CN102893210A

CN102893210A - Liquid crystal alignment agent for use in photo-alignment process, and liquid crystal alignment film using same

Info

Publication number: CN102893210A
Application number: CN201180024064XA
Authority: CN
Inventors: 作本直树; 饭沼洋介; 野口勇步; 长尾将人
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2010-03-15
Filing date: 2011-03-14
Publication date: 2013-01-23
Also published as: WO2011115079A1; KR20130038243A; JPWO2011115079A1; TW201202306A

Abstract

Alignment film which exhibits satisfactory liquid crystal alignment properties irrespective of the exposure dose of polarised ultraviolet light, and which induces a uniform, satisfactory photo-alignment process even when the exposure dose varies. The liquid crystal alignment agent contains component (A) and component (B). Component (A): at least one type of compound selected from a group comprising polyamic acid esters having a repeating unit represented by general formula (1), and imide compounds of said polyamic acid esters. Component (B): a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine. (In general formula (1), Y represents a divalent organic group, R1 represents a C1-5 alkyl group, R2 - R5 independently represent hydrogen atoms, halogen atoms or C1-20 hydrocarbon groups, and can be the same or different).

Description

Light orientation process method is with aligning agent for liquid crystal and the liquid crystal orientation film that utilizes this alignment agent

Invention field

The present invention relates to for the aligning agent for liquid crystal of making liquid crystal orientation film and the liquid crystal orientation film that is made by this aligning agent for liquid crystal.Specifically, relate to can be by replacing friction treatment light orientation process method, namely shine the liquid crystal orientation film of giving the liquid crystal aligning ability through the ultraviolet ray of polarization and form and use aligning agent for liquid crystal, and the liquid crystal orientation film that is made by described aligning agent for liquid crystal.

Background of invention

The liquid crystal display cells that is used for LCD TV, liquid crystal display etc. is provided for suppressing the liquid crystal orientation film of the state of orientation of liquid crystal usually in element.

At present, according to the most general industrial method, this liquid crystal orientation film be by with the cloth such as cotton, nylon, polyester towards a direction wiping be formed on the electrode base board by polyamic acid and/or with its imidizate the film surface that forms of polyimide, be that so-called friction treatment is made.

In the orientation process of liquid crystal orientation film, the industrial useful method that the friction treatment method of face is easy and productivity is excellent.But, requirement to the high performance of liquid crystal display cells, high resolving power, maximization improves day by day, and impact and then the variety of issues such as unevenness in the orientation process face of scar, airborne dust, mechanical force or the static of the alignment layer surface that is caused by friction treatment are day by day obvious.

The method of friction treatment is instead knownly given the optical alignment method of liquid crystal aligning ability by irradiation through the ultraviolet ray of polarization.Liquid crystal aligning based on optical alignment method is processed, proposed processing, the processing that utilizes photo-crosslinking that utilizes photoisomerization to react, (with reference to the non-patent literatures 1) such as processing that utilizes photolysis reactions according to mechanism.

In patent documentation 1, the polyimide film that has proposed to have the alicyclic structure such as cyclo-butane ring on the main chain is used for the method for optical alignment method.Use has adopted the light orientation of polyimide with in the situation of alignment films, compares with other to have high-fire resistance, therefore can expect its validity.

Above-mentioned this optical alignment method has the industrial advantage that can produce with easy manufacturing process as the friction orientation disposal route, and the liquid crystal aligning disposal route that conduct can be expected gets most of the attention, but when being used for LCD TV or liquid crystal display etc., as the orientation limitations power of liquid crystal or the electrical characteristics of liquid crystal display cells, the existing problems such as stability of these characteristics, usually can't realize practical.

The prior art document

Patent documentation

Patent documentation 1: Japanese patent laid-open 9-297313 communique

Non-patent literature

The wooden family of non-patent literature 1 " liquid crystal photo-alignment film " side of body, city village functional material (" liquid crystal light alignment film " wooden Kobe side, city village Machine energy material) in January, 1997 Vol.17 No.11 13-22 page or leaf

Summary of the invention

In recent years, the giant-screen of liquid crystal display cells is day by day universal, when the giant-screen substrate is implemented friction treatment, the inequality of frictional strength occurs in real estate, becomes during as liquid crystal display cells to show inequality.With respect to this, to compare with rubbing manipulation, it is uneven that optical alignment method can reduce demonstration, therefore expected.But in optical alignment method, liquid crystal aligning can change according to the exposure of polarized UV rays, therefore owing to the uneven possibility that the generation demonstration inequality identical with rubbing manipulation arranged of exposure intensity occurs in the real estate.

A problem of predictable optical alignment method when this problem becomes with the giant-screen generation in order to make the liquid crystal display cells of the advantage of bringing into play to greatest extent optical alignment method, requires not rely on the optical alignment film that exposure ground presents good liquid crystal aligning.

The object of the present invention is to provide to obtain the aligning agent for liquid crystal that following liquid crystal orientation film is purpose, namely adopting optical alignment method to carry out in the situation of orientation process, the exposure ground that does not rely on polarized UV rays presents good liquid crystal aligning, and in the large liquid crystal orientation film of the irradiated area of giant-screen, there is the uneven liquid crystal orientation film that also can carry out even and good orientation process even present the exposure of liquid crystal aligning ability.

The technical scheme of technical solution problem

The inventor has carried out conscientiously research repeatedly, found that by use and contain at least a kind polymkeric substance of the imide amination polymer that is selected from the poly amic acid ester that has the cyclo-butane ring on the main chain and this poly amic acid ester and make the tetracarboxylic dianhydride and the aligning agent for liquid crystal of the polyamic acid that diamine reactant obtains, can solve above-mentioned problem, and finish the present invention.

That is, technology contents of the present invention is as described below.

1. aligning agent for liquid crystal contains following (A) composition and (B) composition.

(A) composition: be selected from least a kind the polymkeric substance that has by the imide amination polymer of the poly amic acid ester of the repetitive of following formula (1) expression and this poly amic acid ester.

[changing 1]

In the formula (1), Y is the divalent organic group, R ₁The alkyl of carbon number 1～5, R ₂～R ₅Be the alkyl of hydrogen atom, halogen atom or carbon number 1～30 independently respectively, can be identical or different,

(B) composition: the polyamic acid that is made by tetracarboxylic dianhydride and diamines.

2. the aligning agent for liquid crystal of above-mentioned 1 record, wherein, (A) composition and (B) proportionally count 1/9～9/1 with mass ratio (A/B) containing of composition.

3. the aligning agent for liquid crystal of above-mentioned 1 or 2 records, wherein, (A) composition is at least a kind of polymkeric substance that is selected from the imide amination polymer of the poly amic acid ester of repetitive of above-mentioned formula (1) expression that has more than 40 % by mole and this poly amic acid ester.

4. the aligning agent for liquid crystal of each record in above-mentioned 1～3, wherein, composition (A) is the poly amic acid ester that has by the repetitive of following formula (3) expression.

[changing 2]

In the formula (3), Y is the divalent organic group, R ₆It is the alkyl of carbon number 1～5.

5. the aligning agent for liquid crystal of each record in above-mentioned 1～3, wherein, composition (A) is the poly amic acid ester that has by the repetitive of following formula (4) expression.

[changing 3]

In the formula (4), Y is the divalent organic group, R ₆It is the alkyl of carbon number 1～5.

6. the aligning agent for liquid crystal of each record in above-mentioned 1～5, wherein, in the formula (1), Y is selected from least a kind of following structural formula.

[changing 4]

7. the aligning agent for liquid crystal of each record in above-mentioned 1～6, wherein, composition (B) is the polyamic acid that utilizes at least a kind tetracarboxylic dianhydride comprising the tetracarboxylic dianhydride who is selected from following formula (B-1)～(B-9) to make.

[changing 5]

8. the aligning agent for liquid crystal of above-mentioned 7 records, wherein, composition (B) is the polyamic acid that the tetracarboxylic dianhydride more than 20 % by mole that utilizes at least a kind of tetracarboxylic dianhydride being selected from above-mentioned formula (B-1)～(B-9) to account for tetracarboxylic dianhydride's total amount makes.

9. the aligning agent for liquid crystal of each record in above-mentioned 1～8, wherein, composition (B) is to utilize to comprise the polyamic acid that at least a kind diamines being selected from following formula (B-10)～(B-13) makes.

[changing 6]

10. the aligning agent for liquid crystal of above-mentioned 9 records, wherein, composition (B) is the polyamic acid that the diamines more than 20 % by mole that utilizes at least a kind of diamines being selected from above-mentioned formula (B-10)～(B-13) to account for the diamines total amount makes.

11. liquid crystal orientation film is to the aligning agent for liquid crystal that is coated with each record in above-mentioned 1～10 and burn till and the tunicle irradiation polarized UV rays that obtains and making.

The invention effect

Even the liquid crystal orientation film that exposure ground obtains good liquid crystal aligning so generation exposure intensity inequality also can provide the industry member limit for width with even and good liquid crystal aligning in real estate that the liquid crystal orientation film that is made by aligning agent for liquid crystal of the present invention can provide the exposure scope of the polarized UV rays that can obtain good liquid crystal aligning wide, can not rely on polarized UV rays.

The preferred embodiment for the present invention

[(A) composition]

Poly amic acid ester of the present invention is converted to polyimide through the effect of heating or catalyzer by imidization reaction shown below.Poly amic acid ester can not cause because of reversed reaction the minimizing of molecular weight, can obtain the high polyimide of molecular weight after therefore burning till yet.Thus, can obtain to have the liquid crystal display cells of better liquid crystal aligning and reliability excellence.In addition, imide amination polymer of the present invention refers to the polymkeric substance by the poly amic acid ester imidizate is obtained.Be insoluble to sometimes organic solvent for liquid crystal orientation film according to the structure imide amination polymer, therefore as (A) of the present invention composition, the spy is poly amic acid ester well.

[changing 7]

Contained (A) composition of aligning agent for liquid crystal of the present invention is to be selected from least a kind of polymkeric substance that has by the imide amination polymer of the poly amic acid ester of the repetitive of following formula (1) expression and this poly amic acid ester.

[changing 8]

In formula (1), R ₁Being the alkyl of carbon number 1～5, better is the alkyl of carbon number 1 or 2.Along with R ₁Carbon number increase and temperature that imidizate carries out raises.Therefore, from being easy to be undertaken by heat the viewpoint consideration of imidizate, R ₁The spy is methyl well.In the formula (1), R ₂～R ₅Be hydrogen atom independently respectively, halogen atom or carbon number 1～30, be more preferably the alkyl of carbon number 1～10, can be identical or different.

As the concrete example of halogen atom, can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.As the example of the alkyl of carbon number 1～30, be selected from the group that alkyl, alkenyl, alkynyl, aryl and they combine, they can have substituting group.As the concrete example of abovementioned alkyl, but exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, decyl, cyclopentyl, cyclohexyl, dicyclohexyl etc.Can exemplify and to be present in the CH more than 1 of abovementioned alkyl as alkenyl ₂-CH ₂Structure replaces the group of CH=CH structure, more specifically, but exemplified by vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.

Can exemplify and to be present in the CH more than 1 of abovementioned alkyl as alkynyl ₂-CH ₂Structure replaces the group of C ≡ C-structure, more specifically, can exemplify ethinyl, 1-propinyl, 2-propynyl etc.But as aryl such as exemplified by phenyl, Alpha-Naphthyl, betanaphthyl, ortho-, meta-or p-xenyl, meta-xenyl, p-xenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl etc.

Total carbon number of abovementioned alkyl, alkenyl, alkynyl, aryl is 1～30, better be can have substituting group in 1～10 the situation, formed ring structure by substituting group even can be situated between.

As this substituent example, can exemplify halogen group, hydroxyl, sulfydryl, nitro, organic alkoxy, organic alkylthio group, organosilicon alkyl, acyl group, ester group, thioester substrate, phosphate-based, amide group, aryl, alkyl, alkenyl, alkynyl.

As substituent halogen group, can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.

Can be represented with-structure that O-R-represents by alkoxy, alkenyloxy, aryloxy group etc. as substituent organic alkoxy.As this R, can exemplify out aforesaid alkyl, alkenyl, aryl etc.These R can further be replaced by aforesaid substituting group.As the concrete example of alkoxy, can exemplify methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, bay oxygen base etc.

Can be represented with-structure that S-R-represents by alkyl sulfenyl, alkenylthio group, arylthio etc. as substituent organic alkylthio group.As this R, can exemplify out aforesaid alkyl, alkenyl, aryl etc.These R can further be replaced by aforesaid substituting group.As the concrete example of alkylthio group, can exemplify methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, hot sulfenyl, ninth of the ten Heavenly Stems sulfenyl, last of the ten Heavenly stems sulfenyl, bay sulfenyl etc.

Can be by-Si-(R) as substituent organosilicon alkyl ₃The structure of-expression represents.This R can be identical or different, can the aforesaid alkyl of illustration, aryl etc.These R can further be replaced by aforesaid substituting group.As the concrete example of alkyl tin groups, alkyl silane groups, can exemplify TMS, triethyl silyl, tripropyl silylation, tributyl silylation, three amyl group silylation, three hexyl silane bases, amyl group dimethylsilyl, hexyl dimethylsilyl, octyldimethyl silylation, decyl dimethylsilyl etc.

As substituent acyl group can by-C(O)-structure that R represents represents.As this R, can exemplify out aforesaid alkyl, alkenyl, aryl etc.These R can further be replaced by aforesaid substituting group.As the concrete example of acyl group, can exemplify formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc.

As substituent ester group can by-C(O) O-R or-structure that OC (O)-R represents represents.As this R, but the aforesaid alkyl of illustration, alkenyl, aryl etc.These R can further be replaced by aforesaid substituting group.

As substituent mercapto ester group can by-C(S) O-R or-structure shown in OC (S)-R represents.As this R, but the aforesaid alkyl of illustration, alkenyl, aryl etc.These R can further be replaced by aforesaid substituting group.

As substituent phosphate-based can be by-OP (O)-(OR) ₂Shown structure represents.This R can be identical or different, can the aforesaid alkyl of illustration, aryl etc.These R can further be replaced by aforesaid substituting group.

Can be by-C (O) NH as substituent amide group ₂,-C (O) NHR ,-NHC (O) R ,-C (O) N (R) ₂, or-structure shown in NRC (O) R represents.This R can be identical or different, can the aforesaid alkyl of illustration, aryl etc.These R can further be replaced by aforesaid substituting group.

As substituent aryl, can exemplify the group identical with aforesaid aryl.This aryl can further be replaced by aforesaid other substituting groups.

As substituent alkyl, can exemplify the group identical with aforesaid alkyl.This alkyl can further be replaced by aforesaid other substituting groups.

As substituent alkenyl, can exemplify the group identical with aforesaid alkenyl.This alkenyl can further be replaced by aforesaid other substituting groups.

As substituent alkynyl, can exemplify the group identical with aforesaid alkynyl.This alkynyl can further be replaced by aforesaid other substituting groups.

R ₂～R ₅In the situation for bulky structure, may hinder liquid crystal aligning, better be alkyl or the phenyl of hydrogen atom, carbon number 1～6 therefore, is more preferably hydrogen atom or methyl.

(A) of the present invention composition can by the tetracarboxylic acid derivatives of use following formula (6)～(8) or by the tetracarboxylic acid derivatives of following formula (6)～(8) expression and the tetracarboxylic acid derivatives that is represented by following formula (9)～(11), make with these tetracarboxylic acid derivatives with by the diamines polycondensation of following formula (12) expression.

[changing 9]

[changing 10]

[changing 11]

H ₂N-Y-NH ₂ (12)

In the formula, R ₂～R ₅Be respectively the group identical with the definition in the above-mentioned formula (1).R ₆Be the alkyl of carbon number 1～5, be more preferably the alkyl of carbon number 1 or 2.Poly amic acid ester is the increase along with the carbon number of alkyl, and the temperature that imidizate carries out raises.Therefore, from carry out easily the viewpoint consideration of imidizate, R by heat ₆The spy is methyl well.

The content of the tetracarboxylic acid derivatives of above-mentioned formula (6)～(8) with respect to the total amount of tetracarboxylic acid derivatives, better is 1 % by mole～100 % by mole.If the content of the tetracarboxylic acid derivatives of above-mentioned formula (6)～(8) is very few, therefore then the light orientation is insufficient, can't obtain good liquid crystal aligning, with respect to the total amount of tetracarboxylic acid derivatives, better be 20 % by mole～100 % by mole, be more preferably 40 % by mole～100 % by mole.

The X of above-mentioned formula (9)～(11) is 4 valency organic groups, and its structure is not particularly limited.Its concrete example can exemplify the structure that is represented by following X-1～X-46.In addition, these tetracarboxylic acid derivatives can use more than 2 kinds.

[changing 12]

[changing 13]

[changing 14]

[changing 15]

Y is the divalent organic group in the above-mentioned formula (12), and its structure is not particularly limited.Its concrete example can exemplify the structure that is represented by following Y-1～Y-108.In addition, diamine compound can be for more than 2 kinds.

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

[changing 21]

[changing 22]

[changing 23]

[changing 24]

[changing 25]

[changing 26]

[changing 27]

[changing 28]

[changing 29]

[changing 30]

[changing 31]

[changing 32]

[changing 33]

In order to obtain good liquid crystal aligning, better be to import the high diamines of rectilinearity as Y.Be more preferably the diamines that Y is Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98, Y-100, Y-101, Y-102, Y-103, Y-104, Y-105, Y-106, Y-107 or Y-108.With respect to the total amount of diamines, add 30～100 % by mole, better be these diamines of 50～100 % by mole, can obtain good liquid crystal aligning thus.

In addition, when wanting to increase tilt angle, better be that the diamines that has the structure that chain alkyl, aromatic ring, aliphatics ring, steroid skeleton or they combine on the side chain is introduced poly amic acid ester.Be more preferably the diamines that Y is 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, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97.By adding 1～50 % by mole of whole diamines, being more preferably these diamines of 5～30 % by mole, can present arbitrarily tilt angle.

Wherein, better be to be selected from least a kind of following structural formula as Y.

[changing 34]

[(B) composition]

(B) of the present invention composition is the polyamic acid that the polycondensation of the diamines of the tetracarboxylic dianhydride by the structure with following formula (13) and the structure with following formula (14) obtains, and has the polymkeric substance that can be carried out by heating the position of imidization reaction

[changing 35]

[changing 36]

[changing 37]

H ₂N-Y ₁-NH ₂ (14)

In the formula (13), X ₁Be 4 valency organic groups, its structure is not particularly limited.As concrete example, can exemplify the structure of above-mentioned formula (X-1)～(X-46).In addition, the tetracarboxylic dianhydride can be for more than 2 kinds.

Better be photolysis reactions can not occur or compare the slow polyamic acid of reaction velocity that light decomposes with aforementioned (A) composition as (B) composition.Therefore, as X ₁Structure, better be X-1, X-5, X-6, X-7, X-8, X-16, X-17, X-18, X-19, X-21, X-22, X-23, X-24, X-25, X-26, X-27, X-28, X-29, X-30, X-31, X-32, X-33, X-39, X-40, X-41, X-42, X-42 or X-46.

Has above-mentioned preferred X ₁Tetracarboxylic dianhydride's the use amount of structure better be 5～100 % by mole with respect to whole tetracarboxylic dianhydrides.Described tetracarboxylic dianhydride's ratio is more, and the surface free energy of polymkeric substance is higher, and more can obtain the high polyamic acid of dissolubility, better is 20～100 % by mole therefore, is more preferably 40～100 % by mole.

Wherein, as mentioned above, in order further to improve liquid crystal aligning by (A) composition being concentrated be positioned at the film surface, better be the polyamic acid that surface free energy is high, dissolubility is high as the polyamic acid of (B) composition.Therefore, as the X in (B) composition ₁Structure, in the situation that the difficulty that obtains is also taken into account, better be X-1, X-5, X-6, X-8, X-16, X-19, X-25, X-26 or X-32, the spy is well X-25 or X-32.

Has above-mentioned preferred X ₁The tetracarboxylic dianhydride of structure represent that with following (B-1)～(B-9) wherein, the spy is well (B-1) or (B-9).

[changing 38]

In the formula (14), Y ₁Be the divalent organic group, its structure is not particularly limited.As concrete example, can exemplify the structure of above-mentioned formula (Y-1)～(Y-108).In addition, diamines can be for more than 2 kinds.

Can reduce the ghost that causes because of accumulating of DC voltage by the specific insulation that reduces polyamic acid, therefore better be to introduce the diamines with structure, Ppolynuclear aromatic structure or biphenyl backbone of containing heteroatom in polyamic acid.Therefore, as Y ₁Better be Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y-34, Y-35, Y-36, Y-40, Y-41, Y-42, Y-44, Y-45, Y-49, Y-50, Y-51 or Y-61.

Has above-mentioned preferred Y ₁The use amount of the diamine compound of structure better is 5～100 % by mole with respect to whole diamines.This use amount is higher, and the polarity of polymkeric substance film higher and (A) composition surface ratio is higher, better is 20 % by mole～100 % by mole therefore, is more preferably 40 % by mole～100 % by mole.

Wherein, as mentioned above, can further improve liquid crystal aligning by (A) composition being concentrated be positioned at the film surface, therefore, as the high polyamic acid of polyamic acid preferred surface free energy of (B) composition, better be in polyamic acid, to introduce secondary amino group, hydroxyl, amide group, urea groups, substituting group that the carboxyl isopolarity is high.Therefore, as Y ₁Be more preferably Y-19, Y-31, Y-40, Y-45, Y-98 or Y-99, the spy is well Y-98 or the Y-99 that contains carboxyl.

Has above-mentioned preferred Y ₁The tetracarboxylic dianhydride of structure represents with following (B-10)～(B-13), and wherein, the spy is well (B-10) or (B-11).

[changing 39]

[(A) composition and (B) manufacturing of composition]

(manufacturing of polyamic acid)

Polyamic acid can make by the polycondensation of tetracarboxylic dianhydride and diamine compound.

When making polyamic acid, better be in the presence of organic solvent, make tetracarboxylic dianhydride and diamine compound-20 ℃～140 ℃, better be 0 ℃～50 ℃ lower reactions 30 minutes～24 hours, better be that reaction obtained in 1～12 hour.From monomer and structure adaptability consideration, the solvent that uses in the manufacturing of polyamic acid better is DMF, METHYLPYRROLIDONE or gamma-butyrolacton, and these can use one kind or two or more mixing to use.Cause easily separating out of polymkeric substance during the excessive concentration of the polymkeric substance during manufacturing, cross that molecular weight does not increase when low, so tetracarboxylic dianhydride and the total amount of diamine compound in reactant liquor better be 1～30 quality %, be more preferably 5～20 quality %.

The polyamic acid that as above makes can be with its reaction solution as the raw material of (A) of the present invention composition or (B) composition, but do not wanting to make the solvent that uses in the polymerization to be included in the situation in the aligning agent for liquid crystal, be re-used as polyamic acid of the present invention after polymkeric substance can being reclaimed with solid and use.

Polymkeric substance can be by fully injecting Weak solvent so that polymkeric substance is separated out and reclaimed in the stirring reaction solution.Can be by after carrying out that several is separated out and cleaning with Weak solvent, at normal temperatures or heat drying and obtain the powder of sublimed polyamic acid.

Aforementioned Weak solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.

(manufacturing of poly amic acid ester)

Poly amic acid ester can make by known manufacture method, can exemplify the method for following (a)～(c) particularly, but be not limited to these.

(a) made the situation of poly amic acid ester by polyamic acid

Poly amic acid ester of the present invention can be by the invention described above the esterification of polyamic acid make.Poly amic acid ester is specific as follows to be made, namely in the presence of organic solvent in-20 ℃～140 ℃, better be under 0 ℃～50 ℃, make polyamic acid and esterifying agent reaction 30 minutes～24 hours, better be that reaction was made in 1～4 hour.

Better be can be by purifying and the esterifying agent of easily removing as aforementioned esterifying agent, can exemplify N, dinethylformamide dimethylacetal, N, dinethylformamide diethyl acetal, N, dinethylformamide dipropyl acetal, N, dinethylformamide di neo-pentyl butyl acetal, DMF di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes etc.The repetitive of the polyamic acid of the addition of esterifying agent with respect to 1 mole is 2～6 molar equivalents preferably.

From monomer and structure adaptability consideration, the solvent that uses in the manufacturing of poly amic acid ester better is DMF, METHYLPYRROLIDONE or gamma-butyrolacton, and these can use one kind or two or more mixing to use.If the concentration of the polymkeric substance during manufacturing is too high, then cause easily separating out of polymkeric substance, if excessively low, then molecular weight does not increase, so polyamic acid and the total amount of esterifying agent in reactant liquor better be 1～30 quality %, is more preferably 5～20 quality %.

(b) made the situation of poly amic acid ester by acyl chlorides and diamine compound

Poly amic acid ester can make by the polycondensation of two (chlorocarbonyl) compounds and diamine compound.

Particularly, in the presence of alkali and organic solvent, in-20 ℃～140 ℃, better be under 0 ℃～50 ℃, make two (chlorocarbonyl) compounds and diamine compound reaction 30 minutes～24 hours, better be that reaction was made in 1～4 hour.Described alkali can use pyridine, triethylamine or 4-dimethylaminopyridine, leniently carries out in order to make reaction, preferred pyridine.The addition of alkali is difficult to when too much remove, when very few the molecule quantitative change little, better be 2～4 times of moles with respect to two (chlorocarbonyl) compound therefore.

From monomer and structure adaptability consideration, the solvent that uses in the manufacturing of poly amic acid ester better is METHYLPYRROLIDONE or gamma-butyrolacton, and these can use one kind or two or more mixing to use.Cause easily separating out of polymkeric substance during the excessive concentration of the polymkeric substance during manufacturing, cross that molecular weight does not increase when low, therefore two (chlorocarbonyl) compounds and the total amount of diamine compound in reactant liquor better are 1～30 quality %, are more preferably 5～20 quality %.In addition, in order to prevent the hydrolysis of two (chlorocarbonyl) compounds, the solvent that uses in the manufacturing of poly amic acid ester better is dehydrated as far as possible, better is in blanket of nitrogen, prevents sneaking into of external gas.

(c) made the situation of poly amic acid ester by dicarboxylic acid dialkyl esters and diamine compound

Poly amic acid ester can be made by utilizing condensation agent that tetrabasic carboxylic acid dialkyl and diamine compound are carried out polycondensation.

Particularly, in the presence of condensation agent, alkali and organic solvent, in 0 ℃～140 ℃, better be under 0 ℃～100 ℃, make dicarboxylic acid dialkyl esters and diamine compound reaction 30 minutes～24 hours, better be that reaction was made in 3～15 hours.

Described condensation agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methyl morpholine, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) hexafluorophosphoric acid ester, (2,3-dihydroxy-2-sulfo--3-benzoxazolyl) phosphonic acid diphenyl ester etc.The addition of condensation agent better is 2～3 times of moles with respect to dicarboxylic acid dialkyl esters.

Described alkali can use the tertiary amines such as pyridine, triethylamine.The addition of alkali is difficult to remove when too much, when very few the molecule quantitative change little, therefore better be 2～4 times of moles with respect to two amine components.

In addition, in above-mentioned reaction, by adding lewis acid as adjuvant, reaction is effectively carried out.As lewis acid, better be the lithium halides such as lithium chloride, lithium bromide.Lewis acidic addition better is 0～1.0 times of mole with respect to two amine components.

In the manufacture method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular, the spy is well the manufacture method of above-mentioned (a) or above-mentioned (b).

The solution of the poly amic acid ester that makes as mentioned above can be by separating out polymkeric substance at the well-beaten Weak solvent that injects simultaneously.By after carrying out that several is separated out and cleaning with Weak solvent, at normal temperatures or heat drying, can obtain the powder of sublimed poly amic acid ester.

Consider that from the viewpoint of control molecular weight the ratio of employed two amine components and tetracarboxylic acid derivatives in above-mentioned polycondensation reaction (tetracarboxylic dianhydride, tetrabasic carboxylic acid dialkyl derivatives) better is as 1:0.7～1:1.2 take molar ratio computing.This mol ratio is more near 1: 1, and the molecular weight of poly amic acid ester becomes larger.The molecular weight of poly amic acid ester impacts the viscosity of varnish and the physical strength of polyimide film, if the molecular weight of poly amic acid ester is excessive, the then sometimes coating of varnish or the homogeneity variation of filming, if molecular weight is too small, the polyimide film strength that then sometimes obtains becomes insufficient.Therefore, to haggle over weight-average molecular weight be 2000～500000 to the molecular weight of used poly amic acid ester in the aligning agent for liquid crystal of the present invention, is more preferably 5000～300000, is 10000～100000 well further.

[manufacturing of polyimide]

Polyimide of the present invention can be made by the imidizate of aforementioned poly amic acid ester.Made in the polyimide situation by poly amic acid ester, the chemical imidization that adds catalyzer in the solution of the aforementioned polyamic acid that the reaction by two amine components and tetracarboxylic dianhydride makes is easy.Chemical imidization is to carry out imidization reaction under lower temperature, and is difficult to occur the reduction of polymer molecular weight in the process of imidizate, and is therefore desirable.

Chemical imidization can want the polymkeric substance of imidizate to carry out by stirring in the presence of base catalyst and acid anhydrides in organic solvent.As organic solvent, used solvent in the time of can using above-mentioned polyreaction.As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein preferred pyridine reacts the suitable alkalescence of carrying out because it has to make.In addition, as acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., wherein, be easy to react the purifying after the end when using acetic anhydride, therefore preferred.

When carrying out imidization reaction can take temperature as-20 ℃～140 ℃, better be 0 ℃～100 ℃, the reaction time is that 1～100 hour condition is carried out.The amount of base catalyst is 0.5～30 mole times of acid amides acidic group, and preferred 2～20 moles times, the amount of acid anhydrides is 1～50 mole times of acid amides acidic group, preferred 3～30 moles times.The acid imide rate of the polymkeric substance that obtains can be controlled by adjusting catalytic amount, temperature, reaction time.Therefore the residual catalyzer that interpolation is arranged etc. in the solution after the imidization reaction better is by following method, after reclaiming the imide amination polymer that makes and dissolving with organic solvent again, as aligning agent for liquid crystal of the present invention.

The solution of the polyimide that makes as mentioned above can be by making polymkeric substance separate out well-beaten being injected into simultaneously in the Weak solvent.By after carrying out that several is separated out and cleaning with Weak solvent, at normal temperatures or heat drying, can obtain the powder of sublimed poly amic acid ester.

Aforementioned Weak solvent is not particularly limited, can exemplifies methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.

[aligning agent for liquid crystal]

Aligning agent for liquid crystal of the present invention is that the poly amic acid ester with ad hoc structure that will as above make or polyimide ((A) composition) and polyamic acid ((B) composition) are dissolved in the solution in the solvent equably.

(A) composition in the aligning agent for liquid crystal of the present invention and (B) contain proportional (A/B) of composition better be 1/9～9/1 by quality ratio, be more preferably 3/7～7/3.With respect to the content of (B) composition, (A) in the few situation of the content of composition, liquid crystal aligning is insufficient, greatly in the situation, can't give full play to effect of the present invention in addition, and is therefore undesirable.

As employed solvent in the aligning agent for liquid crystal of the present invention, can use and to dissolve above-mentioned (A) composition and (B) solvent of composition.

As described solvent, so long as can dissolve (A) composition and (B) solvent of composition get final product, be not particularly limited.Its concrete example can exemplify N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl-N, N-dimethyl propylene acid amides etc.These can use one kind or two or more mixing to use.In addition, even solvent that can't dissolve polymer when using separately as long as in the scope that polymkeric substance can not be separated out, then can mix use.In addition, the solvent of dissolving (A) composition and the solvent of dissolving (B) composition can be identical or different, also can be the mixed solvent more than 2 kinds.

In addition, in the present invention, can use also that the dissolubility of composition is little but can improve the inhomogeneity solvent of filming when aligning agent for liquid crystal coated substrate (below, Weak solvent) to (A) composition with (B).As Weak solvent, get final product so long as can improve the inhomogeneity solvent of filming with low surface tension, be not particularly limited.Enumerate its concrete example, can exemplify ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetic acid esters, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single acetic acid propylene glycol ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, the single ether of propylene glycol-1--2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.These solvents can be also with more than 2 kinds.

Aligning agent for liquid crystal of the present invention can comprise the various adjuvants such as silane coupling agent or crosslinking chemical.The adaptation that silane coupling agent improves between the substrate that is coated with aligning agent for liquid crystal and the liquid crystal orientation film formed thereon is that order adds.The below exemplifies the object lesson of silane coupling agent, but is not limited to this.

The amine silane coupling agents such as APTES, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, 3-TSL 8330,3-phenyl amino propyl trimethoxy silicane, 3-triethoxysilicane alkyl-N-(1,3-dimethyl-butylidene) propylamine, 3-aminopropyl diethoxymethyl silane; The vinyl silane coupling agents such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, allyltrimethoxysilanis, p-styryl trimethoxy silane; The epoxies silane coupling agents such as 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane; The methacrylic silane coupling agents such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane; The acrylic compounds silane coupling agents such as 3-acryloxy propyl trimethoxy silicane; The ureas silane coupling agents such as 3-urea groups propyl-triethoxysilicane; Two (3-(triethoxysilicane alkyl) propyl group) disulfide, two (3-(triethoxysilicane alkyl) propyl group) tetrasulfide sulfides one type of silane coupling agent; 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, the 3-caprylyl sulfo--mercapto one type of silane coupling agents such as 1-propyl-triethoxysilicane; The isocyanates silane coupling agents such as 3-isocyanate group propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane; The aldehydes silane coupling agents such as triethoxysilicane alkyl butyraldehyde; The carbamates silane coupling agents such as tri-ethoxy silylpropyl methyl carbamate, (3-tri-ethoxy silylpropyl) tert-butyl group carbamate.

When the addition of above-mentioned silane coupling agent is too much, unreacted reactant causes harmful effect to liquid crystal aligning, therefore when very few, can't present the effect to adaptation, the solid constituent with respect to polymkeric substance better is 0.01～5.0 % by weight, is more preferably 0.1～1.0 % by weight.

When adding above-mentioned silane coupling agent, in order to prevent separating out of polymkeric substance, better be to add before the solvent of purpose in the aforementioned homogeneity of filming take raising of interpolation.In addition, when adding silane coupling agent, can before mixed polyamide acid esters solution and polyamic acid solution, add in the polyamic acid ester solution, in the polyamic acid solution or among polyamic acid ester solution and the polyamic acid solution both sides.Also can add in poly amic acid ester-polyamic acid mixed solution.Silane coupling agent adds take the adaptation between raising polymkeric substance and the substrate as purpose, therefore as the adding method of silane coupling agent, better be to add to concentrate the polyamic acid solution that is arranged in film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, the method for mixing with the polyamic acid ester solution.

In order more effectively to carry out burning till the imidizate that makes poly amic acid ester when filming, can add imidizate promoter.Below, exemplify the concrete example of the imidizate promoter of poly amic acid ester, but be not limited to these.

[changing 40]

[changing 41]

D is tert-butoxycarbonyl or 9-fluorenylidene methoxycarbonyl respectively independently in the above-mentioned formula (B-1)～(B-17).In (B-14)～(B-17), there are a plurality of D in the formula, they can be identical or different.

The content of imidizate promoter is as long as in the scope of the effect of the hot-imide that can obtain to promote poly amic acid ester, be not particularly limited, but the amic acid esters position of the following formula (12) that the poly amic acid ester in the aligning agent for liquid crystal with respect to 1 mole is contained, (B) composition better is more than 0.01 mole, be more preferably more than 0.05 mole, further be more preferably more than 0.1 mole.In addition, the harmful effect that imidizate promoter from will residue in the film after burning till itself is caused many characteristics of liquid crystal orientation film is controlled at MIN angle and considers, the amic acid esters position of the following formula (12) that the poly amic acid ester in the aligning agent for liquid crystal with respect to 1 mole is contained, imidizate promoter is more fortunately below 2 moles, better below 1 mole, further better below 0.5 mole.

[changing 42]

When adding imidizate promoter, in order to carry out imidizate by heating, better be with adding after good solvent and the Weak solvent dilution.

Can also use the various adjuvants such as crosslinking chemical in the obvious aligning agent for liquid crystal of the present invention.In addition, the polymkeric substance of (A) of the present invention composition and (B) polyamic acid of composition respectively can be for more than 2 kinds.

Comprise in the aligning agent for liquid crystal of the present invention (A) composition and (B) polymer concentration of composition can suitably change according to the setting of the thickness of the liquid crystal orientation film of wanting to form, but better be 1～10 quality %, be more preferably 2～8 quality %.If less than 1 quality % then is difficult to form even and flawless filming, if be higher than 10 quality %, the storage stability variation of solution sometimes then.

[manufacture method of aligning agent for liquid crystal]

Aligning agent for liquid crystal of the present invention comprises at least a kind polymkeric substance ((A) composition) and the polyamic acid ((B) composition) of the imide amination polymer that is selected from poly amic acid ester with ad hoc structure and this poly amic acid ester.

With respect to (A) composition and (B) ratio of (A) composition of the total amount of composition better be 5 quality %～95 quality %.If (A) component ratio is few, then might can't obtain enough liquid crystal alignings, if (B) ratio of composition is few, then might can't obtain the effect as target of the present invention.Therefore, (A) component ratio better is 20 quality %～80 quality %, is more preferably 30 quality %～70 quality %.

As mix (A) composition and (B) method of composition comprise the polymkeric substance of mixing (A) composition and (B) composition the polyamic acid powder and be dissolved in the method for solvent, powder and (B) method of the polyamic acid solution of composition of mixing the polymkeric substance of (A) composition, mix the polymer solution of (A) composition and (B) method of the polyamic acid powder of composition, mix the polymer solution of (A) composition and (B) method of the polyamic acid solution of composition.Even in the polymkeric substance of dissolving (A) composition situation different with the good solvent of the polyamic acid of (B) composition, also can obtain uniformly the mixed solution of the polyamic acid of composition of the polymkeric substance of (A) composition-(B), therefore more preferably mix the polymer solution of (A) composition and (B) method of the polyamic acid solution of composition.

As the method for polymer solution of preparation (A) composition comprise make (A) thus the powder dissolution of the polymkeric substance of composition directly uses the method for reaction solution of polymkeric substance of polymer solution, (A) composition of (A) composition in described good solvent.(A) composition is in the situation of imide amination polymer of poly amic acid ester or poly amic acid ester, the more preferably method of dissolve polymer powder, and (A) composition is in the situation of polyamic acid, more preferably directly uses the method for polymeric reaction solution.At this moment, polymer concentration better is 10～30%, and the spy is 10～15% well.In addition, the dissolving (A) composition polymer powder the time can heat.Heating-up temperature better is 20 ℃～150 ℃, and the spy is well 20～80 ℃.

As the method for polyamic acid solution of preparation (B) composition comprise make the polyamic acid powder dissolution in aforementioned good solvent and with it as the method for polyamic acid solution, directly use the method for polymeric reaction solution, more preferably directly use the method for polymeric reaction solution.In the situation that the polyamic acid powder is dissolved again, polymer concentration better is 10～30%, and the spy is 10～15% well.In addition, can heat during the dissolve polymer powder.Heating-up temperature better is 20 ℃～150 ℃, and the spy is well 20～80 ℃.

When adding silane coupling agent, can be at the polymer solution that mixes (A) composition with (B) before the polyamic acid solution of composition, add in the polymer solution of (A) composition, in the polyamic acid solution of (B) composition or (A) composition polymer solution and (B) among the polyamic acid solution both sides of composition.Also can add in the polyamic acid mixed solution of the composition of the polymkeric substance of (A) composition-(B).Silane coupling agent adds take the adaptation between raising polymkeric substance and the substrate as purpose, therefore as the adding method of silane coupling agent, more preferably add the polyamic acid solution that to concentrate (B) composition that is arranged in film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, the method for mixing with the polymer solution of (A) composition.Therefore when the addition of silane coupling agent was too much, unreacted reactant caused harmful effect to liquid crystal aligning, when very few, can't present the effect to adaptation, and the solid constituent with respect to polymkeric substance better is 0.01～5.0 % by weight, is more preferably 0.1～1.0 % by weight.

Mix the polymer solution of (A) composition and (B) during the polyamic acid solution of composition, the concentration of polymkeric substance better is 10～30% in these solution, the spy is 10～15% well.In addition, can heat during mixing, heating-up temperature better is 20 ℃～100 ℃, and the spy is well 20 ℃～60 ℃.

Adding in the situation of silane coupling agent or crosslinking chemical, in order to prevent separating out of polymkeric substance, better is to add before adding Weak solvent.In addition, (A) polymkeric substance of composition is in the situation of poly amic acid ester, in order more effectively to carry out burning till the imidizate that makes poly amic acid ester when filming, can add imidizate promoter.When adding imidizate promoter, in order to carry out imidizate by heating, better be with adding after good solvent and the Weak solvent dilution.

By adding aforementioned good solvent and aforementioned Weak solvent and be diluted to the polymer concentration that reaches certain in the polyamic acid mixed solution of composition at the polymkeric substance of (A) composition that makes with (B), from obtaining aligning agent for liquid crystal of the present invention.

[liquid crystal orientation film]

Liquid crystal orientation film of the present invention better is that the aligning agent for liquid crystal of the invention described above is coated substrate and drying, burnt till and filmed after filtration.Substrate as coating aligning agent for liquid crystal of the present invention, so long as the high substrate of the transparency then limits without special, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate or polycarbonate substrate etc., from the angle that production technology is simplified, the preferred substrate that is formed with for the ITO electrode of liquid crystal drive etc. that uses.In addition, in the reflection type liquid crystal display element, if only limit to the substrate of a side then can use the opaque material such as silicon wafer, the electrode of this moment also can use the reflectorized materials such as aluminium.

The coating process of aligning agent for liquid crystal can exemplify spin-coating method, print process, ink-jet method etc.After being coated with aligning agent for liquid crystal of the present invention, better being drying and burning till.In order fully to remove the organic solvent that contains in the aligning agent for liquid crystal, better be under 50～120 ℃, to make its drying 1～10 minute.Then, better be at 150～300 ℃, be more preferably under 150～250 ℃ and burn till.Firing time can be different according to firing temperature, but better are 5～120 minutes, are more preferably 5～60 minutes.

Thickness to liquid crystal orientation film is not particularly limited, if but excessively thin, then the reliability of liquid crystal display cells can reduce sometimes, is 5～300nm therefore, better is 10～200nm.By the orientation process that described coated surface is rubbed etc., can be used as liquid crystal orientation film and use.

Liquid crystal orientation film of the present invention is to give the liquid crystal orientation film of liquid crystal aligning ability by the irradiation polarized UV rays.And then, compare with light aligned liquid-crystal alignment films in the past, even liquid crystal orientation film of the present invention is the liquid crystal orientation film that can present the irradiation wide ranges of liquid crystal aligning and also can obtain even and good liquid crystal aligning in the uneven situation in the real estate of exposure intensity occurs.

As the concrete example of light orientation process method, can exemplify the ultraviolet ray of aforementioned film coated surface irradiation towards the certain orientation polarization, according to circumstances further under 150～250 ℃ temperature, carry out heat treated, give the method for liquid crystal aligning ability.Do the ultraviolet ray that outer ultraviolet ray preferably has 100～400nm wavelength, particularly preferably have the ultraviolet ray of 200～400nm wavelength.In addition, in order to improve liquid crystal aligning, can be when substrate be filmed in 50～250 ℃ of lower heating irradiation ultraviolet radiation.Aforementioned ultraviolet irradiation amount better is 1～10000mJ/cm ², the spy is 100～5000mJ/cm well ²

Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited thereto.

Embodiment

Below, abbreviation and the structure of the compound that uses in present embodiment and the comparative example are shown.

1,3DMCBDE-Cl:1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2,4-dimethyl dicarboxylate

BDA:1,2,3,4-butane tetracarboxylic acid dianhydride

CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride

PMDA: pyromellitic acid anhydride

1,3DMCBDA:1,3-dimethyl cyclo-butane tetracarboxylic dianhydride

DA-A:4,4 '-diaminodiphenyl-methane

DA-B:4,4 '-diamino-diphenylamine

DA-C:4,4 '-diaminodiphenyl ether

DA-D:3, the 5-diaminobenzoic acid

(organic solvent)

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

BCS: butyl cellosolve

γ-BL: gamma-butyrolacton

Below, illustrate ¹Each assay method of HNMR, viscosity, molecular weight, liquid crystal aligning and ghost evaluating characteristics.

[ ¹HNMR]

Device: Fourier transform type superconduction nuclear magnetic resonance device (FT-NMR) INOVA-400 (Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. (Varian) system): 400MHz.

Standard substance: tetramethylsilane (TMS)

Solvent: DMSO-d6

[viscosity]

In synthesis example, the viscosity of poly amic acid ester and polyamic acid solution is utilized E type viscosity meter TVE-22H ((East Machine industry society of Toki Sangyo Co., Ltd.) system), (measure under the condition that the TE-1 (1 ° 34 ', R24) of コ-Application ロ-タ), temperature are 25 ℃ at sample size 1.1mL, coniform rotor.

[molecular weight]

In addition, the molecular weight of poly amic acid ester adopts GPC(normal temperature gel permeation chromatography) device measures, and calculates number-average molecular weight (below, be also referred to as Mn) and weight-average molecular weight (below, be also referred to as Mw) with polyglycol, polyethylene oxide scaled value.

GPC device: Shodex (Showa Denko K. K) company's system (GPC-101)

Post: Showa Denko K. K's system (series connection of KD803, KD805)

Column temperature: 50 ℃

Eluent: N, and the N'-dimethyl formamide (as adjuvant, lithium bromide-hydrate (LiBrH ₂O) be that 30mmol/L, phosphoric acid anhydrous crystal (adjacent phosphoric acid) are 10ml/L for 30mmol/L, tetrahydrofuran (THF))

Flow velocity: 1.0ml/ minute

Calibration curve is made and to be used standard sample: (East ソー society of eastern Cao company) TSK standard polyethylene oxide processed (weight-average molecular weight (Mw) about 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リマーラボラトリー society) polyglycol processed (peak molecular weight (Mp) about 12000,4000,1000).Repeat for fear of peak value, measured respectively 2 samples, namely mixed 900000,100000,12000,1000 these samples of 4 kinds and mixed 150000,30000,4000 these samples of 3 kinds.

[liquid crystal aligning]

To the coating of liquid crystalline alignment agent and burn till and the polarized UV rays of tunicle irradiation 254nm, make liquid crystal orientation film of the present invention.The irradiation amount of this moment is made as 100mJ, 200mJ, 300mJ, 400mJ.Use is carried out the liquid crystal orientation film of orientation process with each exposure, make the liquid crystal structure cell after, with polarized light microscope observing liquid crystal aligning, and according to following standard evaluation liquid crystal aligning.

Evaluation criterion

◎: the variation (can confirm liquid crystal aligning) that has light and shade when making the structure cell rotation.Almost there is not light leak under the cross Nicols.

Zero: observe slightly light leak under the cross Nicols, the variation (can confirm the orientation of liquid crystal) that has light and shade when making the structure cell rotation.

△: observe flow orientation and under cross Nicols, observe light leak, but make the variation (can confirm the orientation of liquid crystal) that structure cell when rotation have light and shade.

*: make structure cell when rotation without the variation (liquid crystal aligning is not oriented) of light and shade.

Two (chlorocarbonyl)-1 of 1,3-, 3-dimethyl cyclo-butane-2, the 4-dimethyl dicarboxylate (1,3DMCBDE-Cl) synthetic

A-1: tetrabasic carboxylic acid dialkyl group ester synthesis

[changing 43]

In nitrogen stream, in the 3L four-hole boiling flask, add 220g(0.981mol) 1,3-dimethyl cyclo-butane-1,2,3,4-tetracarboxylic dianhydride (the compound of formula (5-1), hereinafter to be referred as 1,3-DM-CBDA) and 2200g(6.87mol, with respect to 1,3-DM-CBDA be 10wt doubly) methyl alcohol, under 65 ℃, add hot reflux, become uniform solution after 30 minutes.Reaction solution directly added under the hot reflux at 4 hours 30 minutes and stirs.(hereinafter to be referred as HPLC) measured this reactant liquor by high performance liquid chromatography.Analysis to this measurement result is set forth below.

After removing solvent in this reactant liquor with evaporator distillation, the ethyl acetate that adds 1301g is heated to 80 ℃, and it was refluxed 30 minutes.Afterwards, be cooled to interior temperature with per 10 minutes 2～3 ℃ speed and reach 25 ℃, keep intact and under 25 ℃, stirred 30 minutes.By filter taking out the white crystals of having separated out, and after washing this crystallization 2 times with the ethyl acetate of 141g, by the white crystals of drying under reduced pressure acquisition 103.97g.

According to the result that 1H NMR analyzes and X ray crystalline texture is analyzed, confirming this crystallization is compound (1-1) (the HPLC relative area is 97.5%) (yield is 36.8%).

1H NMR(DMSO-d6,δppm)；12.82(s,2H),3.60(s,6H),3.39(s,2H),1.40(s,6H)。

A-2.1,3-DM-CBDE-Cl's is synthetic

[changing 44]

In nitrogen stream, in the four-hole boiling flask of 3L, add 234.15g(0.81mol) compound (1-1), 1170.77g(11.68mol, 5wt is doubly) normal heptane after, add 0.64g(0.01mol) pyridine, be stirred to 75 ℃ with heating under the magnetic stirrer.Then, with dripping 289.93g(11.68mol in 1 hour) thionyl chloride.Begin immediately foaming after the dropping, drip 30 minutes afterreaction solution becomes of end and get evenly, stopped foaming.Then, directly 75 ℃ lower stir 1 hour 30 minutes after, the inner capacities of utilizing evaporator that the solvent distillation is removed to 40 ℃ of water-baths reaches 924.42g.Be heated to 60 ℃, make the dissolving crystallized of separating out when distilling desolventizing, and behind the filtration insolubles, with per 10 minutes 1 ℃ speed filtrate is cooled to 25 ℃ carrying out thermosol to filter under 60 ℃.Keep intact and, the white crystals of separating out is taken out after filtration, and wash this crystallization with the normal heptane of 264.21g after 30 minutes 25 ℃ of lower stirrings.By with its drying under reduced pressure, obtain the white crystals of 226.09g.

Then, in nitrogen stream, after the normal heptane of the adding above-mentioned white crystals that makes of 226.09g and 452.18g, heating is stirred to 60 ℃, makes dissolving crystallized in the four-hole boiling flask of 3L.Afterwards, with per 10 minutes speed cooling and stirring to 25 of 1 ℃ ℃, make crystallization.Keep intact 25 ℃ lower stir 1 hour after, the white crystals of separating out is taken out after filtration, and after washing this crystallization with the normal hexane of 113.04g, by the white crystals of drying under reduced pressure acquisition 203.91g.Confirming this crystallization by 1H NMR analysis result is compound (3-1), namely 1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2, and the 4-dimethyl dicarboxylate (1,3-DM-CBDE-C1) (the HPLC relative area is 99.5%) (yield 77.2%).

1H NMR(CDCl3,δppm):3.78(s,6H),3.72(s,2H),1.69(s,6H)。

＜synthesis example 1〉poly amic acid ester

To be made as blanket of nitrogen with the four-hole boiling flask of the 300ml (liter) of stirring apparatus, add the DA-A of 8.0102g (40.35mmol), add the NMP of 158.1g and the pyridine as alkali of 7.20g (91.03mmol), make its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 2.3419g (37.93mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.

The polyamic acid ester solution that makes is added in the water of 1757g while stirring, filters and take out the white precipitate of separating out, then, with the water washing of 1757g 1 time, ethanol with 1757g washs 1 time, uses the ethanol of 439g to wash 3 times, and drying obtains the white poly amic acid ester toner of 16.63g.Yield is 94.6%.In addition, the molecular weight of this poly amic acid ester is Mn=10180, Mw=21476.

The poly amic acid ester toner that 14.8252g is obtained is taken in the Erlenmeyer flask of 200ml, adds the NMP of 99.3048g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (PAE-1).

＜synthesis example 2 〉

In the four-hole boiling flask with the 300mL of stirring apparatus and nitrogen ingress pipe, be taken into the DA-A of 3.9687g (20.017mmol), add γ-BL, the NMP of 30.08g of 26.44g, stir and make its dissolving when supplying with nitrogen.CBDA while stirring this two amine aqueous solution and add 4.4701g (19.941mmol) adds NMP again and makes solid component concentration reach 10 quality %, at room temperature stirs 24 hours, obtains polyamic acid (PAA-1) solution.The viscosity of this polyamic acid solution under 25 ℃ of temperature is 41.4mPas.In addition, the molecular weight of this polyamic acid is Mn=10724, Mw=22520.

＜synthesis example 3 〉

The DA-D of 6.0852g (39.99mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 29.24g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.BDA while stirring this two amine aqueous solution and add 7.8503g (39.62mmol) adds NMP again and makes solid component concentration reach 25 quality %, at room temperature stirs 24 hours, obtains polyamic acid solution.The viscosity of this polyamic acid solution under 25 ℃ of temperature is 2676mPas.In addition, the molecular weight of this polyamic acid is Mn=9024, Mw=17757.

The above-mentioned polyamic acid solution of 27.1035g is taken into the Erlenmeyer flask of 100ml, adds the NMP of 18.069g, at room temperature stirred 4 hours, obtain polyamic acid solution (PAA-2).

＜synthesis example 4 〉

The DA-D of 3.0467g (20.02mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 27.23g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.CBDA while stirring this two amine aqueous solution and add 3.8974g (19.87mmol) adds NMP again and makes solid component concentration reach 15 quality %, at room temperature stirs 24 hours, obtains the solution of polyamic acid (PAA-3).The viscosity of this polyamic acid solution under 25 ℃ of temperature is 448.4mPas.In addition, the molecular weight of this polyamic acid is Mn=18772, Mw=48808.

＜synthesis example 5 〉

The DA-D of DA-B, the 1.5246g (10.02mmol) of 7.9719g (40.01mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 40.64g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.BDA while stirring this two amine aqueous solution and add 9.8377g (49.65mmol) adds NMP again and makes solid component concentration reach 25 quality %, at room temperature stirs 24 hours, obtains polyamic acid solution.The viscosity of this polyamic acid solution under 25 ℃ of temperature is 14550mPas.In addition, the molecular weight of this polyamic acid is Mn=16230, Mw=34539.

The polyamic acid solution that 45.1642g is obtained is taken in the Erlenmeyer flask of 100ml, adds the NMP of 33.87g, at room temperature stirs 24 hours and makes its dissolving, makes the polyamic acid solution (PAA-4) of 15 quality %.

＜synthesis example 6 〉

The DA-D of DA-C, the 2.1025g (13.82mmol) of 1.848g (9.23mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 39.7g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.PMDA while stirring this two amine aqueous solution and add 4.8162g (22.08mmol) adds NMP again and makes solid component concentration reach 15 quality %, at room temperature stirs 24 hours, obtains the solution of polyamic acid (PAA-5).The viscosity of this polyamic acid solution under 25 ℃ of temperature is 257mPas.In addition, the molecular weight of this polyamic acid is Mn=13620, Mw=28299.

＜embodiment 1 〉

Stopple coupon at the 20mL that has put into stirrer, be taken into the polyamic acid solution (PAA-2) that makes in the synthesis example 3 of the polyamic acid ester solution (PAE-1) that makes in the synthesis example 1 of 1.5339g, 1.3574g, add NMP, the BCS of 1.0164g of 1.1775g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (I).

＜embodiment 2 〉

Stopple coupon at the 20mL that has put into stirrer, be taken into the polyamic acid solution (PAA-3) that makes in the synthesis example 4 of the polyamic acid ester solution (PAE-1) that makes in the synthesis example 1 of 1.5160g, 0.9026g, add NMP, the BCS of 1.0121g of 1.6340g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (II).

＜embodiment 3 〉

Stopple coupon at the 20mL that has put into stirrer, be taken into the polyamic acid solution (PAA-4) that makes in the synthesis example 5 of the polyamic acid ester solution (PAE-1) that makes in the synthesis example 1 of 1.5293g, 0.8973g, add NMP, the BCS of 1.0150g of 1.6160g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (III).

＜embodiment 4 〉

Stopple coupon at the 20mL that has put into stirrer, be taken into the polyamic acid solution (PAA-5) that makes in the synthesis example 6 of the polyamic acid ester solution (PAE-1) that makes in the synthesis example 1 of 1.5018g, 1.1008g, add NMP, the BCS of 1.0214g of 1.4859g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (IV).

＜comparative example 1 〉

At the stopple coupon of the 20mL that has put into stirrer, be taken into the polyamic acid ester solution (PAE-1) that makes in the synthesis example 1 of 4.253g, add NMP, the BCS of 1.4194g of 1.4419g, use magnetic stirrer 30 minutes, make aligning agent for liquid crystal (a).

＜comparative example 2 〉

At the stopple coupon of the 20mL that has put into stirrer, be taken into the polyamic acid ester solution (PAA-1) that makes in the synthesis example 2 of 3.095g, add NMP, the BCS of 1.0322g of 1.0163g, use magnetic stirrer 30 minutes, make aligning agent for liquid crystal (c).

＜embodiment 5〉making of structure cell

Behind the aligning agent for liquid crystal (I) that makes among the filtrator filtration embodiment 1 with 1.0 μ m, be spun on the glass substrate with transparency electrode, and through in the drying of heating plate upper 5 minute of 80 ℃ of temperature, the burning till of lower 1 hour of 250 ℃ of temperature, obtained the polyimide film of thickness 100nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm ², obtain the substrate with liquid crystal orientation film.

Prepare 2 this substrates with liquid crystal orientation film, after the liquid crystal aligning face of a substrate scatters the sept of 6 μ m, with the antiparallel condition of the orientation of 2 substrates with 2 substrate in combination, sealing on every side, but stay liquid crystal injecting port, making structure cell opening (cell gap) is the negative crystal born of the same parents of 6 μ m.Vacuum is injected liquid crystal (MLC-2041, Merck Co., Ltd. (メ Le Network society) system) in this negative crystal born of the same parents at normal temperatures, with the inlet sealing, makes the liquid crystal structure cell.Confirmed the liquid crystal aligning of this liquid crystal structure cell with polarizing microscope, results verification is to being good liquid crystal aligning state.

The exposure of polarized UV rays is made as 200mJ/cm ², 300mJ/cm ², 400mJ/cm ²The time the liquid crystal aligning evaluation result be shown in table 1 described later.

＜embodiment 6 〉

The aligning agent for liquid crystal (II) that in using embodiment 2, makes, made the liquid crystal structure cell with method similarly to Example 5.For this liquid crystal structure cell, confirmed its liquid crystal aligning with polarizing microscope.The results are shown in table 1 described later.

＜embodiment 7 〉

The aligning agent for liquid crystal (III) that in using embodiment 3, makes, made the liquid crystal structure cell with method similarly to Example 5.To this liquid crystal structure cell, confirmed its liquid crystal aligning with polarizing microscope.The results are shown in table 1 described later.

＜embodiment 8 〉

The aligning agent for liquid crystal (IV) that in using embodiment 4, makes, made the liquid crystal structure cell with method similarly to Example 5.To this liquid crystal structure cell, confirmed its liquid crystal aligning with polarizing microscope.The results are shown in table 1 described later.

＜comparative example 3 〉

The aligning agent for liquid crystal that in usage comparison example 1, makes (a), made the liquid crystal structure cell with method similarly to Example 5.To this liquid crystal structure cell, confirmed its liquid crystal aligning with polarizing microscope.The results are shown in table 1 described later.

＜comparative example 4 〉

The aligning agent for liquid crystal that in usage comparison example 2, makes (c), made the liquid crystal structure cell with method similarly to Example 5.To this liquid crystal structure cell, confirmed its liquid crystal aligning with polarizing microscope.The results are shown in table 1 described later.

[table 1]

	Aligning agent for liquid crystal	100mJ	200mJ	300mJ	400mJ
						Embodiment 5	Aligning agent for liquid crystal (I)	◎	○	○	△
Embodiment 6	Aligning agent for liquid crystal (II)	◎	○	×	×
						Embodiment 7	Aligning agent for liquid crystal (III)	◎	◎	○	○
Embodiment 8	Aligning agent for liquid crystal (IV)	◎	○	×	×
						Comparative example 3	Aligning agent for liquid crystal (a)	○	×	×	×
Comparative example 4	Aligning agent for liquid crystal (c)	○	△	×	×

By embodiment 5～8 and comparative example 3,4 more as can be known, the scope of the irradiation amount of the liquid crystal aligning ability that presents of aligning agent for liquid crystal of the present invention broadens.

The possibility of utilizing on the industry

By the liquid crystal orientation film that aligning agent for liquid crystal of the present invention makes, can in optical alignment method, not rely on polarized UV rays ground and obtain good liquid crystal aligning.Especially, be widely used in the display element of giant-screen or televisor etc.

In addition, quote all the elements of Japanese patent application 2010-058559 number instructions, claims, accompanying drawing and the summary of filing an application on March 15th, 2010 here as the announcement of instructions of the present invention.

Claims

1. aligning agent for liquid crystal is characterized in that, contains following (A) composition and (B) composition,

(A) composition: be selected from least a kind the polymkeric substance that has by the imide amination polymer of the poly amic acid ester of the repetitive of following formula (1) expression and this poly amic acid ester,

[changing 1]

2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, (A) composition and (B) proportionally count 1/9～9/1 with mass ratio (A/B) containing of composition.

3. aligning agent for liquid crystal as claimed in claim 1 or 2, it is characterized in that (A) composition is to be selected from least a kind of polymkeric substance by the imide amination polymer of the poly amic acid ester of the repetitive of above-mentioned formula (1) expression and this poly amic acid ester that has more than 40 % by mole.

4. such as each described aligning agent for liquid crystal in the claim 1～3, it is characterized in that composition (A) is the poly amic acid ester that has by the repetitive of following formula (3) expression,

[changing 2]

5. such as each described aligning agent for liquid crystal in the claim 1～3, it is characterized in that composition (A) is the poly amic acid ester that has by the repetitive of following formula (4) expression,

[changing 3]

6. such as each described aligning agent for liquid crystal in the claim 1～5, it is characterized in that in the formula (1), Y is selected from least a kind of following structural formula,

[changing 4]

7. such as each described aligning agent for liquid crystal in the claim 1～6, it is characterized in that composition (B) is the polyamic acid that utilizes at least a kind tetracarboxylic dianhydride comprising the tetracarboxylic dianhydride who is selected from following formula (B-1)～(B-9) to make,

[changing 5]

8. aligning agent for liquid crystal as claimed in claim 7, it is characterized in that composition (B) is the polyamic acid that the tetracarboxylic dianhydride more than 20 % by mole that utilizes at least a kind of tetracarboxylic dianhydride being selected from above-mentioned formula (B-1)～(B-9) to account for tetracarboxylic dianhydride's total amount makes.

9. such as each described aligning agent for liquid crystal in the claim 1～8, it is characterized in that composition (B) is to utilize to comprise the polyamic acid that at least a kind diamines being selected from following formula (B-10)～(B-13) makes,

[changing 6]

10. aligning agent for liquid crystal as claimed in claim 9 is characterized in that, composition (B) is the polyamic acid that the diamines more than 20 % by mole that utilizes at least a kind of diamines being selected from above-mentioned formula (B-10)～(B-13) to account for the diamines total amount makes.

11. liquid crystal orientation film is characterized in that, to being coated with each described aligning agent for liquid crystal in above-mentioned 1～10 and burning till and the tunicle irradiation polarized UV rays that obtains and making.