CN105940343A

CN105940343A - Liquid crystal aligning agent, and liquid crystal display element using same

Info

Publication number: CN105940343A
Application number: CN201480074334.1A
Authority: CN
Inventors: 新津新平; 高桥真文
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-11-28
Filing date: 2014-11-27
Publication date: 2016-09-14
Anticipated expiration: 2034-11-27
Also published as: KR20160090880A; TW201538569A; TWI657099B; WO2015080186A1; KR102278975B1; CN105940343B; JPWO2015080186A1; JP6558543B2

Abstract

A liquid crystal alignment agent containing an imidized polymer obtained by ring-closing a polyimide precursor having repeating units represented by formula (1), at least a part of the Y in formula (1) having the structure represented by the following formula (2). In formula (1), Y is a divalent organic group derived from a diamine component, X is a tetravalent organic group derived from a tetracarboxylic acid derivative, A1 and A2 are, independently, a hydrogen atom or a C1-10 alkyl group which may have a substituent group, a C2-10 alkenyl group which may have a substituent group, or a C2-10 alkynyl group which may have a substituent group, and R1 is a hydrogen atom or a C1-10 alkyl group.

Description

Aligning agent for liquid crystal and the liquid crystal employing it represent element

Technical field

The aligning agent for liquid crystal that the present invention relates to represent element for manufacturing liquid crystal, the liquid crystal obtained by this aligning agent for liquid crystal take To film and employ the liquid crystal of this liquid crystal orientation film and represent element.

Background technology

Liquid crystal represents that element is known as light weight, volume is thin and power consumption is low expression device.In recent years, towards city Mobile phone, the high-resolution liquid crystal of panel type terminal that field occupation rate expands rapidly represent that element also achieves requirement height and represents quality journey The notable development of degree.

Liquid crystal represents that element is to constitute by possessing a pair transparency carrier clamping liquid crystal layer of electrode.Further, liquid crystal Represent in element, employ as liquid crystal orientation film for make liquid crystal present between substrate expectation state of orientation by organic material The organic membrane that material is formed.That is, liquid crystal orientation film is the component parts that liquid crystal represents element, and it is formed at the substrate of clamping liquid crystal The one side of contact liquid crystal, plays and makes liquid crystal effect along certain direction orientation between this substrate.And then, taken by liquid crystal The tilt angle of liquid crystal can be controlled to film.It is known that mainly improved the side of tilt angle by the structure of selection polyimides The method (with reference to patent documentation 2) etc. of method (with reference to patent documentation 1) and reduction tilt angle.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 09-278724 publication

Patent documentation 2: Japanese Unexamined Patent Publication 10-123532 publication

Summary of the invention

The problem that invention is to be solved

In recent years, liquid crystal is used to represent element towards the mobile purposes such as smart phone, mobile phone.In these purposes, in order to Guarantee expression face as much as possible, in order to make liquid crystal represent between the substrate of element to carry out the width of sealant that is bonding and that use Need the narrowest.And then, for above-mentioned reasons, also require to be set to the position of sealant close to bonding with sealant bonding The position of the end of the liquid crystal orientation film that property is weak or be set to the top of liquid crystal orientation film.In this case, especially at height When using under temperature super-humid conditions, the water capacity is easily mixed between sealant and liquid crystal orientation film, and liquid crystal represents the adjacent edges of element Occur to represent inequality.

Thus, it is an object of the invention to, it is provided that sealant and the cementability of liquid crystal orientation film, suppression high temperature can be improved Under super-humid conditions, liquid crystal represents that the adjacent edges of element occurs to represent uneven aligning agent for liquid crystal.

For solving the scheme of problem

The present inventor etc. conduct in-depth research to solve above-mentioned problem, and result completes the present invention.That is, the present invention Purport as follows.

1. an aligning agent for liquid crystal, it is characterised in that it is for containing selected from making diamine component react with tetracarboxylic acid derivatives And the polyimide precursor obtained and this polyimide precursor is carried out imidizate and in the imide amination polymer that obtains The aligning agent for liquid crystal of at least one, this polyimide precursor has the repetitive shown in following formula (1).

In formula (1), Y is the divalent organic group being derived from diamine component, and X is the 4 valency organic groups being derived from tetracarboxylic acid derivatives Group, A¹And A²Be each independently hydrogen atom or optionally have substituent group carbon number 1～10 alkyl, optionally there is substituent group Carbon number 2～10 thiazolinyl, optionally there is the alkynyl of the carbon number 2～10 of substituent group, R¹For hydrogen atom or the alkane of carbon number 1～10 Base, at least some of Y is the structure of following formula (2).

2. according to the aligning agent for liquid crystal described in above-mentioned 1, wherein, in the repetitive shown in above-mentioned formula (1), at least partially X is the 4 valency organic groups with ester ring type structure or aliphatic structure.

3. according to the aligning agent for liquid crystal described in above-mentioned 2, wherein, in the repetitive shown in above-mentioned formula (1), at least partially X is the structure in following (X-9), (X-26), (X-27).

4. according to the aligning agent for liquid crystal described in above-mentioned 2, wherein, in the repetitive shown in above-mentioned formula (1), X is to have fat The ratio of 4 valency organic groups of ring structures or aliphatic structure is 10～100 moles of %.

5. according to the aligning agent for liquid crystal described in above-mentioned 3, wherein, in the repetitive shown in above-mentioned formula (1), X be (X-9), (X-26), the ratio of the arbitrary structures in (X-27) is 10～100 moles of %.

6. according to the aligning agent for liquid crystal according to any one of above-mentioned 1～5, wherein, the repetitive shown in above-mentioned formula (1) In, Y be the ratio of the structure of above-mentioned formula (2) be 10～100 moles of %.

7. a liquid crystal orientation film, it is that the aligning agent for liquid crystal according to any one of above-mentioned 1～6 is coated substrate and burnt Become and obtain.

8. liquid crystal represents an element, and it has the liquid crystal orientation film described in above-mentioned 7.

The effect of invention

The aligning agent for liquid crystal of the application of the invention, available can improve sealant and liquid crystal orientation film cementability, Suppress hot and humid under the conditions of liquid crystal represent that the adjacent edges of element occurs to represent uneven liquid crystal orientation film.Therefore, have by The liquid crystal of this liquid crystal orientation film obtained represents that element can solve the problem that by improving sealant and the cementability of liquid crystal orientation film The expression of adjacent edges is uneven, can be suitably employed in the liquid crystal display of big picture and high-resolution.

Detailed description of the invention

The aligning agent for liquid crystal of the present invention is characterised by, it is for containing selected from making diamine component react with tetracarboxylic acid derivatives And the polyimide precursor obtained and this polyimide precursor is carried out imidizate and in the imide amination polymer that obtains The aligning agent for liquid crystal of at least one, this polyimide precursor has the repetitive shown in following formula (1).

The tetracarboxylic acid derivatives used in the present invention can list tetracarboxylic dianhydride, tetrabasic carboxylic acid monoester anhydride, tetrabasic carboxylic acid, dicarboxyl Acid dialkyl ester, dicarboxylic acid chloride's dialkyl etc., as long as reacting with diamidogen, be then not limited to them.

In formula (1), X is the 4 valency organic groups being derived from tetracarboxylic acid derivatives, and its structure is not particularly limited.If must The concrete example of X is shown, then can list X-1～X-44 described below.

In formula (X-1), R²～R⁵Represent hydrogen atom, methyl or phenyl independently of one another.

In formula (1), X can be a kind, it is also possible to is mixed two or more, owing to X has ester ring type structure or aliphatic Structure, cementability becomes higher, it is therefore preferable that comprise the X with ester ring type structure or aliphatic structure of more than a kind.As There is the preferred proportion of the X of ester ring type structure or aliphatic structure, for 10 moles of overall for X more than %, more preferably 50 rub You are more than %, more preferably 80 moles of more than %.

As the structure of the X with ester ring type structure or aliphatic structure, be preferably (X-1)～(X-16), (X-23)～ (X-27), (X-41)～(X-43), from the viewpoint of can obtaining strong bonding force, particularly preferably (X-9), (X-26), (X- 27)。

In formula (1), as R¹In the concrete example of abovementioned alkyl, methyl, ethyl, propyl group, isopropyl, positive fourth can be listed Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl etc..

In formula (1), A¹And A²Be each independently hydrogen atom or optionally have substituent group carbon number 1～10 alkyl, The thiazolinyl optionally with the carbon number 2～10 of substituent group, the alkynyl of the carbon number 2～10 optionally with substituent group.

As the concrete example of abovementioned alkyl, methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, the last of the ten Heavenly stems can be listed Base, cyclopenta, cyclohexyl, dicyclohexyl etc..As thiazolinyl, can list more than 1 CH-CH knot present in abovementioned alkyl Set up the thiazolinyl changing C=C structure into and obtain, more specifically, vinyl, pi-allyl, 1-acrylic, isopropyl alkene can be listed Base, crotyl, 1,3-butadienyl, pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc..As Alkynyl, can list more than 1 CH present in aforesaid alkyl₂-CH₂Structure replacing becomes C ≡ C-structure and the alkynyl that obtains, more Specifically, acetenyl, 1-propinyl, 2-propynyl etc. can be listed.

Abovementioned alkyl, thiazolinyl, alkynyl optionally have substituent group, and then, it is also possible to form ring structure by substituent group.Need Be noted that formed by substituent group ring structure refer to substituent group each other or substituent group be bonded with a part for female skeleton and Form ring structure.

As the example of this substituent group, halogen group, hydroxyl, mercapto, nitro, aryl, organic epoxide can be listed, have Machine sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide groups, alkyl, thiazolinyl, alkynyl.

As belonging to the halogen group of substituent group, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be listed.

As belonging to the aryl of substituent group, phenyl can be listed.This aryl can also replace other substituent group aforementioned.

As belonging to organic epoxide of substituent group, the structure shown in O-R can be shown.This R can be the same or different, Aforesaid alkyl, thiazolinyl, alkynyl, aryl etc. can be exemplified.These R can also replace foregoing substituents.As organic epoxide Concrete example, can list methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, epoxide in heptan, octyloxy etc..

As belonging to organic sulfenyl of substituent group, the structure shown in-S-R can be shown.As this R, can exemplify aforementioned Alkyl, thiazolinyl, alkynyl, aryl etc..These R can also replace foregoing substituents.As the concrete example of organic sulfenyl, can enumerate Go out methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, sulfenyl in heptan, pungent sulfenyl etc..

As belonging to the Organosilyl of substituent group ,-Si-(R) can be shown₃Shown structure.This R can identical also Can be different, aforesaid alkyl, thiazolinyl, alkynyl, aryl etc. can be exemplified.These R can also replace foregoing substituents.As having The concrete example of machine silicyl, can list trimethyl silyl, triethylsilyl, tripropylsilyl base, three fourths Base silicyl, three amyl group silicyls, three hexyl silicyls, amyl dimethyl silicyl, hexyl dimethyl silane Base etc..

As belonging to the acyl group of substituent group, the structure shown in-C (O)-R can be shown.As this R, aforementioned alkane can be exemplified Base, thiazolinyl, aryl etc..These R can also replace foregoing substituents.As the concrete example of acyl group, formoxyl, second can be listed Acyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc..

As belonging to the ester group of substituent group, the structure shown in-C (O) O-R or-OC (O)-R can be shown.As this R, can Exemplify aforesaid alkyl, thiazolinyl, alkynyl, aryl etc..These R can also replace foregoing substituents.

As belonging to the thioester substrate of substituent group, the structure shown in-C (S) O-R or-OC (S)-R can be shown.As this R, Aforesaid alkyl, thiazolinyl, alkynyl, aryl etc. can be exemplified.These R can also replace foregoing substituents.

As belonging to the phosphate-based of substituent group ,-OP (O)-(OR) can be shown₂Shown structure.This R can identical also Can be different, aforesaid alkyl, thiazolinyl, alkynyl, aryl etc. can be exemplified.These R can also replace foregoing substituents.

As belonging to the amide groups of substituent group ,-C (O) NH can be shown₂Or-C (O) NHR ,-NHC (O) R ,-C (O) N (R)₂, the structure shown in-NRC (O) R.This R can be the same or different, and can exemplify aforesaid alkyl, thiazolinyl, alkynyl, aryl Deng.These R can also replace foregoing substituents.

As belonging to the aryl of substituent group, the aryl identical with aforesaid aryl can be listed.This aryl can also replace to be had Other substituent group aforementioned.

As belonging to the alkyl of substituent group, the alkyl identical with aforesaid alkyl can be listed.This alkyl can also replace to be had Other substituent group aforementioned.

As belonging to the thiazolinyl of substituent group, the thiazolinyl identical with foregoing alkenyl can be listed.This thiazolinyl can also replace to be had Other substituent group aforementioned.

As belonging to the alkynyl of substituent group, the alkynyl identical with aforementioned alkynyl can be listed.This alkynyl can also replace to be had Other substituent group aforementioned.

When being normally introduced into bulky structure, it is possible to make the reactivity of amino, liquid crystal aligning reduce, accordingly, as A¹And A², more preferably hydrogen atom or optionally there is the alkyl of carbon number 1～5 of substituent group, particularly preferably hydrogen atom, methyl Or ethyl.

In formula (1), at least some of Y is the structure of formula (2).If must illustrate, Y is the ratio of the structure of formula (2), then 10 moles of %～100 moles of % can be listed.It addition, during structure that the 50 of Y moles of more than % are formula (2), bonding force becomes more Height, so preferably, more preferably 70 moles more than %, more preferably 90 moles of more than %.

As it has been described above, Y is not limited to formula (2), it is also possible to comprise other structure.If other Y structure must be illustrated Concrete example, then can list following Y-1～Y-115.

(in formula (Y-102), m, n are respectively the integer of 1～11, and m+n is the integer of 2～12；In formula (Y-107), h be 1～ The integer of 3；In formula (Y-104) and (Y-111), j is the integer of 0～3.)

Among these, Y-7, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-43, Y-44, Y-45, Y-46, Y-48, The highest structure such as Y-56, Y-64, Y-66, Y-67, Y-68, Y-91, Y-92, Y-93 is when making liquid crystal orientation film, it is possible to Improve the orientation of liquid crystal.It addition, such as Y-69, Y-70, Y-71, Y-72, Y-73, Y-74, Y-75, Y-76, Y-77, Y-78, Y- 79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-88, Y-89, Y-90 etc. are such, and side chain has long-chain Alkyl, aromatic ring, aliphatic ring, steroid skeleton or the structure they combined can when making liquid crystal orientation film Improve the tilt angle of liquid crystal.It addition, structure as Y-111 can obtain good brushing when making liquid crystal orientation film resistance to Property.

The polyimide precursor used in the present invention is to be obtained by diamine component and the reaction of tetracarboxylic acid derivatives, can List polyamic acid, poly amic acid ester etc..

The polyimide precursor i.e. polyamic acid used in the present invention can synthesize by the following method.

Specifically, can by make tetracarboxylic dianhydride and diamidogen in presence of organic solvent with-20 DEG C～150 DEG C, excellent Choosing synthesizes with 0 DEG C～50 DEG C reaction for 30 minutes～24 hours, preferably 1～12 hour.

From monomer and the dissolubility of polymer, the organic solvent used in above-mentioned reaction is preferably N, N-dimethyl methyl Amide, METHYLPYRROLIDONE, gamma-butyrolacton, they can use a kind or be mixed with two or more.Difficult from polymer To separate out and from the viewpoint of being readily obtained high molecular body, the concentration of polymer is preferably 1～30 mass %, and more preferably 5 ～20 mass %.

Above-mentioned operation and the polyamic acid that obtains are by being sufficiently stirred for reaction solution while being injected into bad molten In agent, it is possible to make polymer separate out and reclaim.It addition, by separating out for several times and cleaning with poor solvent, often then carry out Temperature is dried or heat drying, it is possible to obtain the powder through refined polyamic acid.Poor solvent is not particularly limited, and can list Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc..

The polyimide precursor i.e. poly amic acid ester used in the present invention can be synthesized by method (1) shown below～(3).

(1) when being synthesized by polyamic acid

Poly amic acid ester can be by carrying out being esterified synthesizing by the polyamic acid obtained by tetracarboxylic dianhydride and diamidogen.

Specifically, can by make polyamic acid and esterifying agent in presence of organic solvent with-20 DEG C～150 DEG C, Preferably 0 DEG C～50 DEG C reaction synthesizes for 30 minutes～24 hours, preferably 1～4 hour.

As esterifying agent, it is preferably capable the esterifying agent easily removed by refining, N, N-dimethyl methyl can be listed Amide dimethyl-acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, Dinethylformamide di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1-methyl-3-are to first Phenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, 4-(4,6-dimethoxy-1, 3,5-triazine-2-base)-4-methylmorpholinium chloride etc..The addition of esterifying agent is excellent relative to the repetitive 1 mole of polyamic acid Elect 2～6 molar equivalents as.

From the dissolubility of polymer, the solvent for above-mentioned reaction be preferably DMF, N-methyl- 2-Pyrrolidone or gamma-butyrolacton, they can use a kind or be mixed with two or more.It is difficult to separate out from polymer And from the viewpoint of being readily obtained high molecular body, concentration during synthesis is preferably 1～30 mass %, more preferably 5～20 matter Amount %.

(2) when being synthesized by the reaction of tetrabasic carboxylic acid diester dichloride Yu diamidogen

Poly amic acid ester can be synthesized by tetrabasic carboxylic acid diester dichloride and diamidogen.

Specifically, can by make tetrabasic carboxylic acid diester dichloride and diamidogen in the presence of alkali and organic solvent with- 20 DEG C～150 DEG C, preferably 0 DEG C～50 DEG C of reactions synthesize for 30 minutes～24 hours, preferably 1～4 hour.

Aforementioned bases can use pyridine, triethylamine, DMAP etc., in order to make reaction leniently carry out, preferably For pyridine.From the viewpoint of being subordinated to the amount that easily removes and being readily obtained high molecular body, the addition of alkali is relative to tetracarboxylic acid Acid diesters dichloride is preferably 2～4 times moles.

From monomer and the dissolubility of polymer, the solvent for above-mentioned reaction be preferably METHYLPYRROLIDONE, Gamma-butyrolacton, they can use a kind or be mixed with two or more.It is difficult to occur separate out and be readily obtained height from polymer From the viewpoint of molecular weight body, polymer concentration during synthesis is preferably 1～30 mass %, more preferably 5～20 mass %.Separately Outward, in order to prevent tetrabasic carboxylic acid diester dichloride from hydrolyzing, the solvent for synthesizing polyamides acid esters is taken off the most as far as possible Water, is preferably carried out to prevent air to be mixed in nitrogen atmosphere.

(3) when being carried out synthesizing polyamides acid by dicarboxylic diester and diamidogen

Poly amic acid ester can synthesize by dicarboxylic diester and diamidogen are carried out polycondensation.

Specifically, can be by making dicarboxylic diester and diamidogen with 0 DEG C in the presence of condensing agent, alkali, organic solvent ～150 DEG C, preferably 0 DEG C～100 DEG C of reactions synthesize for 30 minutes～24 hours, preferably 3～15 hours.

Aforementioned condensation agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino Propyl group) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O-(benzo three Azoles-1-base)-N, N, N ', N '-tetramethylurea Tetrafluoroboric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea six Fluorophosphoric acid ester, diphenyl (2,3-dihydro-2-thia-3-benzothiazole) phosphonate ester etc..The addition of condensing agent is relative to dicarboxyl Acid diesters is preferably 2～3 times moles.

Aforementioned bases can use the tertiary amine such as pyridine, triethylamine.It is subordinated to the amount that easily removes and is readily obtained high molecular From the viewpoint of body, the addition of alkali is preferably 2～4 times moles relative to diamine component.

It addition, in above-mentioned reaction, can effectively carry out as additive, reaction by adding lewis acid.As Louis This acid, the preferably halo such as lithium chloride, lithium bromide lithium.Lewis acidic addition is preferably 0～1.0 times relative to diamine component Mole.

Among the synthetic method of above-mentioned 3 kinds of poly amic acid esters, owing to the poly amic acid ester of high molecular can be obtained, because of This, the most above-mentioned (1) or the synthetic method of above-mentioned (2).

Above-mentioned operation and the solution of poly amic acid ester that obtains are by being sufficiently stirred for while being injected into bad molten In agent, it is possible to make polymer separate out.By separating out for several times and being carried out with poor solvent, then carry out normal temperature drying or Heat drying, it is possible to obtain the powder through refined poly amic acid ester.Poor solvent is not particularly limited, and can enumerate water outlet, first Alcohol, isopropanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc..

The imide amination polymer used in the present invention can be by carrying out imidizate system by aforementioned polyimide precursor Make.When being manufactured imide amination polymer by polyimide precursor, in polyimide precursor solution, add the change of base catalyst It is easy for learning imidizate.Owing to imidization reaction carries out at a lower temperature, is difficult to during imidizate send out The molecular weight of raw polymer reduces, so preferably chemical imidization.

Chemical imidization can be by making to want the polyimide precursor carrying out imidizate in organic solvent in alkalescence In the presence of catalyst, stirring is carried out.As organic solvent, it is possible to use the solvent used when aforementioned polymeric reacts.As Base catalyst, can list pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, due to possess be appropriate to anti- The alkalescence answered, the most preferably triethylamine, pyridine.It addition, as anhydride, acetic anhydride, trimellitic anhydride, equal benzene four can be listed Anhydride etc., wherein, when using acetic anhydride, the most easily refine, so preferably.

Temperature when carrying out imidization reaction is-20 DEG C～140 DEG C, is preferably 0 DEG C～100 DEG C, can be when reaction Between be to carry out under conditions of 1～100 hour.The amount of base catalyst is 0.5～30 mole times of polyimide precursor, is preferably 2～20 moles times.The acid imide rate of resulting polymers can be controlled by adjustment catalytic amount, temperature, response time.Acyl is sub- Solution after aminating reaction remains the catalyst etc. added, it is therefore preferred to, reclaim gained by following means Imide amination polymer, and carry out re-dissolved with organic solvent, thus make the aligning agent for liquid crystal of the present invention.

Above-mentioned operation and the solution of imide amination polymer that obtains are by being sufficiently stirred for while being injected into not Good solvent, it is possible to make polymer separate out.Separate out for several times and clean with poor solvent, then carry out normal temperature drying or heating is dry Dry, it is possible to obtain the powder through refined imide amination polymer.

Aforementioned poor solvent is not particularly limited, can list methanol, acetone, hexane, butyl cellosolve, heptane, first and second Ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene etc..

The aligning agent for liquid crystal used in the present invention has makes aforementioned polyimide precursor or its imide amination polymer (following It is denoted as the polymer of ad hoc structure) dissolve solution morphology in organic solvent.The molecular weight of the polymer of ad hoc structure is with weight Average molecular weight meter is preferably 2,000～500,000, more preferably 5,000～300,000, more preferably 8,000～100, 000.It addition, number-average molecular weight is preferably 1,000～250,000, more preferably 2,500～150,000, more preferably 4, 000～50,000.

The polymer concentration of the aligning agent for liquid crystal used in the present invention can be fitted according to the setting of coating thickness to be formed Work as change, from forming uniform and flawless film this point, more than preferably 1 weight %, stable from the preservation of solution From the viewpoint of property, it is preferably set to below 10 weight %.

If the polymer of the organic solvent uniform dissolution ad hoc structure contained by aligning agent for liquid crystal used in the present invention, Just it is not particularly limited.If listing its concrete example, then can list DMF, N, N-diethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidine Ketone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3-dimethyl-imidazolinone, 3-first Epoxide-N, N-dimethylpropionamide etc..They can use a kind or be mixed with two or more.Furthermore it is possible to be individually to deposit Time cannot the solvent of uniform dissolution polymer, as long as in the range of polymer will not separate out, then can also be mixed in above-mentioned Organic solvent.

In the present invention use aligning agent for liquid crystal except containing for dissolve ad hoc structure polymer organic solvent it Outward, it is also possible to containing for improving the solvent being coated with film uniformity when aligning agent for liquid crystal is coated substrate.Described solvent is usual The solvent that surface tension is lower than above-mentioned organic solvent can be used.If listing its concrete example, then can list ethyl cellosolve, Butyl cellosolve, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-second Epoxide-2-propanol, 1-butoxy-2-propanol, 1-phenoxy group-2-propanol, Propylene glycol monoacetate, propylene-glycol diacetate, third Glycol-1-monomethyl ether-2-acetas, propylene glycol-1-list ether-2-acetas, butyl cellosolve acetate, dipropylene glycol, 2- (2-ethoxy-c epoxide) propanol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..This A little solvents can be applied in combination two or more.

In the aligning agent for liquid crystal of the present invention, in addition to that mentioned above, in the scope not damaging effect of the present invention, it is also possible to add Polymer beyond polymer of the present invention, for changing the electrical characteristics such as dielectric constant or the electric conductivity of liquid crystal orientation film Dielectric substance or conductive materials, for improving the silane coupler of liquid crystal orientation film and the adaptation of substrate, making liquid for raising Film hardness or the cross-linked compound of consistency during brilliant alignment films and pass through for efficiently advancing time film is burnt till The imidizate accelerator etc. of the imidizate of heating polyimide precursor.

The liquid crystal orientation film of the present invention is above-mentioned aligning agent for liquid crystal to be coated substrate and is dried, burns till and the film that obtains. As the substrate of the aligning agent for liquid crystal of the present invention to be coated with, as long as the high substrate of the transparency is just not particularly limited, can make With plastic bases etc. such as glass substrate, silicon nitride board, acrylic substrate, polycarbonate substrates, go out from the viewpoint of Simplified flowsheet Send out, the substrate that be formed with electrode etc. for drive liquid crystal is preferably used.It addition, the liquid crystal of reflection-type represents in element, if only For unilateral substrate, then can also use the opaque materials such as silicon wafer, electrode now can also use aluminum etc. can reflect light Material.

As the coating process of the aligning agent for liquid crystal of the present invention, spin-coating method, print process, ink-jet method etc. can be listed.Coating Dry, firing process after the aligning agent for liquid crystal of the present invention can select arbitrary temperature and time.Generally for fully removing Contained organic solvent, is dried 1 minute～10 minutes with 50 DEG C～120 DEG C, burn till 5 minutes with 150 DEG C～300 DEG C thereafter～ 120 minutes.Coating thickness after burning till is not particularly limited, and when crossing thin, liquid crystal represents that the reliability of element reduces sometimes, therefore It is 5～300nm, is preferably 10～200nm.

As the method that gained liquid crystal orientation film is carried out orientation process, brushing method, light orientation position logos etc. can be listed.

As the concrete example of light orientation position logos, following method can be listed: aforementioned film coated surface is irradiated deflection one Determine the radiation in direction, carry out heat treated with the temperature of 150～250 DEG C the most further, give liquid crystal aligning ability Method.As radiation, it is possible to use have ultraviolet and the luminous ray of 100nm～800nm wavelength.

[liquid crystal represents element]

Liquid crystal about the present invention represents element, is obtained band liquid crystal by said method by the aligning agent for liquid crystal of the present invention and takes To the substrate of film, after carrying out orientation process by brushing process etc., make liquid crystal represent element by known method.

Liquid crystal represents that the manufacture method of the liquid crystal cells of element is not particularly limited, if listing an example, and the most common side Method is: will be formed with 1 pair of substrate of liquid crystal orientation film by liquid crystal orientation film facing to clamp in the way of inner side preferably 1～30 μm, After arranging, surrounding sealant is fixed the sept of more preferably 2～10 μm, injects liquid crystal and seals.About enclosing liquid crystal Method is not particularly limited, and can exemplify: after reducing pressure in making the liquid crystal cells of making, injects the vacuum method of liquid crystal；Dropping The dripping method etc. sealed is carried out after liquid crystal.Above-mentioned operation and obtained by the aligning agent for liquid crystal of the present invention liquid crystal orientation film tool There is a characteristic of excellence, therefore, can be used as the liquid crystal such as VA, TN, STN, TFT, lateral electric-field type and represent element and ferroelectricity and anti- Ferroelectric liquid crystal represents element liquid crystal orientation film.

Embodiment

It is exemplified below out embodiment, illustrates in greater detail the present invention, but the present invention is not limited to these embodiments.

The abbreviation of the compound used in the present embodiment and comparative example and the method for evaluating characteristics are as follows.

NMP:N-N-methyl-2-2-pyrrolidone N

BCS: butyl cellosolve

CA-1: pyromellitic dianhydride

CA-2:3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride

CA-3:1,2,3,4-Tetramethylene. tetracarboxylic dianhydride

Double (methoxycarbonyl) Tetramethylene .-1,3-dicarboxylic acids of CA-4:2,4-

CA-5:1,2,3,4-butane tetracarboxylic acid dianhydride

CA-6:1,2,4,5-pentane tetracarboxylic dianhydride

CA-7: dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride

DA-1: double (4-amino-benzene oxygen) methane

Double (4-amino-benzene oxygen) propane of DA-2:1,3-

Double (4-amino-benzene oxygen) pentane of DA-3:1,5-

Polyimide precursor and the molecular weight of imide amination polymer in synthesis example use room temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Denko K. K's system), post (KD-803, KD-805) (Shodex company system) are grasped as follows Make to measure.

Column temperature: 50 DEG C

Eluent: N, N '-dimethyl Methanamide is (as additive, lithium bromide monohydrate (LiBr H₂O) it is 30mmol/L (liter), phosphoric acid anhydrous crystalline (orthophosphoric acid) are 30mmol/L, oxolane (THF) is 10ml/L)

Flow velocity: 1.0ml/ minute

Standard curve making standard sample: TSK standard poly(ethylene oxide) (molecular weight；About 900,000,150,000, 100,000 and 30,000) (TOSOH Co., Ltd's system) and Polyethylene Glycol (molecular weight；About 12,000,4,000 and 1,000) (Polymer Laboratories Ltd. system).

(mensuration of the acid imide rate of imide amination polymer)

The acid imide rate of the imide amination polymer in synthesis example operates as follows and measures.Imidizate is polymerized Thing powder 20mg puts into NMR (nuclear magnetic resonance, NMR) sample cell (NMR sample cell specification, φ 5 (wasteland science Co., Ltd. system)), adds Add deuterated dimethyl sulfoxide (DMSO-d6,0.05 mass %TMS (tetramethylsilane) melange) (0.53ml), make with ultrasound wave It is completely dissolved.Utilize NMR measuring machine (JNW-ECA500) (NEC デタ system company system) that this solution is measured The proton NMR of 500MHz.The proton of the structure that acid imide rate does not changes before and after being derived from imidizate is as benchmark matter Son determines, the peak integrating value using this proton and the matter of the NH base being derived from the amic acid occurred near 9.5ppm～10.0ppm Sub-peak integrating value, utilizes following formula to obtain.

Acid imide rate (%)=(1-α x/y) × 100

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

[synthesis example 1]

DA-1 (6.9g, 30mmol) is put in the 100ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe, Adding NMP 82.3g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, add CA-1 (5.9g, 27mmol), and then add NMP 9.1g, use oil bath to stir 12 hours with 50 DEG C in a nitrogen atmosphere, thus obtain Resin solid content concentration is the polyamic acid solution of 12 mass %.Use E type viscometer (Toki Sangyo Co., Ltd.'s system) true Recognizing the viscosity at 25 DEG C of this polyamic acid solution is 68mPa s.The molecular weight of this polyamic acid is Mn=8,500, Mw= 22,900。

[synthesis example 2]

Put in the 2000ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe DA-1 (136.5g, 593mmol), adding NMP 1532.8g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, one CA-2 (166.1g, 564.5mmol) is added on limit, and then adds NMP 170.3g, uses oil bath to stir with 50 DEG C in a nitrogen atmosphere Mix 12 hours, thus obtain the polyamic acid solution that resin solid content concentration is 15 mass %.The 25 of this polyamic acid solution Viscosity at DEG C is 504mPa s.The molecular weight of this polyamic acid is Mn=12,000, Mw=30,300.

[synthesis example 3]

Put in the 300ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe DA-1 (20.5g, 89.0mmol), adding NMP 214.43g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, While adding CA-3 (16.2g, 82.8mmol), and then adding NMP 53.6g, stirring 12 hours with 23 DEG C in a nitrogen atmosphere, Thus obtain the polyamic acid solution that resin solid content concentration is 12 mass %.Viscosity at 25 DEG C of this polyamic acid solution For 72mPa s.

[synthesis example 4]

In the 200ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe, by CA-4 (7.5g, 29.1mmol) NMP 135.8g mixes, is added to triethylamine (6.4g, 63mmol) and DA-1 (6.9g, 30mmol), and stirring and Make it dissolve.

While stirring this solution, add diphenyl (2,3-dihydro-2-thia-3-benzothiazole) phosphonate ester (24.2g, 63mmol), and then add NMP 18.7g, it is stirred at room temperature 15 hours, thus obtains the solution of poly amic acid ester. Viscosity at the temperature of this polyamic acid ester solution 25 DEG C is 110mPa s.

This polyamic acid ester solution is put into isopropanol (1,196.7g), leaching gained precipitate.By this precipitate After cleaning with isopropanol, carry out drying under reduced pressure with the temperature of 100 DEG C, obtain the powder of poly amic acid ester.This poly amic acid ester Molecular weight is Mn=9,900, Mw=21,800.

[synthesis example 5]

Put in the 2000ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe DA-1 (97.92g, 425.3mmol), adding NMP 924.8g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, While adding CA-5 (83.41g, 420.7mmol), and then adding NMP 102.8g, using oil bath with 50 DEG C in a nitrogen atmosphere Stir 12 hours, thus obtain the polyamic acid solution that resin solid content concentration is 15 mass %.This polyamic acid solution Viscosity at 25 DEG C is 172mPa s.It addition, the molecular weight of this polyamic acid is Mn=9,800, Mw=19,600.

[synthesis example 6]

After being diluted to 6 mass % to the polyamic acid solution (562.0g) utilizing synthesis example 5 to obtain middle interpolation NMP, make Add acetic anhydride (197.5g) and pyridine (76.6g) for imidization catalyst, make it react 5 hours with 50 DEG C.This is anti- Solution is answered to put into methanol (5772ml), leaching gained precipitate.This precipitate methanol is cleaned, subtracts with 100 DEG C Press dry dry and obtain imide amination polymer powder.The acid imide rate of this imide amination polymer is 84%, number-average molecular weight Be 9,800, weight average molecular weight be 19,300.

[synthesis example 7]

DA-1 (8.1g, 35mmol) is put in the 100ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe, Adding NMP 76.7g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, add CA-6 (7.0g, 32.9mmol), and then add NMP 8.52g, use oil bath to stir 12 hours with 40 DEG C in a nitrogen atmosphere, thus To the polyamic acid solution that resin solid content concentration is 15 mass %.Viscosity at 25 DEG C of this polyamic acid solution is 192mPa·s.The molecular weight of this polyamic acid is Mn=8,300, Mw=23,700.

[synthesis example 8]

Put in the 100ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe DA-1 (5.9g, 26.0mmol), adding NMP 79.9g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, one CA-7 (6.1g, 24.4mmol) is added on limit, and then adds NMP 8.9g, uses oil bath little with 50 DEG C of stirrings 12 in a nitrogen atmosphere Time, thus obtain the polyamic acid solution that resin solid content concentration is 12 mass %.At 25 DEG C of this polyamic acid solution Viscosity is 72mPa s.

[synthesis example 9]

Put in the 1000ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe DA-2 (51.7g, 200mmol), adding NMP 672.2g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, one CA-1 (41.7g, 191.2mmol) is added on limit, and then adds NMP 168.1g, uses oil bath with 50 DEG C of stirrings in a nitrogen atmosphere 24 hours, thus obtain the polyamic acid solution that resin solid content concentration is 12 mass %.25 DEG C of this polyamic acid solution Under viscosity be 135mPa s.It addition, the molecular weight of this polyamic acid is Mn=12,600, Mw=30,900.

[synthesis example 10]

DA-3 (6.9g, 24mmol) is put in the 100ml four-neck flask of subsidiary agitating device and subsidiary nitrogen ingress pipe, Adding NMP 80.0g, supplying nitrogen is while stirring and making it dissolve.While stirring this two amine aqueous solution, add CA-1 (5.0g, 23mmol), adds NMP in the way of solid component concentration reaches 12 mass %, uses oil bath late with 50 DEG C of stirrings one And obtain the solution of polyamic acid.Viscosity at 25 DEG C of this polyamic acid solution is 525mPa s.It addition, this polyamic acid Molecular weight be Mn=14,800, Mw=32,500.

[embodiment 1]

NMP 19.0g, 3-amino is added in the polyamic acid solution 50.0g utilizing the synthetic method of synthesis example 1 to obtain Propyl-triethoxysilicane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal that concentration is 6 mass % and takes To agent (A-1).This aligning agent for liquid crystal (A-1) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as the most molten Liquid.

[embodiment 2]

NMP 29.0g, 3-aminopropan is added in the molten 40.0g of the polyamic acid utilizing the synthetic method of synthesis example 2 to obtain Ethyl triethoxy silicane alkane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal aligning that concentration is 6 mass % Agent (A-2).This aligning agent for liquid crystal (A-2) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as uniform solution.

[embodiment 3]

NMP 19.0g, 3-amino is added in the polyamic acid solution 50.0g utilizing the synthetic method of synthesis example 3 to obtain Propyl-triethoxysilicane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal that concentration is 6 mass % and takes To agent (A-3).This aligning agent for liquid crystal (A-3) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as the most molten Liquid.

[embodiment 4]

NMP (113.3g) is added in the poly amic acid ester powder (10.0g) utilizing the synthetic method of synthesis example 4 to obtain, It is made to dissolve with 23 DEG C of stirrings 12 hours.Adding APTES in this solution is 1.0 weight % Nmp solution 10.0g, BCS (33.3g), obtain aligning agent for liquid crystal (A-4) with 23 DEG C of stirrings 2 hours.This aligning agent for liquid crystal (A- 4) do not observe in that the generation etc. of muddiness, precipitate is abnormal, confirm as uniform solution.

[embodiment 5]

NMP 29.0g, 3-amino is added in the polyamic acid solution 40.0g utilizing the synthetic method of synthesis example 5 to obtain Propyl-triethoxysilicane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal that concentration is 6 mass % and takes To agent (A-5).This aligning agent for liquid crystal (A-5) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as the most molten Liquid.

[embodiment 6]

NMP is added in the imide amination polymer powder (10.0g) utilizing the synthetic method of synthesis example 6 to obtain (113.3g), it is made to dissolve with 23 DEG C of stirrings 12 hours.Adding APTES in this solution is 1.0 Nmp solution 10.0g, BCS (33.3g) of weight %, obtains aligning agent for liquid crystal (A-6) with 23 DEG C of stirrings 2 hours.This liquid crystal takes In agent (A-6), do not observe that the generation etc. of muddiness, precipitate is abnormal, confirm as uniform solution.

[embodiment 7]

NMP 29.0g, 3-amino is added in the polyamic acid solution 40.0g utilizing the synthetic method of synthesis example 7 to obtain Propyl-triethoxysilicane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal that concentration is 6 mass % and takes To agent (A-7).This aligning agent for liquid crystal (A-7) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as the most molten Liquid.

[embodiment 8]

NMP 19.0g, 3-amino is added in the polyamic acid solution 50.0g utilizing the synthetic method of synthesis example 8 to obtain Propyl-triethoxysilicane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal that concentration is 6 mass % and takes To agent (A-8).This aligning agent for liquid crystal (A-8) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as the most molten Liquid.

[comparative example 1]

NMP 19.0g, 3-amino is added in the polyamic acid solution 50.0g utilizing the synthetic method of synthesis example 9 to obtain Propyl-triethoxysilicane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal that concentration is 6 mass % and takes To agent (B-1).This aligning agent for liquid crystal (B-1) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as the most molten Liquid.

[comparative example 2]

NMP 19.0g, 3-amino is added in the polyamic acid solution 50.0g utilizing the synthetic method of synthesis example 10 to obtain Propyl-triethoxysilicane is the nmp solution 6.0g and BCS 25.0g of 1.0 weight %, obtains the liquid crystal that concentration is 6 mass % and takes To agent (B-2).This aligning agent for liquid crystal (B-2) not observed, the generation etc. of muddiness, precipitate is abnormal, confirms as the most molten Liquid.

After being filtered with the filter of 1.0 μm by gained aligning agent for liquid crystal, it is spin-coated on the glass base of subsidiary transparency electrode On plate, after the hot plate of 80 DEG C is dried 2 minutes, obtain the film of thickness 100nm so that 230 DEG C are burnt till 20 minutes.Prepare this 2 substrates that sample operates and obtains, after spreading the pearl sept of 4 μm, drip close on the liquid crystal aligning face of a substrate Envelope agent (Xie Li KCC XN-1500T).Then, with the liquid crystal orientation film of another substrate facing to inner side, substrate Overlapping widths reach the mode of 1cm and fit.Now, the diameter of the sealant after laminating is adjusted in the way of reaching about 3mm The dripping quantity of whole sealant.After 2 substrates of laminating are fixed with fixture, make its heat cure 1 hour with 120 DEG C, thus make The sample of cementability evaluation.

The desktop precision universal testing machine AGS-X 500N manufactured with Shimadzu Seisakusho Ltd. by the sample made is fixing up and down Behind the end of substrate, press from the top in substrate center portion, measure the pressure (N) when peeling off.Further, use with by measuring Sealant diameter estimation area (mm²) pressure (N) is standardized and the value that obtains, implement the evaluation of bonding force.

The result of the bonding force implemented for aligning agent for liquid crystal A-1～A-8, B-1～B-2 is shown in table 1.

[table 1]

After being filtered with the filter of 1.0 μm by gained aligning agent for liquid crystal, it is spin-coated on the glass base of subsidiary transparency electrode On plate, after the hot plate of 80 DEG C is dried 2 minutes, burns till 20 minutes with 230 DEG C, thus obtain the film of thickness 100nm.Should Imide amination polymer film artificial silk cloth carries out brushing and (roller diameter 120mm, rotating speed 1000rpm, translational speed 20mm/ second, presses Signature amount 0.4mm) after, pure water carries out the ultrasonic irradiation of 1 minute, is dried 10 minutes with 80 DEG C.Prepare 2 this band liquid crystal The substrate of alignment films, after the liquid crystal aligning face of a substrate arranges the sept of 4 μm, becomes with the brushing direction of 2 substrates Being combined for antiparallel mode, seal around but leave liquid crystal injecting port, production unit spacing is the dummy cell of 4 μm.? Under room temperature, in this unit, vacuum injects liquid crystal (MLC-2041, MERCK CORPORATION system), seals inlet and makes anti- Parallel liquid crystal cells.

By the state of orientation of this liquid crystal cells of polarized light microscope observing, be denoted as when not being orientated defect " well ", It is denoted as " bad " during orientation defect.

After being heated 30 minutes with 110 DEG C by this liquid crystal cells, carry out the mensuration of tilt angle.Mensuration employs オプトメトリ The Axo Scan Mueller Matrix Polarimeter that Network ス company manufactures.

The result of the tilt angle implemented for aligning agent for liquid crystal A-1～A-8, B-1～B-2 and orientation is shown in table 2.

[table 2]

Industrial applicability

The aligning agent for liquid crystal of the present invention represents in element by improving at the narrow edge liquid crystal being able to ensure that bigger expression face The cementability of sealant and liquid crystal orientation film and can solve the problem that the expression of adjacent edges is uneven, be industrially useful.

Claims

1. an aligning agent for liquid crystal, it is characterised in that it is for obtaining containing selected from making diamine component react with tetracarboxylic acid derivatives To polyimide precursor and this polyimide precursor is carried out imidizate and in the imide amination polymer that obtains at least 1 The aligning agent for liquid crystal planted, this polyimide precursor has the repetitive shown in following formula (1),

In formula (1), Y is the divalent organic group being derived from diamine component, and X is the 4 valency organic groups being derived from tetracarboxylic acid derivatives, A¹With A²Be each independently hydrogen atom or optionally have substituent group carbon number 1～10 alkyl, optionally there is the carbon number of substituent group The thiazolinyl of 1～10, optionally there is the alkynyl of the carbon number 1～10 of substituent group, R¹For hydrogen atom or the alkyl of carbon number 1～10, at least A part of Y is the structure of following formula (2),

Aligning agent for liquid crystal the most according to claim 1, wherein, in the repetitive shown in described formula (1), at least partially X is the 4 valency organic groups with ester ring type structure or aliphatic structure.

Aligning agent for liquid crystal the most according to claim 2, wherein, in the repetitive shown in described formula (1), at least partially X is the structure in following (X-9), (X-26), (X-27),

Aligning agent for liquid crystal the most according to claim 2, wherein, in the repetitive shown in described formula (1), X is to have fat The ratio of 4 valency organic groups of ring structures or aliphatic structure is 10～100 moles of %.

Aligning agent for liquid crystal the most according to claim 3, wherein, in the repetitive shown in described formula (1), X be (X-9), (X-26), the ratio of the arbitrary structures in (X-27) is 10～100 moles of %.

6. according to the aligning agent for liquid crystal according to any one of Claims 1 to 5, wherein, the repetitive shown in described formula (1) In, Y be the ratio of the structure of formula (2) be 10～100 moles of %.

7. a liquid crystal orientation film, it is that the aligning agent for liquid crystal according to any one of claim 1～6 is coated substrate and burnt Become and obtain.

8. liquid crystal represents an element, and it has the liquid crystal orientation film described in claim 7.