CN101724410B

CN101724410B - Liquid crystal orientation agent, liquid crystal orientation membrane and liquid crystal display component

Info

Publication number: CN101724410B
Application number: CN2009102066731A
Authority: CN
Inventors: 近藤史尚; 伊泽启介
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: JNC Corp
Priority date: 2008-10-29
Filing date: 2009-10-28
Publication date: 2013-11-13
Anticipated expiration: 2029-10-28
Also published as: JP5304174B2; TWI450914B; KR20100047819A; TW201016751A; JP2010106091A; KR101613639B1; CN101724410A

Abstract

The invention aims to develop a valuable liquid crystal orientation agent, which has the characteristics for composing the liquid crystal display component achieving high voltage conservation rate and long term stability of the high voltage conservation rate. The liquid crystal orientation agent of the invention is a composition containing polyamide acids or derivatives thereof; the polyamide acids is obtained by reacting the mixture of a specific diamine containing one naphthalene ring and two amino phenyls and other diamines, and tetracarboxylic dianhydride.

Description

Crystal aligning agent, liquid crystal orienting film and liquid crystal display device

Technical field

The present invention relates to a kind of crystal aligning agent, particularly relate to a kind of polyamic acid (polyamic acid) that the diamines (diamine) that contains naphthalene (naphthalene) and tetracarboxylic dianhydride (tetracarboxylicdianhydride) is reacted and obtain that contains.

Background technology

Take the indicating meter (monitor) of notebook computer (notebook computer) or desktop computer (desktop computer) as representative, liquid crystal display device is used to also be used for recently televisor in the various liquid crystal indicators such as the view finder (viewfinder), the projected display (projection display) of Kamera (video camera).In addition, liquid crystal display device also is used to photoelectron (optoelectronics) related elements such as optical print head (optical printer head), optical Fourier transform element (optical fouriertransform element), light valve (light valve).

Known in liquid crystal display device have various elements, the development of liquid crystal display device technology not only realizes by the type of drive of improvement liquid crystal display device or the structure of liquid crystal display device, and by the member of formation of using in the improvement liquid crystal display device, realizes.It is the liquid crystal orienting film of specific direction that liquid crystal display device has to make the liquid-crystal composition orientation in liquid crystal layer usually.Liquid crystal orienting film is one of the important elements that is related to the display quality of liquid crystal display device, and along with high-qualityization of liquid crystal display device, it is important that the effect of liquid crystal orienting film becomes year by year.

Liquid crystal orienting film utilizes crystal aligning agent to prepare.At present, the main crystal aligning agent that uses is to make polyamic acid or soluble polyimide (polyimide) be dissolved in the solution that forms in organic solvent.Liquid crystal orienting film be by with solution coat as above on substrate, then utilize the method such as heating carry out film forming and form.

For the display quality that makes liquid crystal display device improves and, to the key property that liquid crystal orienting film requires, can enumerate voltage retention.If voltage retention is low, the voltage drop that in frame time (frame time), liquid crystal is applied so, result has that brightness descends and normal gradient is shown the situation of (gradation display) obstacles.In addition, even the voltage retention at initial stage is high, but the situation that the voltage retention after the high temperature accelerated test (long-term reliability) descends is also bad.

As the trial that solves described problem, the known polyamic acid component that has to form liquid crystal orienting film for example, this polyamic acid component combination contain the polyamic acid (for example with reference to patent documentation 1 and patent documentation 2) of different two or more of physical property.In addition, the synthesis method (for example with reference to patent documentation 3) of the known polyamic acid that aromatic diamine with naphthalene and tetracarboxylic dianhydride is reacted and obtain.But, recent liquid crystal orienting film is required further improvement, obtain required electrical characteristic in order to make the gained liquid crystal orienting film, still have the leeway of further research for the crystal aligning agent that forms described liquid crystal orienting film.

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

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

[patent documentation 3] US5886131 communique

This shows, above-mentioned existing crystal aligning agent, liquid crystal orienting film and liquid crystal display device in structure and use, obviously still have inconvenience and defect, and demand 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, completed by development but have no for a long time applicable design always, and common product does not have appropriate structure to address the above problem, this is obviously the problem that the anxious wish of relevant dealer solves.Therefore how to found a kind of novel crystal aligning 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 object of the invention is to, overcome existing crystal aligning agent, the defect that liquid crystal orienting film and liquid crystal display device exist, and provide a kind of novel crystal aligning agent, liquid crystal orienting film and liquid crystal display device, technical problem to be solved is the liquid crystal display device that its permanent stability that show required voltage conservation rate and this voltage retention are achieved, realize the liquid crystal orienting film of the permanent stability of the performance of required voltage conservation rate and this voltage retention in this liquid crystal display device, and the crystal aligning agent that can form this liquid crystal orienting film, be very suitable for practicality.

The object of the invention to solve the technical problems realizes by the following technical solutions.For achieving the above object, according to crystal aligning agent of the present invention, the aromatic diamine that will contain to have naphthalene is that the constituent of the polyamic acid of raw material or its derivative is during as crystal aligning agent, in the liquid crystal display device with the liquid crystal orienting film that uses this crystal aligning agent and form, show the required voltage conservation rate, and give the good long-term reliability of this voltage retention, thereby complete the present invention.

Crystal aligning agent of the present invention is shown in following [1] item.

[1] a kind of crystal aligning agent, it is to contain the constituent that selects at least a polymkeric substance in the cohort that free polyamic acid and derivative thereof form, wherein said polymkeric substance be make with the represented diamines of formula (N) at least a or described with at least a of the represented diamines of formula (N) with not with at least a mixture of other diamines of the represented diamines of formula (N), the polyamic acid or its derivative that react with the tetracarboxylic dianhydride and obtain, and the concentration of shared described component of polymer is 0.1 % by weight～40 % by weight in described constituent.

(wherein, A ¹Alkyl, the carbon number that is 1～10 for carbon number independently is 1～10 alkoxyl group, hydroxyl, trifluoromethyl, fluorine, chlorine or bromine; M is 0～3 integer independently; A ²Be independently-O-,-NH-,-N (CH ₃)-or-S-; And two amino is except A for the bond position of phenyl ring ¹And A ²The bond position beyond optional position.)

By the present invention, a kind of liquid crystal display device that can be applied to various type of drive can be provided, its voltage retention is high, and good for the long-term reliability that changes in time of this voltage retention.

The present invention compared with prior art has obvious advantage and beneficial effect.By technique scheme, (crystal aligning agent, liquid crystal orienting film and liquid crystal display device have following advantages and beneficial effect at least: the present invention shows the liquid crystal orienting film of permanent stability of liquid crystal display device, the performance that realizes the required voltage conservation rate in this liquid crystal display device and this voltage retention that the permanent stability of required voltage conservation rate and this voltage retention are achieved and the crystal aligning agent that can form this liquid crystal orienting film, is very suitable for practicality in the present invention.

In sum, the invention relates to a kind of useful crystal aligning agent, described crystal aligning agent can be used for providing the liquid crystal display device that shows required voltage retention and realize the permanent stability of this voltage retention.Crystal aligning agent of the present invention is to contain the constituent that selects at least a polymkeric substance in the cohort that free polyamic acid and derivative thereof form, this polymkeric substance be make with at least a of the represented diamines of formula (N) or should with at least a of the represented diamines of formula (N) with not with at least a mixture of other diamines of the represented diamines of formula (N), and the tetracarboxylic dianhydride reacts and the polyamic acid or its derivative that obtain.A ¹Alkyl, the carbon number that is 1～10 for carbon number independently is 1～10 alkoxyl group, hydroxyl, trifluoromethyl, fluorine, chlorine or bromine, and m is 0～3 integer, and A ²Be independently-O-,-NH-,-N (CH ₃)-or-S-.

Above-mentioned explanation is only 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 and other purpose of the present invention, feature and advantage can be become apparent, below especially exemplified by preferred embodiment, be described in detail as follows.

Embodiment

Reach for further setting forth the present invention technique means and the effect that predetermined goal of the invention is taked, below in conjunction with preferred embodiment, its embodiment of crystal aligning agent, liquid crystal orienting film and liquid crystal display device, structure, feature and effect thereof to foundation the present invention proposes, be described in detail as follows.

At first, the term that uses in the present invention is described.

" crystal aligning agent " refers to form the constituent of liquid crystal orienting film.Sometimes will be called diamines (N) with the represented diamines of formula (N).For with the represented diamines of other chemical formulas too.Sometimes will be called carboxylic acid (1) with the represented tetracarboxylic dianhydride of formula (1).For with the represented tetracarboxylic dianhydride of other chemical formulas too.Other diamines refer to diamines (N) diamines in addition.The term that uses when chemical structural formula is described " arbitrarily ", refer to that not only position is arbitrarily, and number is also arbitrarily.And, the for example statement of " A can be replaced by B, C or D arbitrarily ", refer to except comprise situation that A arbitrarily replaced by B, arbitrarily A situation about being replaced by C and arbitrarily A by D replace situation, comprise that also a plurality of A are by at least two situations about being replaced in B～D.But, arbitrarily-CH ₂Do not comprise in-the situation that can be replaced by-O-continuous a plurality of-CH ₂The situation that-quilt-O-replaces., with the substituting group that forms the clear and definite bond of atom of encircling, be not freely to determine the substituting group of its bond position in the scope of chemically allowing.The symbol that word, for example A are surrounded with sexangle means ring A.

The present invention consists of described [1] item and [2] shown below～[20].

[2] according to [a 1] described crystal aligning agent, the bond position of two amino in its Chinese style (N) is all with respect to A ²For contraposition.

[3] according to [a 1] described crystal aligning agent, wherein said diamines is the mixture that is selected from at least a diamines in the represented compound cohort of formula (N-1)～formula (N-5), formula (N-7), formula (N-8), formula (N-13), formula (N-15) and formula (N-16) or this (these) diamines and other diamines.

(in these chemical formulas, Me refers to methyl.)

[4] according to [3] described crystal aligning agent, wherein said diamines is with at least a of formula (N-1) and the represented diamines of formula (N-3) or should (these) diamines and the mixture of other diamines.

[5] according to [a 1] described crystal aligning agent, wherein said diamines is the mixture with at least a and other diamines of the represented diamines of formula (N), and described other diamines are to be selected from least a with the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII).

(wherein, A ³For singly-bound ,-O-,-CO-,-COO-,-OCO-,-CONH-,-CH ₂O-,-CF ₂O-or carbon number are 1～6 alkylidene group (alkylene), in described alkylidene group arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces; R ¹For group, the carbon number with steroid (steroid) skeleton be 3～30 alkyl, have carbon number be 1～30 alkyl or carbon number be 1～30 alkoxyl group as substituent phenyl or with the represented group of formula (IX), described carbon number be in 3～30 alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces.)

(wherein, A ⁴And A ⁵Independently for singly-bound ,-O-,-COO-,-OCO-,-CONH-, carbon number are that 1～4 alkylidene group, carbon number are that 1～3 oxygen base alkylidene group or carbon number are 1～3 alkylidene group oxygen base; Ring B and ring C are Isosorbide-5-Nitrae-phenylene (phenylene) or Isosorbide-5-Nitrae-cyclohexylidene (cyclohexylidene) independently; R ²And R ³Be fluorine or methyl independently, f and g are 0,1 or 2 independently; C, d and e are 0～3 integer independently, they add up to more than or equal to 1; R ⁴For carbon number be 1～30 alkyl, carbon number is that 1～30 alkoxyl group or carbon number are 2～30 alkoxyalkyl, in these alkyl, alkoxyl group and alkoxyalkyl, hydrogen can be replaced by fluorine arbitrarily, and arbitrarily-CH ₂-can be replaced by difluoro methylene (difluoromethylene).)

(in formula (X) and formula (XI), R ⁵Be hydrogen or methyl independently, R ⁶Be 1～20 alkyl or alkenyl for hydrogen or carbon number, R ⁷And R ⁸Be respectively 1～20 alkyl or phenyl independently for carbon number, A ⁶Be independently singly-bound ,-CO-or-CH ₂-.)

(in formula (XII) and formula (XIII), R ⁹Be 1～30 alkyl for carbon number, in described alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces; R ¹⁰It is 6～22 alkyl for carbon number; R ¹¹It is 1～22 alkyl for carbon number; A ⁷Be 1～6 alkylidene group independently for-O-or carbon number; A ⁸It is 1～3 alkylidene group for singly-bound or carbon number; Ring T is Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene; H is 0 or 1.)

[6] according to [a 3] described crystal aligning agent, wherein said diamines is to be selected from at least a diamines in the represented compound cohort of formula (N-1)～formula (N-5), formula (N-7), formula (N-8), formula (N-13), formula (N-15) and formula (N-16) and the mixture of other diamines, and described other diamines are to be selected from least a with the diamines with side-chain radical in the represented diamines of formula (VIII-2), formula (VIII-4)～formula (VIII-6), formula (XII-2), formula (XII-4) and formula (XII-6).

(in these chemical formulas, R ²³, R ²⁹And R ³⁰Be respectively carbon number and be 1～30 alkyl or carbon number and be 1～30 alkoxyl group.)

[7] according to the described crystal aligning agent of any one in [1] to [6] item, wherein said diamines is the mixture that further contains the diamines with side-chain radical, and the described diamines that does not have side-chain radical is to be selected from least a with in formula (I)～formula (VII) and the represented compound cohort of formula (XV).

H ₂N-X-NH ₂ (I)

(in these chemical formulas, X is that carbon number is 2～12 straight-chain alkyl-sub-; Y be independently singly-bound ,-O-,-CO-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-O-(CH ₂) _t-O-,-S-,-S-S-,-SO ₂-,-S-(CH ₂) _t-S-or carbon number are 1～12 straight-chain alkyl-sub-, and t is 1～12 integer; Z ¹And Z ²For hydrogen, when Y be-NH-,-N (CH ₃)-,-CH ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-time, Z ¹With Z ²Bond and form singly-bound mutually; Ring D is phenylene or Isosorbide-5-Nitrae-diaza cyclohexylidene (diazacyclohexylidene); R ³³And R ³⁴Be respectively 1～3 alkyl or phenyl independently for carbon number; A ³Be 1～6 alkylidene group, phenylene or the phenylene that replaces through alkyl for carbon number independently; M is 1～10 integer; Any hydrogen of cyclohexane ring or phenyl ring can by fluorine, methyl ,-OH ,-COOH ,-SO ₃H ,-PO ₃H ₂, benzyl or hydroxybenzyl replace.)

[8] according to [7] described crystal aligning agent, the wherein said diamines that does not have side-chain radical is at least a with the represented diamines of formula (IV-1), formula (IV-2), formula (IV-15)～formula (IV-17), formula (V-1)～formula (V-12), formula (V-33), formula (V-35)～formula (V-37), formula (VI-7), formula (VII-2) and formula (XV-1).

[9] according to [a 1] described crystal aligning agent, wherein said polymkeric substance is the mixture of following polyamic acid or its derivative, it is for making with at least a of the represented diamines of formula (N) and at least a mixture that is selected from the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII), perhaps comprise at least a with the represented diamines of formula (N), be selected from least a with the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII), and be selected from least a mixture with the diamines that does not have side-chain radical in formula (I)～formula (VII) and the represented diamines cohort of formula (XV), the polyamic acid or its derivative that react with the tetracarboxylic dianhydride and obtain, and at least a at least a mixture with the represented diamines of formula (N) of at least a or described diamines that does not have a side-chain radical that makes the described diamines that does not have a side-chain radical, the polyamic acid that reacts with the tetracarboxylic dianhydride and obtain or the mixture of its derivative.

(wherein, A ³For singly-bound ,-O-,-CO-,-COO-,-OCO-,-CONH-,-CH ₂O-,-CF ₂O-or carbon number are 1～6 alkylidene group, in described alkylidene group arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces; R ¹For group, the carbon number with steroid skeleton be 3～30 alkyl, have carbon number be 1～30 alkyl or carbon number be 1～30 alkoxyl group as substituent phenyl or with the represented group of formula (IX), described carbon number be in 3～30 alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces.)

(wherein, A ⁴And A ⁵Independently for singly-bound ,-O-,-COO-,-OCO-,-CONH-, carbon number are that 1～4 alkylidene group, carbon number are that 1～3 oxygen base alkylidene group or carbon number are 1～3 alkylidene group oxygen base; Ring B and ring C are Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene independently; R ²And R ³Be fluorine or methyl independently, f and g are 0,1 or 2 independently; C, d and e are 0～3 integer independently, they add up to more than or equal to 1; R ⁴For carbon number be 1～30 alkyl, carbon number is that 1～30 alkoxyl group or carbon number are 2～30 alkoxyalkyl, in these alkyl, alkoxyl group and alkoxyalkyl, hydrogen can be replaced by fluorine arbitrarily, and arbitrarily-CH ₂-can be replaced by difluoro methylene.)

H ₂N-X-NH ₂ (I)

(in these chemical formulas, X is that carbon number is 2～12 straight-chain alkyl-sub-; Y be independently singly-bound ,-O-,-CO-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-O-(CH ₂) _t-O-,-S-,-S-S-,-SO ₂-,-S-(CH ₂) _t-S-or carbon number are 1～12 straight-chain alkyl-sub-, and t is 1～12 integer; Z ¹And Z ²For hydrogen, when Y be-NH-,-N (CH ₃)-,-CH ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-time, Z ¹With Z ²Bond and form singly-bound mutually; Ring D is phenylene or Isosorbide-5-Nitrae-diaza cyclohexylidene; R ³³And R ³⁴Be respectively 1～3 alkyl or phenyl independently for carbon number; A ³Be 1～6 alkylidene group, phenylene or the phenylene that replaces through alkyl for carbon number independently; M is 1～10 integer; Any hydrogen of cyclohexane ring or phenyl ring can by fluorine, methyl ,-OH ,-COOH ,-SO ₃H ,-PO ₃H ₂, benzyl or hydroxybenzyl replace.)

[10] according to [a 1] described crystal aligning agent, wherein said polymkeric substance is the mixture of following polyamic acid or its derivative, it is for making with at least a of the represented diamines of formula (N) and at least a mixture that is selected from the diamines that does not have side-chain radical in formula (I)～formula (VII) and the represented diamines cohort of formula (XV), the polyamic acid or its derivative that react with the tetracarboxylic dianhydride and obtain, and make at least a or the described at least a and described at least a mixture that does not have the diamines of side-chain radical with diamines of side-chain radical that is selected from the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII), the polyamic acid that reacts with the tetracarboxylic dianhydride and obtain or the mixture of its derivative.

H ₂N-X-NH ₂ (I)

[11] according to [9] item or [10] described crystal aligning agent, wherein said is with formula (N-1)～formula (N-5) with the represented diamines of formula (N), formula (N-7), formula (N-8), formula (N-13), formula (N-15) or the represented diamines of formula (N-16), described diamines with side-chain radical is with formula (VIII-2), formula (VIII-4)～formula (VIII-6), formula (XII-2), formula (XII-4) or the represented diamines of formula (XII-6), and the described diamines that does not have side-chain radical is with formula (IV-1), formula (IV-2), formula (IV-15)～formula (IV-17), formula (V-1)～formula (V-12), formula (V-33), formula (V-35)～formula (V-37), formula (VI-7), formula (VII-2) or the represented diamines of formula (XV-1).

(in these chemical formulas, Me refers to methyl.)

[12] according to the described crystal aligning agent of any one in [1] to [11] item, wherein said tetracarboxylic dianhydride is the mixture of the tetracarboxylic dianhydride beyond aromatic tetracarboxylic acid's dianhydride or aromatic tetracarboxylic acid's dianhydride and aromatic series.

[13] according to [12] described crystal aligning agent, wherein said aromatic tetracarboxylic acid's dianhydride is to be selected from least a with in the represented compound cohort of formula (1), formula (2), formula (5)～formula (7), formula (11) and formula (14).

[14] according to [a 13] described crystal aligning agent, wherein said aromatic tetracarboxylic acid's dianhydride is with the represented compound of formula (1).

[15] according to [a 12] described crystal aligning agent, the tetracarboxylic dianhydride beyond wherein said aromatic series is ester ring type tetracarboxylic dianhydride and/or aliphatics tetracarboxylic dianhydride.

[16] according to [a 12] described crystal aligning agent, wherein said aromatic tetracarboxylic acid's dianhydride is to be selected from least a with in the represented compound cohort of formula (1), formula (2), formula (5)～formula (7), formula (11) and formula (14), and the tetracarboxylic dianhydride beyond described aromatic series is selected from least a with in the represented compound cohort of formula (19), formula (23), formula (25), formula (35)～formula (39), formula (44) and formula (49).

[17] according to [a 16] described crystal aligning agent, wherein said aromatic tetracarboxylic acid's dianhydride is with the represented compound of formula (1), and the tetracarboxylic dianhydride beyond described aromatic series is with the represented compound of formula (19).

[18] according to the described crystal aligning agent of any one in [1] to [17] item, wherein said crystal aligning agent further contains at least a compound that is selected from the Na Dike of alkenyl substituted imide (nadiimide) compound, the compound with free-radical polymerised unsaturated double-bond, oxazine (oxazine) compound, oxazoline (oxazoline) compound and epoxy compounds.

[19] a kind of liquid crystal orienting film, wherein said liquid crystal orienting film are to form through heating according to filming of the described crystal aligning agent of any one in [1] to [18] item.

[20] a kind of liquid crystal display device, it comprises a pair of substrate, to contain liquid crystal molecule and be formed at liquid crystal layer between described a pair of substrate, liquid crystal layer is executed alive electrode and made described liquid crystal alignment be the liquid crystal orienting film of prescribed direction, and described liquid crystal display device is characterised in that: described liquid crystal orienting film is according to [a 19] described liquid crystal orienting film.

Crystal aligning agent of the present invention contains reaction product polyamic acid or its derivative of tetracarboxylic dianhydride and diamines.The example of the derivative of this polyamic acid is soluble polyimide, poly amic acid ester, polyamic acid acid amides etc.More specifically, can enumerate: 1) polyamic acid carries out the polyimide, 2 that cyclodehydration forms fully) polyamic acid is partial carries out the part polyimide, 3 that cyclodehydration reaction forms) carboxyl of polyamic acid is converted into the poly amic acid ester of ester, 4) mixture that makes tetracarboxylic dianhydride and organic dicarboxylic acid reacts and polyamic acid-polyamide copolymer and 5 of obtaining) make this polyamic acid-polyamide copolymer part or all carry out the polyamidoimide that cyclodehydration forms.And the preferred example of the derivative of polyamic acid is polyimide.Crystal aligning agent of the present invention is the constituent that contains at least a polymkeric substance in the cohort that the derivative that selects free polyamic acid and this polyamic acid forms.

Use at least a with the represented diamines of formula (N) in the present invention.

In formula (N), A ¹Alkyl, the carbon number that is 1～10 for carbon number independently is 1～10 alkoxyl group, hydroxyl, trifluoromethyl, fluorine, chlorine or bromine.A ¹Preferred example be that carbon number is that 1～3 alkyl, carbon number are 1～3 alkoxyl group, hydroxyl and trifluoromethyl.A ¹More preferably example be methyl, methoxyl group, hydroxyl and trifluoromethyl.M is 0～3 integer independently, preferably is 0 or 1.A ²Be independently-O-,-NH-,-N (CH ₃)-or-S-.Two A ²Be preferably identical coordinating group.Two amino for the bond position of phenyl ring for except A ¹And A ²The bond position beyond optional position, preferably all with respect to A ²And be binding on contraposition.

Below list the preferred example of diamines (N).

(Me in these chemical formulas refers to methyl.)

In described diamines, preferred diamines (N-1)～diamines (N-5), diamines (N-7), diamines (N-8), diamines (N-13), diamines (N-15) and diamines (N-16), more preferably diamines (N-1) and diamines (N-3).

While making the polymkeric substance in crystal aligning agent of the present invention, can only use diamines (N), also can be with this diamines with other diamines, namely with the represented diamines of formula (N), do not mix to use.Show required ion density from make liquid crystal display device, and the viewpoint that realizes the permanent stability of described ion density is considered, the total amount of the diamines that uses during with respect to the described polymkeric substance of manufacturing, the usage ratio of diamines (N) is preferably 5 % by mole～100 % by mole, more preferably 5 % by mole～50 % by mole.

In addition, other diamines, according to the difference of its structure, can be divided into two kinds.That is, when the skeleton of bond two amino was regarded main chain as, described other diamines were that having from the group of main chain top set is the diamines of side-chain radical and the diamines that does not have side-chain radical., by diamines and tetracarboxylic dianhydride with side-chain radical are reacted, obtain to have polyamic acid or the polyimide of most side-chain radicals on the main chain of polymkeric substance.While using this polyamic acid that has side-chain radical on main polymer chain or polyimide, can be increased the tilt angle (pretilt angle) of liquid crystal display device by the formed liquid crystal orienting film of the crystal aligning agent that contains this polymkeric substance.That is, this side-chain radical is the group with the effect that increases tilt angle.Side-chain radical with this effect must be carbon number more than or equal to 3 group, and the object lesson of this side-chain radical can be enumerated: carbon number more than or equal to 3 alkyl, carbon number more than or equal to 3 alkoxyl group, carbon number more than or equal to 3 alkoxyalkyl and the group with steroid skeleton.Ring with one or more ring and its end has carbon number and as substituent group also has the effect of side-chain radical more than or equal to 1 alkoxyl group and carbon number more than or equal to any in 2 alkoxyalkyl more than or equal to 1 alkyl, carbon number.Side-chain radical in the present invention is to be selected from these groups.In the following description, sometimes this diamines with side-chain radical is called the side chain type diamines.And, sometimes will not have carbon number and be called non-side chain type diamines more than or equal to the diamines of 3 side-chain radical.

And,, by side chain type diamines and non-side chain type diamines are suitably separately used, can tackle the required tilt angle separately of described various display elements.That is, take twisted nematic (TwistedNematic, TN) mode or vertical orientation (Vertical Aligned, VA) mode in the longitudinal electric field mode of representative, because need larger tilt angle, so mainly use the side chain type diamines.At this moment,, in order further to control tilt angle, may be used 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,, by suitable selection side-chain radical, also can only use the side chain type diamines to deal with.In Transverse electric-field type, because tilt angle is little, and need higher LCD alignment, so can use at least a of non-side chain type diamines.Like this, crystal aligning agent of the present invention can be applied to the liquid crystal display device of any kind.

The object lesson of side-chain radical is as follows.

At first, can enumerate: alkyl, alkyl oxy, alkyl oxy alkyl, alkyl-carbonyl, alkyl-carbonyl oxygen base, alkyl oxy carbonyl, alkyl amino-carbonyl, thiazolinyl, thiazolinyl oxygen base, alkenyl carbonyl, alkenyl carbonyl oxygen base, thiazolinyl oxygen base carbonyl, alkenyl amino carbonyl, alkynyl, alkynyloxy base, alkynyl carbonyl, alkynyl ketonic oxygen base, alkynyloxy base carbonyl, alkynyl aminocarboxyl etc.And the alkyl in these groups, thiazolinyl and alkynyl are carbon number more than or equal to 3 group.Wherein, in the alkyl oxy alkyl, all carbon numbers get final product more than or equal to 3.In addition, these groups can be the straight chain shapes, can be also chains.

secondly, has carbon number more than or equal to 1 alkyl with the ring of end, it is condition that carbon number is used as substituting group more than or equal to 1 alkoxyl group or carbon number more than or equal to 2 alkoxyalkyl, can enumerate: phenyl, phenylalkyl, phenylalkyl oxygen base, phenyl oxygen base, phenylcarbonyl group, phenylcarbonyl group oxygen base, phenyl oxygen base carbonyl, the phenyl amino carbonyl, benzyl ring hexyl oxygen base, carbon number is more than or equal to 3 cycloalkyl, the cyclohexyl alkyl, cyclohexyl oxygen base, cyclohexyl oxygen base carbonyl, cyclohexyl phenyl, the cyclohexyl phenyl alkyl, cyclohexyl phenyl oxygen base, two (cyclohexyl) oxygen base, two (cyclohexyl) alkyl, two (cyclohexyl) phenyl, two (cyclohexyl) phenylalkyl, two (cyclohexyl) oxygen base carbonyl, two (cyclohexyl) phenyl oxygen base carbonyl, and the group of the ring structure such as two (phenyl) oxygen base carbonyls of cyclohexyl.

in addition, can be listed below the set cyclic group, it is the group with two or more phenyl ring, group with two or more cyclohexane rings, two rings or the two above groups of ring that perhaps by phenyl ring and cyclohexane ring, are formed, the coordinating group of described set cyclic group is singly-bound independently,-O-,-COO-,-OCO-,-CONH-or carbon number are 1～3 alkylidene group, and the ring of end has carbon number more than or equal to 1 alkyl, carbon number is more than or equal to 1 the alkyl that replaces through fluorine, carbon number is more than or equal to 1 alkoxyl group, perhaps carbon number more than or equal to 2 alkoxyalkyl as substituting group.Certainly, has a group of steroid skeleton also effective as side-chain radical.

The preferred example of side chain type diamines is with formula (VIII) and formula (X)～represented diamines of formula (XIII).

In formula (VIII), A ³For singly-bound ,-O-,-CO-,-COO-,-OCO-,-CONH-,-CH ₂O-,-CF ₂O-or carbon number are 1～6 alkylidene group, in alkylidene group arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces A ³Preferred example be singly-bound ,-O-,-COO-,-OCO-,-CH ₂O-and carbon number are 1～3 alkylidene group, more preferred example be singly-bound ,-O-,-COO-,-OCO-,-CH ₂O-,-CH ₂-and-CH ₂CH ₂-.R ¹For group, the carbon number with steroid skeleton be 3～30 alkyl, have carbon number be 1～30 alkyl or carbon number be 1～30 alkoxyl group as substituent phenyl or with the represented group of formula (IX), this carbon number be in 3～30 alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces.R ¹Preferred example be that carbon number is 3～30 alkyl, to have carbon number be that 1～30 alkyl or carbon number are that 1～30 alkoxyl group is as substituent phenyl and with the represented group of formula (IX).When with A ³Bond position during as 1, the bond location optimization of two amino and phenyl ring be 3 with 5 or 2 with 5.

In formula (IX), A ⁴And A ⁵Independently for singly-bound ,-O-,-COO-,-OCO-,-CONH-, carbon number are that 1～4 alkylidene group, carbon number are that 1～3 oxygen base alkylidene group or carbon number are 1～3 alkylidene group oxygen base, are preferably singly-bound or carbon number and are 1～4 alkylidene group.Ring B and ring C are Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene independently.R ²And R ³Be fluorine or methyl independently.F and g are 0,1 or 2 independently, are preferably 0.C, d and e are 0～3 integer independently, they add up to more than or equal to 1.R ⁴For carbon number be 1～30 alkyl, carbon number is that 1～30 alkoxyl group or carbon number are 2～30 alkoxyalkyl, in these alkyl, alkoxyl group and alkoxyalkyl, hydrogen can be replaced by fluorine arbitrarily, and arbitrarily-CH ₂-can be replaced by difluoro methylene.R ⁴Preferred example be that carbon number is that 1～30 alkyl and carbon number are 1～30 alkoxyl group.

In formula (X) and formula (XI), R ⁵Be hydrogen or methyl independently.R ⁶For hydrogen, carbon number are that 1～20 alkyl or carbon number are 2～20 thiazolinyl.R ⁷And R ⁸Be respectively 1～20 alkyl or phenyl independently for carbon number.A ⁶Be independently singly-bound ,-CO-or-CH ₂-.In formula (X), be preferably two " NH ₂-Ph-A ⁶-O-" one of them be binding on 3 of steroid skeleton, another is binding on 6.In addition, the bond location optimization of two amino and phenyl ring is for all with respect to A ⁶The bond position be between the position or contraposition.In formula (XI), two " NH ₂-(R ⁶-) Ph-A ⁶-O-" and the bond location optimization of phenyl ring for the carbon of all with respect to steroid skeleton institute bond, be between or contraposition.In addition, the bond location optimization of two amino and phenyl ring is for all with respect to A ⁶The bond position be between the position or contraposition.

In formula (XII) and formula (XIII), R ⁹Be 1～30 alkyl for carbon number, in this alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces R ¹⁰Be 6～22 alkyl for carbon number, R ¹¹It is 1～22 alkyl for carbon number.A ⁷Be 1～6 alkylidene group independently for-O-or carbon number.A ⁸It is 1～3 alkylidene group for singly-bound or carbon number.Ring T is Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene.H is 0 or 1.In formula (XII), the bond location optimization of two amino and phenyl ring is for all with respect to A ⁷The bond position be between the position or contraposition.In formula (XIII), the bond location optimization of two amino and phenyl ring is for all with respect to A ⁷The bond position be between the position or contraposition.

Below list the object lesson of diamines (VIII).

In formula (VIII-1)～formula (VIII-11), R ²³, for carbon number is that 1～30 alkyl or carbon number are 1～30 alkoxyl group, be preferably carbon number and be 5～25 alkyl or carbon number and be 5～25 alkoxyl group.R ²⁴, for carbon number is that 1～30 alkyl or carbon number are 1～30 alkoxyl group, be preferably carbon number and be 3～25 alkyl or carbon number and be 3～25 alkoxyl group.

In formula (VIII-12)～formula (VIII-17), R ²⁵Be 4～30 alkyl for carbon number, be preferably carbon number and be 6～25 alkyl.R ²⁶Be 6～30 alkyl for carbon number, be preferably carbon number and be 8～25 alkyl.

In formula (VIII-18)～formula (VIII-37), R ²⁷, for carbon number is that 1～30 alkyl or carbon number are 1～30 alkoxyl group, be preferably carbon number and be 3～25 alkyl or carbon number and be 3～25 alkoxyl group.R ²⁸For hydrogen, fluorine, carbon number be 1～30 alkyl, carbon number be 1～30 alkoxyl group ,-CN ,-OCH ₂F ,-OCHF ₂Perhaps-OCF ₃, be preferably carbon number and be 3～25 alkyl or carbon number and be 3～25 alkoxyl group.

In described diamines (VIII-1)～diamines (VIII-43), preferred diamines (VIII-1)～diamines (VIII-11), more preferably diamines (VIII-2) and diamines (VIII-4)～diamines (VIII-6).

Below list the object lesson of diamines (X).

Below list the object lesson of diamines (XI).

Below list the object lesson of diamines (XII).

In formula (XII-1)～formula (XII-3), R ²⁹, for carbon number is that 1～30 alkyl or carbon number are 1～30 alkoxyl group, be preferably carbon number and be 3～30 alkyl or carbon number and be 3～30 alkoxyl group.In formula (XII-4)～formula (XII-8), R ³⁰, for carbon number is that 1～30 alkyl or carbon number are 1～30 alkoxyl group, be preferably carbon number and be 3～30 alkyl or carbon number and be 3～30 alkoxyl group.

Below list the object lesson of diamines (XIII).

In formula (XIII-1)～formula (XIII-3), R ³¹Be 6～22 alkyl for carbon number, be preferably carbon number and be 6～20 alkyl.R ³²Be 1～22 alkyl for carbon number, be preferably carbon number and be 1～10 alkyl.

In the object lesson of described side chain type diamines, preferred diamines (VIII-2), diamines (VIII-4)～diamines (VIII-6), diamines (XII-2), diamines (XII-4) and diamines (XII-6).

In the situation that in order to make liquid crystal display device show larger tilt angle, while making the polymkeric substance that uses in crystal aligning agent of the present invention, preferably the ratio of side chain type diamines as above in the diamines total amount is made as 1 % by mole～90 % by mole, more preferably is made as 5 % by mole～70 % by mole.

The diamines that does not have a side-chain radical as above, be that the preferred example of non-side chain type diamines can be enumerated with formula (I)～formula (VII) and the represented compound of formula (XV).

H ₂N-X-NH ₂ (I)

In these chemical formulas, X is that carbon number is 2～12 straight-chain alkyl-sub-.Y be independently singly-bound ,-O-,-CO-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-O-(CH ₂) _t-O-,-S-,-S-S-,-SO ₂-,-S-(CH ₂) _t-S-or carbon number are 1～12 straight-chain alkyl-sub-, and t is 1～12 integer.Z ¹And Z ²For hydrogen, when Y be-NH-,-N (CH ₃)-,-CH ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-time, Z ¹With Z ²Bond and form singly-bound mutually.Ring D is phenylene or Isosorbide-5-Nitrae-diaza cyclohexylidene.R ³³And R ³⁴Be respectively 1～3 alkyl or phenyl independently for carbon number.A ³Be 1～6 alkylidene group, phenylene or the phenylene that replaces through alkyl for carbon number independently.M is 1～10 integer.Any hydrogen of cyclohexane ring or phenyl ring can by fluorine, methyl ,-OH ,-COOH ,-SO ₃H ,-PO ₃H ₂, benzyl or hydroxybenzyl replace.

Below list the example of diamines (I).

H ₂N(CH ₂) ₂NH ₂ H ₂N(CH ₂) ₄NH ₂ H ₂N(CH ₂) ₆NH ₂

(I-1) (1-2) (1-3)

Below list the object lesson of diamines (II).

Below list the object lesson of diamines (III).

Below list the object lesson of diamines (IV).

Below list the object lesson of diamines (V).

Below list the object lesson of diamines (VI).

Below list the object lesson of diamines (VII).

Below list the object lesson of diamines (XV).

in described non-side chain type diamines, preferred diamines (IV-1)～diamines (IV-5), diamines (IV-15)～diamines (IV-17), diamines (V-1)～diamines (V-12), diamines (V-26), diamines (V-27), diamines (V-31), diamines (V-33), diamines (V-35)～diamines (V-37), diamines (VI-1), diamines (VI-2), diamines (VI-6), diamines (VII-1)～diamines (VII-5) and diamines (XV-1), more preferably diamines (IV-1), diamines (IV-2), diamines (IV-15)～diamines (IV-17), diamines (V-1)～diamines (V-12), diamines (V-33), diamines (V-35)～diamines (V-37), diamines (VI-7), diamines (VII-2) and diamines (XV-1).

Show the viewpoint consideration of the required electrical characteristic such as ion density from make liquid crystal display device, the raw material of the polyamic acid of described non-side chain type diamines in crystal aligning agent of the present invention is in the diamines total amount, preferably with molar ratio computing, contain 1%～98%, more preferably contain 10%～95%.

In the diamines that uses in the present invention, can use described diamines (I)～diamines (VIII), diamines (X)～diamines (XIII) and diamines (XV) diamines in addition.It is diamines and diamines (VIII)～diamines (XII) side chain type diamines in addition that such diamines can be enumerated the fluorenes that for example has fluorenes (fluorene) ring.

The example of diamines (VIII)～diamines (XII) side chain type diamines in addition is diamines (1 ')～diamines (8 ').

In these chemical formulas, R ³⁵And R ³⁶Be respectively 3～30 alkyl independently for carbon number.During polyamic acid in making crystal aligning agent of the present invention, these diamines can use in the scope of the degree that does not undermine effect of the present invention.

While making polyamic acid, can add monoamine in diamines., by adding monoamine, can cause the termination (termination) of the polyreaction while generating polyamic acid, thereby can suppress the carrying out of its above polyreaction.That is, can easily control the molecular weight of resulting polymers (polyamic acid or its derivative), for example can not undermine effect of the present invention and improve the coating characteristics of crystal aligning agent.The adding proportion of monoamine can be considered as the polyamic acid molecular weight of target and suitably adjust.Only otherwise undermine effect of the present invention, also can add two or more monoamine.The example of monoamine is aniline, 4-hydroxyanilines, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, dodecyl amine, n-tridecane base amine, n-tetradecane base amine, Pentadecane base amine, n-hexadecyl amine, n-heptadecane base amine, Octadecane base amine and NSC 62789 base amine.

In the following explanation except embodiment, unless otherwise specified, so polyamic acid with and the general name of derivative be to use " polyamic acid ".

In the present invention, diamines and tetracarboxylic dianhydride are reacted and while obtaining polyamic acid, can use as described above the mixture of diamines (N) and other diamines.At this moment, one of preferred example of other diamines is for being selected from least a of side chain type diamines in the cohort of diamines (VIII) and diamines (X)～diamines (XIII).Another preferred example of other diamines is at least a mixture of the non-side chain type diamines at least a cohort with being selected from diamines (I)～diamines (VII) and diamines (XV) that is selected from the side chain type diamines in the cohort of diamines (VIII) and diamines (X)～diamines (XIII).Described [5] to [8] are the preferred example of the combination of diamines (N), side chain type diamines and non-side chain type diamines.

In the present invention, can be with the polyamic acid that hybrid diamine and tetracarboxylic acid reacted and obtain as component of polymer, the mixture of polyamic acid that also can raw material is different is as component of polymer.One of preferred example of the mixture of polyamic acid is the mixture of following polyamic acid: make at least a of diamines (N) and at least a mixture that is selected from the side chain type diamines in the cohort of diamines (VIII) and diamines (X)～diamines (XIII) or further added at least a mixture of the non-side chain type diamines in the cohort that is selected from diamines (I)～diamines (VII) and diamines (XV) in this two amine mixt, and the tetracarboxylic dianhydride reacts and the polyamic acid that obtains; Make at least a mixture of at least a and diamines (N) of at least a of described non-side chain type diamines or this non-side chain type diamines, and the tetracarboxylic dianhydride reacts and the polyamic acid that obtains.

Another preferred example of the mixture of polyamic acid is the mixture of following polyamic acid: make at least a of diamines (N) and at least a mixture that is selected from the non-side chain type diamines in the cohort of diamines (I)～diamines (VII) and diamines (XV), and the tetracarboxylic dianhydride reacts and the polyamic acid that obtains; Make at least a mixture of at least a and described non-side chain type diamines of at least a or this side chain type diamines of the side chain type diamines in the cohort that is selected from diamines (VIII) and diamines (X)～diamines (XIII), and the tetracarboxylic dianhydride reacts and the polyamic acid that obtains.Having put down in writing component of polymer in the item of described [9] to [11] is the preferred example of the mixture of polyamic acid.

The tetracarboxylic dianhydride who uses in the present invention can be a kind of compound, can be also two or more compound.The tetracarboxylic dianhydride can enumerate aromatic tetracarboxylic acid's dianhydride, ester ring type tetracarboxylic dianhydride and aliphatics tetracarboxylic dianhydride.

Below list the example of aromatic tetracarboxylic acid's dianhydride.

In described aromatic tetracarboxylic acid's dianhydride, optimization acid (1), carboxylic acid (2), carboxylic acid (5)～carboxylic acid (7), carboxylic acid (11) and carboxylic acid (14), particularly preferably carboxylic acid (1).

Below list ester ring type tetracarboxylic dianhydride's example.

In described ester ring type tetracarboxylic dianhydride, optimization acid (19), carboxylic acid (25), carboxylic acid (35)～carboxylic acid (37), carboxylic acid (39), carboxylic acid (44) and carboxylic acid (49), more preferably carboxylic acid (19).

Below list aliphatics tetracarboxylic dianhydride's example.Optimization acid in following example (23).

In the present invention, also can use described carboxylic acid (1)～carboxylic acid (67) tetracarboxylic dianhydride in addition.This tetracarboxylic dianhydride's example can be enumerated the tetracarboxylic dianhydride with side-chain radical.The tetracarboxylic dianhydride who has side-chain radical by use, can increase the tilt angle of liquid crystal display device.Tetracarboxylic dianhydride with side-chain radical for example can enumerate carboxylic acid (68) and the carboxylic acid (69) with steroid skeleton.

When making polyamic acid, can add dicarboxylic anhydride in the tetracarboxylic dianhydride and use.So, the termination of the polyreaction while generating polyamic acid can be caused, thereby the carrying out of its above polyreaction can be suppressed.That is, can easily control the molecular weight of resulting polymers (polyamic acid), for example can not undermine effect of the present invention and improve the coating characteristics of crystal aligning agent.The adding proportion of dicarboxylic anhydride can be considered as the polyamic acid molecular weight of target and suitably adjust.In addition, only otherwise undermine effect of the present invention, the kind of the dicarboxylic anhydride that adds can be also two or more.The example of dicarboxylic anhydride is MALEIC ANHYDRIDE (maleic anhydride), Tetra hydro Phthalic anhydride (phthalic anhydride), methene succinic acid acid anhydride (itaconic anhydride), positive decyl succinic anhydride (n-decyl succinic anhydride), dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide and hexamethylene acid anhydrides.

In the present invention, when making polyamic acid, also can further add monoisocyanates (monoisocyanate) compound.By adding the monoisocyanates compound, the end of gained polyamic acid is modified, and molecular weight is adjusted., by this end modified type polyamic acid of use, for example can not undermine effect of the present invention and improve the coating characteristics of crystal aligning agent.Consider from described viewpoint, the addition of monoisocyanates compound is preferably 1 % by mole～10 % by mole with respect to diamines and tetracarboxylic dianhydride's total amount.The monoisocyanates compound for example can be enumerated phenylcarbimide and naphthyl isocyanate.

The polyamic acid that uses in the present invention can form with the film of polyimide the middle known polyamic acid that uses and similarly make.Tetracarboxylic dianhydride's total addition level preferably is roughly etc. mole (mol ratio is 0.9～1.1 left and right) with the total mole number of diamines.

The molecular weight of polyamic acid, with the weight average molecular weight (weight-average molecular weight, Mw) of polystyrene conversion meter, is preferably 10,000～500,000, and more preferably 20,000～200,000.The molecular weight of polyamic acid can be obtained according to the measured value of utilizing gel permeation chromatography (Gel Permeation Chromatography, GPC) method.

Polyamic acid can be by confirming its existence with infrared rays (Infrared, IR), nucleus magnetic resonance (NuclearMagnetic Resonance, NMR) to a large amount of poor solvents, precipitating the solids component analysis that obtains.By the strong alkaline aqueous solution that utilizes KOH or NaOH etc., polyamic acid is decomposed, again to the organic solvent extraction thing of its resolvent, utilize vapor-phase chromatography (GasChromatography, GC), high performance liquid chromatography (High Performance LiquidChromatography, HPLC) or gas chromatography-mass spectrography (Gas Chromatograph-MassSpectrometer, GC-MS) analyze, can confirm the raw material that uses.

Crystal aligning agent of the present invention can further contain other compositions beyond described polyamic acid.For example, from the viewpoint of the electrical characteristic long-term stability that makes liquid crystal display device, consider, crystal aligning agent of the present invention can further contain the imide compound through the Na Dike of alkenyl substituted.Below list the preferred example of this imide compound of Na Dike through alkenyl substituted.

For example from the viewpoint of the electrical characteristic long-term stability that makes liquid crystal display device, consider, crystal aligning agent of the present invention can further contain the compound with free-radical polymerised unsaturated double-bond.Compound with free-radical polymerised unsaturated double-bond, can enumerate: (methyl) acrylic acid derivative and two maleimides such as (methyl) acrylate, (methyl) acrylamide preferably have (methyl) acrylic acid derivatives of two or more free-radical polymerised unsaturated double-bonds.

In addition, for example from the viewpoint of the permanent stability of the electrical characteristic of liquid crystal display device, consider, crystal aligning agent of the present invention is Han You oxazine compounds further.The compound of oxazine compounds shown in for example can enumerative (a)～formula (f).

In formula (a)～formula (f), R ¹And R ²It is 1～30 organic group for carbon number; R ³～R ⁶It is 1～6 alkyl for hydrogen or carbon number; X be singly-bound ,-O-,-S-,-S-S-,-SO ₂-,-CO-,-CONH-,-NHCO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-(CH ₂) _m-,-O-(CH ₂) _m-O-,-S-(CH ₂) _m-S-, m are 1～6 integer; Y be independently singly-bound ,-O-,-S-,-CO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-or carbon number be 1～3 alkylidene group.

For example from the viewpoint of the permanent stability of the electrical characteristic of liquid crystal display device, consider, crystal aligning agent of the present invention can further contain in molecule the epoxy compounds with one or two or two above oxirane rings.This epoxy compounds can be monomer (monomer), oligopolymer (oligomer) or the polymkeric substance with oxirane ring.

Crystal aligning agent of the present invention can further contain various additives.Various additives for example can enumerate polyamic acid with and derivative beyond polymkeric substance and low molecular compound, can carry out choice for use according to various purposes.This polymkeric substance can be enumerated the polymkeric substance that dissolves in organic solvent.Consider from the viewpoint of the electrical characteristic of controlling formed liquid crystal orienting film or regiospecific, preferably such polymkeric substance is made an addition in crystal aligning agent of the present invention.This polymkeric substance for example can be enumerated: polymeric amide, urethane (polyurethane), polyureas (polyurea), polyester (polyester), polyepoxide (polyepoxide), polyester polyol (polyes ter polyol), organic silicon modified polyurethane (silicone modified polyurethane) and organosilicon modified polyester (siliconemodified polyester).

Described low molecular compound, for example: 1) when expectation improves coating, can enumerate the tensio-active agent that conforms to this purpose; 2) in the time that static resistance must be improved, can enumerate static inhibitor; 3) when the adherence of expecting raising and substrate or rub resistance, can enumerate silane coupling agent or titanium is coupler; In addition, 4) when carrying out imidization at low temperatures, can enumerate imidization catalyst.

silane coupling agent for example can be enumerated: 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, APTES, 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-(triethoxysilicane alkyl)-1-propylamine, and N, N '-two [3-(Trimethoxy silane base) propyl group] quadrol.

Imidization catalyst is such as enumerating: the aliphatics amines such as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine; DMA, N, N-Diethyl Aniline, the aromatic amines such as aniline that replace through methyl substituted aniline, through hydroxyl; Pyridine (pyridine), the pyridine that replaces through methyl substituted pyridine, through hydroxyl, quinoline (quinoline), the quinoline that replaces through methyl substituted quinoline, through hydroxyl, isoquinoline 99.9 (isoquinoline), the isoquinoline 99.9 that replaces through methyl substituted isoquinoline 99.9, through hydroxyl, imidazoles (imidazole), the ring type amines such as imidazoles that replace through methyl substituted imidazoles, through hydroxyl.Described imidization catalyst is preferably and is selected from DMA, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine, adjacent pyridone, a pyridone, to a kind of in pyridone and isoquinoline 99.9 or two or more.

Consider from the viewpoint of the adjustment of the concentration of the coating of crystal aligning agent or described polyamic acid, crystal aligning agent of the present invention can further contain solvent.This solvent so long as have the solvent of the ability of dissolve polymer composition, can be applied with no particular limitation.Described solvent extensively comprises the normally used solvent of manufacturing step or purposes aspect of the component of polymer such as polyamic acid, soluble polyimide, can suitably select according to application target.Described solvent can be a kind of solvent, can be also the mixed solvent of two or more solvent.Solvophilic or purpose that such solvent can be enumerated described polyamic acid are to improve other solvents of coating.

be solvophilic non-proton property polar organic solvent for polyamic acid, can enumerate: METHYLPYRROLIDONE (N-methyl-2-pyrrolidone), dimethyl-imidazolinone (dimethylimidazolidinone), N-methyl caprolactam (N-methyl caprolactam), N-methyl propanamide (N-methyl propionamide), N, N-N,N-DIMETHYLACETAMIDE (N, N-dimethylacetamide), dimethyl sulfoxide (DMSO) (dimethyl sulfoxide), N, dinethylformamide (N, N-dimethyl formamide), N, N-diethylformamide (N, N-diethylformamide), diethyl acetamide, gamma-butyrolactone (the lactone such as γ-butyrolactone).

purpose is to improve the example of other solvents of coating etc., can enumerate: lactic acid alkyl ester, 3-methyl-3-methoxybutanol, tetralin (tetralin), isophorone (isophorone), the ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, the Diethylene Glycol monoalky lethers such as diethylene glycol monoethyl ether, glycol monoalkyl or phenylacetic acid ester, the triethylene glycol monoalky lether, the propylene-glycol monoalky lether such as propylene glycol monomethyl ether and propylene glycol monobutyl ether, the dialkyl malonates such as diethyl malonate, the dipropylene glycol monoalky lethers such as dipropylene glycol monomethyl ether, their ester cpds such as acetate esters.

In these solvents, particularly preferred solvent is: METHYLPYRROLIDONE, N,N-dimethylacetamide, 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.

In the present invention, the concentration of the component of polymer that contains described polyamic acid in crystal aligning agent is not particularly limited, preferred 0.1 % by weight～40 % by weight.When being coated on this crystal aligning agent on substrate,, sometimes in order to adjust thickness, must carry out the operation that utilizes in advance solvent to be diluted contained component of polymer.At this moment, from the viscosity with crystal aligning agent, be adjusted into and be suitable for the easily viewpoint consideration of the viscosity of mixed solvent of crystal aligning agent, the concentration of described component of polymer is preferably less than or equal to 40 % by weight.

In addition, the also coating process of with good grounds crystal aligning agent situation about adjusting of the concentration of the described component of polymer in crystal aligning agent.When the coating process of crystal aligning agent is turner (spinner) method or print process, for thickness being remained well, the concentration of described component of polymer is generally less than or equal to 10 % by weight.While utilizing other coating processes for example to flood (dipping) method or ink-jet (inkjet) method, also further reduce possibly concentration.On the other hand, if the concentration of described component of polymer is more than or equal to 0.1 % by weight, the thickness of gained liquid crystal orienting film easily becomes best so.Therefore, the concentration of described component of polymer is more than or equal to 0.1 % by weight in common turner method or print process etc., be preferably 0.5 % by weight～10 % by weight.But,, according to the coating process of crystal aligning agent, also can use under lower concentration.

In addition, in the situation that described crystal aligning agent is used for making liquid crystal orienting film, the viscosity of crystal aligning agent of the present invention can decide according to mechanism or the method for the film that forms this crystal aligning agent.For example, when with printing press, forming the film of crystal aligning agent, consider from the viewpoint that obtains sufficient thickness, the viscosity of crystal aligning agent of the present invention is preferably more than and equals 5mPas, consider from suppressing the uneven viewpoint of printing in addition, the viscosity of crystal aligning agent of the present invention is preferably less than or equal to 100mPas, more preferably 10mPas～80mPas.While when utilizing spin-coating method (spin coat) to carry out coating of liquid crystalline orientation agent, forming the film of crystal aligning agent, from same viewpoint, consider, the viscosity of crystal aligning agent of the present invention is preferably 5mPas～200mPas, more preferably 10mPas～100mPas.The viscosity of crystal aligning agent can be by utilizing solvent dilution or follow the slaking of stirring to reduce.

Liquid crystal orienting film of the present invention is the film of filming and forming through heating of described crystal aligning agent of the present invention.Liquid crystal orienting film of the present invention can obtain by the usual method of being made liquid crystal orienting film by crystal aligning agent, the step of filming that for example liquid crystal orienting film of the present invention can be by forming crystal aligning agent of the present invention, and will describedly film and heat the step of calcining and obtain., for liquid crystal orienting film of the present invention, optionally can carry out to the film that obtains in described calcining step friction treatment (rubbing process).

Described film with the making of common liquid crystal orienting film similarly, also can form by coating crystal aligning agent of the present invention on the substrate of liquid crystal display device.Described substrate can be enumerated the glass substrate processed of the electrodes such as tin indium oxide (Indium Tin Oxide, ITO) electrode can be set or colored filter (colorfilter) etc.

Crystal aligning agent is coated on method on substrate, common known turner method, print process, pickling process, falling drop method (falling-drop method), ink jet method etc.These methods can be applied in the present invention too.

Described calcining of filming can present under the necessary condition of cyclodehydration reaction and carry out at described polyamic acid.Described calcining of filming usually known method of carrying out heat treated in baking oven (oven) or infra-red furnace, carry out the method for heat treated etc. on hot-plate (hot plate).These methods equally also can be applied in the present invention.Usually preferably carried out at the temperature of 150 ℃～300 ℃ of left and right 1 minute～3 hours.

Described friction treatment can be commonly used to that liquid crystal orienting film is carried out the friction treatment that orientation processes and similarly carry out, get final product so long as obtain fully to postpone the condition of (retardation) in liquid crystal orienting film of the present invention.Particularly preferred condition is, the hair amount of being pressed into is 0.2mm～0.8mm, and platform movement speed is 5mm/sec～250mm/sec, and drum rotational speed is 500rpm～2,000rpm.The orientation processing method of liquid crystal orienting film except rubbing manipulation, usually known smooth orientation method or transfer printing etc.In the scope that can obtain effect of the present invention, can and be used for described friction treatment with these other orientation processing methods.

Liquid crystal orienting film of the present invention can utilize the method that further comprises other steps except described step and obtain aptly.Other steps like this can be enumerated the step that makes described dried coating film or the step of the film before and after friction treatment being cleaned with scavenging solution etc.

Drying step and described calcining step similarly, usually knownly carry out the method for heat treated, carry out the method for heat treated etc. on hot-plates in baking oven or infra-red furnace.These methods can be applied in described drying step too.Drying step is preferably implemented at the temperature in the scope that solvent can evaporate, and more preferably with the temperature of described calcining step, is comparing at relatively low temperature and is implementing.

Utilize scavenging solution to the purging method that the liquid crystal orienting film before and after the orientation processing cleans, can enumerate: scrub (brushing), spraying (jet spray), steam purge or ultrasonic cleaning etc.These methods can be carried out separately, also may be used.Scavenging solution can use: pure water, perhaps various alcohols such as methyl alcohol, ethanol, Virahol, benzene,toluene,xylenes etc. are aromatic hydrocarbon based, the halogen series solvents such as methylene dichloride (methylene chloride), the ketone such as acetone, methyl ethyl ketone, but be not limited to these scavenging solutions.Certainly, these scavenging solutions are to use through abundant purifying and the few scavenging solution of impurity.Such purging method also can be applied to form in the described cleaning step of liquid crystal orienting film of the present invention.

The thickness of liquid crystal orienting film of the present invention is not particularly limited, and is preferably 10nm～300nm, more preferably 30nm～150nm.The thickness of liquid crystal orienting film of the present invention can utilize the known determining film thickness devices such as surface profiler (profilometer) or ellipsometer (ellipsometer) to measure.

Liquid crystal display device of the present invention has: a pair of substrate, to contain liquid crystal molecule and be formed at liquid crystal layer between described a pair of substrate, liquid crystal layer is executed alive electrode and made liquid crystal alignment be the liquid crystal orienting film of the present invention of prescribed direction.

Substrate can use at the glass substrate processed described in liquid crystal orienting film of the present invention, and electrode can use the ITO electrode that is formed at as described in liquid crystal orienting film of the present invention on glass substrate processed.Liquid crystal layer is formed by the liquid-crystal composition that is sealed between substrate, and described substrate is take the LCD alignment face as inboard.

There is no particular restriction for the liquid-crystal composition that uses, and can use the various liquid-crystal compositions of dielectric anisotropy (dielectric anisotropy) as plus or minus.dielectric anisotropy is that positive preferred liquid-crystal composition can be enumerated the liquid-crystal composition that discloses in following communique: No. 3086228 communique of Japanese Patent, No. 2635435 communique of Japanese Patent, Japanese Patent JP-A 5-501735 communique, 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, Japanese Patent Laid-Open 2000-087040 communique, Japanese Patent Laid-Open 2001-48822 communique etc.

dielectric anisotropy is that the preferred liquid-crystal composition of bearing can be enumerated the liquid-crystal composition that discloses in following communique: the clear 57-114532 communique of Japanese Patent Laid-Open, 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, Japanese Patent Laid-Open 2000-256307 communique, Japanese Patent Laid-Open 2001-019965 communique, Japanese Patent Laid-Open 2001-072626 communique, Japanese Patent Laid-Open 2001-192657 communique etc.

Even in described dielectric anisotropy, be that the optically active compound that adds one or more in the liquid-crystal composition of plus or minus uses also not at all impact.

Liquid crystal display device of the present invention can form various Electric Field Mode liquid crystal display device.This Electric Field Mode can be enumerated with liquid crystal display device: described electrode with liquid crystal display device or described electrode with respect to described substrate surface is being vertical direction on described liquid crystal layer to be executed alive longitudinal electric field mode liquid crystal display device on the direction that is level, described liquid crystal layer being executed alive Transverse electric-field type with respect to described substrate surface.

Even it is harmless that Transverse electric-field type does not show larger tilt angle with liquid crystal display device yet.Therefore, Transverse electric-field type is with suitable use in liquid crystal display device by the formed liquid crystal orienting film of the crystal aligning agent that contains non-side chain type polyamic acid, and this non-side chain type polyamic acid uses non-side chain type diamines and obtains.

The longitudinal electric field mode need to show larger tilt angle with liquid crystal display device.Therefore, the longitudinal electric field mode is with suitable use in liquid crystal display device by the formed liquid crystal orienting film of the crystal aligning agent that contains the side chain type polyamic acid, and two amine mixt that this side chain type polyamic acid uses side chain type diamines or contains this side chain type diamines obtain.

So, the liquid crystal orienting film that crystal aligning agent of the present invention is made as raw material can pass through suitably selection as the polymkeric substance of this raw material, and is 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 described integrant.About this other integrants, the normally used integrant in 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.

[embodiment]

Below, coming by embodiment that the present invention will be described, the present invention is not limited to these embodiment.The compound that uses in embodiment is as described below.

＜tetracarboxylic dianhydride 〉

Carboxylic acid (1): pyromellitic acid anhydride (pyromellitic dianhydride)

Carboxylic acid (19): 1,2,3,4-tetramethylene tetracarboxylic acid dianhydride

＜diamines 〉

Diamines (VI-7): Isosorbide-5-Nitrae-two (4-aminophenyl)-Isosorbide-5-Nitrae-diaza-cyclohexane

Diamines (V-1): 4,4 '-diaminodiphenyl-methane

Two (4-aminophenyl) ethane of diamines (V-7): 1,2-

Two [4-(4-amino-benzene oxygen) phenyl-4-(trans-4-n-pentyl cyclohexyl) hexanaphthenes of diamines (XII-4-1): 1,1-

Two [4-(4-aminophenyl methyl) the phenyl]-4-n-heptyl hexanaphthenes of diamines (XII-2-1): 1,1-

Diamines (N-1): Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) naphthalene

Diamines (V-36): N, N '-two (4-aminophenyl)-N, N '-dimethyl-ethylenediamine

＜solvent 〉

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

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

＜1. polyamic acid is synthetic 〉

[synthesis example 1]

In the 100mL four-hole boiling flask that possesses thermometer, stirrer, raw material input interpolation mouth and nitrogen inlet, add the diamines (VI-7) of 2.242g, the diamines (N-1) of 1.072g, the diamines (XII-2-1) of 0.569g and the dehydration NMP of 80.0g, at drying nitrogen, flow down and carry out stirring and dissolving.Then add the carboxylic acid (1) of 0.683g and the carboxylic acid (19) of 1.434g, make its reaction 30 hours under room temperature environment.When temperature of reaction in reaction process rises, temperature of reaction is suppressed at and makes its reaction less than or equal to 70 ℃.Then to adding the BC of 14.0g in the solution that obtains, obtaining concentration is the polyamic acid solution of 6 % by weight.With this polyamic acid as PA1.The weight average molecular weight of PA1 is 40,100.

The weight average molecular weight of polyamic acid is to obtain by the following method: utilize phosphoric acid-DMF mixing solutions (phosphoric acid/DMF=0.6/100: weight ratio) polyamic acid that obtains is diluted, so that polyamic acid concentration reaches approximately 1 % by weight, then use 2695 separation modules (separationmodule), 2414 differential refractometers (Waters manufacturing), with described mixing solutions as developping agent, utilize the GPC method to measure, then carry out polystyrene conversion.In addition, tubing string is to use HSPgel RTMB-M (Waters manufacturing), in the tubing string temperature, is that 40 ℃, flow velocity are to measure under the condition of 0.35mL/min.

[synthesis example 2～7]

, except such change tetracarboxylic dianhydride and diamines as shown in table 1, according to synthesis example 1, prepare polyamic acid solution (PA2)～(PA7).Comprise synthesis example 1, result is summarized in table 1.

＜table 1 〉

＜2. the making of liquid crystal display device 〉

[embodiment 1]

Being to add the mixed solvent of NMP/BC=1/1 (weight ratio) in the polyamic acid solution (PA1) of 6 % by weight to the concentration of synthesized in synthesis example 1, is that 4 % by weight are made crystal aligning agent with the integral body dilution.Use the crystal aligning agent that obtains, make in the following manner liquid crystal display device.

The making method of＜liquid crystal display device 〉

Utilize turner that crystal aligning agent is coated on two with on the glass substrate of ITO electrode, forming thickness is the film of 70nm., 80 ℃ of lower heat dryings approximately 5 minutes, then carry out the heat treated of 20 minutes under 210 ℃ after filming, thereby form liquid crystal orienting film.Then, utilize friction gear to carry out friction treatment to the surface of the substrate that forming liquid crystal orienting film, to carry out orientation, process.Then, after liquid crystal orienting film being carried out 5 minutes ultrasonic cleaning in ultrapure water, in baking oven with 120 ℃ of dryings 30 minutes.

Scatter therein the clearance material of 7 μ m on a slice glass substrate, make the face that forming liquid crystal orienting film for inboard and become antiparallel mode with frictional direction and carry out the subtend configuration, then utilizing epoxy curing agent to seal, is the antiparallel unit (antiparallelcell) of 7 μ m thereby make gap.Inject liquid-crystal composition as follows in this unit, and utilize the photo-hardening agent that inlet is sealed.Then, carry out 30 minutes heat treated under 110 ℃, make liquid crystal display device.

＜liquid-crystal composition 〉

[embodiment 2]

Be to add the mixed solvent of NMP/BC=1/1 (weight ratio) in the polyamic acid solution (PA2) of 6 % by weight to the concentration of synthesized in synthesis example 2, integral body is diluted to 4 % by weight and makes crystal aligning agent.Use the crystal aligning agent that obtains, make similarly to Example 1 liquid crystal display device.

[embodiment 3]

Be to add the mixed solvent of NMP/BC=1/1 (weight ratio) in the polyamic acid solution (PA3) of 6 % by weight to the concentration of synthesized in synthesis example 3, integral body is diluted to 4 % by weight and makes crystal aligning agent.Use the crystal aligning agent that obtains, make similarly to Example 1 liquid crystal display device.

[comparative example 1]

Be to add the mixed solvent of NMP/BC=1/1 (weight ratio) in the polyamic acid solution (PA4) of 6 % by weight to the concentration of synthesized in synthesis example 4, integral body is diluted to 4 % by weight and makes crystal aligning agent.Use the crystal aligning agent that obtains, make similarly to Example 1 liquid crystal display device.

[comparative example 2]

Be to add the mixed solvent of NMP/BC=1/1 (weight ratio) in the polyamic acid solution (PA5) of 6 % by weight to the concentration of synthesized in synthesis example 5, integral body is diluted to 4 % by weight and makes crystal aligning agent.Use the crystal aligning agent that obtains, make similarly to Example 1 liquid crystal display device.

[comparative example 3]

Be to add the mixed solvent of NMP/BC=1/1 (weight ratio) in the polyamic acid solution (PA6) of 6 % by weight to the concentration of synthesized in synthesis example 6, integral body is diluted to 4 % by weight and makes crystal aligning agent.Use the crystal aligning agent that obtains, make similarly to Example 1 liquid crystal display device.

[comparative example 4]

Be to add the mixed solvent of NMP/BC=1/1 (weight ratio) in the polyamic acid solution (PA7) of 6 % by weight to the concentration of synthesized in synthesis example 7, integral body is diluted to 4 % by weight and makes crystal aligning agent.Use the crystal aligning agent that obtains, make similarly to Example 1 liquid crystal display device.

＜3. the evaluation of electrical characteristic 〉

Liquid crystal display device to making in embodiment 1～3, comparative example 1～4, carry out the mensuration of voltage retention and the mensuration of long-term reliability as follows.

1) mensuration of voltage retention

Carry out the mensuration of voltage retention with liquid crystal evaluation of physical property device 6254 types that TOYO Technica makes.Condition determination is grid width (gate width): 60 μ s, frequency: 3Hz, arteries and veins are high: ± 1V, measuring temperature is 60 ℃.The value of described voltage retention is higher, can say that electrical characteristic are better.Show the result in table 2.

2) mensuration of the preserving property of voltage retention

To the liquid crystal display device of made, in time through and obtain voltage retention [%], and its preserving property is estimated.Adopt following method in the test method of preserving property: it is in the environmental gas of 100 ℃ that liquid crystal display device is placed on temperature, midway in time through and take out, measure voltage retention [%].The minimizing of voltage retention less (for example utilize decrement that following formula obtains less than 10%), can say that the preserving property of voltage retention is better, and can say that the long-term reliability of electrical characteristic is better.

The voltage retention at decrement (%)=(voltage retention-500 at initial stage (0 hour) hour after voltage retention)/initial stage * 100

With after 300 hours and the data after 500 hours be shown in Table 2.

＜table 2 〉

As shown in table 2, when the raw material diamines that use contains diamines (N) is made polyamic acid, contain the crystal aligning agent of this polymkeric substance and in making the liquid crystal display device of liquid crystal orienting film, the effect that reduces in time that suppresses voltage retention obtains showing to be improved in use.

the above, it is only preferred embodiment of the present invention, not the present invention is done any pro forma restriction, although the present invention discloses as above with preferred embodiment, yet not in order to limit the present invention, any those skilled in the art, within 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, any simple modification that foundation technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.

Claims

1. crystal aligning agent, it is characterized in that it is to contain the constituent that selects at least a polymkeric substance in the cohort that free polyamic acid and derivative thereof form, wherein said polymkeric substance be make be selected from at least a in the cohort of the represented diamines of formula (N-1)～formula (N-4) or be selected from in the cohort of the represented diamines of formula (N-1)～formula (N-4) at least a with not with at least a mixture of other diamines of the represented diamines of formula (N-1)～formula (N-4), the polyamic acid or its derivative that react with the tetracarboxylic dianhydride and obtain, and the concentration of shared described component of polymer is 0.1 % by weight～40 % by weight in described constituent,

In formula (N-4), Me refers to methyl.

2. crystal aligning agent according to claim 1, it is characterized in that wherein said diamines is the mixture that is selected from at least a and other diamines in the cohort of the represented diamines of formula (N-1)～formula (N-4), described other diamines are to be selected from least a with the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII)

Wherein, A ³For singly-bound ,-O-,-CO-,-COO-,-OCO-,-CONH-,-CH ₂O-,-CF ₂O-or carbon number are 1～6 alkylidene group, in described alkylidene group arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces; R ¹For group, the carbon number with steroid skeleton be 3～30 alkyl, have carbon number be 1～30 alkyl or carbon number be 1～30 alkoxyl group as substituent phenyl or with the represented group of formula (IX), described carbon number be in 3～30 alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces,

Wherein, A ⁴And A ⁵Independently for singly-bound ,-O-,-COO-,-OCO-,-CONH-, carbon number are that 1～4 alkylidene group, carbon number are that 1～3 oxygen base alkylidene group or carbon number are 1～3 alkylidene group oxygen base; Ring B and ring C are Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene independently; R ²And R ³Be fluorine or methyl independently, f and g are 0,1 or 2 independently; C, d and e are 0～3 integer independently, they add up to more than or equal to 1; R ⁴For carbon number be 1～30 alkyl, carbon number is that 1～30 alkoxyl group or carbon number are 2～30 alkoxyalkyl, in these alkyl, alkoxyl group and alkoxyalkyl, hydrogen can be replaced by fluorine arbitrarily, and arbitrarily-CH ₂-can be replaced by difluoro methylene,

In formula (X) and formula (XI), R ⁵Be hydrogen or methyl independently, R ⁶For hydrogen, carbon number are that 1～20 alkyl or carbon number are 2～20 thiazolinyl, R ⁷And R ⁸Be respectively 1～20 alkyl or phenyl independently for carbon number, A ⁶Be independently singly-bound ,-CO-or-CH ₂-,

In formula (XII) and formula (XIII), R ⁹Be 1～30 alkyl for carbon number, in described alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces; R ¹⁰It is 6～22 alkyl for carbon number; R ¹¹It is 1～22 alkyl for carbon number; A ⁷Be 1～6 alkylidene group independently for-O-or carbon number; A ⁸It is 1～3 alkylidene group for singly-bound or carbon number; Ring T is Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene; H is 0 or 1.

3. crystal aligning agent according to claim 1, it is characterized in that wherein said diamines is to be selected from at least a diamines in the cohort of the represented diamines of formula (N-1)～formula (N-4) and the mixture of other diamines, described other diamines are to be selected from least a with the diamines with side-chain radical in the represented diamines of formula (VIII-2), formula (VIII-4)～formula (VIII-6), formula (XII-2), formula (XII-4) and formula (XII-6)

In these chemical formulas, R ²³, R ²⁹And R ³⁰Be respectively carbon number and be 1～30 alkyl or carbon number and be 1～30 alkoxyl group.

4. crystal aligning agent according to claim 1, it is characterized in that wherein said diamines is the mixture that further contains the diamines with side-chain radical, the described diamines that does not have side-chain radical is to be selected from least a with in formula (I)～formula (VII) and the represented compound cohort of formula (XV)

In these chemical formulas, X is that carbon number is 2～12 straight-chain alkyl-sub-; Y be independently singly-bound ,-O-,-CO-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-O-(CH ₂) _t-O-,-S-,-S-S-,-SO ₂-,-S-(CH ₂) _t-S-or carbon number are 1～12 straight-chain alkyl-sub-, and t is 1～12 integer; Z ¹And Z ²For hydrogen, when Y be-NH-,-N (CH ₃)-,-CH ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-time, Z ¹With Z ²Bond and form singly-bound mutually; Ring D is phenylene or Isosorbide-5-Nitrae-diaza cyclohexylidene; R ³³And R ³⁴Be respectively 1～3 alkyl or phenyl independently for carbon number; A ³Be 1～6 alkylidene group, phenylene or the phenylene that replaces through alkyl for carbon number independently; M is 1～10 integer; Any hydrogen of cyclohexane ring or phenyl ring can by fluorine, methyl ,-OH ,-COOH ,-SO ₃H ,-PO ₃H ₂, benzyl or hydroxybenzyl replace.

5. crystal aligning agent according to claim 4, it is characterized in that the wherein said diamines that does not have side-chain radical is at least a with the represented diamines of formula (IV-1), formula (IV-2), formula (IV-15)～formula (IV-17), formula (V-1)～formula (V-12), formula (V-33), formula (V-35)～formula (V-37), formula (VI-7), formula (VII-2) and formula (XV-1)

6. crystal aligning agent according to claim 1, it is characterized in that wherein said polymkeric substance is the mixture of following polyamic acid or its derivative, it is for making at least a at least a mixture with being selected from the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII) that is selected from in the cohort of the represented diamines of formula (N-1)～formula (N-4), perhaps comprise and be selected from least a with in the cohort of the represented diamines of formula (N-1)～formula (N-4), be selected from least a with the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII), and be selected from least a mixture with the diamines that does not have side-chain radical in formula (I)～formula (VII) and the represented diamines cohort of formula (XV), the polyamic acid or its derivative that react with the tetracarboxylic dianhydride and obtain, and at least a or described diamines that does not have a side-chain radical that makes the described diamines that does not have a side-chain radical at least a be selected from at least a mixture in the cohort of the represented diamines of formula (N-1)～formula (N-4), the polyamic acid that reacts with the tetracarboxylic dianhydride and obtain or the mixture of its derivative

In formula (X) and formula (XI), R ⁵Be hydrogen or methyl independently, R ⁶Be 1～20 alkyl or alkenyl for hydrogen or carbon number, R ⁷And R ⁸Be respectively 1～20 alkyl or phenyl independently for carbon number, A ⁶Be independently singly-bound ,-CO-or-CH ₂-,

In formula (XII) and formula (XIII), R ⁹Be 1～30 alkyl for carbon number, in described alkyl arbitrarily-CH ₂-can by-O-,-CH=CH-or-C ≡ C-replaces; R ¹⁰It is 6～22 alkyl for carbon number; R ¹¹It is 1～22 alkyl for carbon number; A ⁷Be 1～6 alkylidene group independently for-O-or carbon number; A ⁸It is 1～3 alkylidene group for singly-bound or carbon number; Ring T is Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene; H is 0 or 1,

In formula (I)～formula (VII) and formula (XV), X is that carbon number is 2～12 straight-chain alkyl-sub-; Y be independently singly-bound ,-O-,-CO-,-NH-,-N (CH ₃)-,-CONH-,-NHCO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-O-(CH ₂) _t-O-,-S-,-S-S-,-SO ₂-,-S-(CH ₂) _t-S-or carbon number are 1～12 straight-chain alkyl-sub-, and t is 1～12 integer; Z ¹And Z ²For hydrogen, when Y be-NH-,-N (CH ₃)-,-CH ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-time, Z ¹With Z ²Bond and form singly-bound mutually; Ring D is phenylene or Isosorbide-5-Nitrae-diaza cyclohexylidene; R ³³And R ³⁴Be respectively 1～3 alkyl or phenyl independently for carbon number; A ³Be 1～6 alkylidene group, phenylene or the phenylene that replaces through alkyl for carbon number independently; M is 1～10 integer; Any hydrogen of cyclohexane ring or phenyl ring can by fluorine, methyl ,-OH ,-COOH ,-SO ₃H ,-PO ₃H ₂, benzyl or hydroxybenzyl replace.

7. crystal aligning agent according to claim 1, it is characterized in that wherein said polymkeric substance is the mixture of following polyamic acid or its derivative, it is for making at least a at least a mixture with being selected from the diamines that does not have side-chain radical in formula (I)～formula (VII) and the represented diamines cohort of formula (XV) that is selected from in the cohort of the represented diamines of formula (N-1)～formula (N-4), the polyamic acid or its derivative that react with the tetracarboxylic dianhydride and obtain, and make at least a or the described at least a and described at least a mixture that does not have the diamines of side-chain radical with diamines of side-chain radical that is selected from the diamines with side-chain radical in formula (VIII) and the represented diamines cohort of formula (X)～formula (XIII), the polyamic acid that reacts with the tetracarboxylic dianhydride and obtain or the mixture of its derivative,

8. crystal aligning agent according to claim 6, it is characterized in that wherein said diamines with side-chain radical is with formula (VIII-2), formula (VIII-4)～formula (VIII-6), formula (XII-2), formula (XII-4) or the represented diamines of formula (XII-6), and the described diamines that does not have side-chain radical is with formula (IV-1), formula (IV-2), formula (IV-15)～formula (IV-17), formula (V-1)～formula (V-12), formula (V-33), formula (V-35)～formula (V-37), formula (VI-7), formula (VII-2) or the represented diamines of formula (XV-1)

In these chemical formulas, R ²³, R ²⁹And R ³⁰Be respectively carbon number and be 1～30 alkyl or carbon number and be 1～30 alkoxyl group,

9. crystal aligning agent according to claim 7, it is characterized in that wherein said diamines with side-chain radical is with formula (VIII-2), formula (VIII-4)～formula (VIII-6), formula (XII-2), formula (XII-4) or the represented diamines of formula (XII-6), and the described diamines that does not have side-chain radical is with formula (IV-1), formula (IV-2), formula (IV-15)～formula (IV-17), formula (V-1)～formula (V-12), formula (V-33), formula (V-35)～formula (V-37), formula (VI-7), formula (VII-2) or the represented diamines of formula (XV-1)

10. crystal aligning agent according to claim 1, is characterized in that wherein said tetracarboxylic dianhydride is the mixture of the tetracarboxylic dianhydride beyond aromatic tetracarboxylic acid's dianhydride or aromatic tetracarboxylic acid's dianhydride and aromatic series.

11. crystal aligning agent according to claim 10, it is characterized in that wherein said aromatic tetracarboxylic acid's dianhydride is to be selected from least a with in the represented compound cohort of formula (1), formula (2), formula (5)～formula (7), formula (11) and formula (14)

12. crystal aligning agent according to claim 11, is characterized in that wherein said aromatic tetracarboxylic acid's dianhydride is with the represented compound of formula (1).

13. crystal aligning agent according to claim 10, is characterized in that the tetracarboxylic dianhydride beyond wherein said aromatic series is ester ring type tetracarboxylic dianhydride and/or aliphatics tetracarboxylic dianhydride.

14. crystal aligning agent according to claim 11, it is characterized in that wherein said aromatic tetracarboxylic acid's dianhydride is to be selected from least a with in the represented compound cohort of formula (1), formula (2), formula (5)～formula (7), formula (11) and formula (14), and the tetracarboxylic dianhydride beyond described aromatic series is selected from least a with in the represented compound cohort of formula (19), formula (23), formula (25), formula (35)～formula (39), formula (44) and formula (49)

15. crystal aligning agent according to claim 14, is characterized in that wherein said aromatic tetracarboxylic acid's dianhydride is with the represented compound of formula (1), the tetracarboxylic dianhydride beyond described aromatic series is with the represented compound of formula (19).

16. crystal aligning agent according to claim 1, is characterized in that wherein said crystal aligning agent further contains at least a compound that is selected from the Na Dike of alkenyl substituted imide compound, the compound with free-radical polymerised unsaturated double-bond, oxazine compounds, oxazoline compound and epoxy compounds.

17. a liquid crystal orienting film, it is characterized in that wherein said liquid crystal orienting film according to claim 1 to 16 filming of the described crystal aligning agent of any one form through heating.

18. liquid crystal display device, it is characterized in that it comprises a pair of substrate, contains liquid crystal molecule and be formed at liquid crystal layer between described a pair of substrate, liquid crystal layer is executed alive electrode and made described liquid crystal alignment is the liquid crystal orienting film of prescribed direction, described liquid crystal display device is characterised in that: described liquid crystal orienting film is liquid crystal orienting film according to claim 17.