CN105122128B

CN105122128B - The manufacture method of liquid crystal orientation film, liquid crystal orientation film, liquid crystal represent element and aligning agent for liquid crystal

Info

Publication number: CN105122128B
Application number: CN201480020966.XA
Authority: CN
Inventors: 巴幸司; 菊池奈穂; 片山雅章; 三木徳俊
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-02-13
Filing date: 2014-02-12
Publication date: 2017-11-28
Anticipated expiration: 2034-02-12
Also published as: TWI628202B; KR102172134B1; WO2014126102A1; JP6361887B6; TW201446839A; KR20150119199A; JPWO2014126102A1; CN105122128A; JP6361887B2

Abstract

By being burnt till after aligning agent for liquid crystal is coated on into substrate, so as to obtain the liquid crystal orientation film that acid imide rate is 50~70%, the aligning agent for liquid crystal contains：Selected from the polyimide precursor with the repeat unit shown in following formula [1] and with least one of the polyimides of repeat unit and acid imide rate less than 50% shown in following formula [1] polymer.(in formula [1], A₁For divalent organic group；A₂For divalent organic group；C₁And C₂For hydrogen atom or the alkyl of carbon number 1~3, optionally it is same to each other or different to each other.)

Description

The manufacture method of liquid crystal orientation film, liquid crystal orientation film, liquid crystal represent that element and liquid crystal take To agent

Technical field

The present invention relates to the manufacture method of liquid crystal orientation film, liquid crystal orientation film, the liquid crystal of liquid crystal orientation film has been used to represent The aligning agent for liquid crystal used when element and making liquid crystal orientation film.

Background technology

The liquid crystal used in LCD TV, liquid crystal display etc. represents element as realizing the thin light weight of volume Represent equipment and now widely available.In liquid crystal represents element, liquid crystal orientation film, which plays, makes liquid crystal along certain direction It is orientated this effect.Now, the main liquid crystal orientation film industrially utilized is by that will include polyimide precursor i.e. polyamide Acid (also referred to as polyamic acid), poly amic acid ester, polyimides solution aligning agent for liquid crystal be coated on substrate and burn till and Formed.

In the formation of this liquid crystal orientation film, when generation firing temperature is high low substrate of heat resistance etc. can not be used to ask Topic, it is therefore desirable for reducing firing temperature.As the technology of liquid crystal orientation film can be formed with relatively low firing temperature, such as disclose Contain the liquid crystal orientation film of following polymer, the polymer is in same molecule comprising polyureas system constitutional repeating unit and poly- Imide series constitutional repeating unit (with reference to patent document 1).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 08-220542 publications

The content of the invention

Problems to be solved by the invention

However, the liquid crystal orientation film of patent document 1 there are problems that residual DC it is high this.In addition, for liquid crystal orientation film and Speech, as other electrical characteristics, also requires voltage retention height.

It is an object of the present invention to solve above-mentioned prior art problem, its object is to, there is provided can be with easy fired To form liquid crystal aligning film manufacturing method, liquid crystal orientation film, the liquid crystal of the liquid crystal orientation film that residual DC is low and voltage retention is high Represent element and aligning agent for liquid crystal.

The solution used to solve the problem

The present invention for solving above-mentioned problem is used as purport using following content.

1. a kind of manufacture method of liquid crystal orientation film, it is characterised in that laggard by the way that aligning agent for liquid crystal is coated on into substrate Row is burnt till, and so as to obtain the liquid crystal orientation film that acid imide rate is 50~70%, the aligning agent for liquid crystal contains：Selected from under State the polyimide precursor of the repeat unit shown in formula [1] and with the repeat unit and acid imide rate shown in following formula [1] At least one of polyimides less than 50% polymer.

(in formula [1], A₁For divalent organic group；A₂For divalent organic group；C₁And C₂For hydrogen atom or carbon number 1~3 Alkyl, be optionally same to each other or different to each other.)

2. the manufacture method of the liquid crystal orientation film according to 1., it is characterised in that foregoing burning is carried out below 210 DEG C Into.

3. the manufacture method of the liquid crystal orientation film according to 1. or 2., it is characterised in that aforementioned polymer has following Side chain shown in formula [2].

(in formula [2], Y₁For singly-bound ,-(CH₂)_a- (a is 1~15 integer) ,-O- ,-CH₂O- ,-COO- or-OCO-, Y₂For Singly-bound or-(CH₂)_b- (b is 1~15 integer), Y₃For singly-bound ,-(CH₂)_c- (c is 1~15 integer) ,-O- ,-CH₂O-、- COO- or-OCO-, Y₄Represent the divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle or there is steroid skeleton The divalent organic group of carbon number 17~51, any hydrogen atom on aforementioned cyclic group is optionally by the alkane of carbon number 1~3 Base, the alkoxy of carbon number 1~3, carbon number 1~3 it is former containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine Son substitution, Y₅Represent divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle, any hydrogen on these cyclic groups is former Son optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, carbon atom Number 1~3 fluoroalkoxy or fluorine atom substitution, n be 0~4 integer, Y₆For the alkyl of carbon number 1~18, carbon number 1~18 fluoroalkoxy containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1~18.)

4. the manufacture method of the liquid crystal orientation film according to any one of 1.~3., it is characterised in that aforementioned polymer Be make following (a) composition, (b) composition and (c) composition reaction obtained from.

(a) composition：Intramolecular contain 2 NCOs compound,

(b) composition：Intramolecular contain 2 primary amino radicals or secondary amino group compound,

(c) composition：Tetracarboxylic acid derivatives.

5. the manufacture method of the liquid crystal orientation film according to 4., it is characterised in that foregoing (b) composition is with previously described formula [2] compound of the side chain shown in.

6. the manufacture method of the liquid crystal orientation film according to 4., it is characterised in that foregoing (b) composition is following formula [2a] Shown compound.

(in formula [2a], Y₁、Y₂、Y₃、Y₄、Y₅、Y₆, Y in n and formula [2]₁、Y₂、Y₃、Y₄、Y₅、Y₆, n it is identical, m is 1~4 Integer ,-(Y₁-Y₂-Y₃-Y₄-(Y₅)_n-Y₆)_mRepresent substituent Y₁-Y₂-Y₃-Y₄-(Y₅)_n-Y₆There are m, when m is more than 2, respectively take It is optionally identical or different for base.)

7. the manufacture method of the liquid crystal orientation film according to any one of 4.~6., it is characterised in that foregoing (c) composition For the tetracarboxylic dianhydride shown in following formula [3].

(in formula [3], Z₁For the structure shown in following formula [3a]~formula [3j]).

(in formula [3a], Z₂~Z₅For hydrogen atom, methyl, chlorine atom or phenyl ring, optionally it is same to each other or different to each other；Formula [3g] In, Z₆And Z₇For hydrogen atom or methyl, optionally it is same to each other or different to each other).

8. the manufacture method of the liquid crystal orientation film according to any one of 1.~7., it is characterised in that aligning agent for liquid crystal In aforementioned polymer be 0.1~30 mass %.

9. the manufacture method of the liquid crystal orientation film according to any one of 1.~8., it is characterised in that pass through ink-jet method Carry out foregoing coating.

10. a kind of liquid crystal orientation film, it is characterised in that it is by the liquid crystal orientation film any one of 1.~9. Manufacture method and manufacture.

11. a kind of liquid crystal orientation film, it is characterised in that it contains the polyamides with the repeat unit shown in following formula [1] Imines, acid imide rate are 50~70%.

12. according to the liquid crystal orientation film described in 10. or 11., it is characterised in that it is used for possessing a pair of bases of electrode The liquid crystal for having liquid crystal layer between plate and being manufactured via following process represents element, and the process is：In foregoing a pair of substrates Between configure liquid-crystal composition, the liquid-crystal composition includes gathering of polymerize by least one of active energy beam and heat Conjunction property compound, it polymerize aforementioned polymeric compound while applying voltage former electrodes.

13. according to the liquid crystal orientation film described in 10. or 11., it is characterised in that it is used for possessing a pair of bases of electrode The liquid crystal for having liquid crystal layer between plate and being manufactured via following process represents element, and the process is：In foregoing a pair of substrates Between configure liquid crystal orientation film, the liquid crystal orientation film includes gathering of polymerize by least one of active energy beam and heat Conjunction property group, make aforementioned polymeric radical polymerisation while applying voltage former electrodes.

14. a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal aligning any one of 10.~13. Film.

15. a kind of aligning agent for liquid crystal, it is characterised in that it contains the polyamides with the repeat unit shown in following formula [1] Imines precursor.

(in formula [1], A₁For divalent organic group, A₂For divalent organic group, C₁And C₂For hydrogen atom or carbon number 1~3 Alkyl, be optionally same to each other or different to each other.)

The effect of invention

According to the present invention, by using containing the polyimide precursor with the repeat unit shown in formula [1], with formula [1] aligning agent for liquid crystal of the polyimides of repeat unit and acid imide rate less than 50% shown in, be coated and burn till and The liquid crystal orientation film that acid imide rate is 50~70% is formed, the liquid crystal aligning that residual DC is low and voltage retention is high can be obtained Film.Further, it is possible to make the low temperature that firing temperature is such as less than 210 DEG C, therefore as substrate heat resistance can also be used relatively low Plastics substrate etc., in addition, can suppress liquid crystal caused by being burnt till by high temperature represents that the color characteristics of the colour filter of element are bad Change, the cost of energy in reduction liquid crystal expression element manufacture.

Embodiment

Hereinafter, the present invention is described in detail for pin.

The present invention liquid crystal orientation film manufacture method by being burnt till after aligning agent for liquid crystal is coated on into substrate, so as to The liquid crystal orientation film that acid imide rate is 50~70% is obtained, the aligning agent for liquid crystal contains：Selected from above-mentioned formula [1] Suo Shi Repeat unit polyimide precursor and with the repeat unit shown in above-mentioned formula [1] and acid imide rate it is poly- less than 50% At least one of acid imide polymer.

The aligning agent for liquid crystal used in the manufacture of the liquid crystal orientation film of the present invention contains：With the weight shown in above-mentioned formula [1] Answer the polyimide precursor of unit or with the polyamides of repeat unit and acid imide rate less than 50% shown in above-mentioned formula [1] Imines.In the nature of things, can also contain polyimide precursor with the repeat unit shown in above-mentioned formula [1] and with Both the polyimides of repeat unit and acid imide rate less than 50% shown in above-mentioned formula [1].Furthermore it is also possible to contain more Kind of the polyimide precursor with the repeat unit shown in above-mentioned formula [1], a variety of repeat units with shown in above-mentioned formula [1] and Polyimides of the acid imide rate less than 50%.It should be noted that polyimide precursor refers to polyamic acid, polyamic acid Ester.

Polyimide precursor with the repeat unit shown in above-mentioned formula [1], the repeat unit shown in above-mentioned formula [1] And polyimides (be below also denoted as " polymer with repeat unit formula [1] shown in ") of the acid imide rate less than 50% is excellent Choosing is with the side chain shown in above-mentioned formula [2].During with side chain shown in above-mentioned formula [2], can make can make liquid crystal vertical-tropism Liquid crystal orientation film.For example, when the repeat unit shown in formula [1] has the side chain shown in formula [2], A₁、A₂With formula [2] Suo Shi Structure.In addition, specifically, aftermentioned polyimide precursor, the repeat unit of polyimides can have shown in above-mentioned formula [2] Side chain.

In formula [1], Y₁Represent singly-bound ,-(CH₂)_a- (a is 1~15 integer) ,-O- ,-CH₂O- ,-COO- or-OCO-.Its In, from the viewpoint of raw material availability, synthesis easness, preferably singly-bound ,-(CH₂)_a- (a be 1~15 integer) ,-O- ,- CH₂O- or-COO-.More preferably singly-bound ,-(CH₂)_a- (a is 1~10 integer) ,-O- ,-CH₂O- or-COO-.

In formula [1], Y₂Represent singly-bound or-(CH₂)_b- (b is 1~15 integer).Wherein, preferably singly-bound or-(CH₂)_b- (b is 1~10 integer).

In formula [1], Y₃Represent singly-bound ,-(CH₂)_c- (c is 1~15 integer) ,-O- ,-CH₂O- ,-COO- or-OCO-.Its In, from the viewpoint of synthesis easness, preferably singly-bound ,-(CH₂)_c- (c is 1~15 integer) ,-O- ,-CH₂O- or- COO-.More preferably singly-bound ,-(CH₂)_c- (c is 1~10 integer) ,-O- ,-CH₂O- or-COO-.

In formula [1], Y₄Represent the divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle or there is steroids bone The divalent organic group of the carbon number 17~51 of frame, any hydrogen atom on cyclic group is optionally by the alkane of carbon number 1~3 Base, the alkoxy of carbon number 1~3, carbon number 1~3 it is former containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine Son substitution.Wherein, from the viewpoint of synthesis easness, preferably phenyl ring, cyclohexane ring or carbon with steroid skeleton are former The organic group of subnumber 17~51.

In formula [1], Y₅Divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle is represented, on these cyclic groups Any hydrogen atom optionally contains fluothane by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 Base, the fluoroalkoxy of carbon number 1~3 or fluorine atom substitution.Wherein, preferably phenyl ring or cyclohexane ring.

In formula [1], n is 0~4 integer.Wherein, from the viewpoint of raw material availability, synthesis easness, preferably 0 ~3.More preferably 0~2.

In formula [1], Y₆For the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, carbon number 1~18 Alkoxy or carbon number 1~18 fluoroalkoxy.Wherein, the preferably alkyl of carbon number 1~18, carbon number 1 ~10 fluoroalkoxy containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1~10.More preferably carbon is former The alkyl of subnumber 1~12 or the alkoxy of carbon number 1~12.The particularly preferably alkyl or carbon number of carbon number 1~9 1~9 alkoxy.

In formula [1], as Y₁、Y₂、Y₃、Y₄、Y₅、Y₆With n preferred compositions, can include and International Publication publication (2-1)~(2-629) phases described in 6~table of table 47 of 13 of WO2011/132751 (2011.10.27 is disclosed)~34 Same combination.It should be noted that in each table of International Publication publication, the Y in the present invention₁~Y₆It is illustrated as Y1~Y6, but Y1~ Y6 also is understood as Y₁~Y₆。

Polyimide precursor with the repeat unit shown in above-mentioned formula [1] for example can be by making intramolecular contain 2 The compound of NCO is compound i.e. (b) composition and four that (a) composition contains 2 primary amino radicals or secondary amino group with intramolecular Carboxylic acid derivates are the reaction of (c) composition to manufacture.

(a) composition is O=C=N-A₁- N=C=O (A₁With the A in formula [1]₁It is identical) shown in compound.As A₁, can Include hydrogen atom optionally by the phenyl ring of the alkyl-substituted divalent of carbon number 1~5, alkylidene, aliphatic ring or comprising Substituent of combinations thereof etc..As the concrete example of (a) composition, the adjacent benzene two as aromatic diisocyanate can be included Isocyanates, m-benzene diisocyanate, PPDI, toluene di-isocyanate(TDI) class are (for example, 2,4- toluene di-isocyanate (TD.I)s Ester), the isocyanic acid -2- methoxyl groups phenyl esters of 1,4- bis-, 2,5- xylene diisocyanates class, 2,2 '-bis- (isocyanato- benzene of 4- bis- Base) propane, 4,4 '-two isocyanic acid diphenyl methanes, 4,4 '-two isocyanic acid diphenyl ether, 4,4 '-two isocyanic acid diphenyl sulphone (DPS)s, 3,3 '- Two isocyanic acid diphenyl sulphone (DPS)s, 2,2 '-two isocyanic acid benzophenone etc.；Isophorone diisocyanate as aliphatic diisocyanate Ester, hexamethylene diisocyanate, tetramethyl ethylidene diisocyanate etc..Wherein, 2,4- toluene-2,4-diisocyanates are from acquisition It is preferable from the viewpoint of property, polymerisation reactivity, voltage retention.

(b) composition is the compound shown in following formula [b].

(in formula [b], C₁、C₂、A₂With the C in formula [1]₁、C₂、A₂It is identical)

As A₂, can include from (b) composition compound divalent organic group.As the specific of (b) composition Example, can include the compound shown in above-mentioned formula [2a].

Two amino (- NH in above-mentioned formula [2a]₂) bonding position do not limit.Specifically, relative to side chain Binding groups (- (Y₁-Y₂-Y₃-Y₄-(Y₅)_n-Y₆)_m), 2 on phenyl ring, 3 position, 2,4 position, 2,5 position can be included Put, 2,6 position, 3,4 position or 3,5 position.Wherein, from polymer of the synthesis with the repeat unit shown in formula [1] When reactivity from the viewpoint of, preferably 2,4 position, 2,5 position or 3,5 position.Further contemplate synthesis type During easiness during compound shown in [2a], more preferably 2,4 position or 2,5 position.

More specifically, formula [2a] is the structure shown in following formula [2b-1]~formula [2b-29].

(in formula [2b-19]~formula [2b-21], R¹Expression-O- ,-OCH₂-、-CH₂O-、-COOCH₂- or-CH₂OCO-, R²Table Show the alkyl of carbon number 1~18, alkoxy, containing fluoroalkyl or fluoroalkoxy).

(in formula [2b-22]~formula [2b-24], R³Expression-COO- ,-OCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、- OCH₂- or-CH₂-, R⁴Represent the alkyl of carbon number 1~18, alkoxy, containing fluoroalkyl or fluoroalkoxy).

(in formula [2b-25] and formula [2b-26], R⁷Represent the alkyl of carbon number 3~12.It should be noted that Isosorbide-5-Nitrae-ring The cis-trans isomerization of hexylidene is respectively preferably transisomer).

(in formula [2b-27] and formula [2b-28], R⁸Represent the alkyl of carbon number 3~12.It should be noted that Isosorbide-5-Nitrae-ring The cis-trans isomerization of hexylidene is respectively preferably transisomer).

(in formula [2b-29], B⁴Represent the alkyl of carbon number 3~18 being optionally replaced by fluorine atoms, B³Represent 1,4- rings Hexylidene or Isosorbide-5-Nitrae-phenylene, B²Represent oxygen atom or-COO-* (wherein, the keys and B of subsidiary " * "³It is bonded), B¹Represent oxygen Atom or-COO-* (wherein, the keys and (CH of subsidiary " * "₂)a²It is bonded).In addition, a¹Represent 2~10 integer, a³Represent 0 Or 1 integer).

During using compound shown in formula [2a], as described above, liquid crystal vertical-tropism can be made.Shown in formula [2a] Compound is preferably 5 moles of overall more than % and 80 mole of below % of (b) composition.It is further preferred that from liquid crystal aligning Viewpoint is set out, and the compound shown in formula [2a] is 5 moles of overall more than % and 60 mole of % of (b) composition.It is particularly preferred that For 10 moles of more than % and 60 mole of below % that (b) composition is overall.

As (b) composition beyond the compound shown in formula [2a], m-phenylene diamine (MPD), 2,4- dimethyl isophthalic two can be included Amine, 2,6- diaminotoluenes, 2,4- diaminophenols, 3,5- diaminophenols, 3,5- diaminourea benzylalcohol, 2,4- diaminourea benzyls Alcohol, 4,6-diaminoresorcinol, and the diamine compound of following formula [2b-30]~structure shown in [2b-41].

(in [2b-30] and formula [2b-31], R⁵For-COO- ,-OCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、- CH₂- or-O-, R⁶For fluorine-based, cyano group, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl).

(in formula [2b-32]~formula [2b-35], A¹Represent the alkyl of carbon number 1~22 or containing fluoroalkyl).

In addition, formula [2b-36] has the side chain of photoreactivity.The side chain of this photoreactivity refers to send out by light irradiation The part of raw polymerization, can be included for example with acryloyl group, methylacryloyl, lactone group, dimaleoyl imino, ethene Base, pi-allyl, the side chain of styryl.But it is not limited to these.

In addition, as (b) composition beyond the compound shown in formula [2a], 4 can be also included, 4 '-benzidine, 3, 3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy -4,4 '-diamino Base biphenyl, 3,3 '-dicarboxyl -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-biphenyl, 3,3 '-trifluoromethyl -4,4 '-two Aminobphenyl, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4, 4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminourea two Phenylmethane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '- Diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl ether, 4,4 '-sulfonyldianiline, 3, 3 '-sulfonyldianiline, double (4- aminophenyls) silane, double (3- aminophenyls) silane, dimethyl-bis- (4- aminophenyls) silicon Alkane, dimethyl-bis- (3- aminophenyls) silane, 4,4 '-phenothiazine, 3,3 '-phenothiazine, 4,4 '-diaminourea hexichol Base amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino-diphenyl amine, 2,3 '-diaminourea Diphenylamine, N- methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diamino-diphenyl) amine, N- methyl (3,4 '- Diamino-diphenyl) amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-diamino-diphenyl) amine, 4,4 '- Diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 1,4- diaminonaphthalenes, 2,2 '-diamino Base benzophenone, 2,3 '-diaminobenzophenone, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- diaminonaphthalenes, 1,8- bis- Amino naphthalenes, 2,5- diaminonaphthalenes, 2,6- diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, 1,2- are double (4- aminophenyls) Double (3- aminophenyls) ethane of ethane, 1,2-, double (4- aminophenyls) propane of 1,3-, 1,3- double (3- aminophenyls) propane, 1, Double (4- aminophenyls) butane of 4-, 1,4- double (3- aminophenyls) butane, double (3,5- diethyl -4- aminophenyls) methane, 1, Double (4- amino-benzene oxygens) benzene of 4-, double (4- amino-benzene oxygens) benzene of 1,3-, double (4- aminophenyls) benzene of 1,4-, double (the 4- ammonia of 1,3- Base phenyl) benzene, double (4- aminobenzyls) benzene of 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, the 4,4 '-[double (methylenes of 1,4- phenylenes Base)] diphenylamines, 4,4 '-[1,3- phenylenes double (methylene)] diphenylamines, 3,4 '-[1,4- phenylenes are double (methylene)] hexichol Amine, 3,4 '-[1,3- phenylenes double (methylene)] diphenylamines, 3,3 '-[1,4- phenylenes are double (methylene)] diphenylamines, 3,3 '- [1,3- phenylenes are double (methylene)] diphenylamines, 1,4- phenylenes double [(4- aminophenyls) ketones], the double [(3- of 1,4- phenylenes Aminophenyl) ketone], 1,3- phenylenes double [(4- aminophenyls) ketones], 1,3- phenylenes double [(3- aminophenyls) ketones], 1,4- phenylenes double (PABA esters), 1,4- phenylenes double (3- Aminobenzoates), double (the 4- amino of 1,3- phenylenes Benzoic ether), 1,3- phenylenes double (3- Aminobenzoates), double (4- aminophenyls) terephthalates, double (3- aminobenzenes Base) terephthalate, double (4- aminophenyls) isophthalic acid esters, double (3- aminophenyls) isophthalic acid esters, N, N '- (1,4- phenylenes) double (4- aminobenzamides), N, N '-(1,3- phenylenes) double (4- aminobenzamides), N, N '-(1,4- Phenylene) double (3-ABs), N, N '-(1,3- phenylenes) double (3-ABs), N, N '-bis- (4- amino Phenyl) terephthalamide, N, N '-bis- (3- aminophenyls) terephthalamide, N, N '-bis- (4- aminophenyls) isophthalic diformazan Acid amides, N, double (4- aminophenyls) anthracenes of N '-bis- (3- aminophenyls) isophtalamide, 9,10-, 4,4 '-bis- (4- aminobenzene oxygen Base) diphenyl sulfone, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] six Fluoro-propane, 2,2 '-bis- (4- aminophenyls) HFC-236fas, 2,2 '-bis- (3- aminophenyls) HFC-236fas, 2,2 '-bis- (3- ammonia Base -4- aminomethyl phenyls) HFC-236fa, 2,2 '-bis- (4- aminophenyls) propane, 2,2 '-bis- (3- aminophenyls) propane, 2,2 ' - Double (3- amino-benzene oxygens) propane of double (3- amino -4- aminomethyl phenyls) propane, 1,3- pairs of (4- amino-benzene oxygens) propane, 1,3-, Double (4- amino-benzene oxygens) butane of 1,4-, double (3- amino-benzene oxygens) butane of 1,4-, 1,5- double (4- amino-benzene oxygens) pentane, 1, Double (3- amino-benzene oxygens) pentanes of 5-, double (4- amino-benzene oxygens) hexanes of 1,6-, 1,6- double (3- amino-benzene oxygens) hexane, 1,7- Double (4- amino-benzene oxygens) octanes of double (4- amino-benzene oxygens) heptane, 1,7- (3- amino-benzene oxygens) heptane, 1,8-, 1,8- are double Double (4- amino-benzene oxygens) nonanes of (3- amino-benzene oxygens) octane, 1,9-, double (3- amino-benzene oxygens) nonanes of 1,9-, 1,10- are double Double (3- amino-benzene oxygens) decane of (4- amino-benzene oxygens) decane, 1,10-, 1,11- double (4- amino-benzene oxygens) hendecane, 1, Double (3- amino-benzene oxygens) hendecanes of 11-, double (4- amino-benzene oxygens) dodecanes of 1,12-, double (the 3- amino-benzene oxygens) ten of 1,12- Dioxane, double (4- aminocyclohexyls) methane, double (4- amino -3- methylcyclohexyls) methane, 1,3- diaminopropanes, 1,4- diaminos Base butane, 1,5- 1,5-DAPs, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diaminourea Nonane, 1,10- diamino decanes, 1,11- diamino undecanes or 1,12- diamino dodecanes etc..

In addition, as (b) composition, can also include two amine side chains has alkyl, containing fluoroalkyl, aromatic rings, aliphatic ring Or the compound of heterocycle；And substitute the compound of body with the big ring-type formed by them etc..Specifically, can exemplify down Diamine compound shown in formula [DA1]~[DA13].

(in formula [DA1]~formula [DA6], A¹Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂- ,-O- ,-CO- or- NH-, A²Represent the straight-chain or the alkyl of branched or the straight-chain or branched of carbon number 1~22 of carbon number 1~22 Contain fluoroalkyl).

(in formula [DA7], p represents 1~10 integer).

In addition, as (b) composition, the diamine compound shown in following formula [DA8]~formula [DA13] can also be used.

(in formula [DA10], m represents 0~3 integer；In formula [DA13], n represents 1~5 integer).

And then in the range of effect of the present invention is not damaged, it can also use shown in following formula [DA14]~formula [DA17] Diamine compound.

(in formula [DA14], A¹Represent singly-bound ,-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、- NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃) CO-, m¹ And m²0~4 integer, and m are represented respectively¹+m²Represent 1~4 integer；In formula [DA15], m³And m⁴Expression 1~5 is whole respectively Number；In formula [DA16], A²Represent the straight chained alkyl or branched-alkyl of carbon number 1~5, m⁵Represent 1~5 integer；Formula [DA17] In, A³Represent singly-bound ,-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、- CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃) CO-, m⁶Represent 1~4 it is whole Number.)

In addition, in the range of effect of the present invention is not damaged, the diamine compound shown in following formula [DA18] can also be used.

(in formula [DA18], A¹For selected from-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON (CH₃)-or-N (CH₃) divalent organic group in CO-, A²For singly-bound, the aliphatic alkyl of carbon number 1~20, non-aromatic Ring type alkyl or aromatic hydrocarbyl, A³Selected from singly-bound ,-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、- CON(CH₃)-、-N(CH₃) CO- or-O (CH₂)_m- (m is 1~5 integer), A⁴For nitrogenous heteroaromatic, n be 1~4 it is whole Number.)

In addition, as other diamine compounds, two amine compounds shown in following formula [DA19] and formula [DA20] can also be used Thing.

On above-mentioned (b) composition, the polymer of the repeat unit according to formula [1] dissolubility in a solvent, The characteristics such as the coating of aligning agent for liquid crystal, liquid crystal aligning when being made liquid crystal orientation film, voltage retention, accumulated charge, 1 kind can be used or be use mixing two or more.

(c) composition is tetracarboxylic acid derivatives, can include the tetracarboxylic dianhydride shown in for example above-mentioned formula [3].In formula [3], From the viewpoint of the easness of polymerisation reactivity when synthesizing easness, manufacture polymer, Z₁Preferably formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or the structure shown in formula [3g].More preferably formula [3a], formula [3e], formula [3f] or formula Structure shown in [3g], particularly preferably formula [3a], formula [3e], formula [3f] or formula [3g].

Tetracarboxylic dianhydride shown in formula [3] is preferably 1 mole of overall more than % of (c) composition.More preferably 5 moles of % with On, particularly preferably 10 moles of more than %.

In addition, use Z₁For tetracarboxylic dianhydride shown in the formula [3] of the structure of formula [3e], formula [3f] or formula [3g] when, its Dosage is preferably 20 moles of overall more than % of (c) composition, more preferably 30 moles of more than %.And then (c) composition can be with Entirely Z₁For the tetracarboxylic dianhydride shown in the formula [3] of the structure of formula [3e], formula [3f] or formula [3g].

As (c) composition beyond the tetracarboxylic dianhydride shown in formula [3], tetrabasic carboxylic acid chemical combination as shown below can be included Thing, tetracarboxylic dianhydride or tetracarboxylic acid acid ihalide.That is, as (c) composition beyond the tetracarboxylic dianhydride shown in formula [3], can arrange Enumerate pyromellitic acid, 2,3,6,7- naphthalene tetracarboxylic acids, 1,2,5,6- naphthalene tetracarboxylic acids, 1,4,5,8- naphthalene tetracarboxylic acids, 2,3,6,7- anthracenes four Carboxylic acid, 1,2,5,6- anthracenes tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4- biphenyltetracarboxyacid acids, double (3,4- dicarboxyls Phenyl) ether, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, double (3,4- dicarboxyphenyis) sulfones, double (3,4- dicarboxyphenyis) methane, Double (3,4- dicarboxyphenyis) propane of double (3,4- dicarboxyphenyis) propane of 2,2-, 1,1,1,3,3,3- hexafluoros -2,2-, it is double (3, 4- dicarboxyphenyis) dimethylsilane, double (3,4- dicarboxyphenyis) diphenyl silanes, 2,3,4,5- pyridines tetrabasic carboxylic acid, 2,6- Double (3,4- dicarboxyphenyis) pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid, 3,4,9,10- tetrabasic carboxylic acids or 1,3- hexichol Base -1,2,3,4- cyclobutane tetrabasic carboxylic acids.

On (c) composition, the polymer of the repeat unit according to formula [1] dissolubility in a solvent, liquid crystal The characteristics such as the coating of alignment agent, liquid crystal aligning when being made liquid crystal orientation film, voltage retention, accumulated charge, can also Using a kind or it is use mixing two or more.

By making this (a) composition, (b) composition and (c) composition that polymerisation occur, can manufacture with formula [1] Suo Shi Repeat unit polyimide precursor.For example, when using tetracarboxylic dianhydride as (c) composition, can manufacture with formula [1] The polyamic acid of shown repeat unit.Also, the carboxyl that gained is had to the polyamic acid of the repeat unit shown in formula [1] turns When changing ester into, the poly amic acid ester with the repeat unit shown in formula [1] can be manufactured.It should be noted that by making these Polyamic acid with the repeat unit shown in formula [1], the poly amic acid ester closed loop (acyl with the repeat unit shown in formula [1] Imidization), the polyimides with the repeat unit shown in formula [1] can be obtained.

Herein, the repeat unit shown in above-mentioned formula [1] is made up of (a) composition and (b) composition.In addition, by (b) composition with (c) composition forms polyimide precursor, the repeat unit of polyimides.Before the polyimides be made up of (b) composition and (c) composition Body, the repeat unit of polyimides can for example use following formula [8] to represent.In above-mentioned formula [1], A₁For from (a) for belonging to raw material The group of composition, C₁、C₂、A₂For the group from (b) composition for belonging to raw material.In addition, in above-mentioned formula [8], C₁、C₂、A₂For source From the group of (b) composition for belonging to raw material, Z₁For the group from (c) composition for belonging to raw material.

(in formula [8], A₂、C₁、C₂It is identical with formula [b], Z₁With the Z of formula [3]₁It is identical, R₄₁And R₄₂For hydrogen atom or carbon atom The alkyl of number 1~8, is optionally same to each other or different to each other, and j represents positive integer.)

For the repeat unit possessed by the polymer with the repeat unit shown in formula [1] shown in formula [1], Ke Yishi C₁、C₂、A₁And A₂Respectively a kind and be only the repeat unit shown in same formula [1], alternatively, it is also possible to be C₁、C₂、A₁And A₂To be more Kind and be the repeat unit shown in a variety of formulas [1].

In addition, for the repeat unit possessed by the polymer with the repeat unit shown in formula [1] shown in formula [8], Can be C₁、C₂、A₂、R₄₁And R₄₂Respectively a kind and be only the repeat unit shown in same formula [8], alternatively, it is also possible to be C₁、 C₂、A₂、R₄₁And R₄₂To be a variety of and be the repeat unit shown in a variety of formulas [8].

(a) reaction of composition, (b) composition and (c) composition is generally carried out in organic solvent.It is organic as what is now used Solvent, just it is not particularly limited as long as dissolving generated polyimide precursor.As concrete example, N, N- dimethyl can be included Formamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- methyl caprolactams, dimethyl sulfoxide (DMSO), tetramethylurea, Pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropanol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, first Base nonyl ketone, MEK, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve second Acid esters, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol Dan Yi Propyl ether, ethylene glycol monobutyl ether, propane diols, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropyl two Alcohol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropyl Glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, DPG list second Acid esters list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanols, diisopropyl Ether, ethyl isobutyl ether, diisobutylene, pentaacetic acid ester, butyl butyrate, butyl ether, DIBK, methylcyclohexene, Propyl ether, two hexyl ether, dioxanes, n-hexane, pentane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, third Keto acid ethyl ester, 3- methoxy methyl propionates, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, diethylene glycol dimethyl ether or 4- hydroxy-4-methyls -2- Pentanone etc..They can be used alone, and can also be used in mixed way.And then even if not dissolve the solvent of polyimide precursor, In the range of the polyimide precursor generated will not separate out, it can also mix to above-mentioned solvent to use.In addition, organic solvent In moisture can hinder polymerisation, also turn into the reason for hydrolyzing generated polyimide precursor, therefore preferably using de- The dried organic solvent of water.

As the order for making (a) composition, (b) composition and the reaction of (c) composition, can include for example make (a) composition and (b) into Divide after reacting, addition (c) composition makes the method that it reacts.By making its reaction in this wise, gained has shown in formula [1] The polyimide precursor of repeat unit turn into repeat unit shown in repeat unit and formula [8] shown in formula [1] it is randomly-bonded and Into random copolymer, so it is preferred that.

On the other hand, including (a) composition is made to be reacted with (b) composition and obtain including the urea of the repeat unit shown in formula [1] The process of based polymer and react (b) composition and (c) composition and obtain including the polyamides of the repeat unit shown in formula [8] The process of imines precursor, make urea based polymer of the gained comprising the repeat unit shown in formula [1] thereafter and comprising shown in formula [8] In the method that the polyimide precursor of repeat unit reacts, gained have the polymer of the repeat unit shown in formula [1] into For polyureas with structure as the block copolymer of polyimide precursor, i.e. compared with above-mentioned random copolymer by the respective degree of polymerization The polymer architecture that bigger urea based polymer is formed with polyimide precursor.Now, deliquescent reduction is produced sometimes, is made The problems such as deterioration of coating during aligning agent for liquid crystal.

The temperature for alloing (a) composition, (b) composition and (c) composition to react selects -20 DEG C~150 DEG C of any temperature Degree, it is preferably -5 DEG C~100 DEG C of scope.In addition, reaction can be carried out with any concentration, but when concentration is too low, it is difficult to obtain The polyimide precursor with the repeat unit shown in formula [1] for the sub- amount that secures satisfactory grades, during excessive concentration, reaction solution it is sticky too high And it is difficult to uniform stirring.Therefore, the total concentration of (a) composition, (b) composition and (c) composition is preferably 1~50 matter in reaction solution Measure %, more preferably 5~30 mass %.Initial reaction stage is carried out with high concentration and additional organic solvent also may be used thereafter.

The ratio of (a) to be reacted compositions, (b) composition and (c) composition is preferably (a) composition for example with molar ratio computing The total amount of composition (c):(b) composition=0.8:1~1.2:1.(a) composition is shared in the total amount of (a) composition and (c) composition When ratio is 20 moles of %~60 mole %, voltage retention and residual DC can be taken into account, so it is preferred that.Because：(a) composition Ratio it is too small when, voltage retention step-down during easy fired sometimes, when the ratio of (a) composition is excessive, residual DC is easily accumulated Deposit.

In addition, pass through the polyamic acid with the repeat unit shown in above-mentioned formula [1], the tool that make to be used as polyimide precursor There is the poly amic acid ester closed loop (imidizate) of the repeat unit shown in above-mentioned formula [1], the weight for having shown in formula [1] can be obtained The polyimides of multiple unit.Wherein, contained by the aligning agent for liquid crystal used in the manufacture method of liquid crystal orientation film of the invention In polyimides with the repeat unit shown in formula [1], the closed loop rate (also referred to as acid imide rate) of acid amides acidic group must not Foot 50%.It should be noted that the acid imide rate referred in this specification refers to imide from tetracarboxylic dianhydride's Shared ratio in the total amount of imide and carboxyl.

As the method for making polyimide precursor carry out imidizate, can include the solution of polyimide precursor is direct The hot-imide of heating or the catalysis imidizate that catalyst is added into the solution of polyimide precursor.

Temperature when making the polyimide precursor carry out hot-imide in the solution is 100 DEG C~400 DEG C, is preferably 120 DEG C~250 DEG C, it is preferred that while the water generated in imidization reaction is expelled to outside system, while carrying out hot acid imide The method of change.

The catalysis imidizate of polyimide precursor can be by adding base catalysis in the solution to polyimide precursor Agent and acid anhydrides, it is stirred at -20~250 DEG C, preferably 0~180 DEG C to implement.The amount of base catalyst is acid amides acidic group 0.5~30 mole times, be preferably 2~20 moles times, the amount of acid anhydrides, which is 1~50 mole times of acid amides acidic group, is preferably 3~30 rubs You are again.As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc. can be included, wherein, pyridine has Suitable for promoting the alkalescence of reaction, so it is preferred that.As acid anhydrides, acetic anhydride, trihemellitic acid acid anhydride or benzenetetrahydride etc. can be included, When wherein, using acetic anhydride, reaction terminate after it is refined become easy, so it is preferred that.Acid imide based on catalysis imidizate Rate can be controlled by adjusting catalytic amount and reaction temperature, reaction time.

Generated polyimide precursor is reclaimed from the reaction solution of polyimide precursor or polyimides or polyamides is sub- During amine, can put into reaction solution makes its precipitation into solvent.As the solvent for precipitation, can include methanol, ethanol, Isopropanol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc..Put into solvent And polymer that it precipitates air drying or can be heated under normal or reduced pressure and carry out drying after being recovered by filtration.Separately Outside, when the operation that the polymer for making precipitation recovery is dissolved in organic solvent again and carries out reprecipitation recovery is repeated 2~10 times, The impurity in polymer can be reduced.As solvent now, can include such as alcohols, ketone or hydrocarbon, using from these Among select more than 3 kinds solvents when, purification efficiency further improves, so it is preferred that.

On used in the present invention the polyimide precursor with the repeat unit shown in above-mentioned formula [1], with above-mentioned The molecular weight of the polyimides of repeat unit and acid imide rate less than 50% shown in formula [1], it is contemplated that liquid therefrom Crystalline substance orientation film strength, operability when forming film and during film, it is preferred that utilize GPC (gel permeation chromatography, Gel Permeation Chromatography) method measure weight average molecular weight for 5,000~1,000,000, more preferably 10,000 ~150,000.

There is above-mentioned formula [1] institute contained by the aligning agent for liquid crystal used in the manufacture method of the liquid crystal orientation film of the present invention The polyimide precursor of the repeat unit shown, have above-mentioned formula [1] shown in repeat unit and acid imide rate less than 50% The compounding ratio of polyimides is not particularly limited, for example, the polyimide precursor with the repeat unit shown in above-mentioned formula [1] It is 0.1~30 matter with the total amount with the polyimides of repeat unit and acid imide rate less than 50% shown in above-mentioned formula [1] Measure %, be preferably 3~10 mass %.

In addition, in aligning agent for liquid crystal for manufacturing liquid crystal orientation film, component of polymer can be only have above-mentioned formula [1] The polyimide precursor of shown repeat unit, have above-mentioned formula [1] shown in repeat unit and acid imide rate less than 50% Polyimides, alternatively, it is also possible to be mixed with other polymer in addition.Now, the content of other polymer is polymerization The mass % of 0.5 mass % of thing composition total amount~15, it is preferably the mass % of 1 mass %~10.It is other poly- as in addition Compound, polyimide precursor, polyimides without the repeat unit shown in above-mentioned formula [1] can be included.And then it can enumerate Go out acrylic polymer, methacrylic polymer, polystyrene, polyamide or polysiloxanes etc..

It is sub- that as long as the solvent contained by aligning agent for liquid crystal can dissolve the polyamides with the repeat unit shown in above-mentioned formula [1] Amine precursor, have above-mentioned formula [1] shown in the polyimides of repeat unit and acid imide rate less than 50%, just do not limit especially It is fixed, DMF, DMA, METHYLPYRROLIDONE, N- methyl acyl in oneself can be included Amine, 2-Pyrrolidone, N- ethyl-2-pyrrolidones, NVP, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, two Methyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinones, ethyl pentyl group ketone, methyl nonyl ketone, MEK, Methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether and 4- hydroxyls- The organic solvents such as 4-methyl-2 pentanone.They can be used alone, and can also be used in mixed way.

On the solvent contained by aligning agent for liquid crystal, go out from uniform liquid crystal orientation film this viewpoint is formed by coating Hair, the content of solvent is preferably 70~99.9 mass %.The content can suitably become according to the target film thickness of liquid crystal orientation film More.

Liquid during coating of liquid crystalline alignment agent can be made in the range of effect of the present invention is not damaged, in aligning agent for liquid crystal Organic solvent, the i.e. poor solvent that the film of brilliant alignment films, surface smoothness improve.

As raising film, the concrete example of the poor solvent of surface smoothness, ethanol, isopropanol, 1- fourths can be included Alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, 2- amylalcohols, 3- amylalcohols, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- first Base -2- butanol, neopentyl alcohol, 1- hexanols, 2- methyl-1-pentenes alcohol, 2- methyl -2- amylalcohols, 2- ethyls-n-butyl alcohol, 1-heptanol, 2- heptan Alcohol, 3- enanthol, 1- octanols, sec-n-octyl alcohol, 2- ethyl -1- hexanols, cyclohexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3- methyl Cyclohexanol, 1,2- ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 2,3- Butanediol, 1,5- pentanediols, 2- methyl -2,4-PD, 2- ethyl -1,3- hexylene glycols, dipropyl ether, butyl oxide, two hexyl ethers, two Oxane, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, 1,2- butoxy ethane, diethylene glycol dimethyl ether, two Ethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptan Ketone, 3- ethoxybutyls acetic acid esters, 1- methyl amyls acetic acid esters, 2- ethyl-butyls acetic acid esters, 2- ethylhexyl acetates, second two Alcohol monoacetate, ethylene acetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol list Butyl ether, ethylene glycol list isoamyl ether, ethylene glycol monohexylether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether, propane diols, propane diols list Butyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol methyl ether acetate, DPG, dipropylene glycol monomethyl ether, DPG Single ether, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monobutyl ether acetic acid Ester, ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, 2- (2- ethoxy ethoxies) ethylhexoate, diethylene glycol acetic acid esters, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol list Ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, pyruvic acid first Ester, ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethyoxyls Propionic acid, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, methyl lactate, ethyl lactate, lactic acid are just The low organic solvent of the surface tension of propyl ester, n-butyl lactate or isoamyl lactate equal solvent.

These poor solvents, which can use a kind, can also mix a variety of uses.It is excellent during using poor solvent as described above Elect the organic solvent included in aligning agent for liquid crystal 5~80 overall mass %, more preferably 20~60 mass % as.

In the range of effect of the present invention is not damaged, it can also be added with epoxy radicals, isocyanates in aligning agent for liquid crystal The cross-linked compound of base, oxetanyl or cyclocarbonate radical；With selected from hydroxyl, hydroxy alkyl and lower alkoxy alkane The cross-linked compound of at least one kind of substituent in the group of base composition；Or the bridging property chemical combination with polymerism unsaturated bond Thing.These substituents, polymerism unsaturated bond need have more than 2 in cross-linked compound.

As the cross-linked compound with epoxy radicals or NCO, such as bisphenol acetone glycidol can be included Ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, four shrinks are sweet Oil base aminobphenyl, four glycidyl group m-xylene diamine, four glycidyl group -1,3- double (amino-ethyl) hexamethylene, four benzene Base glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, 1,3- pairs (1- (2, 3- glycidoxies) -1- trifluoromethyl -2,2,2- trifluoromethyls) benzene, 4,4- double (2,3- glycidoxies) octafluorobiphenyl, three Glycidyl para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- glycidoxies) phenyl) -2- (4- (1,1- double (4- (2,3- glycidoxies) phenyl) ethyls) phenyl) propane or the double (4- (1- (4- (oxygen of 2,3- epoxies third of 1,3- Base) phenyl) -1- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- Methylethyls) phenyl) ethyl) phenoxy group) -2- propyl alcohol Deng.

Cross-linked compound with oxetanyl is the oxetanyl shown in at least two following formula [4] Cross-linked compound.

Specifically, page 58~the 59 of International Publication publication WO2011/132751 (2011.10.27 is disclosed) can be included The cross-linked compound shown in formula [4a]~formula [4k] described in page.

It is that there is the cyclocarbonate radical shown at least two following formula [5] as the cross-linked compound with cyclocarbonate radical Cross-linked compound.

Specifically, page 76~the 82 of International Publication publication WO2012/01132751 (2012.2.2 is disclosed) can be included The cross-linked compound shown in formula [5-1]~formula [5-42] described in page.

, can as the cross-linked compound with least one kind of substituent in the group for selecting free hydroxyl and alkoxy composition Include the amino resins for example with hydroxyl or alkoxy, such as melamine resin, carbamide resin, guanamine resin, glycoluril-formaidehyde tree Fat, succinamide-formaldehyde resin or ethylene urea-formaldehyde resins etc..Specifically, the hydrogen atom of amino can be used by methylol Or melamine derivative, benzoguanamine derivative or the glycoluril that alkoxy methyl or both substitution form.The melamine derivative Or benzoguanamine derivative can exist in the form of dimer or tripolymer.Their preferably every 1 triazine rings have average 3 Above and the methylol or alkoxy methyl of less than 6.

As this melamine derivative or the example of benzoguanamine derivative, every 1 triazine ring of commercially available product can be included Substitution has the MX-750 of average 3.7 methoxies, the substitution of every 1 triazine ring to have the MW-30 of average 5.8 methoxies (being above Sanwa Chemical Co., Ltd's system), the first such as CYMEL 300,301,303,350,370,771,325,327,703,712 Epoxide methylates melamine；The methoxymethylated butoxymethyl melamine such as CYMEL 235,236,238,212,253,254； The butoxymethyl melamines such as CYMEL 506,508；CYMEL 1141 etc the isobutoxy first of methyl containing Carboxvmethoxv Base melamine；CYMEL 1123 etc methoxymethylated ethoxyl methyl benzoguanamine；CYMEL 1123-10's etc Methoxymethylated butoxymethyl benzoguanamine；CYMEL 1128 etc butoxymethyl benzoguanamine；CYMEL 1125-80 etc the ethoxyl methyl of methyl containing Carboxvmethoxv benzoguanamine (is above three well サイア Na ミ De companies System).In addition, the example as glycoluril, can include CYMEL 1170 etc butoxymethyl glycoluril, CYMEL 1172 it Methylolation glycoluril of class etc.；Powder link 1174 etc methoxyl group methylolation glycoluril etc..

As the benzene with hydroxyl or alkoxy or benzene phenoloid, such as 1,3,5- tri- (methoxy methyls can be included Base) benzene, 1,2,4- tri- (i-propoxymethyl) benzene, double (sec-butoxymethyl) benzene of 1,4- or 2,6- bishydroxymethyls be to the tert-butyl group Phenol etc..

More specifically, can include page 62 of International Publication publication WO2011/132751 (2011.10.27 is disclosed)~ The cross-linked compound shown in formula [6-1]~formula [6-48] described in page 66.

As the cross-linked compound with polymerism unsaturated bond, such as trimethylolpropane tris (methyl) can be included Acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxies There are 3 polymerisms not in base oxethyl trimethylolpropane or poly- (methyl) the acrylate equimolecular of glycerine polyglycidyl ether The cross-linked compound of saturated group；And ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, poly- third Glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane Bisphenol A-type two (methyl) acrylate, expoxy propane bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) propylene Acid esters, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) Acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) There are 2 polymerism unsaturated groups in acrylate or (methyl) acrylate of 3-hydroxypivalic acid neopentyl glycol two equimolecular Cross-linked compound；And (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) propylene Sour 2- hydroxybutyls, 2- phenoxy group -2- hydroxypropyls (methyl) acrylate, 2- (methyl) acryloxy -2- hydroxypropyls Phthalic acid ester, 3- chlorine-2-hydroxyls propyl group (methyl) acrylate, glycerine list (methyl) acrylate, 2- (methyl) propylene There is the friendship of 1 polymerism unsaturated group in trimethylammonium phosphate or N- methylols (methyl) acrylamide equimolecular Connection property compound.

And then the compound shown in following formula [7] can also be used.

(in formula [7], E₁Represent be selected from by cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl basic ring, naphthalene nucleus, Group in the group of fluorenes ring, anthracene nucleus or phenanthrene ring composition, E₂The group in following formula [7a] or formula [7b] is represented, n represents 1~4 Integer.)

Above-claimed cpd is one of cross-linked compound, but is not limited to them.In addition, used in aligning agent for liquid crystal Cross-linked compound can be a kind, can also combine two or more.

The content of cross-linked compound in aligning agent for liquid crystal is preferably relative to all mass parts of component of polymer 100 0.1~150 mass parts.The effect of target is shown in order to promote cross-linking reaction, relative to all mass of component of polymer 100 Part, more preferably 0.1~100 mass parts, especially most preferably 1~50 mass parts.

When liquid crystal orientation film is made using the aligning agent for liquid crystal of the present composition, taken as liquid crystal is promoted Electric charge movement, promotion into film have used the compound of the de- electric charge of the liquid crystal cells of the liquid crystal orientation film, preferably add state Formula [M1]~formula [M156] institute described in border Publication WO2011/132751 (2011.10.27 is disclosed) page 69~page 73 The nitrogen heterocyclic ring amines shown.The amines can be added directly in composition, be preferably made of appropriate solvent dense Spend for the mass % of 0.1 mass %~10, be preferably the mass % of 1 mass %~7 solution after add again.As the solvent, as long as It is the organic solvent for making above-mentioned specific polyimides based polymer dissolving, is just not particularly limited.

In the range of effect of the present invention is not damaged, aligning agent for liquid crystal can contain liquid crystal when making coating of liquid crystalline alignment agent The compound that film thickness uniformity, the surface smoothness of alignment films improve.And then it can also contain and make liquid crystal orientation film and substrate Compound that adaptation improves etc..

As the compound for improving the film thickness uniformity of liquid crystal orientation film, surface smoothness, fluorine system surface can be included Activating agent, silicone based surfactants, nonionic surfactants etc..

More specifically, it (is above Tohkem products that can include such as Eftop EF301, EF303, EF352 Corporation systems)；Megafac F171, F173, R-30 (being above DIC Corporation systems)；Fluorad FC430、 FC431 (being above Sumitomo 3M Limited systems)；AsahiGuard AG710、Surflon S-382、SC101、 SC102, SC103, SC104, SC105, SC106 (being above Asahi Glass Co., Ltd's system) etc..The use of these surfactants Ratio is preferably 0.01~2 mass parts, more preferably relative to the mass parts of all component of polymer 100 contained in aligning agent for liquid crystal For 0.01~1 mass parts.

As the concrete example for making compound that the adaptation of liquid crystal orientation film and substrate improves, can include described below Compound containing functional silanes, the compound containing epoxy radicals.

Such as 3- TSL 8330s, APTES, 2- aminopropyls can be included Trimethoxy silane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, 3- ureas propyl trimethoxy silicane, 3- urea propyl triethoxies Silane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyls-APTES, The second triamine of N- triethoxysilylpropyltetrasulfides three, the second triamine of N- trimethoxy-silylpropyls three, 10- trimethoxy first silicon The azepine decane of alkyl -1,4,7- three, the azepine decane of 10- triethoxysilyls -1,4,7- three, 9- trimethyoxysilanes Base -3,6- diaza nonyls acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyls acetic acid esters, N- benzyl -3- amino Propyl trimethoxy silicane, N- benzyls-APTES, N- phenyl -3- TSL 8330s, Double (oxygen the ethylidene) -3- TSL 8330s of N- phenyl-APTES, N-, N- are double, and (oxygen is sub- Ethyl)-APTES, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propane diols two Glycidol ether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6- hexanediol diglycidyl ethers, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycols diglycidyl ether, 1,3,5,6- tetra- Glycidyl -2,4- hexylene glycols, N, N, N ', N ', double (N, the N- 2-glycidyls of-four glycidyl group m-xylene diamine, 1,3- Amino methyl) hexamethylene or N, N, N ', N ',-four glycidyl group -4,4 '-diaminodiphenyl-methane etc..

It is all relative to what is contained in aligning agent for liquid crystal when making the liquid crystal orientation film compound closely sealed with substrate using these The mass parts of component of polymer 100 are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.During less than 0.1 mass parts, nothing Method expects to improve the effect of adaptation, and during more than 30 mass parts, the storage stability of aligning agent for liquid crystal is deteriorated sometimes.

In aligning agent for liquid crystal, except above-mentioned poor solvent, cross-linked compound, the film thickness uniformity for making liquid crystal orientation film or The compound and make outside its compound closely sealed with substrate that surface smoothness improves, as long as not damaging effect of the present invention In the range of, then it can add dielectric constant, dielectric substance, the conductive material of the electrical characteristics such as electric conductivity for changing liquid crystal orientation film Matter.

In the present invention, by the way that this aligning agent for liquid crystal is coated on substrate, then burnt till, so as to obtain acid imide Rate is 50~70% liquid crystal orientation film.

As substrate, according to target device, glass substrate, silicon wafer, acrylic compounds substrate, makrolon base can be used Plastic bases such as plate etc..From the viewpoint of the chemical industry skill that conforms to the principle of simplicity, preferably use formed with the ITO (Indium for driving liquid crystal Tin Oxide) electrode etc. substrate.In addition, in the liquid crystal of reflection-type represents element, can also if being only single sided substrate Using the opaque substrate such as silicon wafer, as electrode now, the material of the meeting reflected light such as aluminium can also be used.The present invention In, firing temperature can be reduced, therefore can also use and belong to plastic base of the low substrate of heat resistance etc..

The method that aligning agent for liquid crystal is coated on to substrate is not particularly limited, and industrial is usually to utilize dip coating, roller coat The method of the progress such as method, slot coated method, spin-coating method, spray-on process, silk-screen printing, intaglio printing, hectographic printing or ink-jet method.Can To use them according to purpose.

Aligning agent for liquid crystal is coated on substrate, then burnt till.Firing condition is that the liquid crystal obtained after making to burn till takes Reach 50~70% condition to the acid imide rate of film.For example, firing temperature is less than 210 DEG C, is preferably 120~200 DEG C. In addition, firing time is, for example, 5 minutes~2 hours, is preferably 10 minutes~30 minutes.Like this, can be with relatively low temperature Burnt till, therefore the low plastic base of heat resistance can be used.Represented in addition, liquid crystal caused by being burnt till by high temperature can be suppressed The color deterioration in characteristics of the colour filter of element, reduction liquid crystal represent the cost of energy in the manufacture of element.

As the heater meanses burnt till, thermal cycle type baking oven or IR (infrared ray) type baking oven etc. can be included.Carry out It is unfavorable, and thickness mistake in terms of liquid crystal represents the power consumption of element when the thickness of liquid crystal orientation film obtained from burning till is blocked up Bao Shi, liquid crystal represent that the reliability of element reduces sometimes, therefore preferably 5~300nm, more preferably 10~100nm.

When making liquid crystal horizontal alignment, tilted alignment, using brushing or the irradiation of polarisation ultraviolet etc. to liquid obtained from burning till Brilliant alignment films are handled.In addition, in the case of vertical orientated purposes etc., even if can also act as liquid without orientation process Brilliant alignment films.

Like this, by the way that the polyimide precursor with the repeat unit shown in above-mentioned formula [1] will be contained, with above-mentioned formula [1] aligning agent for liquid crystal of the polyimides of repeat unit and acid imide rate less than 50% shown in is burnt after being coated on substrate Into the acid imide rate obtained from be 50~60% liquid crystal orientation film perhaps because acid imide rate is low, a large amount of carboxyls be present And with the repeat unit shown in formula [1], as be described hereinafter shown in embodiment like that, residual DC is low and voltage retention is high.The opposing party Face, such as such as patent document 1, in the repeat unit (the logical formula (I) of patent document 1) comprising polyureas and polyimides In the case of the liquid crystal orientation film of repeat unit (the logical formula (II) of patent document 1), compared with the present invention, residual DC is very high. It should be noted that in patent document 1, burnt till after coating of liquid crystalline alignment agent with low temperature, but the liquid crystal before burning till takes Polyimides, therefore the acid imide rate of the liquid crystal orientation film obtained in patent document 1 and this hair have been made into the stage of agent Bright difference is very high.

Liquid crystal on the present invention represents element, using above method coating of liquid crystalline alignment agent and burns till and obtains subsidiary liquid After the substrate of brilliant alignment films, liquid crystal cells are made using known method, element is represented so as to which liquid crystal be made.If include one Example, then represent element to possess the liquid crystal of following liquid crystal cells, and the liquid crystal cells possess：2 pieces of substrates of relative configuration, set Liquid crystal layer between the substrates and the system for being arranged at the above-mentioned liquid crystal orientation film between substrate and liquid crystal layer and using the present invention Make the liquid crystal orientation film of method formation.Element is represented as this liquid crystal of the invention, twisted nematic (TN can be included： Twisted Nematic) mode, vertical orientated (VA：Vertical Alignment) mode, horizontal alignment (IPS：In- Plane Switching) mode, OCB orientation (OCB：Optically Compensated Bend) etc. various liquid crystal represent Element.

As the preparation method of liquid crystal cells, following method can be exemplified：Prepare a pair of bases formed with liquid crystal orientation film Plate, sept is spread on the liquid crystal orientation film of single substrate, paste another in a manner of liquid crystal orientation film is facing to inner side Substrate, decompression injection liquid crystal and the method sealed；Or to after liquid crystal is added dropwise on the liquid crystal aligning film surface for be scattered with sept, Adhesive substrate and the method that is sealed etc..

Liquid crystal can use positive type liquid crystal, the minus liquid with negative dielectric anisotropic with positive dielectric anisotropy Crystalline substance, specifically, it can use such as Merck Corporation MLC-2003, MLC-6608, MLC-6609.

In addition, the present invention liquid crystal orientation film be also preferably used between a pair of substrates for possessing electrode have liquid crystal layer and The liquid crystal manufactured via following process represents element, and the process is：Liquid-crystal composition is configured between a pair of substrates, it is described Liquid-crystal composition includes the polymerizable compound polymerizeing by least one of active energy beam and heat, applies between the electrodes Making alive, while it polymerize polymerizable compound by irradiating at least one of active energy beam and heating.Herein, as Active energy beam, it is suitably for ultraviolet.The wavelength of ultraviolet is 300~400nm, is preferably 310~360nm.Utilize heating When being polymerize, heating-up temperature is 40~120 DEG C, is preferably 60~80 DEG C.Alternatively, it is also possible to simultaneously carry out ultraviolet irradiation and Heating.

Above-mentioned liquid crystal represents element using PSA (Polymer Sustained Alignment) modes to control liquid crystal point The pre-dumping of son.For example, in the PSA modes using active energy beam, by the way that a small amount of light is mixed into liquid crystal material in advance Polymerizable compound, such as photopolymerization monomer, after assembling liquid crystal cells, in the state of assigned voltage is applied to liquid crystal layer, Ultraviolet isoreactivity energy-ray is irradiated to photopolymerizable compound and makes its polymerization, utilizes generated polymer controls liquid crystal The pre-dumping of molecule.The state of orientation of liquid crystal molecule when generating the polymer is also remembered after voltage is removed, therefore leads to Electric field formed etc. is crossed in control liquid crystal layer, the pre-dumping of liquid crystal molecule can be adjusted.In addition, in PSA modes, it is not necessary to brushing Processing, therefore be suitable for being difficult to the formation for controlling the vertical alignment-type liquid crystal layer of pre-dumping by brushing processing.

The liquid crystal cells making of PSA modes is same as described above, can include following method：Prepare formed with liquid crystal orientation film A pair of substrates, spread sept on the liquid crystal orientation film of a substrate, glued in a manner of liquid crystal orientation film is facing to inner side Paste another substrate, decompression injection liquid crystal and the method sealed；Or to the liquid crystal aligning film surface dropping liquid for being scattered with sept After crystalline substance, method of adhesive substrate and sealing etc..

Also, in the case of PSA modes, the polymerization irradiated and polymerize by heat, active energy beam is mixed into liquid crystal Property compound.As polymerizable compound, can include has more than 1 acrylate-based, methacrylate in intramolecular The compound of the polymerism unsaturated group such as base.Now, polymerizable compound is preferably relative to 100 mass parts of liquid crystal composition 0.01~10 mass parts, more preferably 0.1~5 mass parts.When polymerizable compound is less than 0.01 mass parts, polymerizable compound It will not polymerize and the orientation of uncontrollable liquid crystal, during more than 10 mass parts, unreacted polymerizable compound becomes more and liquid crystal watch Show that the image of element retains (baked I pays I) characteristic and reduced.

After making liquid crystal cells, while liquid crystal cells are applied with the voltage of AC or DC, while heating, irradiating active energy Measure ray and polymerize polymerizable compound.Orientation thus, it is possible to control liquid crystal molecule.

In addition, the present invention liquid crystal orientation film can be also used between a pair of substrates for possessing electrode have liquid crystal layer and The liquid crystal manufactured via following process represents element (SC-PVA), and the process is：Liquid is configured between foregoing a pair of substrates Brilliant alignment films, the liquid crystal orientation film include the polymerizable group polymerizeing by least one of active energy beam and heat, Apply voltage between electrode, while polymerize polymerizable group.Herein, as active energy beam, it is suitably for ultraviolet.It is ultraviolet The wavelength of line is 300~400nm, is preferably 310~360nm.When being polymerize using heating, heating-up temperature be 40~120 DEG C, Preferably 60~80 DEG C.Furthermore it is possible to ultraviolet irradiation and heating are carried out simultaneously.

Taken to obtain the liquid crystal comprising the polymerizable group polymerizeing by least one of active energy beam and heat To film, can include：The method that compound comprising the polymerizable group is added in above-mentioned aligning agent for liquid crystal.In addition, can Include following method：Compound comprising polymerizable group etc. is used as (a) composition, (b) composition, (c) composition, makes liquid crystal The polyimide precursor with the repeat unit shown in above-mentioned formula [1], the weight shown in above-mentioned formula [1] contained in alignment agent Multiple unit is while polyimides of the acid imide rate less than 50% includes polymerizable group.

Also, by prepare formed with comprising it is this because at least one of active energy beam and heat and polymerize polymerization Property group liquid crystal orientation film a pair of substrates after, as described above, on the liquid crystal orientation film of a substrate spread interval Thing, another substrate, decompression injection liquid crystal and the method sealed, Huo Zhexiang are pasted in a manner of liquid crystal orientation film is facing to inner side After being scattered with the liquid crystal aligning film surface dropping liquid crystalline substance of sept, adhesive substrate and the method that is sealed etc., liquid crystal can be made Unit.

Also, after making liquid crystal cells, while liquid crystal cells are applied with the voltage of AC or DC, while heating, irradiation Active energy beam, so as to control the orientation of liquid crystal molecule.

Operate as above, and voltage low using the residual DC of the liquid crystal expression element of the liquid crystal aligning film production of the present invention Conservation rate is high, therefore excellent in reliability, can be suitable for that picture is big and LCD TV of high-resolution etc..Further, since burn till temperature Spend low, therefore plastics of light weight etc. can be used as substrate, can realize that liquid crystal represents the lightweight of element.

Embodiment

Embodiment is exemplified below out to illustrate.It should be noted that the present invention is not by their limited explanation.Below The abbreviation used is as follows.

(diisocyanate)

A-1：2,4 tolylene diisocyanate

(tetracarboxylic dianhydride)

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

(diamine compound)

C-1：1- amino -3- aminomethyl -3,5,5- trimethyl-cyclohexanes

C-2：N- (3- picolyls) -3,5- diaminobenzene formamides

C-3：1,3- diaminourea -4- { 4- (4- n-heptyls cyclohexyl) phenoxy group } benzene

(organic solvent)

NMP：METHYLPYRROLIDONE

BCS：Butyl cellosolve

The assay method carried out in the present embodiment described below.

(molecular weight determination of polymer)

The molecular weight of polyamic acid and polyimides calculates as follows：Determined using GPC (normal temperature gel permeation chromatography) device The polyamic acid, polyimides, number-average molecular weight and Weight-average molecular are calculated in the form of polyethylene glycol, PEO scaled value Amount.

GPC devices：Showa Denko K. K GPC-101,

Post：The post (KD-803, KD-805 series connection) of Shodex companies manufacture

Column temperature：50℃

Eluent：N, N '-dimethyl formamide is (as additive, lithium bromide monohydrate (LiBrH₂O) it is 30mmol/L, phosphoric acid anhydrous crystal (orthophosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow velocity：1.0ml/ minute

Standard curve making standard sample：(molecular weight is about the TSK standards PEO of TOSOH Co., Ltd's manufacture 900,000th, 150,000,100,000,30,000) and Polymer Laboratories Ltd. manufactures polyethylene glycol (molecule Amount about 12,000,4,000,1,000)

(measure of the acid imide rate of polyimides)

The acid imide rate of polyimides operates to determine as follows.

Polyimide powder 20mg is put into NMR sample cells, addition deuterated dimethyl sulfoxide (DMSO-d₆, 0.05% TMS (tetramethylsilane) melange) 0.53ml, it is completely dissolved it.The NMR analyzers manufactured using JEOL DATUM companies (JNM-ECA500) 500MHz proton NMR is determined to the solution.Acid imide rate will not become before and after being derived from imidizate The proton of the structure of change determines as reference proton, uses the peak integrating value of the proton and attached from 9.5ppm~10.0ppm The proton peak integrating value of the NH bases of the amic acid nearby occurred, is obtained using following formula.

Acid imide rate (%)=(1- α x/y) × 100

In above-mentioned formula, x is the proton peak integrating value of the NH bases from amic acid, and the peak integrating value of proton, α are on the basis of y Reference proton during polyamic acid (acid imide rate is 0%) is relative to the sub 1 number ratio of the NH matrix of amic acid.

In the NMP (23g) mixing A-1 (1.56g, 9.00mmol), C-1 (1.53g, 8.98mmol), C-2 (1.30g, 5.36mmol), C-3 (1.37g, 3.59mmol), after being reacted 15 hours with 40 DEG C, addition B-1 (1.65g, 8.46mmol), NMP (19g), and then react 6 hours, (there is the polyamic acid of the repeat unit shown in above-mentioned formula [1] so as to obtain polymer solution A Solution) (polymer concentration is 15 mass %).The number-average molecular weight of the polymer is 16,020, weight average molecular weight 49, 319。

In the NMP (19g) mixing A-1 (0.783g, 4.50mmol), C-1 (1.53g, 8.98mmol), C-2 (1.30g, 5.36mmol), C-3 (1.37g, 3.59mmol), after being reacted 15 hours with 40 DEG C, addition B-1 (2.63g, 13.4mmol), NMP (23g), and then react 6 hours, (there is the polyamic acid of the repeat unit shown in above-mentioned formula [1] so as to obtain polymer solution B Solution) (polymer concentration is 15 mass %).The number-average molecular weight of the polymer is 11,555, weight average molecular weight 37, 656。

In the NMP (50g) mixing A-1 (3.82g, 21.9mmol), C-1 (1.87g, 10.9mmol), C-2 (1.59g, 6.59mmol), after C-3 (1.67g, 4.38mmol), with 40 DEG C react 15 hours, so as to obtain polymer solution C (polyureas it is molten Liquid) (polymer concentration is 15 mass %).The number-average molecular weight of the polymer is 12,731, weight average molecular weight 32,967.

In the NMP (42g) mixing B-1 (3.35g, 17.0mmol), C-1 (1.53g, 8.98mmol), C-2 (1.30g, 5.36mmol), after C-3 (1.37g, 3.59mmol), reacted 15 hours with 40 DEG C, so as to obtain polymer solution D (polyamic acids Solution) (polymer concentration is 15 mass %).The number-average molecular weight of the polymer is 14,833, weight average molecular weight 38, 984。

Addition NMP in the polymer solution A (20g) recorded to synthesis example 1 and be diluted to after concentration reaches 6 mass %, make For imidization catalyst, addition acetic anhydride (3.65g), pyridine (1.70g), reacted 3 hours with 50 DEG C.The reaction solution is noted Enter to methanol (200g), the sediment that leaching is generated.The sediment is cleaned with methanol, is dried under reduced pressure and obtained with 100 DEG C White powder.The acid imide rate of the polyimides is 100%, number-average molecular weight 13,084, weight average molecular weight 40,857.

Into powder 1.99g add NMP 11.3g, with 50 DEG C stir 30 hours and make its dissolve after, obtain polymer (polymer is dense for solution E (solution with the repeat unit and the polyimides of acid imide rate 100% shown in above-mentioned formula [1]) Spend for 15 mass %).

<Embodiment 1>The preparation of aligning agent for liquid crystal and the making of liquid crystal cells

NMP, BCS are added into the polymer solution A obtained using synthesis example 1 and is stirred, 6 matter are reached with polymer Amount %, NMP, which reach 64 mass %, BCS and reach 30 mass % mode, to be prepared.By the film that the solution aperture is 1 μm Filter carries out pressure filtration, so as to obtain aligning agent for liquid crystal.

Gained aligning agent for liquid crystal is spun on to the glass substrate of subsidiary ITO electrode, dried 5 minutes on 80 DEG C of hot plate Afterwards, using 180 DEG C of IR formulas baking oven burn till within 15 minutes, form the film (liquid crystal orientation film) that thickness is 100nm, so as to To the substrate of subsidiary liquid crystal orientation film.Prepare the substrate of the two panels subsidiary liquid crystal orientation film, wherein on 1 liquid crystal aligning film surface After spreading 4 μm of sept, in printing and sealing agent thereon, after another 1 plate base is pasted in a manner of liquid crystal aligning film surface is aspectant, Make sealant cures and make dummy cell.Using injecting liquid crystal MLC-6608 (Merck in decompression injection normal direction dummy cell Japan systems), seal inlet and obtain liquid crystal cells.

Except using respectively by synthesis example 2 and comparing polymer solution B~E that synthesis example 1~3 obtains to replace by synthesizing Outside the polymer solution A that example 1 obtains, operate similarly to Example 1, so as to obtain aligning agent for liquid crystal, liquid crystal orientation film and liquid Brilliant unit.

In addition to firing temperature is set into 200 DEG C, operate similarly to Example 1, so as to obtain aligning agent for liquid crystal, liquid crystal Alignment films and liquid crystal cells.

In addition to firing temperature is set into 230 DEG C, operate similarly to Example 1, so as to obtain aligning agent for liquid crystal, liquid crystal Alignment films and liquid crystal cells.

NMP, BCS are added into the polymer solution A obtained using synthesis example 1 and is stirred, polymer is prepared into and reaches 3.5 Quality %, NMP reaches 66.5 mass %, BCS and reaches 30 mass %.The solution is carried out with the membrane filter that aperture is 1 μm Pressure filtration, after -15 DEG C of keepings 48 hours, carry out the evaluation of ink-jet application.Ink-jet application machine has used HIS-200 (Hitachi Plant Technologies, Ltd. system).The ITO (tin indium oxide) through being cleaned with pure water and IPA is coated on to steam Carried out on plated substrate with injector spacing 0.423mm, sweep span 0.5mm, coating speed 40mm/ seconds.Thereafter place 60 seconds, 80 DEG C hot plate on dry 5 minutes after, using 180 DEG C of IR formulas baking ovens burn till within 15 minutes, form film of the thickness for 100nm (liquid crystal orientation film) and the substrate for obtaining subsidiary liquid crystal orientation film, are operated, so as to obtain liquid crystal cells similarly to Example 1.

For the liquid crystal cells obtained by embodiment 1~4 and comparative example 1~4, apply 60 μ s 1V at a temperature of 80 DEG C Voltage, the voltage after 50ms is determined, which kind of degree voltage can be remained into as voltage retention to evaluate.Show the result in Table 1.

Apply 30Hz, 6Vpp alternating voltage and 1V for the liquid crystal cells obtained by embodiment 1~4 and comparative example 1~4 DC voltage, driven 24 hours at a temperature of 23 DEG C.Thereafter evaluation flicker, its intensity is reached into minimum application voltage and made For residual DC (flicker null method).Show the result in table 1.

The use of by the polymer solution obtained by embodiment 1 A, the polymer solution B apertures obtained by embodiment 2 is 1 μ M membrane filter carries out pressure filtration and with the solution of -15 DEG C of keepings 48 hours, and the making and liquid crystal for carrying out liquid crystal cells take The evaluation (PSA unit) of tropism.The solution is spun on to the pattern spacing of 10 × 10mm of center band through being cleaned with pure water and IPA The substrate of the ITO electrode of substrate (vertical 40mm × horizontal 30mm, thick 0.7mm) and 10 × 40mm of center band for 20 μm of ITO electrode On the ito surface of (vertical 40mm × horizontal 30mm, thick 0.7mm), after being dried 5 minutes on 80 DEG C of hot plate, dried using 180 DEG C of IR formulas Case burn till within 15 minutes, forms thickness and obtains the substrate of subsidiary liquid crystal orientation film for 100nm film (liquid crystal orientation film). After coated surface is cleaned with pure water, heated 15 minutes with 100 DEG C in thermal cycle type cleans baking oven, so as to obtain subsidiary liquid The substrate of brilliant alignment films.

The substrate for attaching liquid crystal orientation film is clamped to 6 μm of sept in a manner of liquid crystal aligning film surface is placed in inner side to enter Row combination, surrounding is bonded with sealant to make dummy cell.Liquid crystal, the liquid are injected in the dummy cell using injection method is depressurized Crystalline substance is to be mixed in nematic liquid crystal (MLC-6608) (Merck Japan systems) relative to the mass % of nematic liquid crystal (MLC-6608) 100 Conjunction has what the mass % of polymerizable compound 0.3 shown in following formula [9] was formed, seals inlet and obtains liquid crystal cells.

While gained liquid crystal cells are applied with exchange 5V voltage, while the use of illumination is 60mW metal halide lamp, Below 350nm wavelength is cut out, is converted according to 365nm and carries out 20J/cm²Ultraviolet irradiation, so as to obtain the orientation side of liquid crystal To by the liquid crystal cells (PSA unit) controlled.The temperature in irradiation unit when liquid crystal cells are irradiated with ultraviolet is 50 DEG C.

Determine the response speed for irradiating the liquid crystal before ultraviolet and after irradiation ultraviolet of the liquid crystal cells.Response speed pin To being measured from transmissivity 90% to T90 → T10 of transmissivity 10%.

On the PSA unit obtained by embodiment, compared with the liquid crystal cells before irradiating ultraviolet, after irradiating ultraviolet The response speed of liquid crystal cells accelerates, therefore confirms that the differently- oriented directivity of liquid crystal is controlled.In addition, any liquid crystal cells are sharp Observed with petrographic microscope (ECLIPSE E600WPOL) (Nikon Corp.'s system), it is thus identified that liquid crystal is equably orientated.

In embodiment 1~4 and comparative example 1~4, in the stage for the substrate for obtaining subsidiary liquid crystal orientation film, measure liquid crystal takes To the acid imide rate of film.The assay method of the acid imide rate of liquid crystal orientation film is as follows.Aligning agent for liquid crystal is spun on band ITO The glass substrate of electrode, after being dried 5 minutes on 80 DEG C of hot plate, burnt till using IR formula baking ovens, it is 100nm to form thickness Film (liquid crystal orientation film), so as to obtain the substrate with liquid crystal orientation film.The liquid crystal orientation film is cut with cutting knife, profit The measure of acid imide rate is carried out based on KBr methods with FT-IR.

As a result, as shown in table 1 like that, there is aligning agent for liquid crystal and acid imide rate using 1~embodiment of embodiment 4 Small, the 1~embodiment of embodiment 4 for the voltage retention height of the liquid crystal cells of 50~70% liquid crystal orientation film, residual DC Aligning agent for liquid crystal contain the polyimide precursor with the repeat unit shown in above-mentioned formula [1].On the other hand, have and only include The voltage retention of the liquid crystal cells of the comparative example 1 of the liquid crystal orientation film of polyureas is high, but residual DC is high.In addition, there is comparative example 2 The liquid crystal orientation film for only including the polyamic acid without the repeat unit shown in formula [1] liquid crystal cells residual DC it is small, But voltage retention is low.In addition, the liquid crystal cells of comparative example 3 and comparative example 4 with the high liquid crystal orientation film of acid imide rate Voltage retention it is high, but residual DC is big.It should be noted that due to determining the electrical characteristics such as residual DC and voltage retention, It can be said that the liquid crystal aligning of the liquid crystal orientation film determined is also good.

[table 1]

Claims

1. a kind of manufacture method of liquid crystal orientation film, it is characterised in that by being burnt after aligning agent for liquid crystal is coated on into substrate Into so as to obtain the liquid crystal orientation film that acid imide rate is 50~70%, the aligning agent for liquid crystal contains：Selected from following formula [1] polyimide precursor of the repeat unit shown in and with the repeat unit shown in following formula [1] and acid imide rate deficiency At least one of 50% polyimides polymer,

In formula [1], A₁For divalent organic group；A₂For divalent organic group；C₁And C₂For hydrogen atom or the alkyl of carbon number 1~3, Optionally it is same to each other or different to each other.

2. the manufacture method of liquid crystal orientation film according to claim 1, it is characterised in that described in being carried out below 210 DEG C Burn till.

3. the manufacture method of liquid crystal orientation film according to claim 1 or 2, it is characterised in that under the polymer has The side chain shown in formula [2] is stated,

In formula [2], Y₁For singly-bound ,-(CH₂)_a-、-O-、-CH₂O- ,-COO- or-OCO-, wherein, a is 1~15 integer；Y₂For Singly-bound or-(CH₂)_b-, wherein, b is 1~15 integer；Y₃For singly-bound ,-(CH₂)_c-、-O-、-CH₂O- ,-COO- or-OCO-, its In, c is 1~15 integer；Y₄Represent the divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle or there is steroids The divalent organic group of the carbon number 17~51 of skeleton, any hydrogen atom on the cyclic group optionally by carbon number 1~ 3 alkyl, the alkoxy of carbon number 1~3, the fluoroalkoxy containing fluoroalkyl, carbon number 1~3 of carbon number 1~3 Or fluorine atom substitution；Y₅Represent divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle, appointing on these cyclic groups Anticipate hydrogen atom optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, Fluoroalkoxy or the fluorine atom substitution of carbon number 1~3；N is 0~4 integer；Y₆For the alkyl of carbon number 1~18, carbon The fluoroalkoxy containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1~18 of atomicity 1~18.

4. the manufacture method of liquid crystal orientation film according to claim 1 or 2, it is characterised in that the polymer is under making Obtained from stating (a) composition, (b) composition and the reaction of (c) composition,

(a) composition：Intramolecular contain 2 NCOs compound,

(c) composition：Tetracarboxylic acid derivatives.

5. the manufacture method of liquid crystal orientation film according to claim 4, it is characterised in that (b) composition is with upper State the compound of the side chain shown in formula [2].

6. the manufacture method of liquid crystal orientation film according to claim 4, it is characterised in that (b) composition is following formula Compound shown in [2a],

In formula [2a], Y₁For singly-bound ,-(CH₂)_a-、-O-、-CH₂O- ,-COO- or-OCO-, wherein, a is 1~15 integer；Y₂For Singly-bound or-(CH₂)_b-, wherein, b is 1~15 integer；Y₃For singly-bound ,-(CH₂)_c-、-O-、-CH₂O- ,-COO- or-OCO-, its In, c is 1~15 integer；Y₄Represent the divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle or there is steroids The divalent organic group of the carbon number 17~51 of skeleton, any hydrogen atom on the cyclic group optionally by carbon number 1~ 3 alkyl, the alkoxy of carbon number 1~3, the fluoroalkoxy containing fluoroalkyl, carbon number 1~3 of carbon number 1~3 Or fluorine atom substitution；Y₅Represent divalent cyclic group in phenyl ring, cyclohexane ring and heterocycle, appointing on these cyclic groups Anticipate hydrogen atom optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, Fluoroalkoxy or the fluorine atom substitution of carbon number 1~3；N is 0~4 integer；Y₆For the alkyl of carbon number 1~18, carbon The fluoroalkoxy containing fluoroalkyl, the alkoxy of carbon number 1~18 or carbon number 1~18 of atomicity 1~18；In addition, m For 1~4 integer；-(Y₁-Y₂-Y₃-Y₄-(Y₅)_n-Y₆)_mRepresent substituent Y₁-Y₂-Y₃-Y₄-(Y₅)_n-Y₆M be present, m be 2 with When upper, each substituent is optionally identical or different.

7. the manufacture method of liquid crystal orientation film according to claim 4, it is characterised in that (c) composition is following formula [3] tetracarboxylic dianhydride shown in,

In formula [3], Z₁For the structure shown in following formula [3a]~formula [3j],

In formula [3a], Z₂~Z₅For hydrogen atom, methyl, chlorine atom or phenyl ring, optionally it is same to each other or different to each other；In formula [3g], Z₆With Z₇For hydrogen atom or methyl, optionally it is same to each other or different to each other.

8. the manufacture method of liquid crystal orientation film according to claim 1 or 2, it is characterised in that the institute in aligning agent for liquid crystal It is 0.1~30 mass % to state polymer.

9. the manufacture method of liquid crystal orientation film according to claim 1 or 2, it is characterised in that institute is carried out by ink-jet method State coating.

10. a kind of liquid crystal orientation film, it is characterised in that it is by liquid crystal orientation film according to any one of claims 1 to 9 Manufacture method and manufacture.

A kind of 11. liquid crystal orientation film, it is characterised in that it contains the polyimides with the repeat unit shown in following formula [1], Acid imide rate is 50~70%,

12. the liquid crystal orientation film according to claim 10 or 11, it is characterised in that it is used in possess electrode a pair The liquid crystal for having liquid crystal layer between substrate and being manufactured via following process represents element, and the process is：In the pair of base Liquid-crystal composition is configured between plate, the liquid-crystal composition includes what is polymerize by least one of active energy beam and heat Polymerizable compound, it polymerize the polymerizable compound while applying voltage the electrode.

13. the liquid crystal orientation film according to claim 10 or 11, it is characterised in that it is used in possess electrode a pair The liquid crystal for having liquid crystal layer between substrate and being manufactured via following process represents element, and the process is：In the pair of base Liquid crystal orientation film is configured between plate, the liquid crystal orientation film includes what is polymerize by least one of active energy beam and heat Polymerizable group, it polymerize the polymerizable group while applying voltage the electrode.

14. a kind of liquid crystal represents element, it is characterised in that it has the liquid crystal aligning any one of claim 10~13 Film.

15. a kind of aligning agent for liquid crystal, it is characterised in that it contains the polyimides with the repeat unit shown in following formula [1] Precursor,