as phenyl, naphthalene can be enumerated etc..The R of formula (7-4)¹⁴The alkyl of carbon number 1~12 can for example enumerate: methyl, second Base, propyl, butyl, amyl, hexyl etc., these groups can be straight-chain, can also be branch-like.R¹⁵Any monovalent organic radical for example may be used It enumerates: the alkyl of carbon number 1~10, the naphthenic base of carbon number 3~10, the aryl of carbon number 6~10, aralkyl of carbon number 7~10 etc..This In a little groups, R¹⁵The aromatic series bases such as the preferably aryl of carbon number 6~10, more preferably phenyl or naphthyl.In addition, formula (the 7- 1) light can also be used not only using heat to deprotect (deprotection) in the represented group of~formula (7-4) difference.

With regard to using heat the high aspect of detachment or can be by the Y by being detached from due to heating when the film¹And the chemical combination come Object is expelled to for the aspect outside film as gas, wherein Y¹Preferably carbamate system protecting group, more preferably tertiary fourth Epoxide carbonyl.

The atom that associative key " * " in the formula (1) is bonded is preferably carbon atom.

Compound (P) may make up at least part of the component of polymer of aligning agent for liquid crystal, or can also with become substrate Component of polymer it is different, contained with the aspect of additive.

[polymer (P)]

It is the polymer (hereinafter also referred to " polymer with part-structure represented by the formula (1) at compound (P) (P) " in the case where), main framing is not particularly limited, such as can be enumerated: polyamic acid, poly amic acid ester, gathers polyimides Siloxanes, polyester, polyamide, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenyl maleic two Acid imide) derivative, poly- (methyl) acrylate, using azobenzene derivatives etc. as polymer of main framing etc..With regard to polymer Dissolubility or for making the good viewpoint of the image retention characteristic of resulting liquid crystal display element, polymer (P) is preferably in main chain The upper polymer with part-structure represented by the formula (1).

In these polymer, for heat resistance or the viewpoints such as mechanical strength and the compatibility of liquid crystal, polymer (P) is excellent It is selected as selected from least one of the group as composed by polyamic acid, poly amic acid ester, polyimides and polyamide polymer (hereinafter also referred to " particular polymers "), the particular polymers more preferably have portion represented by the formula (1) on main chain The polymer of separation structure.In addition, (methyl) acrylate refers to comprising acrylate and methacrylate.

(polyamic acid)

In the case where polymer (P) is polyamic acid, which can be by carrying out tetracarboxylic dianhydride and diamines It reacts and obtains.Specifically, can enumerate: [i] is by including that there is part represented by the formula (1) to tie in monomer composition The polymerization of the tetracarboxylic dianhydride of structure carrys out synthetic method；[ii] is by including to have the formula (1) represented in monomer composition The polymerization of diamines of part-structure carry out synthetic method；[iii] is by including to have the formula (1) institute table in monomer composition The polymerization of the tetracarboxylic dianhydride of the part-structure shown and the diamines with part-structure represented by the formula (1) synthesizes Method etc..In addition, will have the tetracarboxylic dianhydride of part-structure represented by the formula (1) to be also referred to as " specific tetrabasic carboxylic acid below Dianhydride ", and will have the diamines of part-structure represented by the formula (1) to be also referred to as " specific diamines ".

(tetracarboxylic dianhydride)

As long as specific tetracarboxylic dianhydride used in the synthesis of polyamic acid has the knot of part represented by the formula (1) Structure, then there is no particular restriction for remaining structure.Specific tetracarboxylic dianhydride using connect two anhydride groups structure division as In the case where main chain, comprising part-structure represented by the formula (1) preferably in the main chain, as its concrete example, such as Compound represented by following formula (2) etc. can be enumerated.

[changing 4]

(in formula (2), R¹、R²And R⁴Separately indicate divalent organic base；R³For singly-bound or divalent organic base；Y¹For Protecting group；Z¹And Z²Separately indicate trivalent organic group；The integer that m is 1~3, k are 0 or 1)

The R of the formula (2)¹~R⁴Divalent organic base can for example enumerate: the bivalent hydrocarbon radical of carbon number 1~20；By the Asia of alkyl Methyl is with-O- ,-S- ,-CO- ,-COO- ,-COS- ,-NR^a-、-CO-NR^a-、-NR^a-CO-NR^a-、-Si(R^a)₂(wherein, R^aFor The monovalent hydrocarbon or protecting group of carbon number 1~12) ,-N=N- ,-SO₂Wait bilvalent radical made of substitution；Alkyl will be bonded to At least one of hydrogen atom on carbon atom is with halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), hydroxyl, cyano Deng bilvalent radical made of substitution；Bilvalent radical etc. with heterocycle.

Herein, " alkyl " is the meaning comprising chain alkyl, alicyclic type hydrocarbon and aromatic hydrocarbyl in this specification.These In, " chain alkyl " refers on main chain without cyclic structure, but the straight-chain alkyl that is only made of chain structure and point Branch shape alkyl.Wherein, it can be saturation, can also be unsaturation." alicyclic type hydrocarbon " refers to structure conduct only comprising ester ring type hydrocarbon Ring structure, and be free of the alkyl of aromatic ring structure.Wherein, it is not necessarily required only to be made of the structure of ester ring type hydrocarbon, be also contained in With the alkyl of chain structure in part of it." aromatic hydrocarbyl " refers to the alkyl comprising aromatic ring structure as ring structure. Wherein, it is not necessarily required only to be made of aromatic ring structure, can also include chain structure or ester ring type hydrocarbon in part of it Structure.

As R¹~R⁴In carbon number 1~20 bivalent hydrocarbon radical concrete example, chain alkyl can for example enumerate: methylene, Asia Ethyl, glyceryl, Ding Erji, penta diyl, dihexyl, diyl in heptan, Xin Erji, nonyl diyl, last of the ten Heavenly stems diyl, ethenylidene, propylene two Base, butylene diyl etc.；Alicyclic type hydrocarbon can for example be enumerated: cyclohexylidene etc.；Aromatic hydrocarbyl can for example be enumerated: phenylene, Asia Xenyl etc..

Z¹And Z²Trivalent organic group be preferably trivalent chain alkyl, alicyclic type hydrocarbon or aromatic series ring group, more preferably From selected from one of the group as composed by phenyl ring, naphthalene nucleus, pentamethylene ring and cyclohexane ring ring remove three hydrogen atoms and At cyclic group.

M is preferably 1.

As the concrete example of specific tetracarboxylic dianhydride, such as can enumerate represented by following formula (2-1)~formula (2-3) difference Compound etc..

[changing 5]

(in formula, TMS indicates trimethylsilyl)

In addition, when synthesizing polyamides acid, specific tetracarboxylic dianhydride can be used alone and one kind or make two or more combinations With.

Specific tetracarboxylic dianhydride can be by synthesizing the universal method of organic chemistry is appropriately combined.For example, can be by making Tetracarboxylic dianhydride and di-tert-butyl dicarbonate with "-NH-CO- " carry out in the presence of the highly basic such as dimethyl aminopyridine Reaction, Lai Hecheng Y¹For the specific tetracarboxylic dianhydride of tert-butoxycarbonyl.Wherein, the synthetic method of specific tetracarboxylic dianhydride is not It is defined in the method.

Tetracarboxylic dianhydride used in the method for [i] and [iii] can be only specific tetracarboxylic dianhydride, but can also be by specific four Other tetracarboxylic dianhydrides other than carboxylic acid dianhydride are used in combination.In addition, in the method for [ii], when synthesizing polyamides acid, using other four Carboxylic acid dianhydride is as tetracarboxylic dianhydride.

Other tetracarboxylic dianhydrides can for example enumerate: aliphatic tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic series tetracarboxylic acid Acid dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydride can for example be enumerated: butane tetracarboxylic acid dianhydride Deng；

Ester ring type tetracarboxylic dianhydride can for example enumerate: 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxylic basic rings penta Guanidine-acetic acid dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxo -3- furyl)-naphtho- [1,2-c] furans -1, 3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydro -2,5- dioxo -3- furyl)-naphtho- [1,2-c] furan Mutter -1,3- diketone, 3- oxabicyclo [3.2.1] octane -2,4- diketone -6- loop coil -3 '-(tetrahydrofuran -2 ', 5 '-diketone), 5- (2,5- dioxotetrahydro -3- furyl) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 3,5,6- tri- carboxyl -2- carboxyl first Base norbornane -2:3,5:6- dianhydride, bicyclic [3.3.0] octane -2,4, it is 6,8- tetrabasic carboxylic acid 2:4,6:8- dianhydrides, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2:3,5:6- dianhydrides, 4,9- dioxa tricyclic [5.3.1.0^2,6] hendecane -3,5,8, 10- tetrone, 1,2,4,5- cyclopentanetetracarboxylic's dianhydrides, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, ethylenediamine Tetrem acid dianhydride, pentamethylene tetracarboxylic dianhydride, ethylene glycol bis- (dehydrations trimellitate), 1,3-PD is bis- (is dehydrated inclined benzene three Acid esters), TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride) etc.；

Aromatic tetracarboxylic dianhydride can for example be enumerated: pyromellitic acid anhydride etc., in addition to this, can be used Japan Patent special Open the tetracarboxylic dianhydride recorded in 2010-97188 bulletin.In addition, other tetracarboxylic dianhydrides can be by these tetracarboxylic dianhydrides' It is a kind of to be used alone or be used in combination of two or more.

For the viewpoints such as liquid crystal aligning, other tetracarboxylic dianhydrides preferably include selected from by 1,2,3,4- cyclobutane four Carboxylic acid dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, 5- (2,5- dioxotetrahydro furans -3- base) -3a, 4,5,9b- tetra- Hydrogen naphtho- [1,2-c] furans -1,3- diketone, 5- (2,5- dioxotetrahydro furans -3- base) -8- methyl -3a, 4,5,9b- tetrahydros Naphtho- [1,2-c] furans -1,3- diketone, bicyclic [3.3.0] octane -2,4,6,8- tetracarboxylic dianhydrides, pentamethylene tetracarboxylic dianhydride, Group composed by cyclopentanetetracarboxylic's dianhydride, TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride) and pyromellitic acid anhydride At least one of compound.The total amount of tetracarboxylic dianhydride used in synthesis relative to polyamic acid, these it is preferred its The usage amount (being its total amount using two or more) of his tetracarboxylic dianhydride is preferably set as 5 moles of % or more, 10 moles of % or more are more preferably set as, 20 moles of % or more are more preferably set as.

(diamines)

As long as specific diamines has part-structure represented by the formula (1), there is no particular restriction for remaining structure, It include the formula (1) institute preferably in the main chain in the case where using the structure division of two level-one amino of connection as main chain The compound of the part-structure of expression.As preferred concrete example, such as can enumerate: compound represented by following formula (3), under State compound represented by compound represented by formula (3A) and following formula (3B).

[changing 6]

(in formula (3), R⁵、R⁶And R⁸Separately indicate divalent organic base；R⁷For singly-bound or divalent organic base；Y¹For Protecting group；The integer that t is 1~3, s are 0 or 1)

[changing 7]

(in formula (3A), Y²And Y³Separately indicate the alkyl or protecting group of hydrogen atom, carbon number 1~3；Wherein, Y² And Y³At least one be protecting group；R¹¹、R¹²And R¹⁴Separately indicate divalent organic base, R¹³Have for singly-bound or divalent Machine base；The integer that v is 1~3, u are 0 or 1)

[changing 8]

(in formula (3B), R²¹、R²²And R²⁴Separately indicate divalent organic base；R²³For singly-bound or divalent organic base； Y⁴For protecting group；The integer that x is 1~3)

About the R in the formula (3)⁵~R⁸Divalent organic base, the R in the formula (3A)¹¹~R¹⁴Divalent organic base And the R in the formula (3B)²¹~R²⁴Divalent organic base, can apply the formula (2) R¹~R⁴Divalent organic base say It is bright.Wherein, R⁵、R⁸、R¹¹、R¹⁴、R²¹And R²⁴Preferably phenylene or the phenylene being substituted.In addition, substituent group can for example arrange It lifts: the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, halogen atom etc..

T, v and x are respectively preferably 1.

The concrete example of specific diamines can be enumerated: following formula (3-1)~formula (3-21) and formula (ADA1)~formula (ADA8) point Not represented compound etc..

[changing 9]

(in formula, TMS indicates trimethylsilyl)

[changing 10]

[changing 11]

(in formula, R¹⁵And R¹⁶Separately indicate that the monovalent hydrocarbon of halogen atom or carbon number 1~10, n are 2~12 Integer, a1 and a2 separately indicate 0~4 integer, the integer that p is 1~12)

[changing 12]

In addition, when synthesizing polyamides acid, specific diamines, which can be used alone, one kind or to be used in combination of two or more.

Y in the formula (1)¹In the case where through the de-protected group of light, such as following process A can also be used Reaction, the aligning agent for liquid crystal as the light orientation irradiated by the ultraviolet light of polarisation or non-polarized.

[changing 13]

(in process A, " * " indicates associative key)

Specific diamines can be by synthesizing the universal method of organic chemistry is appropriately combined.For example, can by make have "- The diamines and di-tert-butyl dicarbonate of NH-CO- " is reacted, Lai Hecheng Y in the presence of the highly basic such as dimethyl aminopyridine¹ For the specific diamines of tert-butoxycarbonyl.Wherein, the synthetic method of specific diamines is not limited to the method.

Diamines used in the method for [ii] and [iii] can be only specific diamines, but can also and with other than specific diamines Other diamines.In the method for [i], when synthesizing polyamides acid, use other diamines as diamines.

Other diamines can for example be enumerated: aliphatic diamine, ester ring type diamines, aromatic diamine, diamino organosiloxane Deng.As the concrete example of these diamines, aliphatic diamine can for example be enumerated: m-xylene diamine, 1,3- propane diamine, tetramethylene two Bis- (amino methyl) hexamethylenes of amine, five methylene diamine, hexamethylene diamine, 1,3- etc.；

Ester ring type diamines can for example be enumerated: Isosorbide-5-Nitrae-diaminocyclohexane, 4,4 '-di-2-ethylhexylphosphine oxides (cyclo-hexylamine) etc.；

Aromatic diamine can for example be enumerated: dodecyloxy diaminobenzene, tetradecyloxyaniline diaminobenzene, pentadecane epoxide Diaminobenzene, hexadecane epoxide diaminobenzene, octadecane epoxide diaminobenzene, cholesteric alkoxy diaminobenzene, cholesteric alkenyloxy group Diaminobenzene, diaminobenzoic acid cholesteric Arrcostab, diaminobenzoic acid cholestene base ester, diaminobenzoic acid lanostane base Bis- (the 4- amino benzoyl oxygroup) cholestane of ester, 3,6-, bis- (4- amino-benzene oxygen) cholestane of 3,6-, bis- (the 4- ((ammonia of 1,1- Base phenyl) methyl) phenyl) -4- butyl cyclohexane, 1,1- bis- (4- ((aminophenyl) methyl) phenyl) -4- heptylcyclohexanes, 1, Bis- (4- ((amino-benzene oxygen) methyl) the phenyl) -4- heptylcyclohexanes of 1-, bis- (4- ((aminophenyl) methyl) the phenyl) -4- of 1,1- (4- heptyl cyclohexyl) hexamethylene, N- (2,4- diamino-phenyl) -4- (4- heptyl cyclohexyl) benzamide, by following formula (E- 1)

[changing 14]

(in formula (E-1), X^IAnd X^IISeparately indicate singly-bound ,-O- ,-COO- or-OCO-, R^IFor the alkane of carbon number 1~3 Hydrocarbon diyl, R^IIFor the alkane diyl of singly-bound or carbon number 1~3, a is 0 or 1, the integer that b is 0~2, the integer that c is 1~20, d It is 0 or 1；Wherein, 0) a and b will not become simultaneously

The diamines of the bases containing orientation such as represented compound:

P-phenylenediamine, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino diphenyl sulfides, 4- aminophenyl -4 '-ammonia Yl benzoic acid ester, 4, bis- (4- amino-benzene oxygen) pentanes of 4 '-chrysoidines, 1,5-, 1,7- bis- (4- amino-benzene oxygen) heptan Alkane, bis- [2- (4- aminophenyl) ethyl] adipic acids, N, bis- (4- aminophenyl) methyl amines of N-, 1,5-diaminonaphthalene, 2,2 '-two 4,4 '-benzidine of methyl -, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, 2,7- diamino-fluorene, 4,4 '-diaminos Bis- [4- (4- amino-benzene oxygen) phenyl] propane of base diphenyl ether, 2,2-, bis- (4- aminophenyl) fluorenes of 9,9-, the bis- [4- (4- of 2,2- Amino-benzene oxygen) phenyl] hexafluoropropane, 2,2- bis- (4- aminophenyl) hexafluoropropane, 4,4 '-(to phenylenediisopropylidenes) Dianil, 4,4 '-(two isopropylidene of metaphenylene) dianils, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygen) benzene, 4,4 '-bis- (4- amino Phenoxy group) biphenyl, 2,6-diaminopyridine, 3,4- diamino-pyridine, 2,4- di-amino-pyrimidine, 3,6- proflavin, 3,6- Diaminocarbazole, N- methyl -3,6- diaminocarbazole, N- ethyl -3,6- diaminocarbazole, N- phenyl -3,6- diaminocarbazole, N, N '-bis- (4- aminophenyl)-benzidine, N, bis- (4- the aminophenyl)-N of N '-, N '-dimethylbenzidine, Isosorbide-5-Nitrae-be bis--(4- ammonia Base phenyl) other diamines such as-piperazine, 3,5- diaminobenzoic acid etc.；

Diamino organosiloxane can for example be enumerated: 1,3- bis- (3- aminopropyl)-tetramethyl disiloxanes etc.；Except this with Outside, the diamines recorded in Japanese Patent Laid-Open 2010-97188 bulletin can be used.

"-X in the formula (E-1)^I-(R^I-X^II)_d" represented by bilvalent radical be preferably carbon number 1~3 alkane two Base, *-O-, *-COO- or *-O-C₂H₄- O- (wherein, the associative key with " * " and diamino-phenyl are bonded).Group "- C_cH_2c+1" can for example enumerate: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc., this A little groups are preferably straight-chain.Two amino in diamino-phenyl be preferably located at relative to other groups 2,4- or 3,5-.

As the concrete example of compound represented by the formula (E-1), such as following formula (E-1-1)~formula (E- can be enumerated 1-4) the represented compound etc. of difference.

[changing 15]

In addition, other diamines can select two or more use by a kind of exclusive use of these compounds or suitably.

In the case where being applied to the aligning agent for liquid crystal of TN type, STN type or vertical alignment-type liquid crystal display device, The group (orientation base) that liquid crystal aligning ability can be assigned to film can be imported on the side chain of polyamic acid.Orientation base is for example Can enumerate: the alkyl of carbon number 4~20, the fluoroalkyl of carbon number 4~20, the alkoxy of carbon number 4~20, carbon number 17~51 have class The group of sterol skeleton, group with multiring structure etc..Polyamic acid with orientation base for example can be by monomer group In containing the base containing orientation diamines polymerization and obtain.Using the diamines of the base containing orientation, blending amount Relative to whole diamines used in synthesis, 3 moles of % or more are preferably set as, 5 moles of %~70 is more preferably set as and rubs You are %.

It, can also in the case where assigning liquid crystal aligning ability to the film formed by aligning agent for liquid crystal using optical alignment method At least part as the polyamic acid of polymer (P) is set as the polymer with light orientation structure.Light orientation knot The group that light orientation is shown by photoisomerization or photodimerization, photodegradation etc. can be used in the concrete example of structure.It is specific and Speech, such as can enumerate: containing azo-compound or derivatives thereof as basic framework the group containing azo, contain cinnamic acid or Its derivative looks into ear as containing for basic framework as the group containing cinnamic acid of basic framework, containing chalcone or derivatives thereof The group of ketone, containing benzophenone or derivatives thereof as basic framework the group containing benzophenone, containing cumarin or its Derivative contains cyclobutane as basic framework as the group containing cumarin of basic framework, containing cyclobutane or derivatives thereof Structure, containing bicyclic [2.2.2] octene or derivatives thereof as basic framework the structure containing bicyclic [2.2.2] octene, contain Have by following formula (4)

[changing 16]

(in formula (4), X³Indicate sulphur atom, oxygen atom or-NH-；" * " respectively indicates associative key；Wherein, in two " * " At least one is bonded on aromatic rings)

Structure etc. of the represented part-structure as basic framework.

Polyamic acid with light orientation structure for example can be by including to have light orientation structure in monomer composition Tetracarboxylic dianhydride and the diamines with light orientation structure at least polymerization of any one and obtain.In this case, with regard to light It is single used in synthesis of the use ratio of the monomer with light orientation structure relative to polymer for reactive viewpoint The total amount of body is preferably set as 20 moles of % or more, is more preferably set as 30 moles of %~80 mole %.

(synthesis of polyamic acid)

Polyamic acid can by making tetracarboxylic dianhydride as described above and diamines, optionally together with molecular weight regulator into Row is reacted and is obtained.To the synthetic reaction of polyamic acid provide tetracarboxylic dianhydride and diamines use ratio preferably relative to The anhydride group of 1 equivalent of amino of diamines, tetracarboxylic dianhydride becomes 0.2 equivalent~2 equivalents ratio, more preferably becomes 0.8 and works as Measure the ratio of~1.2 equivalents.

When synthesizing polyamic acid as polymer (P), just sufficiently the deliquescent improvement of raising polyamic acid with And for the viewpoint of the reduction effect of image retention, the use ratio of specific tetracarboxylic dianhydride and specific diamines is preferably relative to conjunction The total amount of specific tetracarboxylic dianhydride and specific diamines are set as 10 moles of % or more, more by the total amount of the monomer used in 20 moles of %~80 mole % are preferably set as, 25 moles of %~70 mole % are especially preferably set as.

Molecular weight regulator can for example be enumerated: the single acid anhydride of the acid such as maleic anhydride, phthalic anhydride, itaconic anhydride, benzene The monoamine compounds such as amine, cyclohexylamine, n-butylamine, monoisocyanate compounds such as phenyl isocyanate, isocyanic acid naphthalene ester etc..Phase For total 100 parts by weight of used tetracarboxylic dianhydride and diamines, the use ratio of molecular weight regulator is preferably set as 20 parts by weight are hereinafter, be more preferably set as 10 parts by weight or less.

The synthetic reaction of polyamic acid preferably carries out in organic solvent.Preferably -20 DEG C of reaction temperature at this time~ 150 DEG C, more preferably 0 DEG C~100 DEG C.In addition, the reaction time is preferably 0.1 hour~24 hours, more preferably 0.5 hour~ 12 hours.

Organic solvent used in reaction can for example be enumerated: aprotic polar solvent, phenol system solvent, alcohol, ketone, ester, ether, Halogenated hydrocarbon, hydrocarbon etc..In these organic solvents, it is preferable to use selected from as composed by aprotic polar solvent and phenol system solvent One or more of group (organic solvent of the first group), or one or more of organic solvent selected from the first group with It is mixed selected from one or more of the group as composed by alcohol, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon (organic solvent of the second group) Close object.In the latter case, the total amount relative to the organic solvent of the first group and the organic solvent of the second group, the The use ratio of the organic solvent of two groups is preferably 50 weight % hereinafter, more preferably 40 weight % are hereinafter, especially preferably 30 weight % or less.

Particularly preferred organic solvent preferably using selected from by n-methyl-2-pyrrolidone, n,N-dimethylacetamide, N,N-Dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, hexamethylphosphoramide, metacresol, xylenol and One or more of group composed by halogenation phenol is used as solvent, or uses these organic molten in the range of the ratio More than one mixtures with other organic solvents of matchmaker.The usage amount (a) of organic solvent is preferably set as molten relative to reaction The total amount (b) of the total amount (a+b) of liquid, tetracarboxylic dianhydride and diamines becomes the amount of 0.1 weight of weight %~50 %.

In the manner, reaction solution made of dissolving polyamic acid is obtained.The reaction solution can be mentioned directly The preparation of aligning agent for liquid crystal is supplied, is available to aligning agent for liquid crystal after polyamic acid contained in reaction solution can also being separated Preparation, or isolated polyamic acid can also be available to after purification to the preparation of aligning agent for liquid crystal.The separation of polyamic acid and Purifying can be carried out according to well known method.

(poly amic acid ester)

Poly amic acid ester as polymer (P) is for example using reacting tetracarboxylic acid acid diesters dihalide with diamines Method etc. and obtain.

In addition, " tetracarboxylic acid acid diesters dihalide " so-called in this specification refers in four carboxyls possessed by tetrabasic carboxylic acid Two are esterified, remaining two compound by halogenation.So-called " tetracarboxylic acid acid diesters " refer to four carboxylics possessed by tetrabasic carboxylic acid Two in base are esterified, remaining two compounds for carboxyl.

Used tetracarboxylic acid acid diesters dihalide can be by making the chlorinating agent appropriate such as tetracarboxylic acid acid diesters and thionyl chloride It is reacted and is obtained.Tetracarboxylic acid acid diesters for example can in the synthesis by making polyamic acid illustrated by tetracarboxylic dianhydride it is (specific Tetracarboxylic dianhydride and other tetracarboxylic dianhydrides) it reacts and obtains with alcohols such as methanol or ethyl alcohol.

As the diamines reacted with tetracarboxylic acid acid diesters dihalide, in addition to institute's example in the explanation of the synthesis of polyamic acid Other than the specific diamines and other diamines that show, it can enumerate level-one amino possessed by specific diamines and other diamines to protect The compound (hereinafter also referred to " diamine compound CA1 ") etc. that shield base is protected.The protected diamine compound of level-one amino (CA1) concrete example can enumerate compound represented by following formula (5) etc..

[changing 17]

(in formula (5), R⁹For divalent organic base, Y¹For protecting group；Multiple Y¹Can be identical, can also be different)

R in the formula (5)⁹Divalent organic base explanation can apply the formula (2) R¹~R⁴Divalent organic base Explanation.As the concrete example of compound represented by the formula (5), such as following formula (5-1)~formula (5-16) can be enumerated respectively Represented compound etc..

[changing 18]

[changing 19]

[changing 20]

The use ratio of the tetracarboxylic acid acid diesters dihalide and diamines that provide to the synthetic reaction of polymer (P) is preferably phase For 1 equivalent of amino of diamines, the group "-COX (X is halogen atom) " of tetracarboxylic acid acid diesters dihalide becomes 0.2 equivalent~2 The ratio of equivalent more preferably becomes 0.8 equivalent~1.2 equivalents ratio.

For sufficiently improving the viewpoint of the deliquescent improvement of polyamic acid and the reduction effect of image retention, relatively The total amount of the monomer used in synthesis, tetracarboxylic acid acid diesters dihalide, spy with part-structure represented by the formula (1) The use ratio (being its total amount using a variety of) for determining diamines and the diamine compound (CA1) is preferably set as 10 moles of % or more are more preferably set as 20 moles of %~80 mole %, are especially preferably set as 25 moles of %~70 mole %.

Tetracarboxylic acid acid diesters dihalide reacts preferably in the presence of base with diamines, carries out in organic solvent.This When reaction temperature be preferably -30 DEG C~150 DEG C, more preferably -10 DEG C~100 DEG C.In addition, the reaction time is preferably 0.1 small When~48 hours, more preferably 0.5 hour~36 hours.Organic solvent used in reaction can apply the synthesis of polyamic acid The explanation of workable organic solvent in reaction.The usage amount of organic solvent is preferably the total amount being set as relative to reaction solution, The total amount of tetracarboxylic acid acid diesters dihalide and diamines becomes the amount of the 0.1 weight weight of %~50 %.It is used in the reaction Alkali for example preferably use: the tertiary amines such as pyridine, triethylamine, N- ethyl-N, N- diisopropylamine；Sodium hydride, hydrofining, hydrogen-oxygen Change alkali metal classes such as sodium, potassium hydroxide, sodium, potassium etc..Relative to 1 mole of diamines, the usage amount of alkali is preferably set as 2 moles~4 Mole, more preferably it is set as 2 moles~3 moles.

As previously discussed, reaction solution made of dissolving poly amic acid ester is obtained.The reaction solution can be supplied directly to The preparation of aligning agent for liquid crystal is available to the system of aligning agent for liquid crystal after can also separating poly amic acid ester contained in reaction solution It is standby, or isolated poly amic acid ester can also be available to after purification to the preparation of aligning agent for liquid crystal.The separation of poly amic acid ester And purifying can be carried out according to well known method.Poly amic acid ester can only have amic acid esters structure, can also be amic acid knot Structure and amic acid esters structure and the partial esterification object deposited.

In addition, the poly amic acid ester as polymer (P) is not limited to the synthetic method, such as can also be by making to make The method reacted for the polyamic acid of polymer (P) with alcohols, the method for reacting tetracarboxylic acid acid diesters with diamines etc. And it obtains.

(polyimides)

Polyimides as polymer (P) can for example be closed by the way that the polyamic acid synthesized in this way is carried out dehydration Ring and imidizate obtain.It, can be by polyamide in the case where polyamic acid being carried out dehydration closed-loop and form polyimides The reaction solution of acid is supplied directly to dehydration closed-loop reaction, provides again after can also separating polyamic acid contained in reaction solution To dehydration closed-loop reaction, or isolated polyamic acid can also be available to dehydration closed-loop reaction after purification.

Polyimides can close for amic acid structure possessed by the polyamic acid as its predecessor all to be carried out to dehydration Complete acid imide compound made of ring can also make amic acid structure for a part of amic acid structure is only carried out dehydration closed-loop With imide ring structure and the part acid imide compound deposited.The acid imide rate of polyimides used in reaction is preferably 20% More than, more preferably 30%~99%, especially preferably 40%~99%.The acid imide rate is the acyl relative to polyimides The quantity of the quantity and imide ring structure of amino acid structure it is total, indicated shared by the quantity of imide ring structure with percentage Ratio.Herein, a part of imide ring can also be different imide ring.

The dehydration closed-loop of polyamic acid is preferably carried out using following methods: the method heated to polyamic acid； Or polyamic acid is dissolved in organic solvent, dehydrating agent and dehydration closed-loop catalyst are added in the solution, optionally into The method of row heating.Wherein, the method for the latter is preferably utilized.

In the method for adding dehydrating agent and dehydration closed-loop catalyst in the solution of polyamic acid, dehydrating agent for example be can be used The acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.1 mole of amic acid structure relative to polyamic acid, the use of dehydrating agent Amount is preferably set as 0.01 mole~20 moles.Dehydration closed-loop catalyst for example can be used: pyridine, collidine, two picolins, The tertiary amines such as triethylamine.Relative to 1 mole of used dehydrating agent, the usage amount of dehydration closed-loop catalyst is preferably set as 0.01 Mole~10 moles.Organic solvent used in dehydration closed-loop reaction can be enumerated organic used in the synthesis as polyamic acid Solvent and the organic solvent illustrated.The reaction temperature of dehydration closed-loop reaction is preferably 0 DEG C~180 DEG C, more preferably 10 DEG C~150 ℃.Reaction time is preferably 1.0 hours~120 hours, more preferably 2.0 hours~30 hours.

The reaction solution containing polyimides is obtained in this way.The reaction solution can be supplied directly to aligning agent for liquid crystal Preparation, the preparation that aligning agent for liquid crystal is available to after dehydrating agent and dehydration closed-loop catalyst can also be removed in autoreaction solution, It is available to the preparation of aligning agent for liquid crystal after polyimides can also being separated, or can also be by isolated polyimides after purification again It is supplied to the preparation of aligning agent for liquid crystal.These purification process can be carried out according to well known method.

(polyamide)

The polyamide of polymer (P) can for example be obtained by the method etc. for reacting dicarboxylic acids with diamines.Herein, After dicarboxylic acids preferably carries out chloride using the chlorinating agent appropriate such as thionyl chloride, it is supplied to and is reacted with diamines.This Outside, " dicarboxylic acid dihalide " so-called in this specification refers to that two carboxyls are by the compound of halogenation possessed by dicarboxylic acids.

There is no particular restriction for dicarboxylic acids used in the synthesis of polyamide, such as can enumerate: ethanedioic acid, malonic acid, diformazan Propylmalonic acid, succinic acid, glutaric acid, adipic acid, 2- methyl adipic acid, trimethyladipic acid, pimelic acid, 2,2- dimethyl-penten two The aliphatic dicarboxylic acids such as acid, 3,3- diethyl succinic acid, azelaic acid, decanedioic acid, suberic acid, fumaric acid, muconic acid；

Cyclobutane dicarboxylic acid, 1- cyclobutane dicarboxylic acids, cyclopentane dicarboxylic acid, cyclohexane dicarboxylic acid etc. have ester ring type structure Dicarboxylic acids；

Phthalic acid, M-phthalic acid, terephthalic acid (TPA), oreinol dioctyl phthalate, 5- tert-butyl isophthalic acid, 2,5- dimethyl terephthalic acids, naphthalene dicarboxylic acids, 4,4 '-diphenyldicarboxylic acids, 4,4 '-diphenyl methane dicarboxylic acids, 4,4 '-two Phenyl-propane dicarboxylic acids, 4,4 '-diphenyl ether dicarboxylic acids, 4,4 '-carbonyl dibenzoic acids, 4- o-carboxy cinnamic acid, to phenylene two Acrylic acid, 3,3 '-[4,4 '-(methylene two-is to phenylene)] dipropionic acids, 4,4 '-[4,4 '-(oxygroup two-is to phenylenes)] two Butyric acid, 3,4- diphenyl -1,2- cyclobutane dicarboxylic acid, 4,4 '-dicarboxylic acids of azobenzene-etc. have the dicarboxylic acids etc. of aromatic ring. It one kind or is used in combination of two or more in addition, dicarboxylic acid dihalide can be used alone.

Diamines used in synthesis as polyamide, in addition to the specific diamines illustrated in the explanation of the synthesis of polyamic acid And other than other diamines, compound represented by the formula (5) etc. can be enumerated.At this point, by by specific diamines or diamines Compound (CA1) is used at least part of monomer, can get the polyamide as polymer (P).Diamines can be used alone one Kind is used in combination of two or more.

To the synthetic reaction of polymer (P) provide dicarboxylic acid dihalide and diamines use ratio preferably relative to The group "-COX (X is halogen atom) " of 1 equivalent of amino of diamines, dicarboxylic acid dihalide becomes 0.2 equivalent~2 equivalents ratio Example more preferably becomes 0.8 equivalent~1.2 equivalents ratio.

Dicarboxylic acid dihalide reacts preferably in the presence of base with diamines, carries out in organic solvent.At this time Reaction temperature is preferably set as 0 DEG C~200 DEG C, is more preferably set as 10 DEG C~100 DEG C.In addition, the reaction time is preferably set as It 0.5 hour~48 hours, is more preferably set as 1 hour~36 hours.

Organic solvent used in reaction preferably uses organic solvent, for example, preferably using tetrahydrofuran, dioxanes, Toluene, chloroform, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, n-methyl-2-pyrrolidone etc..Relative to dicarboxyl The usage amount of 100 parts by weight of total amount of acid ihalide and diamines, organic solvent is preferably set as 400 parts by weight~900 Parts by weight are more preferably set as 500 parts by weight~700 parts by weight.

Alkali used in the reaction for example preferably uses: pyridine, triethylamine, N- ethyl-N, N- diisopropylamine etc. three Grade amine；Lithium hydride, sodium hydride, hydrofining, bis- (trimethylsilyl) amide lithiums, bis- (trimethylsilyl) amide sodium, bis- (three Methyl-monosilane base) the alkali gold such as amide potassium, lithium diisopropylamide, diisopropylamide sodium, diisopropylamide potassium, tert-butyl lithium Belong to class.Relative to 1 mole of diamines, the usage amount of alkali is preferably set as 2 moles~4 moles, is more preferably set as 2 moles~3 and rubs You.

In this way, reaction solution made of dissolving polyamide is obtained.The reaction solution can be supplied directly to liquid crystal The preparation of alignment agent is available to the preparation of aligning agent for liquid crystal after can also separating polyamide contained in reaction solution, or The preparation of aligning agent for liquid crystal can also will be available to after isolated polyamide purifying.The separation and purifying of polyamide can utilize public affairs The method known carries out.

The solution viscosity and weight average molecular weight (Mw) of polymer (P) can suitably be selected according to main framing.For example, In the case where polyamic acid, poly amic acid ester, polyimides and polyamide, the solution viscosity of the polymer, which is preferably worked as, to be made When at the solution that concentration is 10 weight %, the solution viscosity with 10mPas~800mPas, more preferably have The solution viscosity of 15mPas~500mPas.In addition, the solution viscosity (mPas) of polymer (P) be to use polymerization The polymerization that the good solvent (such as gamma-butyrolacton, n-methyl-2-pyrrolidone etc.) of object (P) is 10 weight % the concentration for preparing Object solution, the value measured at 25 DEG C using E type rotational viscometer.

In addition, what is measured using gel permeation chromatography (Gel Permeation Chromatographv, GPC) is poly- The weight average molecular weight (Mw) of styrene conversion is preferably 1,000~500,000, more preferably 2,000~300,000.Separately Outside, molecular weight distribution represented by the ratio for the number average molecular weight (Mn) that Mw and the polystyrene measured using GPC are converted It (Mw/Mn) is preferably 15 hereinafter, more preferably 10 or less.

[compound (P) as additive]

In the case where compound (P) is used as additive, the compound with part-structure represented by the formula (1) Preferably using the compound (hereinafter also referred to " photopolymerizable compound (P) ") with multiple optical polymerism bases.As preferred Concrete example, such as compound represented by following formula (6) can be enumerated etc..

[changing 21]

(in formula (6), X⁴And X⁵For optical polymerism base；R¹⁰、R¹¹And R¹³Separately indicate divalent organic base, R¹²For list Key or divalent organic base；Y¹For protecting group；The integer that f is 1~3, g are 0 or 1)

In the formula (6), X⁴And X⁵Optical polymerism base can enumerate the group etc. with polyunsaturated bond.It is specific and Speech, such as can enumerate: (methyl) acryloyl group oxygroup, styryl, (methyl) acrylamido, vinyl, CH₂=C (CH₃)-, vinyl oxygroup (CH₂=CH-O-), group represented by following formula (x-1) or formula (x-2) etc..

[changing 22]

(in formula (x-1), X⁶For oxygen atom or-NH-；" * " indicates associative key)

For the high aspect of photoreactivity, optical polymerism base (methyl) acryloyl group oxygroup preferably therein.In addition, (methyl) acryloyl group oxygroup is the meaning comprising " acryloyl group oxygroup " and " methylacryloyl oxygroup ".(methyl) acryloyl Amido is the meaning comprising " acrylamido " and " methacryl amido ".

R¹⁰~R¹³Divalent organic base explanation can apply the formula (2) R¹~R⁴Divalent organic base explanation.Make For R¹⁰~R¹³, for the viewpoint of the compatibility of liquid crystal, preferably these R¹⁰~R¹³In at least any one for phenylene, Cyclohexylidene or biphenylene, more preferably R¹⁰~R¹³Two or more be phenylene, cyclohexylidene or biphenylene. In addition, for the deliquescent viewpoint of compound (P), preferably R¹⁰~R¹³At least any one be cyclohexylidene.

F is preferably 1.

As the concrete example of photopolymerizable compound (P), such as following formula (6-1)~formula (6-30) institute's table respectively can be enumerated The compound etc. shown.

[changing 23]

[changing 24]

(in formula (6-1)~formula (6-20), R is hydrogen atom or methyl, the integer that n is 1~20；Boc indicates tert-butoxy Carbonyl)

[changing 25]

(in formula (6-21)~formula (6-24), n be 1~20 integer；Boc indicates tert-butoxycarbonyl)

[changing 26]

(in formula (6-25)~formula (6-30), R is hydrogen atom or methyl, m and n separately indicate 1~20 it is whole Number；Boc indicates tert-butoxycarbonyl)

Compound in aligning agent for liquid crystal, relative to 100 parts by weight of total weight of component of polymer, as additive (P) allotment ratio is preferably set as 1 parts by weight~100 parts by weight, is more preferably set as 5 parts by weight~50 parts by weight.In addition, Compound (P) by a kind of described exclusive use or can be used in combination of two or more.The molecular weight of compound (P) is preferably 1,500 hereinafter, more preferably 1, and 200 hereinafter, especially preferably 1, and 000 or less.

<other compositions>

Aligning agent for liquid crystal of the invention optionally can also contain the other compositions other than compound (P).Other compositions example Can such as enumerate: other polymers, intramolecular other than polymer (P) have the compound of at least one epoxy group (hereinafter referred to as " compound containing epoxy group "), functional silanes compound etc..

[other polymers]

The other polymers can in order to improve the various characteristics such as solution properties or electrical characteristics, heat resistance, mechanical strength, or Person for cost effective equal purpose come using.The other polymers are without part-structure represented by the formula (1) Polymer, such as can enumerate: polyamic acid, polyimides, poly amic acid ester, polysiloxane, polyester, polyamide, fibre Tie up plain derivative, polyacetals, polystyrene derivative, poly- (styrene-phenylmaleimide) derivative or with poly- (methyl) acrylate is as main framing and without the polymer etc. of the specific structure.In these polymer, other polymerizations Object preferably uses at least one in the group as composed by polyamic acid, polyimides, poly amic acid ester and polyamide Kind polymer.

By other polymers allotment in aligning agent for liquid crystal, allotment ratio is preferably according to compound (P) type suitably selects.For example, in the case where compound (P) is polymer, relative to contained in aligning agent for liquid crystal Total (polymer (P) is total with other polymers) 100 parts by weight of polymer, the allotment ratio of other polymers are preferably 50 parts by weight are set as hereinafter, being more preferably set as 0.1 parts by weight~40 parts by weight, are especially preferably set as 0.1 parts by weight~30 Parts by weight.

In addition, in the case where aligning agent for liquid crystal of the invention includes that compound (P) is used as additive, the aligning agent for liquid crystal Contain select at least one of group composed by free polymer (P) and other polymers polymer as polymer at Point.The allotment ratio of other polymers in the situation can relative to polymer contained in aligning agent for liquid crystal total amount and It is arbitrarily set in range below 100 weight %.The preferably 10 weight % of weight %~100, more preferably 30 weight % ~90 weight %.

[compound containing epoxy group]

Compound containing epoxy group can make to improve liquid crystal orientation film with cementability or the electrical characteristics of substrate surface With.Such compound containing epoxy group can for example enumerate following compound as preferred: ethylene glycol diglycidylether, poly- second Hexanediol diglycidyl ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentylglycol diglycidyl ether, 1,6- hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane Triglycidyl ether, 2,2- dibromoneopentyl glycol diglycidyl ether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', four glycidyl group -4 N ' -, 4 '-diamino hexichol Methylmethane, N, N- diglycidyl-benzyl amine, N, N- diglycidyl-aminomethyl cyclohexane, N, N- 2-glycidyl Base-cyclo-hexylamine etc..In addition to this, No. 2009/096598 note of International Publication No. can be used in the example of the compound containing epoxy group The polysiloxane containing epoxy group carried.

Will contain epoxy group compound deploy in aligning agent for liquid crystal in the case where, allotment ratio preferably relative to Polymer contained in aligning agent for liquid crystal adds up to 100 parts by weight and is set as 40 parts by weight hereinafter, being more preferably set as 0.1 weight Part~30 parts by weight.

[functional silanes compound]

Functional silanes compound can for improve aligning agent for liquid crystal printing purpose and use.Such functionality silicon Hydride compounds can for example be enumerated: 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropyl three Methoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- Amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy silane, three ethoxy of 3- ureido-propyl Base silane, N- ethoxy carbonyl -3- TSL 8330, N- tri-ethoxy silylpropyl diethylenetriamine, 10- trimethoxy silane base-Isosorbide-5-Nitrae, tri- azepine decane of 7-, 9- trimethoxy silane base -3,6- diaza nonyl acetic acid esters, 9- tri- Methoxy silane base -3,6- diaza methyl pelargonate, N- benzyl -3- TSL 8330, N- phenyl -3- aminopropan Base trimethoxy silane, glycidoxypropyl methyltrimethoxysilane, 2- glycidoxypropyl ethyl trimethoxy silane, 3- Glycidoxypropyltrimewasxysilane etc..

By the allotment of other functional silanes compounds in aligning agent for liquid crystal, allotment ratio is preferably 2 parts by weight are set as hereinafter, being more preferably set as relative to the adding up to 100 parts by weight of polymer contained in aligning agent for liquid crystal 0.02 parts by weight~0.2 parts by weight.

In addition, other than described, can also enumerate intramolecular at least one oxetanylmethoxy as other compositions Compound or antioxidant, meal chelate compounds, hardening accelerator, surfactant, filler, dispersing agent, light increase sense Agent etc..

Aligning agent for liquid crystal of the invention can be only comprising a kind of polymer as component of polymer, containing two or more Polymer.Preferred aspects in the case where containing two or more polymer can for example enumerate [1] below~[3] etc..

[1] contain polymer (P) and other polymers, and polymer (P) and other polymers are selected from polyamic acid, gather The aspect of at least one of amic acid esters, polyimides and polyamide.

[2] contain multiple polymers (P), and these multiple polymers (P) are selected from polyamic acid, poly amic acid ester, gather The aspect of at least one of acid imide and polyamide.

[3] contain various other polymer, and other polymers are selected from polyamic acid, poly amic acid ester, polyimides And the aspect (wherein, being used as additive comprising compound (P)) of at least one of polyamide.

In these aspects, speculate in the aspect of [1] are as follows: by the way that in polymer (P), the amino in amido bond is by Y¹Institute Protection, then the polarity difference between polymer (P) and other polymers becomes larger, and polymerization can be fully generated in liquid crystal orientation film The deviation of the distribution of object.

Relative to the solid component (ingredient other than the solvent of aligning agent for liquid crystal) in aligning agent for liquid crystal, compound (P) Allotment ratio is preferably suitably selected according to the type of compound (P).For example, in the case where compound (P) is polymer, Preferably relative to 100 parts by weight of total weight of the solid component in aligning agent for liquid crystal, the allotment ratio of polymer (P) is set More than 40 parts by weight, 50 parts by weight or more are more preferably set as, are more preferably set as 60 parts by weight or more.

In addition, effect of the invention is just sufficiently obtained, and for the viewpoint of cost of implementation reduction, relative to polymer (P) and 100 parts by weight of total amount of other polymers, the allotment ratio of the polymer (P) in the aspect of [1] is preferably Be set as 1 parts by weight~99 parts by weight, be more preferably set as 10 parts by weight~90 parts by weight, be especially preferably set as 20 parts by weight~ 80 parts by weight.

Total weight 100 in the case where compound (P) is additive, relative to the solid component in aligning agent for liquid crystal The allotment ratio of compound (P) is preferably set as 0.5 parts by weight~50 parts by weight, is more preferably set as 2 parts by weight by parts by weight ~30 parts by weight are especially preferably set as 5 parts by weight~25 parts by weight.

<solvent>

The other compositions that aligning agent for liquid crystal of the invention is prepared into compound (P) and optionally uses preferably are dispersed Or it is dissolved in liquid composition made of in solvent appropriate.

Used organic solvent can for example be enumerated: n-methyl-2-pyrrolidone, gamma-butyrolacton, butyrolactam, N, Dinethylformamide, n,N-dimethylacetamide, 4- hydroxy-4-methyl-2-pentanone, glycol monoethyl ether, butyl lactate, second Acid butyl ester, methyl methoxypropionate, ethyl ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, Ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethyl two Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, two Ethylene glycol monoethylether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, carbon Sour Asia propyl ester etc..These organic solvents can be used alone or be use mixing two or more.

(total weight of the ingredient other than the solvent of aligning agent for liquid crystal is in liquid crystal for solid component concentration in aligning agent for liquid crystal Shared ratio in the total weight of alignment agent) it is contemplated that viscosity, volatility etc. suitably select, preferably 1 weight %~10 The range of weight %.That is, aligning agent for liquid crystal is preferably heated, by being coated on substrate surface in a manner of aftermentioned thus shape At the film as liquid crystal orientation film or as the film of liquid crystal orientation film.At this point, in solid component concentration less than 1 weight % In the case where, the film thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, in solid component concentration In the case where more than 10 weight %, the film thickness of film becomes excessive and is difficult to obtain good liquid crystal orientation film, and additionally, there are liquid The viscosity of brilliant alignment agent increases and the tendency of coating decline.

The range of particularly preferred solid component concentration according to method used in base plate coating aligning agent for liquid crystal and It is different.Such as using rotator method to be coated on substrate, solid component concentration (solvent in aligning agent for liquid crystal with Total weight of outer whole components shared ratio of the total weight of the liquid crystal alignment agent) be particularly preferably 1.5 weight %~ The range of 4.5 weight %.Using print process, solid component concentration is particularly preferably set as 3 weights of weight %~9 Solution viscosity, is thus set as the range of 12mPas~50mPas by the range for measuring %.It is special using ink-jet method Solid component concentration You Xuanwei be set as to the range of 1 weight of weight %~5 %, thus by solution viscosity be set as 3mPas~ The range of 15mPas.Temperature when preparing aligning agent for liquid crystal is preferably 10 DEG C~50 DEG C, more preferably 20 DEG C~30 DEG C.

<liquid crystal display element>

Liquid crystal display element of the invention includes the liquid crystal orientation film formed using the aligning agent for liquid crystal of the explanation.Liquid The operating mode of crystal display element is not particularly limited, such as can be applied to TN type, STN type, VA type (comprising VA-MVA type, VA- PVA type etc.), IPS type, FFS type, a variety of runnings such as optical compensation curved (Optically Compensated Bend, OCB) type Mode.

Liquid crystal display element can for example be manufactured by the inclusion of the step of following step (1)~step (3).Step (1) Different substrates is used according to required operating mode.Step (2) and step (3) are general in each operating mode.

[step (1): the formation of film]

Firstly, the coating of liquid crystalline alignment agent on substrate, then heats coated face, is thus formed and applied on substrate Film.

(1-A) manufacturing such as TN type, STN type or in the case where VA type liquid crystal display element, firstly, will be provided with through Two pieces of substrates of patterned transparent conductive film are as a pair, in its each transparent conductive film forming face, preferably utilize glue Version printing method, spin-coating method, roll coater method or ink jet printing method are respectively coated aligning agent for liquid crystal.Substrate for example can be used: floating The glass such as method glass, soda-lime glass；Include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, poly- carbonic acid The transparent substrate of the plastics such as ester, poly- (ester ring type alkene).The transparent conductive film for being set to the wherein one side of substrate, which can be used, includes Tin oxide (SnO₂) nesa (NESA) film (PPG register of company, U.S. trade mark), include indium oxide-tin oxide (In₂O₃-SnO₂) Tin indium oxide (Indium Tin Oxide, ITO) film etc..In order to obtain patterned transparent conductive film, for example, it is available Following methods: after forming the transparent conductive film of pattern-free, the method for pattern is formed by being etched by light；When forming transparent conductive film Use the method etc. of the mask with required pattern.When coating of liquid crystalline alignment agent, in order to make substrate surface and transparent conductive film It is better with the cementability of film, the face that form film in substrate surface can also be implemented to be pre-coated with functional silanes chemical combination The pretreatment of object, functionality titanium compound etc..

After coating of liquid crystalline alignment agent, the purpose of for the sagging for preventing be coated with aligning agent for liquid crystal, preferably implement pre- It heats (prebake conditions).Prebake conditions temperature is preferably 30 DEG C~200 DEG C, and more preferably 40 DEG C~150 DEG C, particularly preferably 40 DEG C~ 100℃.The prebake conditions time is preferably 0.25 minute~10 minutes, more preferably 0.5 minute~5 minutes.Then, for by solvent Completely remove, optionally will be present in the purpose that amic acid structure in polymer carries out hot-imide, and implement calcining (after Baking) step.Calcination temperature (rear baking temperature) at this time is preferably 80 DEG C~300 DEG C, more preferably 120 DEG C~250 DEG C.Afterwards Baking time is preferably 5 minutes~200 minutes, more preferably 10 minutes~100 minutes.The film thickness of the film formed in this way Preferably 0.001 μm~1 μm, more preferably 0.005 μm~0.5 μm.

(1-B) manufacturing IPS type or in the case where FFS type liquid crystal display element, in the electricity for the substrate for being provided with electrode The opposite substrate of pole forming face and not set electrode is respectively coated aligning agent for liquid crystal on one side, then adds to each coated face Film is consequently formed in heat, wherein the electrode includes patterned transparent conductive film or metal film for interdigitated electrode structure.Institute at this time Heating condition, transparent conductive film or metal film after the material of the substrate and transparent conductive film that use, coating method, coating Patterning method, substrate pretreatment and be formed by film preferred film thickness it is identical as (1-A).Metal film can Use the film for example comprising metals such as chromium.

Under any case of (1-A) and (1-B), by the coating of liquid crystalline alignment agent on substrate after, will have Machine solvent removes and forms liquid crystal orientation film or the film as liquid crystal orientation film.At this point, contained in the aligning agent for liquid crystal Polymer be polyamic acid or be poly amic acid ester or be comprising the acyl with imide ring structure and amic acid structure In the case where imines fluidized polymer, carry out dehydration closed-loop reaction and further heating after film is formed, thus formed into Film of one step through imidizate.

[step (2): orientation process]

In the case where manufacturing TN type, STN type, IPS type or FFS type liquid crystal display element, implement in the step (1) The film of formation assigns the processing (orientation process) of liquid crystal aligning ability.The alignment capability of liquid crystal molecule is imparted to painting as a result, Film and become liquid crystal orientation film.Orientation process can enumerate friction treatment, light orientation processing etc., and the friction treatment, which passes through, utilizes volume It is wound with the roller of the cloth including, for example, fibers such as nylon, artificial silk, cottons, by film to certain orientation friction, to assign to film Liquid crystal aligning ability；The light orientation processing carries out light irradiation to the film being formed on substrate and assigns liquid crystal aligning to film Energy.On the other hand, in the case where manufacturing vertical alignment-type liquid crystal display device, the film that can will be formed in the step (1) It is directly used as liquid crystal orientation film, orientation process can also be implemented to the film.

Light irradiation in light orientation processing is carried out using following methods: (1a) is irradiated the film after rear baking Method；The method that (2a) is irradiated the film after prebake conditions and before rear baking；(3a) toasted in prebake conditions and afterwards to Lack in any one, the method etc. that film is irradiated in the heating of film.

The radioactive ray of polarisation or non-polarized can be set as to the light of film irradiation.It includes 150nm that radioactive ray, which for example can be used, The ultraviolet light and luminous ray of the light of~800nm wavelength.In the case where radioactive ray are polarisation, it can be linear polarization, can also be Part polarisation.In addition, in the case where used radioactive ray are linear polarization or part polarisation, it can be from vertical with real estate Direction be irradiated, can also be irradiated from inclined direction, or can also by these irradiate combination carry out.In irradiation non-polarized Radioactive ray in the case where, the direction of irradiation can be set as inclined direction.

Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance for example can be used in used light source Lamp, xenon lamp, excimer laser etc..The ultraviolet light of preferred wavelength region can be utilized light source and such as optical filter, diffraction grating Deng method etc. and obtain.The exposure of light is preferably 100J/m²~50,000J/m², more preferably 300J/m²~20, 000J/m².In addition, can also be directed at film while heating to film in order to improve reactivity and carry out light irradiation.When heating Temperature be usually 30 DEG C~250 DEG C, preferably 40 DEG C~200 DEG C, more preferably 50 DEG C~150 DEG C.

In addition, can also be to being handled below the liquid crystal orientation film further progress after friction treatment, so that liquid crystal orientation film exists Each region has different liquid crystal aligning energy: by a part irradiation radioactive ray to liquid crystal orientation film, and making liquid crystal aligning The processing of the pre-tilt angle variation in a part of region of film；Or after a part of liquid crystal aligning film surface forms resist film, After carrying out friction treatment on the direction different from friction treatment just now, by the processing of resist film removal.In this case, can Improve the visual field characteristic of liquid crystal display element obtained.

In manufacture polymer stabilizing orientation (Polymer sustained alignment, PSA) type liquid crystal display element Situation or in the case where forming film, institute can be used directly using the aligning agent for liquid crystal of the ingredient containing the base containing polymerism The film that is formed in step (1) is stated to implement following step (3), but for the collapsing of control liquid crystal molecule, using easy Method carries out the purpose of orientation segmentation, can also carry out the orientation process such as weak friction treatment.It is suitable for VA type liquid crystal display The liquid crystal orientation film of element is also suitably adapted for PSA type liquid crystal display element.

[step (3): liquid crystal cells are constructed]

(3-A) prepares two pieces of substrates for being formed with liquid crystal orientation film in this way, between two pieces of oppositely disposed substrates Liquid crystal is configured, liquid crystal cells are thus manufactured.In order to manufacture liquid crystal cells, such as two methods below can be enumerated.First method For previously known method.Firstly, in such a way that each liquid crystal orientation film is opposite, via gap (cell gap) by two pieces of substrates It is oppositely disposed, the peripheral portion of two pieces of substrates is bonded using sealant, in the unit divided by substrate surface and sealant After injecting filling liquid crystal in gap, injection hole is sealed, liquid crystal cells are thus manufactured.In addition, second method is to be referred to as liquid crystal The method of (One Drop Fill, the ODF) mode of instillation.One of base in two pieces of substrates for being formed with liquid crystal orientation film Specified location on plate, such as the sealant of coated UV photo-hardening, so it is set several in liquid crystal alignment film surface After liquid crystal is added dropwise in position, it is bonded another piece of substrate in such a way that liquid crystal orientation film is opposite, and make liquid crystal in the entire surface of substrate On spread out, then the entire surface irradiating ultraviolet light of substrate is cured the sealant, thus manufactures liquid crystal cells.It is any utilizing In the case where kind method, preferably to the liquid crystal cells manufactured in this way, it is further heated to used liquid crystal and takes Until the temperature for obtaining isotropic phase, it is then slowly cooled down to room temperature, thus eliminates flow orientation when liquid crystal filling.

As sealant, such as the epoxy resin etc. of the alumina balls containing curing agent and as spacer can be used. In addition, liquid crystal can enumerate nematic crystal and disc-like liquid crystal, wherein preferably nematic crystal, such as can be used: schiff bases It is liquid crystal, biphenyl system liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid that (Schiff base), which is liquid crystal, azoxy (azoxy), Crystalline substance, biphenyl butylcyclohexane system liquid crystal, pyrimidine system liquid crystal, dioxanes system liquid crystal, double-octane system liquid crystal, is stood terphenyl system liquid crystal Square alkane (cubane) is liquid crystal etc..In addition, following substance can also be added to use such as cholesteryl chloride in these liquid crystal (cholesteryl chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate Cholesteryl liquid crystals such as (cholesteryl carbonate) (cholesteric liquid crystal)；With trade name " C- 15 ", " CB-15 " (manufacture of Merck (Merck) company) is come the chiral agent sold；To decyloxy benzylidene-to amino-2-methyl Ferroelectric liquid crystals such as butyl cinnamate etc..

In addition to the injection together with liquid crystal or optical polymerism is added dropwise in the case where manufacturing PSA type liquid crystal display element in (3-B) Other than the aspect of compound, liquid crystal cells are constructed in a manner of identical with (3-A).Then, had to a pair of of substrate Conductive film between apply voltage in the state of to liquid crystal cells carry out light irradiation.The voltage applied herein can be set as such as 5V~ The direct current of 50V or exchange.In addition, the light that is irradiated can be used the light including, for example, 150nm~800nm wavelength ultraviolet light and Luminous ray, the preferably ultraviolet light of the light comprising 300nm~400nm wavelength.Low pressure water for example can be used in the light source of irradiation light Silver-colored lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc..In addition, described preferred The ultraviolet light of wavelength region can obtain ands by light source and the method such as optical filter, diffraction grating etc..The photograph of light The amount of penetrating is preferably 1,000J/m²~200,000J/m², more preferably 1,000J/m²~100,000J/m²。

(3-C) is in the liquid crystal for using the compound with optical polymerism base comprising component of polymer or as additive In the case where forming film on substrate following method can also be used: by a manner of identical with (3-A) in alignment agent Construct liquid crystal cells, then, by between conductive film possessed by a pair of of substrate apply voltage in the state of, to liquid crystal cells The step of carrying out light irradiation, to manufacture liquid crystal display element.According to this method, PSA mould can be realized with few light irradiation amount The advantages of formula.The condition of the voltage applied or the light irradiated can be using the explanation of (3-B).

Then, liquid crystal display element is obtained and the outer surface in liquid crystal cells is bonded polarizer.Fit in liquid crystal The polarizer of the outer surface of unit can be enumerated: be referred to as made of the light polarizing film of " H film " partially with the clamping of cellulose acetate protective film Tabula rasa or comprising itself polarizer of H film, " the H film " are formed on one side making polyvinyl alcohol absorb iodine while extending orientation Film.

Liquid crystal display element of the invention can be effectively applied to a variety of devices, such as can be used for: clock and watch, pocket game Machine, word processor, notes type PC, auto-navigation system, video camera, personal digital assistant (Personal Digital Assistant, PDA), digital camera, mobile phone, smart phone, various monitors, LCD TV, information shows The various display devices such as device.

[embodiment]

Hereinafter, being illustrated to further progress of the present invention, but the present invention is not limited to these implementations by embodiment Example.

In example below, measured using following methods weight average molecular weight Mw, the acid imide rate of polymer with And the solution viscosity of polymer solution.In addition, hereinafter, compound represented by Formula X is abbreviated as " compound X " sometimes.

[the weight average molecular weight Mw of polymer]

Mw is the polystyrene scaled value measured using the GPC of the following conditions.

Tubing string: Tosoh (stock) manufacture, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 DEG C

Pressure: 68kgf/cm²

[the acid imide rate of polymer]

Solution containing polyimides is put into pure water, resulting precipitating is fully dried under reduced pressure at room temperature Afterwards, it is dissolved in deuterodimethylsulfoxide, using tetramethylsilane as primary standard substance, measures at room temperature¹H-NMR.According to institute ?¹H-NMR spectrum finds out acid imide rate using following numerical expressions (1).

Acid imide rate (%)=(1-A¹/A²×α)×100…(1)

(in numerical expression (1), A¹For the peak area of the proton from NH base occurred near chemical shift 10ppm, A²For Peak area from other protons, α are one of other protons relative to the NH base in the predecessor (polyamic acid) of polymer The number ratio of a proton)

[solution viscosity of polymer solution]

Using E type rotational viscometer, the solution viscosity (mPas) of polymer solution is measured at 25 DEG C.

[surface contact angle of film]

Using the contact angle meter DM-700 of consonance surface chemistry limited liability company manufacture, by the ultrapure water of about 2.0 μ L Drop sagging carries out image procossing to the state of the drop behind after dropwise addition 30 seconds, thus measures film on mold (ASL-400) Surface contact angle.

<synthesis of compound>

[synthesis example 1-1: the synthesis of compound (I)]

Compound (I) is synthesized according to following processes 1.

[changing 27]

It is suspended in 4- nitro-N- (4- nitrobenzophenone) benzamide of 2.5g in the THF of 30mL, adds 1.5g thereto N, N- dimethyl aminopyridine.Di-tert-butyl dicarbonate (the Boc of 3.95g is added in the solution₂O).It is stirred at room temperature 3 After hour, suspended solid is filtered, solid is washed with ethyl alcohol.Keep the solid dry, the chemical combination of 2.2g is obtained with purity 99% Object (i-1).

There is the three-necked flask of the Pd/C of 0.3g to carry out nitrogen displacement addition, adds the 40ml's through oxygen degassing thereto THF is stirred.The compound (i-1) of 2.2g is added into the container, 0 DEG C is cooled to and stirs 5 minutes.Thereto Hydrogen is imported, the reduction of nitro is carried out.After being stirred 3 hours under hydrogen environment, reaction solution is filtered after the THF of additional 50mL, Then reaction solution is concentrated.After the solid recycling of precipitation, drying, the target compound (I) of 1.7g is obtained with purity 99%.

[synthesis example 1-2: the synthesis of compound (II)]

Compound (II) is synthesized according to following processes 2.

[changing 28]

Make the N of 2.8g¹, N⁶Bis- (4- nitrophenethyl) adipamides are suspended in the THF of 40mL, are added thereto The N of 2.5g, N- dimethyl aminopyridine.Di-tert-butyl dicarbonate (the Boc of 16g is added in the solution₂O).It stirs at room temperature After mixing 3 hours, suspended solid is filtered, solid is washed with ethyl alcohol.Keep the solid dry, the change of 3.5g is obtained with purity 98% It closes object (ii-1).

There is the three-necked flask of the Pd/C of 0.5g to carry out nitrogen displacement addition, adds the 100ml's through oxygen degassing thereto THF is stirred.The compound (ii-1) of 3.5g is added into the container, 0 DEG C is cooled to and stirs 5 minutes.Thereto Hydrogen is imported, the reduction of nitro is carried out.After being stirred 6 hours under hydrogen environment, after the THF of additional 50mL, reaction solution is filtered, Then reaction solution is concentrated.After the solid recycling of precipitation, drying, the target compound (II) of 2.8g is obtained with purity 99%.

[synthesis example 1-3: the synthesis of compound (III)]

Compound (III) is synthesized according to following processes 3.

[changing 29]

It is suspended in 4- nitro-N- (4- nitrobenzophenone) benzamide of 2.5g in the THF of 30mL, 1.5g is added thereto N, N- dimethyl aminopyridine.N- [2- (trimethylsilyl) ethyoxyl carbonyloxy group] fourth of 10.4g is added in the solution Imidodicarbonic diamide.After being stirred at room temperature 3 hours, suspended solid is filtered, solid is washed with ethyl alcohol.Keep the solid dry, with The compound (iii-1) of the acquisition of purity 98% 1.8g.

There is the three-necked flask of the Pd/C of 0.3g to carry out nitrogen displacement addition, adds the 40ml's through oxygen degassing thereto THF is stirred.The compound (iii-1) of 1.8g is added into the container, 0 DEG C is cooled to and stirs 5 minutes.Xiang Qi Middle importing hydrogen, carries out the reduction of nitro.After being stirred 3 hours under hydrogen environment, after the THF of additional 50mL, by reaction solution mistake Filter, then reaction solution is concentrated.After the solid recycling of precipitation, drying, the target compound of 1.5g is obtained with purity 99% (III)。

[synthesis example 1-4: the synthesis of compound (IV)]

Compound (IV) is synthesized according to following processes 4.

[changing 30]

Make bis- (1,3- dioxo -1,3- dihydroisobenzofuran -5- carboxylic acid)=1,1 '-xenyl -4 of 5.0g, 4 '-two Base ester is suspended in the THF of 60mL, and the N of 0.5g, N- dimethyl aminopyridine are added thereto.Add 40g's in the solution Di-tert-butyl dicarbonate (Boc₂O).After being stirred at room temperature 7 hours, the acetic anhydride of 10mL is added, is reacted 5 hours.In reacting The suspended solid of generation filters, and washs solid with ethyl acetate.Keep the solid dry, the chemical combination of 4.5g is obtained with purity 97% Object (IV).

[synthesis example 1-5: the synthesis of compound (V)]

Compound (V) is synthesized according to following processes 5.

[changing 31]

Make the 4 of 3.7g, 4 '-(pentane -1,5- diyl bis- (oxygroups) bis- (N- (4- nitrobenzophenone) benzamides) is suspended in In the THF of 60mL, the N of 2.7g, N- dimethyl aminopyridine are added thereto.Two dimethyl dicarbonates of 20g are added in the solution Butyl ester (Boc₂O).After being stirred at room temperature 5 hours, suspended solid is filtered, solid is washed with ethyl alcohol.Keep the solid dry, The compound (v-1) of 3.7g is obtained with purity 98%.

There is the three-necked flask of the Pd/C of 0.3g to carry out nitrogen displacement addition, adds the 100mL's through oxygen degassing thereto THF is stirred.The compound (v-1) of 3.7g is added into the container, 0 DEG C is cooled to and stirs 5 minutes.Thereto Hydrogen is imported, the reduction of nitro is carried out.After being stirred 6 hours under hydrogen environment, after the THF of additional 80mL, reaction solution is filtered, Then reaction solution is concentrated.After the solid recycling of precipitation, drying, the target compound (V) of 3.0g is obtained with purity 99%.

[synthesis example 1-6: the synthesis of compound (VI)]

Compound (VI) is synthesized according to following processes 6.

[changing 32]

Two dimethyl dicarbonates of the compound (vi-1) of addition 25.4g, the acetonitrile of 300mL, 48.0g in the eggplant type flask of 1L Butyl ester (Boc₂O) and the N of 1.22g, N- dimethyl aminopyridine react 6 hours at room temperature.After reaction, it will react Liquid is concentrated into 100mL, then makes its reprecipitation in the water of 1L, by filtering by the recycling of generated precipitating, drying, thus obtains Obtain the compound (VI) of 40.9g.

[synthesis example 1-7: the synthesis of compound (VII)]

Compound (VII) is synthesized according to following processes 7.

[changing 33]

Two carbonic acid two of the compound (vii-1) of addition 51.2g, the acetonitrile of 500mL, 48.0g in the eggplant type flask of 1L The tert-butyl ester (Boc₂O) and the N of 1.22g, N- dimethyl aminopyridine react 6 hours at room temperature.It after reaction, will be anti- It answers liquid to be concentrated into 150mL, then makes its reprecipitation in the water of 1L, by filtering by the recycling of generated precipitating, drying, thus Obtain the compound (VII) of 64.2g.

[synthesis example 1-8: the synthesis of compound (VIII)]

Compound (VIII) is synthesized according to following processes 8.

[changing 34]

Isosorbide-5-Nitrae-diaminobenzene of the 4- methacryloxy benzoic acid and 1.08g that make 4.54g is suspended in the two of 30mL In chloromethanes, it is cooling to carry out ice bath.In 1- ethyl -3- (3- dimethylaminopropyl) carbon imidodicarbonic diamide for wherein adding 5.76g The N of hydrochloride and 0.488g, N- dimethyl -4-aminopyridine.After being stirred at room temperature 6 hours, suspended solid is filtered, Solid is washed with ethyl alcohol.Keep the solid dry, the compound (viii-1) of 3.4g is obtained with purity 99%.

It is suspended in the compound (viii-1) of 3.0g in the THF of 30mL, in the solution, makes two dimethyl dicarbonates of 2.0g Butyl ester (Boc₂O it) is dissolved in the THF of 30mL.Di-tert-butyl dicarbonate (the Boc of 1.49g is added in the solution₂O).In room temperature After lower stirring 3 hours, solution is concentrated, keeps solid dry, the compound (VIII) of 3.4g is obtained with purity 99%.

[synthesis example 1-9: the synthesis of compound (C-1)]

Compound (C-1) is synthesized according to following processes 9.

[changing 35]

In the eggplant type flask for the 500mL for having nitrogen ingress pipe and return pipe add 30.2g compound (C-1a), The thionyl chloride of 200mL and the n,N-Dimethylformamide of 0.1mL flow back 1 hour.It after reaction, will concentration, solid and obtain The viscous fluid obtained recrystallizes in hexamethylene, is filtered, dries, thus to obtain the compound (C-1) of 27.1g.

[synthesis example 1-10: the synthesis of compound (ADBA1)]

Compound (ADBA1) is synthesized according to following processes 13.

[changing 36]

Two dimethyl dicarbonates of the compound (DA1) of addition 28.6g, the acetonitrile of 300mL, 45.8g in the eggplant type flask of 1L Butyl ester (Boc₂O) and the triethylamine of 1.01g, react 6 hours at room temperature.After reaction, reaction solution is concentrated into After 100mL, make its reprecipitation in the water of 1L, by filtering by the recycling of generated precipitating, drying, thus to obtain 43.8g's Compound (ADBA1).

[synthesis example 1-11: the synthesis of compound (ADC1)]

Compound (ADC1) is synthesized according to following processes 14.

[changing 37]

In the eggplant type flask for the 500mL for having nitrogen ingress pipe and return pipe add 27.0g compound (DC1), The thionyl chloride of 200mL and the n,N-Dimethylformamide of 0.1mL flow back 1 hour.After reaction, will concentration, it is solid and The viscous fluid of acquisition is recrystallized using hexamethylene, is filtered, is dried, thus to obtain the compound (ADC1) of 27.6g.

[synthesis example 1-12: the synthesis of compound (3-7)]

Compound (3-7) is synthesized according to following processes 17.

[changing 38]

The synthesis of compound (3-7A)

Two dimethyl dicarbonates of the nitrophenethyl amine of 16.6g, the acetonitrile of 200mL, 43.7g are added in the eggplant type flask of 1L Butyl ester (Boc₂O) and the N of 1.22g, N- dimethyl nitrogen yl pyridines, react 6 hours at room temperature.After reaction, it will react After liquid is concentrated into 100mL, make its reprecipitation in the water of 1L, generated precipitating is recycled by filtering, is dry, thus to obtain The compound (3-7A) of 24.0g.

The synthesis of compound (3-7C)

Compound (3-7A), the 17.3g of 24.0g are added in the three-necked flask for the 1L for having return pipe and nitrogen ingress pipe Compound (3-7B) and 500mL methylene chloride, flow back 20 hours.After reaction, it is concentrated under reduced pressure into 100mL, then It (developing solvent hexane: ethyl acetate=6: 4) dissolves out using aluminium oxide tubing string, is concentrated, is solid, thus to obtain 22.9g Compound (3-7C).

The synthesis of compound (3-7)

Put into the autoclave of 2L the compound (3-7C) of 22.9g, the tetrahydrofuran of 200mL, 200mL ethyl alcohol and 1.15g 5%Pd/C.Then, it is blown into hydrogen and becomes 1.4kg/cm²Afterwards, it reacts 20 hours at room temperature.After reaction, The filtrate decompression for carrying out diatomite filtering and obtaining is concentrated into 50mL, makes solution obtained reprecipitation in the water of 1L.It is logical Precipitating is recycled in filtering, after being washed with methanol, is dried in vacuo, thus to obtain the compound (3-7) of 17.9g.

<synthesis of polymer>

[synthesis example 2-1: the synthesis of polymer (P1)]

By the pyromellitic acid anhydride (pyromellitic dianhydride, PMDA) of 100 molar parts, 100 molar parts The compound (I) as diamines be dissolved in n-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), It carries out reacting for 6 hours at room temperature, obtains the solution of the polyamic acid containing 20 weight %.By polyamic acid solution obtained point It takes on a small quantity, adds NMP and the solution that polyamic acid concentration is 10 weight % is made, solution viscosity obtained by measurement is 92mPa s.Will herein polyamic acid obtained as polymer (P1).

[synthesis example 2-2~synthesis example 2-23, synthesis example 2-27 and synthesis example 2-28]

Other than by the type of used tetracarboxylic dianhydride and diamines and quantitative change more as described in following table 1, with Mode identical with the synthesis example 2-1 is respectively synthesized polyamic acid.About synthesis example 2-2, synthesis example 2-5, synthesis example 2-6, Synthesis example 2-8, synthesis example 2-10~synthesis example 2-12, synthesis example 2-14~synthesis example 2-18, synthesis example 2-20~synthesis example 2- 23, using polyamic acid obtained as polymer (P2), polymer (P5), polymer (P6), polymer (P8), it polymerize Object (P10)~polymer (P12), polymer (P14)~polymer (P18), polymer (R2)~polymer (R5).

In addition, about synthesis example 2-3, synthesis example 2-4, synthesis example 2-7, synthesis example 2-9, synthesis example 2-13, synthesis example 2- 19, synthesis example 2-27, synthesis example 2-28 add pyridine and acetic anhydride in polyamic acid solution obtained, carry out chemical acyl Imidization.Reaction solution concentration after chemical imidization, is prepared in such a way that concentration becomes 10 weight % using NMP.

[table 1]

In table 1, the numerical value in () of tetracarboxylic dianhydride indicates tetracarboxylic dianhydride used in the synthesis relative to polymer Total 100 molar parts for use ratio [molar part].Numerical value in () of diamines indicates the synthesis relative to polymer Used in tetracarboxylic dianhydride total 100 molar parts for use ratio [molar part].The letter of acid anhydrides and diamines in table 1 Title respectively indicates compound below.

<tetracarboxylic dianhydride>

A-1: pyromellitic acid anhydride

A-2:1,2,3,4- cyclobutane tetracarboxylic dianhydrides

A-3:2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides

A-4:1R, 2S, 4S, 5R-1,2,4,5- cyclopentanetetracarboxylic's dianhydrides

A-5: TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride)

<diamines>

D-1: p-phenylenediamine

D-2:4- aminophenyl -4 '-aminobenzamide

D-3:N- (4- aminophenyl)-N- phenyl benzene-Isosorbide-5-Nitrae-diamines

D-4:4- aminophenyl -4 '-Aminobenzoate

D-5:3- (3,5- diaminobenzene formoxyl oxygroup) cholestane

[synthesis example 2-24: the synthesis of polymer (P19)]

Come synthetic polymer (P19) according to following processes 10.

[changing 39]

In the 100mL three-necked flask for having nitrogen ingress pipe and thermometer, compound (VI), the 50mL of 4.55g are added Tetrahydrofuran and 0.2mL n,N-Dimethylformamide, it is cooling in 5 DEG C or less progress ice baths.Then, add 3.39g's After compound (C-1), N- ethyl-N, the N- diisopropylamine of 2.84g is slowly added, then, room temperature is reverted to, it is poly- to carry out diel It closes.After reaction, the cyclopentanone of 100mL is added, after carrying out 3 liquid separations washing with the water of 100mL, is added in organic layer The n-methyl-2-pyrrolidone of 100mL after being concentrated into 70g, adds the n-methyl-2-pyrrolidone of 100mL again, then dense It is reduced to 70g, thus to obtain the n-methyl-2-pyrrolidone solution (solid component concentration 10%) of polymer (P19).Polymer (P19) weight average molecular weight is 5,500.

[synthesis example 2-25: the synthesis of polymer (P20)]

Come synthetic polymer (P20) according to following processes 11.

[changing 40]

In the 100mL three-necked flask for having nitrogen ingress pipe and thermometer, compound (VII), the 70mL of 7.12g are added Tetrahydrofuran and 0.2mL n,N-Dimethylformamide, it is cooling in 5 DEG C or less progress ice baths.Then, add 3.25g's After compound (A-6), N- ethyl-N, the N- diisopropylamine of 2.84g is slowly added, then, room temperature is reverted to, it is poly- to carry out diel It closes.After reaction, the cyclopentanone of 140mL is added, after carrying out 3 liquid separations washing with 140mL water, is added in organic layer The n-methyl-2-pyrrolidone of 140mL after being concentrated into 92g, again, is added the n-methyl-2-pyrrolidone of 140mL, is concentrated into 92g, thus to obtain the n-methyl-2-pyrrolidone solution (solid component concentration 10%) of polymer (P20).Polymer (P20) weight average molecular weight is 6,100.

[synthesis example 2-26: the synthesis of polymer (R6)]

Come synthetic polymer (R6) according to following processes 12.

[changing 41]

In the three-necked flask for the 200mL for having thermometer and nitrogen ingress pipe, put into 2.54g compound (vi-1), The sodium hydroxide of the chloroform of 50mL, the water of 50mL and 0.8g, it is cooling in 5 DEG C or less progress ice baths.Then, add 3.39g's Compound (C-1), obtains white precipitate after being vigorously stirred 4 hours.The precipitating does not dissolve in tetrahydrofuran and N- methyl -2- pyrroles In alkanone.

[synthesis example 2-29: the synthesis of polymer (AP3)]

Come synthetic polymer (AP3) according to following processes 15.

[changing 42]

In the 100mL three-necked flask for having addition funnel, nitrogen ingress pipe and thermometer, the compound of 4.87g is added (ADBA1), the sodium hydride of the tetrahydrofuran of 25mL and 4.8g, it is cooling in 5 DEG C or less progress ice baths.Then, being slowly added dropwise will Then solution made of the compound (ADC1) of 2.70g is dissolved in the tetrahydrofuran of 25mL reverts to room temperature, carry out a daytime Night polymerization.After reaction, the cyclopentanone of 100mL is added, after carrying out 3 liquid separations washing with the water of 100mL, is added in organic layer The cyclopentanone for adding 100mL, is concentrated into 61g.Then, the cyclopentanone for adding 100mL again, is then concentrated into 61g, thus to obtain poly- Close the cyclopentanone solution (solid component concentration 10%) of object (AP3).The weight average molecular weight of polymer (AP3) is 5,000.

[synthesis example 2-30: the synthesis of polymer (AP4)]

Come synthetic polymer (AP4) according to following processes 16.

[changing 43]

In the three-necked flask for the 500mL for having airway and thermometer, the N of 60mL, N- dimethylacetamide are put into Amine, the copper chloride of 0.5g, the pyridine of 20mL and 7.24g compound (V).Then, the oxygen of 248mL is imported, at room temperature instead It answers 2 hours.After reaction, the cyclopentanone of 100mL is added, 3 liquid separations washing is carried out with the water of 100mL.Then, in organic layer The cyclopentanone of middle addition 72g, is concentrated into 72g by reduced pressure, adds the cyclopentanone of 72g again, be concentrated into 72g, thus Obtain the cyclopentanone solution (solid component concentration 10%) of polymer (AP4).The weight average molecular weight of polymer (AP4) is 14,000。

[synthesis example 2-31: the synthesis of polymer (P21)]

By the 1R, 2S, 4S, 5R-1,2 as 100 molar parts of tetracarboxylic dianhydride, 4,5- cyclopentanetetracarboxylic's dianhydrides, with And the compound (I) of 70 molar parts as diamines and the compound (3-7) of 30 molar parts are dissolved in n-methyl-2-pyrrolidone (NMP) it in, carries out reacting for 6 hours at room temperature, obtains the solution of the polyamic acid containing 20 weight %.By polyamides obtained Amino acid solution point takes on a small quantity, adds NMP and the solution that polyamic acid concentration is 10 weight % is made, solution viscosity obtained by measurement For 89mPas.Will herein polyamic acid obtained as polymer (P21).

[embodiment 1]

<preparation of aligning agent for liquid crystal>

In the polymer (P1) obtained in the synthesis example 2-1 as polymer, the NMP as organic solvent is added And butyl cellosolve (BC), it is 5.0 weight % that solvent group, which is made, as NMP: BC=50: 50 (weight ratios), solid component concentration Solution.The filter for being 1 μm by using aperture, is filtered the solution, thus prepares aligning agent for liquid crystal.

<evaluation of storage stability>

The aligning agent for liquid crystal of the preparation is added in sample bottle, is placed one week in the baking oven that temperature is 40 DEG C, is measured The variation of viscosity (mPas).Using E type rotational viscometer, viscosity is measured at 25 DEG C.The increase and decrease of the viscosity of observation after a week Variation is evaluated as storage stability " good (zero) ", in the case where 5% more than and less than 10% less than 5% It is evaluated as storage stability " can (Δ) ", storage stability " bad (×) " is evaluated as in the case where 10% or more.Its result To be judged as storage stability " good " in the embodiment.

<manufacture of friction orientation liquid crystal display element>

As substrate, single side have patterned 2 systems comprising chromium for comb teeth-shaped metal electrode (electrode A and Electrode B) glass substrate on, the aligning agent for liquid crystal of the preparation is coated with using rotator, 1 is carried out in 80 DEG C of heating plate It after the prebake conditions of minute, is toasted after ten minutes in 230 DEG C of heating plate, forms film thickness aboutFilm.For institute The coated surface of formation, using the friction machine with the roller for being wrapped around nylon cloth, with the revolution 1 of roller, the shifting of 000rpm, platform Speed 25mm/ seconds dynamic, hair is pressed into length 0.4mm to carry out friction treatment, assigns liquid crystal aligning ability.And then by the substrate super 1 minute ultrasonic washing is carried out in pure water, it is 10 minutes dry in 100 DEG C of cleaning ovens, it thus manufactures and is containing comb teeth-shaped chromium With the substrate of liquid crystal orientation film on the face of electrode.Using the substrate with liquid crystal orientation film as " substrate A ".

Unlike this, in addition do not have electrode the glass substrate with a thickness of 1mm one side, with the identical side Formula forms the film of aligning agent for liquid crystal and carries out friction treatment, is washed and is dried, manufacture takes on single side with liquid crystal To the substrate of film.Using the substrate with liquid crystal orientation film as " substrate B ".

Then, in the outer rim in the face with liquid crystal orientation film of the rubbed processing of substrate, it is 5.5 that coating addition, which has diameter, μm alumina balls epoxy resin adhesive after, with the frictional direction in each liquid crystal orientation film become antiparallel mode, warp It is by gap that two pieces of substrates A, B are oppositely disposed, keep outer edge against each other and crimp, hardens bonding agent.Then, it is infused from liquid crystal Entrance is hard using acrylic acid series light to after filling nematic liquid crystal (Merck (Merck) company manufacture, MLC-2042) between a pair of of substrate Change bonding agent to seal liquid crystal injecting port, thus manufactures the liquid crystal cells of in-plane switching mode.

<evaluation of image retention characteristic (image persistance characteristic)>

In-plane switching mode is manufactured using method identical with " manufacture of friction orientation liquid crystal display element " Liquid crystal display element.The in-plane switching mode liquid crystal display element is placed in 25 DEG C, in the environment of 1 air pressure, not to electrode B Apply voltage, and electrode A is applied resultant voltage 2 hours of 3.5V alternating voltage and 5V DC voltage.Then at once to electrode A And the alternating voltage of this two application of electrode B 4V.It measures since at the time of applying the alternating voltage of 4V to two electrodes, until Time until being visually no longer able to confirm the difference of photopermeability of electrode A and electrode B.By the time less than 100 seconds Situation is evaluated as image retention characteristic " good (zero) ", and by 100 seconds more than and less than 150 seconds the case where is evaluated as image retention characteristic " can (Δ) ", and image retention characteristic the case where by more than 150 seconds is evaluated as " bad (×) ".As a result, being in the embodiment The evaluation of " good ".

[2~embodiment of embodiment 9, embodiment 27 and comparative example 2, comparative example 3, comparative example 5]

Other than in terms of the type of used polymer and amount are set as documented by following table 2, with it is described The identical mode of embodiment 1 prepares aligning agent for liquid crystal respectively.In addition, using prepared aligning agent for liquid crystal, with the implementation It is special that the identical mode of example 1 carries out the evaluation of storage stability, the manufacture of friction orientation liquid crystal display element and image retention respectively The evaluation of property.Their result is shown in following table 2.

[table 2]

In table 2, the numerical value of the allotment ratio of polymer indicate polymer used in preparation relative to aligning agent for liquid crystal at Allotment ratio [parts by weight] for total 100 parts by weight divided.

[10~embodiment of embodiment 22, embodiment 28, embodiment 32, embodiment 33, embodiment 36 and comparative example 1, ratio Compared with example 4]

Other than in terms of the type of used polymer and amount are set as documented by the table 2, with it is described The identical mode of embodiment 1 prepares aligning agent for liquid crystal respectively.In addition, using prepared aligning agent for liquid crystal, with the implementation It is special that the identical mode of example 1 carries out the evaluation of storage stability, the manufacture of friction orientation liquid crystal display element and image retention respectively The evaluation of property.Their result is shown in the table 2.

<evaluation of phase separation property>

The mutual phase separation property of polymer is evaluated for aligning agent for liquid crystal made of blending two kinds of polymer.Firstly, removing Other than one of aspect in two kinds of polymer, operation identical with the embodiment 1 is carried out, is thus prepared Diverse two kinds of aligning agent for liquid crystal of contained polymer.Then, for prepared aligning agent for liquid crystal, production is forged respectively Film is burnt to measure the surface contact angle (benchmark contact angle A1, A2 [°]) of film.In addition, for the aligning agent for liquid crystal of the preparation, Calcining film is made by identical operation, measures the surface contact angle B [°] of film.In the good feelings of phase separation property of polymer Under condition, two kinds of polymer is divided into upper layer and lower layer, thus include two kinds of polymer calcining film surface contact angle B close to two The surface contact angle of one of them (A1 or A2) in kind polymer, in contrast, in the less good situation of phase separation property Under, it is believed that the surface contact angle B becomes the value close to the centre of two kinds of polymer.Therefore, including two kinds of polymer The surface contact angle B of film is calcined close in the case where either one or two of benchmark contact angle A1, A2, it is believed that phase separation property is good, will Surface contact angle B, with the poor Δ θ of either one or two of two benchmark contact angles A1, A2 less than 5% the case where be evaluated as phase separation property " good (zero) ", by 5% more than and less than 10% the case where, are evaluated as " can (Δ) ", 10% or more situation are evaluated as " no Good (×) ".The evaluation result of each embodiment is shown in the table 2.In addition, Δ θ is using value represented by following formula (2).

Δ θ [%]=(| B-A |/B) × 100 ... (2)

(in numerical expression (2), A is either one or two of benchmark contact angle A1, A2, and B is using the liquid crystal aligning comprising two kinds of polymer Agent is come the surface contact angle of the calcining film made)

[embodiment 23]

<preparation of aligning agent for liquid crystal>

Other than in terms of the type of used polymer and amount are set as documented by the table 2, with it is described The identical mode of embodiment 1 prepares aligning agent for liquid crystal.

<evaluation of storage stability>

Using prepared aligning agent for liquid crystal, the preservation of aligning agent for liquid crystal is evaluated in a manner of identical with the embodiment 1 Stability.As a result, being the evaluation of "available" in the embodiment.

<manufacture (1) of light orientation liquid crystal display element>

There is the glass of the metal electrode (electrode A and electrode B) of patterned 2 systems comprising chromium for comb teeth-shaped in single side On the face of the opposite glass substrate of glass substrate and not set electrode, in such a way that film thickness becomes 0.1 μm, rotator is used It is coated with the aligning agent for liquid crystal of the preparation, 1 minute dry in 80 DEG C of heating plate, dry 1 is small in 200 DEG C of cleaning oven When and form film.To the film coated surface, Hg-Xe lamp, the polarisation of open-wire line of the self-reference substrate normal direction irradiation comprising 254nm are used Ultraviolet light 10,000J/m², form liquid crystal orientation film.Then, for having carried out a pair of of substrate of the photo-irradiation treatment, in shape At the face for having liquid crystal orientation film margin residual liquid crystal injecting port, and to addition have diameter be 5.5 μm alumina balls ring Oxygen resin adhesive carries out silk-screen printing coating, and projecting direction of the polarizing axis on real estate when then being irradiated with light becomes anti- Substrate is overlapped and crimps by parallel mode, and 1 hour is spent at 150 DEG C makes bonding agent carry out thermmohardening.Then, from liquid crystal injecting port To after filling nematic liquid crystal (Merck (Merck) company manufacture, MLC-7028) between a pair of of substrate, using epoxy bonding agent by liquid Brilliant inlet sealing.In turn, it in order to eliminate flow orientation when liquid crystal injection, is slowly cooled down to after it is heated at 150 DEG C Room temperature.Then, polarizer is bonded on the outside two sides of substrate to make in-plane switching mode liquid crystal display element.

<evaluation of image retention characteristic>

By method identical with " manufacture (1) of light orientation liquid crystal display element " come in the way of manufacturing in-plane switching Liquid crystal display element, utilize method identical with the embodiment 1 carry out image retention characteristic evaluation.As a result, the implementation It is difficult to generate image retention in example, is the evaluation of " good ".

[24~embodiment of embodiment 26]

Other than in terms of the type of used polymer and amount are set as documented by the table 2, with it is described The identical mode of embodiment 1 prepares aligning agent for liquid crystal respectively.In addition, using prepared aligning agent for liquid crystal, with the implementation The identical mode of example 1 evaluates storage stability.In addition, other than used aligning agent for liquid crystal is changed respectively, with institute It states the identical mode of embodiment 23 and manufactures light orientation liquid crystal display element, for manufactured light orientation liquid crystal display member Part carries out the evaluation of image retention characteristic respectively in a manner of identical with the embodiment 1.Two kinds of polymer blending is prepared into liquid crystal In the embodiment 25 of alignment agent, embodiment 26, it is polymerize using method identical with<evaluation of phase separation property>to evaluate two kinds The phase separation property of object.Their result is shown in the table 2.

[embodiment 29, embodiment 30]

<preparation of aligning agent for liquid crystal>

Other than in terms of the type of used polymer and amount are set as documented by the table 2, with it is described The identical mode of embodiment 1 prepares aligning agent for liquid crystal.

<evaluation of storage stability>

Using prepared aligning agent for liquid crystal, storage stability is evaluated in a manner of identical with the embodiment 1.Its result For embodiment 29, embodiment 30 are the evaluation of " good ".

<manufacture (2) of light orientation liquid crystal display element>

In the metal electrode (electrode A and electrode B) that single side is had to patterned 2 systems comprising chromium for comb teeth-shaped The opposite glass substrate of glass substrate and not set electrode is used as on a pair of real estate, becomes 0.1 μm of side with film thickness Formula is coated with each aligning agent for liquid crystal of the preparation using rotator, calcines 1 minute in 80 DEG C of heating plate.Then, to this Film coated surface uses Hg-Xe lamp, the polarisation ultraviolet light 10,000J/m of open-wire line of the self-reference substrate normal direction irradiation comprising 254nm² Afterwards, it is dried 1 hour in 200 DEG C of cleaning oven and forms liquid crystal orientation film.Then, it for the pair of substrate, is being formed Have the margin residual in the face of liquid crystal orientation film liquid crystal injecting port, to addition have diameter be 5.5 μm alumina balls asphalt mixtures modified by epoxy resin After rouge bonding agent carries out silk-screen printing coating, projecting direction of the polarizing axis on real estate when being irradiated with light becomes antiparallel Substrate is overlapped and crimps by mode, and 1 hour is spent at 150 DEG C makes bonding agent carry out thermmohardening.Then, from liquid crystal injecting port to one After filling nematic liquid crystal (manufacture of Merck (Merck) company, MLC-7028) substrate, liquid crystal is infused using epoxy bonding agent Inlet seal.In turn, in order to eliminate flow orientation when liquid crystal injection, room temperature is slowly cooled down to after it is heated at 150 DEG C. Then, polarizer is bonded on the outside two sides of substrate to make in-plane switching mode liquid crystal display element.

<evaluation of image retention characteristic>

By method identical with " manufacture (2) of light orientation liquid crystal display element " come in the way of manufacturing in-plane switching Liquid crystal display element, utilize method identical with the embodiment 1 carry out image retention characteristic evaluation.As a result, embodiment It is the evaluation of " good " in 29, is the evaluation of "available" in embodiment 30.

<evaluation of phase separation property>

Using prepared aligning agent for liquid crystal, it is poly- that two kinds are evaluated using operation identical with<evaluation of phase separation property> Close the phase separation property of object.As a result, embodiment 29, embodiment 30 are the evaluation of " good ".

As shown in table 2, by using the polymer (P) of protection amido bond, image retention characteristic as a result will not be undermined, and can Improve storage stability.In addition, using (such as the polymerization that acid imide rate is 90% or more of the high polymer of acid imide rate Object) in the case where, about storage stability, also obtain any one good result.And then it is found that as polymer (P20) that Although the strong polymer storage stability of the hydrogen bond knot of sample is less good, by importing protecting group, the dissolution to solvent Property is improved, and can be improved storage stability.In addition, the image retention characteristic of liquid crystal display element obtains good result.Speculate Its reason is: it is detached from due to the Protecting gene heat being directed into polymer, so orientation can be regenerated after rear baking High structure.

The phase separation property of the system made of blending multiple polymers is good in embodiment.Speculate its reason Be: due to the importing effect of protecting group, the hydrophobicity of polymer (P) increases, between the polymer for not having protecting group It is poor to generate polarity, therefore phase separation property improves.In addition, deploying the liquid crystal aligning as polymer (R1) according to the reason Property it is less good and there are in the case where the polymer of the tendency of the image retention characteristic of liquid crystal display element decline, also cause phase It separates and is biased to the film high there are orientation on upper layer, results presumption is to obtain good knot in the evaluation of image retention characteristic Fruit.

[embodiment 31]

<preparation of aligning agent for liquid crystal>

In the solution of the polymer (R5) obtained in containing the synthesis example 2-23 as component of polymer, addition is made For the NMP and butyl cellosolve (BC) of organic solvent, and then relative to 100 parts by weight of polymer (R5), 20 parts by weight are added The compound (VIII) synthesized in the synthesis example 1-8 is used as additive, and solvent group is made as NMP: BC=50: 50 (weight Than), solid component concentration be 6.0 weight % solution.The filter for being 1 μm by using aperture, is filtered the solution, Thus aligning agent for liquid crystal is prepared.

<evaluation of printing>

Using liquid crystal orientation film printing machine (Japan's description printing (stock) manufactures), the aligning agent for liquid crystal of the preparation is coated with In on the transparent electrode face of the glass substrate with the transparent electrode containing ito film, 1 point of (prebake conditions) are heated in 80 DEG C of heating plate Clock and after removing solvent, the heating (rear baking) 10 minutes in 200 DEG C of heating plate, forming average film thickness isPainting Film.The film is observed using the microscope that multiplying power is 20 times, investigates the presence or absence of print unevenness and pin hole.It will print not And pin hole this both unobservable situation is evaluated as printing " good ", will slightly observe print unevenness and pin hole At least any one the case where be evaluated as printing "available", it will be seen that a large amount of print unevenness and pin hole at least any one the case where comment Valence is printing " bad ".In this embodiment, print unevenness and pin hole this do not observe both, printing " good ".

<manufacture of liquid crystal display element>

It is patterned for such as Fig. 1 being respectively provided with using liquid crystal orientation film printing machine (Japan's description printing (stock) manufactures) Shown in slit-shaped and be divided into multiple regions ITO electrode a pair of of glass substrate each electrode surface on be coated with the preparation Aligning agent for liquid crystal, heat (prebake conditions) 1 minute in 80 DEG C of heating plate and after removing solvent, in 200 DEG C of heating plate plus Heat (rear baking) 10 minutes, forming average film thickness isFilm.For the film, rayon cloth is wound with using having Roller friction machine, friction treatment is carried out with roller revolution 400rpm, platform movement speed 3cm/ seconds, hair indentation length 0.1mm. Then, 1 minute ultrasonic washing is carried out in ultrapure water, it is then 10 minutes dry in 100 DEG C of cleaning ovens, thus to obtain tool There is the substrate of liquid crystal orientation film.The operation is repeated, a pair of (two pieces) substrates with liquid crystal orientation film are obtained.In addition, it is described into Capable friction treatment is for control the collapsing of liquid crystal, carries out the purpose of orientation segmentation using simple and easy method and what is carried out weak rubs Erasure reason.

Then, for one of in the pair of substrate, the outer rim in the face with liquid crystal orientation film, which is coated with, to be added After having the epoxy resin adhesive that diameter is 5.5 μm of alumina balls, in the opposite mode of liquid crystal alignment film surface by a pair of of substrate Overlapping crimping, hardens bonding agent.Then, from liquid crystal injecting port to nematic liquid crystal is filled between a pair of of substrate, (Merck (Merck) is public Department's manufacture, MLC-6608) after, liquid crystal injecting port is sealed using acrylic acid series photo-hardening bonding agent, thus manufactures liquid crystal cells. For liquid crystal cells obtained, applies the 10V that frequency is 60Hz between electrode and exchange, in the state of liquid crystal drive, utilize The ultraviolet lamp of metal halide lamp is used in light source, with 10,000J/m²Exposure irradiate ultraviolet light.This Outside, which is the value measured using the quantometer measured with wavelength 365nm benchmark.

<evaluation of image retention characteristic>

The liquid crystal display element of the manufacture is placed in 25 DEG C, in the environment of 1 air pressure, voltage is not applied to electrode B, and Electrode A is applied alternating voltage 300 hours of 10V.After 300 hours, at once to electrode A and this two application of electrode B 3V Alternating voltage, measure two interelectrode light transmission rates poor Δ T [%].At this point, by Δ T less than 2% the case where be evaluated as it is residual As characteristic " good (zero) ", by 2% more than and less than 4% the case where is evaluated as image retention characteristic " can (Δ) ", by 4% or more feelings Condition is evaluated as image retention characteristic " bad (×) ".As a result, being the evaluation of " good " in the embodiment.

[comparative example 6, comparative example 7]

Other than in terms of the type of used additive and amount are set as documented by following Table 3, with it is described The identical mode of embodiment 31 prepares aligning agent for liquid crystal respectively.In addition, using prepared aligning agent for liquid crystal, with the implementation The identical mode of example 31 carries out the evaluation of printing, the manufacture of liquid crystal display element and the evaluation of image retention characteristic respectively.By it Result be shown in following Table 3.

[table 3]

In table 3, the numerical value of the allotment ratio of polymer and additive is indicated used in the preparation relative to aligning agent for liquid crystal Allotment ratio [parts by weight] for total 100 parts by weight of component of polymer.The abbreviation of additive is as described below.

Add-1: compound represented by following formula (Add-1)

Add-2: compound represented by following formula (Add-2)

[changing 44]

As shown in table 3, poly- as light by using the compound for being imported with protecting group in amide key section in embodiment 31 Conjunction property compound, can not only keep the image retention characteristic of liquid crystal display element, and can be improved printing.In contrast, not The printing " bad " in the comparative example 6 that amide key section imports protecting group, image retention characteristic in the comparative example 7 without nitrogen-atoms It is worse compared with embodiment.

[embodiment 34]

<preparation of aligning agent for liquid crystal>

In the polymer (AP3) obtained in the synthesis example 2-29 as polymer, add as organic solvent NMP and butyl cellosolve (BC), solvent group is made as NMP: BC: cyclopentanone=20: 50: 30 (weight ratios), solid component are dense Degree is the solution of 5.0 weight %.The filter for being 1 μm by using aperture, is filtered the solution, thus prepares liquid crystal and take To agent.

<evaluation of storage stability>

Using prepared aligning agent for liquid crystal, the preservation of aligning agent for liquid crystal is evaluated in a manner of identical with the embodiment 1 Stability.As a result, being the evaluation of storage stability " good " in the embodiment.

<manufacture (3) of light orientation liquid crystal display element>

There is the glass of the metal electrode (electrode A and electrode B) of patterned 2 systems comprising chromium for comb teeth-shaped in single side On the face of the opposite glass substrate of glass substrate and not set electrode, in such a way that film thickness becomes 0.1 μm, rotator is used It is coated with the aligning agent for liquid crystal of the preparation, is dried 1 hour in 200 DEG C of cleaning oven and forms film.

For the film coated surface, using Hg-Xe lamp, the polarisation of open-wire line of the self-reference substrate normal direction irradiation comprising 365nm is purple Outside line 5,000J/m², form liquid crystal orientation film.Then, it for having carried out a pair of of substrate of the photo-irradiation treatment, is being formed with The margin residual in the face of liquid crystal orientation film liquid crystal injecting port, to addition have diameter be 5.5 μm alumina balls epoxy resin After bonding agent carries out silk-screen printing coating, projecting direction of the polarizing axis on real estate when being irradiated with light becomes antiparallel side Substrate is overlapped and crimps by formula, and 1 hour is spent at 150 DEG C makes bonding agent carry out thermmohardening.Then, from liquid crystal injecting port to a pair of of base After filling nematic liquid crystal (Merck (Merck) company manufacture, MLC-7028) between plate, using epoxy bonding agent by liquid crystal injecting port Sealing.In turn, in order to eliminate flow orientation when liquid crystal injection, room temperature is slowly cooled down to after it is heated at 150 DEG C.It connects , polarizer is bonded on the outside two sides of substrate to make in-plane switching mode liquid crystal display element.

<evaluation of image retention characteristic>

By method identical with " manufacture (3) of light orientation liquid crystal display element " come in the way of manufacturing in-plane switching Liquid crystal display element, utilize method identical with the embodiment 1 carry out image retention characteristic evaluation.As a result, the implementation It is difficult to generate image retention in example, is the evaluation of " good ".

[embodiment 35]

Other than replacing polymer (AP3) and using polymer (AP4), the preparation solution in a manner of identical with embodiment 34 Brilliant alignment agent.In addition, being evaluated in a manner of identical with embodiment 34 using aligning agent for liquid crystal obtained.By its result It is shown in following table 4.

[table 4]

As shown in table 4, in the case where the polymer on using main chain with azobenzene structure is as polymer (P), liquid The storage stability of brilliant alignment agent is also good.In addition, also obtaining good knot in the evaluation of the image retention characteristic of liquid crystal display element Fruit.

Claims (9)

1. a kind of aligning agent for liquid crystal contains the compound (P) with part-structure represented by following formula (1),

In formula (1), Y¹For protecting group；" * " indicates associative key,

The protecting group is tert-butoxycarbonyl, benzyloxycarbonyl, 1,1- dimethyl -2- halogenated ethyl Epoxide carbonyl, 1,1- Dimethyl -2- cyano ethyl Epoxide carbonyl, 9- fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) Ethoxy carbonyl or following formula (7-1)~represented group of formula (7-5) difference,

In formula (7-1)~formula (7-5), Ar¹For the monovalence fragrance ring group of carbon number 6~10, R¹⁴For the alkyl of carbon number 1~12, R¹⁵For Any monovalent organic radical；" * " indicates the associative key being bonded on nitrogen-atoms.

2. aligning agent for liquid crystal according to claim 1, wherein the compound (P) is with represented by the formula (1) The polymer of part-structure.

3. aligning agent for liquid crystal according to claim 2, wherein the compound (P) is selected from by polyamic acid, polyamide At least one of group composed by acid esters, polyimides and polyamide.

4. aligning agent for liquid crystal according to claim 1 contains selected from by polyamic acid, poly amic acid ester, polyimides And at least one of group composed by polyamide polymer and the compound (P) as additive.

5. a kind of liquid crystal orientation film is formed using aligning agent for liquid crystal according to any one of claim 1 to 4.

6. a kind of liquid crystal display element comprising liquid crystal orientation film according to claim 5.

7. a kind of polymer, using polyamic acid, poly amic acid ester, polyimides or polyamide as main framing, and under having Part-structure represented by formula (1) is stated,

In formula (1), Y¹For protecting group；" * " indicates associative key,

The protecting group is tert-butoxycarbonyl, benzyloxycarbonyl, 1,1- dimethyl -2- halogenated ethyl Epoxide carbonyl, 1,1- Dimethyl -2- cyano ethyl Epoxide carbonyl, 9- fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) Ethoxy carbonyl or following formula (7-1)~represented group of formula (7-5) difference,

In formula (7-1)~formula (7-5), Ar¹For the monovalence fragrance ring group of carbon number 6~10, R¹⁴For the alkyl of carbon number 1~12, R¹⁵For Any monovalent organic radical；" * " indicates the associative key being bonded on nitrogen-atoms.

8. a kind of diamines, with part-structure represented by following formula (1),

In formula (1), Y¹For protecting group；" * " indicates associative key,

The protecting group is tert-butoxycarbonyl, benzyloxycarbonyl, 1,1- dimethyl -2- halogenated ethyl Epoxide carbonyl, 1,1- Dimethyl -2- cyano ethyl Epoxide carbonyl, 9- fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) Ethoxy carbonyl or following formula (7-1)~represented group of formula (7-5) difference,

In formula (7-1)~formula (7-5), Ar¹For the monovalence fragrance ring group of carbon number 6~10, R¹⁴For the alkyl of carbon number 1~12, R¹⁵For Any monovalent organic radical；" * " indicates the associative key being bonded on nitrogen-atoms.

9. a kind of tetracarboxylic dianhydride, with part-structure represented by following formula (1),

In formula (1), Y¹For protecting group；" * " indicates associative key,

The protecting group is tert-butoxycarbonyl, benzyloxycarbonyl, 1,1- dimethyl -2- halogenated ethyl Epoxide carbonyl, 1,1- Dimethyl -2- cyano ethyl Epoxide carbonyl, 9- fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) Ethoxy carbonyl or following formula (7-1)~represented group of formula (7-5) difference,

In formula (7-1)~formula (7-5), Ar¹For the monovalence fragrance ring group of carbon number 6~10, R¹⁴For the alkyl of carbon number 1~12, R¹⁵For Any monovalent organic radical；" * " indicates the associative key being bonded on nitrogen-atoms.