CN108604028A

CN108604028A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Info

Publication number: CN108604028A
Application number: CN201680080402.4A
Authority: CN
Inventors: 小西玲久; 新津新平
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2015-11-30
Filing date: 2016-11-30
Publication date: 2018-09-28
Also published as: KR20180087396A; JPWO2017094786A1; TW201734088A; WO2017094786A1

Abstract

A kind of aligning agent for liquid crystal is provided, be used to form the charge accumulation caused by the un-symmetrical change for inhibiting exchange driving, quickly mitigate residual charge that DC voltage is accumulated, inhibit exchange driving caused by ghost, particularly suitable for the liquid crystal orientation film of light orientation processing.A kind of aligning agent for liquid crystal contains following (A), (B) ingredient.(A) ingredient：Selected from least one kind of polymer used in polyimide precursor and polyimides obtained from tetracarboxylic dianhydride's ingredient and diamine component, the diamine component contains at least one kind of diamines in the diamines selected from the structure with following formula [A 1] and the diamines of the structure with following formula [A 2].(B) ingredient：By the polyamic acid obtained comprising the tetracarboxylic dianhydride of tetracarboxylic dianhydride shown in formula (B 1) and the diamines comprising diamines shown in formula (B 2).(definition of the symbol in formula is as described in specification.)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Technical field

The liquid crystal orientation film that is obtained the present invention relates to aligning agent for liquid crystal, by the aligning agent for liquid crystal and use the liquid crystal orientation film Liquid crystal indicate element.

Background technology

The liquid crystal used in LCD TV, liquid crystal display etc. indicates that element is typically by the arrangement for controlling liquid crystal Obtained from the liquid crystal orientation film of (being also referred to as orientated) state is set in element.

Liquid crystal orientation film makes as follows：To be formed on electrode base board resin coating (for example, polyamic acid, Poly amic acid ester, by the film of polyimides obtained from their imidizates) surface implement the processing for making liquid crystal aligning, To make.

As the processing for making liquid crystal aligning, it is known to：By resin coating with the cloth of cotton, nylon, polyester etc. along one Brushing facture that direction rubs, so-called；With by irradiating the ultraviolet light of polarization to control the state of orientation of liquid crystal Light orientation position logos.

Light orientation position logos have industrially also can be with easy fabrication process the advantages of.In particular, (flat in IPS Face switches (In-Plane Switching)) type of drive, boundary electric field switching (also referred to as FFS) type of drive liquid crystal indicate In element, compared with the liquid crystal orientation film obtained by brushing facture, can improve can expect liquid crystal indicate element contrast, The liquid crystal of angle of visibility characteristic raising etc. indicates the performance of element.Therefore, light orientation position logos are handled as liquid crystal aligning from now on Method has received special attention.

It is proposed using the liquid crystal aligning processing method of light orientation position logos, using the method for photoisomerization reaction, is utilized The method and then method of utilization photolysis reactions etc. of photo-crosslinking (with reference to non-patent literature 1).

It is proposed in patent document 1, it will be by the polyimides system resins shape with alicyclic structures such as cyclobutane rings on main chain At resin coating be used for light orientation position logos.In particular, polyimides system resins to be used for the liquid crystal orientation film of optical alignment method When, compared with other resins, there is high heat resistance therefore can expect its serviceability.

On the other hand, IPS type of drive, FFS type of drive liquid crystal indicate in element, except being accumulated due to DC voltage Residual charge, exchange driving caused by ghost except, the problem peculiar as its structure, can enumerate exchange driving it is non- Charge accumulation caused by symmetrization is as problem.

A kind of method as the liquid crystal orientation film for being resolved these problems, it is proposed that aligning agent for liquid crystal is by liquid Brilliant orientation is excellent, liquid crystal orientation restraint is strong ingredient, with take into account the electricity caused by the un-symmetrical change that inhibits exchange and drive Lotus is accumulated and is quickly mitigated obtained from the ingredient blending for the residual charge accumulated due to DC voltage (with reference to patent document 2).However, above-mentioned aligning agent for liquid crystal especially may not solve the above subject in light orientation position logos.

Existing technical literature

Patent document

Patent document 1：The flat 9-297313 bulletins of Japanese Laid-Open

Patent document 2：WO2015/060357 bulletins

Non-patent literature

Non-patent literature 1：" liquid crystal photo-alignment film " functional material in November, 1997 Vol.17 No.11 13-22 page

Invention content

Problems to be solved by the invention

The object of the present invention is to provide a kind of aligning agent for liquid crystal, the orientation restraint containing liquid crystal aligning, liquid crystal The high ingredient of excellent, liquid crystal aligning stability, with take into account inhibit exchange drive un-symmetrical change caused by charge accumulation and The un-symmetrical change of the ingredient for quickly mitigating the residual charge accumulated due to DC voltage, the exchange driving that can be inhibited is led The charge accumulation of cause, quickly mitigation are residual the residual charge that DC voltage is accumulated and then caused by inhibiting exchange driving The liquid crystal orientation film of shadow.

It is further an object that providing：The liquid crystal orientation film obtained by above-mentioned aligning agent for liquid crystal；With, have should The liquid crystal of liquid crystal orientation film indicates element.

The solution to the problem

Present inventor has performed further investigations, as a result, it has been found that：In order to achieve the above objectives, the liquid crystal containing specific structure takes It is very effective to agent, so far completes the present invention.That is, the present invention has purport below.

1. a kind of aligning agent for liquid crystal, which is characterized in that contain：Following (A) ingredients and following (B) ingredients.

(A) ingredient：Selected from by making tetracarboxylic dianhydride's ingredient carry out polyimides obtained from polycondensation reaction with diamine component At least one kind of polymer in the group of precursor and the polyimides of acid imide compound as polyimide precursor composition, it is described Diamine component contains selected from the diamines group by the diamines of the structure with following formula [A-1] and the structure with following formula [A-2] At group at least one kind of diamines.

(in formula [A-1], R¹、R²It is each independently hydrogen atom, the alkyl of carbon number 1~4 or hydrogen original is substituted by by heat Son heat leaving away property group, it is therein at least one be above-mentioned leaving away property of heat group.In formula [A-2], R₁、R₂、R₃And R₄Respectively solely It is on the spot hydrogen atom or optionally there is the alkyl of 1 valence of the carbon number 1~20 of substituent group.D is is substituted by hydrogen atom by heat Heat leaving away property group.)

(B) ingredient：Make containing tetracarboxylic dianhydride's ingredient of tetracarboxylic dianhydride shown in following formula (B-1) and contains (B-2) institute Show that the diamines of diamines carries out polyamic acid obtained from polycondensation reaction.

(in formula (B-2), R₅For hydrogen atom or COOH bases.B₁~B₂It is each independently hydrogen atom or optionally there is substitution Base has carbon number 1~10, alkyl, alkenyl or alkynyl.)

The effect of invention

By using the aligning agent for liquid crystal of the present invention, it is good, inhibition exchange driving non-right that liquid crystal aligning can be obtained The caused charge accumulation of titleization, the mitigation for the residual charge accumulated by DC voltage is fast, exchange driving can be inhibited to be led The liquid crystal orientation film of the ghost of cause.In particular, the liquid crystal of light orientation position logos obtained from the radiation polarized for irradiation Alignment films are useful.

Liquid crystal with the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention indicates that the reliability of element becomes excellent It is different, large screen and the LCD TV of high-resolution, middle-size and small-size auto-navigation system, smart mobile phone etc. can be suitable for.

Specific implementation mode

＜ (A) ingredients ＞

(A) ingredient contained in the aligning agent for liquid crystal of the present invention is to be selected from and use tetracarboxylic dianhydride's ingredient and diamine component Obtained from least one kind of polymer (hereinafter also referred to as particular polymers (A)) in polyimide precursor and polyimides, institute Diamine component is stated to contain in the diamines selected from the structure with following formula [A-1] and the diamines of the structure with following formula [A-2] At least one kind of diamines.

In formula [A-1], R¹、R²With A as defined in above-mentioned.

Wherein, R¹And R²Preferably wherein at least one, or both be the leaving away property of heat that hydrogen atom is substituted by by heat Group.Heat the leaving away property group is the protecting group of amino, is tied to it as long as the functional group to be substituted by hydrogen atom by heat Structure is not particularly limited.Leaving away property of heat group preferably stays at room temperature, it is preferred that preferably 80 DEG C or more, more preferably Heat occurs at 100 DEG C or more to leave away.Preferably, preferably 300 DEG C of the upper limit, 250 DEG C more preferable for the temperature that heat is left away.

As above-mentioned leaving away property of heat group, preferably group shown in following formula (1).In formula (1), the preferred singly-bounds of A.Herein, A In the case of singly-bound, the group of formula (1) is tert-butoxycarbonyl (in the present invention, also referred to as Boc yls).

It can be arbitrary two as long as meeting above-mentioned condition that intramolecular, which has the diamines of structure shown in above-mentioned formula [A-1], Amine.As its preference, diamines shown in following formula [A-1-1] can be enumerated.

In above-mentioned formula [A-1-1], R¹And R², further include respectively including preferred mode, it is identical as the situation in formula [A-1]. M, n is each independently 0~3 integer, the easiness obtained from raw material, and preferably 0 or 1, more preferable 1.

In addition, in formula [A-1-1], the amino (- NH in each phenyl ring₂) relative to alkylidene bonding position can be it is adjacent, Between or centering any position, from the easiness of synthesis and polymerisation reactivity aspect, preferred meta or para position, more preferably Contraposition.

As the example of diamines shown in formula [A-1-1], diamines below can be preferably enumerated.It should be noted that with In lower in exemplary formula, Boc be it is following shown in group.

In formula [A-2], R₁、R₂、R₃And R₄It is each independently the 1 of hydrogen atom or the optional carbon number 1~20 with substituent group The alkyl of valence.In particular, if it is bulky substituent group, there is the possibility for making liquid crystal aligning reduce, it is therefore preferable that hydrogen Atom, 1~6 alkyl of carbon number or phenyl, particularly preferred hydrogen atom or methyl.

D is is substituted by heat the leaving away property group of hydrogen atom above by heat.The temperature that the heat of heat the leaving away property group is left away Degree and concrete example are described also described above.From the temperature aspect left away, the particularly preferred tert-butoxycarbonyls of D or 9- fluorenyls Methoxycarbonyl.

As the diamines with structure shown in above-mentioned formula [A-2], wherein diamines shown in preferred following formula [A-2-1].

Wherein, in the case of shown in following formula [A-2-2], the liquid crystal aligning of gained liquid crystal orientation film is got higher, therefore especially It is preferred that.

A¹And A⁵It is each independently the alkylidene of singly-bound or carbon number 1~5, the reactivity of the functional group from sealant Aspect set out, preferably singly-bound or methylene.A²And A⁴For the alkylidene of carbon number 1~5, preferably methylene or ethylidene.

A³For the alkylidene or cycloalkylidene of carbon number 1~6, from the functional group in sealant it is reactive in terms of go out Hair, preferably methylene or ethylidene.

B¹And B²It is each independently singly-bound ,-O- ,-NH- ,-NMe- ,-C (=O)-,-C (=O) O- ,-C (=O) NH- ,-C (=O) NMe- ,-OC (=O)-,-NHC (=O)-or-N (Me) C (=O)-, from the liquid crystal aligning of gained liquid crystal orientation film Aspect is set out, preferably singly-bound or-O-.

D₁It is tert-butoxycarbonyl or 9- fluorenylmethoxycarbonyl groups, from the temperature of deprotection for above-mentioned leaving away property of heat group Aspect set out, preferred tert-butoxycarbonyl.A is 0 or 1.

As the concrete example of diamines shown in formula [A-2-2], following formula (1-1)~formula (1-21) can be enumerated.It needs It is bright, in these formulas, omit the record of the amino at the both ends being bonded with benzyl ring.

In formula (1-1)~(1-21), Me indicates methyl, D₂Indicate tert-butoxycarbonyl.

Wherein, more preferable formula (1-1)~(1-4), particularly preferred formula (1-1).

Selected from the diamines of structure shown in above-mentioned formula [A-1] and the diamines with structure shown in above-mentioned formula [A-2] In at least one kind of diamines dosage relative to whole diamine components for using in the manufacture of the particular polymers of the present invention, preferably For 5~80 moles of %, more preferably 10~50 moles of %.

As the diamine component used in (A) ingredient for containing in the aligning agent for liquid crystal of the present invention, can with selected from Above-mentioned formula [A-1] is used together other diamines at least one kind of diamines in the diamines of structure shown in [A-2] and (is also referred to as other Diamines).

Specifically, can enumerate：2,4- dimethyl-m-phenylene diamine (MPD), 2,6- diaminotoluenes, m-phenylene diamine (MPD), to benzene two Amine, 4,4 '-benzidines, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3,3 '-dihydroxy -4,4 '-benzidine, 3,3 '-dicarboxyls -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-biphenyl, 3,3 '-trifluoromethyls -4,4 '-benzidine, 3,4 '-benzidines, 3,3 '-benzidines, 2,2 '-diamino connection Benzene, 2,3 '-benzidines, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diamino two Phenylmethane, 2,2 '-diaminodiphenyl-methanes, 2,3 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl ethers, 3, 3 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 2,2 '-diamino-diphenyl ethers, 2,3 '-diamino-diphenyls Ether, 4,4 '-sulfonyldianilines, 3,3 '-sulfonyldianilines, bis- (4- aminophenyls) silane, bis- (3- aminophenyls) silane, It is bis- (4- aminophenyls) silane of dimethyl-, bis- (3- aminophenyls) silane of dimethyl-, 4,4 '-phenothiazines, 3,3 '-thio Diphenylamines, 4,4 '-diamino-diphenylamines, 3,3 '-diamino-diphenylamines, 3,4 '-diamino-diphenylamines, 2,2 '-diamino hexichol Amine, 2,3 '-diamino-diphenylamines, 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 two Phenyl) amine, 4,4 '-diaminobenzophenones, 3,3 '-diaminobenzophenones, 3,4 '-diaminobenzophenones, 1,4- diaminos Base naphthalene, 2,2 '-diaminobenzophenones, 2,3 '-diaminobenzophenones, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- bis- Amino naphthalenes, 1,8- diaminonaphthalenes, 2,5- diaminonaphthalenes, 2,6 diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, 1,2- are bis- Bis- (3- aminophenyls) ethane of (4- aminophenyls) ethane, 1,2-, bis- (4- aminophenyls) propane of 1,3-, bis- (the 3- amino of 1,3- Phenyl) propane, bis- (4 aminophenyl) butane of 1,4-, bis- (3- aminophenyls) butane of 1,4-, bis- (3,5- diethyl -4- aminobenzenes Base) methane, bis- (4- amino-benzene oxygens) benzene of 1,4-, bis- (4- amino-benzene oxygens) benzene of 1,3-, bis- (4- aminophenyls) benzene of 1,4-, 1, Bis- (4- aminophenyls) benzene of 3-, bis- (4- aminobenzyls) benzene of 1,4-, bis- (4- amino-benzene oxygens) benzene of 1,3-, 4,4 '-[Asias 1,4- benzene Base is bis- (methylene)] diphenylamines, 4,4 '-[1,3- phenylenes are bis- (methylene)] diphenylamines, 3,4 '-[bis- (methylenes of 1,4- phenylenes Base)] diphenylamines, 3,4 '-[1,3- phenylenes are bis- (methylene)] diphenylamines, 3,3 '-[1,4- phenylenes are bis- (methylene)] hexichol Amine, 3,3 '-[1,3- phenylenes are bis- (methylene)] diphenylamines, 1,4- phenylenes bis- [(4- aminophenyls) ketones], the Asias 1,4- benzene Base bis- [(3- aminophenyls) ketones], 1,3- phenylenes bis- [(4- aminophenyls) ketones], bis- [(the 3- aminobenzenes of 1,3- phenylenes Base) ketone], 1,4- phenylenes bis- (4-aminobenzoic acid esters), 1,4- phenylenes bis- (3- Aminobenzoates), 1,3- phenylenes It is bis- (4-aminobenzoic acid esters), 1,3- phenylenes bis- (3- Aminobenzoates), bis- (4- aminophenyls) terephthalates, double (3- aminophenyls) terephthalate, bis- (4- aminophenyls) isophthalic acid esters, bis- (3- aminophenyls) M-phthalic acids Ester, N, N '-(1,4- phenylenes) bis- (4- aminobenzamides), N, N '-(1,3- phenylenes) bis- (4- aminobenzamides), N, N '-(1,4- phenylenes) bis- (3-ABs), N, N '-(1,3- phenylenes) bis- (3-ABs), N, N '-are bis- (4- aminophenyls) terephthalamide, N, bis- (3- aminophenyls) terephthalamides of N '-, N, N '-bis- (4- aminophenyls) Isophtalamide, N, bis- (3- aminophenyls) isophtalamides of N '-, bis- (4- aminophenyls) anthracenes of 9,10-, 4,4 '-bis- (4- Amino-benzene oxygen) diphenyl sulfone, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-bis- [4- (4- aminobenzene oxygen Base) phenyl] hexafluoropropane, 2,2 '-bis- (4- aminophenyls) hexafluoropropane, 2,2 '-bis- (3- aminophenyls) hexafluoropropane, 2, 2 '-bis- (3- amino -4- aminomethyl phenyls) hexafluoropropane, 2,2 '-bis- (4- aminophenyls) propane, 2,2 '-bis- (3- aminophenyls) Propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) propane, bis- (4- amino-benzene oxygens) propane of 1,3-, bis- (the 3- aminobenzenes of 1,3- Oxygroup) propane, bis- (4- amino-benzene oxygens) butane of 1,4-, bis- (3- amino-benzene oxygens) butane of 1,4-, bis- (the 4- aminobenzene oxygen of 1,5- Base) pentane, bis- (3- amino-benzene oxygens) pentanes of 1,5-, bis- (4- amino-benzene oxygens) hexanes of 1,6-, bis- (the 3- aminobenzene oxygen of 1,6- Base) hexane, bis- (4- amino-benzene oxygens) heptane of 1,7-, 1,7- (3- amino-benzene oxygens) heptane, 1,8- bis- (4- amino-benzene oxygens) Bis- (3- amino-benzene oxygens) octanes of octane, 1,8-, bis- (4- amino-benzene oxygens) nonanes of 1,9-, bis- (3- amino-benzene oxygens) nonyls of 1,9- Alkane, 1,10- (4- amino-benzene oxygens) decane, 1,10- (3- amino-benzene oxygens) decane, 1,11- (4- amino-benzene oxygens) hendecane, 1,11- (3- amino-benzene oxygens) hendecane, 1,12- (4- amino-benzene oxygens) dodecane, 1,12- (3- amino-benzene oxygens) 12 Alkane, bis- (4- aminocyclohexyls) methane, bis- (4- amino -3- methylcyclohexyls) methane, 1,3- diaminopropanes, 1,4- diamino Butane, 1,5- 1,5-DAPs, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonyls Alkane, 1,10- diamino decanes, 1,11- diamino undecanes or 1,12- diamino dodecanes and then their amino are parahelium The diamines of base.

Other diamines used in (A) ingredient contained in the aligning agent for liquid crystal of the present invention can also be according to (A) ingredient pair Liquid crystal aligning, voltage retention, charge when the dissolubility of solvent, the coating of aligning agent for liquid crystal, formation liquid crystal orientation film Accumulation etc. characteristics and be used in mixed way using a kind or by two or more.

As the tetracarboxylic acid sour component of (A) ingredient contained in the aligning agent for liquid crystal for making the present invention, it is preferable to use under State tetracarboxylic dianhydride shown in formula [4].At this point, can not only use specific tetracarboxylic dianhydride shown in formula [4], can also use Tetrabasic carboxylic acid, two carboxylic acid halides of two carboxylic acid halides of tetrabasic carboxylic acid, tetracarboxylic acid acid dialkyl ester or tetracarboxylic acid acid dialkyl ester as the tetracarboxylic acid derivatives (tetracarboxylic dianhydride and its derivative above-mentioned are also referred to as specific tetracarboxylic acid sour component).

Z indicates at least one kind of structure in following formula [4a]~formula [4q].

Z¹~Z⁴Each independently represent hydrogen atom, methyl, ethyl, propyl, chlorine atom or phenyl ring.Z⁵And Z⁶It is respectively independent Ground indicates hydrogen atom or methyl.

As Z, the easiness aspect of the polymerisation reactivity when easiness of synthesis, manufacture polymer, preferably Structure shown in formula [4a], formula [4c]~formula [4g], formula [4k]~formula [4m] or formula [4p].More preferable formula [4a], formula [4e]~ Structure shown in formula [4g], formula [4l], formula [4m] or formula [4p].Particularly preferably [4a], formula [4e], formula [4f], formula [4l], formula Structure shown in [4m] or formula [4p].

Formula [4a] preferably following formula [4a-1] or formula [4a-2].

Specific tetracarboxylic acid sour component in particular polymers (A) 50 is rubbed in 100 moles of % of whole tetracarboxylic acid sour components, preferably You are %~100 mole %.Wherein, preferably 70 moles of %~100 mole %.More preferable 80 moles of %~100 mole %.

The specific tetracarboxylic acid sour component of the present invention can with particular polymers according to the present invention (A) to the dissolubility of solvent, The characteristics such as the coating of aligning agent for liquid crystal, orientation, voltage retention, the charge accumulation of liquid crystal when forming liquid crystal orientation film and Using one kind or two or more.

Other in addition to specific tetracarboxylic acid sour component can also be used in the polyimides based polymer of particular polymers (A) Tetracarboxylic acid sour component.

As other tetracarboxylic acid sour components, can enumerate it is following described in tetrabasic carboxylic acid or its acid dianhydride, sour two carboxylic acid halides, acid Dialkyl ester, two carboxylic acid halides of acid dialkyl ester etc..

1,2,5,6- naphthalene tetracarboxylic acids, 1,4,5,8- naphthalene tetracarboxylic acids, 1,2,5,6- anthracenes tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyl tetracarboxylic acids Acid, 2,3,3 ', 4- biphenyltetracarboxyacid acids, bis- (3,4- dicarboxyphenyis) ethers, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, bis- (3,4- Dicarboxyphenyi) sulfone, bis- (3,4- dicarboxyphenyis) methane, bis- (3,4- dicarboxyphenyis) propane of 2,2-, 1,1,1,3,3,3- Bis- (3,4- dicarboxyphenyis) propane of hexafluoro -2,2-, bis- (3,4- dicarboxyphenyis) dimethylsilanes, bis- (3,4- dicarboxyl benzene Base) diphenyl silane, 2,3,4,5- pyridines tetrabasic carboxylic acid, bis- (3,4- dicarboxyphenyis) pyridines of 2,6-, 3,3 ', 4,4 '-diphenyl Sulfone tetrabasic carboxylic acid, 3,4,9,10- tetrabasic carboxylic acids or 1,3- diphenyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids etc..

Other above-mentioned tetracarboxylic acid sour components can be with particular polymers according to the present invention (A) to solvent dissolubility, liquid crystal The characteristics such as the coating of alignment agent, liquid crystal aligning, voltage retention, charge accumulation when forming liquid crystal orientation film and use 1 Two or more is used in mixed way by kind.

＜ (B) ingredients ＞

(B) ingredient contained in the aligning agent for liquid crystal of the present invention is by comprising tetracarboxylic dianhydride shown in following formula (B-1) Tetracarboxylic dianhydride's ingredient and (also referred to as specific comprising polyamic acid obtained from the diamine component of diamines shown in following formula (B-2) Polymer (B)).

In formula (B-2), R₅For the group in hydrogen atom or COOH bases, B₁~B₂It is each independently hydrogen atom or appoints Select alkyl, alkenyl, the alkynyl of the carbon number 1~10 with substituent group.

When the ratio of tetracarboxylic dianhydride shown in formula (B-1) is very few, it is unable to get the effect of the present invention.Formula (B-1) institute as a result, Show the usage rate of tetracarboxylic dianhydride relative to whole tetracarboxylic dianhydride's ingredients, preferably 10~100 moles of %, more preferably 30 ~100 moles of %, further preferably 50~100 moles of %.

Particular polymers (B) in the present invention can use following formula in addition to tetracarboxylic dianhydride shown in above-mentioned formula (B-1) (B-3) tetracarboxylic dianhydride shown in.

In formula (B-3), X is the organic group of 4 valences can enumerate following formula (X-1)~(X-43's) as specific example Structure.

In formula (X-1), R³~R⁶It is each independently the alkyl or phenyl of hydrogen atom, carbon number 1~6, more preferable hydrogen atom, Or methyl.

As tetracarboxylic dianhydride, from the viewpoint of acquired, it is preferably selected from the structure composition shown in following formula (B-4) Group at least one kind of tetrabasic carboxylic acid.

(X₁It is at least one kind of in the group of structure composition shown in above-mentioned formula (X-1)~(X-14) to be selected from.)

In formula (B-2), R₁For the group in hydrogen atom or COOH bases, particularly preferred hydrogen atom.

B₁And B₂It is each independently hydrogen atom or optionally there is alkyl, alkenyl, the alkynyl of the carbon number 1~10 of substituent group. Wherein, preferred hydrogen atom.

The concrete example of formula (B-2) is for example following, but is not limited to these.

The usage rate of diamines is relative to whole diamine components, preferably 10 shown in formula (B-2) in particular polymers (B) ~100 moles of %, more preferably 30~70 moles of %, further preferably 20~50 moles of %.

Particular polymers (B) in the present invention can also use following formula (B- in addition to diamines shown in above-mentioned formula (B-2) 4) diamines shown in.Y in formula (B-4)₂For the organic group of divalent, organic group of more than two kinds can be mixed.If Its concrete example is shown, then can enumerate following Y-1~Y-100.B in formula (B-4)₁And B₂Further include preference, is formula (B- 2) B₁And B₂In identical definition.

As Y₂, wherein the high diamines of good liquid crystal aligning in order to obtain, preferably linearity, more preferable Y-7, Y- 21、Y-22、Y-23、Y-25、Y-26、Y-27、Y-43、Y-44、Y-45、Y-46、Y-48、Y-63、Y-71、Y-73、Y-74、Y- The diamines of 75 or Y-76.

The usage rate of diamines shown in formula (B-4) is preferably 20~80 moles of %, more excellent relative to whole diamine components It is selected as 50~80 moles of %.

The manufacturing method ＞ of ＜ particular polymers (A), (B)

In the present invention, the method for making particular polymers (A) and particular polymers (B) is not particularly limited.Generally For, following method can be enumerated：Make at least one kind of in the group that the derivative by tetracarboxylic dianhydride and the tetrabasic carboxylic acid forms Tetracarboxylic acid sour component carries out polycondensation reaction with the diamine component comprising one or more diamines, obtains polyamic acid.Specifically, can With with the following method：The method for making tetracarboxylic dianhydride carry out polycondensation with primary diamines or secondary diamine and obtaining polyamic acid；Make four The method that carboxylic acid obtains polyamic acid with primary diamines or secondary diamine progress dehydrating polycondensation reaction；Or, make two carboxylic acid halides of tetrabasic carboxylic acid with Primary diamines or secondary diamine carry out polycondensation and the method that obtains polyamic acid.

Diamine component usually makes diamine component be reacted in a solvent with tetracarboxylic acid sour component with reacting for tetracarboxylic acid sour component. As the solvent used at this time, it is not particularly limited as long as the polyimide precursor dissolving generated.In following, enumerate in reaction The concrete example of the solvent used, but it is not limited to these examples.

For example, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones or gamma-butyrolacton, N, N- dimethyl Formamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) or 1,3- dimethyl-imidazol alkanones.In addition, polyimide precursor is molten In the case of agent dissolubility height, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4- hydroxy-4-methyl-2-pentanones or following formula can be used Solvent shown in [D-1]~formula [D-3].

D¹Indicate the alkyl of carbon number 1~3, D²Indicate the alkyl of carbon number 1~3, D³Indicate the alkyl of carbon number 1~4.

These solvents can be used alone, and can also mix and use.In turn, even if for insoluble polyimide precursor Solvent can also be blended in aforementioned solvents and use in the range of the polyimide precursor of generation is not precipitated.In addition, molten Moisture in agent interferes polymerisation, and then the reason of as making the polyimide precursor of generation hydrolyze, and therefore, solvent preferably makes With the solvent dehydrated.

When diamine component being made to be reacted in a solvent with tetracarboxylic acid sour component, it can enumerate：Two will have been dispersed or dissolved in solvent The solution of amine component is stirred, and so that tetracarboxylic acid sour component is directly added or is dispersed or dissolved in solvent and the method added；Phase Instead, the method that diamine component is added into the solution for dispersing or dissolving tetracarboxylic acid sour component in a solvent；Alternately addition diamines The method etc. of ingredient and tetracarboxylic acid sour component can use above-mentioned any means.In addition, using a variety of diamine components or four respectively Carboxylic acid composition and make its react in the case of, its reaction can be made in the state of being pre-mixed, can also be reacted successively respectively, And then it can also be made to distinguish low-molecular weight obtained by the reaction and carry out hybrid reaction and form polymer.Polymerization temperature at this time It can select -20 DEG C~150 DEG C of arbitrary temp, preferably -5 DEG C~100 DEG C of range.In addition, reaction can be arbitrary dense Degree is lower to carry out, but when concentration is too low, it is difficult to obtain the polymer of high molecular weight, when excessive concentration, the viscosity of reaction solution became Height, uniform stirring become difficult.It is therefore preferable that for 1~50%, more preferably 5~30%.It can be in reaction initially with high concentration It carries out, later, additional solvent.

In polycondensation reaction, the ratio between the total mole number of diamine component and the total mole number of tetracarboxylic acid sour component preferably 0.8~ 1.2.In the same manner as common polycondensation reaction, closer to 1.0, the molecular weight of the polyimide precursor of generation becomes to get over the molar ratio Greatly.

The polyimides of the present invention is to make polyimides obtained from aforementioned polyimide precursor closed loop, the polyimides In, the closed loop rate (also referred to as acid imide rate) of amide acidic group may not be necessary for 100%, can be arbitrary according to purposes, purpose Adjustment.

As the method for making polyimide precursor imidizate, can enumerate：The solution of polyimide precursor is directly added The hot-imide of heat or the catalysis imidizate that catalyst is added in the solution of polyimide precursor.

Make polyimide precursor in the solution hot-imide when temperature be 100 DEG C~400 DEG C, preferably 120 DEG C~250 DEG C, preferably the water generated by imidization reaction is expelled to the method carried out outside system by side.

The catalysis imidizate of polyimide precursor can carry out as follows：Alkalinity is added in the solution of polyimide precursor Catalyst and acid anhydrides are stirred at -20 DEG C~250 DEG C, preferably 0 DEG C~180 DEG C, to carry out.The amount of basic catalyst It is 0.5 mole times~30 moles times, preferably 2 moles times~20 moles times of amide acidic group, the amount of acid anhydrides is rubbed for the 1 of amide acidic group You times~50 moles times, preferably 3 moles times~30 moles times.As basic catalyst, pyridine, triethylamine, front three can be enumerated Amine, tri-n-butylamine or trioctylamine etc., wherein pyridine have be suitable for make reaction carry out alkalinity, therefore it is preferred that.As acid anhydrides, Ke Yiju Going out acetic anhydride, trimellitic anhydride or pyromellitic dianhydride etc., wherein when using acetic anhydride, purifying after reaction becomes easy, therefore It is preferred that.It can be controlled by adjusting catalytic amount, reaction temperature and reaction time using the acid imide rate of catalysis imidizate System.

The polyimide precursor or polyimides generated is recycled from the reaction solution of polyimide precursor or polyimides In the case of, reaction solution can be put into a solvent and make its precipitation.As the solvent used in precipitation, can enumerate methanol, Ethyl alcohol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc..Input is extremely , can under normal or reduced pressure after the polymer filtration being settled out in solvent and recycling, air drying or heat drying.Separately It outside, can be with when the polymer that precipitation recycles will be made to be re-dissolved in solvent and carrying out the operation of reprecipitation recycling and be repeated 2 times~10 times Reduce the impurity in polymer.As the solvent at this point, for example, alcohols, ketone or hydrocarbon etc., using in them 3 kinds or more of solvent when, the efficiency of purifying further improves, therefore it is preferred that.

＜ aligning agent for liquid crystal ＞

The aligning agent for liquid crystal of the present invention is to be used to form the coating solution of liquid crystal orientation film, and to contain particular polymers (A), the coating solution for being used to form liquid crystal orientation film of particular polymers (B) and solvent.

About the ratio of particular polymers (A) and particular polymers (B) in the aligning agent for liquid crystal of the present invention, relative to spy Determine 100 parts of polymer (A), particular polymers (B) preferably 10~900 mass parts.Wherein, preferably 25~400 mass parts, more preferably 40~250 mass parts.Most preferably 100~250 mass parts.

Whole component of polymer in the aligning agent for liquid crystal of the present invention can with the particular polymers (A) of all present invention and Particular polymers (B), can also mix other polymers in addition to this.As polymer in addition to this, can enumerate not The polyimide precursor and polyimides of specific structure (1A), specific structure (1B) and specific structure (2) with the present invention.Into And cellulose-based polymer, acrylic polymer, methacrylic polymer, polystyrene, polyamide can also be enumerated Or polysiloxanes etc..At this point, the content of other polymers in addition to this is relative to incorporating particular polymers (A) and specific poly- 100 mass parts of particular polymers for closing object (B) are 0.5~15 mass parts.Wherein, preferably 1~10 mass parts.

In addition, the content of the solvent in aligning agent for liquid crystal is preferably 70~99.9 mass %.The content can be according to liquid crystal The coating method of alignment agent, the suitable change as the film thickness of the liquid crystal orientation film of target.

As long as the solvent used in the aligning agent for liquid crystal of the present invention is to keep particular polymers (A) and particular polymers (B) molten The solvent (also referred to as good solvent) of solution is just not particularly limited.In following, the concrete example of good solvent is enumerated, but is not limited to these Example.

For example, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- second Base -2-Pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolacton, 1,3- dimethyl-imidazols alkanone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4- hydroxy-4-methyl-2-pentanones etc..Wherein, preferably n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones, γ-Ding Nei Ester.

In turn, particular polymers (A) and particular polymers (B) in the case of the dissolubility height of solvent, it is preferable to use preceding State solvent shown in formula [D-1]~formula [D-3].

Good solvent in the aligning agent for liquid crystal of the present invention is preferably whole 20~99 of solvent contained in aligning agent for liquid crystal Quality %.Wherein, preferably 20~90 mass %.More preferable 30~80 mass %.

The aligning agent for liquid crystal of the present invention can use the film for liquid crystal orientation film when improving coating of liquid crystalline alignment agent Property, surface smoothness solvent (also referred to as poor solvent).In following, the specific example of poor solvent is enumerated, but is not limited to These examples.

For example, ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, 2- amylalcohols, 3- Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanols, 2- methyl-1-pentenes alcohol, 2- Methyl -2- amylalcohols, 2- ethyls-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanols, sec-n-octyl alcohol, 2- ethyl -1- hexanols, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 1,5- pentanediols, 2- methyl -2,4-PD, 2- second Base -1,3- hexylene glycols, dipropyl ether, butyl oxide, two hexyl ether, dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol two Butyl ether, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, two fourth of diethylene glycol Ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- ethoxybutyls acetic acid esters, 1- methyl amyls acetic acid esters, 2- Ethyl-butyl acetic acid esters, 2- ethylhexyl acetates, ethylene glycol acetate, ethylene acetate, propylene carbonate, carbonic acid Ethyl, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, ethylene glycol monohexylether, 2- (hexyls Oxygroup) ethyl alcohol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol monomethyl ether Acetic acid esters, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dimethyl ether, Tripropylene glycol monomethyl Ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol acetate, second two Alcohol diacetate esters, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, 2- (2- ethoxy ethoxies) ethyl second Acid esters, diethylene glycol acetic acid esters, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3- methoxyl groups Methyl propionate, 3- ethoxy-propionic acids Methylethyl, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- first Oxygroup propyl propionate, 3- methoxy propyls acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, lactic acid are different Solvent etc. shown in pentyl ester or previously described formula [D-1]~formula [D-3].

Wherein, it is preferable to use 1- hexanols, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol Monobutyl ether or dimethyl ether.

These poor solvents are preferably 1~80 mass % of solvent entirety contained in aligning agent for liquid crystal.Wherein, preferably 10 ~80 mass %.More preferable 20~70 mass %.

It is preferred that importing following cross-linked compounds into the aligning agent for liquid crystal of the present invention：With epoxy group, isocyanate group, The cross-linked compound of oxetanyl or cyclocarbonate radical；With selecting free hydroxyl, hydroxy alkyl and lower alkoxy alkane The cross-linked compound of at least one kind of substituent group in the group of base composition；Alternatively, the bridging property chemical combination with polyunsaturated bond Object.These substituent groups, polyunsaturated bond must there are 2 or more in cross-linked compound.

As the cross-linked compound with epoxy group or isocyanate group, such as bisphenol acetone glycidol can be enumerated Ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl isocyanurate, four glycidols Base aminodiphenyl support (tetraglycidyl amino diphenylene), four glycidyl group m-xylene diamine, four shrinks are sweet Bis- (amino-ethyl) hexamethylenes of oil base -1,3-, tetraphenyl glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol six Bis- (1- (2,3- the glycidoxies) -1- trifluoromethyl -2,2,2- trifluoromethyls) benzene of acetyl fluoride base diglycidyl ether, 1,3-, Bis- (2,3- glycidoxies) octafluorobiphenyls of 4,4-, triglycidyl group para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- glycidoxies) phenyl) -2- (4- (bis- (4- (2,3- glycidoxies) phenyl) ethyls of 1,1-) phenyl) propane Or bis- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- first of 1,3- Base ethyl) phenyl) ethyl) phenoxy group) -2- propyl alcohol etc..

Cross-linked compound with oxetanyl is with oxetanes shown at least two following formula [4A] The compound of base.

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

As the cross-linked compound with cyclocarbonate radical, for ring carbon acid shown at least two following formula [5A] The compound of ester group.

Specifically, 76~82 of International Publication bulletin WO2012/014898 (2012.2.2 is disclosed) can be enumerated Described in formula [5-1]~formula [5-42] shown in cross-linked compound.

It, can as the cross-linked compound at least one kind of substituent group in the group for selecting free hydroxyl and alkoxy to form Enumerate such as amino resins with hydroxyl or alkoxy, such as melamine resin, Lauxite, guanamine resin, glycoluril-formaidehyde Resin, succinyl amine-formaldehyde resin or ethylene urea-formaldehyde resins etc..Specifically, the hydrogen atom of amino can be used by hydroxyl first Melamine derivative, benzoguanamine derivative or glycoluril made of base or alkoxy methyl or the two substitution.The melamine derives Object or benzoguanamine derivative can exist in the form of dimer or tripolymer.They have preferably with respect to every 1 triazine ring There are average 3 or more and 6 methylols or alkoxy methyl below.

As such melamine derivative or the example of benzoguanamine derivative, can enumerate commercially available product relative to every 1 A triazine ring averagely replaces the MX-750 for having 3.7 methoxies, averagely replaces relative to every 1 triazine ring and has 5.8 first The MW-30 (be above Sanwa Chemical Co., Ltd's system) of oxygroup methyl, CYMEL 300,301,303,350,370,771,325, 327, the methoxymethylated melamine such as 703,712；The methoxymethylated fourth oxygen such as CYMEL 235,236,238,212,253,254 Ylmethyl melamine；The butoxymethyls melamines such as CYMEL 506,508；The methyl containing Carboxvmethoxv of CYMEL 1141 etc Change isobutoxymethyl melamine；The methoxymethylated ethoxyl methyl benzoguanamine of CYMEL 1123 etc；CYMEL The methoxymethylated butoxymethyl benzoguanamine of 1123-10 etc；The butoxymethyl benzene of CYMEL 1128 etc And guanamines；The ethoxyl methyl benzoguanamine of methyl containing Carboxvmethoxv of CYMEL 1125-80 etc (is above Mitsui Cyanamid Co., Ltd.s system).In addition, the example as glycoluril, can enumerate the butoxymethyl of CYMEL 1170 etc The methoxyl group methylolation glycoluril of methylolation glycoluril of glycoluril, CYMEL 1172 etc etc., Powder link 1174 etc Deng.

As benzene or phenol cross-linked compound with hydroxyl or alkoxy, such as 1,3,5- tri- (methoxies can be enumerated Ylmethyl) benzene, 1,2,4- tri- (i-propoxymethyl) benzene, bis- (sec-butoxymethyl) benzene of 1,4- or 2,6- bishydroxymethyls be to uncle Butylphenol etc..

More specifically, the 62~66 of International Publication bulletin WO2011/132751. (2011.10.27 is disclosed) can be enumerated Described in page, formula [6-1]~formula [6-48] cross-linked compound.

As the cross-linked compound with polyunsaturated bond, such as trimethylolpropane tris (methyl) can be enumerated 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 It is saturated the cross-linked compound of base；In turn, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, four Ethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, poly- the third two Alcohol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene oxide are double Phenol A types two (methyl) acrylate, propylene oxide bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) acrylic acid Ester, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) third Olefin(e) acid ester, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) third Crosslinking with 2 polymerism unsaturated groups in olefin(e) acid ester or 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate equimolecular Property compound；And (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxyls Base butyl ester, (methyl) acrylic acid 2- phenoxy group -2- hydroxy propyl esters, 2- (methyl) acryloxy -2- hydroxypropyl phthalic acids Ester, (methyl) acrylic acid 3- chlorine-2-hydroxyls propyl ester, glycerine list (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl phosphorus Cross-linked compound etc. with 1 polymerism unsaturated group in acid esters or N- methylols (methyl) acrylamide equimolecular.

Alternatively, it is also possible to use following formula [7A] compound represented.

(in formula [7A], E₁Indicate selected from by cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, Group in the group of fluorenes ring, anthracene nucleus or phenanthrene ring composition, E₂Group of the expression in following formula [7a] or formula [7b], n expressions 1~ 4 integer.)

Above compound is an example of cross-linked compound, but is not limited to them.In addition, the aligning agent for liquid crystal of the present invention The middle cross-linked compound used can be a kind, can also combine two or more.

In the aligning agent for liquid crystal of the present invention, cross-linked compound content is relative to 100 mass of whole component of polymer Part is preferably 0.1~150 mass parts.Wherein, in order to promote cross-linking reaction and embody target effect, relative to whole polymer at Divide 100 mass parts, preferably 0.1~100 mass parts, more preferably 1~50 mass parts.

The aligning agent for liquid crystal of the present invention can use the film thickness for liquid crystal orientation film when improving coating of liquid crystalline alignment agent Uniformity, the compound of surface smoothness.

＜ liquid crystal orientation film liquid crystal indicates element ＞

The liquid crystal orientation film of the present invention is that foregoing liquid crystal alignment agent is applied to film obtained from substrate and drying, firing. As the substrate for wanting coating of liquid crystalline alignment agent, it is not particularly limited as long as the high substrate of the transparency, glass base can be used Plate, silicon nitride board, and plastic bases such as acrylic compounds substrate, polycarbonate substrate etc. can also be used.At this point, from simplification , it is preferable to use being formed with the substrate of ITO electrode for driving liquid crystal etc. from the perspective of technique.In addition, for reflection-type For liquid crystal indicates element, if being only unilateral substrate, opaque substance, the electrodes at this time such as silicon wafer can be used also may be used To use the material of the meeting reflected light such as aluminium.

The coating method of aligning agent for liquid crystal is not particularly limited, and industrial is usually to utilize silk-screen printing, intaglio printing, soft The method of the progress such as version printing or ink-jet method.As other coating methods, there are infusion process, rolling method, slot coated method, spin coating Method or spray coating method etc. can use them according to purpose.

After aligning agent for liquid crystal is coated on substrate, hot plate, thermal cycle type baking oven or IR (infrared ray) type can be utilized to dry The heating meanss such as case make evaporation of the solvent liquid crystal orientation film is made.It is coated with the drying after the aligning agent for liquid crystal of the present invention, firing work Sequence can select arbitrary temperature and time.Generally for the contained solvent of abundant removal, can enumerate：At 50~120 DEG C Lower firing 1~10 minute, later, is burnt into 5~120 minutes conditions at 150~300 DEG C.Liquid crystal orientation film after firing Thickness is not particularly limited, but it is excessively thin when, liquid crystal indicate element reliability reduce sometimes, it is therefore preferable that 5~300nm.Its In, preferably 10~200nm.

As the method for carrying out orientation process to liquid crystal orientation film, aforementioned brushing facture, light orientation processing can be enumerated Method etc..

As the concrete example of light orientation position logos, can enumerate：The surface of liquid crystal orientation film is irradiated along certain orientation The radiation of polarization is according to circumstances further heated at a temperature of 150~250 DEG C, to assign liquid crystal aligning Property (also referred to as liquid crystal aligning ability) method.As radiation, can use ultraviolet light with 100~800nm wavelength or Luminous ray.Wherein, preferably there is the ultraviolet light of the wavelength of 100~400nm, the more preferably purple of the wavelength with 200~400nm Outside line.

In addition, in order to improve liquid crystal aligning, the substrate of liquid crystal orientation film can be coated on one side with 50~250 DEG C into Row heating, one side illumination radiation line.In addition, the exposure of aforementioned radiation line preferably 1²~10000mJ/cm², preferably 100~ 5000mJ/cm²。

In turn, in the present invention, the liquid crystal orientation film that water, solvent control can also be used to have penetrated polarized radiation line is contacted Processing.As the solvent used in contact treatment, as long as the decomposition that dissolving is generated due to irradiation with radiation by liquid crystal orientation film The solvent of object, is just not particularly limited.As concrete example, water outlet, methanol, ethyl alcohol, 2- propyl alcohol, acetone, methyl ethyl ketone, 1- can be enumerated Methoxy-2-propanol, 1- methoxy-2-propanols acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- Methoxy methyl propionate, 3- ethoxyl ethyl propionates, propyl acetate, butyl acetate or cyclohexyl acetate etc..Wherein, from general From the perspective of property, solvent security, preferably water, 2- propyl alcohol, 1- methoxy-2-propanols or ethyl lactate, more preferably water, 1- methoxy-2-propanols or ethyl lactate.These solvents can be a kind, can also combine two or more.

Aforementioned contact in the present invention is handled, i.e., to the liquid crystal orientation film water, the solvent that have irradiated polarized radiation line is carried out Processing, impregnation, spraying treatment (also referred to as spray treatment) can be enumerated.From effectively dissolving due to radiation by liquid crystal From the perspective of the decomposition product that alignment films generate, the processing time in these processing is preferably 10 seconds~1 hour.Wherein, preferably Carry out impregnation in 1 minute~30 minutes.In addition, solvent when aforementioned contact is handled can be room temperature, can also carry out Heating, preferably 10~80 DEG C.Wherein, preferably 20~50 DEG C.In addition, from the viewpoint of the dissolubility of decomposition product, according to It needs that ultrasonication etc. can also be carried out.

After aforementioned contact processing, preferably carry out utilizing the low boilings such as water, methanol, ethyl alcohol, 2- propyl alcohol, acetone or methyl ethyl ketone The cleaning (also referred to as rinsing) of point solvent, the firing for carrying out liquid crystal orientation film.At this point, appointing in can also being rinsed and being burnt into Both one, or carry out.The temperature of firing is preferably 150~300 DEG C.Wherein, preferably 180~250 DEG C, more preferably 200~230 DEG C.In addition, the time of firing is preferably 10 seconds~30 minutes, more preferably 1~10 minute.

The liquid crystal that the liquid crystal orientation film of the present invention is suitable as the Transverse electric-field types such as IPS modes, FFS modes indicates element Liquid crystal orientation film, especially as FFS modes liquid crystal indicate element liquid crystal orientation film for be useful.

The liquid crystal of the present invention indicates that element may be formed：Obtain the liquid crystal that the subsidiary aligning agent for liquid crystal by the present invention obtains After the substrate of alignment films, profit makes liquid crystal cells by known method, and indicates element using the liquid crystal cells to form liquid crystal.

As an example of liquid crystal cells production method, illustrated so that the liquid crystal of passive-matrix structure indicates element as an example. It should be explained that, or each pixel portion for constituting graphical representation be provided with TFT (Thin Film Transistor, it is thin Film transistor) etc. the active matrix structure of conversion elements liquid crystal indicate element.

Specifically, preparing transparent glass substrate of electrode, common electrode (common is set on one substrate Electrode), segment electrode (segment electrode) is set on another substrate.These electrodes can for example be made ITO electrode is patterned to realize desired graphical representation.Then, insulating film is set on each substrate to cover altogether With electrode and segment electrode.Insulating film can such as be made by sol-gel method formed by SiO₂-TiO₂The film of formation.It connects It, under the conditions of above-mentioned, forms liquid crystal orientation film on each substrate, faced on one substrate with mutual liquid crystal orientation film The mode set is overlapped another substrate, and periphery is bonded with sealant.It, usually can be with thing in sealant for control base board gap First it is mixed into spacer.Additionally, it is preferred that also spreading the interval of substrate gap control in advance in the face inside points that sealant is not arranged Object.Being provided in advance in a part for sealant can be from the opening portion of external filling liquid crystal.

Later, by the opening portion being arranged in sealant, liquid is injected into the space surrounded by two plate bases and sealant Brilliant material.Thereafter, which is sealed with bonding agent.Injection can use vacuum impregnation, can also use big The method that capillarity is utilized in gas.As liquid crystal material, appointing in positive type liquid crystal material, negative type liquid crystal material can be used One.Then, the setting of polarizing film is carried out.Specifically, being pasted on the surface with liquid crystal layer opposite side of two plate bases A pair of of polarizing film.

Embodiment

It is exemplified below embodiment and further illustrates the present invention, but the present invention is not limited to them.It needs to illustrate Be, below in use compound abbreviation and each characteristic assay method it is as follows.

NMP：N-methyl-2-pyrrolidone, GBL：Gamma-butyrolacton

BCS：Butyl cellosolve,

DA-1：Bis- (4- amino-benzene oxygens) ethane of 1,2-

DA-2：Reference following formula (DA-2),

DA-3：4,4 '-diamino-diphenylamines,

DA-4：P-phenylenediamine, DA-5：3,5- diaminobenzoic acids

DA-6：Bis- (4- amino-benzene oxygens) methane of 1,2-

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

DAH-2：With reference to following formula (DAH-2), DAH-3：With reference to following formula (DAH-3)

[¹H NMR]

Device：Fourier transform type superconduction nuclear magnetic resonance device (FT-NMR) INOVA-400 (Varian systems) 400MHz

Solvent：Deuterated dimethyl sulfoxide (DMSO-d₆))

Standard substance：Tetramethylsilane (TMS)

Cumulative frequency：8 or 32

[viscosity]

In synthesis example, the viscosity of polyimides and polyamic acid solution uses TVE-22H (the eastern machine industry strains of E type viscosimeters Formula commercial firm system), it is measured at sample size 1.1mL, cone rotor TE-1 (1 ° 34 ', R24), 25 DEG C of temperature.

[molecular weight]

It is measured by GPC (room temperature gel permeation chromatography) device, with polyethylene glycol and polyethylene oxide scaled value Form calculates number-average molecular weight (Mn) and weight average molecular weight (Mw).

GPC devices：Shodex corporations (GPC-101)

Column：Shodex corporations (series connection of KD803, KD805)

Column temperature：50℃

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

Flow velocity：1.0ml/ minute

Standard curve making standard sample：The TSK standard polyethylene oxide (weight average molecular weight of TOSOH Co., Ltd's manufacture (Mw) be about 900000,150000,100000,30000) and Polymer Laboratories Ltd. manufacture poly- second two Alcohol (peak molecular weight (Mp) is about 12000,4000,1000).In order to avoid the overlapping at peak, measure respectively to two kinds of samples below Product are measured：By 900000,100000,12000,1000 this 4 kinds of samples mixed；And by 150000,30000, 4000 this 3 kinds of samples mixed.

[measurement of acid imide rate]

The acid imide rate of polyimides measures as follows.Polyimide powder 20mg is put into (NMR takes to NMR sample cells Sample pipe standards, φ 5 (wasteland section length of schooling)), (DMSO-d6,0.05%TMS (tetramethylsilane) are mixed for addition deuterated dimethyl sulfoxide Conjunction product) (0.53ml), apply ultrasonic wave and makes it completely dissolved.For solution NMR measuring machines (JNW-ECA500) (Japan Electronic Datum systems), measure the proton NMR of 500MHz.Acid imide rate is found out as follows：It will be originated from before imidizate The proton of unchanged structure determines to be used as reference proton afterwards, using the peak integrated value of the proton and in 9.5ppm~10.0ppm The proton peak integrated value of the NH bases from amic acid nearby occurred is found out by the following formula.

Acid imide rate (%)=(1- α x/y) × 100

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

[making of liquid crystal cells]

Making has boundary electric field switching (Fringe Field Switching：Hereinafter referred to as FFS) mode liquid crystal expression The liquid crystal cells of the composition of element.

Prepare electroded substrate first.Substrate is the glass substrate that size is 30mm × 35mm and thickness is 0.7mm. On substrate, as the 1st layer, the ITO electrode of solid shape pattern is formd for structure paired electrode and had.At the 1st layer to electricity On extremely, as the 2nd layer, SiN (silicon nitride) film to form a film using CVD method is formd.Film thickness as the 2nd layer of SiN film is 500nm is functioned as interlayer dielectric.On the SiN film as the 2nd layer, as the 3rd layer, configure ito film figure Case and the comb teeth-shaped pixel electrode formed, to form the 1st pixel and the 2nd pixel the two pixels.The size of each pixel is： Vertical 10mm and horizontal about 5mm.At this point, the 1st layer to electrode is in because of the effect of the 2nd layer of SiN film with the 3rd layer of pixel electrode Electrical isolation.

The comb that 3rd layer of pixel electrode is constituted with " ＜ " shape electrode element that the multiple center portions of arrangement bend Tooth shape.The width of the width direction of each electrode element is 3 μm, between electrode element between be divided into 6 μm.Form the picture of each pixel Plain electrode is " ＜ " shape electrode element that the multiple center portions of arrangement bend and constitutes, therefore the shape of each pixel is not Oblong-shaped, but have the shape of ＜ words bending in center portion in the same manner as electrode element, similar to runic. Also, each pixel is divided up and down by boundary of the bending part in the center, with the 1st region and downside on the upside of bending part 2nd region.

When comparing the 1st region and 2 region of each pixel, the formation direction of the electrode element of their pixel electrode is constituted It is different.That is, using the direction of illumination of rectilinearly polarized light as when benchmark, in the 1st region of pixel ,+10 ° of angle is presented The mode of (clockwise) forms the electrode element of pixel electrode, in the 2nd region of pixel, -10 ° of angle (up time is presented Needle) mode form the electrode element of pixel electrode.That is, following constituted：In the 1st region of each pixel and the 2nd region, by Pixel electrode and apply voltage between electrode and the direction of the spinning movement (plane switching) of the liquid crystal that induces in real estate Opposite direction each other.

Then, with after 1.0 μm of filter filtering gained aligning agent for liquid crystal, by spin coating be coated on prepared it is above-mentioned Electroded substrate and back side film forming have ito film and on the glass substrate highly for 4 μm of column spacer.At 80 DEG C After being dried 2 minutes in heating plate, with 230 DEG C of IR formulas baking oven be burnt within 15 minutes, form the film that film thickness is 100nm.It is right The coated surface implements the orientation process such as brushing, polarized UV rays irradiation, obtains the substrate with liquid crystal orientation film.By above-mentioned two chip base Plate is as one group, the printing and sealing agent on substrate, by another plate base with liquid crystal alignment film surface face-to-face and differently- oriented directivity be 0 ° Mode be bonded after, make sealant cures, to make dummy cell.It is injected in the normal direction dummy cell by decompression and injects liquid Brilliant MLC-7026-100 (MERCK CORPORATION systems) seals inlet, obtains FFS driving liquid crystal cells.Thereafter, by institute It obtains liquid crystal cells to heat 1 hour with 110 DEG C, after placing a night, is used for each evaluation.

[the ghost evaluation caused by long-term exchange driving]

Prepare the liquid crystal cells with the liquid crystal cells same structure used in the evaluation of above-mentioned ghost.

It is small with the alternating voltage 120 of frequency 60Hz applications ± 7V under 60 DEG C of isoperibol using the liquid crystal cells When.Later, it in the state of the pixel electrode and the short circuit between electrode for making liquid crystal cells, directly places one day at room temperature.

After placement, between liquid crystal cells are set to 2 polarizing films configured in such a way that polarizing axis becomes orthogonal, in nothing Backlight is lighted in the state of application voltage, the arrangement angles that least way adjusts liquid crystal cells are become with the brightness of transmitted light. Then, calculating, which makes liquid crystal cells be rotated from the 2nd region of the 1st pixel to the 1st region as most dark angle, becomes most dark angle Rotation angle when spending is as angle delta.Similarly, the 2nd region of comparison and the 1st region calculate same angle to 2nd pixel Δ.Then, angle delta of the average value of the angle delta value of the 1st pixel and the 2nd pixel as liquid crystal cells is calculated, exchange is driven Afterimage Δ is denoted as that " good ", it above is denoted as " bad " less than 0.1.

[voltage retention]

Aligning agent for liquid crystal is spun on the glass substrate with transparent electrode, is passed through 2 minutes on the hot plate of 80 DEG C of temperature Drying, pass through firing in 15 minutes in 230 DEG C of IR formula baking ovens, obtain the film of the imidizate of film thickness 100nm.To the painting Film surface implements orientation process, obtains the substrate with liquid crystal orientation film.Substrate with liquid crystal orientation film as preparing 2, one After spreading 6 μm of spacer in the liquid crystal alignment film surface of a substrate, group is carried out in such a way that the orientation of 2 substrates becomes antiparallel It closes, remains liquid crystal injecting port, surrounding is sealed, the dummy cell that production unit gap is 6 μm.The vacuum in dummy cell at normal temperatures Liquid crystal (MLC-7026-100, MERCK CORPORATION systems) is injected, inlet is sealed, forms liquid crystal cells.By the liquid crystal Unit is placed 5 days under white light and is cured.

For example following progress of the measurement of the voltage retention of above-mentioned liquid crystal cells.

Apply the time of the 60 μ s of voltage of 1V, measure the voltage after 5s, to calculate the variation from initial value as voltage Conservation rate.When measurement, the temperature of liquid crystal cells is set as 60 DEG C and is measured.At this point, being 60% or more by voltage retention Situation is denoted as " good ", less than being denoted as the case where its " bad ".

(synthesis example 1)

In the 1000mL four-hole boiling flasks with agitating device and with nitrogen ingress pipe, bis- (4- amino-benzene oxygens) second of 1,2- are taken NMP 586g are added in alkane 42.75g (175mmol), DA-2 59.7g (175mmol), and being stirred when being sent into nitrogen keeps its molten Solution.1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydrides 74.53g is added when stirring the diamine solution (332.5mmol), and then NMP is added in such a way that solid component concentration becomes 18 mass %, it is stirred at room temperature 24 hours To the solution (viscosity of polyamic acid (PAA-1)：832mPa·s).

(synthesis example 2)

Take the polyamic acid solution (PAA-1) obtained in the 1000mL four-hole boiling flasks with agitating device and with nitrogen ingress pipe NMP 100g are added in 200g, stir 30 minutes.Acetic anhydride 21.78g, pyridine 2.81g are added in gained polyamic acid solution, It is heated 3 hours at 60 DEG C, carries out chemical imidization.Reaction solution obtained by being put into while stirring in the methanol of 624.2g, mistake It filters the sediment being precipitated then to be cleaned 3 times with the methanol of 624.2g, be cleaned 2 times with the methanol of 1248g.By gained resin Powder is 12 hours dry at 60 DEG C, to obtain polyimide resin powder end.The acid imide rate of the polyimide resin is 68%, molecular weight Mn=9189, Mw=18252.

The polyimide resin powder end 32.70g obtained in the 200ml sample cells for add stirrer is taken, NMP is added 239.8g stirs 20 hours at 70 DEG C, makes it dissolve, obtains polyimide solution (SPI-1).

(synthesis example 3)

In the 100mL four-hole boiling flasks with agitating device and with nitrogen ingress pipe, take DA-3 4.30g (21.6mmol) and The 1 of NMP and GBL is added in DA-4 0.58g (5.4mmol)：1 mixed solvent 73.65g, being stirred when being sent into nitrogen makes it Dissolving.DAH-2 7.67g (26.06mmol) are added when stirring the diamine solution, and then become 12 with solid component concentration The 1 of NMP and GBL is added in the mode of weight %：1 mixed solvent is stirred at room temperature 20 hours, obtains polyamic acid (PAA-2) Solution (viscosity：980mPa·s).

(synthesis example 4)

In the 100mL four-hole boiling flasks with agitating device and with nitrogen ingress pipe, take DA-3 2.07g (10.4mmol) and The 1 of NMP and GBL is added in DA-5 0.40g (2.6mmol)：1 mixed solvent 31.52g, being stirred when being sent into nitrogen makes it Dissolving.DAH-2 3.67g (12.5mmol) are added when stirring the diamine solution, and then 12 weights are become with solid component concentration The mode of amount % is added the 1 of NMP and GBL：1 mixed solvent is stirred at room temperature 20 hours, obtains polyamic acid (PAA-3) Solution (viscosity：830mPa·s).

(synthesis example 5)

In the 100mL four-hole boiling flasks with agitating device and with nitrogen ingress pipe, DA-3 2.39g (12.0mmol) are taken, are added Enter the 1 of NMP and GBL：1 mixed solvent 34.12g is stirred when being sent into nitrogen and makes it dissolve.While the diamine solution is stirred DAH-2 3.42g (11.6mmol) are added on side, and then NMP and GBL is added in such a way that solid component concentration becomes 12 weight % 1：1 mixed solvent is stirred at room temperature 20 hours, obtains the solution (viscosity of polyamic acid (PAA-4)：1050mPa·s).

(synthesis example 6)

In the 100mL four-hole boiling flasks with agitating device and with nitrogen ingress pipe, take DA-6 5.71g (24.8mmol) and The 1 of NMP and GBL is added in DA-4 0.67g (6.2mmol)：1 mixed solvent 25.19g, being stirred when being sent into nitrogen makes it Dissolving.DAH-3 2.33g (9.3mmol) are added when stirring the diamine solution, are stirred at room temperature 5 hours.Later, it adds DAH-2 6.13g (20.8mmol), and then it is added the 1 of NMP and GBL in such a way that solid component concentration becomes 15 weight %：1 is mixed Bonding solvent is stirred at room temperature 20 hours, obtains the solution (viscosity of polyamic acid (PAA-5)：867mPa·s).

(synthesis example 7)

In the 100mL four-hole boiling flasks with agitating device and with nitrogen ingress pipe, DA-6 7.14g (31.0mmol) are taken, are added Enter the 1 of NMP and GBL：1 mixed solvent 61.86 is stirred when being sent into nitrogen and makes it dissolve.While the diamine solution is stirred DAH-3 2.33g (9.3mmol) are added on side, are stirred at room temperature 5 hours.Later, addition DAH-2 6.13g (20.83mmol), And then it is added the 1 of NMP and GBL in such a way that solid component concentration becomes 15 weight %：1 mixed solvent, is stirred at room temperature 20 Hour, obtain the solution (viscosity of polyamic acid (PAA-6)：787mPa·s).

(embodiment 1)

In the 50mL conical flasks for adding stirrer, the polyimide solution (SPI-1) obtained in synthesis example 2 is taken NMP 1.92g, GBL 1.89g, BCS is added in polyamic acid solution (PAA-2) 3.89g obtained in 1.84g, synthesis example 3 2.40g obtains aligning agent for liquid crystal (AL-1) with one night of magnetic stirrer.

(embodiment 2)

In the 50mL conical flasks for adding stirrer, the polyimide solution (SPI-1) obtained in synthesis example 2 is taken NMP 1.95g, GBL 1.92g, BCS is added in polyamic acid solution (PAA-3) 3.82g obtained in 1.84g, synthesis example 4 2.40g obtains aligning agent for liquid crystal (AL-2) with one night of magnetic stirrer.

(embodiment 3)

In the 50mL conical flasks for adding stirrer, the polyimide solution (SPI-1) obtained in synthesis example 2 is taken NMP 3.73g, GBL 3.59g, BCS is added in polyamic acid solution (PAA-5) 4.32g obtained in 2.77g, synthesis example 6 3.60g obtains aligning agent for liquid crystal (AL-4) with one night of magnetic stirrer.

(comparative example 1)

In the 50mL conical flasks for adding stirrer, the polyimide solution (SPI-1) obtained in synthesis example 2 is taken NMP 1.89g, GBL 1.85g, BCS is added in polyamic acid solution (PAA-4) 3.96g obtained in 1.84g, synthesis example 4 2.40g obtains aligning agent for liquid crystal (AL-3) with one night of magnetic stirrer.

(comparative example 2)

In the 50mL conical flasks for adding stirrer, the polyimide solution (SPI-1) obtained in synthesis example 2 is taken NMP 3.73g, GBL 3.58g, BCS is added in polyamic acid solution (PAA-6) 4.32g obtained in 2.77g, synthesis example 4 3.60g obtains aligning agent for liquid crystal (AL-5) with one night of magnetic stirrer.

(embodiment 4)

After the aligning agent for liquid crystal (AL-1) obtained in 1.0 μm of filter. EXAMPLE 1, it is coated on by spin coating The above-mentioned electroded substrate prepared and back side film forming have ito film and the glass base with height for 4 μm of column spacer On plate.After drying 2 minutes in 80 DEG C of heating plate, with 230 DEG C of IR formulas baking oven be burnt within 15 minutes, forming film thickness is The film of 100nm.Extinction ratio 26 is irradiated across polarizing film to the coated surface：The ultraviolet light of the wavelength 254nm of 1 linear polarization 0.2J/cm².Make isopropanol/pure water=50/50 solution 5 minutes that the substrate is impregnated in 25 DEG C, is then impregnated in 25 DEG C of pure water 1 minute, with 230 DEG C of IR formulas oven drying 15 minutes, obtain the substrate with liquid crystal orientation film.Using above-mentioned 2 substrates as one Group, the printing and sealing agent on substrate, by another plate base by liquid crystal alignment film surface face-to-face and differently- oriented directivity be 0 ° in a manner of into After row fitting, make sealant cures, to make dummy cell.Injection liquid crystal MLC- in the normal direction dummy cell is injected by decompression 7026-100 (MERCK CORPORATION systems) seals inlet, obtains FFS driving liquid crystal cells.Later, by gained liquid crystal Unit heats 1 hour at 110 DEG C, places a Dinner.

Liquid crystal cells are driven for the FFS, implement the ghost evaluation caused by long-term exchange driving, as a result long-term exchange is driven The value of the angle delta of the liquid crystal cells after dynamic is 0.1 degree hereinafter, being good.

(embodiment 5)

In addition to this method similarly to Example 4 is utilized using the aligning agent for liquid crystal (AL-2) obtained in embodiment 2 It makes FFS and drives liquid crystal cells.

(embodiment 6)

In addition to this method similarly to Example 4 is utilized using the aligning agent for liquid crystal (AL-4) obtained in embodiment 3 It makes FFS and drives liquid crystal cells.

(comparative example 3)

In addition to this method similarly to Example 4 is utilized using the aligning agent for liquid crystal (AL-3) obtained in comparative example 1 It makes FFS and drives liquid crystal cells.

Liquid crystal cells are driven for the FFS, implement the ghost evaluation caused by long-term exchange driving, as a result long-term exchange is driven The value of the angle delta of the liquid crystal cells after dynamic is 0.1 degree or more, is undesirable.

(comparative example 4)

In addition to this method similarly to Example 4 is utilized using the aligning agent for liquid crystal (AL-5) obtained in comparative example 2 It makes FFS and drives liquid crystal cells.Liquid crystal cells are driven for the FFS, implement the ghost evaluation caused by long-term exchange driving, knot The value that fruit exchanges the angle delta of the liquid crystal cells after driving for a long time is 0.1 degree or more, is undesirable.

(embodiment 7)

The aligning agent for liquid crystal (AL-1) obtained in embodiment 1 is spun on the glass substrate with transparent electrode, in temperature Drying on 80 DEG C of hot plate by 2 minutes, the firing in 230 DEG C of IR formula baking ovens by 15 minutes, obtain film thickness 100nm Imidizate film.Extinction ratio 26 is irradiated across polarizing film to the coated surface：The wavelength 254nm's of 1 linear polarization is ultraviolet Line 0.2J/cm².Make in the solution of isopropanol/pure water that the substrate is impregnated in 25 DEG C=50,/50 5 minutes, is then impregnated in 25 DEG C 1 minute in pure water, with 230 DEG C of IR formulas oven drying 15 minutes, the substrate with liquid crystal orientation film is obtained.Prepare as 2 Substrate with liquid crystal orientation film, after spreading 6 μm of spacer in the liquid crystal alignment film surface of a substrate, with taking for 2 substrates It is combined to as antiparallel mode, remains liquid crystal injecting port, surrounding is sealed, the sky that production unit gap is 6 μm is single Member.Vacuum injection liquid crystal (MLC-7026-100, the MERCK CORPORATION systems) in the dummy cell at normal temperatures, will inject Mouth sealing, forms liquid crystal cells.The liquid crystal cells are placed 5 days under white light and are cured.

Above-mentioned liquid crystal cells are applied with the time of the 60 μ s of voltage of 1V, measures the voltage after 5s, so as to find out from initial value Variation as voltage retention.When said determination, the temperature of liquid crystal cells is set as 60 DEG C and is measured.At this point, voltage is protected Holdup is 60% or more, is good.

(embodiment 8)

In addition to this method similarly to Example 7 is utilized using the aligning agent for liquid crystal (AL-2) obtained in embodiment 2 Make liquid crystal cells.Above-mentioned liquid crystal cells are applied with the time of the 60 μ s of voltage of 1V, measures the voltage after 5s, so as to find out from just The variation of initial value is as voltage retention.When said determination, the temperature of liquid crystal cells is set as 60 DEG C and is measured.At this point, electric It is 60% or more to press conservation rate, is good.

(embodiment 9)

In addition to this method similarly to Example 7 is utilized using the aligning agent for liquid crystal (AL-4) obtained in embodiment 3 Make liquid crystal cells.

(comparative example 5)

In addition to this method similarly to Example 7 is utilized using the aligning agent for liquid crystal (AL-3) obtained in comparative example 1 Make liquid crystal cells.

Above-mentioned liquid crystal cells are applied with the time of the 60 μ s of voltage of 1V, measures the voltage after 5s, so as to find out from initial value Variation as voltage retention.When said determination, the temperature of liquid crystal cells is set as 60 DEG C and is measured.At this point, voltage is protected Holdup is less than 60%, is undesirable.

(comparative example 6)

In addition to this method similarly to Example 7 is utilized using the aligning agent for liquid crystal (AL-5) obtained in comparative example 2 Liquid crystal cells are made.

[table 1]

[table 2]

Industrial availability

The liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention is especially as IPS type of drive, FFS type of drive Liquid crystal indicate element, LCD TV liquid crystal orientation film be useful.

It should be noted that by the specification of Japanese patent application filed in 30 days November in 2015 2015-233844, Claims, drawings and abstract full content introduce so far, as the present invention specification disclosure be introduced into.

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that contain：Following (A) ingredients and following (B) ingredients,

(A) ingredient：Selected from by make tetracarboxylic dianhydride's ingredient and diamine component carry out polyimide precursor obtained from polycondensation reaction, At least one kind of polymer in the group formed with the polyimides of the acid imide compound as the polyimide precursor, the diamines Ingredient contains selected from being made of the diamines of the diamines of the structure with following formula [A-1] and the structure with following formula [A-2] At least one kind of diamines in group,

In formula [A-1], R¹、R²It is each independently hydrogen atom, the alkyl of carbon number 1~4 or hydrogen atom is substituted by by heat Heat leaving away property group, it is therein at least one be leaving away property of the heat group, in formula [A-2], R₁、R₂、R₃And R₄Each independently For hydrogen atom or the alkyl of optional 1 valence of the carbon number 1~20 with substituent group, D be by heat be substituted by hydrogen atom it is hot from Going property group,

(B) ingredient：Make containing tetracarboxylic dianhydride's ingredient of tetracarboxylic dianhydride shown in following formula (B-1) and containing shown in (B-2) two The diamines of amine carries out polyamic acid obtained from polycondensation reaction,

In formula (B-2), R₅For hydrogen atom or COOH bases, B₁~B₂It is each independently hydrogen atom or the optionally tool with substituent group There are carbon number 1~10, alkyl, alkenyl or alkynyl.

2. aligning agent for liquid crystal according to claim 1, wherein the diamines following formula of the structure with the formula [A-1] [A-1-1] is indicated, the diamines of the structure with the formula [A-2] is indicated with following formula [A-2-1],

R¹And R²It is each independently hydrogen atom, the alkyl of carbon number 1~4 or heat the leaving away property base of hydrogen atom is substituted by by heat Group, and it is therein at least one to be substituted by heat the leaving away property group of hydrogen atom by heat, m, n are each independently 0~3, Wherein, in formula (1), A is the group of singly-bound or the divalent formed by the alkyl of carbon number 1~4,

A¹、A⁵It is each independently the alkylidene of singly-bound or carbon number 1~5, A²And A⁴For the alkylidene of carbon number 1~5, A³For carbon number 1 ~6 alkylidene or cycloalkylidene, B¹、B²It is each independently singly-bound ,-O- ,-NH- ,-NMe- ,-C (=O)-,-C (=O) O- ,-C (=O) NH- ,-C (=O) NMe- ,-OC (=O)-,-NHC (=O)-or-N (Me) C (=O)-, D₁To be taken by heat On behalf of heat the leaving away property group of hydrogen atom, a is 0 or 1.

3. aligning agent for liquid crystal according to claim 1 or 2, wherein the tetracarboxylic dianhydride of the raw material as (A) ingredient Ingredient is tetracarboxylic dianhydride shown in following formula [4],

Z indicates at least one kind of structure in the group being made of following formula [4a]~formula [4q],

In formula [4a], Z¹~Z⁴Each independently represent hydrogen atom, methyl, ethyl, propyl, chlorine atom or phenyl ring, in formula [4g], Z⁵And Z⁶Each independently represent hydrogen atom or methyl.

4. aligning agent for liquid crystal according to claim 3, wherein the Z in the formula [4] is to select free style [4a], formula [4e] It is at least one kind of in the group that~formula [4g], formula [4l], formula [4m] and formula [4p] form.

5. aligning agent for liquid crystal according to any one of claims 1 to 4, wherein leaving away property of the heat group is following formula (1) group shown in,

A is the alkyl of singly-bound or carbon number 1~4.

6. aligning agent for liquid crystal according to any one of claims 1 to 5, wherein in formula (B) ingredient, including opposite The tetracarboxylic dianhydride shown in the formula (B-1) that tetracarboxylic dianhydride's ingredient is 10~100 moles of %.

7. according to aligning agent for liquid crystal according to any one of claims 1 to 6, wherein in (B) ingredient, including relative to Diamine component is diamines shown in the formula (B-2) of 10~100 moles of %.

8. aligning agent for liquid crystal according to any one of claims 1 to 7, wherein diamines shown in the formula (B-2) be selected from It is at least one kind of in the group that the diamines shown in following formula forms,

9. according to aligning agent for liquid crystal according to any one of claims 1 to 8, wherein (B) ingredient is relative to (A) 100 mass parts of ingredient are 40~400 mass parts.

10. aligning agent for liquid crystal according to claim 9 is used to form the liquid crystal orientation film of light orientation processing.

11. a kind of liquid crystal orientation film is obtained by aligning agent for liquid crystal according to any one of claims 1 to 10.

12. a kind of liquid crystal indicates element, with the liquid crystal orientation film described in claim 11.