CN109791330A

CN109791330A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Info

Publication number: CN109791330A
Application number: CN201780060320.8A
Authority: CN
Inventors: 金尔润
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-09-29
Filing date: 2017-09-28
Publication date: 2019-05-21
Anticipated expiration: 2037-09-28
Also published as: KR102465496B1; TW201827576A; TWI754675B; WO2018062437A1; KR20190055196A; JPWO2018062437A1; JP7089228B2; CN109791330B

Abstract

A kind of aligning agent for liquid crystal, it is characterized in that, contain: at least one kind of polymer and organic solvent in the imide amination polymer selected from polyamic acid and the polyamic acid, the polyamic acid are to be obtained using including the tetrabasic carboxylic acid of tetracarboxylic dianhydride shown in following formula (1) and aliphatic tetracarboxylic dianhydride and the diamines comprising diamines shown in following formula (2) with the ratio of 10:90~90:10.

Description

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

Technical field

The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression member for using it that element is indicated for liquid crystal Part.

Background technique

All the time, liquid-crystal apparatus is widely used as the expressed portion of PC, mobile phone, television receiver etc..Liquid crystal dress It sets and for example has: the pixel electrode for being held on the liquid crystal layer between device substrate and filter substrate, applying electric field to liquid crystal layer The electric signal that pixel electrode is supplied with common electrode, the alignment films of the orientation for the liquid crystal molecule for controlling liquid crystal layer, conversion Thin film transistor (TFT) (TFT) etc..Driving method as liquid crystal molecule, it is known to the longitudinal electric fields mode such as TN mode, VA mode； The Transverse electric-field types (such as patent document 1) such as IPS mode, boundary electric field switching (hereinafter referred to as FFS) mode.

And in recent years, liquid crystal indicates that the economy of element and organic EL element in production process is also extremely important, therefore It is required that the regeneration of device substrate.That is, being checked after forming liquid crystal orientation film by aligning agent for liquid crystal to orientation etc. And when defective generation, it is desirable that can easily implement to remove liquid crystal orientation film from substrate and recycle the rework process of substrate. But baking does not dissolve in organic solvent later the obtained liquid crystal orientation film of the aligning agent for liquid crystal by proposing is instead in the past after Target is used as etc. to reduce film loss.In addition, the aligning agent for liquid crystal that even if research will be carried out to re-workability so far Composition be directly used in the composition of transverse electric field aligning agent for liquid crystal, it is also different surely to reach desired purpose, it is necessary to Actual evaluation is carried out whether excellent to the re-workability of aligning agent for liquid crystal again, and most suitable composition is constituted and is carried out repeatedly Research.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-167782 bulletin

Summary of the invention

Problems to be solved by the invention

The object of the present invention is to provide the liquid crystal alignings that one kind can obtain the excellent liquid crystal orientation film of re-workability Agent.

The solution to the problem

The inventors of the present invention have made intensive studies to solve the above subject, as a result, it has been found that, by using by comprising specific Aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride tetrabasic carboxylic acid and diamines with specific structure obtained from gather The imide amination polymer of amic acid and polyamic acid can obtain the excellent liquid crystal orientation film of re-workability, so as to complete The present invention.

The present invention is the invention based on above-mentioned opinion as a result, with following purports.

1. a kind of aligning agent for liquid crystal, which is characterized in that contain: the imidizate selected from polyamic acid and the polyamic acid is poly- At least one kind of polymer and organic solvent in object are closed, the polyamic acid is to include using with the ratio of 10:90~90:10 Tetracarboxylic dianhydride's ingredient of tetracarboxylic dianhydride shown in following formula (1) and aliphatic tetracarboxylic dianhydride and include following formula (2) Shown in diamines diamine component obtained from.

(in formula (1), i is 0 or 1, and X is singly-bound, the straight chain of ehter bond, carbonyl, ester bond, phenylene, carbon atom number 1~20 is sub- Alkyl, the branched alkylidene of carbon atom number 2~20, the cyclic alkylidene of carbon atom number 3~12, sulfonyl, amido bond or by The group that they are composed, wherein the alkylidene of carbon atom number 1~20 is optionally interrupted by the key selected from ester bond and ehter bond, sub- The carbon atom of phenyl and alkylidene is optionally by halogen atom, cyano, alkyl, halogenated alkyl, alkoxy and halogenated alkoxy One or more identical or different substituent groups replace.

In formula (2), Y₁For 2 at least one kind of structure in the group being made of amino, imino group and nitrogen-containing heterocycle Valence organic group, or be 2 in amino, imino group and the nitrogen-containing heterocycle replaced on nitrogen-atoms by hot detachment group Valence organic group, B₁、B₂It is separately hydrogen atom or alkyl, alkenyl, the alkynes of the optionally carbon number 1~10 with substituent group Base.)

2. the aligning agent for liquid crystal according to 1, which is characterized in that 10~100 in aforementioned tetracarboxylic dianhydride's ingredient rub Your % is tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride shown in previously described formula (1).

3. according to aligning agent for liquid crystal described in 1 or 2, which is characterized in that 10~100 moles of % in aforementioned diamine component are The diamines of formula (2).

4. the aligning agent for liquid crystal according to any one of 1~3, wherein the Y in formula (2)₁For selected from following formula (YD-1) It is at least one kind of in the structure of~(YD-5).

(in formula (YD-1), A₁For the nitrogen atom heterocycle of carbon number 3~15, Z₁For hydrogen atom or optionally with substituent group Carbon number 1~20 alkyl.In formula (YD-2), W₁For the alkyl of carbon number 1~10, A₂For the carbon number 3 with nitrogen atom heterocycle~ 15 1 valence organic group or the disubstituted amido replaced by the aliphatic group of carbon number 1~6.In formula (YD-3), W₂For carbon Number 6~15 and the divalent organic group with 1~2 phenyl ring, W₃For the alkylidene or biphenylene of carbon number 2~5, Z₂For hydrogen original Son, the alkyl of carbon number 1~5, phenyl ring or hot detachment group, the integer that a is 0~1.In formula (YD-4), A₃For carbon number 3~15 Nitrogen atom heterocycle.In formula (YD-5), A₄For the nitrogen atom heterocycle of carbon number 3~15, W₅For the alkylidene of carbon number 2~5.)

5. the aligning agent for liquid crystal according to 4, wherein described in formula (YD-1), (YD-2), (YD-4) and (YD-5) A₁、A₂、A₃And A₄For selected from by pyrrolidines, pyrroles, imidazoles, pyrazoles, oxazole, thiazole, piperidines, piperazine, pyridine, pyrazine, indoles, It is at least one kind of in the group that benzimidazole, quinoline, isoquinolin form.

6. the aligning agent for liquid crystal according to any one of 1~5, wherein the Y in formula (2)₁For selected from by with following formula (YD-6) at least one kind of in the group of the divalent organic group composition of~(YD-21) structure.

(in formula (YD-17), the integer that h is 1~3, in formula (YD-14) and (YD-21), j for 1~3 integer.)

7. the aligning agent for liquid crystal according to 6, which is characterized in that the Y in formula (2)₁For selected from by with above-mentioned formula (YD- 14) at least one kind of and in the group of the divalent organic group of the structure of (YD-18) composition.

8. the aligning agent for liquid crystal according to any one of 1~7, wherein tetracarboxylic dianhydride shown in previously described formula (1) is 3, 3 ', 4,4 '-biphenyltetracarboxylic dianhydrides.

9. the aligning agent for liquid crystal according to any one of 1~8, wherein aforementioned aliphatic tetracarboxylic dianhydride is bicyclic [3.3.0] octane 2,4,6,8- tetrabasic carboxylic acid 2,4:6,8 dianhydride (bicyclo [3.3.0] octane-2,4,6,8- tetracarboxylic acid-2,4:6,8-dianhydride)。

10. a kind of liquid crystal orientation film is obtained from aligning agent for liquid crystal described in any one of coating 1~9 and firing.

11. a kind of liquid crystal indicates element, have 10 described in liquid crystal orientation film.

The effect of invention

The re-workability of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention is excellent.

Specific embodiment

Aligning agent for liquid crystal of the invention is characterized in that, is contained: the imidizate selected from polyamic acid He the polyamic acid At least one kind of polymer and organic solvent in polymer, the polyamic acid are using comprising four shown in following formula (1) The tetracarboxylic acid sour component of carboxylic acid dianhydride and aliphatic tetracarboxylic dianhydride and diamine component comprising diamines shown in following formula (2) Obtained from.

In formula (1), i be 0 or 1, X be singly-bound, ehter bond, carbonyl, ester bond, phenylene, carbon atom number 1~20 straight chain alkylene Base, the branched alkylidene of carbon atom number 2~20, the cyclic alkylidene of carbon atom number 3~12, sulfonyl, amido bond or by it The group that is composed, wherein the alkylidene of carbon atom number 1~20 is optionally interrupted by the key selected from ester bond and ehter bond, sub- benzene The carbon atom of base and alkylidene is optionally by 1 in halogen atom, cyano, alkyl, halogenated alkyl, alkoxy and halogenated alkoxy A or multiple identical or different substituent groups replace.

In formula (2), Y₁For 2 at least one kind of structure in the group being made of amino, imino group and nitrogen-containing heterocycle Valence organic group, or be 2 in amino, imino group and the nitrogen-containing heterocycle replaced on nitrogen-atoms by hot detachment group Valence organic group, B₁、B₂It is separately hydrogen atom or alkyl, alkenyl, the alkynes of the optionally carbon number 1~10 with substituent group Base.

Hereinafter, each constitutive characteristic is described in detail.

As tetracarboxylic dianhydride shown in above-mentioned formula (1), following compound can be enumerated, but be not limited to these.

(in formula, q indicates 1~20 integer.)

In the tetracarboxylic dianhydride shown in these formulas (1), from the viewpoint of re-workability improvement is good, preferred formula (1) i is 1 in tetracarboxylic dianhydride, i.e. with the tetracarboxylic dianhydride of 2 or more phenyl ring, preferred (1-2) among above-mentioned concrete example~ (1-11), from the viewpoint of containing biphenyl structural and there is rigid structure, 3,3 ', 4,4 '-shown in particularly preferred formula (1-5) Biphenyltetracarboxylic dianhydride.

Specific aliphatic tetracarboxylic dianhydride used in the present invention, can enumerate tetrabasic carboxylic acid shown in following formula (3) Dianhydride.

In formula, X₁For any one of following (X-1)~(X-28).

In formula (X-1), R₃~R₆Separately for hydrogen atom, carbon number 1~6 alkyl or phenyl, more preferable hydrogen atom or Methyl.

Among above-mentioned, (X-1)~(X-20) be from the viewpoint of not including aromatic series position it is preferred, (X-10) is from outstanding It is most preferred from the perspective of being not susceptible to hot-imide.

In tetracarboxylic dianhydride's ingredient entirety of (A) ingredient for manufacturing the present invention, if tetrabasic carboxylic acid two shown in formula (1) Total amount shared by acid anhydride and aliphatic acid dianhydride is very few, then can not obtain effect of the invention.Therefore, tetrabasic carboxylic acid shown in formula (1) The total amount of dianhydride and aliphatic acid dianhydride is relative to 1 mole of whole tetracarboxylic dianhydrides, preferably 10~100 moles of %, more preferably For 50~100 moles of %, further preferably 80~100 moles of %.

The containing ratio of tetracarboxylic dianhydride shown in formula (1) and aliphatic acid dianhydride is the ratio of 10:90~90:10, excellent It is selected as 20:80~80:20, the ratio of further preferably 40:60~60:40, the ratio of particularly preferably 46:54~54:46, It is most preferably essentially equivalent.

Tetracarboxylic dianhydride shown in formula (1) and aliphatic tetracarboxylic dianhydride can be used alone respectively, and can also combine makes With a variety of, in this case tetracarboxylic dianhydride shown in preferred formula (1) and aliphatic tetracarboxylic dianhydride amount to using it is above-mentioned preferably Amount.

Polyamic acid contained by aligning agent for liquid crystal of the invention is in addition to using tetracarboxylic dianhydride and fat shown in formula (1) Other than race tetracarboxylic dianhydride, tetracarboxylic dianhydride shown in following formula (4) also can be used.

In formula (4), X is 4 valence organic groups, its structure is not particularly limited.It, can be with if enumerating specific example Enumerate following formula (X-31)~(X-36) structure.

Diamine component used in the manufacture of aligning agent for liquid crystal of the invention contains the diamines of above-mentioned formula (2).Formula (2) In, Y₁For the divalent organic group at least one kind of structure in the group being made of amino, imino group and nitrogen-containing heterocycle, or Person is the divalent organic group in amino, imino group and the nitrogen-containing heterocycle replaced on nitrogen-atoms by hot detachment group, B₁、B₂It is separately hydrogen atom or alkyl, alkenyl, the alkynyl of the optionally carbon number 1~10 with substituent group.

As the concrete example of abovementioned alkyl, methyl, ethyl, propyl, butyl, tert-butyl, hexyl, octyl, the last of the ten Heavenly stems can be enumerated Base, cyclopenta, cyclohexyl etc..As alkenyl, it can enumerate and replace 1 or more present in abovementioned alkyl CH-CH structure At group obtained from C=C structure, more specifically, vinyl, allyl, 1- acrylic, isopropenyl, 2- fourth can be enumerated Alkenyl, 1,3- butadienyl, 2- pentenyl, 2- hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc..It, can as alkynyl To enumerate 1 or more present in aforesaid alkyl CH₂-CH₂Structure is replaced to group obtained from C ≡ C-structure, more specifically Ground can enumerate acetenyl, 1- propinyl, 2-propynyl etc..

Abovementioned alkyl, alkenyl, alkynyl can have substituent group as long as whole carbon number is 1~10, and then can also be by Substituent group and form ring structure.Refer to it should be noted that forming ring structure by substituent group, substituent group is each other or substituent group It is bonded with a part of female skeleton and forms ring structure.

Example as the substituent can enumerate halogen group, hydroxyl, sulfydryl, nitro, aryl, organic oxygroup, organic Sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide groups, alkyl, alkenyl, alkynyl.

As the halogen group for belonging to substituent group, fluorine atom, chlorine atom, bromine atom, iodine atom can be enumerated.

As the aryl for belonging to substituent group, phenyl can be enumerated.The aryl is optionally further taken by aforementioned other substituent groups Generation.

As the organic oxygroup for belonging to substituent group, structure shown in O-R can be shown.The R can be the same or different, It may be exemplified out aforesaid alkyl, alkenyl, alkynyl, aryl etc..These R are optionally further substituted with by foregoing substituents.As alcoxyl The concrete example of base can enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy etc..

As the organic sulfenyl for belonging to substituent group, structure shown in-S-R can be shown.As the R, before may be exemplified out State alkyl, alkenyl, alkynyl, aryl etc..These R are optionally further substituted with by foregoing substituents.It, can as the concrete example of alkylthio group To enumerate methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, sulfenyl in heptan, pungent sulfenyl etc..

As the Organosilyl for belonging to substituent group ,-Si- (R) can be shown₃Shown in structure.The R can be identical Can be different, it may be exemplified out aforesaid alkyl, alkenyl, alkynyl, aryl etc..These R are optionally further substituted with by foregoing substituents. As the concrete example of aIkylsilyl groups, trimethyl silyl, triethylsilyl, tripropylsilyl can be enumerated Base, tributylsilyl, three amyl silicyls, three hexyl silicyls, amyl dimethyl silicyl, hexyl dimethyl Silicyl etc..

As the acyl group for belonging to substituent group, structure shown in-C (O)-R can be shown.As the R, may be exemplified out aforementioned Alkyl, alkenyl, aryl etc..These R are optionally further substituted with by foregoing substituents.As the concrete example of acyl group, first can be enumerated Acyl group, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc..

As the ester group for belonging to substituent group, structure shown in-C (O) O-R or-OC (O)-R can be shown.It, can as the R To exemplify aforesaid alkyl, alkenyl, alkynyl, aryl etc..These R are optionally further substituted with by foregoing substituents.

As the thioester substrate for belonging to substituent group, structure shown in-C (S) O-R or-OC (S)-R can be shown.As the R, It may be exemplified out aforesaid alkyl, alkenyl, alkynyl, aryl etc..These R are optionally further substituted with by foregoing substituents.

As the phosphate-based of substituent group is belonged to ,-OP (O)-(OR) can be shown₂Shown in structure.The R can be identical Can be different, it may be exemplified out aforesaid alkyl, alkenyl, alkynyl, aryl etc..These R are optionally further substituted with by foregoing substituents.

As the amide groups for belonging to substituent group ,-C (O) NH can be shown₂Or-C (O) NHR ,-NHC (O) R ,-C (O) N (R)₂, structure shown in-NRC (O) R.The R can be the same or different, and may be exemplified out aforesaid alkyl, alkenyl, alkynyl, virtue Base etc..These R are optionally further substituted with by foregoing substituents.

As the aryl for belonging to substituent group, group identical with aforesaid aryl can be enumerated.The aryl optionally by it is aforementioned its Its substituent group is further substituted with.

As the alkyl for belonging to substituent group, group identical with aforesaid alkyl can be enumerated.The alkyl optionally by it is aforementioned its Its substituent group is further substituted with.

As the alkenyl for belonging to substituent group, group identical with foregoing alkenyl can be enumerated.The alkenyl optionally by it is aforementioned its Its substituent group is further substituted with.

As the alkynyl for belonging to substituent group, group identical with aforementioned alkynyl can be enumerated.The alkynyl optionally by it is aforementioned its Its substituent group is further substituted with.

In general, when importing the structure of large volume, it is possible to the reactivity of amino, liquid crystal aligning are reduced, therefore, as B₁And B₂, the more preferably alkyl of hydrogen atom or the optionally carbon number 1~5 with substituent group, particularly preferably hydrogen atom, methyl Or ethyl.

As the Y in formula (2)₁Structure, as long as have in the group being made of amino, imino group and nitrogen-containing heterocycle At least one kind of structure, or in amino, imino group and the nitrogen-containing heterocycle replaced on nitrogen-atoms by hot detachment group At least one kind of structure, then its structure is not particularly limited.To specially enumerate its concrete example, then following formula can be enumerated (YD-1) there are 2 of at least one kind of structure in the group being made of amino, imino group and nitrogen-containing heterocycle shown in~(YD-5) Valence organic group.

In formula (YD-1), A₁For the nitrogen atom heterocycle of carbon number 3~15, Z₁For hydrogen atom or optionally with substituent group The alkyl of carbon number 1~20.

In formula (YD-2), W₁For the alkyl of carbon number 1~10, A₂1 valence for the carbon number 3~15 with nitrogen atom heterocycle has Machine group or the disubstituted amido replaced by the aliphatic group of carbon number 1~6.

In formula (YD-3), W₂For carbon number 6~15 and with the divalent organic group of 1~2 phenyl ring, W₃For the Asia of carbon number 2~5 Alkyl or biphenylene, Z₂For hydrogen atom, the alkyl of carbon number 1~5, phenyl ring or hot detachment group, a be 0~1 it is whole Number.

In formula (YD-4), A₃For the nitrogen atom heterocycle of carbon number 3~15.

In formula (YD-5), A₄For the nitrogen atom heterocycle of carbon number 3~15, W₅For the alkylidene of carbon number 2~5.)

As formula (YD-1), (YD-2), (YD-4) and (YD-5) A₁、A₂、A₃And A₄Carbon number 3~15 nitrogen atom Heterocycle is not particularly limited as long as well known structure.Wherein it is possible to enumerate pyrrolidines, pyrroles, imidazoles, pyrazoles, oxazole, Thiazole, piperidines, piperazine, pyridine, pyrazine, indoles, benzimidazole, quinoline, isoquinolin, carbazole, more preferable piperazine, piperidines, indoles, Benzimidazole, imidazoles, carbazole and pyridine.

In addition, for hot detachment group, as long as at room temperature without departing from, be detached from and replace when alignment films are burnt into At the substituent group of hydrogen atom, specifically, tert-butoxycarbonyl and 9- fluorenylmethoxycarbonyl groups can be enumerated.

In turn, as the Y in formula (2)₂Concrete example, can enumerate has shown in following formula (YD-6)~(YD-52) The divalent organic group of nitrogen-atoms, in order to inhibit charge accumulation caused by driving because of exchange, more preferable formula (YD-14)~formula (YD-21), particularly preferably (YD-14) and (YD-18).

In formula (YD-14) and (YD-21), j be 0~3 integer.

In formula (YD-24), (YD-25), (YD-28) and (YD-29), j be 0~3 integer.In formula (YD-17), h be 1~ 3 integer.

(in formula (YD-50), m, n are respectively 1~11 integer, the integer that m+n is 2~12.)

For the ratio of diamines shown in the formula (2) in the imide amination polymer of polyamic acid and polyamic acid of the invention Example, preferably with respect to 1 mole of whole diamines for 10~100 moles of %, more preferably 30~100 moles of %, further preferably 50~100 moles of %.

As shown in the formula (2) in the polyamic acid of (A) ingredient and the imide amination polymer of polyamic acid of the invention Diamines may be used alone, can also be used in combination a variety of, diamines shown in preferred formula (2) is amounted to using upper in this case State preferred amounts.

Polyamic acid contained by aligning agent for liquid crystal of the invention other than using diamines shown in above-mentioned formula (2), Diamines shown in following formula (5) can be used.Y in following formula (5)₂For divalent organic group, its structure is not limited especially It is fixed, two or more can also be mixed.To specially enumerate its concrete example, then can enumerate following (Y-1)~(Y-49) and (Y-57)~(Y-97).

H₂N-Y₂-NH₂ (5)

Contained by aligning agent for liquid crystal of the invention as the polyamic acid of (A) ingredient and the imidizate of polyamic acid In polymer, when the increasing proportion of diamines shown in formula (5), it is possible to damage effect of the invention, thus be undesirable.Cause This, the ratio of diamines shown in formula (5) 0~50 is rubbed relative to 1 mole of whole diamines preferably 0~90 mole of %, more preferably You are %, further preferably 0~20 mole of %.

Polyamic acid used in the present invention as polyimide precursor can be synthesized by method as shown below.

Specifically, can by make tetracarboxylic dianhydride and diamines in presence of organic solvent with -20~150 DEG C, it is excellent It selects 0~70 DEG C to react 30 minutes~24 hours, react 1~12 hour preferably to synthesize.

From the viewpoint of the dissolubility of monomer and polymer, organic solvent used in above-mentioned reaction is preferably N, N- bis- Methylformamide, n-methyl-2-pyrrolidone, gamma-butyrolacton etc., they can be used a kind or are mixed with two or more.

From the viewpoint of polymer is not easy to be precipitated and be easy to get high molecular weight body, the concentration of polymer is preferably 1~ 30 mass %, more preferably 5~20 mass %.

Polyamic acid obtained from above-mentioned such operation is bad molten by being injected into while reaction solution is sufficiently stirred In agent, so as to which polymer is precipitated and is recycled.In addition, passing through after being repeatedly precipitated and being cleaned with poor solvent Air drying or heat drying can obtain the polyamic acid powder through refining.Poor solvent is not particularly limited, Ke Yiju Water outlet, methanol, ethyl alcohol, 2- propyl alcohol, hexane, butyl cellosolve, acetone, toluene etc., preferably water, methanol, ethyl alcohol, 2- propyl alcohol Deng.

Polyimides used in the present invention can be manufactured by carrying out imidizate to foregoing polyamides acid.

In the case where manufacturing polyimides by polyamic acid, to obtained from being reacted as diamine component with tetracarboxylic dianhydride It is easy that the chemical imidization of catalyst is added in the solution of foregoing polyamides acid.Chemical imidization is at a lower temperature Imidization reaction is carried out, the molecular weight that polymer is not susceptible to during imidizate reduces, and is therefore preferred.

Chemical imidization can be by the way that stirring is wanted to make in the presence of basic catalyst and acid anhydrides in organic solvent The polymer of its imidizate carries out.As organic solvent, solvent used when aforementioned polymeric reaction can be used.As alkali Property catalyst, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, pyridine have for make to react into Appropriate alkalinity for row, thus be preferred.In addition, acetic anhydride, trimellitic anhydride, equal benzene four can be enumerated as acid anhydrides Acid anhydrides etc., wherein when using acetic anhydride, be easy purification after reaction, thus be preferred.

Temperature when carrying out imidization reaction is -20~140 DEG C, preferably 0~100 DEG C, the reaction time can with 1~ It carries out within 100 hours.The amount of basic catalyst is 0.5~30 times mole, preferably 2~20 times moles of polyamide acidic group, acid The amount of acid anhydride is 1~50 times mole, preferably 3~30 times moles of polyamide acidic group.The acid imide rate of resulting polymers can be with It is controlled by adjusting catalytic amount, temperature, reaction time.

Due to remaining added catalyst etc. in the solution after the imidization reaction of polyamic acid, it is therefore preferable that Obtained imide amination polymer is recycled by following means, and is redissolved with organic solvent, so that this hair be made Bright aligning agent for liquid crystal.

The solution of polyimides obtained from operation can be bad by injecting while being sufficiently stirred as described above In solvent, so that polymer be made to be precipitated.It is precipitated and is cleaned with poor solvent for several times, then carried out air drying or heating is dry It is dry, it is hereby achieved that the polymer powder through refining.

Aforementioned poor solvent is not particularly limited, can enumerate methanol, 2- propyl alcohol, acetone, hexane, butyl cellosolve, Heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene etc., preferably methanol, ethyl alcohol, 2- propyl alcohol, acetone etc..

Aligning agent for liquid crystal used in the present invention is dissolved in organic solvent with component of polymer and the solution shape of formation State.The molecular weight of polymer with Weight-average molecular meter, preferably 2,000~500,000, more preferably 5,000~300,000, Further preferably 10,000~100,000.In addition, number-average molecular weight is preferably 1,000~250,000, more preferably 2,500 It~150,000, is more preferably 5,000~50,000.

The polymer concentration of aligning agent for liquid crystal used in the present invention can setting according to the thickness for thinking film to be formed Fixed and suitable change, from the viewpoint of forming uniform and flawless film, preferably 1 mass % or more, from the guarantor of solution From the perspective of depositing stability, it is preferably set to 10 mass % or less.The concentration of particularly preferred polymer is 2~8 mass %.

Organic solvent contained in the aligning agent for liquid crystal used for the present invention, as long as keeping component of polymer equably molten The solvent of solution is just not particularly limited.If enumerating its concrete example, n,N-Dimethylformamide, N, N- diethyl can be enumerated Formamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N- methyl caprolactam, 2- Pyrrolidones, n-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3- methylimidazole quinoline Ketone, 3- methoxyl group-N, N- dimethylpropionamide etc..They can be used a kind or are mixed with two or more.Even in addition, single The solvent that component of polymer can not be made equably to dissolve in only situation, as long as in the range of polymer will not be precipitated, it can also be with It is mixed in above-mentioned organic solvent.

In addition, the organic solvent contained in aligning agent for liquid crystal is usually using mixed solvent, the mixed solvent is in addition to above-mentioned Except such solvent, the molten of the surface smoothness of coating when improving coating of liquid crystalline alignment agent or film has also been applied in combination Agent, it is also preferred that using this mixed solvent in aligning agent for liquid crystal of the invention.The tool for the organic solvent being applied in combination is enumerated below Body example, but it is not limited to these examples.

For example, ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanol, 2- methyl-1-pentene alcohol, 2- Methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, sec-n-octyl alcohol, 2- ethyl -1- hexanol, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 2,6- 2,6-dimethyl-4-heptanol, 1,2- ethylene glycol, 1,2- Propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, 2- first Base -2,4-PD, 2- ethyl -1,3- hexylene glycol, diisopropyl ether, dipropyl ether, butyl oxide, two hexyl ethers, dioxanes, ethylene glycol two Methyl ether, ethylene glycol diethyl ether, butyl cellosolve, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4- hydroxy-4-methyl-2-pentanone, diethylene glycol ethylmethyl ether, dibutyl ethylene glycol ether, 2 pentanone, propione, methyl-n-butyl ketone, 2- heptan Ketone, 4- heptanone, valerone, 4,6- dimethyl -2-HEPTANONE, 3- ethoxybutyl acetic acid esters, 1- methyl amyl second Acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol acetate, ethylene acetate, polypropylene carbonate Ester, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, ethylene glycol monohexylether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propyleneglycol monobutyl Ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol list Ether, dimethyl ether, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, second two Alcohol monobutyl ether-acetate, ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol list Butyl ether acetic acid esters, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol acetic acid esters, triethylene glycol, triethylene glycol list first Ether, Triethylene glycol ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, dihydroxypropane single-ether Acetic acid esters, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxyl ethyl propionate, 3- ethoxy-propionic acid first Base ethyl ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl Acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, following formula [D-1]~[D-3] Shown in solvent etc..

In formula [D-1], D¹The alkyl for indicating carbon number 1~3, in formula [D-2], D²Indicate the alkyl of carbon number 1~3, formula [D-3] In, D³Indicate the alkyl of carbon number 1~4.

Wherein, the combination as preferred solvent can enumerate: n-methyl-2-pyrrolidone, gamma-butyrolacton and second two Alcohol monobutyl ether；N-methyl-2-pyrrolidone, gamma-butyrolacton and propylene glycol monobutyl ether；N- ethyl-2-pyrrolidone and propylene glycol Monobutyl ether；N-methyl-2-pyrrolidone, gamma-butyrolacton, 4- hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether；N- first Base -2-Pyrrolidone, gamma-butyrolacton, propylene glycol monobutyl ether and valerone；N-methyl-2-pyrrolidone, γ- Butyrolactone, propylene glycol monobutyl ether and diisopropyl ether；N-methyl-2-pyrrolidone, gamma-butyrolacton, propylene glycol monobutyl ether and 2,6- 2,6-dimethyl-4-heptanol；N-methyl-2-pyrrolidone, gamma-butyrolacton and dimethyl ether etc..The type of such solvent It is suitable for selection according to apparatus for coating, application conditions, coating environment of aligning agent for liquid crystal etc. with content.

In addition, addition as follows can be added in aligning agent for liquid crystal of the invention in order to improve the mechanical strength of film Object.

These additives are 0.1~30 matter preferably with respect to 100 mass parts of component of polymer contained in aligning agent for liquid crystal Measure part.Effect can not be expected when lower than 0.1 mass parts, and the orientation of liquid crystal can be reduced when more than 30 mass parts, thus more preferably For 0.5~20 mass parts.

Apart from the above, aligning agent for liquid crystal of the invention can add within the scope of the effect of the invention: poly- Close the polymer other than object；The dielectric or conductive material of the electrical characteristics such as dielectric constant, electric conductivity for changing liquid crystal orientation film Matter；For improving the silane coupling agent of the adaptation of liquid crystal orientation film and substrate；Film when liquid crystal orientation film is made for improving The cross-linked compound of hardness, consistency；In turn, the imidizate for making polyamic acid when film is burnt into efficiently promotes Imidizate promotor etc..

Liquid crystal orientation film of the invention is that above-mentioned aligning agent for liquid crystal is coated on substrate and is dried, is burnt into and obtains Film.As the substrate for being coated with aligning agent for liquid crystal of the invention, it is not particularly limited as long as the high substrate of the transparency, it can be with Using plastic bases such as glass substrate, silicon nitride board, acrylic compounds substrate, polycarbonate substrate etc., the sight simplified from process Point sets out, it is preferable to use being formed with the substrate of ITO electrode for liquid crystal drive etc..In addition, indicating element in reflective liquid crystal In, if only if single sided substrate, the opaque substance such as Silicon Wafer also can be used, the meetings such as aluminium are also can be used in electrode at this time The material of reflected light.

As the coating method of aligning agent for liquid crystal of the invention, spin-coating method, print process, ink-jet method etc. can be enumerated.Coating Drying, firing process after aligning agent for liquid crystal of the invention can choose arbitrary temperature and time.It is contained in order to sufficiently remove Some organic solvents, usually with 50 DEG C~120 DEG C drying 1 minute~10 minutes, then with 150 DEG C~300 DEG C be burnt into 5 minutes~ 120 minutes.Coating thickness after firing is not particularly limited, when excessively thin, liquid crystal indicates that the reliability of element reduces sometimes, It therefore is 5~300nm, preferably 10~200nm.

As the method for carrying out orientation process to gained liquid crystal orientation film, brushing method, light orientation position logos etc. can be enumerated. Brushing processing can use existing brushing device and carry out.As the material of brushing cloth at this time, can enumerate cotton, nylon, Artificial silk etc..As the condition of brushing processing, usually using 300~2000rpm of revolving speed, 5~100mm/s of feed speed, indentation Measure the condition of 0.1~1.0mm.Then, the residue generated by brushing is removed by ultrasonic cleaning using pure water, alcohol etc..

As the concrete example of light orientation position logos, following method can be enumerated: aforementioned film coated surface is irradiated along certain side To the radiation of polarization, according to circumstances further heated with 150~250 DEG C of temperature, to assign liquid crystal aligning The method of ability.As radiation, the ultraviolet light and luminous ray of the wavelength with 100nm~800nm can be used.This it In, preferably there is the ultraviolet light of the wavelength of 100nm~400nm, the particularly preferably ultraviolet light of the wavelength with 200nm~400nm. In addition, in order to improve liquid crystal aligning, it can be with the illumination radiation line when being heated with 50~250 DEG C to painting ilm substrate.It is aforementioned The exposure of radiation is preferably 1~10,000mJ/cm², particularly preferably 100~5,000mJ/cm².Operation as described so And the liquid crystal orientation film prepared can be such that liquid crystal molecule is steadily orientated along certain orientation.

The extinction ratio of polarized UV rays is higher, then more can assign higher anisotropy, thus is preferred.It is specific and Speech, the extinction ratio of the ultraviolet light of linear polarization are preferably 10:1 or more, more preferably 20:1 or more.

For by the above-mentioned film for having irradiated polarized radiation line, next can with comprising selected from water and organic solvent at least 1 kind of solvent carries out contact treatment.

As solvent used in contact treatment, as long as the solvent of the decomposition product generated is irradiated in dissolution by light, just It is not particularly limited.As concrete example, water, methanol, ethyl alcohol, 2- propyl alcohol, acetone, methyl ethyl ketone, 1- methoxyl group -2- third can be enumerated Alcohol, 1- methoxy-2-propanol acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methoxypropionic acid first Ester, 3- ethoxyl ethyl propionate, propyl acetate, butyl acetate and cyclohexyl acetate etc..These solvents can be applied in combination 2 kinds with On.

From the viewpoint of versatility, safety, Free water, 2- propyl alcohol, 1- methoxy-2-propanol and cream are more preferably selected It is at least one kind of in the group of acetoacetic ester composition.The particularly preferably mixed solvent of water, 2- propyl alcohol and water and 2- propyl alcohol.

In the present invention, the contact treatment of the film and the solution containing organic solvent that have irradiated polarized radiation line passes through at dipping Processing that reason, spraying (spray) processing etc. can be such that film preferably comes into full contact with liquid carries out.These, it is preferred to containing The method that preferably 10 seconds~1 hour, more preferable impregnation in 1~30 minute are carried out to film in the solution of organic solvent.Contact position Reason can be room temperature or heating, preferably be implemented with 10~80 DEG C, more preferably with 20~50 DEG C.Furthermore it is possible to implement as needed The means of the raisings such as ultrasonic wave contact.

After above-mentioned contact treatment, in order to remove the organic solvent in solution used, it can carry out utilizing water, methanol, second The low boiling point solvents such as alcohol, 2- propyl alcohol, acetone, methyl ethyl ketone carry out rinsing (flushings), dry in any one or both.

In turn, the reorientation of the strand in the drying and film in order to carry out solvent can utilize solvent to by above-mentioned The film of contact treatment has been carried out to be heated with 150 DEG C or more.

As the temperature of heating, preferably 150~300 DEG C.Temperature is higher, more promotes the reorientation of strand, but temperature When excessively high, it is possible to the decomposition of strand.Therefore, as heating temperature, more preferably 180~250 DEG C, particularly preferably It is 200~230 DEG C.

When the time of heating is too short, it is possible to be unable to get the effect of the reorientation of strand, when too long, strand has can It can decompose, therefore preferably 10 seconds~30 minutes, more preferably 1 minute~10 minutes.

In addition, obtained liquid crystal orientation film is to be easy to be dissolved in the excellent film of reprocessing material, re-workability.

It as solvent used in reprocessing, can enumerate: glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol list The glycol ethers such as methyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether；Methylcellosolve acetate, ethyl cellosolve acetate, The diol-lipids such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid esters；Diethylene glycol, propylene glycol, butanediol, hexylene glycol etc. Glycols；The alcohols such as methanol, ethyl alcohol, 2- propyl alcohol, butanol；Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-HEPTANONE, gamma-butyrolacton Equal ketones；2 hydroxy propanoic acid methyl esters, 2- hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxyl Base -3 Methylbutanoic acid methyl esters, 3- methoxy methyl propionate, 3- methoxy methyl propionate, 3- ethoxyl ethyl propionate, 3- ethyoxyl The esters such as methyl propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate；N,N- The amides such as dimethylformamide, DMAC N,N' dimethyl acetamide and n-methyl-2-pyrrolidone.

As reprocessing material, comprising the alkaline components such as ethanol amine preferably in above-mentioned solvent, and include antirust agent so that The alkalinity will not cause to damage to other components such as electrodes.As the manufacturer of this reprocessing material is provided, Korea Spro can be enumerated The bright Industry Co., Ltd of the meeting of state, KPX Chemial etc..

Reprocessing passes through following process progress: the above-mentioned reprocessing material enumerated is with room temperature or is heated to 30 DEG C~100 DEG C Later, the substrate with liquid crystal orientation film is impregnated in wherein 1 second~1000 seconds, preferably 30 seconds~500 seconds；Or material will be reprocessed Material is sprayed with fountain, is then removed liquid and is cleaned with alcohols solvent or pure water.It should be noted that from operation The viewpoints such as efficiency are set out, and the temperature of rework solution when reprocessing is preferably low temperature, usually room temperature~60 DEG C, more preferably room Temperature~40 DEG C.

Liquid crystal of the invention indicates that element obtains as follows: being orientated by aligning agent for liquid crystal of the invention by foregoing liquid crystal The manufacturing method of film and after obtaining the substrate with liquid crystal orientation film, liquid crystal cells are prepared by well known method, are made using it Liquid crystal indicates element.

As an example of liquid crystal cells production method, with the liquid crystal of passive-matrix structure indicate element as an example into Row explanation.It should be noted that or being provided with TFT (thin film transistor (TFT) constituting each pixel portion that image is shown (Thin Film Transistor)) etc. the active matrix structure of switch elements liquid crystal indicate element.

Firstly, preparing transparent glass substrate of electrode, common electrode is set on one substrate, section is set on another substrate Electrode.These electrodes can for example form ITO electrode, form pattern in a manner of it can carry out desired image and show.It connects , on each substrate, insulating film is set in a manner of covering common electrode and segment electrode.Insulating film can such as be made by molten Glue-gel method formation is by SiO₂-TiO₂The film of formation.

Then, liquid crystal orientation film of the invention is formed on each substrate by the above method.

Then, it is overlapped another substrate to be orientated the mutually opposed mode of film surface on one substrate, by periphery sealant Bonding.In sealant, for control base board gap, it is usually mixed into spacer in advance.In addition, in the face for being not provided with sealant Part it is also preferred that be scattered with the spacer of substrate gap control in advance.Being previously provided in a part of sealant can be by outer The opening portion of portion's filling liquid crystal.

Then, by being set to the opening portion of sealant, liquid crystal is injected into the space surrounded by 2 plate bases and sealant Material.Then, the opening portion is sealed with bonding agent.Vacuum impregnation can be used in injection, also can be used and utilizes in an atmosphere The method of capillarity.Then, the setting of polarization plates is carried out.Specifically, being opposite side in 2 plate bases and liquid crystal layer Paste a pair of of polarization plates in face.Process more than, so that obtaining liquid crystal of the invention indicates element.

In the present invention, as sealant, it can be used for example with epoxy group, acryloyl group, methylacryloyl, hydroxyl Base, allyl, acetyl group isoreactivity group pass through ultraviolet light irradiation, the cured resin of heating.Particularly preferably using tool There is the solidified resin system of the reactive group of both epoxy group and (methyl) acryloyl group.

To improve cementability, moisture-proof can be compounded inorganic filler in sealant of the invention.As being able to use Inorganic filler, be not particularly limited, specifically, spherical silicon dioxide, fused silica, crystal dioxy can be enumerated SiClx, titanium oxide, titanium be black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talcum, Clay, aluminium oxide, magnesia, zirconium oxide, aluminium hydroxide, calcium silicates, alumina silicate, lithium aluminium silicate, zirconium silicate, barium titanate, glass Fiber, carbon fiber, molybdenum disulfide, asbestos etc., preferably spherical silicon dioxide, fused silica, crystalline silica, oxidation Titanium, titanium be black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminium oxide, aluminium hydroxide, silicon Sour calcium, alumina silicate.Aforementioned inorganic filler can be mixed with two or more.

The liquid crystal indicates the liquid crystal orientation film that element has used the manufacturing method of liquid crystal orientation film through the invention to obtain As liquid crystal orientation film, therefore re-workability is excellent, can be suitably used for the LCD TV etc. of big picture and high-resolution.

Embodiment

In the following, enumerating the reality studied raw material composition, mixed ratio for the details of the manufacturing method of the present invention The embodiment etc. of proved recipe method and its result and typical manufacturing method is illustrated.It should be noted that the present invention does not limit In these embodiments.

The explanation of abbreviation used in the present embodiment

(organic solvent)

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

GBL: gamma-butyrolacton

BCS: butyl cellosolve

Acid dianhydride (A): following formula (A)

Acid dianhydride (B): following formula (B)

Acid dianhydride (C): following formula (C)

Acid dianhydride (D): following formula (D)

DA-1: following formula (DA-1)

DA-2: following formula (DA-2)

DA-3: following formula (DA-3)

DA-4: following formula (DA-4)

DA-5: following formula (DA-5)

In the following, for the measurement of viscosity, the measurement of acid imide rate, the evaluation of re-workability, the production of liquid crystal cells with And the method for charge relaxation properties evaluation is recorded.

[measurement of viscosity]

In synthesis example, the viscosity of poly amic acid ester and polyamic acid solution uses E type viscosimeter TV-25H (eastern machine industry strain The manufacture of formula commercial firm) to be measured under conditions of sample size 1.1mL, CORD-1 (1 ° 34 ', R24), 25 DEG C of temperature.

[evaluation of re-workability]

Aligning agent for liquid crystal of the invention is coated on ito substrate by spin-coating method.It is 1 point 30 dry on 60 DEG C of hot plate After second, be burnt within 20 minutes with 230 DEG C of heated air circulation type baking oven, form the film of film thickness 100nm.It then, will be prepared Substrate be impregnated in the reprocessing material (HM-R20) for be heated to 55 DEG C 300 seconds and develop, then with ultrapure water into Row flowing water cleans 20 seconds.Then, carry out air blast, be set as zero for what liquid crystal orientation film completely disappeared, have it is remaining be set as ×.For Acquired results are shown in table 3 by the case where predetermined temperature of rework solution is 35 DEG C and 55 DEG C.

(comparing polymerization example 1)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-4) 0.96g, and NMP25.7g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (C) 3.00g is added on one side, NMP11.2g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid adding dianhydride (D) 0.77g, is further added NMP4.4g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 50 DEG C It mixes 16 hours, obtains polyamic acid solution (PAA-1).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 358cps.

(comparing polymerization example 2)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-2) 0.46g, and NMP22.3g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (C) 2.00g is added on one side, NMP6.3g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (D) 1.51g, is further added NMP8.5g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 50 DEG C 16 hours, obtain polyamic acid solution (PAA-2).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 333cps.

(comparing polymerization example 3)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-2) 0.46g, and NMP22.3g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (A) 4.5g is added on one side, NMP20.5g is further added, and is stirred 2 hours with 23 DEG C in a nitrogen atmosphere, then with 50 DEG C stirring 16 hours, obtain polyamic acid solution (PAA-3).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 350cps。

(comparing polymerization example 4)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-2) 0.49g, and NMP22.3g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (C) 3.00g is added on one side, NMP12.0g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid adding dianhydride (D) 0.72g, is further added NMP4.1g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 50 DEG C It mixes 16 hours, obtains polyamic acid solution (PAA-4).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 333cps.

(polymerization example 1)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-5) 0.78g, and NMP24.4g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (B) 1.75g is added on one side, NMP4.3g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (D) 1.41g, is further added NMP8.0g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 50 DEG C 16 hours, obtain polyamic acid solution (PAA-5).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 240cps.

(polymerization example 2)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-2) 0.49g, and NMP22.3g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (A) 2.35g is added on one side, NMP8.3g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (C) 1.80g, is further added NMP10.2g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 70 DEG C 16 hours, obtain polyamic acid solution (PAA-6).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 380cps.

(polymerization example 3)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-3) 0.63g, and NMP23.4g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (A) 2.35g is added on one side, NMP8.0g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (C) 1.80g, is further added NMP10.2g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 70 DEG C 16 hours, obtain polyamic acid solution (PAA-7).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 350cps.

(polymerization example 4)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-4) 0.95g, and NMP25.7g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (A) 2.35g is added on one side, NMP7.5g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (C) 1.80g, is further added NMP10.2g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 70 DEG C 16 hours, obtain polyamic acid solution (PAA-8).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 365cps.

(polymerization example 5)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-5) 0.78g, and NMP24.4g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (A) 2.35g is added on one side, NMP7.8g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (C) 1.80g, is further added NMP10.2g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 70 DEG C 16 hours, obtain polyamic acid solution (PAA-9).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 389cps.

(polymerization example 6)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-2) 0.49g, and NMP22.3g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (A) 2.35g is added on one side, NMP8.3g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (D) 1.41g, is further added NMP8.0g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred with 70 DEG C 16 hours, obtain polyamic acid solution (PAA-10).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 321cps.

(polymerization example 7)

Nitrogen atmosphere is made in 50mL four-hole boiling flask with agitating device, takes (DA-1) 2.55g, (DA-2) 0.49g, and NMP22.3g is added, is stirred while supplying nitrogen and dissolves it at 23 DEG C.The diamine solution is stirred on one side Acid dianhydride (A) 1.41g is added on one side, NMP2.9g is further added, and is stirred 2 hours with 23 DEG C, is then added in a nitrogen atmosphere Acid dianhydride (B) 1.41g, is further added NMP7.9g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, acid dianhydride is added (C) 1.00g further adds NMP5.7g, is stirred 2 hours with 23 DEG C in a nitrogen atmosphere.Then, it is stirred 16 hours with 70 DEG C, Obtain polyamic acid solution (PAA-11).Viscosity at 25 DEG C of temperature of the polyamic acid solution is 365cps.

(comparative example 1~4)

Into the 50mL conical flask for be placed with stirrer, polyamic acid solution 15.0g obtained in synthesis example is compared in a point taking-up, NMP11.25g, BCS11.25g is added and obtained aligning agent for liquid crystal (A-1)~(A- of table 1 with magnetic stirrer 2 hours 4)。

[table 1]

Compare polymerization example	Comparing embodiment
		PAA-1	A-1
PAA-2	A-2
		PAA-3	A-3
PAA-4	A-4

(Examples 1 to 7)

Into the 50mL conical flask for be placed with stirrer, the molten acid solution 15.0g of polyamide obtained in point taking-up synthesis example, is added NMP11.25g, BCS11.25g obtained aligning agent for liquid crystal (B-1)~(B-7) of table 2 with magnetic stirrer 2 hours.

[table 2]

It polymerize example	Embodiment
		PAA-5	B-1
PAA-6	B-2
		PAA-7	B-3
PAA-8	B-4
		PAA-9	B-5
PAA-10	B-6
		PAA-11	B-7

[table 3]

		55℃	35℃
				Comparative example 1	A-1	×	×
Comparative example 2	A-2	×	×
				Comparative example 3	A-3	×	×
Comparative example 4	A-4	×	×
				Embodiment 1	B-1	○	×
Embodiment 2	B-2	○	○
				Embodiment 3	B-3	○	○
Embodiment 4	B-4	○	○
				Embodiment 5	B-5	○	○
Embodiment 6	B-6	○	○
				Embodiment 7	B-7	○	○

Industrial availability

Liquid crystal watch of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention in IPS driving method, FFS driving method The charge accumulation as caused by exchange driving asymmetry can be reduced by showing in element, and quickly mitigate the residual accumulated by DC voltage Therefore charge can obtain the excellent IPS driving method of image retention speciality, the liquid crystal of FFS driving method indicates element.Therefore, make It is particularly useful for the liquid crystal expression element of IPS driving method, FFS driving method, the liquid crystal orientation film of LCD TV.

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that contain: the imide amination polymer selected from polyamic acid He the polyamic acid In at least one kind of polymer and organic solvent, the polyamic acid be using with the ratio of 10:90~90:10 include it is following Tetracarboxylic dianhydride's ingredient of tetracarboxylic dianhydride shown in formula (1) and aliphatic tetracarboxylic dianhydride and comprising shown in following formula (2) Diamines diamine component obtained from,

In formula (1), i be 0 or 1, X be singly-bound, ehter bond, carbonyl, ester bond, phenylene, carbon atom number 1~20 straight-chain alkyl-sub, The branched alkylidene of carbon atom number 2~20, the cyclic alkylidene of carbon atom number 3~12, sulfonyl, amido bond or by their groups Group made of conjunction, wherein the alkylidene of carbon atom number 1~20 is optionally interrupted by the key selected from ester bond and ehter bond, phenylene and The carbon atom of alkylidene optionally by 1 in halogen atom, cyano, alkyl, halogenated alkyl, alkoxy and halogenated alkoxy or Multiple identical or different substituent groups replace,

In formula (2), Y₁Have for the divalent at least one kind of structure in the group being made of amino, imino group and nitrogen-containing heterocycle Machine group, or for selected from being had on nitrogen-atoms by the divalent in amino, imino group and nitrogen-containing heterocycle that hot detachment group replaces Machine group, B₁、B₂It is separately hydrogen atom or alkyl, alkenyl, the alkynyl of the optionally carbon number 1~10 with substituent group.

2. aligning agent for liquid crystal according to claim 1, which is characterized in that 10~100 in tetracarboxylic dianhydride's ingredient Mole % is tetracarboxylic dianhydride and aliphatic acid dianhydride shown in the formula (1).

3. aligning agent for liquid crystal according to claim 1 or 2, which is characterized in that 10~100 in the diamine component rub Your % is the diamines of formula (2).

4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein the Y in formula (2)₁For selected from following formula It is (YD-1) at least one kind of in~(YD-5) structure,

In formula (YD-1), A₁For the nitrogen atom heterocycle of carbon number 3~15, Z₁For hydrogen atom or optionally with the carbon number of substituent group 1~20 alkyl；In formula (YD-2), W₁For the alkyl of carbon number 1~10, A₂It is 1 of the carbon number 3~15 with nitrogen atom heterocycle Valence organic group or the disubstituted amido replaced by the aliphatic group of carbon number 1~6；In formula (YD-3), W₂For carbon number 6~ 15 and with 1~2 phenyl ring divalent organic group, W₃For the alkylidene or biphenylene of carbon number 2~5, Z₂For hydrogen atom, carbon Alkyl, phenyl ring or the hot detachment group of number 1~5, the integer that a is 0~1；In formula (YD-4), A₃For containing for carbon number 3~15 Nitrogen-atoms heterocycle；In formula (YD-5), A₄For the nitrogen atom heterocycle of carbon number 3~15, W₅For the alkylidene of carbon number 2~5.

5. aligning agent for liquid crystal according to claim 4, wherein described in formula (YD-1), (YD-2), (YD-4) and (YD-5) A₁、A₂、A₃And A₄For selected from by pyrrolidines, pyrroles, imidazoles, pyrazoles, oxazole, thiazole, piperidines, piperazine, pyridine, pyrazine, Yin It is at least one kind of in the group that diindyl, benzimidazole, quinoline, isoquinolin form.

6. aligning agent for liquid crystal according to any one of claims 1 to 5, wherein the Y in formula (2)₁For under by having State formula (YD-6)~(YD-21) structure divalent organic group composition group in it is at least one kind of,

In formula (YD-17), the integer that h is 1~3, in formula (YD-14) and (YD-21), j for 1~3 integer.

7. aligning agent for liquid crystal according to claim 6, which is characterized in that the Y in formula (2)₁For selected from by with above-mentioned formula (YD-14) at least one kind of and in the group of the divalent organic group of the structure of (YD-18) composition.

8. aligning agent for liquid crystal according to any one of claims 1 to 7, wherein tetracarboxylic dianhydride shown in the formula (1) It is 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides.

9. aligning agent for liquid crystal described according to claim 1~any one of 8, wherein the aliphatic tetracarboxylic dianhydride is double Ring [3.3.0] octane 2,4,6,8- tetrabasic carboxylic acid 2,4:6,8 dianhydride.

10. a kind of liquid crystal orientation film is coating aligning agent for liquid crystal according to any one of claims 1 to 9 and is burnt into and obtains It arrives.

11. a kind of liquid crystal indicates element, has liquid crystal orientation film described in any one of claim 10.