CN102206495A

CN102206495A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device

Info

Publication number: CN102206495A
Application number: CN201110050954XA
Authority: CN
Inventors: 近藤史尚; 藤原武; 藤田幸宏; 藤马大亮
Original assignee: Chisso Petrochemical Corp; Chisso Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2010-03-30
Filing date: 2011-02-25
Publication date: 2011-10-05
Also published as: JP2011209505A; KR20110109839A; TW201132704A

Abstract

The invention discloses a liquid crystal aligning agent containing polyamide acids or other derivatives obtained by reaction between the diamine represented by the formula I or mixture of the diamine and other diamines and tetracarboxylic dianhydride. The liquid crystal aligning agent can be used to form liquid crystal alignment layers of liquid crystal display devices with various display driving modes. The liquid crystal display devices formed by the liquid crystal aligning agent has high voltage holding ratio and high reliability of long-term light and can suppress residual DC. In formula I, A1 is singly-bound -O-, -COO-, -CO-, -CONH- or alkylidene of 1-6 carbons, and R independently represents hydrogen or alkyl of 1-6 carbons.

Description

LCD alignment agent, liquid crystal orienting film and liquid crystal display device

Technical field

The present invention relates to a kind of LCD alignment agent that mainly contains the polyamic acid or derivatives thereof.

Background technology

Liquid crystal display device is used to also be used to TV recently in the various liquid crystal indicators such as indicating meter with the view finder of the pick up camera headed by the watch-dog of notebook computer or desktop computer, projection formula.And then liquid crystal display device also is used as photoelectron related elements such as optical print head, optical Fourier transform element, light valve.The main flow of previous liquid crystal display device is to use the display element of nematic liquid crystal, as an example, have 1) twisted twisted-nematic (the Twisted Nematic of 90 degree, TN) type liquid crystal display device or 2) twisted the supertwist more than 180 degree usually to row (Super TwistedNematic, STN) type liquid crystal display device, in addition, as the element that switches driving voltage, 3) use thin film transistor (Thin Film Transistor, TFT) the type liquid crystal display device practicability of thin film transistor.

These liquid crystal display device have following shortcoming: suitably the visual angle of recognition image is narrow, when when tilted direction is watched, can produce brightness or decrease of contrast, and the brightness counter-rotating of shadow tone.In recent years, the problem at this visual angle is by 1) use the TN-TFT type liquid crystal display device of optical compensation films, 2) arranged vertical (the Vertical Alignment of use vertical orientation and optical compensation films, VA) type liquid crystal display device, 3) and with multizone arranged vertical (the Multi Domain Vertical Alignment of the technology of vertical orientation and projection structure, MVA) type liquid crystal display device, perhaps 4) plane conversion (the In-Plane Switching of transverse electric field mode, IPS) type liquid crystal display device, 5) electrically conerolled birefringence (Electrically Controlled Birefringence, ECB) type liquid crystal display device, 6) optical compensation curved (Optically Compensated Bend or optics self compensation double refraction (Optically self-Compensated Birefringence, OCB)) technology such as type liquid crystal display device and obtain improvement, these display elements are practicability, or studying they practicability.

The development of liquid crystal display device technology is not merely reached by type of drive or the component construction of improveing them, and reaches by employed component parts in the improvement display element.Among the employed component parts, especially liquid crystal orienting film is one of important factor relevant with the display quality of liquid crystal display device in the display element, and along with high-qualityization of display element, 1 year year of the effect of liquid crystal orienting film is important.

Liquid crystal orienting film is to utilize the LCD alignment agent to prepare.At present, the main LCD alignment agent of using is to make the polyimide of polyamic acid or solubility be dissolved in the solution that forms in the organic solvent.After on the substrate, utilize means such as heating to carry out film forming, thereby the formation polyimide is a liquid crystal orienting film this kind solution coat.Industry is also used the various LCD alignment agent of the polyimide polymkeric substance in addition of polyamic acid or solubility in research, but with regard to viewpoints such as thermotolerance, chemical-resistant (anti-liquid crystal liquid crystal property), coating, LCD alignment, electrical specification, optical characteristics, display characteristic, major part is practicability not.

As with the display quality that promotes liquid crystal display device being purpose and, can enumerating to the desired key property of liquid crystal orienting film: voltage retention and residual DC electricity (direct current, DC).If voltage retention is low, the voltage that then is applied to liquid crystal in the frame period can descend, and brightness as a result descends, and shows for normal GTG and brings obstacle.On the other hand, if remaining DC is big, though make voltage become OFF after then applying voltage, but still can produce by so-called " image retention " of the image retention of cancellation.

As the trial that addresses these problems, propose to have several method recently.

(1) knownly is useful on the polyamic acid component (patent documentation 1 and patent documentation 2) that the two or more polyamic acid that rerum natura is different that forms liquid crystal orienting film is used in combination.

(2) known have use the component of polymer utilized polyamic acid and polymeric amide, the varnish constituent (patent documentation 3) that reaches solvent.

(3) known have use the different two or more polyamic acid of rerum natura and the varnish constituent of polymeric amide and solvent.(patent documentation 4).

(4) the known varnish constituent that the use macromolecular material is arranged, this macromolecular material use and utilize (patent documentations 5) such as amine component institute synthetic polyamic acids with ad hoc structure.

Yet, do not solve the problem of voltage retention and residual DC fully by these prior arts, still proceeding many researchs at present.

In addition, use diamines as the raw material that is used to form the polyimide of liquid crystal orienting film, but this diamines use non-side chain type diamines promptly not have the diamines of side chain radical and the diamines that the side chain type diamines promptly has side chain radical.Among these diamines, side chain type diamines major part is used to give tilt angle (patent documentation 6), how not to be used to improve the exploitation of the side chain type diamines of electrical specifications such as residual DC, has room for improvement.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese patent laid-open 11-193345 communique

[patent documentation 2] Japanese patent laid-open 11-193347 communique

[patent documentation 3] international 00/061684 trumpeter's volume that discloses

[patent documentation 4] international 01/000733 trumpeter's volume that discloses

[patent documentation 5] Japanese Patent spy opens the 2002-162630 communique

[patent documentation 6] Japanese patent laid-open 3-179323 communique

Consider described situation, the LCD alignment agent of the improved used for liquid crystal display element of problem of industry expectation a kind of voltage retention of exploitation and residual DC.And expectation will use the formed liquid crystal orienting film of this orientation agent to be applied to liquid crystal display device.

This shows that above-mentioned prior art obviously still has inconvenience and defective, and demands urgently further being improved.In order to solve the problem of above-mentioned existence, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, and this obviously is the problem that the anxious desire of relevant dealer solves.Therefore how to found a kind of new LCD alignment agent, liquid crystal orienting film and liquid crystal display device, real one of the current important research and development problem that belongs to, also becoming the current industry utmost point needs improved target.

Summary of the invention

The objective of the invention is to, overcome the defective that prior art exists, and provide a kind of new LCD alignment agent, liquid crystal orienting film and liquid crystal display device, technical problem to be solved is when the diamines of the side chain radical that will have end-OH is made polyamic acid as raw material, the LCD alignment agent that contains it is very suitable for practicality for the problem that solves described voltage retention and residual DC.

The object of the invention to solve the technical problems realizes by the following technical solutions.For achieving the above object, according to LCD alignment agent of the present invention by shown in following [1].

[1] a kind of LCD alignment agent, it contains makes the polyamic acid or derivatives thereof that is obtained by the mixture of the represented diamines of formula (I) or this diamines and other diamines and tetracarboxylic dianhydride's reaction:

Herein, A ¹For singly-bound ,-O-,-COO-,-CO-,-alkylidene group of CONH-or carbon number 1～6; R is the alkyl of hydrogen or carbon number 1～6 independently.

The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, the present invention has following advantage and beneficial effect at least:

LCD alignment agent of the present invention can be used for the formation of liquid crystal orienting film of the liquid crystal display device of various display driver modes, in the liquid crystal display device of any display driver mode, all has effect to improving voltage retention and residual DC.

In sum, the present invention is LCD alignment agent, liquid crystal orienting film and liquid crystal display device.Above-mentioned LCD alignment agent can be used for the formation of liquid crystal orienting film of the liquid crystal display device of various display driver modes.Use the voltage retention height of the liquid crystal display device of liquid crystal orienting film of the present invention, residual DC is inhibited, and long-term light reliability height.

Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.

Description of drawings

Do not have

Embodiment

Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, LCD alignment agent, liquid crystal orienting film and liquid crystal display device to foundation the present invention proposition, its embodiment, structure, feature and effect thereof, describe in detail as after.

At first, employed term among the present invention is described.Sometimes will be called diamines (I) by the represented diamines of formula (I).Sometimes also represent by the diamines that other formulas are represented with identical summary notation.Sometimes the tetracarboxylic dianhydride slightly is designated as acid anhydrides, for example will slightly be designated as acid anhydrides (H-1) by the represented tetracarboxylic dianhydride of formula (H-1) sometimes.

Employed term " arbitrarily " expression " not only the position can freely be selected, and quantity also can freely be selected " in the definition of chemical formula.For example, " A can be replaced by B, C, D or E arbitrarily " this phraseology is removed 1 A of expression and can be replaced by B, C, D or E, and beyond any of a plurality of A can replace by any of B, C, D or E, the A that also represents to be replaced, the A that is replaced by C, the A that is replaced by D by B, and at least two of the A that replaced by E can mix existence.But, when being set at arbitrarily-CH ₂-in the time of can being replaced by other bases, do not comprise successive a plurality of-CH ₂-by the situation of identical base replacement.

Not with the carbon that constitutes ring any clearly the substituting group of bond represent that its bond position is free in chemically not in-problem scope.

When using identical mark in a plurality of formulas, represent that this base has the identical range of definition, must not be identical base simultaneously but be not illustrated in all formulas.In such cases, can in a plurality of formulas, select identical base, also can in each formula, select different bases.At this moment, when in 1 formula, using a plurality of identical mark, can be all with other formulas in basic different, also can be a part of difference.

" alkyl " that be not particularly limited is to use as the general name of straight chained alkyl and branched-chain alkyl.

The present invention be by described [1] with [2]～[20] formation shown below.

[2] according to [1] described LCD alignment agent, A ¹Be the alkylidene group of-COO-or carbon number 1～3, R is the alkyl of hydrogen or carbon number 1～4.

[3] according to [1] or [2] described LCD alignment agent, other diamines are at least a diamines that select in the cohort of the represented diamines of free style (1-1)～formula (1-3), formula (2-1), formula (2-2), formula (3), formula (4-1) and formula (4-2):

Herein, in the formula (1-1), a is 0 or 1; Ring A is 1,4-cyclohexylidene, 1,3-phenylene, 1,4-phenylene or 1,2,4-triazole-3,5-two bases; The hydrogen arbitrarily of cyclohexylidene and phenylene can be by the amino replacement of methyl, diethylamino or divinyl;

W in the formula (1-2) ¹For-CH ₂-or-NH-;

B in the formula (1-3) is 0～2 integer:

Herein, X ¹Alkylidene group for singly-bound or carbon number 1～10; This alkylidene group arbitrarily-CH ₂-can by-O-,-S-,-NH-,-N (CH ₃)-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-CO-,-SO ₂-,-CH=CH-,-C ≡ C-,-N=N-, 1,3-phenylene, 1,4-phenylene or piperazine-1,4-two bases replace; The hydrogen arbitrarily of phenyl ring can by fluorine, methyl, methoxyl group ,-CF ₃Or-OCF ₃Replace:

Herein, Y ¹It is the alkyl of carbon number 3～30; This alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or 1, the 4-cyclohexylidene replaces; Y ²Be hydrogen or Y ¹:

In the formula (3), X ²For singly-bound ,-O-,-COO-,-OCO-,-alkylidene group of CONH-or carbon number 1～6; R ¹Be the alkyl, cholesteryl of carbon number 3～30 or by the represented base of formula (a);

In the formula (a), X ³And X ⁴Be the alkylidene group of singly-bound or carbon number 1～4 independently; Ring B and ring C are 1 independently, 4-phenylene or 1,4-cyclohexylidene; R ²And R ³Be fluorine or methyl independently, f and g are 0,1 or 2 independently; C, d and e are 0 or 1 independently, and c, d and e add up to 1～3; R ⁴Be the alkyl of carbon number 1～30, the alkoxyl group of carbon number 1～30, the alkoxyalkyl of carbon number 2～30 or the thiazolinyl of carbon number 2～30, in these alkyl, alkoxyl group, alkoxyalkyl and the thiazolinyl, hydrogen can be replaced by fluorine arbitrarily:

Herein, X ⁵Be independently-alkylidene group of O-or carbon number 1～6; J is 0 or 1; R ⁵Be the alkyl of carbon number 1～30, the alkoxyl group of carbon number 1～30, the alkoxyalkyl of carbon number 2～30 or the thiazolinyl of carbon number 2～30; Ring T is 1,4-phenylene or 1,4-cyclohexylidene; X ⁶Alkylidene group for singly-bound or carbon number 1～3; H is 0 or 1;

Herein, X ⁵Be independently-alkylidene group of O-or carbon number 1～6; J is 0 or 1; R ⁶Be the alkyl of hydrogen, carbon number 1～30, the alkoxyl group of carbon number 1～30, the alkoxyalkyl of carbon number 2～30 or the thiazolinyl of carbon number 2～30; R ⁷Be the alkyl or the cholesteryl of carbon number 6～30.

[4] according to [3] described LCD alignment agent, other diamines are at least a diamines that select in the cohort of the represented diamines of free style (3).

[5] according to [3] described LCD alignment agent, other diamines are at least a by the represented diamines of formula (3-1)～formula (3-7), formula (3-21)～formula (3-25), formula (3-34) and formula (3-35):

Herein, Y ⁴Be the alkyl of carbon number 2～10, the alkoxyl group of carbon number 2～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10; Y ⁵Be the alkyl of carbon number 1～10, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10.

[6] according to [3] described LCD alignment agent, other diamines are at least a diamines that select in the cohort of the represented diamines of free style (4-1).

[7] according to [3] described LCD alignment agent, other diamines are at least a by the represented diamines of formula (4-1-1)～formula (4-1-8):

Herein, Y ⁶Be the alkyl of carbon number 1～10, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10.

[8] according to [3] described LCD alignment agent, other diamines are at least a diamines that select in the cohort of the represented diamines of free style (1-1)～formula (1-3) and formula (2-1).

[9] according to [3] described LCD alignment agent, other diamines are at least a by the represented diamines of formula (1-1-3), formula (1-1-5), formula (1-1-8), formula (1-1-9), formula (1-1-12)～formula (1-1-14), formula (1-2-2), formula (1-3-1), formula (1-3-2), formula (2-1-1), formula (2-1-7), formula (2-1-10), formula (2-1-13), formula (2-1-27), formula (2-1-28), formula (2-1-32)～formula (2-1-35), formula (2-1-54)～formula (2-1-56) and formula (2-1-66)～formula (2-1-68):

[10] according to [9] described LCD alignment agent, other diamines are by formula (1-1-8), formula (1-1-9), formula (1-1-12), formula (1-2-2), formula (1-3-1), formula (1-3-2), formula (2-1-32), formula (2-1-33), reach at least a of the represented diamines of formula (2-1-66)～formula (2-1-68), or contain the mixture of this (these) diamines.

[11] according to each described LCD alignment agent in [1] Xiang Zhidi [10] item, the tetracarboxylic dianhydride is at least a of aromatic tetracarboxylic acid's dianhydride.

[12] according to each described LCD alignment agent in [1] Xiang Zhidi [10] item, the tetracarboxylic dianhydride is at least a of aromatic tetracarboxylic acid's dianhydride tetracarboxylic dianhydride in addition.

[13] according to each described LCD alignment agent in [1] Xiang Zhidi [10] item, the tetracarboxylic dianhydride is at least a mixture of the tetracarboxylic dianhydride beyond at least a of aromatic tetracarboxylic acid's dianhydride and the aromatic tetracarboxylic acid's dianhydride.

[14] according to [13] described LCD alignment agent, aromatic tetracarboxylic acid's dianhydride is by formula (H-1), formula (H-5), formula (H-8)～formula (H-10), formula (H-15), formula (H-19), formula (H-20) and the represented compound of formula (H-21), and the tetracarboxylic dianhydride beyond aromatic tetracarboxylic acid's dianhydride is by formula (S-1), formula (S-6), formula (S-9)～formula (S-11), formula (S-21), formula (S-22), formula (S-30), formula (S-43), formula (S-44), formula (S-45), formula (S-48) and the represented compound of formula (S-53):

[15] according to [14] described LCD alignment agent, aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (H-1), and the tetracarboxylic dianhydride beyond aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (S-1).

[16] according to [14] described LCD alignment agent, aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (H-1), and the tetracarboxylic dianhydride beyond aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (S-48).

[17] according to each described LCD alignment agent among [1] Xiang Zhidi [16], it also contains and does not use by the represented polyamic acid or derivatives thereof that diamines obtained of formula (I).

[18] a kind of liquid crystal orienting film, it is to film to heat and form what obtained by each described LCD alignment agent among [1] Xiang Zhidi [17] being coated on the substrate.

[19] a kind of liquid crystal display device, it has according to [18] described liquid crystal orienting film.

[20] a kind of diamines, it is to be represented by formula (I-2):

LCD alignment agent of the present invention is to contain at least a polymkeric substance that is selected from polyamic acid and derivative thereof and the constituent of solvent.As the derivative of polyamic acid, can enumerate: the polyimide that makes polyamic acid all carry out dehydration closed-loop reaction to be obtained, the part imidization polyamic acid that makes polyamic acid partly carry out the dehydration closed-loop reaction to be obtained, poly amic acid ester, tetracarboxylic dianhydride's a part replaced with polyamic acid-polyamide copolymer that dicarboxylic acid obtains and makes this polyamic acid-polyamide copolymer part or all carry out the polyamidoimide that the dehydration closed-loop reaction is obtained.Among these derivatives, preferred polyimide and part imidization polyamic acid, more preferably polyimide.In the following description except that example, do not specify, then use " polyamic acid " to plant the general name of the derivative of polyamic acid therewith as polyamic acid as long as have in advance.

When preparation LCD alignment agent of the present invention, use the mixture conduct of diamines (I) or diamines (I) and other diamines and the diamines of anhydride reaction.

In the formula (I), A ¹For singly-bound ,-O-,-COO-,-CO-,-alkylidene group of CONH-or carbon number 1～6, the alkylidene group of preferred-COO-or carbon number 1～3, more preferably-COO-or-CH ₂-.R is the alkyl of hydrogen or carbon number 1～6 independently, the alkyl of preferred hydrogen or carbon number 1～4, the more preferably hydrogen or the tertiary butyl (in the following description, abbreviating t-butyl or t-Bu sometimes as).

As the preferable example of diamines (I), can enumerate: diamines (I-1) and diamines (I-2).

As the preference of other diamines, can enumerate: diamines (1-1)～diamines (1-3), diamines (2-1), diamines (2-2), diamines (3), diamines (4-1) and diamines (4-2).

Herein, a is 0 or 1, and ring A is 1,4-cyclohexylidene, 1, and 3-cyclohexylidene, 1,4-phenylene, 1,3-phenylene or 1,2,4-triazole-3,5-two bases, preferred 1,4-cyclohexylidene, 1,4-phenylene or 1,2,4-triazole-3,5-two bases.And, the hydrogen arbitrarily of cyclohexylidene and phenylene can by methyl ,-CF ₃, diethylamino or divinyl are amino replaces.

The preference of below representing diamines (1-1).

Among described diamines (1-1-1)～diamines (1-1-15), more preferably diamines (1-1-3), diamines (1-1-5), diamines (1-1-8), diamines (1-1-9), and diamines (1-1-12)～diamines (1-1-14).

Herein, W ¹For-CH ₂-or-NH-.That is, particularly, diamines (1-2) is diamines (1-2-1) and diamines (1-2-2).

Herein, b is 0～2 integer, preferred 0 or 2.That is, the preference of diamines (1-3) is diamines (1-3-1) and diamines (1-3-2).

Herein, X ¹Be the alkylidene group of singly-bound or carbon number 1～10, this alkylidene group arbitrarily-CH ₂-can by-O-,-S-,-NH-,-N (CH ₃)-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-CO-,-SO ₂-,-CH=CH-,-C ≡ C-,-N=N-, 1,3-phenylene, 1,4-phenylene or piperazine-1,4-two bases replace.The hydrogen arbitrarily of phenyl ring can by fluorine, methyl, methoxyl group ,-CF ₃Or-OCF ₃Replace.And, preferred X ¹For in singly-bound or the base arbitrarily-CH ₂-can be by-O-, 1,4-phenylene or piperazine-1, the alkylidene group of the carbon numbers 1～10 that 4-two bases replace, 1 hydrogen of phenyl ring can be by methyl substituted.In addition, the position of the amino of bond on phenyl ring is with respect to X ¹Be a contraposition or a position, preferred contraposition.

The preference of below representing diamines (2-1).

Among described diamines (2-1-1)～diamines (2-1-76), more preferably diamines (2-1-1), diamines (2-1-7), diamines (2-1-10), diamines (2-1-13), diamines (2-1-27), diamines (2-1-28), diamines (2-1-32)～diamines (2-1-35), diamines (2-1-54)～diamines (2-1-56) and diamines (2-1-66)～diamines (2-1-68).

Herein, Y ¹Be the alkyl of carbon number 3～30, the alkyl of preferred carbon number 3～20, the more preferably alkyl of carbon number 3～10.And, these alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or 1, the 4-cyclohexylidene replaces.Y ²Be hydrogen or Y ¹

The preference of below representing diamines (2-2).

In these formulas, Y ³Be the alkyl of carbon number 3～10, the alkoxyl group of carbon number 3～10 or the thiazolinyl of carbon number 3～10, Y ⁴Be the alkyl of carbon number 2～10, the alkoxyl group of carbon number 2～10 or the thiazolinyl of carbon number 2～10.And, Y ⁵Be the alkyl of carbon number 1～10, the alkoxyl group of carbon number 1～10 or the thiazolinyl of carbon number 2～10.

In the formula (3), X ²For singly-bound ,-O-,-COO-,-OCO-,-alkylidene group of CONH-or carbon number 1～6, R ¹Be the alkyl, cholesteryl of carbon number 3～30 or by the represented base of formula (a).R ¹The alkyl of preferred carbon number 3～10 or by the represented base of formula (a).And the position of preferred 2 amino of bond on phenyl ring is with respect to X ²Position between being.

In the formula (a), X ³And X ⁴Be the alkylidene group of singly-bound or carbon number 1～4 independently.Ring B and ring C are 1 independently, 4-phenylene or 1,4-cyclohexylidene.R ²And R ³Be fluorine or methyl independently, f and g are 0,1 or 2 independently.C, d and e are 0 or 1 independently, they add up to 1～3.R ⁴Be the alkyl of carbon number 1～30, the alkoxyl group of carbon number 1～30, the alkoxyalkyl of carbon number 2～30 or the thiazolinyl of carbon number 2～30, alkyl, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10 of preferred carbon number 1～10.And in these alkyl, alkoxyl group, alkoxyalkyl and the thiazolinyl, hydrogen can be replaced by fluorine arbitrarily.

The preference of below representing diamines (3).In the following example, Y ³Be the alkyl of carbon number 3～10, the alkoxyl group of carbon number 3～10, the alkoxyalkyl of carbon number 3～10 or the thiazolinyl of carbon number 3～10, Y ⁴Be the alkyl of carbon number 2～10, the alkoxyl group of carbon number 2～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10.And, Y ⁵Be the alkyl of carbon number 1～10, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10.

Among described diamines (3-1)～diamines (3-37), more preferably diamines (3-1)～diamines (3-7), diamines (3-21)～diamines (3-25), diamines (3-34) and diamines (3-35), most preferably diamines (3-2)～diamines (3-7).

In the formula (4-1), X ⁵Be independently-alkylidene group of O-or carbon number 1～6, j is 0 or 1.R ⁵Be the alkyl of carbon number 1～30, the alkoxyl group of carbon number 1～30, the alkoxyalkyl of carbon number 2～30 or the thiazolinyl of carbon number 2～30, alkyl, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10 of preferred carbon number 1～10.Ring T is 1,4-phenylene or 1,4-cyclohexylidene, X ⁶Be the alkylidene group of singly-bound or carbon number 1～3, h is 0 or 1.And when j was 1, the position of preferred 2 amino of bond on phenyl ring was with respect to X ⁵Be contraposition.

The preference of below representing diamines (4-1).In the following example, Y ⁶Be the alkyl of carbon number 1～10, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10.

In the formula (4-2), X ⁵Be independently-alkylidene group of O-or carbon number 1～6; J is 0 or 1; R ⁶Be the alkyl of hydrogen, carbon number 1～30, the alkoxyl group of carbon number 1～30, the alkoxyalkyl of carbon number 2～30 or the thiazolinyl of carbon number 2～30, preferred hydrogen, the alkyl of carbon number 1～10, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10.And, R ⁷Be the alkyl or the cholesteryl of carbon number 6～30, the alkyl of preferred carbon number 6～10.

The preference of below representing diamines (4-2).In the following example, Y ⁷Be the alkyl of hydrogen, carbon number 1～10, the alkoxyl group of carbon number 1～10, the alkoxyalkyl of carbon number 2～10 or the thiazolinyl of carbon number 2～10.And, Y ⁸It is the alkyl of carbon number 6～10.

Herein, described side chain type diamines and non-side chain type diamines are elaborated.Diamines can be divided into two kinds according to the difference of its structure.That is, have the diamines of side chain radical and the diamines that does not have side chain radical, this side chain radical is when regarding the skeleton that connects 2 amino as main chain, the base that branch comes out from main chain.By making diamines and tetracarboxylic dianhydride's reaction, can obtain to have the polyamic acid of a plurality of side chain radicals with respect to the main chain of polymkeric substance with side chain radical.When using this kind to have the polyamic acid of side chain radical, can enlarge the tilt angle of liquid crystal display device by the formed liquid crystal orienting film of LCD alignment agent that contains this polymkeric substance with respect to main polymer chain.That is, this side chain radical is the base with the effect that enlarges tilt angle.Side chain radical with this kind effect must be the base of carbon number more than 3, in the present invention, the base of this carbon number more than 3 is defined as side chain radical.As its concrete example, can enumerate: not containing ring and its end is alkyl, carbon number alkoxyl group, carbon number alkoxyalkyl 3 or more or the base of carbon number thiazolinyl 3 or more 3 or more of carbon number more than 3, and the base with the ring more than 1.And, in base with the ring more than 1, when require enlarging the effect of tilt angle more consumingly, preferably the ring of its end be have alkoxyl group more than 1 of the alkyl of carbon number more than 1, carbon number, carbon number more than 2 alkoxyalkyl and any one of the thiazolinyl of carbon number more than 2 as substituent base.When the diamines that will have this kind side chain radical as the side chain type diamines, with the diamines that do not have this kind side chain radical during as non-side chain type diamines, diamines (I) is the side chain type diamines, and, among described other diamines, diamines (1-1)～diamines (1-3) and diamines (2-1) are non-side chain type diamines, and diamines (2-2), diamines (3), diamines (4-1) and diamines (4-2) are the side chain type diamines.

And, by suitably separately using side chain type diamines and non-side chain type diamines, can be corresponding to the required separately tilt angle of various display elements.That is, owing to be to need bigger tilt angle in the longitudinal electric field mode of representative with TN mode or VA mode, the therefore main side chain type diamines that uses.At this moment, for further control tilt angle, as long as and with non-side chain type diamines.The allotment ratio of non-side chain type diamines and side chain type diamines can decide according to the size of target tilt angle.Certainly, also can be by suitably selecting side chain radical, and only use the side chain type diamines to deal with.Because therefore little the and high LCD alignment of needs of tilt angle uses at least a of non-side chain type diamines to get final product in the transverse electric field mode.

In the present invention, when when showing big tilt angle and be purpose, with at least a of diamines (I) and at least a being used in combination that is selected from diamines (2-2), diamines (3), diamines (4-1) and diamines (4-2) as the side chain type diamines.The preference of this combination is a diamines (I) and the combination of diamines (3), and the combination of diamines (I) and diamines (4-1).

And, when when showing little tilt angle and be purpose, at least a of at least a and non-side chain type diamines of diamines (I) is used in combination.When regularly, side chain type diamines and non-side chain type diamines being used in combination according to the target tilt angle.

In the present invention, be used in combination by diamines and the diamines (I) that has secondary amino, tertiary amine base or nitrogen heterocycle in the skeleton with residue, can utilize the synergistic effect of OH base with the nitrogen-atoms of diamines (I), and further increase diamines (I) for long-term light reliability, promptly at the effect of long light-struck reliability.Below enumerate the preference that has the diamines of secondary amino, tertiary amine base or nitrogen heterocycle in the skeleton of this kind residue.

Among the described example, more preferably diamines (1-1-8), diamines (1-1-9), diamines (1-1-12), diamines (1-2-2), diamines (1-3-1), diamines (1-3-2), diamines (2-1-32), diamines (2-1-33), and diamines (2-1-66)～diamines (2-1-68).

Employed acid anhydrides can be divided into aromatic anhydride and aromatic anhydride acid anhydrides in addition among the present invention.Aromatic anhydride is meant the dianhydride by the compound dehydration that has 4 carboxyls that directly are binding on aromatic nucleus in 1 molecule is obtained.If use aromatic anhydride, the effect that then can obtain to improve the sunproof effect of liquid crystal display device and reduce residual DC.In the LCD alignment agent of the present invention, 0 mole of %～70 mole % during preferably with synthesizing polyamides acid in the employed acid anhydrides total amount is set at aromatic anhydride, more preferably is set at 10 moles of %～60 mole %.The preference of below representing aromatic anhydride.

Among these aromatic anhydrides, more preferably acid anhydrides (H-1), acid anhydrides (H-5), acid anhydrides (H-8)～acid anhydrides (H-10), acid anhydrides (H-15), and acid anhydrides (H-17)～acid anhydrides (H-21), most preferably acid anhydrides (H-1), acid anhydrides (H-5), acid anhydrides (H-8)～acid anhydrides (H-10), acid anhydrides (H-15), and acid anhydrides (H-19)～acid anhydrides (H-21).

The preference of below representing aromatic anhydride acid anhydrides in addition.

Among the acid anhydrides beyond these aromatic anhydrides, more preferably acid anhydrides (S-1), acid anhydrides (S-6), acid anhydrides (S-9), acid anhydrides (S-11), acid anhydrides (S-21), acid anhydrides (S-22), acid anhydrides (S-30), acid anhydrides (S-43), acid anhydrides (S-44), acid anhydrides (S-45), acid anhydrides (S-48) and acid anhydrides (S-53), most preferably acid anhydrides (S-1), acid anhydrides (S-6), acid anhydrides (S-48) and acid anhydrides (S-53).If use the acid anhydrides beyond the aromatic anhydride, promptly ester ring type acid anhydrides or aliphatic anhydride then can obtain to improve the stable on heating effect of liquid crystal display device and improve transparent effect.In the LCD alignment agent of the present invention, 30 moles of %～100 mole % during preferably with synthesizing polyamides acid in the employed acid anhydrides total amount are set at the acid anhydrides beyond the aromatic anhydride, more preferably are set at 40 moles of %～90 mole %.

Describedly be used in combination the effect that produced by diamines that has secondary amino, tertiary amine base or nitrogen heterocycle in the skeleton with residue and diamines (I) and also can obtain by acid anhydrides and diamines (I) reaction that has secondary amino, tertiary amine base or nitrogen heterocycle in the skeleton that makes residue.The preferable example that has the acid anhydrides of secondary amino, tertiary amine base or nitrogen heterocycle in the skeleton of residue is acid anhydrides (S-48).

Among the present invention, at least a mixing of the acid anhydrides beyond at least a and aromatic anhydride of aromatic anhydride used the storage stability that can promote the LCD alignment agent, therefore preferred.And, the acid anhydrides (H-1) in the preferred especially described acid anhydrides and the combination of acid anhydrides (S-1), the combination of also special preferred anhydrides (H-1) and acid anhydrides (S-48).

In addition, also the part of acid anhydrides can be replaced with dicarboxylic anhydride.Thus, the termination of the polyreaction when generating polyamic acid can be caused, and the carrying out of polyreaction can be suppressed.Therefore, can easily control the molecular weight of the polyamic acid that is obtained, for example can can't harm effect of the present invention and improve the coating characteristics of LCD alignment agent.As long as dicarboxylic anhydride is set at the scope of harmless effect of the present invention with respect to the ratio of acid anhydrides, but as standard, total be preferably set to 10 moles of acid anhydrides amount below the %.The example of dicarboxylic anhydride has maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide and cyclohexane dicarboxylic acid acid anhydride.

The molecular weight of the polyamic acid among the present invention is in the weight average molecular weight (Mw) of polystyrene conversion, and is preferred 10,000～500,000, and more preferably 20,000～200,000.This molecular weight can be obtained by the mensuration of utilizing gel permeation chromatography (GPC) method.

Polyamic acid among the present invention can be confirmed its existence in the following way: utilize ir radiation (Infrared Radiation, IR), nucleus magnetic resonance (Nuclear Magnetic Resonance, NMR) analyze by the solids component that obtains using a large amount of poor solvents to make the polyamic acid precipitation.In addition, can confirm employed starting compound in the following way: utilize vapor-phase chromatography (GasChromatography, GC), high performance liquid chromatography (High Performance LiquidChromatography, HPLC) or gaschromatographic mass spectrometry method (Gas Chromatograph-MassSpectrometer, GC-MS) to after using the alkaline aqueous solution such as KOH or NaOH that polyamic acid is decomposed, with an organic solvent the composition that is extracted from its resolvent is analyzed.

LCD alignment agent of the present invention also can further contain other compositions beyond the described polyamic acid.Other compositions can be a kind of, also can be two or more.

With regard to prevent characteristic through the time deterioration or with regard to the viewpoint of the caused deterioration of environment, orientation agent of the present invention also can further contain the compound that has more than 2 with the functional group of the carboxyl reaction of polyamic acid, promptly so-called linking agent.As the example of this kind linking agent, can enumerate as Japanese Patent No. 3049699 communique, Japanese Patent spy and open the multi-functional epoxyization thing put down in writing in 2005-275360 communique, the Japanese patent laid-open 10-212484 communique etc., isocyanate material etc.

In addition, also can will become cancellated polymkeric substance, thereby the linking agent that promotes the film toughness of polyamic acid is used for and described identical purpose as linking agent reaction itself.As this kind linking agent, can enumerate as Japanese patent laid-open 10-310608 communique, Japanese Patent spy and open multifunctional Vinyl Ether, maleimide and the alkenyl substituted Na Dike imide compound of being put down in writing in 2004-341030 communique etc.When using these linking agents, its preferred ratio counts 0.01～1.00 with the weight ratio with respect to the total amount of component of polymer, and more preferably 0.01～0.5.

The example of below representing particularly preferred alkenyl substituted Na Dike imide compound.

With regard to the viewpoint of the electrical specification long-term stability that makes liquid crystal display device, LCD alignment agent of the present invention also can further contain the compound with free-radical polymerised unsaturated double-bond.This example with compound of free-radical polymerised unsaturated double-bond has (methyl) acrylic acid derivative and bismaleimidess such as (methyl) acrylate, (methyl) acrylamide.Compound with free-radical polymerised unsaturated double-bond more preferably has (methyl) acrylic acid derivative of free-radical polymerised unsaturated double-bond more than 2.

With regard to the viewpoint of the permanent stability of the electrical specification of liquid crystal display device, LCD alignment agent of the present invention also can further contain the oxazines compound.An example of expression oxazines compound.

Herein, W ¹Alkyl for phenyl or carbon number 1～20.

With regard to the viewpoint of the permanent stability of the electrical specification of liquid crystal display device, LCD alignment agent of the present invention also can further contain epoxy compounds.But epoxy compounds illustration: glycidyl ether, glycidyl ester, glycidyl amine, the acrylic resin that contains epoxy group(ing), Racemic glycidol acid amides, tricarbimide glycidyl ester, chain aliphatics type epoxy compounds, and annular aliphatic type epoxy compounds.

LCD alignment agent of the present invention also can further contain various additives.The example of various additives has polymkeric substance beyond the polyamic acid, and low molecular compound, can select to use according to various purposes.For example, by polymeric amide, urethane, polyureas, polyester, polyepoxide, polyester polyol, organic silicon modified polyurethane or organosilicon modified polyester being added in the LCD alignment agent of the present invention, can expect to improve the voltage retention of liquid crystal display device, reduce ion density, and raising photostabilization and thermotolerance, the liquid crystal display device that fabrication reliability is high.

As described low molecular compound, when expectation promotes coating, but illustration meets the interfacial agent of this purpose, when needs promote static resistance, but the illustration static inhibitor, when the connecting airtight property of expecting lifting and substrate or rub resistance, but the coupler of illustration silane coupling agent or titanium system, in addition, when carrying out imidization at low temperatures, but the illustration imidization catalyst.

The concrete example of silane coupling agent has: vinyltrimethoxy silane, vinyltriethoxysilane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-aminopropyl methyltrimethoxy silane, the p-aminophenyl Trimethoxy silane, the p-aminophenyl triethoxyl silane, m-aminophenyl base Trimethoxy silane, m-aminophenyl ethyl triethoxy silicane alkane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, N-(1,3-dimethyl butylidene)-3-(triethoxysilyl)-1-propylamine, and N, N '-two [3-(trimethoxysilyl) propyl group] quadrol.When using silane coupling agent, its preferred addition counts 0.001～0.05 with the weight ratio with respect to the gross weight of polyamic acid.

The concrete example of imidization catalyst can be enumerated: aliphatics amines such as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine; N, accelerine, N, aromatic amines such as N-Diethyl Aniline, methyl substituted aniline, hydroxyl-substituted amine; Ring type amines such as pyridine, methyl substituted pyridine, hydroxyl substituted pyridines, quinoline, methyl substituted quinoline, hydroxyl substd quinolines, isoquinoline 99.9, methyl substituted isoquinoline 99.9, hydroxyl substituted isoquinoline, imidazoles, methyl substituted imidazoles, hydroxyl substituted imidazole.Imidization catalyst is preferably selected from N, accelerine, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine, adjacent pyridone, a pyridone, in pyridone and the isoquinoline 99.9 one or more.When using imidization catalyst, its preferred addition is 0.01 equivalent～0.5 equivalent with respect to the carbonyl of polyamic acid, preferred 0.05 equivalent～0.3 equivalent.

LCD alignment agent of the present invention contains solvent.Solvent can suit to select from the common employed solvent of manufacturing step or purposes aspect of polyamic acid.Solvent can be a kind of, also can be with two or more as mixed solvent.Solvent roughly be divided into the solvophilic of polyamic acid with to improve other solvents that coating is a purpose.

Solvophilic is non-protic polar organic solvent, its concrete example has: N-N-methyl-2-2-pyrrolidone N-, dimethyl-imidazolinone, N-methyl caprolactam, N-methyl propanamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-diethylformamide, diethyl acetamide, and lactone such as gamma-butyrolactone.

But to improve coating etc. is other solvent illustrations of purpose: lactic acid alkyl ester, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether, Diethylene Glycol monoalky lether, glycol monomethyl phenyl ether, triethylene glycol monoalky lether, propylene glycol monomethyl ether, propylene-glycol monoalky lether, dialkyl malonate, dipropylene glycol monoalky lether, and the ester cpds such as acetic ester of these compounds.

Among these solvents, preferred especially N-N-methyl-2-2-pyrrolidone N-, dimethyl-imidazolinone, gamma-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

LCD alignment agent of the present invention is to be supplied in practicality so that contain the form that the component of polymer of described polyamic acid is dissolved in the solution that forms in the solvent.The preferred concentration of the component of polymer of this moment is 0.1wt% (weight percent)～40wt%.When being coated on this LCD alignment agent on the substrate, the operation that need utilize solvent that the component of polymer that is contained is diluted sometimes in order to adjust thickness in advance.At this moment, be adjusted to regard to viscosity and be adapted in the LCD alignment agent easily with regard to the viewpoint of the viscosity of mixed solvent, below the preferred 40wt% of the concentration of described component of polymer the LCD alignment agent.

The concentration of the described component of polymer in the LCD alignment agent also will be adjusted according to the coating process of LCD alignment agent sometimes.When the coating process of LCD alignment agent was spin-coating method or print process, in order to keep thickness well, most usually concentration with described component of polymer was set at below the 10wt%.At other coating processes, for example in pickling process or the ink jet method, further reduce concentration possibly.On the other hand, if the concentration of component of polymer is more than the 0.1wt%, then the thickness of the liquid crystal orienting film that is obtained reaches best easily.Therefore, in common spin-coating method or print process etc., the concentration of described component of polymer is more than the 0.1wt%, preferred 0.5wt%～10wt%.But,, also can use sometimes with lower concentration according to the coating process of LCD alignment agent.

In addition, when being used to make liquid crystal orienting film, the viscosity of LCD alignment agent of the present invention can decide according to the means or the method for the film that forms this LCD alignment agent.For example, when using printing press to form the film of LCD alignment agent, with regard to the viewpoint that obtains sufficient thickness, more than the preferred 5mPas of the viscosity of LCD alignment agent, in addition, with regard to suppressing the uneven viewpoint of printing, below the preferred 100mPas, more preferably 10mPas～80mPas.When forming the film of LCD alignment agent when utilizing spin-coating method to come coating of liquid crystalline orientation agent, with regard to identical viewpoint, the preferred 5mPas～200mPas of the viscosity of LCD alignment agent, more preferably 10mPas～100mPas.The viscosity of LCD alignment agent can be by utilizing the dilution that solvent carries out or following the curing of stirring to reduce.

In the present invention, except that by the polyamic acid that mixture and anhydride reaction obtained (polymer A) that makes diamines (I) or diamines (I) and other diamines, the polyamic acid (polymer B) that also can use diamines (I) to be obtained.These two kinds of polyamic acids and with being so-called polymkeric substance fusion.Particularly, the polyamic acid that does not use diamines (I) to be obtained is the polyamic acid that described other diamines and anhydride reactions are obtained.

And, use the effect that has the diamines of secondary amino, tertiary amine base or nitrogen heterocycle in the skeleton of described residue also can obtain in the following way: the polyamic acid that mixture and anhydride reaction obtained that will make this diamines or this diamines and other diamines is as polymer B, and itself and polymer A are carried out fusion.Have other diamines of diamines blended of secondary amino, tertiary amine base or nitrogen heterocycle as long as select at this moment, with in the skeleton of residue according to the target tilt angle.

Liquid crystal orienting film of the present invention can obtain by described LCD alignment agent being coated on the step on the substrate and filming of being obtained thus being carried out the incinerating step, optionally, preferably the film that is obtained in the described calcining step is carried out friction treatment.

Identical with the making of common liquid crystal orienting film, film and can form by coating LCD alignment agent of the present invention on the substrate of liquid crystal display device.As preferred substrate, can enumerate: tin indium oxide (Indium Tin Oxide, ITO) substrate of the glass of electrode such as electrode or colored filter etc. can be set.

As the method that the LCD alignment agent is coated on the substrate, common known have spin-coating method, print process, pickling process, dripping method, ink jet method etc.These methods equally also can be used in the present invention.

The calcining of filming can present under the required condition of dehydration-ring-closure reaction at polyamic acid to be carried out.As the calcining method of filming, usually known have in baking oven or infra-red furnace, carry out methods of heating treatment, on hot-plate, carry out methods of heating treatment etc.These methods equally also can be used in the present invention.Usually preferably carried out 1 minute～3 hours with about 150 ℃～300 ℃ temperature.

Friction treatment can be carried out in the mode identical with the friction treatment of the orientation processing that is generally used for liquid crystal orienting film, so long as the condition that can obtain to postpone fully in liquid crystal orienting film of the present invention gets final product.Particularly preferred condition is that the hair amount of being pressed into is 0.2mm～0.8mm, and the platform translational speed is 5mm/sec～250mm/sec, and the roller speed of rotation is 500rpm～2,000rpm.As the orientation processing method of liquid crystal orienting film, except that rubbing manipulation, common known have light orientation method or transfer printing etc.In the scope that can obtain effect of the present invention, these other orientation processing method can be replaced with described friction treatment, also can and use with friction treatment.

In the present invention, make polyamic acid, and when using this polyamic acid to prepare the LCD alignment agent, can utilize described smooth orientation method to obtain alignment film when the diamines that will have the photosensitivity base and diamines (I) are used in combination.For example, if be formed at polyimide film irradiation on the substrate to using the agent of this kind LCD alignment through the UV-light of linear polarization, fit then and enclose liquid-crystal composition in the liquid crystal cell of 2 substrate manufacturings, then can obtain to have the liquid crystal display device of the liquid crystal that has been endowed desired orientation state.Secondly, expression has the example of the diamines of photosensitivity base.

Contain in the liquid crystal display device of alignment film of LCD alignment agent manufacturing of polymkeric substance that main chain has the photosensitivity base having to use, when desiring to show the tilt angle of regulation, following method can suit to select: when irradiating ultraviolet light from angle arbitrarily to substrate irradiation linear polarization method or will to substrate carry out from the linear polarization irradiation of vertical direction with substrate is carried out from there being the method that the polarisation irradiation is made up at any angle.

Liquid crystal orienting film of the present invention can preferably obtain by the method that further comprises described step other steps in addition.As other steps of this kind, can enumerate described filming carried out the exsiccant step or utilized step that scavenging solution cleans the film before and after the friction treatment etc.

Drying step is identical with described calcining step, usually known have in baking oven or infra-red furnace, carry out methods of heating treatment, on hot-plate, carry out methods of heating treatment etc.These methods can be used too.Drying step is preferably implemented under the temperature in the scope that solvent can evaporate, and more preferably implements under temperature lower for the temperature in the calcining step.

As the purging method that utilizes the liquid crystal orienting film of scavenging solution before and after orientation is handled to clean, can enumerate: scrub, spraying, steam purge or ultrasonic cleaning etc.These methods can be carried out separately, also can and use.As scavenging solution, can use: pure water, or various alcohols such as methyl alcohol, ethanol, Virahol, benzene,toluene,xylenes etc. are aromatic hydrocarbon based, halogen series solvents such as methylene dichloride, ketones such as acetone, methyl ethyl ketone, but be not limited to these.Certainly, these scavenging solutions are to use the few scavenging solution of impurity through abundant purifying.In described cleaning step when this kind purging method also can be applied to form liquid crystal orienting film of the present invention.

The thickness of liquid crystal orienting film of the present invention is not particularly limited, preferred 10nm～300nm, more preferably 30nm～150nm.The thickness of liquid crystal orienting film of the present invention can use known determining film thickness devices such as profile measurer or ellipsometer to measure.

Liquid crystal display device of the present invention comprises: a pair of substrate, be formed at liquid crystal layer between this a pair of substrate, liquid crystal layer is applied the electrode of voltage and makes the liquid crystal orienting film of liquid crystal molecule towards the direction orientation of regulation.Liquid crystal orienting film can use described liquid crystal orienting film of the present invention.

Substrate can use the substrate of described glass, and electrode can use formed ITO electrode on the substrate of illustrated glass in the explanation of liquid crystal orienting film.

Dielectric constant anisotropy can be enumerated the Japanese Patent spy for negative preferred liquid-crystal composition and open clear 57-114532 communique, Japanese patent laid-open 2-4725 communique, Japanese patent laid-open 4-224885 communique, Japanese patent laid-open 8-40953 communique, Japanese patent laid-open 8-104869 communique, Japanese patent laid-open 10-168076 communique, Japanese patent laid-open 10-168453 communique, Japanese patent laid-open 10-236989 communique, Japanese patent laid-open 10-236990 communique, Japanese patent laid-open 10-236992 communique, Japanese patent laid-open 10-236993 communique, Japanese patent laid-open 10-236994 communique, Japanese patent laid-open 10-237000 communique, Japanese patent laid-open 10-237004 communique, Japanese patent laid-open 10-237024 communique, Japanese patent laid-open 10-237035 communique, Japanese patent laid-open 10-237075 communique, Japanese patent laid-open 10-237076 communique, Japanese patent laid-open 10-237448 communique (EP967261A1 specification sheets), Japanese patent laid-open 10-287874 communique, Japanese patent laid-open 10-287875 communique, Japanese patent laid-open 10-291945 communique, Japanese patent laid-open 11-029581 communique, Japanese patent laid-open 11-080049 communique, the Japanese Patent spy opens the 2000-256307 communique, the Japanese Patent spy opens the 2001-019965 communique, the Japanese Patent spy opens the 2001-072626 communique, the Japanese Patent spy opens the liquid-crystal composition that is disclosed in 2001-192657 communique etc.

When driving the liquid crystal display device with the liquid crystal orienting film that utilizes LCD alignment agent manufacturing of the present invention with TN mode or IPS mode, also can use dielectric constant anisotropy in liquid crystal display device is positive liquid-crystal composition.Dielectric constant anisotropy is that positive preferred liquid-crystal composition can be enumerated No. 3086228 communique of Japanese Patent, No. 2635435 communique of Japanese Patent, the flat 5-501735 communique of the special table of Japanese Patent, Japanese patent laid-open 8-157826 communique, Japanese patent laid-open 8-231960 communique, Japanese patent laid-open 9-241644 communique (EP885272A1 specification sheets), Japanese patent laid-open 9-302346 communique (EP806466A1 specification sheets), Japanese patent laid-open 8-199168 communique (EP722998A1 specification sheets), Japanese patent laid-open 9-235552 communique, Japanese patent laid-open 9-255956 communique, Japanese patent laid-open 9-241643 communique (EP885271A1 specification sheets), Japanese patent laid-open 10-204016 communique (EP844229A1 specification sheets), Japanese patent laid-open 10-204436 communique, Japanese patent laid-open 10-231482 communique, the Japanese Patent spy opens the 2000-087040 communique, the Japanese Patent spy opens the liquid-crystal composition that is disclosed in 2001-48822 communique etc.

Can be that the optically active compound that adds more than one in the liquid-crystal composition of plus or minus uses also at described dielectric constant anisotropy.

Liquid crystal display device of the present invention can obtain in the following way: form liquid crystal orienting film of the present invention at least one of a pair of substrate, so that liquid crystal orienting film mode inwards makes a pair of substrate that obtained in opposite directions by spacer, liquid-crystal composition enclosed to formed gap between substrate and form liquid crystal layer.When making liquid crystal display device of the present invention, optionally also may further include the step that on substrate, attaches light polarizing film etc.

Can be by the suitable polymkeric substance of selecting as its raw material with LCD alignment agent of the present invention as the liquid crystal orienting film of raw material made, and be applied in the liquid crystal display device of various display driver modes.

Liquid crystal display device of the present invention also can further have the key element beyond the described integrant.As other integrants of this kind, normally used integrant in the liquid crystal display device such as Polarizer (light polarizing film), wavelength plate, light-diffusing films, driving circuit can be installed in liquid crystal display device of the present invention.

[example]

Below, utilize example that the present invention is described.

At first, below employed acid anhydrides, diamines and solvent and compound number or contracted notation in the example are represented in the lump.In addition, the unit liter of representing capacity in the example with contracted notation L.Therefore, milliliter is to represent with mL.

＜acid anhydrides 〉

Acid anhydrides (H-1)

Acid anhydrides (S-1)

Acid anhydrides (S-6)

Acid anhydrides (S-48)

＜diamines 〉

Diamines (I-1)

Diamines (I-2)

Diamines (2-1-1)

Diamines (2-1-66)

Diamines (3-7-1) (Y ⁵=n-pentyl)

Diamines (4-1-4-1) (Y ⁶=n-pentyl)

＜solvent 〉

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

BC: ethylene glycol butyl ether (ethylene glycol monobutyl ether)

[synthesis example 1]

Synthesizing of＜diamines (I-1) (4-(3,5-diamino benzyl) phenol) 〉

Open the 2006-124371 communique according to the Japanese Patent spy, synthetic 4-(3,5-dinitrobenzene benzyl) phenol.This compound 10g is mixed in dimethyl formamide 100mL with 5% palladium activated carbon 1g, under 40 ℃, carry out hydrogenation (hydrogen pressure is 680kPa) then.After the reaction, temperature is cooled to room temperature till, remove catalyzer by filtering, decompression is heated up in a steamer and is desolvated and obtain target compound (output is 7.5g, and productive rate is 81%) then.

Fusing point; 230.4 ℃-233.8 ℃

¹H?NMR；9.15(s，1H)，6.98(d，2H，J＝8.35Hz)，6.72(d，2H，J＝8.52Hz)，5.66(s，3H)，4.63(br s，4H)

[synthesis example 2]

Synthesizing of＜diamines (I-2) (3,5-two-tert-butyl-hydroxy phenyl-3,5-diaminobenzoic acid ester) 〉

In the there-necked flask of the 2L that thermometer, stirrer and dropping funnel are installed, add commercially available sodium borohydride 6.4g (170mmol), add dehydration tetrahydrofuran (THF) 500mL then.Solution is cooled to below 5 ℃, makes commercially availablely 2 to wherein dripping, 6-two-tertiary butyl benzoquinones 50g (230mmol) is dissolved in the solution that forms among the dehydration tetrahydrofuran (THF) 500mL.Till reaction solution is warming up to room temperature, and at room temperature stirred 8 hours.After the stirring, the reaction solution that is obtained is poured among the hydrochloric acid 1L of 3M, utilized vinyl acetic monomer 1L to extract.After utilizing pure water 1L that organic layer is cleaned 2 times, add anhydrous magnesium sulfate and carry out drying.After anhydrous magnesium sulfate filtration removal, decompression is heated up in a steamer and is desolvated, and obtains 2,6-two-Tert. Butyl Hydroquinone (output is 46g, and productive rate is 91%).

In the there-necked flask of the 1L that thermometer, stirrer and dropping funnel are installed, add commercially available 3,5 dinitrobenzoylchloride 47g (204mmol), add methylene dichloride 300mL then.Solution is cooled to below 5 ℃, makes by previous to wherein dripping that method obtained 2,6-two-Tert. Butyl Hydroquinone 45g (202mmol), and triethylamine 42mL (303mmol) be dissolved in the solution that forms among the methylene dichloride 200mL.Till reaction solution is warming up to room temperature, under nitrogen environment and at room temperature stirred 3 hours.After the stirring, reaction solution is poured among the pure water 1L, utilized methylene dichloride 500mL to extract.Utilize saturated aqueous ammonium chloride 1L that organic layer is cleaned 2 times, then utilize pure water 1L that organic layer is cleaned 2 times after, add anhydrous magnesium sulfate and carry out drying.After anhydrous magnesium sulfate filter removed, decompression was heated up in a steamer and is desolvated and obtain coarse crystallization.By tubing string chromatography (toluene) with the coarse crystallization separation and purification that is obtained, utilize ethanol-toluene mixed solvent (volume ratio=1/1) to make its recrystallize, obtain 3,5-two-tert-butyl-hydroxy phenyl-3,5-dinitrobenzoic acid ester (output is 46g, and productive rate is 55%).

Add by previous to the autoclave of 1L that method obtained 3 in reaction tubes, 5-two-tert-butyl-hydroxy phenyl-3,5-dinitrobenzoic acid ester 45g (108mmol), Pd/C powder 4.5g add toluene 150mL and ethanol 150mL then.At hydrogen pressure 8kgf/cm ²And reaction after 12 hours under the room temperature, by filter removing the pd/C powder, decompression is heated up in a steamer and is desolvated and obtain coarse crystallization.By tubing string chromatography (toluene: vinyl acetic monomer=1: 1) with the coarse crystallization separation and purification, utilize toluene to make its recrystallize, obtain 3,5-two-tert-butyl-hydroxy phenyl-3,5-diaminobenzoic acid ester (output is 31g, and productive rate is 81%).

Fusing point; 203.1 ℃-206.5 ℃

¹H-NMR(ppm)；1.44(18H，s，-CH ₃)，3.74(4H，br·s，-NH ₂)，5.11(1H，s，-OH)，6.24(1H，m，arm·H)，6.92(2H，m，arm·H)，7.26(2H，m，arm·H).

[synthesis example 3]

＜polyamic acid synthetic 1

In the four-hole boiling flask of the 100mL that possesses thermometer, stirrer, raw material input interpolation mouth and nitrogen inlet, add diamines (I-1) 2.55g, diamines (2-1-1) 0.591g and dehydration NMP 60.0g, under the drying nitrogen air-flow, carry out stirring and dissolving.Then, add acid anhydrides (H-1) 1.30g, acid anhydrides (S-1) 1.75g, reaction is 30 hours under room temperature environment.When temperature of reaction in the reaction process rises, temperature of reaction is suppressed to react after below 70 ℃ to about.

Add BC 34.0g in the solution that is obtained, preparation concentration is the polyamic acid solution (PA1) of 6wt%.The viscosity of the PA1 that is obtained is 26.8mPas.In addition, the weight average molecular weight of the polyamic acid that is generated is 55,000.

Herein, the weight average molecular weight of polymkeric substance is to obtain in the following way: utilize (phosphoric acid/DMF=0.6/100: weight ratio) diluent, so that reaching the mode of about 1wt%, polymer concentration dilutes the polymkeric substance that is obtained, utilize chromatographic data processor C-R7A (Shimadzu Seisakusho Ltd.'s manufacturing) then, described diluent is measured as developping agent and by the GPC method, then carried out polystyrene conversion.In addition, tubing string is to use GF-7HQ (clear and electrician limited-liability company makes), and measures under the condition of 50 ℃ of tubing string temperature, flow velocity 0.6mL/min.

[synthesis example 4 and synthesis example 5]

The Synthetic 2 of＜polyamic acid and polyamic acid synthetic 3

Except that the composition with acid anhydrides, diamines and solvent changes to the ratio shown in the table 1, prepare polyamic acid solution (PA2, PA3) according to synthesis example 1.

[synthesis example 6]

＜polyamic acid synthetic 4

In the four-hole boiling flask of the 100mL that possesses thermometer, stirrer, raw material input interpolation mouth and nitrogen inlet, add diamines (3-7-1) 1.17g, diamines (2-1-1) 2.14g, reach dehydration NMP 60.0g, under the drying nitrogen air-flow, carry out stirring and dissolving.Then, add acid anhydrides (H-1) 0.59g, acid anhydrides (S-1) 2.11g, reaction is 30 hours under room temperature environment.When temperature of reaction in the reaction process rises, temperature of reaction is suppressed to react after below 70 ℃ to about.

Add BC 34.0g in the solution that is obtained, preparation concentration is the polyamic acid solution (PA4) of 6wt%.The viscosity of the PA1 that is obtained is 23.6mPas.In addition, the weight average molecular weight of the polyamic acid that is generated is about 36,000.This PA4 is as using in order to the polymers soln that carries out fusion with PA1～PA3.

[relatively synthesis example 1 and relatively synthesis example 2]

Except that change diamines as shown in table 1, prepare polyamic acid solution CA1 and the polyamic acid solution CA2 that the concentration of not using diamines (I) is 6wt% according to synthesis example 3.Comprise synthesis example 3, raw material is formed and the weight average molecular weight of the polyamic acid that obtained is summarized in table 1.

＜table 1 〉

(notes) PA acid is meant polyamic acid.

[example 1]

Be that concentration prepared in polyamic acid solution (PA1) and the synthesis example 6 of 6wt% is that the polyamic acid solution (PA4) of 6wt% is mixed with weight ratio 2/8 with concentration prepared in the synthesis example 3.Utilize the mixed solvent of NMP/BC=1/1 (weight ratio) that the mixture diluted that is obtained is made the LCD alignment agent to 4wt%.Use the LCD alignment agent, as following, make liquid crystal display device.

Utilize spin-coating method that LCD alignment agent AL1 is coated on a pair of substrate that has an ito transparent electrode, with 80 ℃ on hot-plate dry 90 seconds.Then, heating and calcining is 60 minutes in setting 200 ℃ baking oven for, obtains to be formed with the substrate of liquid crystal orienting film.Making the face that is formed with alignment film become the inboard, on a substrate, is that adhesive coated becomes band in the filling orifice of the residual liquid crystal of periphery and with epoxy, scatters on another piece substrate and the clearance material of the 4.25 μ m that fit.Following liquid-crystal composition A vacuum is injected in the liquid crystal cell that is obtained, utilizes the sealing agent of UV sclerotic type to seal filling orifice.Under 110 ℃, carry out 30 minutes heat treated (isotropy processing) at last, obtain VA type liquid crystal display device.

＜liquid-crystal composition A 〉

At the liquid crystal display device that is obtained, carry out the evaluation of voltage retention, residual DC and tilt angle by following method.Show the result in table 2.

The mensuration of＜voltage retention (VHR) 〉

Use liquid crystal evaluation of physical property device 6254 types of Dongyang Te Kenika (TOYO Corporation) manufacturing, carry out the mensuration of the VHR of liquid crystal display device.Condition determination is that grid width is 60 μ sec, and frequency is 3Hz, and wave height is ± 1V that measuring temperature is 60 ℃.

The evaluation of the long-term light reliability of＜VHR 〉

VA type used for liquid crystal display element is more in the situation of home-use TV, owing to use for a long time under various environment, the light during therefore long-time the use is sintered into problem, and requires long-term light reliability.The evaluation of long-term light reliability is to carry out in the following way: the liquid crystal display device that will measure voltage retention is positioned in the 5000cd/m through lighting ²Liquid-crystal display with on the cold cathode cast backlight, measure voltage retention after 2 weeks once more.We can say to be positioned in that backlight is gone forward the voltage retention measured and the difference of the voltage retention measured again after 2 weeks is more little, long-term light reliability is high more.

＜utilize the mensuration of the residual DC of dielectric absorption method 〉

Liquid crystal evaluation of physical property device 6254 types that use Dongyang Te Keni blocking to make utilize the mensuration of the residual DC of dielectric absorption method.Condition determination is direct current short circuit 1 second after 1 hour that liquid crystal cell is applied 5V, and observes potential difference 30 minutes.The residual DC of maximum and minimum residual DC are documented in the table.In addition, measuring temperature is 60 ℃.We can say that this value is more little, electrical specification is good more.

The mensuration of＜tilt angle 〉

Tilt angle is that the value of obtaining the sample rotation angle that becomes minimum according to transmitance behind sample rotation angle-transmittance curve under cross-polarized light is calculated.

[example 2, example 3 and comparative example 1～comparative example 3]

Except that using PA2, PA3 and CA1 to replace the PA1 respectively, make liquid crystal display device in the mode identical, and carry out the evaluation of characteristic in the mode identical with example 1 with example 1.In addition, about using CA2 to replace the situation (comparative example 3) of PA4, and use CA1 to replace PA1, use CA2 to replace the situation (comparative example 2) of PA4, other conditions and example 1 are identical and make liquid crystal display device, and carry out the evaluation of characteristic in the mode identical with example 1.With their table 2 that the results are shown in.

＜table 2 〉

According to these results as can be known, can obtain the booster tension conservation rate by using diamines (I) and improve the effect of long-term light reliability.In addition, residual DC is also significantly suppressed.And, according to example 1 and example 2 and example 3 more as can be known, be used in combination by acid anhydrides and the diamines (I) that will have the tertiary amine base in the residue, the effect of improving long-term light reliability further improves.

[synthesis example 7～synthesis example 11 and comparison synthesis example 3～comparison synthesis example 7]

Except that the composition of change acid anhydrides, diamines and solvent, prepare polyamic acid solution (PA5～PA9 and CA3～CA7) according to synthesis example 3.Show the result in table 3.

＜table 3 〉

(notes) PA acid is meant polyamic acid.

[example 4]

Utilize the mixed solvent of NMP/BC (weight ratio is 1/1) that the polyamic acid solution PA5 shown in the table 3 is diluted to 4wt% and make the LCD alignment agent.Utilize turner that this LCD alignment agent is coated on two glass substrates that have an ITO electrode, forming thickness is the film of 70nm.Film the back after carrying out about 5 minutes heat dryings under 80 ℃, carry out 10 minutes heat treated, form liquid crystal orienting film at 220 ℃.

Use Iinuma-gauge to make the friction treatment device that limited-liability company of institute makes, (staple length is 1.9mm: the hair amount of being pressed into artificial silk) is 0.40mm at friction cloth, the platform translational speed is 60mm/sec, the roller speed of rotation is under the condition of 1000rpm, and a glass substrate that is formed with alignment film is carried out friction treatment.After frictional direction being changed 90 °, similarly another piece glass substrate is carried out friction treatment with the orthogonal mode of the frictional direction of described glass substrate.After in ultrapure water, these substrates being carried out 5 minutes ultrasonic cleaning, in baking oven, these substrates are carried out 30 minutes dryings with 120 ℃.On another piece glass substrate, scatter the clearance material of 7 μ m.

So that after being formed with the face of alignment film and becoming inboard and the orthogonal mode of frictional direction two substrates are disposed in opposite directions, utilize epoxy curing agent to seal, thus make the gap be 7 μ m distortion 90 ° liquid crystal cell.In this liquid crystal cell, inject with respect to following liquid-crystal composition B 100 weight parts, add as Cholesteryl pelargonate 5 weight parts of optically active substance and form the constituent of homogeneous, utilize photo-hardening agent sealing inlet then.Then, under 110 ℃, carry out 30 minutes heat treated, make TN type liquid crystal display device.

＜liquid-crystal composition B 〉

At the TN type liquid crystal display device that is obtained, by following assay method carry out voltage retention, the residual DC of (flicker free) of utilizing the flicker free method and the evaluation of tilt angle.Show the result in table 4.

The mensuration of＜voltage retention (VHR) 〉

Liquid crystal evaluation of physical property device 6254 types that use Dongyang Te Keni blocking to make carry out the mensuration of the VHR of liquid crystal display device.Condition determination is that grid width is 60 μ sec, and frequency is 3Hz, and wave height is ± 1V that measuring temperature is 60 ℃.

The evaluation of the long-term light reliability of＜VHR 〉

About TN type liquid crystal display device, also similarly estimate long-term light reliability in the mode identical with example 1 with VA type liquid crystal display device.

＜utilize the mensuration of the residual DC of flicker free method 〉

At TN type liquid crystal display device, utilize flicker free method shown below to measure residual DC.

The FG110 type function producer that uses Yokogawa Motor (share) to make is installed in utilizing anchor clamps Polarizer is configured to the square wave that TN type liquid crystal display device on the polarizing microscope that the Nikons (share) of 90 degree make applies 30Hz, 3V.The volts DS of overlapping 3V is after 30 minutes in this square wave, stop the overlapping of volts DS, by the photoelectron-multiplier-tube of the oscillographic Hamamatsu Photonics manufacturing of the DSO3062 type that is connected in the manufacturing of Agilent Technologies company, detect the light quantity that sees through of liquid crystal display device then.So that the offset voltage that becomes minimum mode adjustment function producer by the variation of the waveform of the variation of the shown expression light quantity that goes out of oscilloscope, and with this offset voltage as flicker cancellation voltage record in addition.The residual DC of maximum and minimum residual DC are documented in the table.We can say that this value is more little, electrical specification is good more.

The mensuration of＜tilt angle 〉

The tilt angle of TN type liquid crystal display device is to utilize the liquid crystal characteristic evaluating apparatus OMS-CA3 type of central smart machine manufacturing to measure.

[example 5～example 7 and comparative example 4～comparative example 6]

About each polyamic acid solution of polyamic acid solution PA6～polyamic acid solution PA8 and polyamic acid solution CA3～polyamic acid solution CA5, make liquid crystal display device with the method identical, and estimate with example 4.Show the result in table 4.

＜table 4 〉

(notes) PA acid is meant polyamic acid.

According to the data of table 4 as can be known, by the polyamic acid that use utilizes diamines (I) to be obtained, long-term light reliability gets a promotion.And, also show significant effect for residual DC.Tilt angle is the value that is suitable for TN type liquid crystal display device, also is suitable for OCB type liquid crystal display device.In addition, if voltage retention after the rayed of example 4～example 6 and example 7 are compared, then obviously can see difference, example 4～example 6 shows better value.Can think that this is to have the diamines of secondary amino, tertiary amine base or nitrogen heterocycle or acid anhydrides and diamines (I) in the skeleton with residue to be used in combination effect for long-term light reliability.

[example 8 and comparative example 7, comparative example 8]

Except that PA9, the CA6 and CA7 that are put down in writing in the independent use table 3 respectively, make VA type liquid crystal display device in the mode identical, and estimate with example 1.Show the result in table 5.

＜table 5 〉

(notes) PA acid is meant polyamic acid.

According to the data of table 5 as can be known, identical with the situation of described TN type liquid crystal display device, when for VA type liquid crystal display device and when using the PA acid solution separately,, also can obtain and promote long-term light reliability and suppress the relevant significant effect of residual DC by using diamines (I).

As mentioned above, LCD alignment agent of the present invention can be used for the formation of liquid crystal orienting film of the liquid crystal display device of various display driver modes.And in the liquid crystal display device of any display driver mode, long-term light reliability is all higher, and residual DC all is inhibited.

[utilizability on the industry]

According to the present invention, can provide residual DC low, the liquid crystal display device that the long-term light reliability of voltage retention is also excellent.

The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.

Claims

1. LCD alignment agent is characterized in that: it contains makes the polyamic acid or derivatives thereof that is obtained by the mixture of the represented diamines of formula (I) or this diamines and other diamines and tetracarboxylic dianhydride's reaction:

2. LCD alignment agent according to claim 1 is characterized in that: A ¹Be the alkylidene group of-COO-or carbon number 1～3, R is the alkyl of hydrogen or carbon number 1～4.

3. LCD alignment agent according to claim 1 is characterized in that: described other diamines are at least a diamines that select in the cohort of the represented diamines of free style (1-1)～formula (1-3), formula (2-1), formula (2-2), formula (3), formula (4-1) and formula (4-2):

W in the formula (1-2) ¹For-CH ₂-or-NH-;

B in the formula (1-3) is 0～2 integer:

4. LCD alignment agent according to claim 3 is characterized in that: described other diamines are at least a diamines that select in the cohort of the represented diamines of free style (3).

5. LCD alignment agent according to claim 3 is characterized in that: described other diamines are at least a by the represented diamines of formula (3-1)～formula (3-7), formula (3-21)～formula (3-25), formula (3-34) and formula (3-35):

6. LCD alignment agent according to claim 3 is characterized in that: described other diamines are at least a diamines that select in the cohort of the represented diamines of free style (4-1).

7. LCD alignment agent according to claim 3 is characterized in that: described other diamines are at least a by the represented diamines of formula (4-1-1)～formula (4-1-8):

8. LCD alignment agent according to claim 3 is characterized in that: described other diamines are at least a diamines that select in the cohort of the represented diamines of free style (1-1)～formula (1-3) and formula (2-1).

9. LCD alignment agent according to claim 3 is characterized in that: described other diamines are at least a by the represented diamines of formula (1-1-3), formula (1-1-5), formula (1-1-8), formula (1-1-9), formula (1-1-12)～formula (1-1-14), formula (1-2-2), formula (1-3-1), formula (1-3-2), formula (2-1-1), formula (2-1-7), formula (2-1-10), formula (2-1-13), formula (2-1-27), formula (2-1-28), formula (2-1-32)～formula (2-1-35), formula (2-1-54)～formula (2-1-56) and formula (2-1-66)～formula (2-1-68):

10. LCD alignment agent according to claim 9, it is characterized in that: described other diamines are by formula (1-1-8), formula (1-1-9), formula (1-1-12), formula (1-2-2), formula (1-3-1), formula (1-3-2), formula (2-1-32), formula (2-1-33), reach at least a of the represented diamines of formula (2-1-66)～formula (2-1-68), or contain the mixture of this (these) diamines.

11. according to each described LCD alignment agent in the claim 1 to 10, it is characterized in that: described tetracarboxylic dianhydride is at least a of aromatic tetracarboxylic acid's dianhydride.

12. according to each described LCD alignment agent in the claim 1 to 10, it is characterized in that: described tetracarboxylic dianhydride is at least a of aromatic tetracarboxylic acid's dianhydride tetracarboxylic dianhydride in addition.

13. according to each described LCD alignment agent in the claim 1 to 10, it is characterized in that: described tetracarboxylic dianhydride is at least a and described aromatic tetracarboxylic acid's dianhydride tetracarboxylic dianhydride's in addition of described aromatic tetracarboxylic acid's dianhydride an at least a mixture.

14. LCD alignment agent according to claim 13, it is characterized in that: described aromatic tetracarboxylic acid's dianhydride is by formula (H-1), formula (H-5), formula (H-8)～formula (H-10), formula (H-15), formula (H-19), tetracarboxylic dianhydride beyond formula (H-20) and the represented compound of formula (H-21), described aromatic tetracarboxylic acid's dianhydride is by formula (S-1), formula (S-6), formula (S-9)～formula (S-11), formula (S-21), formula (S-22), formula (S-30), formula (S-43), formula (S-44), formula (S-45), formula (S-48) and the represented compound of formula (S-53):

15. LCD alignment agent according to claim 14 is characterized in that: described aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (H-1), and the tetracarboxylic dianhydride beyond described aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (S-1).

16. LCD alignment agent according to claim 14 is characterized in that: described aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (H-1), and the tetracarboxylic dianhydride beyond described aromatic tetracarboxylic acid's dianhydride is by the represented compound of formula (S-48).

17. according to each described LCD alignment agent in the claim 1 to 10, it is characterized in that: it also contains and does not use by the represented polyamic acid or derivatives thereof that diamines obtained of formula (I).

18. a liquid crystal orienting film is characterized in that: it is to film to heat and form what obtained by each described LCD alignment agent in the claim 1 to 17 being coated on the substrate.

19. a liquid crystal display device is characterized in that: it has liquid crystal orienting film according to claim 18.

20. a diamines is characterized in that: it is to be represented by formula (I-2):