CN105038817B

CN105038817B - Aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal display element, polymer and compound

Info

Publication number: CN105038817B
Application number: CN201510170080.XA
Authority: CN
Inventors: 冈田敬; 秋池利之; 安池伸夫; 野辺洋平
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2014-04-23
Filing date: 2015-04-10
Publication date: 2019-02-01
Anticipated expiration: 2035-04-10
Also published as: TWI655245B; CN105038817A; KR20150122584A; JP2015215591A; TW201540777A; JP6492688B2; KR102225384B1

Abstract

The present invention provides a kind of aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal display element, polymer and compound.The present invention is contained in the polymer (P) with part-structure represented by following formula (1) on main chain in aligning agent for liquid crystal.*-X¹‑Y¹‑X¹‑*(1)(X¹For divalent organic group, Y¹For divalent concatenating group or singly-bound；Wherein, 2 X¹At least one be divalent aromatic heterocycle, in 2 X¹Only one of them in the case where divalent aromatic heterocycle, Y¹For the divalent concatenating group with 1 or more nitrogen-atoms, and 2 X¹It is bonded to Y¹In identical or different nitrogen-atoms on；2 X¹It may be the same or different；" * " indicates associative key).

Description

Aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal display element, polymerization Object and compound

Technical field

The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method, liquid crystal display element, polymer and Compound.

Background technique

In recent years, liquid crystal display element is applied not only to as in the past for the display terminals such as personal computer, Er Qieyong In multiple uses such as such as LCD TV, auto-navigation system, mobile phone, smart phone, information displays.In addition, liquid crystal Display element requires the further high-quality of display quality with multipurpose, provides more to meet this requirement Kind aligning agent for liquid crystal (referring for example to 1~patent document of patent document 3).

Disclosed in 1~patent document of patent document 3: using make the diamines with piperazine ring, with tetracarboxylic dianhydride carry out Reaction and polyamic acid or derivatives thereof for obtaining as aligning agent for liquid crystal component of polymer.Specifically, patent document 1 In disclose: will have the aromatic diamine of the part-structure of "-phenyl ring-piperazine ring-phenyl ring-" for monomer, in patent document 3 It discloses: will have the diamines of the part-structure of "-alkylidene chain-piperazine ring-alkylidene chain-" for monomer.By using institute Diamines is stated, to attempt to obtain ion concentration suitably and the liquid crystal orientation film with long-term reliability.In addition, public in patent document 2 It opens: by making the polyimides obtained and the polymerization by the diamines with piperazine ring to be used for monomer be contained in aligning agent for liquid crystal In, to improve the heat resistance and charging voltage (charged voltage) leaks of liquid crystal orientation film.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2009-175684 bulletin

[patent document 2] Japanese Patent Laid-Open 2010-2501 bulletin

[patent document 3] Japanese Patent Laid-Open 2011-28223 bulletin

Summary of the invention

[the problem of invention is to be solved]

In order to improve display quality and to liquid crystal orientation film requirement various characteristics, such as liquid crystal aligning, image retention can be enumerated An example as key property of generation difficulty (image retention characteristic), reliability etc..Especially reliability, with liquid crystal display element Multipurpose, it is contemplated that used under the harsh environments such as prolonged Continuous Drive or thermal stress, photostress, in order to be subjected to Use under the harsh environment, the reliability are critically important.Liquid crystal display element in order to realize that further quality improves, And it requires further to improve these various characteristics.

The present invention is formed in view of described problem, and main purpose is to provide a kind of aligning agent for liquid crystal, is capable of forming The good film of liquid crystal aligning, and reliability and the good liquid crystal display element of image retention characteristic can be obtained.

[technical means to solve problem]

The inventors of the present invention are artificial to reach problem of the prior art as described above and has carried out positive research, as a result sends out It is existing, by contain the polymer of the specific part structure on main chain with nitrogen atom as aligning agent for liquid crystal polymer at Point, it is able to solve described problem, so as to complete the present invention.Specifically, provided by the present invention aligning agent for liquid crystal below, Liquid crystal orientation film, the manufacturing method of liquid crystal orientation film and liquid crystal display element.

On the one hand of the invention is wherein to provide a kind of aligning agent for liquid crystal, contain has following formula (1) institute on main chain The polymer (P) of the part-structure of expression.

[changing 1]

*-X¹-Y¹-X¹-* (1)

(in formula (1), X¹For divalent organic group, Y¹For divalent concatenating group or singly-bound；Wherein, 2 X¹At least one for divalent virtue Fragrant race's heterocycle, in 2 X¹Only one of them in the case where divalent aromatic heterocycle, Y¹For with 1 or more nitrogen-atoms Divalent concatenating group, and 2 X¹It is bonded to Y¹In identical or different nitrogen-atoms on；2 X¹It may be the same or different；" * " table Show associative key (bonding hand))

On the one hand of the invention is wherein to provide: a kind of manufacturing method of liquid crystal orientation film comprising: the liquid crystal is taken The step for assigning liquid crystal aligning ability on substrate the step of forming film and to film progress light irradiation is coated on to agent Suddenly；And the manufacturing method of another liquid crystal orientation film comprising: using the aligning agent for liquid crystal come the step of forming film； And friction treatment is carried out come the step of assigning liquid crystal aligning ability to the film.In addition, the present invention also provides taken by the liquid crystal To dosage form at liquid crystal orientation film and including the liquid crystal display element of the liquid crystal orientation film.

Another aspect of the invention is a kind of polymer is provided, for selected from by polyamic acid, poly amic acid ester and polyamides At least one of group composed by imines, and there is part-structure represented by the formula (1) on main chain.

In addition, another aspect of the invention is provide compound represented by a kind of following formula (3).

[changing 2]

(in formula (3), X¹For divalent organic group, wherein 2 X¹At least one be divalent aromatic heterocycle；Z¹For level-one Amino or following formula (z-1)

[changing 3]

(in formula (z-1), " * " is indicated and X¹Associative key)

Represented group；R¹For singly-bound, the alkane diyl of carbon number 1~6 or cyclohexylidene, R²For hydrogen atom or carbon number 1 ~6 alkyl or 2 R²Mutually bond and with 2 nitrogen-atoms and R¹It is formed together the divalent ester ring type heterocycle of carbon number 2~10 Base；2 X¹It may be the same or different, 2 R²It may be the same or different；P is 0 or 1)

[The effect of invention]

Aligning agent for liquid crystal according to the present invention, can be by specific comprising having at least part of component of polymer The polymer of structure forms the good film of liquid crystal aligning, and can obtain reliability and the good liquid crystal of image retention characteristic Show element.

Specific embodiment

Hereinafter, to each ingredient contained in aligning agent for liquid crystal of the invention and optionally and arbitrarily deploy other at Divide and is illustrated.

Aligning agent for liquid crystal of the invention contains the polymer (P) with structure represented by following formula (1) on main chain and makees For an at least ingredient for component of polymer.

[changing 4]

*-X¹-Y¹-X¹-* (1)

(in formula (1), X¹For divalent organic group, Y¹For divalent concatenating group or singly-bound；Wherein, 2 X¹At least one for divalent virtue Fragrant race's heterocycle, in 2 X¹Only one of them in the case where divalent aromatic heterocycle, Y¹For with 1 or more nitrogen-atoms Divalent concatenating group, and 2 X¹It is bonded to Y¹In identical or different nitrogen-atoms on；2 X¹It may be the same or different；" * " table Show associative key)

X in the formula (1)¹Divalent aromatic heterocycle be from heteroaromatic composition ring atom in remove 2 Group made of hydrogen atom can also import substituent group in loop section.X¹Loop section be preferably nitrogen atom aromatic series Heterocycle, concrete example can for example be enumerated: pyrroles, imidazoles, pyrazoles, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indoles, benzo miaow Azoles, purine, quinoline, isoquinolin, naphthyridines, quinoxaline, phthalazines, triazine, nitrogen Boom, phenodiazine Boom, acridine, azophenlyene, phenanthroline, oxazole, Thiazole, carbazole, thiadiazoles, benzothiazole, phenthazine, oxadiazoles etc..

X can be directed into¹Aromatic heterocycle loop section in substituent group can for example enumerate: fluorine atom, chlorine atom, bromine The halogen atoms such as atom, iodine atom；The alkyl of the chains such as methyl, ethyl, propyl or the carbon number of branch-like 1~6；Methoxyl group, second The alkoxy etc. of the carbon numbers such as oxygroup, propoxyl group 1~6.

The synthesis easness of monomer, the image retention (image sticking) of liquid crystal display element are reduced and reliable For the viewpoint of property, in the heteroaromatic, the X¹Aromatic heterocycle possessed by ring skeleton be preferably pyrroles, miaow Azoles, pyrazoles, pyridine, pyrimidine, pyridazine, pyrazine perhaps triazine more preferably pyridine, pyrimidine or pyrazine.X¹In 2 associative keys Preferably it is located at Isosorbide-5-Nitrae-position relative to other groups.

X¹Divalent organic group can for example enumerate: divalent chain alkyl, divalent alicyclic type hydrocarbon and divalent aromatic hydrocarbyl etc..This In a little groups, for the viewpoint of the reliability of liquid crystal display element and the improvement of image retention characteristic, preferably divalent is fragrant Race's alkyl, concrete example can for example be enumerated: phenylene, biphenylene (biphenylene group), naphthylene etc..It is preferably sub- Phenyl or biphenylene.

For the aspect that the image retention of liquid crystal display element is reduced and the improvement of reliability is high, the formula (1) 2 X in¹Preferably two are divalent aromatic heterocycle.

Y¹The concrete example of divalent concatenating group can for example enumerate :-O- ,-CO- ,-COO- ,-NR^a-、-CONR^a-、-NR^aCONR^a- (wherein, R^aFor hydrogen atom or the alkyl of carbon number 1~6) ,-N=N- ,-COS-, the divalents functional group such as-S-；Divalent chain alkyl, 2 The divalent alkyls such as valence alicyclic type hydrocarbon and divalent aromatic hydrocarbyl；By at least one methylene in divalent alkyl with the divalent function Group made of base replaces；Divalent base with heterocycle etc..

Herein, so-called " the chain alkyl " in this specification refers to without cyclic structure on main chain, but only by chain Structure is come the straight-chain alkyl and branch-like alkyl that constitute.Wherein it is possible to be saturation, it is also possible to unsaturation.So-called " ester ring type Alkyl " refers to that only the structure comprising ester ring type hydrocarbon is as ring structure, and is free of the alkyl of aromatic ring structure.Wherein, unrequired It to be only made of the structure of ester ring type hydrocarbon, be also contained in the alkyl in part of it with chain structure.So-called " aromatic hydrocarbon Base " 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, It can include the structure of chain structure or ester ring type hydrocarbon in part of it.

For the viewpoint of the reduction of the image retention of liquid crystal display element and reliability, Y¹Divalent concatenating group be preferably Group at least one nitrogen-atoms, more preferably with the group of 2 or more nitrogen-atoms.Y¹Possessed nitrogen-atoms numbers There is no particular restriction for the upper limit, and preferably 4 hereinafter, more preferably 3 or less.

In Y¹In the case where for the divalent organic group with 1 or more nitrogen-atoms, preferably 2 X¹It is bonded to Y respectively¹In On nitrogen-atoms.In Y¹In the case where the divalent concatenating group with 2 or more nitrogen-atoms, 2 X¹Y can be bonded to¹In identical nitrogen On atom, it can also be bonded on different nitrogen-atoms, preferably be bonded to Y¹In different nitrogen-atoms on.In addition, in 2 X¹In Only wherein 1 in the case where divalent aromatic heterocycle, Y¹As the divalent concatenating group with 1 or more nitrogen-atoms.The feelings 2 X under condition, in the formula (1)¹It is bonded to Y¹In identical or different nitrogen-atoms on.

Particularly preferred Y¹Concrete example can for example enumerate group represented by following formula (Y-1) etc..

[changing 5]

(in formula (Y-1), R¹For singly-bound, the alkane diyl of carbon number 1~6 or cyclohexylidene, R²For hydrogen atom or carbon number 1~ 6 alkyl or 2 R²Mutually bond and with 2 nitrogen-atoms and R¹It is formed together the divalent ester ring type heterocycle of carbon number 2~10；2 A R²It may be the same or different；P is 0 or 1；" * " is indicated and X¹Associative key)

R in the formula (Y-1)¹The alkane diyl of carbon number 1~6 can for example enumerate: methylene, ethylidene, glyceryl, fourth Diyl, penta diyl, dihexyl etc., these alkane diyls can be straight-chain, are also possible to branch-like.R¹Preferably carbon number 1~6 Alkane diyl, more preferably carbon number 1~4.In R¹In the case where for cyclohexylidene, preferably 1 or 4 cyclohexylidene.

R²The alkyl of carbon number 1~6 can for example enumerate methyl, ethyl, propyl, butyl, amyl, hexyl etc., these alkyl It can be straight-chain, be also possible to branch-like.The alkyl is preferably carbon number 1~4, more preferably carbon number 1~3.

P is 0 or 1, for the good viewpoint of reliability and image retention characteristic for making liquid crystal display element, preferably p= 1。

In the case where p=1, there are 2 R in formula (Y-1)².Pass through these 2 R²The divalent alicyclic ring for being mutually bonded and being formed Formula heterocycle is to remove group made of 2 hydrogen atoms from the atom of the composition ring of ester ring type heterocycle, specifically, can be under It is represented to state formula (Y-1-1).

[changing 6]

(in formula (Y-1-1), R¹¹For 1 valence substituent group, k is the integer of 0~(a+b)；A and b is to meet 0 of a+b >=2 or more Integer；" * " indicates associative key)

The R of the formula (Y-1-1)¹¹Such as can enumerate: halogen atom, the alkyl of carbon number 1~6, carbon number 1~6 alkoxy Deng.K is preferably 0.

Ester ring type heterocycle represented by the formula (Y-1-1) is preferably ring element number 5~12, more preferably 5~7.With regard to storing The mitigation speed of accumulated charge is fast, for the high aspect of the reduction effect of image retention, particularly preferably Isosorbide-5-Nitrae-piperazine diyl.

Structure represented by the formula (1) is preferably structure represented by following formula (2).

[changing 7]

(in formula (2), X¹For divalent organic group, wherein 2 X¹At least one be divalent aromatic heterocycle；R¹、R²And p It is identical as the formula (Y-1) meaning；" * " indicates associative key)

The preferred concrete example of structure represented by the formula (1) can for example be enumerated: following formula (2-1-1)~formula (2-1-8), Formula (2-2-1)~formula (2-2-5), formula (2-3-1)~formula (2-3-3), formula (2-4-1)~formula (2-4-5), formula (2-5-1)~formula The represented structure etc. of (2-5-6) and formula (2-6-1) difference.

[changing 8]

(in formula, " * " indicates associative key).

[changing 9]

(in formula, " * " indicates associative key).

The main chain of the polymer (P) can for example be enumerated comprising polyamic acid, polyimides, poly amic acid ester, polyester, gather The skeleton of amide etc..In addition, in this specification so-called polymer " main chain ", be by monomer more than a kind or 2 benefits key repeatedly The structure tied and formed, refers to " dry " part longest in polymer.Therefore, so-called " to there is the formula (1) institute on main chain The part-structure of expression " refers to that the structure constitutes a part of " dry " of polymer.Wherein, in the polymer (P), not It excludes structure represented by the formula (1) and exists in the part other than main chain, such as side chain (" dry " top set of auto polymerization object Part) on situation.

Polymer (P) is for example carried out using by the compound with structure represented by the formula (1) for monomer The method of polymerization and obtain.

The polymer (P) can suitably select the one kind or two or more of polymer in these to use.Wherein, excellent It is selected as the polymer (P) being set as in the group as composed by polyamic acid, polyimides and poly amic acid ester extremely Few one kind.

[polyamic acid (P)]

In the case where the polymer (P) is polyamic acid (hereinafter also referred to " polyamic acid (P) "), the polyamic acid (P) it can for example be obtained and reacting tetracarboxylic dianhydride with diamines.Specifically, can for example be obtained using following methods : (i) will have the tetracarboxylic dianhydride (hereinafter also referred to " specific tetracarboxylic dianhydride ") of part-structure represented by the formula (1) The method being polymerize for monomer；(ii) there will be the diamines of part-structure represented by the formula (1) (hereinafter also referred to " specific diamines ") for monomer come the method that is polymerize；(iii) specific tetracarboxylic dianhydride and the specific diamines are used for list Body is come the method that is polymerize.

[tetracarboxylic dianhydride]

(specific tetracarboxylic dianhydride)

Specific tetracarboxylic dianhydride for synthesizing the polyamic acid (P) can for example enumerate represented by following formula (3-1b) Compound etc..

[changing 10]

(in formula (3-1b), X¹And Y¹Meaning it is identical as the formula (1) respectively)

X about the formula (3-1b)¹And Y¹, the X of the formula (1) can be applied respectively¹And Y¹Explanation.

The concrete example of compound represented by the formula (3-1b) can for example enumerate following formula (4-1)~formula (4-8) respectively Represented compound etc..In addition, specific tetracarboxylic dianhydride can be used alone and a kind or two or more be applied in combination.

[changing 11]

The specific tetracarboxylic dianhydride is preferably the Y in the formula (3-1b)¹Be by the formula (Y-1) represented by base It rolls into a ball, specifically compound represented by following formula (3-B).

[changing 12]

(in formula (3-B), R¹、R²And the meaning of p is identical as the formula (Y-1), X¹Meaning it is identical as the formula (2))

X about the formula (3-B)¹, the X of the formula (1) can be applied¹Explanation.In addition, about R¹And R², can answer respectively With the R of the formula (Y-1)¹And R²Explanation.P is preferably 1.

The concrete example of compound represented by the formula (3-B) can for example enumerate the formula (4-1)~formula (4-4), formula (4- 7) and formula (4-8) distinguishes represented compound etc..

In addition, compound represented by the formula (3-B) can be synthesized the well-established law of organic chemistry is appropriately combined.If enumerating Wherein an example, then can by diamines (compound represented by following formula (3-A)) with structure represented by the formula (2), Then pass through and divided to synthesize the tetrabasic carboxylic acid with structure represented by the formula (2) with reacting for carboxylic halide Dehydrating condensation obtains compound represented by the formula (3-B) in son.

(other tetracarboxylic dianhydrides)

The specific tetracarboxylic dianhydride can be used alone by tetracarboxylic dianhydride for synthetic polymer (P), can also incite somebody to action Other tetracarboxylic dianhydrides use simultaneously with specific tetracarboxylic dianhydride.

Other described tetracarboxylic dianhydrides can for example enumerate: aliphatic tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic series Tetracarboxylic dianhydride etc..As the concrete example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydride can for example be enumerated: 1,2,3,4- fourth Alkane tetracarboxylic dianhydride etc.；

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 Bicyclic [3.3.0] octane -2:4, the 6:8- dianhydride of base norbornane -2:3,5:6- dianhydride, 2,4,6,8- tetracarboxylics, 4,9- dioxa Tricyclic [5.3.1.0^2,6] hendecane -3,5,8,10- tetrones, 1,2,4,5- cyclopentanetetracarboxylic's dianhydrides, TOPOT 2,2′ p phenylenebis (inclined benzene Front three acid monoester acid anhydride) (p-phenylenebis (trimellitic acid monoester anhydride)) etc.；

Aromatic tetracarboxylic dianhydride can for example be enumerated: pyromellitic acid anhydride etc.；

In addition to this, the tetracarboxylic dianhydride etc. recorded in Japanese Patent Laid-Open 2010-97188 bulletin can be used.In addition, Tetracarboxylic dianhydride, which can be used alone, or two or more to be applied in combination by a kind.

The specific tetracarboxylic dianhydride that it is preferable to use ratios is different according to the synthetic method of polyamic acid (P).Such as In the case where the method for (i), relative to the total amount of the tetracarboxylic dianhydride for synthesizing polyamides sour (P), preferably will The use ratio of specific tetracarboxylic dianhydride is set as 5 moles of % or more, is more preferably set as 10 moles of % or more, especially preferably sets For 20 moles of % or more.There is no particular restriction for the upper limit value of the use ratio, can suitably select in the range of 100 moles of % or less It selects.

[diamines]

(specific diamines)

Specific diamines for synthesizing the polyamic acid (P) can be aliphatic diamine, ester ring type diamines, aromatic diamine Deng it is any, specifically, it is preferable that for compound represented by following formula (3-1a).

[changing 13]

H₂N-X¹-Y¹-X¹-NH₂ (3-1a)

(in formula (3-1a), X¹And Y¹Meaning it is identical as the formula (1))

X about the formula (3-1a)¹And Y¹, the X of the formula (1) can be applied¹And Y¹Explanation.Specific diamines is preferably Aromatic diamine.

The concrete example of specific diamines can for example enumerate following formula (3-1)~represented compound etc. of formula (3-83) difference.

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

The preferred concrete example of the specific diamines is the Y in the formula (3-1a)¹For group represented by the formula (Y-1) Compound, specifically, represented by can be by following formula (3-A).

[changing 21]

(in formula (3-A), R¹、R²And the meaning of p is identical as the formula (Y-1), the Formula X¹Meaning and the formula (2) phase Together)

X about the formula (3-A)¹, the X of the formula (1) can be applied¹Explanation.In addition, about R¹And R², can answer respectively With the R of the formula (Y-1)¹And R²Explanation.P is preferably 1.

The concrete example of compound represented by the formula (3-A) can for example be enumerated: the formula (3-1)~formula (3-13), formula Compound represented by (3-16), formula (3-19), formula (3-64), formula (3-65) and formula (3-68)~formula (3-83) difference etc..

In addition, compound represented by the formula (3-A) can be by synthesizing the well-established law of organic chemistry is appropriately combined.Make For its an example, method can be listed below: synthesizing the dinitro for having nitro to replace 2 level-one amino in the formula (3-A) Intermediary is then to carry out amination to the nitro of resulting dinitro intermediary using reduction appropriate.Synthesize dinitro The method of intermediary can suitably be selected according to the compound as target.

1 kind of these compounds can be used alone or suitably select by the specific diamines for synthesizing the polyamic acid Two or more come using.

(other diamines)

Diamines for synthetic polymer (P) can be used alone the specific diamines, can also by other diamines with it is specific Diamines uses simultaneously.

Other described diamines can for example be enumerated: aliphatic diamine, ester ring type diamines, aromatic diamine, diamino organosilicon Oxygen alkane etc..As the concrete example of these diamines, aliphatic diamine can for example be enumerated: m-xylene diamine, 1,3- propane diamine, four methylenes Base diamines, five methylene diamine, hexamethylene diamine etc.；

Ester ring type diamines can for example be enumerated: Isosorbide-5-Nitrae-diaminocyclohexane, 4, and 4 '-di-2-ethylhexylphosphine oxides (cyclo-hexylamine), 1,3- are bis- (amino methyl) hexamethylene etc.；

Aromatic diamine can for example be enumerated: o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diamino-diphenyl first Alkane, 4,4 '-diamino diphenyl sulfides, 4,4 '-diamino-diphenyl amine, 4- aminophenyl -4 '-Aminobenzoate, 1,7- Bis- (4- amino-benzene oxygen) heptane, 2,2 '-dimethyl -4,4 '-benzidines, 2,2 '-bis- (trifluoromethyl) -4,4 '-diaminos Base biphenyl, 4,4 '-diamino-diphenyl ethers, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, bis- (the 4- aminobenzenes of 9,9- Base) fluorenes, bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-, 2,2- bis- (4- aminophenyl) hexafluoropropane, 4,4 '- (to phenylenediisopropylidene) dianil, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygen) benzene, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 2,6-diaminopyridine, N, bis- (4- the aminophenyl)-benzidine of N ' -, 3,5- diaminobenzoic acid, dodecyloxy -2,4- bis- Aminobenzene, dodecyloxy -2,5- diaminobenzene, cholesteric alkoxy -3,5- diaminobenzene, cholesteric alkoxy -2,4- diamino Bis- (the 4- amino benzoyl oxygroup) cholestane of benzene, 3,5- diaminobenzoic acid cholesteric Arrcostab, 3,6-, 4- (4 '-trifluoro methoxies Base benzoyloxy) cyclohexyl -3,5- diaminobenzoic acid ester, 2,4- diamino-N, N- diallyl aniline, 4- aminobenzyl Amine, 1- (2,4- diamino-phenyl) piperazine -4- carboxylic acid, 1,3- bis- (N- (4- aminophenyl) piperidyl) propane, 1- (4- aminobenzene Base) -2,3- dihydro -1,3,3- trimethyl -1H- indenes -5- amine, 1- (4- aminophenyl) -2,3- dihydro -1,3,3- trimethyl -1H- Indenes -6- amine, 4- aminophenyl -4 '-Aminobenzoate, 4,4 '-[4,4 '-propane -1,3- diyls are bis- (piperidines-Isosorbide-5-Nitrae-diyl)] Diphenylamines and following formula (A-1)

[changing 22]

(in formula (A-1), X^IAnd X^IIIt is separately singly-bound ,-O- ,-COO- or-OCO-, R^IFor the alkane of carbon number 1~3 Diyl, R^IIFor the alkane diyl of singly-bound or carbon number 1~3；A be 0 or 1, b be 0~2 integer, c be 1~20 integer, d be 0 or 1；Wherein, a and b will not be simultaneously for 0)

Represented compound 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 (A-1)¹-(R¹-X¹¹)_d" represented by divalent base be preferably carbon number 1~3 alkane diyl ,- O-, *-COO- or-O-C₂H₄- O- (wherein, the associative key with " * " and diamino-phenyl are bonded).Base "-C_cH_2c+1" tool Body example can for example be enumerated: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, just Decyl, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, positive 18 Alkyl, NSC 77136 base, n-eicosane base etc..2 amino in diamino-phenyl are preferably located at relative to other groups 2,4- or 3,5-.

The concrete example of compound represented by the formula (A-1) can for example enumerate following formula (A-1-1)~formula (A-1-4) point Not represented compound etc..

[changing 23]

In addition, other diamines for synthesizing the polyamic acid can be by a kind of exclusive use of these compounds, Huo Zheshi When select two or more come using.

The specific diamines that it is preferable to use ratios is different according to the synthetic method of polyamic acid (P).Such as in described (ii) in the case where method, relative to the total amount of the diamines for synthesizing polyamides sour (P), preferably by the specific diamines Use ratio be set as 5 moles of % or more, be more preferably set as 10 moles of % or more, be especially preferably set as 20 moles of % with On.There is no particular restriction for the upper limit value of the use ratio, can be according to various characteristics (such as the pre-tilt angle characteristic assigned to polymer Deng), and arbitrarily set in the range of 100 moles of % or less.

By aligning agent for liquid crystal of the invention be used to manufacture twisted nematic (twisted nematic, TN) type, super twisted to It, can be by the liquid in the case where the liquid crystal display element of (super twisted nematic, the STN) type of arranging or vertical orientating type At least part of polymer contained in brilliant alignment agent (P) is set as with the base that can assign pre-tilt angle expressive ability to film The polymer of group's (hereinafter also referred to as " pre-tilt angle expression power base ").Pre-tilt angle expression power base can for example enumerate the alkane of carbon number 4~20 Base, the fluoroalkyl of carbon number 4~20, the alkoxy of carbon number 4~20, carbon number 17~51 the group with steroid skeleton, have The group etc. of multiring structure.

For example, the polyamic acid (P) with pre-tilt angle expression power base can be by including to have pre-tilt angle in monomer composition The diamines of expression power base as other diamines polymerization and obtain.Using the diamines with pre-tilt angle expression power base In the case of, as long as usage amount is suitably set according to the size of target pre-tilt angle, relative to whole two for synthesis Amine, such as it can be set as 1 mole of % or more, preferably it is set as 3 moles of %~70 mole %.

Optical alignment method is being utilized, the film made to aligning agent for liquid crystal of the invention is used assigns liquid crystal aligning ability In the case of, at least one of polymer contained in the aligning agent for liquid crystal (P) can also be set as with light orientation structure Polymer.

Herein, so-called light orientation structure is the concept comprising both light orientation base and breakdown type light orientation portion. Specifically, light orientation structure, which can be used, shows light orientation by photoisomerization or photodimerization, photodegradation etc. Group, such as can enumerate: containing azobenzene or derivatives thereof as the group containing azobenzene of basic framework, containing cinnamic acid or Its derivative is as the group with cinnamic acid structure of basic framework, containing chalcone or derivatives thereof as basic framework Group containing chalcone, containing benzophenone or derivatives thereof as basic framework the group containing benzophenone, contain tonka-bean Element or derivatives thereof is as the group containing cumarin of basic framework, containing polyimides or derivatives thereof as basic framework Structure containing polyimides, the structure containing unsaturated bond, the following formula that carbon-to-carbon unsaturated bond is imported on the main chain of polymer (p-1)

[changing 24]

(in formula (p-1), X³For sulphur atom, oxygen atom or-NH-；" * " respectively indicates associative key；Wherein, in 2 " * " extremely Few one is bonded on aromatic rings)

Represented part-structure is directed into the structure etc. of-CO containing aromatic rings on the main chain of polymer.

In the formula (p-1), with X³And carbonyl at least any one bond aromatic nucleus can such as enumerate phenyl ring, naphthalene nucleus, Anthracene nucleus etc..In these aromatic rings, for the viewpoint of liquid crystal aligning and the transparency, preferably phenyl ring.In the formula (p-1) In 2 " * ", the structure with the side of aromatic rings bond is not particularly limited, such as can enumerate chain hydrocarbon structure, aliphatic Ring, aromatic rings (including aromatic series hydrocarbon ring and heteroaromatic), ester ring type heterocycle etc..In these structures, just to the sensitivity of light For aspect, preferably 2 " * " are bonded on aromatic rings, are more preferably bonded in aromatic series hydrocarbon ring.Just to the sensitivity of light Aspect for, X³Preferably sulphur atom is easy for the extensive aspect of options of the aspect and workable monomer that obtain For, X³Preferably oxygen atom.

In the case where aligning agent for liquid crystal of the invention is used for light orientation purposes, at least part of polymer (P) is excellent It is selected as the polymer on main chain with light orientation structure, more preferably there is the structure containing polyimides or contains fragrance The polymer of the structure of ring-CO.

In the case where polymer (P) has the structure containing polyimides, which preferably has bicyclic [2.2.2] Octene skeleton or cyclobutane skeleton.The polymer for example can be by making comprising cyclobutane tetracarboxylic dianhydride and bicyclic [2.2.2] octyl- 7- alkene -2,3, at least tetracarboxylic dianhydride of any one in 5,6- tetracarboxylic dianhydrides, with include specific diamines Diamine compound is reacted and is obtained.

In addition, the polymer is preferably on main chain in the case where polymer (P) has the structure of-CO containing aromatic rings With part-structure represented by "-phenyl ring-COO- " or "-phenyl ring-OCO- ".The polymer for example can be by monomer At least any one polymerization comprising the tetracarboxylic dianhydride with the part-structure and the diamines with the part-structure obtains ?.The concrete example of the monomer can for example enumerate following formula (p-1-1)~represented compound etc. of formula (p-1-6) difference.

[changing 25]

In the case where the polymer on synthesizing main chain with light orientation structure, for the viewpoint of photoreactivity, phase For the total amount of the monomer for synthetic polymer, the use ratio of the monomer with light orientation structure is preferably established as 20 Mole % or more, is more preferably set as 30 moles of %~80 mole %.

[synthesis of polyamic acid (P)]

The tetracarboxylic dianhydride of the synthetic reaction of polyamic acid (P) and the use ratio of diamines are supplied to preferably relative to two The anhydride group of 1 equivalent of amino of amine, tetracarboxylic dianhydride becomes 0.2 equivalent~2 equivalents ratio, more preferably becomes 0.3 equivalent The ratio of~1.2 equivalents.

When synthesizing polyamides acid (P), appropriate point can also be used simultaneously with tetracarboxylic dianhydride as described above and diamines Son amount regulator, to synthesize the polymer of end modified type.By the way that the polymer of the end modified type is made, can not damage And further improve the coating (printing) of aligning agent for liquid crystal in the case where effect of the present invention.

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, cyclo-hexylamine, n-butylamine, monoisocyanate compounds such as phenyl isocyanate, naphthyl isocyanate 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.Organic solvent used in reaction can for example arrange Lift 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 one or more of group as composed by aprotic polar solvent and phenol system solvent (organic solvent of the first group), Or one or more of organic solvent selected from the first group with selected from as composed by alcohol, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon The mixture of one or more of group (organic solvent of the second group).In the latter case, having relative to the first group The total amount of the organic solvent of solvent and the second group, the use ratio of the organic solvent of the second group are preferably 50 weights % is measured hereinafter, more preferably 40 weight % are hereinafter, especially preferably 30 weight % or less.

Particularly preferably using selected from by n-methyl-2-pyrrolidone, n,N-dimethylacetamide, N, N- dimethyl formyl Amine, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, hexamethylphosphoramide, metacresol, xylenol and halogenation phenol institute group At one or more of group be used as solvent, or a kind or more of these solvents is preferably used in the range of the ratio With the mixture of other organic solvents.

The usage amount (a) of organic solvent is preferably the total amount (a+b) being set as relative to reaction solution, tetracarboxylic dianhydride and two The total amount (b) of amine becomes the amount of 0.1 weight of weight %~50 %.Reaction temperature in the synthetic reaction of polyamic acid is preferred It is -20 DEG C~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.

It carries out, is obtained reaction solution made of polyamic acid (P) dissolution as described above.The reaction solution can be direct It is supplied to the preparation of aligning agent for liquid crystal, is available to liquid crystal after polyamic acid contained in reaction solution (P) can also being separated The preparation of alignment agent, or isolated polyamic acid (P) is available to the preparation of aligning agent for liquid crystal after purification.By polyamide Sour (P) carries out dehydration closed-loop in the case where polyimides is made, and it is anti-the reaction solution can be supplied directly to dehydration closed-loop It answers, can also will be available to dehydration closed-loop reaction after polyamic acid contained in reaction solution (P) separation, or can also incite somebody to action Isolated polyamic acid (P) is available to dehydration closed-loop reaction after purification.The separation and purifying of polyamic acid can be according to well known Method carries out.

[poly amic acid ester (P)]

Poly amic acid ester (hereinafter also referred to poly amic acid ester (P)) as the polymer (P) is for example using following Method obtains: it is anti-that [I] carries out the compound of the polyamic acid (P) obtained by the synthetic reaction and hydroxyl and esterifying agent The method answered；The method that [II] reacts tetracarboxylic acid acid diesters with diamines；[III] makes tetracarboxylic acid acid diesters dihalide and diamines The method etc. reacted.

Herein, esterifying agent used in method [I] can for example enumerate acetal based compound, halide, the change containing epoxy group Close object etc..As the concrete example of these compounds, the compound of hydroxyl can for example be enumerated: the alcohols such as methanol, ethyl alcohol, propyl alcohol, Phenols such as phenol, cresols etc.；Acetal based compound can for example be enumerated: n,N-Dimethylformamide diethyl acetal, N, N- diethyl Base formamide diethyl acetal etc.；Halide can for example be enumerated: bromomethane, bromic ether, bromo-octadecane, chloromethane, Chlorooctadecane, 1,1,1- tri- fluoro- 2- iodoethane etc.；Compound containing epoxy group can for example be enumerated: propylene oxide etc..

Tetracarboxylic acid acid diesters used in method [II] can be carried out open loop to tetracarboxylic dianhydride and be obtained by using the alcohols ?.In addition, tetracarboxylic acid acid diesters dihalide used in method [III] can be by making the tetracarboxylic acid acid diesters obtained in this way It is reacted and is obtained with the chlorinating agent appropriate such as thionyl chloride.Diamines used in method [II] and method [III] is preferably Comprising the specific diamines, optionally other described diamines can also be used.In addition, poly amic acid ester (P) can only have acyl Amino acid ester structure, the partial esterification object for being also possible to amic acid structure and amic acid esters structure and depositing.

[polyimides (P)]

Polyimides (hereinafter also referred to polyimides (P)) as the polymer (P) for example can be by will be with described The polyamic acid (P) that mode synthesizes carries out dehydration closed-loop, is subject to imidizate and obtains.

The polyimides (P) can be will be complete as amic acid structure possessed by the polyamic acid of its predecessor (P) Portion carries out complete acid imide compound made of dehydration closed-loop, is also possible to that a part of amic acid structure is only carried out dehydration closed-loop And the part acid imide compound for making amic acid structure and imide ring structure and depositing.Contained in aligning agent for liquid crystal of the invention The acid imide rate of polyimides is preferably 30% or more, and more preferably 40%~99%, especially preferably 50%~99%.It should Acid imide rate is the total of the quantity of the amic acid structure relative to polyimides and the quantity of imide ring structure, with percentage Rate indicates ratio shared by the quantity of imide ring structure.Herein, a part of imide ring is also possible to 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 may be used Use the acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.1 mole of amic acid structure relative to polyamic acid, dehydrating agent Usage amount is preferably set as 0.01 mole~20 moles.Pyridine, collidine, diformazan pyrrole for example can be used in dehydration closed-loop catalyst The tertiary amines such as pyridine, 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 enumerate as synthesizing polyamides acid and example The organic solvent shown.The reaction temperature of dehydration closed-loop reaction is preferably 0 DEG C~180 DEG C, more preferably 10 DEG C~150 DEG C.Reaction Time is preferably 1.0 hours~120 hours, more preferably 2.0 hours~30 hours.

The reaction solution for containing polyimides (P) is obtained in this way.The reaction solution can be supplied directly to liquid crystal and take It, can also be to be available to aligning agent for liquid crystal after removal dehydrating agent and dehydration closed-loop catalyst in autoreaction solution to the preparation of agent Preparation is available to the preparation of aligning agent for liquid crystal after can also separating polyimides, or can also be sub- by isolated polyamides Amine is available to the preparation of aligning agent for liquid crystal after purification.These purification process can be carried out according to well known method.In addition to this, Polyimides (P) can also be obtained by the imidizate of poly amic acid ester (P).

Polyamic acid (P), poly amic acid ester (P) and the polyimides (P) obtained in this way, 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 the polymer is poly- to this is used The concentration for closing the good solvent (such as gamma-butyrolacton, n-methyl-2-pyrrolidone etc.) of object to prepare is the polymer of 10 weight % Solution is worth obtained by being measured at 25 DEG C using E type rotational viscometer.

Utilization gel permeation chromatography (the Gel of the polyamic acid, poly amic acid ester and polyimides Permeation Chromatography, GPC) come measure polystyrene conversion weight average molecular weight (Mw) preferably 1,000~500,000, more preferably 2,000~300,000.In addition, being converted by Mw with the polystyrene measured using GPC Number average molecular weight (Mn) ratio represented by molecular weight distribution (Mw/Mn) be preferably 15 hereinafter, more preferably 10 or less.It is logical It crosses in the molecular weight ranges, it can be ensured that the good orientation and stability of liquid crystal display element.

Aligning agent for liquid crystal of the invention contains the polymer (P), optionally can also contain other compositions.It can add Other compositions in the aligning agent for liquid crystal can for example be enumerated: other polymers, intramolecular other than the polymer (P) have The compound (hereinafter referred to as " compound containing epoxy group ") of at least one epoxy group, functional silanes compound etc..

[other polymers]

The other polymers can be used for improving solution properties or electrical characteristics.The other polymers are that do not have the formula (1) polymer of the part-structure represented by its main framing and is not particularly limited.Specifically, can for example enumerate polyamides Amino acid, polyimides, poly amic acid ester, polysiloxane, polyester, polyamide, cellulose derivative, polyacetals, polyphenyl second Ene derivative, poly- (styrene-phenylmaleimide) derivative, poly- (methyl) acrylate etc. are as the poly- of main framing Close object.In these polymer, it is preferably selected from by polyamic acid, poly amic acid ester, polyimides and polysiloxane institute group At at least one of group polymer.

In the case where making an addition to other polymers in aligning agent for liquid crystal, it polymerize relative to contained in aligning agent for liquid crystal Total 100 parts by weight of object, the allotment ratio of the other polymers are preferably set as 50 parts by weight 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 or less.

[compound containing epoxy group]

Compound containing epoxy group can be used for improving liquid crystal orientation film with cementability or electrical characteristics of substrate surface.It is described Compound containing epoxy group can for example enumerate following compound as preferred: ethylene glycol diglycidylether, polyethylene glycol two Glycidol ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, new penta Hexanediol diglycidyl ether, 1,6- hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane tris shrink sweet Oily ether, 2,2- dibromoneopentyl glycol diglycidyl ether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3- it is bis- (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', four glycidyl group -4 N ' -, 4 '-diaminodiphenyl-methanes, N, N- diglycidyl-benzyl amine, N, N- diglycidyl-aminomethyl cyclohexane, N, N- diglycidyl-cyclohexyl Amine etc..In addition to this, what the example of the compound containing epoxy group can be used the record of International Publication No. 2009/096598 contains epoxy The polysiloxane of base.

In the case where making an addition to these epoxides in aligning agent for liquid crystal, relative to contained in aligning agent for liquid crystal Total 100 parts by weight of polymer, the allotment ratio of the epoxide are preferably set as 40 parts by weight hereinafter, more preferably It is set as 0.1 parts by weight~30 parts by weight.

[functional silanes compound]

The functional silanes compound can for improve aligning agent for liquid crystal printing purpose come using.The function Property silane compound can for example be enumerated: 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropan Base trimethoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy silane, 3- ureido-propyl three Ethoxysilane, N- ethoxy carbonyl -3- TSL 8330, N- tri-ethoxy silylpropyl triethylene three Amine, 10- trimethoxy silane base-Isosorbide-5-Nitrae, tri- azepine decane of 7-, 9- trimethoxy silane base -3,6- diaza nonyl acetic acid esters, 9- trimethoxy silane base -3,6- diaza methyl pelargonate, N- benzyl -3- TSL 8330, N- phenyl -3- ammonia Base propyl trimethoxy silicane, glycidoxypropyl methyltrimethoxysilane, 2- glycidoxypropyl ethyl trimethoxy silicon Alkane, 3- glycidoxypropyltrimewasxysilane etc..

In the case where making an addition to these functional silanes compounds in aligning agent for liquid crystal, relative in aligning agent for liquid crystal Total 100 parts by weight of contained polymer, the allotment ratio of the functional silanes compound be preferably set as 2 parts by weight with Under, more preferably it is set as 0.02 parts by weight~0.2 parts by weight.

In addition, can be used the additive for being commonly used for preparing aligning agent for liquid crystal as other compositions.Addition other than described Agent can for example enumerate compound, antioxidant, the surfactant etc. that intramolecular has at least one oxetanylmethoxy.

The other compositions that aligning agent for liquid crystal of the invention is prepared into the polymer (P) and optionally uses are preferably It is dispersed or 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 used in mixed way two or more.

Solid component concentration (total weight of the ingredient other than the solvent of aligning agent for liquid crystal in aligning agent for liquid crystal of the invention Measure ratio shared of the total weight of the liquid crystal alignment agent) it is contemplated that viscosity, volatility etc. suitably select, preferably 1 weight Measure the range of the weight of %~10 %.That is, aligning agent for liquid crystal of the invention is by being coated on substrate surface in a manner of aftermentioned, preferably To be heated, to form the film as liquid crystal orientation film or the film as liquid crystal orientation film.At this point, solid at In the case that point concentration is less than 1 weight %, the film thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.Another party Face, in the case where solid component concentration is more than 10 weight %, the film thickness of film becomes excessive and is difficult to obtain good liquid crystal Alignment films, additionally, there are the viscosity of aligning agent for liquid crystal to increase, the tendency of coating decline.

The range of particularly preferred solid component concentration is according to used method when coating of liquid crystalline alignment agent on substrate And it is different.Such as using rotator method, solid component concentration (other than the solvent in aligning agent for liquid crystal all at Point total weight shared ratio of the total weight of the liquid crystal alignment agent) be particularly preferably 1.5 weight of weight %~4.5 %'s Range.Using print process, solid component concentration is particularly preferably set as to the range of 3 weight of weight %~9 %, Solution viscosity is set as to the range of 12mPas~50mPas whereby.Using ink-jet method, particularly preferably will Solid component concentration is set as the range of 1 weight of weight %~5 %, and solution viscosity is set as 3mPas~15mPas's whereby Range.Temperature when preparing aligning agent for liquid crystal of the invention is preferably 10 DEG C~50 DEG C, more preferably 20 DEG C~30 DEG C.

[liquid crystal orientation film and liquid crystal display element]

Liquid crystal orientation film can be manufactured by the aligning agent for liquid crystal of the invention of the explanation.Liquid crystal display member of the invention Part includes the liquid crystal orientation film formed using the aligning agent for liquid crystal.The operating mode of liquid crystal display element of the invention has no It is particularly limited to, such as can be applied to TN type, STN type, vertical orientation (Vertical Alignment, VA) type (comprising vertically taking To-multidomain vertical orientation (Vertical Alignment-Multidomain Vertical Alignment, VA-MVA) type, Vertical orientation-pattern is vertically oriented (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) Type etc.), coplanar switching (In-Plane Switching, IPS) type, fringing field switching (Fringe Field Switching, FFS) the multiple operation modes such as type, optical compensation curved (Optically Compensatory Bend, OCB) type.

Liquid crystal display element of the invention can for example come by the inclusion of the step of following step (1-1)~step (1-3) Manufacture.Step (1-1) uses different substrates according to required operating mode.Step (1-2) and step (1-3) are in each running It is shared in mode.

[step (1-1): the formation of film]

Firstly, being coated with aligning agent for liquid crystal of the invention on substrate, then coated face is heated, thus on substrate Form film.

(1-1A) is in the case where manufacturing such as liquid crystal display element of TN type, STN type or VA type, firstly, will be arranged There are two pieces of substrates of patterned transparent conductive film as a pair, in each transparent conductive film forming face, preferably Liquid crystal aligning of the invention is respectively coated using flexographic printing process, method of spin coating, roll-coater method or ink jet printing method Agent.Substrate for example can be used: the glass such as float glass, soda-lime glass；Include polyethylene terephthalate, poly terephthalic acid fourth The transparent substrate of the plastics such as diester, polyether sulfone, polycarbonate, poly- (ester ring type alkene).It is set to the saturating of the wherein one side of substrate It includes tin oxide (SnO that bright conductive film, which can be used,₂) nesa (NESA) film (PPG register of company of U.S. trade mark), include indium oxide- Tin oxide (In₂O₃-SnO₂) tin indium oxide (Indium Tin Oxide, ITO) film etc..It is patterned transparent in order to obtain Conductive film, such as using following methods: after forming the transparent conductive film of pattern-free, the side of pattern is formed by being etched by light Method；The method etc. of the mask with required pattern is used when formation transparent conductive film.When coating of liquid crystalline alignment agent, in order to make substrate The cementability of surface and transparent conductive film and film is better, can also implement pre- to the face for forming film in substrate surface First it is coated with the pretreatment of functional silanes compound, 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 firing (after Baking) step.Firing 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.

(1-1B) is being provided with electrode (comprising warp in the case where manufacturing the liquid crystal display element of IPS type or FFS type The transparent conductive film or metal film of patterned interdigitated electrode structure) substrate electrode forming surface, with the opposite base of not set electrode In the one side of plate, it is respectively coated aligning agent for liquid crystal of the invention, then each coated face is heated, film is consequently formed.It closes Heating condition, transparent conductive film or gold after the material of the substrate and transparent conductive film that use at this time, coating method, coating Belong to the pretreatment of the patterning method, substrate of film and is formed by the preferred film thickness of film, it is identical as (1-1A).Gold Belonging to film can be used such as the film comprising metal chromium.

Under any case of (1-1A) and (1-1B), by the coating of liquid crystalline alignment agent on substrate after, will Organic solvent removes and forms liquid crystal orientation film or the film as liquid crystal orientation film.At this point, can also be by film shape At rear further heating, and make the polyamic acid deployed in aligning agent for liquid crystal of the invention, poly amic acid ester and polyimides Dehydration closed-loop reaction is carried out, so that film further through imidizate be made.

[step (1-2): alignment capability imparting processing]

In the case where manufacturing the liquid crystal display element of TN type, STN type, IPS type or FFS type, implement to the step The film formed in (1-1) assigns the processing of liquid crystal aligning ability.Whereby, the alignment capability of liquid crystal molecule is imparted on film And become liquid crystal orientation film.Alignment capability imparting processing can enumerate it is following processing etc.: friction treatment, using be wound with including, for example, The roller of the cloth of the fibers such as nylon, artificial silk, cotton wipes film to certain orientation；And light orientation processing, film is irradiated inclined The radioactive ray of light or non-polarized.It on the other hand, can be by the step (1- in the case where manufacturing VA type liquid crystal display element 1) film formed in is directly used as liquid crystal orientation film, can also implement alignment capability imparting processing to the film.

By light orientation processing to film assign liquid crystal aligning ability in the case where, to film irradiation radioactive ray for example The ultraviolet light and luminous ray of the light comprising 150nm~800nm wavelength can be used.It, can be in the case where radioactive ray are polarisation It is linear polarization, is also possible to part polarisation.In addition, the case where used radioactive ray are linear polarization or part polarisation Under, it can be irradiated, can also be irradiated from inclined direction from the direction vertical with real estate, or combine these irradiations It carries out.In the case where irradiating the radioactive ray of non-polarized, the direction of irradiation is set as inclined direction.

Used light source for example can be used: Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance 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 radioactive ray is preferably 100J/m²~50,000J/m², more preferably 300J/m²~ 20,000J/m².In addition, can be directed at film while heating to film in order to improve reactivity and carry out light irradiation.Heating When 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 it is also possible to make liquid crystal orientation film exist to handling below the liquid crystal orientation film further progress after friction treatment Each region has different liquid crystal aligning abilities: making liquid crystal aligning by a part irradiation ultraviolet light to liquid crystal orientation film 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 resulting liquid crystal display element.The liquid crystal orientation film for being suitable for VA type liquid crystal display element can also be suitble to Liquid crystal display element for polymer stabilizing orientation (Polymer sustained alignment, PSA) type.

[step (1-3): liquid crystal cells are constructed]

Prepare 2 pieces of substrates for being formed with liquid crystal orientation film in this way, configures liquid between 2 pieces of oppositely disposed substrates Crystalline substance manufactures liquid crystal cells whereby.In order to manufacture liquid crystal cells, such as following 2 kinds of methods can be enumerated.First method is previous known Method.Firstly, it is via gap (cell gap) that 2 pieces of substrates are oppositely disposed in such a way that each liquid crystal orientation film is opposite, make The peripheral portion of 2 pieces of substrates is bonded with sealant, filling is injected in the cell gap divided by substrate surface and sealant After liquid crystal, injection hole is sealed, manufactures liquid crystal cells whereby.Second method be referred to as liquid crystal drip-injection (One Drop Fill, ODF) the method for mode.Specified location on one of substrate in 2 pieces of substrates for being formed with liquid crystal orientation film, such as apply The sealant of cloth ultraviolet light photopolymerization, and then after set several positions dropwise addition liquid crystal in liquid crystal alignment film surface, with liquid crystal The mode of alignment films opposite direction is bonded another piece of substrate, and spreads out liquid crystal in the entire surface of substrate, then, to the whole of substrate A face irradiating ultraviolet light and cure the sealant, manufacture liquid crystal cells whereby.It is ideal using any method Be to the liquid crystal cells manufactured in this way, and then liquid crystal used in being heated to obtains the temperature of isotropic phase and is Only, it is then slowly cooled down to room temperature, removes flow orientation when liquid crystal filling whereby.

As sealant, such as the epoxy resin etc. of the alumina balls containing curing agent and as spacer can be used.

Liquid crystal can enumerate nematic crystal (nematic liquid crystal) and Smectic liquid crystal (smectic Liquid crystal), wherein preferably nematic crystal, such as can be used: schiff bases (Schiff base) are liquid crystal, oxygen Changing azo (azoxy) is liquid crystal, biphenyl system liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) system Liquid crystal, biphenyl butylcyclohexane system liquid crystal, pyrimidine system liquid crystal, dioxanes system liquid crystal, double-octane system liquid crystal, cubane (cubane) It is liquid crystal etc..Alternatively, it is also possible to add in these liquid crystal following substance to use such as cholesteryl chloride (cholesteryl Chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl The cholesteryl liquid crystals (cholesteric liquid crystal) such as carbonate)；As trade name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) is come the chiral agent (chiral agent) sold；To decyloxy benzylidene-to amino -2- The ferroelectricities such as methyl butyl cinnamate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) Liquid crystal (ferroelectric liquid crystal) etc..

Then, liquid crystal display element of the invention can be obtained and the outer surface in liquid crystal cells is bonded polarizer. The polarizer for fitting in the outer surface of liquid crystal cells can be enumerated: be referred to as the polarisation of " H film " with the clamping of cellulose acetate protective film Polarizer made of film or comprising itself polarizer of H film, " the H film " inhales polyvinyl alcohol while extending orientation Receive film made of iodine.

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 personal computer, auto-navigation system, video camera, personal digital assistant (Personal Digital Assistant, PDA), digital camera, mobile phone, smart phone, various monitors, LCD TV, information The various display devices such as display.

[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, the solution viscosity of polymer solution is measured using following methods.In addition, hereinafter, sometimes will Compound represented by Formula X is referred to as " compound X ".

[solution viscosity of polymer solution]

The solution viscosity [mPas] of polymer solution is to be prepared into 10 weight of polymer concentration to set solvent is used The solution for measuring %, is measured at 25 DEG C using E type rotational viscometer.

[embodiment 1-1: the synthesis of compound (DA-1)]

Compound represented by following formula (DA-1) is synthesized according to following processes 1.

[changing 26]

It is suspended in 2- chloro-5-nitropyridine 2.5g in toluene 25ml, adds triethylamine 1.88g thereto.It will make piperazine 0.5g is dissolved in solution made of in chloroform 2ml and is slowly added dropwise in its container.After being stirred at room temperature 30 minutes, at 80 DEG C Stirring 12 hours.At this point, yellow solid is precipitated as reaction carries out.After cooling, solid is filtered, is sufficiently washed with water Afterwards, toluene is removed using ethyl acetate.Keep resulting solid dry, obtains the compound (DA-1-1) that purity is 99% 1.94g。

Then, to dividing the three-necked flask for having taken the Pd/C of 0.3g to carry out nitrogen displacement, the second to deaerate through oxygen is added thereto Alcohol 40ml, is stirred.Compound (DA-1-1) 1.94g is made an addition in the container, is cooled to 0 DEG C, is stirred 5 minutes.Stirring Afterwards, hydrazine monohydrate 5ml is slowly added dropwise into reaction solution.

It stirs 3 hours, is stirred at room temperature 6 hours at 0 DEG C, reaction is made to finish.Add ethyl acetate 100ml and THF 80ml then adds pure water 60ml, is carried out liquid separation.It after carrying out liquid separation again with pure water, is concentrated, with yellow~white The form of solid obtains compound (DA-1) 1.5g that purity is 99%.

[embodiment 1-2: the synthesis of compound (DA-2)]

Compound represented by following formula (DA-2) is synthesized according to following processes 2.

[changing 27]

So that 2- chloro-5-nitropyridine 2.68g is suspended in toluene 25ml, adds triethylamine 1.99g thereto.It will make N, N '- Dimethyl-ethylenediamine 0.51g is dissolved in solution made of in chloroform 2ml and is slowly added dropwise in its container.It is stirred at room temperature 30 points Zhong Hou is stirred 12 hours at 80 DEG C.At this point, yellow solid is precipitated as reaction carries out.After cooling, which was carried out Filter, after sufficiently washing with water, removes toluene using ethyl acetate.Keep the solid dry, obtains the compound that purity is 96% (DA-2-1)1.69g。

Then, to dividing the three-necked flask for having taken the Pd/C of 0.3g to carry out nitrogen displacement, the second to deaerate through oxygen is added thereto Alcohol 40ml, is stirred.Compound (DA-2-1) 1.69g is made an addition in the container, is cooled to 0 DEG C, is stirred 5 minutes.Stirring Afterwards, hydrazine monohydrate 5ml is slowly added dropwise into reaction solution.

It stirs 3 hours, is stirred at room temperature 6 hours at 0 DEG C, reaction is made to finish.Add ethyl acetate 100ml and THF 80ml then adds pure water 60ml, is carried out liquid separation.It after carrying out liquid separation again with pure water, is concentrated, with yellow solid Form obtains compound (DA-2) 1.18g that purity is 97%.

[embodiment 1-3: the synthesis of compound (DA-3)]

Compound represented by following formula (DA-3) is synthesized according to following processes 3.

[changing 28]

So that the chloro- 5- nitro-pyrimidine 2.82g of 2- is suspended in toluene 25ml, adds triethylamine 1.99g thereto.It will make piperazine 0.5g is dissolved in solution made of in chloroform 2ml and is slowly added dropwise in its container.After being stirred at room temperature 30 minutes, at 80 DEG C Stirring 12 hours.At this point, yellow solid is precipitated as reaction carries out.After cooling, which is filtered, is sufficiently washed with water After washing, toluene is removed using ethyl acetate.Keep the solid dry, obtains compound (DA-3-1) 1.51g that purity is 98%.

Then, to dividing the three-necked flask for having taken the Pd/C of 0.3g to carry out nitrogen displacement, the second to deaerate through oxygen is added thereto Alcohol 40ml, is stirred.Compound (DA-3-1) 1.51g is made an addition in its container, is cooled to 0 DEG C, is stirred 5 minutes.Stirring Afterwards, hydrazine monohydrate 5ml is slowly added dropwise into reaction solution.

It stirs 3 hours, is stirred at room temperature 6 hours at 0 DEG C, reaction is made to finish.Add ethyl acetate 100ml and THF 80ml then adds pure water 60ml, is carried out liquid separation.It after carrying out liquid separation again with pure water, is concentrated, with yellow solid Form obtains compound (DA-3) 1.02g that purity is 98%.

[embodiment 1-4: the synthesis of compound (DA-4)]

Compound represented by following formula (DA-4) is synthesized according to following processes 4.

[changing 29]

So that the chloro- 2- nitropyridine 2.5g of 4- is suspended in toluene 25ml, adds triethylamine 1.88g thereto.It will make piperazine 0.5g is dissolved in solution made of in chloroform 2ml and is slowly added dropwise in its container.After being stirred at room temperature 30 minutes, at 80 DEG C Stirring 12 hours.At this point, yellow solid is precipitated as reaction carries out.After cooling, which is filtered, is sufficiently washed with water After washing, toluene is removed using ethyl acetate.Keep the solid dry, obtains compound (DA-4-1) 1.78g that purity is 96%.

Then, to dividing three mouthfuls of firings for having taken the Pd/C of 0.3g to carry out nitrogen displacement, the second to deaerate through oxygen is added thereto Alcohol 40ml, is stirred.Compound (DA-4-1) 1.78g is made an addition in its container, is cooled to 0 DEG C, is stirred 5 minutes.Stirring Afterwards, hydrazine monohydrate 5ml is slowly added dropwise into the reaction solution.

It stirs 3 hours, is stirred at room temperature 6 hours at 0 DEG C, reaction is made to finish.Add ethyl acetate 100ml and THF 80ml then adds pure water 60ml, is carried out liquid separation.It after carrying out liquid separation again with pure water, is concentrated, with yellow~white It is 98% compound (DA-4) 1.44g that the form of solid, which obtains purity,.

[embodiment 1-5: the synthesis of compound (DC-1)]

Compound represented by following formula (DC-1) is synthesized according to following processes 5.

[changing 30]

It is suspended in compound (DA-1) 2.7g in pure water 25ml, adds potassium hydroxide 5.6g, bromoacetic acid 13.9g thereto Afterwards, it is stirred 12 hours at 90 DEG C.At this point, it is dark brown for changing as reaction carries out.After cooling, which is put into cold In concentrated hydrochloric acid 100mL, solid obtained by reprecipitation will be carried out and be filtered, sufficiently washed with water.Keep the solid dry, obtains pure Compound (DC-1-1) 3.6g that degree is 98%.

Then, compound (DC-1-1) 3.6g, acetic anhydride 20mL are made an addition in container, is stirred 6 hours at 60 DEG C.It will The solid being precipitated after cooling is filtered, and the compound (DC-1) that purity is 98% is obtained in the form of yellow~white solid 2.2g。

[embodiment 2-1: the synthesis of polyamic acid (P1)]

By 2 as tetracarboxylic dianhydride, 3,5- tricarboxylic cyclopentyl acetic acid dianhydride, 50 molar part and pyromellitic acid anhydride 50 molar part of 50 molar parts, 50 molar part of p-phenylenediamine as diamines and compound (DA-1), is dissolved in N- methyl -2- It in pyrrolidones (NMP), carries out reacting for 6 hours at 60 DEG C, obtains the solution of the polyamic acid containing 20 weight %.By gained Polyamic acid solution point take a small amount of, add NMP and the solution that polyamic acid concentration is 10 weight % be made, it is molten obtained by measurement Fluid viscosity is 80mPas.

[embodiment 2-2~embodiment 2-28 and synthesis example 2-29~synthesis example 2-32]

Other than by the type of used tetracarboxylic dianhydride and diamines and quantitative change more as described in following table 1, with The identical mode of the embodiment 2-1 is respectively synthesized polyamic acid (P2)~polyamic acid (P32).

[table 1]

In table 1, the numerical value in the parantheses of tetracarboxylic dianhydride and diamines is indicated relative to the tetrabasic carboxylic acid for synthetic polymer Use ratio [molar part] for total 100 molar parts of dianhydride.Abbreviation in table 1 is respectively following meanings.

T-1:2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides

T-2: pyromellitic acid anhydride

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

T-4: TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride)

T-5:1R, 2S, 4S, 5R-1,2,4,5- cyclopentanetetracarboxylic's dianhydrides

T-6: ethylenediamine tetra-acetic acid dianhydride

D-1: p-phenylenediamine

D-2:4,4 '-diamino-diphenyl ethers

D-3:3,5- diaminobenzoic acid

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

D-5: compound represented by following formula (d-5)

D-6: compound represented by following formula (d-6)

D-7: compound represented by following formula (d-7)

DA-5: compound represented by following formula (DA-5)

DA-6: compound represented by following formula (DA-6)

[changing 31]

[embodiment 1A]

(1) preparation of aligning agent for liquid crystal

In the polyamic acid (P1) obtained in the embodiment 2-1 as polymer, NMP and butyl cellosolve are added (butyl cellosolve, BC) is used as solvent, and it is dense as NMP: BC=50: 50 (weight ratios), solid component that solvent group is made Degree is the solution of 6.0 weight %.The filter for the use of aperture being 1 μm, which is filtered, prepares aligning agent for liquid crystal whereby (S1)。

(2) manufacture of friction orientation liquid crystal display element

Have on the glass substrate with a thickness of 1mm for the chromium electrode for being set as comb teeth-shaped in wherein one side, utilizes rotation Device is coated with the aligning agent for liquid crystal (S1) of the preparation.Then, after 1 minute prebake conditions is carried out in 80 DEG C of heating plate, It is toasted after ten minutes in 230 DEG C of heating plate, forming film thickness is aboutFilm.For being formed by coated surface, make With the friction machine with the roller for being wound with nylon cloth, with the revolving speed 1 of roller, 000rpm, platform movement speed 25mm/ seconds, Hair is pressed into length 0.4mm to carry out friction treatment, assigns liquid crystal aligning ability.In turn, which is carried out to 1 point in ultrapure water Clock ultrasonic washing, carries out drying in 10 minutes in 100 DEG C of cleaning ovens, and manufacture has on the face with comb teeth-shaped chromium electrode The substrate of liquid crystal orientation film.Using the substrate with the liquid crystal orientation film as " substrate A ".

In addition to this, do not have electrode the glass substrate with a thickness of 1mm one side, by with it is described it is identical in a manner of shape At the film of aligning agent for liquid crystal (S1), friction treatment is carried out, washing, drying, manufacturing has liquid crystal orientation film in wherein one side Substrate.Using the substrate with the liquid crystal orientation film as " substrate B ".

Then, in the outer rim in the face with liquid crystal orientation film of substrate A, it is 5.5 μm of aluminium oxide that coating addition, which has diameter, After the epoxy resin adhesive of ball, antiparallel mode is become with the frictional direction in each liquid crystal orientation film, via gap by 2 Block substrate A, B is oppositely disposed, keeps outer edge against each other and crimps, hardens bonding agent.Then, from liquid crystal injecting port to one After filling nematic crystal (manufacture of Merck (Merck) company, MLC-2042) substrate, it is bonded using acrylic acid series photo-hardening Agent seals liquid crystal injecting port, manufactures IPS type liquid crystal cells whereby.

(3) evaluation of reliability

Reliability is evaluated using the liquid crystal cells manufactured in (2).Proceed as follows evaluation.Firstly, for The liquid crystal cells, with the application time of 60 microseconds, 167 milliseconds span apply 5V voltage after, measurement from apply release Voltage retention (VHR1) after 167 milliseconds.Then, by liquid crystal cells light emitting diode (Light Emitting Diode, LED it after) standing 200 hours in 80 DEG C of baking ovens under light irradiation, stands and cooled to room temperature at room temperature.After cooling, with After the application time of 60 microseconds, 167 milliseconds of span apply the voltage of 5V to liquid crystal cells, measurement 167 milli from applying and releasing Voltage retention (VHR2) after second.In addition, measurement device is manufactured using Dongyang Te Kenika (Toyo Technica) (stock) " VHR-1 ".The change rate (Δ VHR) that VHR at this time is calculated using following numerical expressions (2) is evaluated reliable according to Δ VHR Property.About evaluation, by Δ VHR less than 1% the case where is determined as reliability " good (◎) ", by 1% feelings more than and less than 2% Condition is determined as reliability " can (zero) ", and 2% or more situation is determined as reliability " bad (×) ".As a result, embodiment It is in 1A reliability " good ".

Δ VHR [%]=(VHR1-VHR2)/(VHR1) × 100 (2)

(4) evaluation of liquid crystal aligning

To the liquid crystal cells manufactured in (2), on-off (apply and release) is observed using petrographic microscope The case where region without exception, is determined as liquid crystal aligning " good ", will be present even 1 by the presence or absence of abnormal area when voltage The case where a abnormal area, is determined as liquid crystal aligning " bad ".As a result, the liquid crystal aligning of the liquid crystal cells of the embodiment Property be " good ".

(5) image retention characteristic (image retention characteristic)

In addition to there is the metal of patterned 2 systems comprising chromium for comb teeth-shaped using in wherein one side as substrate Electrode (glass substrate of electrode a and electrode b), with the opposite glass substrate of not set electrode as other than a pair of, with it is described (2) identical mode manufactures IPS type liquid crystal cells.Then, polarizer, manufacture are bonded on the outside two sides of the substrate of liquid crystal cells Liquid crystal display element.The IPS type liquid crystal display element is placed in 25 DEG C, in the environment of 1 air pressure, voltage is not applied to electrode b, Electrode a is applied resultant voltage 2 hours of alternating voltage 3.5V and DC voltage 5V.Then, at once to electrode a and electrode b this Two apply the voltage of exchange 4V.It measures since at the time of applying the voltage of exchange 4V to two electrodes, until with visual nothing Method confirms the time until the difference of the photopermeability of electrode a and electrode b again.Image retention when by the time for less than 100 seconds is special Property is evaluated as " good ", and image retention characteristic when by 100 seconds more than and less than 150 seconds is evaluated as "available", and will be more than 150 seconds In the case of image retention characteristic be evaluated as " bad ".As a result, being image retention characteristic " good " in the liquid crystal cells of embodiment 1A As a result.

[embodiment 2A~embodiment 11A, embodiment 28A and comparative example 1, comparative example 2]

In addition to the type of used polymer is changed to as described in Table 2 other than, with the embodiment 1A phase With solvent ratio and solid component concentration prepare aligning agent for liquid crystal (S2)~aligning agent for liquid crystal (S11) and liquid crystal aligning respectively Agent (S28)~aligning agent for liquid crystal (S30).In addition, manufacturing liquid crystal in a manner of identical with embodiment 1A using each aligning agent for liquid crystal Unit, and various evaluations are carried out using resulting liquid crystal cells.It the results are shown in following table 2.

[embodiment 12A]

(1) preparation of aligning agent for liquid crystal

Other than the type of used polymer is changed to polyamic acid (P12), with the embodiment 1A phase With solvent when solid component concentration prepares aligning agent for liquid crystal (S12).

(2) manufacture of optical alignment film liquid crystal display element

Have on the glass substrate with a thickness of 1mm for the chromium electrode for being set as comb teeth-shaped in wherein one side, is become with film thickness 0.1 μm of mode is coated with the aligning agent for liquid crystal (S12) of the preparation using rotator, and 1 point is carried out in 80 DEG C of heating plate After the prebake conditions of clock, rear baking in 10 minutes is carried out in 230 DEG C of heating plate, forms film.By the substrate with the film As " substrate A ".

In addition to this, do not have electrode the glass substrate with a thickness of 1mm one side, by with it is described it is identical in a manner of shape At the film of aligning agent for liquid crystal (S12).Using the substrate with the film as " substrate B ".

Then, for the film coated surface of substrate A and substrate B, using Hg-Xe lamp, the irradiation of self-reference substrate normal direction includes The polarisation ultraviolet light 10,000J/m of the open-wire line of 254nm², form liquid crystal orientation film.

Then, for having carried out a pair of of substrate of the photo-irradiation treatment, at the edge in the face for being formed with liquid crystal orientation film Liquid crystal injecting port is remained, being coated with to be added by screen painting has diameter for the adhering with epoxy resin of 5.5 μm of alumina balls After agent, projecting direction of the polarizing axis on real estate when being irradiated with light becomes antiparallel mode, and substrate is overlapped and is crimped, 1 hour is spent at 150 DEG C makes bonding agent carry out thermmohardening.Then, from liquid crystal injecting port, nematic liquid is filled between a pair of of substrate After brilliant (manufacture of Merck (Merck) company, MLC-7028), liquid crystal injecting port is sealed using epoxy bonding agent.In turn, in order to Flow orientation when liquid crystal injection is removed, is slowly cooled down to room temperature after it is heated at 150 DEG C.Then, in substrate Outside two sides is bonded polarizer to make liquid crystal display element.

(3) evaluation of reliability

Other than using the liquid crystal display element manufactured in (2), in a manner of identical with the embodiment 1A into The evaluation of row reliability, as a result, Δ VHR=1.6% in the embodiment is the result of reliability "available".

(4) evaluation of liquid crystal aligning

Other than using the liquid crystal display element manufactured in (2), in a manner of identical with the embodiment 1A into The evaluation of row reliability, as a result, be the result of liquid crystal aligning " good " in the embodiment.

(5) image retention characteristic (image retention characteristic)

In addition to evaluating image retention in a manner of identical with the embodiment 1A other than for the use of aligning agent for liquid crystal (S12) Characteristic, as a result, be the evaluation of image retention characteristic "available" in the embodiment.

[embodiment 13A~embodiment 27A and comparative example 3, embodiment 4]

In addition to the type of used polymer is changed to as described in Table 2 other than, with the embodiment 1A phase With solvent when solid component concentration prepares aligning agent for liquid crystal (S13)~aligning agent for liquid crystal (S27), aligning agent for liquid crystal respectively (S31), aligning agent for liquid crystal (S32).In addition, manufacturing liquid crystal list in a manner of identical with embodiment 12A using each aligning agent for liquid crystal Member, and various evaluations are carried out using resulting liquid crystal cells.It the results are shown in following table 2.

[table 2]

As shown in table 2, in embodiment 1A~embodiment 28A are as follows: even if for a long time (200 hours) be exposed to photostress and After under thermal stress environment, the decline of voltage retention is still few, and reliability is good.In contrast, in 1~comparative example of comparative example 4, Due to the imparting of photostress and thermal stress, voltage retention sharp fall is the evaluation of reliability " bad ".

In addition, not observing that orientation is bad about liquid crystal aligning, in embodiment 1A~embodiment 28A, about image retention Characteristic, any sample is also the evaluation of " good " or "available" in embodiment.

Confirm as previously discussed: the liquid crystal orientation film with structure used in embodiment will not upset liquid crystal aligning Property, the characteristic with high reliablity.

Claims

1. a kind of aligning agent for liquid crystal, it is characterised in that: contain the gathering with part-structure represented by following formula (2) on main chain Close object (P), the polymer (P) be in the group as composed by polyamic acid, poly amic acid ester and polyimides extremely Few one kind,

In formula (2), 2 X¹For divalent aromatic heterocycle；R¹For singly-bound, the alkane diyl of carbon number 1~6 or cyclohexylidene, R²For The hydrogen atom perhaps alkyl of carbon number 1~6 or 2 R²Mutually bond and with 2 nitrogen-atoms and R¹It is formed together carbon number 2~10 Divalent ester ring type heterocycle；2 X¹It may be the same or different, 2 R²It may be the same or different；P is 0 or 1；" * " indicates associative key.

2. aligning agent for liquid crystal according to claim 1, it is characterised in that: the polymer (P) is by monomer composition In the polymerization comprising compound represented by following formula (3) and the polymer that obtains,

In formula (3), 2 X¹For divalent aromatic heterocycle；Z¹For base represented by level-one amino or following formula (z-1)；

In formula (z-1), " * " is indicated and X¹Associative key；

R¹For singly-bound, the alkane diyl of carbon number 1~6 or cyclohexylidene, R²For the hydrogen atom perhaps alkyl of carbon number 1~6 or 2 R²Mutually bond and with 2 nitrogen-atoms and R¹It is formed together the divalent ester ring type heterocycle of carbon number 2~10；2 X¹It can be identical Difference, 2 R²It may be the same or different；P is 0 or 1.

3. a kind of manufacturing method of liquid crystal orientation film, characterized by comprising: use liquid crystal according to claim 1 or 2 Alignment agent is come the step of forming film；And light irradiation is carried out come the step of assigning liquid crystal aligning ability to the film.

4. a kind of manufacturing method of liquid crystal orientation film, characterized by comprising: use liquid crystal according to claim 1 or 2 Alignment agent is come the step of forming film；And friction treatment is carried out come the step of assigning liquid crystal aligning ability to the film.

5. a kind of liquid crystal orientation film, it is characterised in that: it is to utilize aligning agent for liquid crystal institute according to claim 1 or 2 shape At.

6. a kind of liquid crystal display element, it is characterised in that: including liquid crystal orientation film according to claim 5.

7. a kind of polymer, it is characterised in that: it is selected from the group as composed by polyamic acid, poly amic acid ester and polyimides At least one of group, and there is part-structure represented by following formula (2) on main chain,

8. a kind of compound, which is characterized in that its be by following formula (3) represented by:

In formula (3), X¹For divalent organic group, wherein 2 X¹At least one be divalent aromatic heterocycle；Z¹For level-one amino or Group represented by person's following formula (z-1)；

In formula (z-1), " * " is indicated and X¹Associative key；