CN103797409B

CN103797409B - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: CN103797409B
Application number: CN201280044376.1A
Authority: CN
Inventors: 石井秀则; 小野豪
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2011-07-14
Filing date: 2012-07-13
Publication date: 2017-05-24
Anticipated expiration: 2032-07-13
Also published as: JP5633714B2; JPWO2013008906A1; TW201309784A; KR101610559B1; CN103797409A; TWI499656B; KR20140041834A; WO2013008906A1

Abstract

The invention provides a liquid crystal aligning agent. The liquid crystal aligning agent comprises a polyamic acid that is obtained by a reaction between a tetracarboxylic acid dianhydride component and a diamine component. The tetracarboxylic acid dianhydride component contains a tetracarboxylic acid dianhydride having an alicyclic structure or an aliphatic structure. The diamine component contains a diamine having a urea structure and a diamine having a secondary amine at a polymerization reaction site.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Technical field

The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells.

Background technology

At present, liquid crystal display cells are by widely used as display device.As the member of formation of liquid crystal display cells In the case that liquid crystal orientation film is the film for making liquid crystal evenly distributed, but liquid crystal aligning deficiency, easily trigger display uneven and residual The display defects such as shadow.The generation of display defect might have ionic impurity in liquid crystal and participate in, used as making what the impurity was reduced Method, proposes just like the grade motion of patent document 1.

Additionally, in liquid crystal orientation film, it is general to use with the orientation process for being referred to as friction on cloth friction polymeric membrane surface.But It is that, if the friction tolerance of liquid crystal orientation film is not enough, film is ground and produces scar and dust, or film is peeled off in itself, is led The display quality of liquid crystal display cells is caused to decline.It is therefore desirable to liquid crystal orientation film has friction tolerance high, propose just like patent Method shown in document 2~5.

It is also known that Accumulating charge is difficult mitigation, ghost disappearance consumption if the specific insulation of liquid crystal orientation film is high Time taking problem.Method as ghost extinction time is shortened, proposes just like the use specific insulation shown in patent document 6 The method of low liquid crystal orientation film.

Prior art literature

Patent document

Patent document 1:Japanese Patent Laid-Open 2002-323701 publications

Patent document 2:Japanese Patent Laid-Open 7-120769 publications

Patent document 3:Japanese Patent Laid-Open 9-146100 publications

Patent document 4:Japanese Patent Laid-Open 2008-90297 publications

Patent document 5:Japanese Patent Laid-Open 9-258229 publications

Patent document 6:International Publication No. 2004/053583

The summary of invention

The technical problems to be solved by the invention

In recent years as liquid crystal display cells the exploitation of one of type of drive FFS (fringe field switching, Fringe Field Switching) in mode, have been found that using the low liquid crystal orientation film of specific insulation, then being relaxed to Accumulating charge Time is short, but electric charge is easily gathered.In the case of the liquid crystal display cells of the FFS modes that electric charge is easily gathered, even if confirming short The driving of time, also easily produces ghost.

Meet as various needed for liquid crystal display cells it is an object of the invention to provide while solving the above problems The liquid crystal orientation film of characteristic.That is, it is an object of the invention to provide with good liquid crystal orientation film and friction tolerance, ion Density is small and FFS mode liquid crystal display cells in the few liquid crystal orientation film of Accumulating charge.

Additionally, the aligning agent for liquid crystal of above-mentioned liquid crystal orientation film can be obtained the present invention also aims to provide.

In addition, the present invention also aims to provide display quality good liquid crystal display cells.

Solve the technical scheme that technical problem is used

The present inventor to achieve these goals and is conscientiously studied, and is as a result found by comprising using with alicyclic ring The diamines that the tetracarboxylic dianhydride of race's structure or aliphatic structure, the diamines with urea structure and polymerisation position have secondary amine is obtained The aligning agent for liquid crystal of the polyamic acid for arriving, is capable of achieving above-mentioned purpose.

Thus, the present invention includes following technology contents.

1. aligning agent for liquid crystal, wherein, comprising the polyamide obtained by the reaction of tetracarboxylic dianhydride's composition and diamine component Acid, tetracarboxylic dianhydride's composition includes the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure, the diamine component There is the diamines of secondary amine including the diamines with urea structure and polymerisation position.

2. the aligning agent for liquid crystal as described in 1, it is characterised in that in tetracarboxylic dianhydride's composition, including 50 moles of more than % Tetracarboxylic dianhydride with alicyclic structure or aliphatic structure.

3. the aligning agent for liquid crystal as described in 1 or 2, it is characterised in that in diamine component, including 10~70 moles of polymerizations of % Reactive site has the diamines of secondary amine.

4. the aligning agent for liquid crystal as described in any one of 1~3, it is characterised in that in diamine component, including 10~70 rub The diamines with urea structure of your %.

5. the aligning agent for liquid crystal as described in any one of 1~4, it is characterised in that polymerisation position has secondary amine Diamines is the diamines represented with following formula (1)；

[changing 1]

In formula (1), X represents aromatic rings, R¹Represent the alkylidene of carbon number 1~5, R²Represent the alkyl of carbon number 1~4.

6. the aligning agent for liquid crystal as described in any one of 1~5, it is characterised in that the diamines with urea structure is following The diamines that formula (2) is represented；

[changing 2]

In formula (2), Y represents oxygen atom or sulphur atom, R³、R⁴Independently represent the alkylidene of carbon number 1~3, Z¹、 Z²Independently represent singly-bound ,-O- ,-S- ,-OCO- or-COO-.

7. liquid crystal orientation film, it is characterised in that obtained using any one of 1~6 described aligning agent for liquid crystal.

8. liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in 7.

The effect of invention

If using the present invention, can provide with highly oriented control function, the i.e. good liquid crystal aligning for liquid crystal Property and with height friction tolerance, be made liquid crystal display cells when ion concentration is small, the product in FFS mode liquid crystal display cells The few aligning agent for liquid crystal of poly- electric charge, the liquid crystal orientation film obtained using the aligning agent for liquid crystal, and possess the liquid crystal orientation film Liquid crystal display cells.

The mode for carrying out an invention

Aligning agent for liquid crystal of the invention includes the polyamic acid for making diamine component be reacted with tetracarboxylic dianhydride's composition and obtaining. In addition, in the present invention, including that there is alicyclic structure or aliphatic knot as tetracarboxylic dianhydride's composition of the raw material of polyamic acid The tetracarboxylic dianhydride of structure, the diamine component as the raw material of polyamic acid includes the diamines with urea structure and polymerisation position Diamines with secondary amine.Diamines included by tetracarboxylic dianhydride and diamine component included by tetracarboxylic dianhydride's composition respectively can be with It is one or more.

Hereinafter, the tetracarboxylic dianhydride included by the diamines included by diamine component and tetracarboxylic dianhydride's composition is carried out in detail Explanation.

In diamine component as the raw material of the polyamic acid contained by aligning agent for liquid crystal of the invention, as must be into subpackage The specific example that the polymerisation position for including has the diamines of secondary amine can enumerate the diamines for for example being represented with following formula (1).Certainly, two Amine component may include the diamines represented with formula (1), or the diamines including being represented with formula (1) and with diamines that formula (1) is represented with Outer polymerisation position has the diamines of secondary amine.Polymerisation position refers to the position reacted with tetracarboxylic dianhydride's composition, is gathered The secondary amine, i.e.-NH- that closing reactive site has the diamines of secondary amine reacts with tetracarboxylic dianhydride's composition.

[changing 3]

X in formula be in order that there is the diamines of secondary amine to possess the position at aromatic amine position at polymerisation position, therefore As long as aromatic rings, is not particularly limited.From the point of view of the viewpoints such as the difficulty for obtaining and synthesizing, liquid crystal aligning from raw material, X Preferably phenylene, naphthylene, from from the perspective of versatility, particularly preferably phenylene.In the case that X is phenylene, i.e., H₂In the case that N-X is aminobenzene, R¹The position of substitution be preferably meta or para position.

R¹Represent the alkylidene of carbon number 1~5.From the viewpoint of being assigned from the dissolubility of polymer (polyamic acid), R¹As long as It is that in the range of the carbon number, with branch or ring structure can be used, from liquid crystal aligning and the viewpoint of friction tolerance From the point of view of, preferably linear chain structure, from reagent obtain difficulty from the viewpoint of, particularly preferably carbon number is 1 or 2 alkylidene.

R²The alkyl of carbon number 1~4 is represented, straight chain or branched structure can be used.On the other hand, from liquid crystal aligning and two From the viewpoint of the reactivity of amine, preferably as small as possible group, particularly preferably methyl and ethyl.

The preferred example of the diamines represented with formula (1) described below, it is not limited to these examples.

[changing 4]

It is preferably whole diamine components that the polymerisation positions such as the diamines represented with formula (1) have the content of the diamines of secondary amine 10~70 moles of %, from from the viewpoint of taking into account friction tolerance high and few accumulated charge amounts, more preferably 15~65 moles %, Particularly preferably 20~60 moles of %.

In diamine component as the raw material of the polyamic acid contained by aligning agent for liquid crystal of the invention, as must be into subpackage The specific example of the diamines with urea structure for including can enumerate the diamines represented with following formula (2).Certainly, diamine component may include with Beyond the diamines that formula (2) is represented, or the diamines including being represented with formula (2) and the diamines that is represented with formula (2) with urea structure Diamines.

[changing 5]

It is urea groups in formula (2), when Y is oxygen atom, for ghiourea group (is below also united urea groups and ghiourea group when Y is sulphur atom Referred to as (sulphur) urea groups).In addition, urea groups and ghiourea group are urea structure.

Here, oxygen atom and sulphur atom are electronegativity atom high.Additionally, there is two donors hydrogen high on nitrogen-atoms Atom.Therefore, the oxygen atom or sulphur atom of (sulphur) urea groups form non-covalent bond with two hydrogen atoms of other (sulphur) urea groups, so that Self aggregation strongly.In the present invention, the urea structure of the diamines with urea structure is preferably urea groups, and the Y in formula (2) is preferably oxygen Atom.If because oxygen atom and sulphur atom are compared, the electronegativity of oxygen atom is higher, thus with thiocarbamide structure Compare, urea structure is easier strength self aggregation.In addition, aligning agent for liquid crystal of the invention is in macromolecular chain (polyamic acid chain) Possesses (sulphur) urea groups from diamines with urea structure such as the diamines represented with formula (2).Therefore, by between (sulphur) urea groups Electrostatic interaction (non-covalent bond), can make friction tolerance improve.In this respect, in the present invention and liquid crystal orientation film field What is typically used is different by will improve the method for friction tolerance between strand with crosslinking agent connection.

In formula (2), R³And R⁴The alkylidene of carbon number 1~3 is independently represented, during its structure can be straight chain or branched chain Any one.As specific example, methylene, ethylidene, 1,3- propylidene, 1- methyl ethylidene, 2- methyl Asia second can be enumerated Base etc..Wherein, from from the viewpoint of liquid crystal aligning and friction tolerance, preferably have as far as possible and rotate freely position and position The small structure of resistance, specific preferably methylene, ethylidene, 1,3- propylidene.

In formula (2), Z¹And Z²It is each independently singly-bound ,-O- ,-S- ,-OCO- or-COO-.For Z¹And Z²Structure, from From the viewpoint of liquid crystal aligning and friction tolerance, be also preferably as soft as possible and the small structure of steric hindrance, preferably singly-bound ,- O- or-S-.

From form film density film high and for forming the angle of stronger liquid crystal orientation film, (sulphur) urea groups and phenyl ring it Between structure be preferably symmetrical centered on (sulphur) urea groups, preferably-R³-Z¹- and-R⁴-Z²- it is same structure.Additionally, with formula (2) In the diamines of expression, the compound for preferably being represented with following formulas (2-a)~formula (2-c).In formula (2-a), R¹¹And R²¹It is The alkylidene of the equal carbon number 1~3 of carbon number.Additionally, in formula (2-b), R¹²And R²²It is the Asia of the mutually different carbon number 1~3 of carbon number Alkyl.In addition, in formula (2-c), R¹³And R²³It is each independently the alkylidene of carbon number 1~3.

[changing 6]

In formula (2), the amino (- NH on phenyl ring₂) binding site be not particularly limited, but come from the viewpoint of liquid crystal aligning See, preferably 3- aminophenyls structure or 4- aminophenyl structures, particularly preferably 4- aminophenyls structure.For example, formula (2) is preferably It is any one in following formula (2-1), formula (2-2) or formula (2-3), particularly preferably formula (2-1).Formula (2-1), formula (2-2) and formula In (2-3), Z¹、Z²、R³And R⁴It is synonymous with definition in formula (2).

[changing 7]

As the specific example of formula (2), the compound represented with formula (2-4)~formula (2-15) is shown.Wherein, particularly preferably The diamines that use is represented with above-mentioned (2-8)~formula (2-11).

[changing 8]

The content of the diamines represented with formula (2) is preferably 10~70 moles of % of whole diamine components, from taking into account friction high From the viewpoint of tolerance and few accumulated charge amounts, more preferably 15~65 moles %, particularly preferably 20~60 moles of %.

In aligning agent for liquid crystal of the invention, as long as not destroying effect of the invention, as the diamines of the raw material of polyamic acid Composition in addition to above-mentioned polymerisation position has the diamines of secondary amine and the diamines with urea structure, can also comprising other two Amines.Hereinafter, the specific example of other diamine compounds is enumerated.

2,3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl-p-phenylenediamines, p-phenylenediamine, m-phenylene diamine (MPD), 2 can be enumerated, 4- dimethyl-m-phenylenediamines, 2,5- diaminotoluenes, 2,6- diaminotoluenes, 2,5- diaminophenols, 2,4- diaminophenols, 3,5- diaminophenols, 3,5- diaminourea benzylalcohol, 2,4- diaminourea benzylalcohol, 4,6- diamino resorcins, 4,4'- diaminourea connection Benzene, 3,3'- dimethyl -4,4'- benzidines, 3,3'- dimethoxy-4 's, 4'- benzidines, 3,3'- dihydroxy -4, The fluoro- 4,4'- benzidines of 4'- benzidines, 3,3'- bis-, 3,3'- trifluoromethyl -4,4'- benzidines, 3,4'- bis- Aminobphenyl, 3,3'- benzidines, 2,2'- benzidines, 2,3'- benzidines, 4,4'- diamino-diphenyl first Alkane, 3,3'- diaminodiphenyl-methanes, 3,4'- diaminodiphenyl-methanes, 2,2'- diaminodiphenyl-methanes, 2,3'- bis- Aminodiphenylmethane, 4,4'- diamino-diphenyls ether, 3,3'- diamino-diphenyls ether, 3,4'- diamino-diphenyls ether, 2, It is 2'- diamino-diphenyls ether, 2,3'- diamino-diphenyls ether, 4,4'- sulfonyldianilines, 3,3'- sulfonyldianilines, double (4- aminophenyls) silane, double (3- aminophenyls) silane, dimethyl-bis- (4- aminophenyls) silane, dimethyl-bis- (3- ammonia Base phenyl) silane, 4,4'- diamino diphenyl sulfides, 3,3'- diamino diphenyl sulfides, 4,4'- diamino-diphenyls amine, 3,3'- diamino-diphenyls amine, 3,4'- diamino-diphenyls amine, 2,2'- diamino-diphenyls amine, 2,3'- diamino-diphenyls Amine, N- methyl (4,4'- diamino-diphenyls) amine, N- methyl (3,3'- diamino-diphenyls) amine, N- methyl (3,4'- diaminourea Diphenyl) amine, N- methyl (2,2'- diamino-diphenyls) amine, N- methyl (2,3'- diamino-diphenyls) amine, 4,4'- diaminourea Benzophenone, 3,3'- diaminourea benzophenone, 3,4'- diaminourea benzophenone, 1,4- diaminonaphthalenes, 2,2'- diaminourea benzophenone, 2, 3'- diaminourea benzophenone, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- diaminonaphthalenes, 1,8- diaminonaphthalenes, 2,5- diaminos Double (4- aminophenyls) ethane of base naphthalene, 2,6- diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, 1,2-, the double (3- of 1,2- Aminophenyl) ethane, double (4- aminophenyls) propane of 1,3-, double (3- aminophenyls) propane of 1,3-, double (the 4- aminobenzenes of 1,4- Base) butane, double (3- aminophenyls) butane of 1,4-, double (3,5- diethyl -4- aminophenyls) methane, double (the 4- aminobenzenes of 1,4- Epoxide) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, double (4- aminophenyls) benzene of 1,4-, 1,3- double (4- aminophenyls) benzene, 1,4- Double (the 4- amino propoxyl group) benzene of double (4- aminobenzyls) benzene, 1,3-, 4,4'- [1,4- phenylenes are double (methylene)] diphenylamines, 4, 4'- [1,3- phenylenes are double (methylene)] diphenylamines, 3,4'- [1,4- phenylenes are double (methylene)] diphenylamines, 3,4'- [1,3- Phenylene is double (methylene)] diphenylamines, 3,3'- [1,4- phenylenes are double (methylene)] diphenylamines, [1,3- phenylenes are double for 3,3'- (methylene)] diphenylamines, 1,4- phenylenes double [(4- aminophenyls) ketone], double [(3- aminophenyls) first of 1,4- phenylenes Ketone], 1,3- phenylenes double [(4- aminophenyls) ketone], 1,3- phenylenes double [(3- aminophenyls) ketone], 1,4- phenylenes Double (PABA esters), 1,4- phenylenes double (3- Aminobenzoates), 1,3- phenylenes double (PABA esters), 1,3- phenylenes double (3- Aminobenzoates), double (4- aminophenyls) phthalic acid esters, double (3- aminophenyls) neighbour benzene two Formic acid esters, double (4- aminophenyls) isophthalic acid esters, double (3- aminophenyls) isophthalic acid esters, N, N'- (1,4- Asias benzene Base) double (4- aminobenzamides), N, N'- (1,3- phenylenes) double (4- aminobenzamides), N, N'- (1,4- phenylenes) is double (3-AB), N, N'- (1,3- phenylenes) double (3-ABs), N, N'- double (4- aminophenyls) neighbour's benzene Diformamide, N, N'- couples of (3- aminophenyls) phthalic amide, N, N'- double (4- aminophenyls) isophtalamide, N, Double (3- aminophenyls) isophtalamides of N'-, double (4- aminophenyls) anthracenes of 9,10-, double (4- amino-benzene oxygens) hexichol of 4,4'- Double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of double [4- (4- amino-benzene oxygens) phenyl] propane of base sulfone, 2,2'-, 2,2'-, Double (4- aminophenyls) HFC-236fas of 2,2'-, double (3- aminophenyls) HFC-236fas of 2,2'-, the double (3- amino -4- methyl of 2,2'- Phenyl) HFC-236fa, double (4- aminophenyls) propane of 2,2'-, double (3- aminophenyls) propane of 2,2'-, 2,2'- it is double (3- amino- 4- aminomethyl phenyls) propane, double (4- amino-benzene oxygens) propane of 1,3-, double (3- amino-benzene oxygens) propane of 1,3-, double (the 4- ammonia of 1,4- Phenoxyl) butane, double (3- amino-benzene oxygens) butane of 1,4-, double (4- amino-benzene oxygens) pentanes of 1,5-, double (the 3- amino of 1,5- Phenoxy group) pentane, double (4- amino-benzene oxygens) hexanes of 1,6-, double (3- amino-benzene oxygens) hexanes of 1,6-, double (the 4- aminobenzenes of 1,7- Epoxide) heptane, double (3- amino-benzene oxygens) heptane of 1,7-, double (4- amino-benzene oxygens) octanes of 1,8-, double (the 3- aminobenzene oxygen of 1,8- Base) octane, double (4- amino-benzene oxygens) nonanes of 1,9-, double (3- amino-benzene oxygens) nonanes of 1,9-, double (the 4- aminobenzene oxygen of 1,10- Base) decane, double (3- amino-benzene oxygens) decane of 1,10-, double (4- amino-benzene oxygens) hendecanes of 1,11-, double (the 3- amino of 1,11- Phenoxy group) hendecane, double (4- amino-benzene oxygens) dodecanes of 1,12-, 1,12- double (3- amino-benzene oxygens) dodecane, double (4- ammonia Butylcyclohexyl) methane, double (4- amino -3- methylcyclohexyls) methane, 1,3- diaminopropanes, 1,4- diaminobutanes, 1,5- 1,5-DAP, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonanes, 1,10- Diamino decane, 1,11- diamino undecanes, 1,12- diamino dodecanes etc..

Other diamine compounds exemplified as above can be tolerated according to specific insulation when being made liquid crystal orientation film, friction The characteristic such as property, ion concentration characteristic, transmissivity, liquid crystal aligning, voltage retention performance and Accumulating charge, using one or two It is mixed above to use.

As in tetracarboxylic dianhydride's composition of the raw material of the polyamic acid contained by aligning agent for liquid crystal of the invention as required The tetracarboxylic dianhydride with alicyclic structure or aliphatic structure included by composition is, for example, the tetracarboxylic acid represented with following formula (3) Acid dianhydride.Certainly, tetracarboxylic dianhydride's composition may include the tetracarboxylic dianhydride represented with formula (3), or including being represented with formula (3) The tetrabasic carboxylic acid two with alicyclic structure or aliphatic structure beyond tetracarboxylic dianhydride and the tetracarboxylic dianhydride represented with formula (3) Acid anhydride.In addition, it may further comprise tetracarboxylic dianhydride with alicyclic structure or aliphatic structure and with alicyclic structure or fat Tetracarboxylic dianhydride beyond the tetracarboxylic dianhydride of race's structure.

Here, in formula (3), R⁵Represent the 4 valency alkyl with alicyclic structure or aliphatic structure.Alicyclic structure is for example Do not have the structure with carbocyclic ring of armaticity for cycloalkane, cycloolefin etc..Additionally, aliphatic structure is, for example, with alkanes hydrocarbon The structure of the chain alkyl such as base, olefines alkyl, acetylene class alkyl (for example, the carbon number of chain alkyl adds up to more than 4).As R⁵Specific example, the 4 valency groups represented with following formulas (3-1)~formula (3-30) can be enumerated.

[changing 9]

[changing 10]

[changing 11]

[changing 12]

In polyamic acid contained by aligning agent for liquid crystal of the invention, preferably 50 moles of more than % of tetracarboxylic dianhydride's composition, Preferably 70 moles % are above is formula (3-1)~formula (3-25) and formula (3-30) are such with alicyclic structure or aliphatic knot The R of structure⁵.The voltage retention of liquid crystal display cells can be improved into being grouped into by using such, accumulation can be particularly reduced The quantity of electric charge.In addition, using R⁵In these alicyclic structures or aliphatic structure selected from formula (3-1), formula (3-2), formula (3-6), In the case of the tetracarboxylic dianhydride of formula (3-25) and formula (3-30), the less liquid crystal orientation film of accumulated charge amounts can be obtained.

Tetracarboxylic dianhydride's composition is preferably including aromatic tetracarboxylic acid's dianhydride.Thus, the orientation of liquid crystal orientation film can be made It is improved particularly.At this moment, if using excessive aromatic tetracarboxylic acid's dianhydride relative to the total amount of tetracarboxylic dianhydride's composition, can go out Now friction deteriorated durability and cause the display quality of liquid crystal display cells to decline.Accordingly, with respect to tetracarboxylic dianhydride's composition Total amount, aromatic tetracarboxylic acid's dianhydride is preferably 50 moles of below %, more preferably 30 moles below %.As aromatic tetracarboxylic acid two Acid anhydride, can enumerate the tetracarboxylic dianhydride represented with following formula (4).In formula (4), R⁶It is the group with aromatic structure.Aromatic series knot Structure refers to the structure of the aromatic rings that armaticity is presented with phenyl ring etc..As R⁶Specific example, can enumerate with following formula (3- 31) the 4 valency groups that~formula (3-47) is represented.

[changing 13]

[changing 14]

Above-mentioned diamine component is set to react to obtain this hair with tetracarboxylic dianhydride's composition (also abbreviation tetracarboxylic dianhydride below) The method of the polyamic acid contained by bright aligning agent for liquid crystal is not particularly limited, can be using known method.Typically, can by Hybrid diamine composition makes it carry out polymerisation to be made polyamic acid with tetracarboxylic dianhydride's composition in organic solvent.

Method as making tetracarboxylic dianhydride's composition mix in organic solvent with diamine component, can enumerate stirring makes diamines Composition directly or after being dispersed or dissolved in organic solvent adds tetrabasic carboxylic acid after being dispersed or dissolved in solution obtained by organic solvent The method of two anhydride components, diamine component obtained added to making tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent on the contrary Solution method, method etc. of alternately addition tetracarboxylic dianhydride's composition and diamine component.Additionally, tetracarboxylic dianhydride's composition and two In the case that at least one party in amine component includes multiple compounds, it can be made in the state of this Multiple components is pre-mixed Carry out polymerisation, it is also possible to carry out polymerisation successively respectively.

Temperature when making tetracarboxylic dianhydride's composition and diamine component carry out polymerisation in organic solvent is usually 0~ 150 DEG C, more preferably preferably 5~100 DEG C, 10~80 DEG C.Temperature is higher, then polymerisation terminates sooner, but if temperature mistake It is high, it is likely that the polymer (polyamic acid) of HMW cannot be obtained.Additionally, polymerisation can be dense arbitrarily to feed Degree is carried out, if but dosage concentration is too low, it is difficult to obtain the polymer of HMW, if dosage concentration is too high, reaction solution Viscosity is excessive, it is difficult to stir, preferably 1~50 mass %, more preferably 5~30 mass %.The initial stage of polymerisation is in height Carried out under concentration, can behind add organic solvent.Additionally, dosage concentration refers to the conjunction of tetracarboxylic dianhydride's composition and diamine component Meter mass concentration.

As long as the organic solvent used in above-mentioned reaction can dissolve the polyamic acid of generation, do not limit particularly It is fixed.As specific example, DMF, DMA, METHYLPYRROLIDONE, N- can be enumerated Methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide or gamma-butyrolacton etc..They can be single Solely use, it is also possible to be used in mixed way.Even in addition, cannot make polyamic acid dissolve solvent, generation polyamic acid not In the range of separating out, can mix into above-mentioned solvent and use.

Moisture in organic solvent hinders polymerisation, the polyamic acid hydrolysis of generation is also resulted in, so organic solvent The solvent after being dehydrated preferably is used as far as possible.

For obtaining tetracarboxylic dianhydride's composition of the polymerisation of polyamic acid and the ratio of diamine component with molar ratio computing Preferably 1:0.8~1:1.2, the mol ratio is closer to 1:1, then the molecular weight of the polyamic acid of gained is bigger.Polyamic acid If molecular weight is too small, may be not enough by its painting film strength for obtaining, if the molecular weight of opposite polyamic acid is excessive, The viscosity of the aligning agent for liquid crystal being then produced from it is too high, and the workability, the uniformity of film when film is formed may be deteriorated.Cause This, the weight average molecular weight of the polyamic acid that aligning agent for liquid crystal of the invention is used is preferably 2000~500000, and more preferably 5000 ~300000.

Aligning agent for liquid crystal of the invention includes more than a kind polyamic acid for as above obtaining.By using comprising by such The aligning agent for liquid crystal of the polyamic acid that specific diamine component is obtained with the reaction of specific tetracarboxylic dianhydride's composition, as be described hereinafter Shown in embodiment, can obtain with good liquid crystal aligning and friction tolerance, ion concentration be small and FFS mode liquid crystal displays The few liquid crystal orientation film of Accumulating charge in element.Aligning agent for liquid crystal of the invention is generally used is dissolved in above-mentioned polyamic acid The coating fluid of organic solvent, but as long as uniform film can be formed on substrate, aligning agent for liquid crystal of the invention can be Other forms.

Additionally, in aligning agent for liquid crystal of the invention, as long as not destroying effect of the invention, as component of polymer, in bag Containing by it is above-mentioned including the tetracarboxylic dianhydride's composition with alicyclic structure or the tetracarboxylic dianhydride of aliphatic structure with include Diamines and polymerisation position with urea structure have the polyamic acid that the reaction of the diamine component of the diamines of secondary amine obtains Meanwhile, can also include the polymer with other structures.As the polymer with other structures, can enumerate and be gathered by with above-mentioned Polyamic acid and poly amic acid ester of the different molecular structure formation of amic acid etc..In view of the polyimide film (liquid crystal of gained Alignment films) required characteristic is realized, preferably make by above-mentioned including the tetracarboxylic acid with alicyclic structure or aliphatic structure Tetracarboxylic dianhydride's composition of acid dianhydride and two of the diamines including the diamines with urea structure and polymerisation position with secondary amine The content of the polyamic acid that the reaction of amine component is obtained is 10 moles of %~80 relative to component of polymer total amount (100 moles of %) Mole %.

As long as the organic solvent contained by aligning agent for liquid crystal makes the solvent of the component of polymer such as contained polyamic acid dissolving , it is not particularly limited.As the specific example of organic solvent, DMF, N, N- dimethylacetamides can be enumerated Amine, METHYLPYRROLIDONE, N- methyl caprolactams, 2-Pyrrolidone, N- ethyl pyrrolidones, N- ethenyl pyrrolidones Ketone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton or 1,3- dimethyl-imidazolinones Deng.They can be used in mixed way using one kind or two or more.

Even additionally, cannot individually make component of polymer dissolve solvent, as long as component of polymer will not separated out In the range of, it is also possible to mix into aligning agent for liquid crystal of the invention.It is known especially by making the molten fibre of ethyl cellosolve, butyl Agent, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanols, 1- ethyoxyls -2- Propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propane diols -1- Monomethyl ether -2- acetic acid esters, propane diols -1- list ether -2- acetic acid esters, DPG, 2- (2- ethoxy-cs epoxide) propyl alcohol, lactic acid The solvent mixing with low surface tension such as methyl esters, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate and isoamyl lactate is deposited In the painting film uniformity raising to substrate.Therefore, these solvents can be used a kind, it is also possible to be used in mixed way various.

The usage amount of the solvent with low surface tension is preferably 5~80 matter of contained solvent total amount in aligning agent for liquid crystal Amount %, more preferably 20~60 mass %.

Aligning agent for liquid crystal of the invention can also include various additions in addition to above-mentioned component of polymer and organic solvent Agent.

For example, as the additive for improving film thickness uniformity and surface smoothness, fluorine class surfactant, silicon can be enumerated Oxygen alkanes surfactant, nonionic surfactant etc..

For example, eftop EF301, EF303, EF352 (Tuo Kaimu products Co., Ltd. (トーケ system プロダ Network can be enumerated Star society) system), MEGAFACE F171, F173, R-30 (Dainippon Ink. ＆ Chemicals Inc (イ Application キ societies of big Japan) System), Fluorad FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリーエ system society) system), AashiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) Deng.The use ratio of these surfactants is preferably relative to the mass parts of component of polymer 100 contained by aligning agent for liquid crystal 0.01~2 mass parts, more preferably 0.01~1 mass parts.

As the specific example of the additive of the adaptation for improving liquid crystal orientation film and substrate, can enumerate containing functional silanes Compound, the compound containing epoxy radicals etc..

For example, 3- TSL 8330s, APTES, 2- aminopropyls three can be enumerated Methoxy silane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- Amino-ethyl) -3- amino propyl methyls dimethoxysilane, 3- ureido-propyl trimethoxy silanes, the ethoxy of 3- ureido-propyls three Base silane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- aminopropyl triethoxysilicanes Alkane, N- tri-ethoxy silylpropyls diethylenetriamine, N- trimethoxysilylpropyls diethylenetriamine, 10- front threes The azepine decane of TMOS base -1,4,7- three, the azepine decane of 10- triethoxysilicane alkyl -1,4,7- three, 9- trimethoxy silanes Base -3,6- diaza nonyls acetic acid esters, 9- triethoxysilicane alkyl -3,6- diaza nonyls acetic acid esters, N- benzyl -3- aminopropans Base trimethoxy silane, N- benzyls-APTES, N- phenyl -3- TSL 8330s, N- Double (the oxyethylene group) -3- TSL 8330s of phenyl-APTES, N-, double (the oxygen ethene of N- Base)-APTES, ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base ether, propane diols Diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol two shrink sweet Oleyl ether, 1,6-HD diglycidyl ether, glycerine diglycidyl ether, 2,2- dibromoneopentyl glycol 2-glycidyls Base ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycols, N, N, N ', N '-four glycidyl group m-xylene diamine, 1,3- Double (N, N- diglycidyl amino methyl) hexamethylenes or N, N, N ', N '-four glycidyl group -4,4 '-diamino-diphenyl Methane etc..The addition of these compounds is preferably 0.1 relative to the mass parts of component of polymer 100 included in aligning agent for liquid crystal ~30 mass parts, more preferably 1~20 mass parts.If being less than 0.1 mass parts, the effect that adaptation is improved cannot be expected；Such as Fruit is higher than 30 mass parts, then liquid crystal aligning may be deteriorated.

In aligning agent for liquid crystal of the invention, can in order to change the electrical characteristics such as dielectric constant and electric conductivity of liquid crystal orientation film and Add dielectric or conductive materials, the hardness and consistency of film when can also be made liquid crystal orientation film to improve and add crosslinking Property compound etc..

The concentration of the solid constituent in aligning agent for liquid crystal of the invention can be according to the thickness of the liquid crystal orientation film as target It is appropriate to change, but do not have defective film and obtain the reasons why being suitable as the thickness of liquid crystal orientation film based on that can be formed, preferably It is 1~20 mass parts, more preferably 2~10 mass parts.

Aligning agent for liquid crystal of the invention is coated after being burnt till on substrate, and orientation position is carried out with friction treatment or illumination etc. Manage and be used as liquid crystal orientation film, or for the liquid crystal display cells of vertical orientated property when, orientation process is not carried out and As liquid crystal orientation film.As long as the substrate transparency at this moment using substrate high, is not particularly limited, glass base can be used Plastic base such as plate or acrylic acid substrate and polycarbonate substrate etc., but from from the viewpoint of technique simplification, preferably use shape Into the substrate having for driving the ITO of liquid crystal (Indium Tin Oxide) electrode etc..Additionally, the liquid crystal display cells of reflection-type In, substrate that can be only unilateral uses the opaque substrates such as silicon wafer.As electrode in this case, aluminium etc. is it is also possible to use anti- Penetrate the material of light.

The coating method of aligning agent for liquid crystal is not particularly limited, it is industrial generally using by silk-screen printing, hectographic printing, The method that flexographic printing or ink-jet etc. are coated.As other coating methods, there is infusion process or use roll coater, slot coated Method of machine or spin coater etc. etc., can suitably select according to purpose.

Burning till for substrate after coating of liquid crystalline alignment agent can be carried out under 100~350 DEG C of arbitrary temp, and preferably 150 ~300 DEG C, more preferably 180~250 DEG C.Polyamic acid in aligning agent for liquid crystal and the poly amic acid ester that includes as needed are to poly- Imido conversion ratio changes according to the firing temperature, but aligning agent for liquid crystal of the invention and does not need certain 100% acyl sub- Amination.Therefore, firing time may be set to random time, but if firing time is too short, then may be because of the shadow of residual solvents Ring and produce display defect, so preferably 5~60 minutes, more preferably 10~40 minutes.

It is unfavorable in terms of the power consumption of liquid crystal display cells if the thickness of the film after burning till is excessive, if Too small, then the reliability of liquid crystal display cells may be reduced, so preferably 5~300nm, more preferably 10~100nm.Make liquid In the case of brilliant horizontal alignment or tilted alignment, to burning till after film by friction or polarized UV rays irradiate etc. locate Reason.

Liquid crystal display cells of the invention are to obtain band liquid crystal aligning by aligning agent for liquid crystal of the invention by the above method After the substrate of film, liquid crystal cell is made by known method, so as to be made liquid crystal display cells.

It is as follows if enumerating of liquid crystal cell making.First, preparation is formed with a pair of substrates of liquid crystal orientation film. Then, sept is spread on the liquid crystal orientation film of the substrate of a side, liquid crystal aligning face is located at inner side, bonding the opposing party's After substrate, decompression is injected liquid crystal and is sealed.Or, can be glued after to the liquid crystal aligning face dropping liquid crystalline substance for having spread sept Close substrate and sealed.Now, the thickness of sept is preferably 1~30 μm, more preferably 2~10 μm.

The display quality of the liquid crystal display cells being made using aligning agent for liquid crystal of the invention is good, and reliability is also good, LCD TV of big picture, fine etc. can be performed well in.

As described above, by using aligning agent for liquid crystal of the invention, when can obtain friction treatment to the damage on film surface and Grinding is less, liquid crystal aligning is good, ion concentration small liquid crystal orientation film when being made liquid crystal display cells.

Additionally, the use of the liquid crystal orientation film that aligning agent for liquid crystal of the invention is obtained being probably due to secondary amine structure and urea structure The influence of generation, compared with general polyamic acid, hence it is evident that with specific insulation higher.The value be considered to have body high Accumulate the equal level of the soluble polyimide of resistivity.But, using the liquid crystal obtained using aligning agent for liquid crystal of the invention Accumulated charge amounts in the FFS mode liquid crystal display cells of alignment films are few, it is possible to provide the liquid crystal of the low high-quality of ghost level Show element.That is, the liquid crystal orientation film for being obtained using aligning agent for liquid crystal of the invention has specific insulation high, but accumulated charge amounts It is considerably less, so the generation of ghost can be suppressed, it is believed that the ghost time-consuming problem of disappearance will not be produced.

Aligning agent for liquid crystal of the invention cannot be only used for the liquid crystal orientation film being orientated by friction treatment, it may also be used for constitute The liquid crystal orientation film of light orientation, the liquid crystal orientation film that orientation process is carried out by illumination.

Embodiment

Hereinafter, embodiment is enumerated to be described in detail present embodiment, but the present invention is not limited in these Embodiment is explained.

Hereinafter, the abbreviation of compound and the structure used in this synthesis example are shown.

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

CA-2:Pyromellitic acid dianhydride

CA-3:Bicyclic [3.3.0] octane -2,4,6,8- tetracarboxylic dianhydrides

DA-1:4- (2- (methylamino) ethyl) aniline

DA-2:Double (4- aminophenethyls) ureas of 1,3-

DA-3:3- ((methylamino) methyl) aniline

DA-4:Double (4- amino-benzene oxygens) pentanes of 1,5-

DA-5:P-phenylenediamine

DA-6:4,4 '-diamino-diphenyl amine

[changing 15]

In formula, Me represents methyl.

Hereinafter, show viscosity, solid component concentration, voltage retention, ion concentration, specific insulation, residual DC it is each Assay method, friction tolerance, each evaluation method of liquid crystal aligning and vertical electric field liquid crystal cell (Japanese：Longitudinal Electricity circle liquid crystal セ Le), transverse electric liquid crystal cell (Japanese：Horizontal Electricity circle liquid crystal セ Le) (FFS modes liquid crystal cell) each preparation method.

[viscosimetric analysis]

Synthesis example compares synthesis example, and the viscosity of polyamic acid solution uses E type viscosimeters TVE-22H (eastern machine industries (East Machine Industry Co., Ltd of Co., Ltd.) system) with sample size 1.1mL, cone rotor TE-1 (1 ° of 34 ', R24), 25 DEG C of temperature Condition is determined.

[solid component concentration measure]

Synthesis example compares synthesis example, and being calculated as follows for the solid component concentration of polyamic acid solution is carried out.

It is molten about 1.1g polyamic acids to be weighed in aluminium cup 2 (A Ziwang Co., Ltd. (アズワ Application society) system) with handles Liquid, after being heated 2 hours at 200 DEG C with baking oven DNF400 (Ya Matuo companies (Yamato societies) system), places 5 minutes at room temperature, Measurement residues in the weight of the solid constituent in aluminium cup.Solid is calculated by the value of the solids by weight and original solution weight Constituent concentration.

[evaluation of friction tolerance]

It is transparent in band after the polyamic acid solution that synthesis example or compare is obtained in synthesis example is filtered with 1.0 μm of filter It is coated by spin coating on the glass substrate of electrode, after being dried 5 minutes in 50 DEG C of heating plate, 30 points is carried out at 230 DEG C Burning till for clock, obtains the polyimide film of thickness 100nm.Rubbed (roller diameter with rayon cloth to the polyimide film 120mm, roller rotating speed 1000rpm, translational speed 20mm/ seconds, is pressed into apart from 0.6mm).By confocal laser microscope (multiple 10 times) whether there is damage to observe the polyimide film surface.Undamaged sample is evaluated as " good ", there is damage Sample is evaluated as " bad ".

[vertical electric field liquid crystal cell makes]

It is whole in band ITO after the polyamic acid solution that synthesis example or compare is obtained in synthesis example is filtered with 1.0 μm of filter It is coated by spin coating on the glass substrate (whole face is provided with the substrate of ito film on glass substrate) of face electrode, in 50 DEG C add After being dried 5 minutes on hot plate, carry out at 230 DEG C burning till for 30 minutes, obtain the polyimide film of thickness 100nm.Use artificial silk Cloth is rubbed (roller diameter to the polyimide film:120mm, roller rotating speed:1000rpm, translational speed:20mm/ seconds, intrusion: After 0.3mm), the ultrasonic irradiation of 1 minute is carried out in pure water to clean, after air blast removes water droplet, in 80 DEG C of dryings 15 Minute and obtain the substrate with liquid crystal orientation film.Substrate with liquid crystal orientation film as preparing 2 pieces, in one block of liquid crystal of substrate After orientation face spreads 6 μm of sept, combined in the mode that the frictional direction of 2 pieces of substrates is antiparallel, leave liquid crystal injection Mouthful, will around seal, it is made the sylphon that box spacing is 6 μm.To the sylphon at normal temperatures vacuum injection liquid crystal (MLC-2041, write from memory Gram Co., Ltd. (メルク Co., Ltd.) system), seal inlet and be made antiparallel liquid crystal cell.

[liquid crystal aligning evaluation]

The state of orientation of the vertical electric field liquid crystal cell by petrographic microscope to being made as described above is observed, by No yield point The sample of defect is evaluated as " good ", and the sample for having orientation defect is evaluated as " bad ".

[voltage retention measure]

Using the vertical electric field liquid crystal cell being made as described above, by Dongyang (East Yang テ Network ニカ societies of science and technology Co., Ltd.) system VHR-1 type voltage retention measurement systems be measured.In measure, the μ s of alternating voltage 60 of applying ± 4V determine 16.67ms Voltage afterwards, calculates from the change of initial value, using this as voltage retention.During measure, the temperature of liquid crystal cell is set to 60 DEG C, will More than 98% is evaluated as " good ", is evaluated as " bad " less than 98%.

[ion concentration measure]

Using the vertical electric field liquid crystal cell being made as described above, by 6254 type liquid crystal physical property of Dongyang science and technology Co. Ltd. system Evaluation system is measured.In measure, applying ± 10V, the triangular wave of 0.01Hz, the ripple as obtained by triangle approximation method is calculated The area corresponding to ion concentration of shape, as ion concentration.During measure, the temperature of liquid crystal cell is set to 23 DEG C, will be less than 100pC/cm²It is evaluated as " good ", 100pC/cm²More than it is evaluated as " bad ".

[measure of specific insulation]

It is saturating in band ITO after the polyamic acid solution that synthesis example or compare is obtained in synthesis example is filtered with 1.0 μm of filter It is coated by spin coating on the glass substrate of prescribed electrode, after being dried 2 minutes in 70 DEG C of heating plate, 15 is carried out at 230 DEG C Burning till for minute, forms the film (liquid crystal orientation film) of thickness about 220nm.Jie makes aluminium-vapour deposition in the film coated surface, shape with mask Specific insulation measurement sample is made into the upper electrode (aluminium electrode) of 1.0mm φ.To the ITO electrode and aluminium electricity of the sample Apply the voltage of 5V between pole, the current value since the applied voltage after 180 seconds is measured, according to the value and electrode surface Product, the measured value of thickness calculate specific insulation.

[making of FFS modes liquid crystal cell]

After the polyamic acid solution that synthesis example or compare is obtained in synthesis example is filtered with 1.0 μm of filter, in glass base On plate the 1st layer there is IZO (tin indium oxide, Indium Zinc Oxide) whole face electrode of thickness 50nm, the 2nd layer with thickness 500nm Silicon nitride insulating film, the 3rd layer have thickness 50nm IZO comb electrode (electrode widths:3 μm, electrode gap:6 μm) can FFS It is coated by spin coating on the substrate that mode drives, after being dried 5 minutes in 50 DEG C of heating plate, 30 points is carried out at 230 DEG C Burning till for clock, obtains the polyimide film of thickness 100nm.Rubbed (roller diameter with rayon cloth to the polyimide film: 120mm, roller rotating speed:500rpm, translational speed:30mm/ seconds, intrusion:0.3mm, frictional direction:Relative to the 3rd layer of IZO pectination The direction that 10 ° of electrode incline) after, the ultrasonic irradiation of 1 minute is carried out in pure water to clean, after air blast removes water droplet, The substrate with liquid crystal orientation film is obtained in 80 DEG C of dryings 15 minutes.Additionally, in the electrode of being formed without as opposite substrate Polyimide film is also formed as described above on glass substrate with 4 μm of column spacer, by similar to the above Step implements orientation process and obtains the substrate with liquid crystal orientation film.Using this 2 pieces of substrates with liquid crystal orientation film as 1 group, with 2 The mode that the frictional direction of block substrate is antiparallel is combined, and is remained liquid crystal injecting port and will around be sealed, and is made box at intervals of 4 μm Sylphon.To sylphon vacuum injection liquid crystal (ZLI-4792, Merck Co., Ltd. (メルク Co., Ltd.) system) at normal temperatures, Seal inlet and be made antiparallel liquid crystal cell.

[residual DC (dielectric absorption process) measure]

Using the FFS mode liquid crystal cells being made as described above, by 6254 type liquid crystal things of Dongyang science and technology Co. Ltd. system Property evaluation system is measured.In measure, apply the DC voltage of+4V after 30 minutes, discharge 1 second, measure 60 minutes thereafter Residual DC amount.During measure, the temperature of liquid crystal cell is set to 60 DEG C, and situation of the residual DC amount less than 2.0V after discharging 60 minutes is commented Valency is " good ", and more than 2.0V is evaluated as " bad ".

(synthesis example 1)

To taking 2.83g (18.8mmol) DA-1,5.61g in the 200mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (18.8mmol) DA-2 and 2.70g (9.40mmol) DA-4, adds 126g METHYLPYRROLIDONEs, in the same of feeding nitrogen When be stirred and dissolve it.8.84g (45.1mmol) CA-1 is added while the diamine solution is stirred, N- first is added Base -2-Pyrrolidone makes solid component concentration for 10 mass %, is stirred at room temperature in a nitrogen atmosphere 2 hours, obtains polyamide The solution of sour (A-1).Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 135mPas.

The 21.2g polyamic acid solutions are taken to the 50mL conical flasks that have stirrer are added, add 2.67g N- methyl- 2-Pyrrolidone, 2.08g3- aminopropyltriethoxywerene werenes be 1.0 mass % METHYLPYRROLIDONE solution and 8.66g butyl cellosolves, stirring 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 6.0.

(synthesis example 2)

To taking 3.55g (23.6mmol) DA-1 and 10.6g in the 300mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (35.4mmol) DA-2, adds 136g METHYLPYRROLIDONEs, and being stirred while nitrogen is sent into dissolves it. 11.3g (57.6mmol) CA-1 is added while stirring the diamine solution, adding METHYLPYRROLIDONE makes solid constituent Concentration is 10 mass %, is stirred at room temperature in a nitrogen atmosphere 5 hours, obtains the solution of polyamic acid (A-2).The polyamic acid Viscosity during 25 DEG C of the temperature of solution is 156mPas.

The 168g polyamic acid solutions are taken to the 500mL conical flasks that have stirrer are added, add 55.1g N- methyl- 2-Pyrrolidone, 16.5g3- aminopropyltriethoxywerene werenes be 1.0 mass % METHYLPYRROLIDONE solution and 60.0g butyl cellosolves, stirring 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 5.7.

(synthesis example 3)

To taking 72.1g (480mmol) DA-1,71.5g in the removable flasks of the 5L with agitating device and nitrogen ingress pipe (240mmol) DA-2 and 137g (480mmol) DA-4, adds 3200g METHYLPYRROLIDONEs, while nitrogen is sent into Being stirred dissolves it.227g (1.16mmol) CA-1 is added while the diamine solution is stirred, N- methyl -2- is added Pyrrolidones makes solid component concentration for 10 mass %, is stirred at room temperature in a nitrogen atmosphere 1 hour, obtains polyamic acid (A- 3) solution.Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 155mPas.

The 176g polyamic acid solutions are taken to adding the 500mL conical flasks that have stirrer, 48.0g N- methyl -2- pyrroles Pyrrolidone, 16.5g3- aminopropyltriethoxywerene werenes are the METHYLPYRROLIDONE solution and 60.0g fourths of 1.0 mass % Base cellosolve, stirring 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 5.7.

(synthesis example 4)

To taking 1.68g (11.2mmol) DA-1,6.68g in the 300mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (22.4mmol) DA-2 and 6.42g (22.4mmol) DA-4, adds 157g METHYLPYRROLIDONEs, in the same of feeding nitrogen When be stirred and dissolve it.10.6g (54.0mmol) CA-1 is added while the diamine solution is stirred, N- first is added Base -2-Pyrrolidone makes solid component concentration for 10 mass %, is stirred at room temperature in a nitrogen atmosphere 5 hours, obtains polyamide The solution of sour (A-4).Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 148mPas.

The 172g polyamic acid solutions are taken to the 500mL conical flasks that have stirrer are added, add 51.6g N- methyl- 2-Pyrrolidone, 16.5g3- aminopropyltriethoxywerene werenes be 1.0 mass % METHYLPYRROLIDONE solution and 60.0g butyl cellosolves, stirring 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 5.6.

(synthesis example 5)

To taking 5.41g (36.0mmol) DA-1,3.59g in the 300mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (12.0mmol) DA-2 and 3.44g (12.0mmol) DA-4, adds 151g METHYLPYRROLIDONEs, in the same of feeding nitrogen When be stirred and dissolve it.11.5g (58.7mmol) CA-1 is added while the diamine solution is stirred, N- first is added Base -2-Pyrrolidone makes solid component concentration for 10 mass %, is stirred at room temperature in a nitrogen atmosphere 2 hours, obtains polyamide The solution of sour (A-5).Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 159mPas.

The 215g polyamic acid solutions are taken to the 500mL conical flasks that have stirrer are added, add 43.2g N- methyl- 2-Pyrrolidone, 20.9g3- aminopropyltriethoxywerene werenes be 1.0 mass % METHYLPYRROLIDONE solution and 69.7g butyl cellosolves, stirring 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 6.0.

(synthesis example 6)

To taking 3.30g (22.0mmol) DA-1,16.4g in the 500mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (55.0mmol) DA-2 and 9.45g (33.0mmol) DA-4, adds 229g METHYLPYRROLIDONEs, in the same of feeding nitrogen When be stirred and dissolve it.Addition 15.1g (77.0mmol) CA-1 and 7.79g while the diamine solution is stirred (31.1mmol) CA-3, adding METHYLPYRROLIDONE makes solid component concentration for 12 mass %, in a nitrogen atmosphere in 40 DEG C are stirred 40 hours, obtain the solution of polyamic acid (A-6).Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 295mPa·s。

The 751g polyamic acid solutions are taken to the 3L conical flasks that have stirrer are added, 461g N- methyl -2- pyrroles are added Pyrrolidone, 92.1g3- aminopropyltriethoxywerene werenes are the METHYLPYRROLIDONE solution and 225g fourths of 1.0 mass % Base cellosolve, stirring 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 6.0.

(synthesis example 7)

To taking 1.57g (10.4mmol) DA-1 and 4.65g in the 100mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (15.6mmol) DA-2, adds 57.9g METHYLPYRROLIDONEs, and being stirred while nitrogen is sent into dissolves it. 3.44g (17.6mmol) CA-1 and 1.70g (7.80mmol) CA-2 is added while the diamine solution is stirred, N- first is added Base -2-Pyrrolidone makes solid component concentration for 12 mass %, is stirred at room temperature in a nitrogen atmosphere 5 hours, obtains polyamide The solution of sour (A-7).Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 196mPas.

The 45.1g polyamic acid solutions are taken to the 100mL conical flasks that have stirrer are added, 27.2g N- first is added Base -2-Pyrrolidone and 18.0g butyl cellosolves, stirring 2 hours and obtain the polyamic acid of the mass % of solid component concentration 6.0 Solution.

(synthesis example 8)

To taking 3.49g (23.2mmol) DA-1,6.92g in the 200mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (23.2mmol) DA-2 and 2.31g (11.6mmol) DA-6, adds 125g METHYLPYRROLIDONEs, in the same of feeding nitrogen When be stirred and dissolve it.Addition 9.10g (46.4mmol) CA-1 and 2.57g while the diamine solution is stirred (10.3mmol) CA-3, adding METHYLPYRROLIDONE makes solid component concentration for 12 mass %, in a nitrogen atmosphere in 40 DEG C are stirred 24 hours, obtain the solution of polyamic acid (A-8).Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 348mPa·s。

The 19.8g polyamic acid solutions are taken to the 50mL conical flasks that have stirrer are added, add 8.07g N- methyl- 2-Pyrrolidone, 2.42g3- aminopropyltriethoxywerene werenes be 1.0 mass % METHYLPYRROLIDONE solution and 10.1g butyl cellosolves, stirring 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 6.0.

(synthesis example 9)

To taking 1.68g (11.2mmol) DA-1,2.51g in the 100mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (8.40mmol) DA-2 and 0.91g (8.40mmol) DA-5, adds 43g METHYLPYRROLIDONEs, in the same of feeding nitrogen When be stirred and dissolve it.5.30g (27.0mmol) CA-1 is added while the diamine solution is stirred, N- first is added Base -2-Pyrrolidone makes solid component concentration for 10 mass %, is stirred at room temperature in a nitrogen atmosphere 2 hours, obtains polyamide The solution of sour (A-9).Viscosity during 25 DEG C of the temperature of the polyamic acid solution is 125mPas.

The 54.0g polyamic acid solutions are taken to the 100mL conical flasks that have stirrer are added, 3.60g γ-Ding Nei are added Ester, 5.40g3- aminopropyltriethoxywerene werenes are the gamma-butyrolacton solution and 27.0g butyl cellosolves of 1.0 mass %, are stirred Mix 2 hours and obtain the polyamic acid solution of the mass % of solid component concentration 6.0.

(synthesis example 10)

To taking 1.64g (12.0mmol) DA-3 and 5.38g in the 100mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (18.0mmol) DA-2, adds 64.7g METHYLPYRROLIDONEs, and being stirred while nitrogen is sent into dissolves it. Stir the diamine solution while add 5.68g (29.0mmol) CA-1, add METHYLPYRROLIDONE make solid into Divide concentration to be 12 mass %, be stirred at room temperature in a nitrogen atmosphere 3.5 hours, obtain the solution of polyamic acid (A-10).This gathers Viscosity during 25 DEG C of the temperature of acid amides acid solution is 211mPas.

The 47.1g polyamic acid solutions are taken to the 100mL conical flasks that have stirrer are added, 28.3g N- first is added Base -2-Pyrrolidone and 18.7g butyl cellosolves, stirring 2 hours and obtain the polyamic acid of the mass % of solid component concentration 6.0 Solution.

(comparing synthesis example 1)

To taking 31.7g (294mmol) DA-5 and 37.6g in the removable flasks of the 2L with agitating device and nitrogen ingress pipe (126mmol) DA-2, adds 864g METHYLPYRROLIDONEs, and being stirred while nitrogen is sent into dissolves it. 78.2g (399mmol) CA-1 is added while stirring the diamine solution, adding METHYLPYRROLIDONE makes solid constituent Concentration is 12 mass %, is stirred at room temperature in a nitrogen atmosphere 6 hours, obtains the solution of polyamic acid (B-1).The polyamic acid Viscosity during 25 DEG C of the temperature of solution is 308mPas.

The 1155g polyamic acid solutions are taken to the 3L conical flasks that have stirrer are added, 482gN- methyl -2- pyrroles are added Pyrrolidone, 133g3- aminopropyltriethoxywerene werenes are the METHYLPYRROLIDONE solution and 442g butyl of 1.0 mass % Cellosolve, stirring 3 hours and obtain the polyamic acid solution of the mass % of solid component concentration 6.0.

(comparing synthesis example 2)

To 5.25g (35.0mmol) DA-1 is taken in the 100mL four-hole boiling flasks with agitating device and nitrogen ingress pipe, add 60.5g METHYLPYRROLIDONEs, being stirred while nitrogen is sent into dissolves it.Stirring the same of the diamine solution Shi Tianjia 6.79g (34.7mmol) CA-1, adding METHYLPYRROLIDONE makes solid component concentration for 12 mass %, It is stirred at room temperature under nitrogen atmosphere 4.5 hours, obtains the solution of polyamic acid (B-2).25 DEG C of the temperature of the polyamic acid solution When viscosity be 275mPas.

The 47.0g polyamic acid solutions are taken to the 100mL conical flasks that have stirrer are added, 28.2g N- first is added Base -2-Pyrrolidone and 18.8g butyl cellosolves, stirring 2 hours and obtain the polyamic acid of the mass % of solid component concentration 6.0 Solution.

(comparing synthesis example 3)

To taking 3.16g (21.0mmol) DA-1 and 2.69g in the 100mL four-hole boiling flasks with agitating device and nitrogen ingress pipe (9.00mmol) DA-2, adds 62.3g METHYLPYRROLIDONEs, and being stirred while nitrogen is sent into dissolves it. Stir the diamine solution while add 6.28g (29.7mmol) CA-2, add METHYLPYRROLIDONE make solid into Divide concentration to be 12 mass %, be stirred at room temperature in a nitrogen atmosphere 5 hours, obtain the solution of polyamic acid (B-3).The polyamide Viscosity during 25 DEG C of the temperature of acid solution is 65mPas.

The 49.7g polyamic acid solutions are taken to the 100mL conical flasks that have stirrer are added, 29.8g N- first is added Base -2-Pyrrolidone and 19.8g butyl cellosolves, stirring 2 hours and obtain the polyamic acid of the mass % of solid component concentration 6.0 Solution.

Above-mentioned synthesis example described in table 1 and compare the formula in synthesis example.

[table 1]

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-1) obtained in synthesis example 1 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.8%, " good ", and ion concentration is 6pC/cm², " good ", specific insulation is 1.9 × 10¹⁵Ω cm, residual DC be 10 minutes after 1.05V, after 20 minutes 1.08V, 1.11V after 60 minutes, " good ".

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-2) obtained in synthesis example 2 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.7%, " good ", and ion concentration is 0pC/cm², " good ", residual DC is 0.87V, 0.96V, 0.99V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-3) obtained in synthesis example 3 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.4%, " good ", and ion concentration is 59pC/cm², " good ", residual DC is 0.69V, 0.74V, 0.81V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-4) obtained in synthesis example 4 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.1%, " good ", and ion concentration is 73pC/cm², " good ", residual DC is 1.03V, 1.06V, 1.14V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-5) obtained in synthesis example 5 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 99.1%, " good ", and ion concentration is 2pC/cm², " good ", residual DC is 0.38V, 0.52V, 0.65V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-6) obtained in synthesis example 6 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.1%, " good ", and ion concentration is 13pC/cm², " good ", residual DC is 1.28V, 1.43V, 1.50V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-7) obtained in synthesis example 7 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.5%, " good ", and ion concentration is 8pC/cm², " good ", residual DC is 0.61V, 0.71V, 0.79V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-8) obtained in synthesis example 8 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.7%, " good ", and ion concentration is 0pC/cm², " good ", residual DC is 1.58V, 1.79V, 1.88V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-9) obtained in synthesis example 9 and the result of each measure It is that friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.8%, " good ", and ion concentration is 0pC/cm², " good ", residual DC is 1.15V, 1.39V, 1.51V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation of the polyamic acid solution comprising the polyamic acid (A-10) obtained in synthesis example 10 and the knot of each measure Fruit is that friction tolerance is " good ", and liquid crystal aligning is " good ", and voltage retention is 98.7%, " good ", ion concentration It is 2pC/cm², " good ", residual DC is 0.19V, 0.27V, 0.43V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation and each measure comprising the polyamic acid solution for comparing the polyamic acid (B-1) obtained in synthesis example 1 As a result, friction tolerance is " good ", liquid crystal aligning is " good ", and voltage retention is 98.4%, " good ", and ion is close It is 1pC/cm to spend², " good ", residual DC is 1.99V, 2.07V, 2.12V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation and each measure comprising the polyamic acid solution for comparing the polyamic acid (B-2) obtained in synthesis example 2 As a result, friction tolerance is " bad ", liquid crystal aligning is " bad ", and voltage retention is 99.0%, " good ", and ion is close It is 0pC/cm to spend², " good ", residual DC is 0.95V, 1.21V, 1.42V after 60 minutes, " good " after 20 minutes after 10 minutes.

Each evaluation and each measure comprising the polyamic acid solution for comparing the polyamic acid (B-3) obtained in synthesis example 3 As a result, friction tolerance is " bad ", liquid crystal aligning is " good ", and voltage retention is 98.8%, " good ", and ion is close It is 3pC/cm to spend², " good ", residual DC is 0.29V, 0.42V, 0.67V after 60 minutes, " good " after 20 minutes after 10 minutes.

Result is shown in Table 2.In these results, the embodiment of aligning agent for liquid crystal of the invention (polyamic acid solution) is used 1~10 liquid crystal aligning is good, and with height friction tolerance, ion concentration is small.In addition, in embodiment 1~10, FFS modes Under residual DC it is low, therefore Accumulating charge in liquid crystal display cells is few.The voltage retention of embodiment 1~10 might as well.Additionally, Embodiment 1 with the polyamic acid solution using synthesis example 1 is same, uses the reality of each polyamic acid solution of synthesis example 2~10 Apply in example 2~10, specific insulation is also high.

[table 2]

The possibility utilized in industry

By using aligning agent for liquid crystal of the invention, can obtain that friction tolerance is good, liquid crystal aligning is good, be made liquid The liquid crystal orientation film that voltage retention is high, ion concentration is small during crystal display element.Additionally, liquid crystal orientation film of the invention due to Accumulating charge in FFS mode liquid crystal display cells is few, therefore can be used for the FFS modes liquid crystal display unit of requirement display quality high Part.

Claims

1. aligning agent for liquid crystal, it is characterised in that comprising the polyamides obtained by the reaction of tetracarboxylic dianhydride's composition and diamine component Amino acid, tetracarboxylic dianhydride's composition includes the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure, the diamines into Divide the diamines that there is secondary amine including the diamines with urea structure and polymerisation position.

2. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that in tetracarboxylic dianhydride's composition, including 50 moles of % with On the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure.

3. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that in diamine component, including 10~70 moles of %'s is poly- Closing reactive site has the diamines of secondary amine.

4. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that in diamine component, including 10~70 moles of tools of % There is the diamines of urea structure.

5. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that it is following that polymerisation position has the diamines of secondary amine The diamines that formula (1) is represented；

[changing 1]

6. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the diamines with urea structure is to be represented with following formula (2) Diamines；

[changing 2]

In formula (2), Y represents oxygen atom or sulphur atom, R³、R⁴Independently represent the alkylidene of carbon number 1~3, Z¹、Z²Respectively It is independent to represent singly-bound ,-O- ,-S- ,-OCO- or-COO-.

7. liquid crystal orientation film, it is characterised in that the described aligning agent for liquid crystal of usage right requirement any one of 1~6 is obtained.

8. liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in claim 7.