CN101925850B

CN101925850B - Liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element

Info

Publication number: CN101925850B
Application number: CN2009801032007A
Authority: CN
Inventors: 后藤耕平; 三木德俊; 矢田研造; 片山雅章
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2008-01-25
Filing date: 2009-01-23
Publication date: 2012-06-06
Anticipated expiration: 2029-01-23
Also published as: TW200948860A; JPWO2009093709A1; KR20100103583A; CN101925850A; JP5177150B2; WO2009093709A1; KR101589322B1; TWI438226B

Abstract

Provided is a liquid-crystal alignment material capable of giving a liquid-crystal alignment film which has a high voltage retention and which, even after having been exposed to a high-temperature atmosphere over long, is reduced in residual charge accumulated by direct-current voltage. Also provided is a liquid-crystal display element employing the liquid-crystal alignment film. The liquid-crystal alignment material comprises a copolymer obtained by reacting a diamine ingredient comprising at least one diamine compound (A) and a diamine compound (B) with a tetracarboxylic dianhydride. Diamine compound (A): at least one compound selected from the group consisting of compounds of the formulae [T1], [T2], and [T3], which are diamine compounds having a tertiary nitrogen atom. Diamine compound (B): a diamine compound having a carboxy group in the molecule. (Chemical formula 1) [T1] [T2] [T3] (In the formulae [T1] to [T3], W1 is a benzene ring or nitrogenous aromatic heterocycle; W2 is an aromatic group having 6 to 15 carbon atoms and having one or two benzene rings; W3 is C2-5 alkylene or biphenylene; W4 is cycloalkylene having 4 to 6 carbon atoms and substituted by a tertiary nitrogen atom; W5 is C2-5 alkylene; Z1 is amino substituted by two C1-6 aliphatic groups when W1 is a benzene ring, or Z1 is hydrogen or amino substituted by two C1-6 aliphatic groups when W1 is a nitrogenous aromatic heterocycle; Z2 is C1-5 alkyl or a benzene ring; and g is an integer of 0 or 1.

Description

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

Technical field

The aligning agent for liquid crystal that uses when the present invention relates to make liquid crystal orientation film and used the liquid crystal display cells of this alignment agent.

Background technology

At present; Liquid crystal orientation film as liquid crystal display cells; The main polyimide liquid crystal orientation film that uses, this polyimide liquid crystal orientation film are to burn till behind the aligning agent for liquid crystal of major component to make with the solution of polyimide precursor such as polyamic acid or soluble polyimide through coating on glass substrate etc.

Liquid crystal orientation film be with control liquid crystal state of orientation be the film that purpose is used.But; High resolving powerization along with liquid crystal display cells; Require the contrast of control liquid crystal display cells to descend and reduce persistence of vision, therefore the fast such characteristic of the voltage retention of the used liquid crystal orientation film release of accumulating electric charge residual charge few and/or that accumulate because of DC voltage high, when having applied DC voltage is more and more important.

In the polyimide liquid crystal orientation film; As the short liquid crystal orientation film of time till the after image disappearance that produces because of DC voltage; The known liquid crystal orientation film that the aligning agent for liquid crystal that has used the tertiary amine that except that the polyamic acid of polyamic acid or imido-, also contains ad hoc structure is arranged (for example with reference to patent documentation 1) has perhaps used the liquid crystal orientation film (for example with reference to patent documentation 2) of the aligning agent for liquid crystal that contains in the raw material soluble polyimide that adopts the specific diamines with pyridine skeleton etc. etc.In addition; Short liquid crystal orientation film of time till high and after image that produce because of DC voltage disappears as voltage retention, known having have used the liquid crystal orientation film (for example with reference to patent documentation 3) of aligning agent for liquid crystal that compound, molecule that molecule contains 1 carboxyl contain the compound of 1 carboxylic acid anhydride group's compound and the compound that molecule contains 1 uncle's amino that is selected from that except that polyamic acid or its imide amination polymer etc., also comprises minute quantity.

But; Big in recent years picture and high-resolution LCD TV are widely used; Liquid crystal display cells in this purposes with present serve as that the main display applications that shows is compared with literal or still frame; Its requirement for after image is stricter, and requires to possess the resistance characteristics that under harsh environment for use, can use for a long time.Therefore, the reliability that is used for the liquid crystal orientation film of this purposes must be higher than existing liquid crystal orientation film, for the electrical characteristics of liquid crystal orientation film, not only requires initial characteristic good, also can keep good characteristic after also requiring for example to be exposed under the high temperature for a long time.

Patent documentation 1: japanese patent laid-open 9-316200 communique

Patent documentation 2: japanese patent laid-open 10-104633 communique

Patent documentation 3: japanese patent laid-open 8-76128 communique

The announcement of invention

The present invention is the invention of accomplishing in view of above situation.That is, can to obtain voltage retention high and be exposed to high temperature under afterwards the aligning agent for liquid crystal of the also less liquid crystal orientation film of the residual charge accumulated because of DC voltage for a long time even the problem that the present invention will solve provides.

But the present invention also is provided at the high liquid crystal display cells of long term reliability under the harsh environment for use.

The present inventor has found the aligning agent for liquid crystal that can reach this purpose for realizing after above-mentioned purpose is conscientiously studied.The present invention is based on the invention that these achievements in research are accomplished, and comprises following technology contents.

(1) aligning agent for liquid crystal, comprise two amine components that contain diamine compound (A) and diamine compound (B) and tetracarboxylic dianhydride reaction and multipolymer,

Diamine compound (A): be selected from following formula [T1], formula [T2] and formula [T3] at least a kind of diamine compound that contains tertiary N atom,

Diamine compound (B): carboxylic diamine compound in the molecule,

Formula [T1]～formula [T3] in, W < > 1 <> Be phenyl ring or nitrogenous fragrant heterocycle, W < > 2 <> For having 6～15 carbon atoms and having the aromatic group of 1～2 phenyl ring, W < > 3 <> Be the alkylidene or the biphenylene of carbon number 2～5, W < > 4 <> For by the cycloalkylidene of the substituted carbon number 4～6 of tertiary N atom, W < > 5 <> Be the alkylidene of carbon number 2～5, Z < > 1 <> At W < > 1 <> Represent during for phenyl ring by the substituted disubstituted amido of the aliphatic group of carbon number 1～6, at W < > 1 <> Represent hydrogen atom during for nitrogenous fragrant heterocycle or by the substituted disubstituted amido of the aliphatic group of carbon number 1～6, Z < > 2 <> Be the alkyl or the phenyl ring of carbon number 1～5, g is 0 or 1 integer.

(2) aligning agent for liquid crystal of above-mentioned (1) record, diamine compound (A) are the compound of following formula [1]～formula [4] expression,

In formula [1]～formula [4], A < > 1 <> Be nitrogenous fragrant heterocycle, A < > 2 <> For having 6～15 carbon atoms and having the aromatic group of 1～2 phenyl ring, A < > 3 <> Be the alkylidene or the biphenylene of carbon number 2～5, A < > 4 <> Be formula [4a] or formula [4b] expression group, A < > 5 <> Be the alkylidene of carbon number 2～5, Y < > 1 <> For by the substituted disubstituted amido of the aliphatic group of carbon number 1～6, Y < > 2 <> Be the alkyl or the phenyl ring of carbon number 1～5, k is 0 or 1 integer.

(3) aligning agent for liquid crystal of above-mentioned (2) record, diamine compound (A) is formula [1] or formula [2].

(4) aligning agent for liquid crystal of above-mentioned (2) record, the A of formula [3] < > 2 <> Be phenyl ring or following formula [3a],

Formula [3a] in, P be selected from singly-bound ,-linking group of O-,-NH-, methylene or amide group.

(5) aligning agent for liquid crystal of above-mentioned (1) or (2) record, diamine compound (A) is for being selected from following formula [5]～[18] at least a kind of diamine compound,

Formula [13] in, m, n are respectively 1～11 integer, and m+n is 2～12 integer, formula [15] in, j is 0～3 integer, formula [18] in, h is 1～5 integer.

(6) aligning agent for liquid crystal of each record in above-mentioned (1)～(5), diamine compound (B) is following formula [19] diamine compound of expression,

Formula [19] in, X < > 1 <> Be the organic group of aromatic ring with carbon number 6～30, n is 1～4 integer.

(7) aligning agent for liquid crystal of above-mentioned (6) record, diamine compound (B) is for being selected from following formula [20]～formula [24] diamine compound,

Formula [20] in, m1 is 1～4 integer, formula [21] in, X < > 2 <> For singly-bound ,-CH < > 2 <>-,-C < > 2 <> H < > 4 <>-,-C(CH < > 3 <> ) < > 2 <>-,-CF < > 2 <>-,-C(CF < > 3 <> ) < > 2 <>-,-O-,-CO-,-NH-,-N(CH < > 3 <> )-,-CONH-,-NHCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-COO-,-OCO-,-CON(CH < > 3 <> )-or-N(CH < > 3 <> )CO-m2, m3 represent 0～4 integer respectively, and m2+m3 representes 1～4 integer, formula [22] in, m4, m5 represent 1～5 integer, formula [23 respectively] in, X < > 3 <> Be the straight or branched alkyl of carbon number 1～5, m6 is 1～5 integer, formula [24] in, X < > 4 <> For singly-bound ,-CH < > 2 <>-,-C < > 2 <> H < > 4 <>-,-C(CH < > 3 <> ) < > 2 <>-,-CF < > 2 <>-,-C(CF < > 3 <> ) < > 2 <>-,-O-,-CO-,-NH-,-N(CH < > 3 <> )-,-CONH-,-NHCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-COO-,-OCO-,-CON(CH < > 3 <> )-or-N(CH < > 3 <> )CO-m7 is 1～4 integer.

(8) aligning agent for liquid crystal of above-mentioned (7) record, formula [20] in, m1 is 1～2 integer.

(9) aligning agent for liquid crystal of above-mentioned (7) record, formula [21] in, X < > 2 <> For singly-bound ,-CH < > 2 <>-,-C < > 2 <> H < > 4 <>-,-C(CH < > 3 <> ) < > 2 <>-,-O-,-CO-,-NH-,-N(CH < > 3 <> )-,-CONH-,-NHCO-,-COO-or-OCO-, m2, m3 are integer 1.

(10) the aligning agent for liquid crystal of above-mentioned (7) record, formula [24] in, X < > 4 <> For singly-bound ,-CH < > 2 <>-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-COO-or-OCO-, m7 is 1～2 integer.

(11) the aligning agent for liquid crystal of each record in above-mentioned (1)～(10), with respect to diamine compound (A)1 mole, the content of the diamine compound in two amine components (B) is 0.01～99 mole.

(12) the aligning agent for liquid crystal of each record in above-mentioned (1)～(11), 5～80 quality % in the solvent that aligning agent for liquid crystal comprises are Weak solvent.

(13) the aligning agent for liquid crystal of each record in above-mentioned (1)～(12), the multipolymer that aligning agent for liquid crystal comprises be make the polyamic acid dehydration closed-loop and polyimide.

(14) liquid crystal orientation film is formed by the aligning agent for liquid crystal of each record in above-mentioned (1)～(13).

(15) liquid crystal display cells possesses above-mentioned (14) record liquid crystal orientation film.

Aligning agent for liquid crystal of the present invention can use easier method to obtain.In addition, even can obtain the voltage retention height and be exposed to the also less liquid crystal orientation film of residual charge that accumulate because of DC voltage the back under the high temperature for a long time by aligning agent for liquid crystal of the present invention.Therefore, possess the reliability height of the liquid crystal display cells of the liquid crystal orientation film that obtains by aligning agent for liquid crystal of the present invention, be applicable to big picture and high-resolution liquid crystal TV set etc.

The best mode that carries out an invention

The present invention for the aligning agent for liquid crystal of the multipolymer that comprises two amine components that contain diamine compound (A) and diamine compound (B) and tetracarboxylic dianhydride reaction and get, used the liquid crystal orientation film of this aligning agent for liquid crystal and possessed the liquid crystal display cells of this liquid crystal orientation film.

< two amine components >

Being used for diamine compound of the present invention (A) is formula [T1]～formula [T3] expression the diamine compound that contains tertiary N atom.Tertiary N atom is meant the nitrogen-atoms that 3 covalent bonds (Japanese:

closes hand) of nitrogen-atoms combine with the atom beyond the hydrogen atom, preferred carbon atom among the present invention.

The tertiary N atom that is used for diamine compound of the present invention (A) plays a role through the jump of its conjugated structure as electronics, so promote the transfer of the electric charge in the gained liquid crystal orientation film.In addition, carboxyl contained in the molecule of said tertiary N atom and diamine compound (B) combines through salify or the such electrostatic interaction of hydrogen bond, and electric charge moves between tertiary N atom and carboxyl.Follow this move, the electric charge of accumulating can be efficiently in the molecule of multipolymer, intermolecular moving.

That is, even aligning agent for liquid crystal of the present invention can obtain the voltage retention height and be exposed to the also less liquid crystal orientation film of residual charge that accumulate because of DC voltage the back under the high temperature for a long time when forming liquid crystal orientation film.

[diamine compound (A)]

Being used for diamine compound of the present invention (A) is to be selected from following formula [T1], formula [T2] and formula [T3] at least a kind of compound, this compound is the diamine compound that contains tertiary N atom.

Formula [T1]～[T3] in, W < > 1 <> Be phenyl ring or nitrogenous fragrant heterocycle, W < > 2 <> For having 6～15 carbon atoms and having the aromatic group of 1～2 phenyl ring, W < > 3 <> Be the alkylidene or the biphenylene of carbon number 2～5, W < > 4 <> For by the cycloalkylidene of the substituted carbon number 4～6 of tertiary N atom, W < > 5 <> Be the alkylidene of carbon number 2～5, Z < > 1 <> At W < > 1 <> Represent during for phenyl ring by the substituted disubstituted amido of the aliphatic group of carbon number 1～6, at W < > 1 <> Represent hydrogen atom during for nitrogenous fragrant heterocycle or by the substituted disubstituted amido of the aliphatic group of carbon number 1～6, Z < > 2 <> Be the alkyl or the phenyl ring of carbon number 1～5, g is 0 or 1 integer.

As formula [T1]～formula [T3] preferred compound in the diamine compound of expression, the diamine compound of the following formula of can giving an example [1]～formula [4] expression.

In formula [1]～formula [4], A < > 1 <> Be nitrogenous fragrant heterocycle, A < > 2 <> For having 6～15 carbon atoms and having the aromatic group of 1～2 phenyl ring, A < > 3 <> Be the alkylidene or the biphenylene of carbon number 2～5, A < > 4 <> Be formula [4a] or formula [4b] expression group, A < > 5 <> Be the alkylidene of carbon number 2～5, Y < > 1 <> Be the aliphatic group of the carbon number 2～12 that contains tertiary carbon atom, Y < > 2 <> Be the alkyl or the phenyl ring of carbon number 1～5, k is 0 or 1 integer.

A in the formula [1] < >1 <>Be nitrogenous fragrant heterocycle, the pyrrole ring of specifically can giving an example, imidazole ring,

Azoles ring, thiazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, carbazole ring, purine ring, thiadiazoles ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring,

Diazole ring and acridine ring.Preferably pyrrole ring, imidazole ring,

oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, pyrazoline ring.Better for the pyrrole ring, imidazole ring,

oxazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring.

Concrete example following formula [the 5]～formula [12 that can give an example] diamine compound.

Y in the formula [2] < > 1 <> Be the aliphatic group of the carbon number 2～12 that contains tertiary N atom, the concrete preference following formula [13 that can give an example] or formula [14] diamine compound.

A in the formula [3] < > 2 <> For having 6～15 carbon atoms and having the aromatic group of 1～2 phenyl ring, A < > 3 <> Be the alkylidene or the biphenylene of carbon number 2～5, Y < > 2 <> Be the alkyl or the phenyl ring of carbon number 1～5, k is 0 or 1 integer.

A in the formula [3] < > 2 <> Be preferably phenyl ring or formula [3a] expression structure.

As the preferred concrete example of formula [3], following formula [15 can give an example]～[17] diamine compound.

Formula [13] in, m, n are respectively 1～11 integer, and m+n is 2～12 integer, formula [15] in, j is 0～3 integer.

A in the formula [4] < > 4 <> Be formula [4a] or formula [4b] expression group, A < > 5 <> Alkylidene for carbon number 2～5.

The preferred concrete example of formula [4] the following formula [18 that can give an example] diamine compound.

Formula [18] in, h is 1～5 integer.

Among the present invention, diamine compound (A) can use a kind also can multiple combination to use separately.

[diamine compound (B)]

Being used for diamine compound of the present invention (B) is carboxylic diamine compound in the molecule.Be preferably the compound that molecule includes 1～4 carboxyl.Structure for diamine compound (B) does not have special qualification, preferred formula [19] expression diamine compound.

As formula [19] preferred structure, following formula [20 can give an example]～[24] structure.

Be preferably formula [20] in m1 be the structure of 1～2 integer; Formula [21] in X < > 2 <> For singly-bound ,-CH < > 2 <>-,-C < > 2 <> H < > 4 <>-,-C(CH < > 3 <> ) < > 2 <>-,-O-,-CO-,-NH-,-N(CH < > 3 <> )-,-CONH-,-NHCO-,-COO-or-OCO-, m2 and m3 are the structure of integer 1; Formula [24] in X < > 4 <> For singly-bound ,-CH < > 2 <>-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-COO-or-OCO-, m7 is the structure of 1～2 integer.Wherein, special good be formula [20] structure of expression.

As the concrete example of diamine compound (B), following formula [25 can give an example]～formula [35] diamine compound.

Formula [34] in, X < > 5 <> For singly-bound ,-CH < > 2 <>-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-COO-or-OCO-, formula [35] in, X < > 6 <> For singly-bound ,-CH < > 2 <>-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-COO-or-OCO-.

[other diamine compound]

Among the present invention, can be also with diamine compound (A), diamine compound (B) other diamine compound in addition under the condition of harmless effect of the present invention as two amine components.Its concrete example is given an example as follows.

P-phenylenediamine (PPD), 2,3 for example, 5; 6- tetramethyl-p-phenylenediamine (PPD), 2,5- dimethyl-p-phenylenediamine (PPD), m-phenylene diamine (MPD), 2,4- dimethyl-m-phenylene diamine (MPD), 2; 5- diaminotoluene, 2,6- diaminotoluene, 2,5- diaminophenol, 2; 4- diaminophenol, 3,5- diaminophenol, 3,5- diaminobenzene methyl alcohol, 2; 4- diaminobenzene methyl alcohol, 4,6- diamino resorcin, 4,4 '-benzidine, 3; 3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 '; 4 '-benzidine, 3,3 '-dihydroxy-4,4 '-benzidine, 3; 3 '-two fluoro- 4,4 '-biphenyl, 3,3 '-trifluoromethyl-4; 4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2; 2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3; 3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2; 3 '-diaminodiphenyl-methane, 4; 4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 2; 2 '-diamino-diphenyl ether, 2; 3 '-diamino-diphenyl ether, 4,4 '-sulfonyl diphenylamines, 3,3 '-sulfonyl diphenylamines, two (4- aminophenyl) silane, two (3- aminophenyl) silane, dimethyl-two (4- aminophenyl) silane, dimethyl-two (3- aminophenyl) silane, 4; 4 '-phenothiazine, 3; 3 '-phenothiazine, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3; 4 '-diamino-diphenyl amine, 2; 2 '-diamino-diphenyl amine, 2,3 '-diamino-diphenyl amine, N- methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3; 3 '-diamino-diphenyl) amine, N- methyl (3; 4 '-diamino-diphenyl) amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-diamino-diphenyl) amine, 4; 4 '-diaminobenzophenone, 3; 3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 1,4- diaminonaphthalene, 2; 2 '-diaminobenzophenone, 2; 3 '-diaminobenzophenone, 1,5- diaminonaphthalene, 1,6- diaminonaphthalene, 1; 7- diaminonaphthalene, 1; 8- diaminonaphthalene, 2,5- diaminonaphthalene, 2,6- diaminonaphthalene, 2; 7- diaminonaphthalene, 2; 8- diaminonaphthalene, 1, two (4- aminophenyl) ethane, 1 of 2-, two (3- aminophenyl) ethane, 1 of 2-; Two (4- aminophenyl) propane, 1 of 3-; Two (3- aminophenyl) propane, 1 of 3-, two (4- aminophenyl) butane, 1 of 4-, two (3- aminophenyl) butane, two (3 of 4-; 5- diethyl-4- aminophenyl) methane, 1; Two (4- amino-benzene oxygen) benzene, 1 of 4-, two (4- amino-benzene oxygen) benzene, 1 of 3-, two (4- aminophenyl) benzene, 1 of 4-; Two (4- aminophenyl) benzene, 1 of 3-; Two (the 4- aminobenzene methyl) benzene, 1 of 4-, two (4- amino-benzene oxygen) benzene, 4 of 3-, 4 '-[1; 4- phenylene two (methylene)] diphenylamines, 4; 4 '-[1,3- phenylene two (methylene)] diphenylamines, 3,4 '-[1; 4- phenylene two (methylene)] diphenylamines, 3; 4 '-[1,3- phenylene two (methylene)] diphenylamines, 3,3 '-[1; 4- phenylene two (methylene)] diphenylamines, 3; 3 '-[1,3- phenylene two (methylene)] diphenylamines, 1,4- phenylene two [(4- aminophenyl) ketone], 1; 4- phenylene two [(3- aminophenyl) ketone], 1; 3- phenylene two [(4- aminophenyl) ketone], 1,3- phenylene two [(3- aminophenyl) ketone], 1,4- phenylene two (4- Aminobenzoate), 1; 4- phenylene two (3- Aminobenzoate), 1; 3- phenylene two (4- Aminobenzoate), 1,3- phenylene two (3- Aminobenzoate), two (4- aminophenyl) terephthalate, two (3- aminophenyl) terephthalate, two (4- aminophenyl) isophthalic acid ester, two (3- aminophenyl) isophthalic acid ester, N, N '-(1; The 4- phenylene) two (4- aminobenzamides), N; N '-(1, the 3- phenylene) two (4- aminobenzamides), N, N '-(1; The 4- phenylene) two (3- aminobenzamides), N; N '-(1, the 3- phenylene) two (3- aminobenzamides), N, N '-two (4- aminophenyl) terephthalamide, N; N '-two (3- aminophenyl) terephthalamide, N; Benzenedicarboxamide, N between N '-two (4- aminophenyl), benzenedicarboxamide, 9 between N '-two (3- aminophenyl), two (4- aminophenyl) anthracenes, 4 of 10-; 4 '-two (4- amino-benzene oxygen) diphenyl sulfone, 2; 2 '-two [the 4-(4- amino-benzene oxygen) phenyl] propane, 2,2 '-two [the 4-(4- amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-two (4- aminophenyl) HFC-236fa, 2; 2 '-two (3- aminophenyl) HFC-236fa, 2; 2 '-two (3- amino-4- aminomethyl phenyl) HFC-236fa, 2,2 '-two (4- aminophenyl) propane, 2,2 '-two (3- aminophenyl) propane, 2; 2 '-two (3- amino-4- aminomethyl phenyl) propane, 1; Two (4- amino-benzene oxygen) propane, 1 of 3-, two (3- amino-benzene oxygen) propane, 1 of 3-, two (4- amino-benzene oxygen) butane, 1 of 4-; Two (3- amino-benzene oxygen) butane, 1 of 4-; Two (4- amino-benzene oxygen) pentanes, 1 of 5-, two (3- amino-benzene oxygen) pentanes, 1 of 5-, two (4- amino-benzene oxygen) hexanes, 1 of 6-; Two (3- amino-benzene oxygen) hexanes, 1 of 6-; Two (4- amino-benzene oxygen) heptane, 1 of 7-, two (3- amino-benzene oxygen) heptane, 1 of 7-, two (4- amino-benzene oxygen) octanes, 1 of 8-; Two (3- amino-benzene oxygen) octanes, 1 of 8-; Two (4- amino-benzene oxygen) nonanes, 1 of 9-, two (3- amino-benzene oxygen) nonanes, 1 of 9-, 10-(4- amino-benzene oxygen) decane, 1; The 10-(3- amino-benzene oxygen) decane, 1; The 11-(4- amino-benzene oxygen) hendecane, 1, the 11-(3- amino-benzene oxygen) hendecane, 1, the 12-(4- amino-benzene oxygen) dodecane, 1; The 12-(3- amino-benzene oxygen) dodecane, two (4- aminocyclohexyl) methane, two (4- amino-3- methylcyclohexyl) methane, 1; 3- diaminopropanes, 1,4- diaminobutane, 1,5- diaminourea pentane, 1; 6- diamino hexane, 1; 7- diaminourea heptane, 1,8- diaminourea octane, 19- diaminourea nonane, 1,10- diamino decane, 1; 11- diaminourea hendecane, 1, diamine compounds such as 12- diaminourea dodecane.

In addition, can give an example have alkyl on two amine side chains, contain fluoroalkyl, the diamines of aromatic ring, aliphatics ring, heterocycle and the big ring-type replacement body that forms by them.But the concrete following formula of illustration [DA1]～[DA26] diamine compound.

In formula [DA1]～formula [DA5], R < > 1 <> Be carbon number alkyl below 22 or contain fluoroalkyl more than 1.

In formula [DA6]～formula [DA9], R < > 2 <> Expression-COO-,-OCO-,-CONH-,-NHCO-,-CH < > 2 <>-,-O-,-CO-or-NH-, R < > 3 <> Expression carbon number alkyl below 22 or contain fluoroalkyl more than 1.

Formula [DA10] and formula [DA11] in, R < > 4 <> Expression-O-,-OCH < > 2 <>-,-CH < > 2 <> O-,-COOCH < > 2 <>-or-CH < > 2 <> OCO-, R < > 5 <> Expression the carbon number alkyl below 22, alkoxy more than 1, contain fluoroalkyl or fluoroalkoxy.

Formula [DA12]～formula [DA14] in, R < > 6 <> Expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH < > 2 <>-,-CH < > 2 <> OCO-,-CH < > 2 <> O-,-OCH < > 2 <>-or-CH < > 2 <>-, R < > 7 <> Expression the carbon number alkyl below 22, alkoxy more than 1, contain fluoroalkyl or fluoroalkoxy.

Formula [DA15] and formula [DA16] in, R < > 8 <> Expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH < > 2 <>-,-CH < > 2 <> OCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-CH < > 2 <>-,-O-or-NH-, R < > 9 <> Represent fluorine-based, cyanic acid, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl.

In addition, as other diamine compound, following formula [DA27 also can give an example] the diamido siloxane etc. of expression.

Formula [DA27] in, m is 1～10 integer.

Liquid crystal aligning property, the voltage retention performance of said other diamine compound when forming liquid crystal orientation film, accumulate characteristics such as electric charge, can use a kind also can mix use more than 2 kinds separately.

< tetracarboxylic dianhydride >

At least a kind of compound that is used for tetracarboxylic dianhydride of the present invention and is the tetracarboxylic dianhydride gets final product.Concrete example is given an example as follows.

Can exemplify for example pyromellitic acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 1,4,5; 8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ', 4; 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) sulfone, two (3; 4-dicarboxyl phenyl) methane, 2, two (3, the 4-dicarboxyl phenyl) propane, 1,1,1,3,3 of 2-, 3-hexafluoro-2,2-two (3; 4-dicarboxyl phenyl) propane, two (3,4-dicarboxyl phenyl) dimethylsilane, two (3,4-dicarboxyl phenyl) diphenyl silane, 2,3,4,5-pyridine tetracarboxylic dianhydride, 2, two (3, the 4-dicarboxyl phenyl) pyridines, 3 of 6-, 3 '; 4, オキシジ Off タ Le テトラカ Le ボ Application acid two anhydrides), 14 '-diphenyl sulfone tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride (Japanese:; 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1; 2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3; 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2,3; 4,5-oxolane tetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl butanedioic acid dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, two rings [3; 3,0] octane-2,4,6,8-tetracarboxylic dianhydride, two ring [4,3,0] nonanes-2,4,7; 9-tetracarboxylic dianhydride, two ring [4,4,0] decane-2,4,7,9-tetracarboxylic dianhydride, two ring [4,4,0] decane-2,4; 8,10-tetracarboxylic dianhydride, three ring [6.3.0.0 < 2,6 >] hendecanes-3,5,9,11-tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, 4-(2; 5-dioxo oxolane-3-yl)-1,2,3,4-naphthane-1,2-dicarboxylic acid dianhydride, two ring [2,2,2] suffering-7-alkene-2,3,5; 6-tetracarboxylic dianhydride, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid dianhydride, Fourth Ring [6,2,1,1,0,2,7] dodecane-4; 5,9,10-tetracarboxylic dianhydride, 3,5,6-three carboxyl norbornane-2:3,5:6-dicarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride etc.

Wherein, be preferably to use to comprise and be selected from 1,2,3; 4-cyclo-butane tetracarboxylic dianhydride, 2,3,4-cyclopentane tetracarboxylic dianhydride, 4,5-cyclohexane tetracarboxylic dianhydride, 2,4-tetramethyl-1,2,3; 4-cyclo-butane tetracarboxylic dianhydride, 2-dimethyl-1,2,3; 4-cyclo-butane tetracarboxylic dianhydride, 3-dimethyl-1,2,3; 4-cyclo-butane tetracarboxylic dianhydride, 2,3,4-cycloheptane tetracarboxylic dianhydride, 4,5-tetrahydrofuran tetracarboxylic dianhydride, 4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 5-tricarboxylic basic ring amyl group acetate dianhydride, 4-dicarboxyl-1,2,4-tetrahydrochysene-1-naphthalene succinic dianhydride; Two ring [3,3,0] octane-2,6, the 8-tetracarboxylic dianhydride; Two ring [4,3; 0] nonane-2,4,7, the 9-tetracarboxylic dianhydride; Two ring [4,0] decane-2,4,7; The 9-tetracarboxylic dianhydride; Two ring [4,4,0] decane-2,4, the 10-tetracarboxylic dianhydride; Three ring [6.3.0.0 < 2,6 >] undecane-3,9,11-tetracarboxylic dianhydride, 3,4-butane tetracarboxylic acid dianhydride; 5-dioxo tetrahydrofuran-3-yl)-1,2,3; 4-naphthane-1, the 2-dicarboxylic acid dianhydride; Two ring [2,2; 2] suffering-7-alkene-2,3,5; The 6-tetracarboxylic dianhydride; 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid dianhydride; Fourth Ring [6,1,1,2,7] dodecane-4,9,10-tetracarboxylic dianhydride, 6-three carboxyl norbornane-2:3,5:6-dicarboxylic acid dianhydride and 1,4, the tetracarboxylic dianhydride of at least a kind of compound of 5-cyclohexane tetracarboxylic dianhydride.Be more preferably and be selected from 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 3,4-cyclopentane tetracarboxylic dianhydride, 2,5-cyclohexane tetracarboxylic dianhydride, 4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3; 5-tricarboxylic basic ring amyl group acetate dianhydride; Two ring [3,3,0] octane-2,4, the 8-tetracarboxylic dianhydride; Two ring [4,3,0] nonane-2,7, the 9-tetracarboxylic dianhydride; Two ring [4,4; 0] decane-2,4,7, the 9-tetracarboxylic dianhydride; Two ring [4,0] decane-2,4, the 10-tetracarboxylic dianhydride; Three ring [6.3.0.0 < 2,6 >] undecane-3,9,11-tetracarboxylic dianhydride, 3,4-butane tetracarboxylic acid dianhydride; 5-dioxo tetrahydrofuran-3-yl)-1,2,3; 4-naphthane-1, the 2-dicarboxylic acid dianhydride; Two ring [2,2; 2] suffering-7-alkene-2,3,5; The 6-tetracarboxylic dianhydride; 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid dianhydride; Fourth Ring [6,1,1,2,7] dodecane-4,9,10-tetracarboxylic dianhydride, 6-three carboxyl norbornane-2:3,5:6-dicarboxylic acid dianhydride and 1,4, at least a kind of compound of 5-cyclohexane tetracarboxylic dianhydride.

Liquid crystal aligning property, the voltage retention performance of said tetracarboxylic dianhydride when forming liquid crystal orientation film, accumulate characteristics such as electric charge, can use a kind also can mix use more than 2 kinds separately.

< multipolymer >

Being used for multipolymer of the present invention is polyamic acid and polyimide.Polyamic acid is the polyamic acid that the reaction through two amine components that contain diamine compound (A) and diamine compound (B) and tetracarboxylic dianhydride gets.Polyimide of the present invention be make this polyamic acid dehydration closed-loop and polyimide.Said polyamic acid and polyimide all can be used as the multipolymer that obtains aligning agent for liquid crystal.

The content of the diamine compound in two amine components (A) multivoltage conservation rate more is high more, even and to be exposed under the high temperature residual charge of accumulating because of DC voltage the back for a long time also less.

The effect of diamine compound (B) is further to improve said effect.The content of the diamine compound in two amine components (B) is preferably 0.01～99 mole with respect to diamine compound (A)1 mole, better is 0.1～50 mole, is 0.5～20 mole better further, is preferably 0.5～10 mole.

Among the present invention, under the condition that does not influence effect of the present invention can and with diamine compound (A), diamine compound (B) other diamine compound in addition as two amine components.The consumption of other diamine compound that use this moment is preferably 0.01～10 mole with respect to diamine compound (A)1 mole, better is 0.1～5 mole.

[manufacturing approach of multipolymer]

Being used for polyamic acid of the present invention can obtain through known polymerization.It generally is the method that in organic solvent, makes tetracarboxylic dianhydride and the reaction of two amine components.Being reflected in the organic solvent of tetracarboxylic dianhydride and two amine components than being easier to carry out and do not generate accessory substance, therefore preferably.

As long as the organic solvent that use this moment is the polyamic acid that solubilized generates.Its concrete example of below giving an example.

May, for example N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2 - pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, Rokko sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone , methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol , ethyl carbitol, ethylene glycol, ethylene glycol monoethyl acetate, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether , dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monopropyl ether monoacetate, 3 - methyl - 3 - methoxy-butyl acetate, triethylene glycol methyl ether, 3-- A -3 - methoxy butanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, two

alkyl, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl 3 - methoxy-propyl ester, 3 - ethoxy-propionic acid methyl ester 3 - methoxy- ethyl 3 - ethoxy-propionic acid 3 - methoxy-propionic acid 3 - methoxy-propyl propionate 3 - methoxy-propionic acid, butyl diglyme 4 - hydroxy-4 - methyl - 2 - pentanone and the like.

These solvents can use separately also can mix use.In addition, even the insoluble solvent of separating polyamic acid, as long as in the scope that the polyamic acid that generates is not separated out, can use with above solvent.In addition, because the moisture in the organic solvent can suppress polyreaction, and makes the polyamic acid hydrolysis of generation, the organic solvent that therefore preferred use dehydrates as much as possible.

As the method that tetracarboxylic dianhydride and two amine components are reacted in organic solvent; Can give an example is dispersed or dissolved in organic solvent and the solution that forms stirs to two amine components, directly adds the tetracarboxylic dianhydride or makes the tetracarboxylic dianhydride be dispersed or dissolved in the method for adding again behind the organic solvent; On the contrary, be dispersed or dissolved in organic solvent and the method for adding two amine components in the solution that forms the tetracarboxylic dianhydride; Alternately add the method for tetracarboxylic dianhydride and two amine components etc.Can adopt any method wherein.In addition; When no matter which side of tetracarboxylic dianhydride and two amine components is formed by multiple compound; Can be pre-mixed and make gained potpourri and the reaction of another composition behind the multiple compound, also can react successively respectively make again react respectively and low-molecular-weight body hybrid reaction and form the HMW body.

The polymeric reaction temperature of polyamic acid can be selected-20 ℃～150 ℃ arbitrary temp, preferred-5 ℃～100 ℃ scope.In addition; Though reaction can carried out under the concentration arbitrarily; If but concentration is low excessively; Then be difficult to obtain the multipolymer of HMW; If excessive concentration, then the viscosity of reactant liquor becomes too high, is difficult to carry out the stirring of homogeneous; Therefore tetracarboxylic dianhydride and the total concentration of two amine components in reaction solution are preferably 1～50 quality %, better are 5～30 quality %.Can implement reaction with high concentration in initial reaction stage, append organic solvent afterwards again.

In the synthetic reaction of polyamic acid, with respect to 1 mole of tetracarboxylic dianhydride, the molal quantity of two amine components is preferably 0.8～1.2.This mol ratio is more near 1.0, and the molecular weight of the polyamic acid of generation is big more.

The polyimide that is used for polyimide of the present invention and is making the polyamic acid dehydration closed-loop that obtains through above method get can be used as the multipolymer of acquisition liquid crystal orientation film.

The dehydration closed-loop rate (imidizate rate) that is used for the acid amides acidic group of polyimide of the present invention not necessarily wants 100%, can regulate use arbitrarily according to purposes and purpose.

As the method that makes the polyamic acid imidizate, the catalysis imidizate that can give an example and directly heat the hot-imide of the solution of polyamic acid, in the solution of polyamic acid, add catalyzer.

Temperature when in solution, making the polyamic acid hot-imide is 100 ℃～400 ℃, is preferably 120 ℃～250 ℃, is preferably in and implements reaction when the water that imidization reaction is generated is discharged to outside the reactive system.

The catalysis imidizate of polyamic acid can through in the solution of polyamic acid, add behind base catalyst and the acid anhydrides-20～250 ℃, be preferably to stir under 0～180 ℃ the temperature and implement.The amount of base catalyst is 0.5～30 mole a times of acid amides acidic group, is preferably 2～20 moles doubly, and the amount of acid anhydrides is 1～50 mole a times of acid amides acidic group, is preferably 3～30 moles doubly.

As base catalyst, can give an example pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc., wherein, pyridine possesses the reaction of making and carries out required suitable alkalescence, and is therefore preferred.As acid anhydrides, can give an example acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., if wherein use acetic anhydride, refining the becoming easily after then reaction finishes, therefore preferred.The imidizate rate of catalysis imidizate can be controlled through regulating catalytic amount and temperature of reaction, reaction time.

The dehydration closed-loop rate of the acid amides acidic group of polyimide of the present invention (imidizate rate) not necessarily wants 100%, can regulate arbitrarily according to purposes and purpose.The spy is well more than 50%.

When the reaction solution of polyamic acid or polyimide reclaims the multipolymer that generates, can reaction solution be dropped into Weak solvent makes it form deposition.As the Weak solvent that is used to precipitate, can give an example methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water etc.The polymkeric substance that drops into Weak solvent and precipitate can carry out air drying or heat drying after the filtered and recycled under normal pressure or decompression.If the multipolymer that deposition is reclaimed repeats 2～10 times being dissolved in organic solvent once more and precipitating the operation of reclaiming once more, then can reduce the impurity in the multipolymer.If this moment, used Weak solvent used the for example Weak solvents more than 3 kinds such as alcohols, ketone, hydrocarbon, purification efficiency is further improved, therefore preferred.

About the polyamic acid that is used for aligning agent for liquid crystal of the present invention and the molecular weight of polyimide; From by the intensity of filming of its acquisition and the angle of the operability when forming of filming, the homogeneity of filming consider; With the GPC(gel permeation chromatography) weight-average molecular weight that records of method is preferably 5000～1000000 respectively, better is 10000～150000.

< aligning agent for liquid crystal >

Aligning agent for liquid crystal of the present invention is the coating fluid that is used to make liquid crystal orientation film, and its major component comprises resinous principle that is used to form resin coating and the organic solvent that makes this resinous principle dissolving.Among the present invention, said resinous principle is to comprise to be selected from the said resinous principle that is used at least a kind of multipolymer of polyamic acid of the present invention and polyimide.At this moment, the content of the resinous principle in the coating fluid is 1 quality %～20 quality %, is preferably 2 quality %～10 quality %.

Among the present invention, said resinous principle can all be to be used for multipolymer of the present invention, also can be mixed with other polymkeric substance beyond the multipolymer of the present invention.At this moment, the content of other polymkeric substance in addition in the resinous principle is 0.5 quality %～15 quality %, is preferably 1 quality %～10 quality %.

Can give an example two amine components of for example conduct and tetracarboxylic dianhydride's composition reaction of this other polymkeric substance use diamine compound (A) and diamine compound (B) diamines and the polyamic acid that obtains or polyimide etc. in addition.

Be used for the organic solvent of aligning agent for liquid crystal of the present invention so long as the organic solvent of said resinous principle dissolving is got final product, do not have qualification especially.Its concrete example is given an example as follows.

For example N '-dimethyl formamide the '-dimethyl acetamide of can giving an example; The N-N-methyl-2-2-pyrrolidone N-; The N-methyl caprolactam; 2-Pyrrolidone; The N-ethyl pyrrolidone; The N-vinyl pyrrolidone; Dimethyl sulfoxide; Tetramethylurea; Pyridine; Dimethyl sulfone; The hexamethyl sulfoxide; Gamma-butyrolacton, the 3-dimethyl-2-imidazolidinone; Cinene; Ethyl pentyl group ketone; Methyl nonyl ketone; Methyl ethyl ketone; Methyl isoamyl ketone; Methyl isopropyl Ketone; Cyclohexanone; Ethylene carbonate; Propylene carbonate; Diethylene glycol dimethyl ether; 4-hydroxy-4-methyl-2 pentanone etc.These solvents can mix use more than 2 kinds.

When making polyimide be dissolved in organic solvent, for the dissolving that promotes polyimide can be heated.If heating-up temperature is too high, the molecular weight and molecular weight of polyimide sometimes then, so temperature is preferably 30～100 ℃.

Aligning agent for liquid crystal of the present invention can contain said composition in addition.Comprise thickness homogeneity and the raising of surface smoothing property when making the coating of liquid crystalline alignment agent solvent or compound, make compound that the adaptation of liquid crystal orientation film and substrate improves etc.

The concrete example of the solvent (Weak solvent) of thickness homogeneity and the raising of surface smoothing property is given an example as follows.

The for example isopropyl alcohol of can giving an example; The methoxy amylalcohol; Methyl cellosolve; Ethyl cellosolve; Butyl cellosolve; Methylcellosolve acetate; Ethyl cellosolve acetate; BC; Ethyl carbitol; The ethyl carbitol acetic acid esters; Monoethylene glycol; Ethylene glycol acetate; The glycol monomethyl isopropyl ether; Ethylene glycol monobutyl ether; Propylene glycol; The propylene glycol monoacetate; Propylene glycol monomethyl ether; The glycol tertiary butyl ether; Dipropylene glycol monomethyl ether; Diglycol; The diglycol monotertiary acetic acid esters; Diethylene glycol dimethyl ether; DPG monoacetate monomethyl ether; Dipropylene glycol monomethyl ether; DPG list ether; DPG monoacetate list ether; DPG list propyl ether; DPG monoacetate list propyl ether; 3-methyl-3-methoxyl butylacetic acid ester; The tripropylene glycol methyl ether; 3-methyl-3-methoxybutanol; Di Iso Propyl Ether; The ethyl isobutyl ether; Diisobutylene; Pentyl acetate; Butyl butyrate; Butyl ether; DIBK; Methylcyclohexene; Propyl ether; Hexyl ether; Normal hexane; N-pentane; Normal octane; Ether; Methyl lactate; Ethyl lactate; Methyl acetate; Ethyl acetate; N-butyl acetate; The acetate dihydroxypropane single-ether; Methyl pyruvate; Ethyl pyruvate; 3-methoxypropionic acid methyl esters; 3-ethoxy-propionic acid methyl ethyl ester; 3-methoxy propyl acetoacetic ester; The 3-ethoxy-propionic acid; The 3-methoxypropionic acid; 3-methoxy propyl propyl propionate; 3-methoxy propyl acid butyl ester; 1-methoxyl-2-propyl alcohol; The 1-hexanol; 1-ethoxy-2-propyl alcohol; 1-butoxy-2-propyl alcohol; 1-phenoxy group-2-propyl alcohol; The propylene glycol monoacetate; Propylene-glycol diacetate; Propylene glycol-1-monomethyl ether-2-acetic acid esters; The single ether of propylene glycol-1--2-acetic acid esters; DPG ethoxy propoxyl group) propyl alcohol; Methyl lactate; Ethyl lactate; Lactic acid n-propyl ester; N-butyl lactate; Isoamyl lactates etc. have the solvent of low surface tension etc.

Wherein, be more preferably butyl cellosolve, propylene glycol monomethyl ether, ethyl lactate.

These Weak solvents can use a kind also can multiple mixing to use.When using said solvent, its amount is preferably 5～80 quality % of all solvents that aligning agent for liquid crystal comprises, and better is 20～60 quality %.

As the compound that makes thickness homogeneity and the raising of surface smoothing property, the fluorine class of can giving an example surfactant, silicone based surfactant, non-ionics etc.

For example F Top EF301, EF303, EF352(Tao Ke nurse (Tokem Products more specifically can give an example) corporate system) F171, F173, the big Japanese ink of R-30(chemical company system) C430, FC431(Sumitomo 3M corporate system), Asahi Guard G710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106(Asahi Glass Co., Ltd system) etc.The usage ratio of these surfactants is to be preferably 0.01～2 mass parts with respect to resinous principle 100 mass parts that aligning agent for liquid crystal comprises, and better is 0.01～1 mass parts.

The concrete example of the compound that improves as the adaptation that makes liquid crystal orientation film and substrate, the compound that contains functional silanes shown in following or contain the compound etc. of epoxy radicals of can giving an example.

The for example 3-TSL 8330 of can giving an example; The 3-aminopropyltriethoxywerene werene; The 2-TSL 8330; 2-aminopropyltriethoxywerene werene amino-ethyl)-3-TSL 8330 amino-ethyl)-3-aminopropyl methyl dimethoxysilane; 3-urea groups propyl trimethoxy silicane; 3-urea groups propyl-triethoxysilicane; N-ethoxy carbonyl-3-TSL 8330; N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene; N-triethoxysilylpropyltetrasulfide diethylenetriamine; N-trimethoxy-silylpropyl diethylenetriamine trimethoxysilyl-1; 4; 7-three azepine decane triethoxysilyl-1; 4; 7-three azepine decane; 9-trimethoxysilyl-3; 6-diaza nonyl acetic acid esters; 9-triethoxysilyl-3; 6-diaza nonyl acetic acid esters; N-benzyl-3-TSL 8330; N-benzyl-3-aminopropyltriethoxywerene werene; N-phenyl-3-TSL 8330; N-phenyl-3-aminopropyltriethoxywerene werene; Two (the oxygen ethylidene)-3-TSL 8330s of N-; Two (the oxygen ethylidene)-3-aminopropyltriethoxywerene werene of N-; Ethylene glycol diglycidylether; Polyethyleneglycol diglycidylether; Propylene glycol diglycidylether; Tripropyleneglycol diglycidyl ether; Polypropylene glycol diglycidyl ether; Neopentylglycol diglycidyl ether; 1; The 6-hexanediol diglycidyl ether; Glycerin diglycidyl ether; 2; 2-dibromoneopentyl glycol diglycidyl ether; 5; 6-four glycidyl group-2; 4-hexanediol ' '-four glycidyl group-m-xylene diamine; 1; Two (the N of 3-; N-diglycidyl amino methyl) cyclohexane ' '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.

With respect to resinous principle 100 mass parts that aligning agent for liquid crystal comprises, these used raisings are preferably 0.1～30 mass parts with the amount of the compound of the adaptation of substrate, better are 1～20 mass parts.If less than 0.1 mass parts then can not obtain the effect that adaptation improves, if surpass 30 mass parts, the orientation of liquid crystal variation sometimes then.

In the aligning agent for liquid crystal of the present invention except above composition can add in the scope of external harmless effect of the present invention so that electrical characteristics such as the specific inductive capacity of liquid crystal orientation film and electric conductivity change is the dielectric or the conductive materials of purpose, film hardness and the density that also can add when forming liquid crystal orientation film with raising are the cross-linked compound of purpose.

< liquid crystal orientation film liquid crystal display cells >

Coat on the substrate aligning agent for liquid crystal of the present invention and after burning till, handle, perhaps in vertical orientated purposes etc., can not carry out orientation process and use as liquid crystal orientation film through implementation orientations such as friction treatment or illumination.At this moment, used substrate does not have qualification especially so long as the high substrate of transparency gets final product, and can use plastic bases such as glass substrate, acrylic acid substrate or polycarbonate substrate etc.In addition, from the angle of work simplification, better be to use the substrate that has formed ITO electrode of being used for liquid crystal drive etc.In addition, for reflection type liquid crystal display element, also can only use opaque materials such as silicon wafer at one-sided substrate, electrode at this moment can use catoptrical materials such as aluminium.

Coating process for aligning agent for liquid crystal does not have special qualification, generally adopts screen painting, hectographic printing, flexible printing, ink-jet method etc. at industrial circle.As other coating process, the dip coating of can giving an example, rolling method, slit printing, rotary printing etc. can use according to various objectives.

With aligning agent for liquid crystal coat behind the substrate burn till can through heater meanses such as hot plate 50～300 ℃, be preferably and under 80～250 ℃ the temperature solvent evaporation formed to film.If filming after burning till is blocked up, be disadvantageous aspect the power consumption of liquid crystal display cells then, if thin excessively, then the reliability of liquid crystal display cells can descend, so coating thickness better is 5～300nm, is more preferably 10～100nm.When making liquid crystal horizontal alignment or tilted alignment, filming after burning till handled through friction or polarized ultraviolet irradiation etc.

Liquid crystal display cells of the present invention is after being obtained having the substrate of liquid crystal orientation film by aligning agent for liquid crystal of the present invention through said method, to process the liquid crystal structure cell with known method, thereby obtain liquid crystal display cells.

The example that the liquid crystal structure cell is made if will give an example; But illustration prepares to be formed with 1 pair of substrate of liquid crystal orientation film, on the liquid crystal orientation film of 1 substrate, scatters sept, with the liquid crystal aligning face as the inboard; With other 1 baseplate-laminating, the method that seals behind the liquid crystal is injected in decompression; The method that perhaps after liquid crystal is dripped on the liquid crystal orientation film surface that is scattered with sept, baseplate-laminating is also sealed etc.The thickness of the sept of this moment better is 1～30 μ m, is more preferably 2～10 μ m.

As stated, adopt the reliability of the liquid crystal display cells that aligning agent for liquid crystal of the present invention makes high, can be used for big picture and high-resolution LCD TV etc.

Embodiment

Below give an example embodiment and comparative example, the present invention will be described in more detail, but these embodiment do not carry out determinate explanation to the present invention.

Below be depicted as the breviary symbol and the structural formula of the compound that uses among the embodiment.

(tetracarboxylic dianhydride)

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

ODA: dicyclo [3,3,0] octane-2,4,6, the 8-tetracarboxylic dianhydride

(diamines)

PCH7DAB:1,3-diamido-4-[4-(4-heptyl cyclohexyl) phenoxy group] benzene

BA:3, the 5-diaminobenzoic acid

2,4-DAA:2,4-diamino-N, N-diallyl aniline

Me-DADPA:N-methyl-4,4 '-diamino-diphenyl amine

Diamines (1) :(is with reference to following formula)

Diamines (2) :(is with reference to following formula)

(organic solvent)

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

BCS: butyl cellosolve

< molecular weight determination >

Molecular weight employing Showa Denko K. K's system normal temperature gel permeation chromatography (GPC) device (GPC-101 of the polyimide in the synthetic example), Japanese nitre moral (Shodex) corporate system post (KD-803, KD-805) following mensuration.

Column temperature: 50 ℃

Eluent :N, and N '-dimethyl formamide (as adjuvant, lithium bromide monohydrate (LiBrH < > 2 <> O)30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid)30mmol/L, tetrahydrofuran (THF)10ml/L)

Flow velocity :1.0mL/ minute

Calibration curve is made and is used standard sample: TOSOH Co., Ltd's system TSK standard polyethylene oxide (molecular weight 900000,150000,100000,30000) and polymkeric substance laboratory (Polymer Laboratory) corporate system polyglycol (molecular weight about 12000,4000,1000).

< mensuration of imidizate rate >

The imidizate rate of the polyimide in the synthetic example is measured as follows.With the 20mg polyimide powder NMR test tube (wasteland's science Co., Ltd. system NMR stopple coupon standard φ 5) of packing into, add deuterate dimethyl sulfoxide (DMSO-d < > 6 <> , the 0.05%TMS(TMS) and melange)0.53ml, utilize ultrasound wave that it is dissolved fully.With NEC's data (デ-タ system) Co., Ltd. system NMR analyzer (JNW-ECA500) measure the proton NMR of the 500MHz of this solution.The imidizate rate is that the benchmark proton is confirmed with the proton from unconverted structure before and after the imidizate, with the peak integrated value of this proton and near trying to achieve through following formula from the basic proton peak integrated value of the NH of amic acid of 9.5～10.0ppm, occurring.

Imidizate rate (%)=(1-α x/y) * 100

In the following formula, x is that y is a benchmark proton peak integrated value from the proton peak integrated value of the NH base of amic acid, and α is the number ratio of the benchmark proton with respect to the NH matrix of 1 amic acid of polyamic acid (the imidizate rate is 0%).

< synthetic example 1 >

At NMP(114.0g) in mix BODA(18.8g), Me-DADPA(6.3g), DBA(6.1g) and PCH7DAB(11.4g, 30mmol), in 40 ℃ of reactions after 3 hours; Add CBDA(4.8g) and NMP(76.0g), in 40 ℃ of reactions 12 hours, obtaining resin content was the polyamic acid solution [A] of 20 quality %.The number-average molecular weight of this polyamic acid solution is 28100, and weight-average molecular weight is 72300.

< synthetic example 2 >

Polyamic acid solution [A in synthetic example 1 acquisition) add NMP in, dilution is the acetic anhydride (8.6g that adds behind the 6 quality % as imidization catalyst) and pyridine (6.7g), in 80 ℃ of reactions 3 hours.This reaction solution is dropped into methyl alcohol (990ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [B] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 53%, and number-average molecular weight is 0100, and weight-average molecular weight is 8300.

< synthetic example 3 >

At NMP(114.0g) in mix BODA(18.8g), Me-DADPA(6.3g), DBA(6.1g) and PCH7DAB(11.4g, 30mmol), in 40 ℃ of reactions after 3 hours; Add CBDA(4.8g) and NMP(76.0g),, obtain polyamic acid solution in 40 ℃ of reactions 12 hours.

At this polyamic acid solution (80.0g) in add NMP, dilution is the acetic anhydride (17.2g that adds behind the 6 quality % as imidization catalyst) with pyridine (13.3g), reacted 3 hours in 90 ℃.This reaction solution is dropped into methyl alcohol (1040ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [C] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 81%, and number-average molecular weight is 19300, and weight-average molecular weight is 51600.

< synthetic example 4 >

At NMP(63.0g) in mix BODA(9.4g), diamines (1)(5.9g), DBA(3.0g) and PCH7DAB(5.7g, 15mmol), in 80 ℃ of reactions after 3 hours; Add CBDA(2.3g) and NMP(42.4g),, obtain polyamic acid solution in 40 ℃ of reactions 12 hours.

At this polyamic acid solution (50.0g) in add NMP, dilution is the acetic anhydride (10.1g that adds behind the 6 quality % as imidization catalyst) with pyridine (3.9g), reacted 3 hours in 100 ℃.This reaction solution is dropped into methyl alcohol (650ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [D] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 53%, and number-average molecular weight is 21200, and weight-average molecular weight is 60400.

< synthetic example 5 >

At NMP(85.0g) in mix CBDA(9.7g, 50mmol), 2,4-DAA(2.0g 10mmol), DBA(3.8g, 25mmol) and PCH7DAB(5.7g, 15mmol), in 23 ℃ of reactions 20 hours, obtains polyamic acid solution.

At this polyamic acid solution (50.5g) in add NMP, dilution is the acetic anhydride (7.2g that adds behind the 6 quality % as imidization catalyst) with pyridine (3.2g), reacted 3 hours in 50 ℃.This reaction solution is dropped into methyl alcohol (630ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [E] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 92%, and number-average molecular weight is 18700, and weight-average molecular weight is 46400.

< synthetic example 6 >

At NMP(49.2g) in mix BODA(7.5g), DBA(3.7g), diamines (2)(2.8g) and PCH7DAB(4.6g, 12.0mmol), in 80 ℃ of reactions after 5 hours; Add CBDA(1.9g) and NMP(32.6g),, obtain polyamic acid solution in 40 ℃ of reactions 3 hours.

At this polyamic acid solution (50.0g) in add NMP, dilution is the acetic anhydride (5.0g that adds behind the 6 quality % as imidization catalyst) with pyridine (3.7g), reacted 2 hours 45 minutes in 80 ℃.This reaction solution is dropped into methyl alcohol (600ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [F] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 50%, and number-average molecular weight is 20800, and weight-average molecular weight is 0200.

< synthetic example 7 >

At NMP(1290g) in mix BODA(150.1g, 600mmol), DBA(60.9g, 400mmol) and PCH7DAB(152.2g), after 5 hours, add CBDA(38.8g in 80 ℃ of reactions) and NMP(320g),, obtain polyamic acid solution in 40 ℃ of reactions 3 hours.

At this polyamic acid solution (600.2g) in add NMP, dilution is the acetic anhydride (63.9g that adds behind the 6 quality % as imidization catalyst) with pyridine (49.6g), reacted 3 hours in 80 ℃.This reaction solution is dropped into methyl alcohol (7700ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [G] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 57%, and number-average molecular weight is 23000, and weight-average molecular weight is 0200.

< synthetic example 8 >

Polyamic acid solution (101.2g in synthetic example 7 acquisitions) add NMP in, dilution is the acetic anhydride (21.3g that adds behind the 6 quality % as imidization catalyst) and pyridine (16.5g), in 90 ℃ of reactions 3 hours.This reaction solution is dropped into methyl alcohol (1300ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [H] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 81%, and number-average molecular weight is 20400, and weight-average molecular weight is 63000.

< synthetic example 9 >

At NMP(74.9g) in mix CBDA(7.8g, 40mmol), 2,4-DAA(4.9g 24mmol) and PCH7DAB(6.1g, 16mmol), in 23 ℃ of reactions 20 hours, obtains polyamic acid solution.

At this polyamic acid solution (80.0g) in add NMP, dilution is the acetic anhydride (10.4g that adds behind the 6 quality % as imidization catalyst) with pyridine (4.6g), reacted 3 hours in 50 ℃.This reaction solution is dropped into methyl alcohol (1000ml) in, leach the gained sediment.With this sediment of methanol wash,, obtain polyimide powder [I] in 100 ℃ of drying under reduced pressure.The imidizate rate of this polyimide is 97%, and number-average molecular weight is 8300, and weight-average molecular weight is 44200.

[table 1]

In the table, these diamine compounds are not used in "-" expression in " diamine compound (A) " hurdle and " diamine compound (B) " hurdle.

[the modulation evaluation of aligning agent for liquid crystal of the present invention]

< embodiment 1 >

Polyimide solution [A in synthetic example 1 acquisition) add NMP(8.1g in) and BCS(16.0g),, obtain aligning agent for liquid crystal [1] in 25 ℃ of stirrings 2 hours.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

[making of liquid crystal structure cell]

The aligning agent for liquid crystal [1] of above acquisition is spun on the glass substrate of being with the ITO electrode, and the recirculation furnace with 210 ℃ after on 80 ℃ the hot plate dry 5 minutes carries out 1 hour burning till, and obtains the liquid crystal orientation film of thickness 100nm.Prepare 2 should the band liquid crystal orientation films substrates, printing and sealing agent above that behind the sept of 6 μ m is scattered on the surface of 1 liquid crystal orientation film therein, makes sealant cures make the negative crystal born of the same parents after fitting.In this negative crystal born of the same parents, inject liquid crystal MLC-6608(Japan Mai Luke (メ Le Network) Co., Ltd.'s system through the decompression injection method), the sealing inlet obtains the nematic crystal structure cell.

[evaluation of voltage retention]

Under 80 ℃ temperature, the above liquid crystal structure cell that makes is applied 4V voltage 60 μ s, measure behind the 16.67ms and the voltage behind the 1667ms, can what keep as the voltage retention calculating voltage.Measure and adopt the system HR-1 of Dongyang technology (テ Network ニカ) Co., Ltd. voltage retention determinator, be set at voltage ± 4V, pulsewidth 60 μ s, frame period (frame period)16.67ms or 1667ms and measure.The table of stating after the result is shown in 2.

[evaluation of residual charge]

Liquid crystal structure cell after measuring for voltage retention applied alternating voltage 5.8Vpp and 1V DC voltage 30 hours, and DC voltage is removed the voltage (residual charge) that the back is measured generation in the liquid crystal structure cell at once.The table of stating after the result is shown in 3.

[evaluation after high temperature is placed]

Measure voltage retention and residual charge the liquid crystal structure cell of the above mensuration that is through with placed 10 days in temperature is set at 60 ℃ calibration cell after.Table of stating after the result is shown in 2 and table 3.

< embodiment 2 >

Polyimide powder [B in synthetic example 2 acquisitions) add NMP(24.4g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(12.3g) and BCS(41.7g), stirred acquisition aligning agent for liquid crystal [2] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [2] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

< embodiment 3 >

Polyimide powder [C in synthetic example 3 acquisitions) add NMP(24.5g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(23.9g) and BCS(30.0g), stirred acquisition aligning agent for liquid crystal [3] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [3] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

< embodiment 4 >

Polyimide powder [D in synthetic example 4 acquisitions) add NMP(25.0g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(20.1g) and BCS(33.2g), stirred acquisition aligning agent for liquid crystal [4] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [4] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

< embodiment 5 >

Polyimide powder [E in synthetic example 5 acquisitions) add NMP(24.5g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(29.0g) and BCS(25.3g), stirred acquisition aligning agent for liquid crystal [5] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [5] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

< embodiment 6 >

Polyimide powder [F in synthetic example 6 acquisitions) add NMP(25.0g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(11.5g) and BCS(42.9g), stirred acquisition aligning agent for liquid crystal [6] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [6] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

< comparative example 1 >

Polyimide powder [G in synthetic example 7 acquisitions) add NMP(25.0g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(23.1g) and BCS(28.5g), stirred acquisition aligning agent for liquid crystal [7] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [7] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

< comparative example 2 >

Polyimide powder [H in synthetic example 8 acquisitions) add NMP(25.0g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(30.4g) and BCS(23.3g), stirred acquisition aligning agent for liquid crystal [8] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [8] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

< comparative example 3 >

Polyimide powder [I in synthetic example 9 acquisitions) add NMP(24.8g in), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP(36.4g) and BCS(17.3g), stirred acquisition aligning agent for liquid crystal [9] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.

With aligning agent for liquid crystal [9] that obtains and the embodiment 1 same evaluation of operating after the evaluation, the evaluation of residual charge, the high temperature that make the liquid crystal structure cell and carry out voltage retention are placed.Table of stating after the result is shown in 2 and table 3.

In table 2 and the table 3, the imidizate rate is not calculated in "-" of imidizate rate expression.

[table 2]

[table 3]

The possibility of utilizing on the industry

Even aligning agent for liquid crystal of the present invention can obtain the voltage retention height and be exposed to the also less liquid crystal orientation film of residual charge that accumulate because of DC voltage the back under the high temperature for a long time.Even thus obtained liquid crystal display cells uses the burning screen of also may command picture for a long time and shows inhomogeneous such poor display phenomenon, is the higher display element of reliability, can be used for big picture, high-resolution liquid crystal TV set etc.Consequently, can be used for TN element, STN element, TFT liquid crystal cell, also can be used for vertical orientating type or horizontal alignment type (IPS) liquid crystal display cells etc.

Here quote the announcement of all the elements of Japanese patent application 2008-014973 number instructions, claims and the summary of filing an application on January 25th, 2008 as instructions of the present invention.

Claims

1. aligning agent for liquid crystal is characterized in that, comprise two amine components that contain diamine compound (A) and diamine compound (B) and tetracarboxylic dianhydride reaction and multipolymer,

Diamine compound (B): following formula [19] expression diamine compound,

Formula [T1]～formula [T3] in, W < > 1 <> Be phenyl ring, W < > 2 <> For having 6～15 carbon atoms and having the aromatic group of 1～2 phenyl ring, W < > 3 <> Be the alkylidene or the biphenylene of carbon number 2～5, W < > 4 <> For by the cycloalkylidene of the substituted carbon number 4～6 of tertiary N atom, W < > 5 <> Be the alkylidene of carbon number 2～5, Z < > 1 <> For by the substituted disubstituted amido of the aliphatic group of carbon number 1～6, Z < > 2 <> Be the alkyl or the phenyl ring of carbon number 1～5, g is 0 or 1 integer,

2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, diamine compound (A) is the compound of following formula [2]～formula [4] expression,

In formula [2]～formula [4], A < > 2 <> For having 6～15 carbon atoms and having the aromatic group of 1～2 phenyl ring, A < > 3 <> Be the alkylidene or the biphenylene of carbon number 2～5, A < > 4 <> Be formula [4a] or formula [4b] expression group, A < > 5 <> Be the alkylidene of carbon number 2～5, Y < > 1 <> For by the substituted disubstituted amido of the aliphatic group of carbon number 1～6, Y < > 2 <> Be the alkyl or the phenyl ring of carbon number 1～5, k is 0 or 1 integer.

3. aligning agent for liquid crystal as claimed in claim 2 is characterized in that, diamine compound (A) is formula [2].

4. aligning agent for liquid crystal as claimed in claim 2 is characterized in that, the A of formula [3] < > 2 <> Be phenyl ring or following formula [3a],

5. according to claim 1 or claim 2 aligning agent for liquid crystal is characterized in that, diamine compound (A) is for being selected from following formula [13]～[18] at least a kind of diamine compound,

6. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, diamine compound (B) is for being selected from following formula [20]～formula [24] diamine compound,

7. aligning agent for liquid crystal as claimed in claim 6 is characterized in that formula [20] in, m1 is 1～2 integer.

8. aligning agent for liquid crystal as claimed in claim 6 is characterized in that formula [21] in, X < > 2 <> For singly-bound ,-CH < > 2 <>-,-C < > 2 <> H < > 4 <>-,-C(CH < > 3 <> ) < > 2 <>-,-O-,-CO-,-NH-,-N(CH < > 3 <> )-,-CONH-,-NHCO-,-COO-or-OCO-, m2, m3 are integer 1.

9. aligning agent for liquid crystal as claimed in claim 6 is characterized in that formula [24] in, X < > 4 <> For singly-bound ,-CH < > 2 <>-,-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH < > 2 <> O-,-OCH < > 2 <>-,-COO-or-OCO-, m7 is 1～2 integer.

10. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, with respect to diamine compound (A)1 mole, the content of the diamine compound in two amine components (B) is 0.01～99 mole.

11. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, 5～80 quality % in the solvent that aligning agent for liquid crystal comprises are Weak solvent.

12. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the multipolymer in the aligning agent for liquid crystal be make the polyamic acid dehydration closed-loop and polyimide.

13. liquid crystal orientation film is characterized in that, is formed by each described aligning agent for liquid crystal in the claim 1～12.

14. liquid crystal display cells is characterized in that, possesses the described liquid crystal orientation film of claim 13.