TW200927790A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display - Google Patents

Abstract

This invention provides a liquid crystal display device having demanded ion density and improved the long-term reliability of the ion density, a liquid crystal alignment film having demanded ion density and improved the long-term reliability of the ion density in the liquid crystal display device, and a liquid crystal aligning agent for forming the liquid crystal alignment film. A liquid crystal aligning agent, which contains polyamic acid and its derivatives, is used to form a liquid crystal alignment film, and the liquid crystal alignment film is used in a liquid crystal display device. The polyamic acid is a reaction product of a specific diamine and tetracarboxylic dianhydride. The specific diamine is a diamine of N-substituded aniline which contains piperazine.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, wherein the liquid crystal alignment agent contains A diamine with a piperazine on the primary bond and a tetracarboxylic dianhydride

Poly Polyamic acid obtained by the reaction or a derivative thereof. [Prior Art] The liquid crystal display element is used as a camera (vide〇camera) represented by a monitor (note pers〇nal computer) or a desktop (desktop pers〇nal c〇mputer) monitor (monitor) Various liquid crystal display devices such as viewfinders and projection displays have recently been used for televisions. Further, the liquid crystal display element is also used for an optoelectronic electronically related element such as an optical printer head, an optical Fourier transform device, or a light valve. Various components are known in the liquid crystal display element, and the technical development of the liquid crystal display element is not only the riding mode of the through-chip reading or the structure riding of the liquid crystal display element, but also the liquid crystal display element (four) The components are improved and implemented. In general, liquid crystal display elements are used to align the H-pads in a particular area. The liquid crystal alignment film is an essential element for display of a liquid crystal display element, and the function of the liquid crystal alignment film is important in accordance with the quality of the liquid crystal display element. The liquid crystal alignment film is prepared by a liquid crystal alignment agent. The liquid crystal alignment agent used in the present invention is a solution in which polylysine or =, mainly polyimide is dissolved in an organic solvent, and the film is formed by heating or the like, in order to improve the film. The display characteristics of the liquid crystal display element, the important characteristics to be mentioned, may be exemplified by the ion density. If the film is separated from the second film: ❹ ❹ «The voltage applied to the liquid crystal during the frame period is lowered to prevent the normal gradation display. Moreover, π fruit people try to solve the problem, such as an acid composition, which is used to form a liquid crystal alignment film, and combines two or more kinds of poly-proline (for example, ruthenium).

It is said that the 345th bulletin and the Japanese Patent Special Report). A another aspect is a liquid crystal alignment agent which is used to form a liquid crystal alignment agent which is calcined at a low temperature: a liquid crystal alignment agent is known as a polyamine amine obtained by reacting a diamine with a read acid dianhydride. The acid-white diamine has a nitrogen-containing acid (see, for example, Japanese Patent Laid-Open Publication No. Hei 9-194725). (IV) Machine group In addition, it is known that a kind of aromatic diamine and tetradecanoic acid dianhydride are provided. The ligament obtained by the reaction (for example, tilting; 嶋^ Polymer Science: Part A: P〇lymer chemistry vol 3〇5 200927790 ρ1099-1102 (1992)) ° room for the invention [invention] In the prior art, In order to form a liquid crystal alignment agent of a liquid crystal alignment film which is required to be further improved, the present invention provides a desired ion density and realization in terms of the properties of the obtained liquid crystal alignment film or the material for obtaining a desired electrical impurity. a long-term stability liquid crystal display element having an ion density, a liquid crystal alignment film exhibiting a desired ion density in the liquid crystal display element, and a long-term stability of the ion density, and a liquid crystal alignment film can be formed The present inventors have found that a composition containing a polyaminic acid having a polydiamine having a pyridazine as a raw material or a derivative thereof can be used for a liquid crystal alignment agent. The liquid crystal display element of the formed liquid crystal alignment film imparts good ion density and long-term reliability', thereby completing the present invention. The present invention includes the following constitutions. [1] A liquid crystal alignment agent comprising, as a reaction product of a tetracarboxylic dianhydride and a diamine, or a derivative thereof, the liquid crystal alignment agent characterized in that the diamine comprises the following formula ( Diamine

(Ν) In the formula (Ν), Α1 independently represents a monovalent organic group, Α2 independently represents a monovalent organic group, m represents an integer of 〇~3, and η represents an integer of 〇~4 6 200927790. [2] The liquid crystal alignment agent according to [1], wherein a1 is independently a number, a burning base of 1 to 10, a charcoal number of a (7) alkoxy group, acetamide, fluorine, chlorine or Bromine, A2 is independently an alkyl group having a carbon number of i to 3. [3] The liquid crystal alignment agent according to [1] or [2], wherein the diamine represented by the formula (N) has an amino group in the para position in the phenyl group at both ends.

[4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the diamine represented by the formula (N) is selected from the group consisting of the following structural formula (N)-1. Formula (N) — 2, Structural Formula (N) Structural Formula (N) — 7, Structural Formula (N) _9, Structural Formula (N) _1 〇, Structural Formula (N) — 14, Structural Formula (n) — 17 , the structural formula (N) - 18, the structural formula (N) - 21 - structural formula (n) - 23, the structural formula (N) - 26 and the structural formula (N) - 28 represent a group of compounds in the group Kind or more.

(Ν)·10 (Ν)-14 7 200927790

(N)-17 h2n

(N)-23 HsCqi^CHa ΗΖΟΟ^ΟΟΗ3 Η2Ν"ν--ν~Ν\_NH2

(N)-22 (N)-26

(N)-28. The liquid crystal alignment agent according to [4], wherein the diamine represented by the formula (N) is the structural formula (N)_1 and the structural formula (N). One or both of the compounds represented by 2. [6] The liquid crystal alignment agent according to any one of [1] to [5] wherein the diamine further comprises the following general formula (VIII) and the general formula (X) to the general formula ( A diamine having a side chain structure represented by XIII).

In the formula (VIII), A3 represents a single bond, -〇_, -COO-, -OCO-, -CO---C0NH_ or -(CH2)m- (m represents an integer of 1 to 6), and R1 represents a group having a steroid skeleton and a group represented by the following formula (IX): when the positional relationship of the two amino groups bonded to the benzene ring is para, R1 further contains a carbon number of 1 to 3 The alkyl group of ruthenium, when the positional relationship is meta-R', further includes an alkyl group having a carbon number of 1 to 3 Å or a phenyl group, 8 200927790 'any arbitrary '<: Η2- can be independently -CF2-, -CHF-, _〇-(here is discontinuous), -CH=CH- or substituted, -CH3 may be substituted by -CHJ, -CHF2 or _CF3, the hydrogen of the phenyl group may be independently The ground is replaced by _F, -ch3, -〇ch3, -OCH2F, -ochf2 or -〇cf3.

In the formula (IX), A4 and A5 each independently represent a single bond, -〇 (here, discontinuous), -COO-, -OCO-, -CONH-, or an alkylene group having a carbon number of 1 to 12 The bases, R2 and R3 each independently represent _F or -CH3, and the ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxin-2,5-diyl (l,3-dioxane-2,5_diyl), pyrimidine-2,5-diyl, pyridine-2,5-diyl Naphthalene-1,5-diyl, naphthalene 2,7-diyl or anthracene-9, l〇-diyl ' R4 represents _h , -F, a carbon group having a carbon number of 1 to 30, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, -CN, -OCH2:F, -〇CHF2 or _0Cf3, a and 匕〇 respectively represent integers of 〇~4, c, d, and e represent integers of 〇~3, respectively, and f and g each independently represent an integer of 0~2, and c + d + eg 1.

B1 9 200927790

In the general formulae (X) and (XI), R5 independently represents _H or _CH3, R6. An alkyl group or an alkenyl group which represents -Η or a carbon number, a6 independently represents a single bond, -C(=0)- or -CH2-, and in the formula (XI), R7 and r8 each independently represent a carbon number of Alkyl or phenyl. R9 plO p11 In the general formula (XII) and (XIII), a7 independently represents _〇_ or an alkylene group having a carbon number of 1 to 6, and in the formula (χπ), R9 represents or the carbon number is 1 to 30. An alkyl group in which any -CH2_ of an alkyl group having a carbon number of 2 to 3 Å may be substituted by -〇- (here, discontinuous), _ch=CH- or _〇C-, A8 represents a single bond or an alkylene group having a carbon number of 1 to 3, a ring τ represents a 1,4-phenylene group or a 1,4-cyclohexylene group, h represents fluorene or 1, and in the formula (XIII), R1G represents The alkyl group has a carbon number of 6 to 22, and RU represents a hospital base having a carbon number of 1 to 22. [7] The liquid crystal alignment agent according to [6], wherein the diamine having a side chain structure is selected from the group consisting of the following general formula (VIII-2) and the general formula (νιπ 200927790-4) At least one of the compounds represented by the formula (VIII-6), the formula (XII-2), the formula (XII-4) and the formula (XII-6).

(VIII-5)

In the above formula, R23, R29 and R3G each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. [8] The liquid crystal alignment agent according to any one of [1] to [7] wherein the diamine further comprises the following general formula (I) to general formula (VII) 11 200927790 and a general formula (xv) a diamine which does not have a side bond structure. H2N—X-NH2 (I) η η2ν^—^νη2

’ In the general formula (I), 'X represents -(CH2)m_ (m represents an integer of 1 to 6), and in the general formula (III) and the general formula (V) to the general formula (VII), Y independently represents

Show single key, -〇_, _s_, -SS-, -S02-, -CO-, -CONH-, -NHCO-, -NH- . -N(CH3)-(CH2)mN(CH3)- > -C(CH3)2- > -C(CF3)2- ' **(CH2)m-, -O(CH2)m-0_, -S-(CH2)mS- (m represents an integer from 1 to 6 In the general formula (V), z represents a single bond or does not exist. In the formula (χν), R33 and R34 each independently represent an alkyl group having a carbon number of i 〜3 or a group, and A3 independently represents an anthracene. A phenylene group or a substituted group substituted with an alkyl group. 1 represents an integer of 1 to 6 'm represents an integer of 1 to 10, and in the formula (π) to (VII), a hydrogen bonded to a cyclohexane ring or a benzene ring may be independently substituted with -F, - CH3, -CF3, -OH, -COOH, -S03H, _Ρ〇3η2, 12 200927790 The ruthenium bonded to the benzene ring in the formula (ιν) can be substituted with a benzyl group. [9] The liquid crystal alignment agent according to [8], wherein the diamine having no side chain structure is selected from the group consisting of the following structural formula (IV-1), structural formula (IV-2), and structure Formula (IV-15)~Structure Formula (IV-17), Structural Formula (V-1)~Structure Formula (V-12), Structural Formula (V-33), Structural Formula (V-35)~Structure Formula ( At least one of a compound represented by V-37), structural formula (VII-2), and structural formula (XV-1).

(V-1) (V-2) (V-3)

(V-10)

(V-11)

(V-12)

(V-33) 13 200927790 H2N^Q^nhQ^nh2 (V-35)

(V-37) ch3 ch3 H2N-C3H6_?i~〇-Si-C3H6-NH2 CH3 ch3

(VIW) (XV-1)

[10] The liquid crystal alignment agent according to any one of [1] to [9] wherein the tetraacid dianhydride comprises an aromatic tetracarboxylic dianhydride. [11] The liquid crystal alignment agent according to [10], wherein the aromatic tetracarboxylic dianhydride is a structural formula (丨), a structural formula (2), and a structural formula (5) to a structural formula. (7) and the chemical house represented by the structural formula (14)

The aromatic tetracarboxylic dianhydride is a compound represented by the above structural formula (1). The liquid crystal alignment agent according to any one of [1] to [12] wherein the tetracarboxylic acid two needles comprise an alicyclic tetrahydro acid dianhydride and an aliphatic tetrasulphur acid J The towel - square or both. [12] The liquid crystal alignment agent according to [11], wherein the liquid crystal alignment agent according to [13], characterized in that the alicyclic tetracarboxylic dianhydride And the aliphatic tetracarboxylic dianhydride is represented by the following structural formula (19), structural formula (23), structural formula (25), structural formula (35) to structural formula (39), structural formula (44), and structural formula ( 49) at least one of the compounds indicated.

[15] The liquid crystal alignment agent according to [14], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the structural formula (19), structural formula (23) At least one of the compounds represented by the structural formula (37) and the structural formula (49). The liquid crystal alignment agent according to any one of [6] to [15] wherein the liquid crystal alignment agent contains the polyamic acid or derivatives A and B thereof, and the polyamine The acid or derivative A thereof comprises the diamine having a side chain structure in the diamine, and one or both of the poly-brenamic acid or a derivative thereof and a diamine of B contain a general formula (N) 15 Diamine represented by 200927790. The liquid crystal alignment agent according to any one of [1] to [16] wherein the liquid crystal alignment agent further contains an alkenyl-substituted nadic-based imine compound having a radical One or more of a compound having a polymerizable unsaturated double bond, an oxazine compound, an oxazoxaine compound, and an epoxy compound. [18] The liquid crystal alignment agent according to [17], wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo® [2.2.1] g-5 -ene-2,3-dimethylimine imine) phenyl} decane (bis{4-(allylbicyclo[2.2.1] ept-5_ene-2,3-dicarboxyimide)phenyl}methane), N,N'- m-Phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine) and N,M_hexamethylene-bis(allylbicyclo[2.2 .1] one or more of the group consisting of hept-5-ene-2,3-dimethylimine. [19] The liquid crystal alignment agent according to [18], wherein the alkenyl-substituted nadicilide compound is bis{4-(allylbicyclo[2.2.1]hepta-5-ene -2,3-dimethylimine)phenyl}methane. [20] The liquid crystal alignment agent according to [17], wherein the compound having a radical polymerizable unsaturated double bond is selected from N, N'-fluorenylene bis acrylamide (N, N) '-methylenebisacrylamide), N,N'-dihydroxy ethylene bisacrylamide, ethylene bisacrylate, and 4,4'-methylene One or more of the group consisting of 4,4'-methylene bis (N, N-dihydroxy ethylene acrylate 16 200927790 aniline). [21] The liquid crystal alignment agent according to [20], wherein the compound having a radical polymerizable unsaturated double bond is -diylbispropeneSiamine. [4] The liquid crystal alignment agent according to [17], wherein the azine compound is selected from the group consisting of the following formula (b-丨), Ο (d-6), (e-3), (e-4) and the species represented by the compound represented by the formula (Bu 4) or _ meaning

17 200927790

[23] The liquid crystal alignment agent according to [22], wherein the azine compound is a compound represented by the formula (c-1). [24] The liquid crystal alignment agent according to [17] characterized in that the oxazoline compound is 2,2,_bis(2-oxazoline) and 1,3-bis(4,5- 〆18 200927790 or both of the benzene (1,3-bis(4,5-dihydro-2-oxazolyl)benzene). [25] The liquid crystal alignment agent according to [24], wherein the oxazoline compound is 1,3-bis(4,5-dihydro-2-oxazolyl)benzene. [26] The liquid crystal alignment agent according to [17], wherein the epoxy compound is selected from the group consisting of ruthenium, osmium, iridium, Ν'-tetraglycidyl-m-xylylenediamine (N, N) , N', N'-tetraglycidyl_m-xylenediamine), 1,3-bis(indole, Ν-diglycidylaminomethyl)cyclohexane, hydrazine, hydrazine, hydrazine, hydrazine, -tetraglycidyl _4 , 4'-diaminodiphenylmethane, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3 -Epoxypropoxy]phenyl]]ethyl]phenyl]propane (2-[4-(2,3-epoxy propoxy)phenyl]-2-[4-[l,l-bis[4-( [2,3-epoxy propoxy]phenyl)] ethyl] henyl]ropane), 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexanoic acid vinegar (3,4_epOXy CyCi 〇hexenyi methyl-3',4'-epoxy cyclohexene carboxylate), N-phenylmaleimide-glycidyl methacrylate copolymer with ❹ and 2-( One or more of the groups consisting of 3,4-epoxycyclohexyl)ethyltrimethoxysilane (2_(3,4_ep()xy cyclohexyl)ethyl trimethoxy silane ). [27] The liquid crystal alignment agent according to P6, wherein the epoxy compound is 3,4-epoxycyclohexenyl indenyl 3',4,-epoxycyclohexenecarboxylate Or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane. [28] A liquid crystal alignment film, wherein the liquid crystal alignment film is formed by adding heat to a coating film of the liquid crystal alignment agent according to any one of [1] to [27]. [29] A liquid crystal display device having a pair of substrates, a liquid crystal layer containing a liquid crystal and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and aligning the liquid crystal molecules at a predetermined A liquid crystal alignment film in a direction, wherein the liquid crystal alignment film is a liquid crystal alignment film according to P8]. [Effect of the Invention] According to the present invention, it is possible to provide a liquid crystal display element which has a high ion density and is excellent in long-term reliability in accordance with the variation of the ion density with time, and can be applied to various driving methods. The above described features and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] The liquid crystal alignment agent of the present invention contains polyamic acid or a derivative thereof as an inverse f product of tetracarboxylic dianhydride and diamine. The derivative of the poly-proline is a component which is dissolved in a solvent when the liquid crystal alignment agent described later contains a solvent, and can be formed into a polymer when the liquid crystal alignment agent is formed into a liquid crystal alignment agent. A component of a liquid crystal alignment film containing quinone imine as a main component. Examples of such a derivative of polylysine include soluble polyimine, polyphthalate, and polyamidamine, and more specifically, all of the amino group of the n-polyglycolic acid and the carboxyl group are dehydrated. Polyimine which is formed by ring closure reaction, 2) partial polyimine which is partially subjected to dehydration ring closure reaction, 3) polyphthalate which converts carboxyl group of polylysine into ester, 4) A part of the acid dianhydride contained in the tetracarboxylic dianhydride compound is replaced by an organic dicarboxylic acid. 20 200927790 The reaction of the (tetra) aminic acid/poly lysine copolymer can be enumerated. 5) The polyamine can be used. The acid amine copolymer # may be partially or completely subjected to a dehydration ring-closing reaction. The polyamine or the derivative thereof may be a compound or two or more compounds. The diamine contains a diamine represented by the following formula (Ν). The diamine used in the present invention may be a quinone compound or two or two

The above compounds.

In the formula (Ν), Α1 independently represents a monovalent organic group, Α2 independently represents a monovalent organic group, m represents an integer of 〇~3, and η represents an integer of 〇~4. Further, in the present invention, halogen is included in the organic group. The oxime and oxime 2 may each use various monovalent organic groups. Αι is preferably an alkyl group having a carbon number of 1 to 10 independently and having a carbon number of i 〜1 〇.

Alkoxy, acetamide, fluorine, chlorine or bromine. A2 is preferably an alkyl group independently having a charcoal number of 1 to 3. The diamine represented by the formula (N) has an amino group at each of the phenyl groups at both ends. These amino assays can be (iv) slanted, independently in the ortho position, the equi-position of the two-position of the f-position. From the viewpoint of easy production of the diamine, the positions of these amino groups are preferably all para-position. The diamine represented by the formula (N) is exemplified by the following compounds in the present invention. 21 200927790 〇

(Ν)-3 (Ν)-4

(Ν)-12 (Ν)-11

(Ν)-13 22 200927790

ΗζΝ~^Ζ^~Ν\_/Ν—ΝΗζ (Ν)-14 ❹

Η2Ν Ρ〇Η3 H3CO

Βγ η2ν

O^L//^NH2 (Ν)-22 Βγν/Ί^ΝΗ2 (Ν)-24

NHCOCH3 NHCOCH3 H2NHWKNCNHVJ^NH2 (Ν)-21 Cl

Cl η2ν

NV_yNHi /ΓΗΗζ (N)-23 h2n

N N

/-nh2 (N)-25 h3c h2n ch3 nh2 (N)-27 (N)-26 H3C〇〇ch3 h3c〇〇CH3 η2νη0^νΟν vVnh2 (N)-28 The two expressed by the general formula (N) The amine preferably has the structural formula (N)-1, structural formula (N)-2, structural formula (N)-5~ structural formula (N) 23 200927790-7, structural formula (N)-9, structural formula ( N) -1〇, structural formula (N) -14, structural formula (N) -17, structural formula (N) -18, structural formula (N) -21~ structural formula (N) -23, structural formula (N -26 and the compound represented by the structural formula (N)-28 are more preferably a compound represented by the structural formula (N)-1 and the structural formula (N)~~2. From the viewpoint of exhibiting a desired ion density in a liquid crystal display element and exhibiting long-term stability of the ion density, the diamine represented by the general formula (N) is set to form a polystyrene in the liquid crystal alignment agent of the present invention. The diamine of the amine acid preferably contains 2% by weight to 1% by mole based on the molar ratio, and more preferably 35% to 1% by weight. The diamine represented by the above formula (N) can be produced by a known method. For example, as described in JP-A-52-14780, it is possible to have a corresponding enthalpy under ordinary reducing conditions using a reducing agent such as tin or a citric acid. The nitro group of the compound obtained by subjecting the nitrobenzene (Nitrobenzene) or its derivative to the pyridazine reaction reaction is reduced to an amino group. © The diamine may contain only the diamine represented by the above formula (N), and may further contain other diamines. The other diamine may, for example, be a monoamine having a side chain structure and a diamine having no side bond structure. Such other diamine may be one compound or two or more compounds. The diamine having a side chain structure means an amine having a substituent (side chain) which branches autonomously when a substituent linking two amino groups is used as a primary bond, and can exhibit a desired pre Inclination (pretm angl). 24 200927790 A side chain-bound diamine towel _ chain yarn may be selected as appropriate. For example, the side chain may be a group having a carbon number of 2 = . The diamine having a side chain structure may be exemplified by the following two (10) broad and general formula (X) to general formula (leg) filaments.

H2N (VIII) In the formula (vm), A3 represents a single bond, _〇_, _c〇〇_, _〇c〇❹-CO·, -CONH_ or _(CH2)m_ (m represents an integer of 6 i is a group having no steroid skeleton, represented by the following formula (IX), and when the positional relationship of the two amino groups bonded to the stupid ring is opposite, R includes two carbon atoms in the second step. The calcining group, when in the meta position, R1 further comprises a decyl group having a carbon number of Ν30 or a benzene H alkyl group, and any -CH2- may be independently discontinuous via _CF2_, _CHF_, _〇), -CHKH· Alternatively, -CH3 may be substituted, and -CH3 may be substituted by -CH2F, -CHF2 or _Cf3. Further, the hydrogen of the phenyl group can be simply _F, TM ΠΗ 3, _qch 2f, _ 〇 2 or - OCFq.

In the general formula (IX), A4 and A5 independently represent a single bond, -〇_ (here is discontinuous), -COO-, -0C0-, -CONH·, -CH=CH- or carbon. Wei Ke, number 1~12, r2j^r3 stands for _F or -CH3, and ring s independently represents L4-phenylene, anthracene, 4_cyclohexylene, R4 (IX) 25 200927790 1,3 -2° dioxin-2,5-diyl, mouth bite, 2,5·diyl, π-precipitate-2,5-diyl, qin-1,5-diyl, naphthalene-2,7-di Or -9,10.diyl, R4 represents -Η, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, and an alkoxy group having 1 to 30 carbon atoms. Base, -CN, -OCH2:F, -OCHF2 or -OCF3, a and b respectively represent integers of 0 to 4, c, d, and e represent integers of 0 to 3, respectively, and f and g independently represent 0 to 2, respectively. The integer, and c + d + 1.

In the general formulae (X) and (XI), R5 independently represents -Η or -CH3, R6 represents -Η or an alkyl or alkenyl group having a carbon number of 1 to 20, and A6 independently represents a single bond, -C(= 0) - or -CH2-. Further, in the formula (XI), R7 and R8 each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group.

26 200927790

〇 In the formulae (XII) and (XIII), Α7 independently represents -o- or a pyridene group having a stone inverse of 1 to 6. Further, in the formula (XII), R9 represents -Η or an alkyl group having 1 to 30 carbon atoms, and any -CH2_ of the alkyl group having 2 to 3 carbon atoms in the alkyl group may be -? Here is discontinuous), _ch=:ch- or substituted, A8 represents a single bond or an alkylene group having a carbon number of i~3, and ring T represents a 1,4-phenylene group or a 1,4-cyclohexylene group. , h means 〇 or 〗. Further, in the formula (XIII), R10 represents an alkyl group having 6 to 22 carbon atoms, and R11 represents an alkyl group having 1 to 22 carbon atoms.

Examples of the diamine represented by the formula (VIII) include a diamine represented by the following formula (yin-υ~ formula (VIII-37) and a structural formula (vm_38) to a structural formula (VIII-43).

(VIII-5) R23

H2N (Vlll«6) 27 200927790

(VIII-9) (VIII-10)

(VIII-11) In the formula (VIII-1) to the formula (VIII-11), R23 preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably It is an alkyl group having a carbon number of 5 to 25 or an alkoxy group having a carbon number of 5 to 25. Further, R24 preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 25 carbon atoms or a carbon number of 3 to 25 carbon atoms. Alkoxy.

R25 r25 R25

(VIII-12) (VIII-13) (VIII-14) (VIIJ-15) R26

(VIII-16) (VIII-17) 28 200927790 In the formula (VIII-12) to the formula (VIII-15), R25 preferably represents an alkyl group having a carbon number of 4 to 30, and more preferably represents carbon. The number is 6 to 25 alkyl groups. In the formula (VIII-16) and the formula (VIII-17), R26 preferably represents an alkyl group having 6 to 30 carbon atoms, and more preferably an alkyl group having a carbon number of 8 to 25 in h2n. H2n h2n

(VIII-18) h2n (VIII-19)

H2N (VI"-24)

(VIII-25)

29 200927790

H2n h2n (VIII-27) (VIII-28)

(VIII-29)

(VIII-30)

SI

(VIII-32)

H2N (VIII-33) (VIII-34) Η2Ν ο 普1 h2n (VIII-35) (VIII-36) \ r,~λ Γ~\ ?h3 ?h3 ^jK^Si-O-Si-R27 ch3 ch3 R28 (Vill-37) In the formula (VIII-18) to the formula (VIII-37), R27 preferably represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more Preferably, it is an alkyl group having a carbon number of 3 to 25 or an alkoxy group having a carbon number of 3 to 25. Further, R28 is preferably an alkyl group having -H, -F, a carbon number of 1 to 30 30 200927790, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH2F, -OCHF2 or -OCF3, more preferably It is an alkyl group having a carbon number of 3 to 25 or an alkoxy group having a carbon number of 3 to 25.

Among these diamines, a diamine represented by the formula (VIII-1) to the formula (VIII-11) is preferred, and a formula (VIII-2) and a formula (VIII-4) to a formula (VIII) are more preferred. -6) represents a diamine. The diamine represented by the above formula (X) is preferably one of two "NHyPh λ 6 positions, another bond" in the formula (X) 31 200927790 bonded to the 3 carbon of the steroid skeleton. Upper, _"^ position; ^ and 'two amino groups are respectively bonded to the stupid ring position. For the bonding position of the oxime, bonding to the meta position or for the diamine represented by fY ^, formula (X), for example The following structural formula (X-1) to structure can be cited.

Ο

(X-3), NH2 (X^), NH2 ο In the diamine represented by the formula (XI), in the formula (XI), two "NH2_(R-)Ph_A6, respectively, are bonded On the carbon of the benzene ring, it is preferred that the carbon bonded to the skeletal bond is bonded to the meta or para carbon, and the 6 and the amino group are respectively bonded to the abaxial carbon, preferably relative to In the case of the diamine represented by the formula (XI), for example, a diamine represented by the following structural formula OQ-"~ structural formula (χί-8) can be exemplified. 32 points.

Q 200927790 h2n ❹

Nh2

33 200927790

34 200927790 In the diamine represented by the above formula (XII), in the formula (XII), two amino groups are bonded to the carbon of the benzene ring, respectively, preferably bonded to the meta or relative to A7. On the bit. The diamine represented by the formula (XII) may, for example, be a diamine represented by the following formula (XII-1) to (XII-8). R29 R29

35 200927790

R30

29, Η, an alkyl group having a carbon number of 1 to 30 or an alkoxy group having a carbon number of 1 to 30, more preferably an alkyl group having a carbon number of 3 to 30 or an alkane having a carbon number of 3 to 30 Oxygen. Further, in the general formulae (XII-4) to (?-8), R3G preferably represents -Η, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably It is an alkyl group having a carbon number of 3 to 30 or an alkoxy group having a carbon number of 3 to 30. In the diamine represented by the above formula (XIII), in the general formula (XIII), in the breaking of the benzene ring, preferably, the diamine represented by the bond (ΧΙΠ) can be exemplified by the following formula (ΧΠΙ- 3) The diamine represented.

(ΧΙΙΙ-3) /-νη2 η2ν-/

In the formula (Xm_3), r31 is preferably a group of 6 to 22, and preferably has a carbon number of 6 to alkyl. R preferably represents -H or an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. The diamine having a side bond structure is preferably selected from the group consisting of the formula (viii 2), the formula (VIII-4) to the formula (νπι-6), the formula (χπ-2), and the formula (XII). — 4) and at least one of the compounds represented by the formula (ΧΠ_6). From the viewpoint of exhibiting a desired pretilt angle in the liquid crystal display element, the diamine having a side chain structure is preferably selected from a molar ratio of a polyamine of a polylysine constituting the liquid crystal alignment agent of the present invention. It is contained in an amount of 1% to 90%, and more preferably contains 5% to 70%. The diamine having no side chain structure means a diamine having no substituent (side chain) which branches autonomously when a substituent linking an amino group is used as a main chain, and can exhibit a desired Pretilt angle. The above-mentioned diamine having a side chain structure may be a compound represented by the following general formula (i) to the general formula (νπ) and the general formula (??).

HgN—X—NH2 (I) H2N〇NH2 (,,) Η2Ν〇-γ-〇ΝΗ2 (丨丨丨)

In the formula (I), X represents -(CH2)m- (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), γ independently represents a single bond , -0-, each, -SS-, -S〇2-, -CO-, -CONH-, -NHCO-, -NH- > -N(CH3HCH2)mN(CH3)- > -C(CH3 ) 2- > -C(CF3)2- ' -(CH2)m-, -0-(CH2)m_0-, -S-(CH2)mS- (m represents an integer from 1 to 6), In V), 'Z represents a single bond or does not exist. In the formula (χν), 'R33 and R34 each independently represent an alkyl group having a carbon number of 1 to 3 or 3&200927790 phenyl 'A3 independently represents an anthracenylene group, A phenylene group or an alkyl substituted phenylene group. 1 represents an integer of 1 to ό, and an integer represented by m. In the general formula (II) to (VII), a hydrogen bonded to a cyclohexane ring or a benzene ring may be independently substituted with -F, -CH3, - CF3, -oh,, -P〇3H2 '

The hydrogen bonded to the soil in the general formula (IV) may be substituted by a benzyl group. The monoamine represented by the formula (I) is, for example, a diamine represented by the following structural formula (I-1) to structural formula (I-3). H2N(CH2)2NH2 H2N(CH2)4NH2 H2N(CH2)6NH2 (1-1) (I-2) (I-3) The diamine represented by the formula (II) can be, for example, the following structural formula (II- 1) A diamine represented by the formula (II-2). H2N^3^NH2 H2N-0pNH2 (11-1) (11-2) Two examples represented by the general formula (III) Structural formula (III-1) to structural formula (III-3)

Ch3 -NHa CH3 The diamine represented by the formula (w) is exemplified by the structural formula (IV-1) to the structural formula (IV-17) 矣 别 别 J J J • • • • • •

Nh2 (IV-1) (IV-2)

H2N

Nh3 (inM) (IV-3) 39 200927790

The diamine represented by the formula (v) is, for example, a diamine represented by the following structural formula (V-1) to structural formula (V-37).

40 /)-^2 200927790 ❹

(V-12) η2ν-〇^°^〇ρ' nh2 h2n

(V-15) (V-13) (V-14) Η2Ν_〇κ〇^〇ν〇κνη2 (V-16)

/-nh2 (V-17) h2n^〇^c

Nh2 H2N—^

/-NH2 (V-19) (V-18) nh2 h2n-〇^°^^°^nh2 (V-20) (V-21) H2N~^~^~s~s~C~^~NH2 h2n — ❹ (V-22) (V-23) (V-25) (V-24)

H2N (V-26) v^/ NHz h2n (V-27) NH2 41 200927790

Ο

Ηη2 (V-31) ΝΗ2

(V-33) (V-32) OH ΟΗ

(V-34)

(V-37)

(V-36)

The diamine represented by the formula (VI) is, for example, a diamine represented by the following structural formula (VI-1) to structural formula (VI-6).

(VI-D

(VI-2) ΝΗ 2 (V1-3) (VI-4)

(VI-5) (VI-6) 42 200927790

丨 2 H2N- (VIM) (VII-2) ❹

/—nh2 h2n (VII-7)

(VII-4) NHa H2N

(VII-6) /-nh2 h2n

(VII-8) H2N~^^0s^3^0^〇v0^nh2 hjn~(^0v〇^ch2^C^〇vC)knh2 (VII-9) (VII-10) ❿ h2n

(νιμιΐ) h3c ch3 (VH-12) distinct order. ^_〇^〇~nh2

(VII-14) o II (VIM 5) (VII-16) The diamine represented by the formula (XV) is, for example, a compound represented by the following structural formula Cxv-1). (VII-13) f3Q cf3

Ch3 ch3 HaN-CsHe-知一0-‘C3H6-NH2 ch3 ch3 (XV-1) 43 200927790 ❹

Among these diamines, the diamine having no side bond structure preferably has the structural formula GV-1) to the structural formula (IV-5), the structural formula (IV-15) to the structural formula (IV-17), and the structural formula. (vy)~Structure (v-12), Structural Formula (V-26), Structural Formula (v_27), Structural Formula (v_3i), Structural Formula (V 33), Structural Formula (v_35)~Structure Formula (v_37) , structural formula (vi-i), structural formula (VI_2), structural formula (νι-6), structural formula (V11-1)~ structural formula (VII-5), and structural formula (diamine represented by χν-D, More preferably, it is a structural formula Gv-丨), a structural formula (ιν-2), a structural formula (IV-15)~ a structural formula (IV-17), a structural formula (v_ υ~ structural formula (V-12), a structural formula (V-33), structural formula (v_35)~Structure formula (V-37), structural formula (VII_2) and structural formula (χν-1) represent diamines. From the viewpoint of the required electrical characteristics such as the ion density, it is considered that the diamine having a ship structure has a polyamine in the polyhydric acid constituting the liquid crystal alignment agent of the present invention, preferably 1% to 98° in terms of a molar ratio. ° 'More preferably contains 10% ~ 9 5%. The other diamines other than the diamines other than the diamines represented by the above formula (1) to the formula m to the formula (χπι) can be used, for example, as the naphthalene structure. ϋ~uf(flu〇rene) structure (IV) is a diamine having a side chain structure other than a diamine and a formula ιχπ). The chemical expression 2 can be, for example, a general formula (1') to a general formula (9) 44 200927790

(3,)

The polyfluorene = other diamine constituting the liquid crystal alignment agent of the present invention may be in a range that does not impair the effects of the present invention = within the range of the diamine, in the case of the diamine, a single (m_amine) may be used in each diamine. The ratio of diamine is 4 〇 mole % or less, and the partial diamine is replaced by a monoamine. j 7 can cause the termination of the polymerization reaction when the poly(tetra) acid is formed. Thus, it is possible to suppress the progress of the polymerization reaction. By such substitution, it can be easily controlled: Because of the amount of arginine or its touch, it is better to improve the liquid crystal alignment coating and the present hair/, or to damage the effect of the hair. TC_ Ί _* » is replaced by the second amine

N-decylamine, n-decylamine, n-undecamine, tetraamine, n-pentadecylamine, n-hexadecylamine, n-heptadecane saddle may be one type or two types: aniline, 4-hydroxy stupid • positive Amine, n-heptylamine, n-octylamine, n-dodecylamine, n-tridecylamine, n-decene, n-octadecylamine and n-dodecylamine. The tetra-retensive dianhydride used in the present invention may be a compound ' or two or more compounds. The tetracarboxylic acid may, for example, be an aromatic 0 aryl tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, or an aliphatic tetracarboxylic acid; the aromatic tetracarboxylic dianhydride, which is at least one of two acid anhydrides. It is a compound of an acid anhydride obtained by bonding two secrets on an aromatic compound. The aromatic smear is as good as the compound represented by the structural formula (1).

(1) (2) (3)

46 200927790

The aromatic tetracarboxylic dianhydride is preferably a compound represented by the above structural formula (1), structural formula (2), structural formula (5) to structural formula (7), and structural formula (14), and more preferably The compound represented by the structural formula (1). The alicyclic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride obtained by bonding two carboxyl groups bonded to the alicyclic compound. Examples of the alicyclic tetracarboxylic dianhydride include the following structural formula (19) to structural formula (22), structural formula (24) to structural formula (44), and structural formula (49) to structural formula (65). The compound represented. 47 200927790

48 200927790

(42) (43) (44)

(54) (55) (56)

49 200927790 The ruthenium ring type tetrakispernic acid dianhydride preferably has the structural formula (I9), the structural formula (35) to the structural formula (37), the structural formula (39), the structural formula and the structural formula (49). The compound represented by the formula (19), the structural formula (37), and the structural formula (49) are more preferably a compound represented by the formula (49). The bismuth tetracarboxylic dianhydride has two bonds bonded to an aliphatic group

A compound of an anhydride obtained from two mercapto groups on a compound. The aliphatic tetracarboxylic dianhydride may, for example, be a compound represented by the following structural formula (23), structural formula (45) to structural formula (48), structural formula (66) and structural formula (67).

(66) (67) The aliphatic tetracarboxylic dianhydride is preferably a compound represented by the structural formula (23). As the tetrabasic acid sf, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the structural formula (1) to the structural formula (67) can be used. Other four 50 200927790 Side pre-tilt of the two-position. Fiber - Xuan, can be a big LCD _ 兀 pieces. And the combination of the alcohol skeleton represented by the formula (69)

Any ==ΓΧ can also be used within the range of the real-time hair 也 也 也 也 一部分 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The polymer (the coating property of the polynic liquid crystal alignment agent. The effect of the invention is modified to be compared with the ratio of the tetracarboxylic acid to the tetracarboxylic acid, and the range of the effect of the present invention is (4). 1 G mol% or 10 mol% or less of the amount of γ tetraweishen. As long as the effect of the present invention is not obtained, the tetracarboxylic acid dioxins substituted with the carboxylic anhydride may be used in two or more kinds. Carboxylic acid monoanhydride for example; 歹J lift. Malay _, phthalic acid porphyrin, itaconic acid liver (itac_ two y ri e), n-decyl gamma acid sulphate, sulphide sulphate liver, positive ten The four-burning sulphate is the liver, the hexagram is given _ and the ring is acid 轩. Ο ❹ The tetracarboxylic dianhydride can be 10 mole% or 1G molar in the dicarboxylic acid relative to the tetracarboxylic acid. In the case of less than %, the __ partial tetraacid di if is replaced with a dicarboxylic acid. The tetracarboxylic dianhydride which is substituted with a dicarboxylic acid may be used as long as the effect of the present invention is not impaired. It may be one type or two or more types. The monomer of the polyamic acid or a derivative thereof may further contain a monoisocyanate compound, which is obtained by including a monoisocyanate compound in the monomer. The terminal of the poly-proline or the derivative thereof is modified, and the molecular weight is adjusted. By using the terminal-modified poly-proline or a derivative thereof, for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From this viewpoint, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% with respect to the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. The monoisocyanate compound may, for example, be phenyl isocyanate or isocyanate. The polylysine or a derivative thereof may be a film of a polyimine in addition to the diamine represented by the formula (N). The polyamines or their derivatives known in the art are used in the same manner. The total amount of tetradecanoic acid is preferably the total molar amount of the diamine. The molar ratio is about 0.9 to 1.1. The molecular weight of the polyamic acid or derivative thereof is preferably 10 in terms of polystyrene-equivalent weight average molecular weight (Mw), 〇〇〇~ 5〇〇,〇〇〇, more preferably 20,000 to 200, 〇〇〇. The molecular weight of the polyamic acid or a derivative thereof can be determined by using a gel permeation chromatography (GPC) method. For the poly-proline or its derivatives, infrared spectroscopy (IR) and nuclear magnetic resonance (Nuclear Magnetic) can be performed on solid components obtained by precipitation with a large amount of poor solvent.

Resonance ''NMR) analysis confirmed its presence. Further, gas chromatography (Gas Chromatography 'GC), high-efficiency liquid can be carried out by extracting an extract obtained by extracting an organic solvent of a polyamine derivative or a derivative of a derivative thereof with an aqueous solution of a strong alkali such as KOH or NaOH. The high-performance liquid Chromatography (HPLC) or Gas Chromatograph-Mass Spectrometer (GC-MS) analysis was used to confirm the monomers used. The liquid crystal alignment agent of the present invention may further contain other components other than the polyamic acid or a derivative thereof. The other ingredients may be one type or two or more types. For example, the liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted nadickimine compound from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The group-substituted nadicylimine compound may be 53 200927790 A compound ' or two or more compounds. From the viewpoint of the above, the content of the alkenyl-substituted nadic ylidene imine compound is preferably from 0.01 to 1.00, more preferably 0.01, based on the weight ratio of the polyglycine or the derivative thereof in the liquid crystal alignment agent. More preferably, it is 0.01 to 0.50. The alkenyl-substituted nadicylimine compound is preferably a compound which can be dissolved in a solvent which dissolves the poly-proline or the derivative thereof used in the present invention.

Things. An example of such an alkenyl-substituted nadicylimine compound can be a compound represented by the following formula (Ina). 0

叹八甲, and 1/ respectively molybdenum Λ 1L 士 ❹ ❹ is a burning base, a carbon number of 3 to 6, a rare wind, a carbon number base: an aryl group or an f group, and η is a ring of 5 to 8 When n=l, W represents a fluorenyl group having a carbon number of i—u ～6, a cycloalkyl group having a carbon number of 5 to 8, a carbon two: a ^^^ yl group, and a (Ζι, a square group, a subring group having a carbon number of 2 to 6, q represents a group represented by 〇 or i and ^ independently represents a group represented by 3 〇, an integer, and _(ZVb_二表; 1: indicates a carbon number of 1) ～4 Wei group or carbon (and Z independent group, B represents phenylene group, and s represents a group represented by ring-burning, not -CH2-, -C(CH3)2·, 54 200927790 -Ο a group represented by -, -CO-, -S- or S〇2_), or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group. In this case, a preferred W is a carbon number of 1~ An alkyl group of 8, an alkenyl group having a carbon number of 3 to 4, a cyclohexyl group, a phenyl group, a benzyl group, a poly(ethyleneoxy)ethyl group having a carbon number of 4 to 1 fluorene, a phenoxyphenyl group, or a phenyl fluorenyl group. a phenyl group, a phenylisopropylidene phenyl group, and a group in which one or two hydrogens of these groups are substituted by a hydroxyl group. When n = 2 in the formula (Ina) W represents an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, © a_zl_〇-(z2〇)r-Z3-( a group represented by Z1 to Z3 and r as defined above), a group represented by -Z4-B-Z5- (wherein Z4, Z5 and B are as described above), and -B-(0-B) sT-(B-0)sB- (B represents a phenylene group, T represents an alkylene group having a carbon number of 1 to 3, 〇 _ or _s 〇 2, and s represents a group represented by hydrazine or 1), Or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group. In this case, preferred W is an alkylene group having a carbon number of 2 to 12, a cyclohexylene group, a phenylene group, a phenylarylene group, a group represented by xylylene, -C3H6-0-(Z2-0)r-0-C3H6_ 〇 (Z2 represents a alkylene group having a carbon number of 2 to 6, and r represents 1 or 2), and (B) a group represented by a phenylene group and having a T group not represented by -CH^-, -0_ or -S02-), represented by _b-〇-B-C3H6-B-〇-B- (B represents a phenylene group) a group, and a group in which one or two hydrogens of these groups are substituted by a hydroxyl group. Such an alkenyl-substituted nadicylimine compound can be used, for example, as in Japanese Patent No. 2729565 As described, the obtained compound is synthesized by substituting an alkenyl-substituted nadic anhydride anhydride derivative and a diamine at a temperature of 80 ° C to 220 ° C for 0.55 hours to 2 hours, or a commercially available product. Specific examples of the compound-alkenyl substituted nadic ylidene compound include the compounds shown below. Ν-Methyl-dilylbicyclo[2.2.1]hept-5-ene-2,3-dimethyla Amine (N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N-mercapto-mercaptomethylbicyclo[2.2.1]hept-5-ene-2,3 - Dimethylimine, N-methyl-mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-methyl-decylallyl Bicyclo[2.2.丨]hepteose _2,3_dimethylhydrazine©imine, N-(2·ethylhexyl)-allylbicyclo[2.2.1]g _5_diluted_2,3 _ dimethyl quinone imine, N_(2-ethylhexyl) propyl (methyl) bicyclo [221] hept-5-ene-2,3-diindole, N-dilyl-thin Propylbicyclo[2.2.1]heptene_2,3_diimide, N-allyl-allylmethylbicyclo[2 21]hept-5-ene-2,3_diimine , N-allyl-mercaptopropyl bicyclo [22 g _5_ 稀_2,3_ dimethyl hydrazine , Ν-isopropenyl-allylbicyclo[2 21]hept-5-ene-2,3_diimine, oxime-isopropenyl-allyl (fluorenyl)bicyclo ρ 2丨]g 5-ene-2,3-dimethylimine, N-isopropenyl-methylallyl bicyclo [2 2 ^heptan® ene-2,3-diimine, N-cyclohexyl- Allyl bicyclophene P.2.1]hept-5-ene_2,3-dimethylimine, N-cyclohexyl-propylpropyl (fluorenyl)bicyclo ρ.2.ηg _5_ ene-2,3 -dimethylimine, fluorene-cyclohexyl-decylallyl biscyclo[2 21]hept-5, dilute-2,3-diindole, imine-phenyl-allyl bicyclo ρ.2 .η庚_5_稀_2,3· Diimine, Ν·笨基-Dilyl (methyl)bicyclo[2 2 ^_5_稀_2,3_一甲醯亚,,Ν- Alkyl-allylbicyclo[221]hept-5_wo-2,3-dimethylanimine, anthracene: benzyl-dipylmethylbicyclo[2 21]g_5_lean·2,3 _ dimethyl imino, Ν-knot group 曱 allyl bis bicyclo [2 2 ^ ng · ^ dil _2, 3 _ 曱 亚 亚 56 200927790 amine, N- (2 · thioethyl) _ Dilyl biscyclo[[3)]heptyl], N-side ethyl)g-methyl)di-silver dimethylimineimine' N_(2_-ethyl)-methyl-dip-biguanide, - dilute-2, 3-—I, imino, N-(2 2--methyl 1 1 ) · Ring called _, 3_丄亚- ❹ = propyl ^ methyl a) double ring [2.2.1] Geng Fu 2,3_ two "dipropenylene bicyclo [2.2.1] Geng Fu 2,3 ^ ^ G -5 躲二二N=,双卿.收·5= : Ψ =f ring called stalk (methyl) bisbicyclo[2.2.1]g _5_ene_2 3_ , ^ (4 phenyl) ) allylpropyl (fluorenyl) double heterogeneous heptene 2,3 oxime diyl > dilute phenyl > methallyl bisphenylyl). methyl aryl ... "amine N-(3-hydroxyphenyl)- propylpropyl dimethyl hydrazine-transferred _ group ^) ==, 3_ dilute _2,3-dimethyl urethane, N_( =[2.2.1]g-5 - && dimethyl quinone imine, bicyclo [2.2.1] g _5_ dilute _2 3 - bis, ethoxylated) ethyl bromide Ν - {2- (2. Ethyl) bis-bis: tyrosine, f quinane. 2. ''-Asian two:=ί 57 200927790 ethoxy)ethoxy}ethyl]-dilylbicyclop 2 ηg _5 _ dilute _2,3 bis quinone imine, Ν-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl; I- propyl propyl (fluorenyl) bicyclo [2.2.1 Hg-5-ene-2,3-diimineimine, Ν-[2-{2_(2-hydroxyethoxy)ethoxy}ethyl]-mercaptopropyl bicyclo [22.η Geng_5_ene_2,3-dimethylanimine, Ν-{4·(4.hydroxyphenylisopropylidene)phenyl Diallylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine, Ν-{4-(4-hydroxyphenylisopropylidene) benzyl}•dilyl Methyl)bicyclo[2.2.1]hept-5-indole-2,3-diimineimine, Ν-{4_(4-hydroxyphenylisopropylidene)phenyl}-mercaptopropyl double ring [2.2.1] G--5-ene-2,3-one brewed imine, and their oligomers (〇iig〇mer); N,N'-ethylene-bis(allylbicycloindole) (N,N-ethylene-bisCallylbicyclol^HJhept-S-eneJ'S-dicarboximide) , N,N'-ethylene bis(dipropyl fluorenylbicyclo[ 221] G-5-Wo-2,3-dimethylimine), N,N,·Ethylene-bis(methylallylbicyclo[2.2.1]hept-5-rare-2,3 - bismuth imine), ν, Ν'·triamyl bis(dipropylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), ν, Ν, - Hexamethylene-bis(allylbicyclo[2.2.1]hept-5-female-2,3-carboximine), ν, Ν,-hexamethylene-® bis (l-propyl hydrazine) Bicyclo[2.2.1]hept-5-ene-2,3-diindoleimine), ν, Ν, - 12 fluorenyl bis(allylbicyclo[2·2 ”h-, ene 2,3_dimethylimine ), Ν,Ν'-docamethylene-bis(allylmethylbicyclic guanidine.21]hept-5-ene-2,3-diimineimine), ruthenium, osmium, _cyclohexylene _Bis(allylbicyclo[2 21]hept-5-ene-2,3-dimethylimineimine), ν,Ν,-cyclohexylene-bis(allylhydrazylbicycloindole.2.1) -5-ene·2,3-diimineimine), bis, 〆 propyl bisbicyclic P.2.1] g _5_ roasted-2,3-dimethyl quinone imine) propoxy} Alkane, u-double {3, _ (propyl propyl methyl bicyclic P.2.1) hept-5-ene 2,3-dimethylimine imine) propoxy} ethyl 58 200927790 , alkane, 1,2- Double {3,-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)propoxy}ethyl bromide, biguanide··{3'·(lean Propylbicyclo[2.2.1]hept-5·ene·2,3_dimethylimine imine)propoxy}ethyl]ether, bis[2,-{3l (allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-diimineimine)propoxy}ethyl]ether, i 4•double {3·-(dilylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine imine)propoxy}butane, 1,4-bis{3'-(allylmethylbicyclic oxime^heptene-ene^diimide)propoxy丁丁丁, N, N'-p-phenylene-bis(dil-propylbicyclo[2 2.1]hept-5-ene -2,3_dimethylimine imine), N,N'-p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dimethylimine ), n, N'-meta-phenylene _ bis (allyl bicyclo [2.2.1] hept-5-ene-2,3-diimine imine), N, N, _ m-phenylene _ Bis($propylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), nkoiyl)-2,4-phenylene}-bis(allylbiscycloolefin 3_dimethylimine imine), N,N,-p-diphenylene phenyl-bis(allylbicyclo[2·2 ηhept-5-ene-2,3·diimide), Ν, Ν, _ p-diphenyl phenyl bis (allyl fluorenylbicyclo [2.2.1] hept-5-ene-2,3-dimethyl quinone imine), hydrazine, hydrazine, - mica曱Phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), hydrazine, hydrazine, m-xylene-based bis-allyl Bicyclic guanidine .2.1] hept-5-ene-2,3-dimethyl quinone imine), 2,2 bis [Μ4·(allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethyl imidate) phenoxy} phenyl] propane, 2,2 bis [4_{4_(allylmethylbicyclo[2 21]hept-5-dimethyl dimethylimine) phenoxy }phenyl]propane, 2,2_bis[4_{4曱曱ylallylbicycloindole.2.1]hept-5-ene-2,3-dimethylhydrazine Imine)phenoxy}phenyl]propane, bis{4-(allylbiscycloalkenene-2,3-dimethylimine)phenyl}H, bis{4-(dilylmethylbicyclo[ 2·2· 1]g _5·埽·2,3_: formazan 1 amine) stupid} methane, double {((methylallyl bis-cyclic 59 200927790 bis-imine) phenyl} decane, Double {4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine)phenyl}methane, double {4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dimethyleneimine)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, double { 4-(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)phenyl}indole, bis{4-(allylhydrylbicyclo[2.2.1]g -5-ene-2,3-diimineimine)phenyl}sulfone, bis{4-(mercaptoallylbicyclo[2.2.1]hept-5-ene-2,3-dioxime Amine)phenyl} © sulfone, 1,6-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 dimethylimine)-3-hydroxy-hexane, U2-double ( Mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine)-3,6-dihydroxy-dodecane, 1,3-bis(allyl Ring [2.2.1] hept-5-ene-2,3-diimineimine)-5-hydroxy-cyclohexane, 1,5-bis{3·-(allylbicycloP.2.1]g -5-ene-2,3-diimineimine)propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2·2·1]hept-5-ene- 2,3-dimethylimine)-2-hydroxybenzene, 1,4-bis(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)- 2,5-dihydroxy-benzene, N,N'-p-(2-hydroxy)-xylylene-bis(allyl-ylbicyclo-P.2.1]hept-5-ene-2,3-dimethyl Imine), N, N'-p-(2-hydroxy) stilbene phenyl-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-diimine ),N,N'-m-(2-hydroxy)pyridinium-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, hydrazine ·---(2-hydroxy) stilbene phenyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, Ν'- P-(2,3-dihydroxy)pyridinium-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), 2,2-dual [ 4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine)-2-hydroxy-indolyl}phenyl]propane, double {4-( Allyl 200927790 J-based f-ene '3-dimethylanimine>_2-trans-phenyl·methyl}methyl, bis (3_(allylbicyclo[2.2.. phenyl-phenyl} ether, double {3 彳 μ μ imide blanket II ( Ft-propyl bicyclic guanidine .2.1]g _5_rare-2,3-dimethyl, / },, three {4_(allyl-propylbicyclo). Oxydecylpropane, N,N',N"--(Ethylene-methylallylbicyclo[2 2"]hept_5_diluted_2,3•2? Iridoids, isocyanurates, and oligomers thereof.

Further, the alkenyl-substituted nadicylimine compound used in the present invention may be an asymmetric compound containing an alkylene group or a phenylene group as a structural formula.

61 200927790 Preferred among imine compounds The following alkenyl substituted nadik 醯

Dilute-2,3·dimethylanimine), N, NL ethylene·bis(allylbicyclo[2.2.1]hept-5-ene-2,3 hept-5_rare-2,3· Dimethyl imine), Yeriya fakilu ^| De silly

- bis(allylmethylbicyclo[221]hept-5ethylene-bis(methyl-propionate ring [2 2 ηhept, hydrazine, hydrazine, _trientylene-bis(allylbicyclo[2.2] .1] ΙΜ, Γ, 卜, methylene dimethyl quinone imine), NJST-docamethylene-bis (l-propyl fluorenyl bicyclo [2.2.1] G · 542, 3 · A Brewed amines, hydrazine, hydrazine, - cyclohexylene-bis (dilyl propyl bicyclo [2 21] g _5_ dil _2 3 bis-imine), hydrazine, hydrazine, - cyclohexylene bis ( Propylmethylbicyclo[221]heptadiene-2,3-diimineimine), anthracene, fluorene,-p-stylene-bis(allylbicyclo[2 2丨]hept-5-ene- 2,3-dimethylimine), hydrazine, hydrazine, _p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine) , Ν, Ν, - m-phenylene-bis(allyl hydrazine double soil [2.2.1] hept-5-lean-2,3-·one brewed imine), hydrazine, Ν'-m-phenylene Base_bis(f-propyl decylbicyclo[2·2·1]hept-5-ene-2,3-dimethylenimine), ν ν,_{(1-methyl)-2,4- Substrate } bis (allyl bicyclo [2.2.1] g · 5 ^ 2, 3 - dimethyl quinone imine), hydrazine, hydrazine - p-indenyl quinone-bis (propyl propyl bicyclo [2.2. 1] G-5-Moth-2,3-diimine), Ν Ν·-p-p-phenylene-bis(allylmethylbicycloindole.2.1]hept-5-lean-2,3-dimethylimine), hydrazine, Ν'·m-xylylene _ Bis(dilylbiscyclo[2.2.1]hept-5-rare-2,3-diindoleimine), ν,ν,_m-xylylene-bis(trimylmethylbicyclo[2.2. 1]g-5-rare-2,3-di-anthracene imine), 2,2- 62 200927790 bis [4-{4·(dilyl bis-bicyclo[2.2.1]hept-5|2,3_ Dimethyl imidate) phenoxy} phenyl] propyl ketone, 2, 2- bis [M 4 · (dilyl propyl bis bicyclo [ 克 · · 5 5 . . , , , , ) ) ) ) ) )) Phenoxy}phenyl]propane, 2,2_bis[4_(tetra)methyldipylbicyclo[2·2.1]hept-5m曱iimide) phenyloxy}phenyl]propane, double {4· (dilyl propyl bicyclic cations, 3 dimethyl imipenem) phenyl} methane, double {4_(enmethylbicyclo[2.2 g·

Amine) phenyl} 甲院, the final (▼ base ally propyl double-called g--5-U · : methyl imine) phenyl} A hospital, double {4_ (methyl propyl propyl bicyclo [2 21] Geng-5, 2,3-dimethylimine, phenyl}, and bis(dipropylbicyclo[2.2.1]hept-5-ene·2,3_:carnimine)benzene Base, double {4_(propyl propyl hydrazinobicyclo[2.2:1]g _5_埽_2,3_dimethylimine) phenyl} scale, bis(tetra)methyl propyl propyl = [Ζ2 .1] G-5-晞_2,3-dimethylenimine)phenyl, bis(tetra)propylidene hydrazide.2.1]hept-5-ene-2,3_diphenylenimine)phenyl } hard, bis (tetra) propyl propyl double bad [2.2.1] g _5_ 埽 2, 3- dimethyl imino) phenyl} 飒, bis (methyl propyl bicyclo [2.2. Lm_5|2,3·dimethylenimine)phenyl} The more preferred alkenyl substituted nadic quinone imine compound is listed below. N,N ethylidene-bis(allylbicyclo P.2.1]hept-5-female-2,3-dimethylimine]} 'N'N'•ethylene·bis(l-propylmethyl) Bicyclophene P.2.1]hept-5-oxime-2,3--carboimine), N,N'-ethylidene.bis(methylpropylpropylbicyclo[2 21]hepta-5_zinc-2, 3-dimethylimine), _,_trimethylenebis(dilylbicyclo[(2)]hept-5-ene-2,3-dimethylimine), hydrazine, hydrazine, _hexamethylene fluorenyl _ bis (allyl bicyclo [2.2.1] hept-5-ene 2,3-dimethyl quinone imine), n, n, _a methylene _ bis (allyl methyl bicyclo [2.2.1 ]g _5·lean·2,3·4 yimine), N, NL, tau, p-group 63 200927790 amine), t-mercaptobicyclopurine.1]g. 2,3·dimethyl ya 23 1 sparse; π; π-hexyl-bisallylmethylbicyclo[2.2.1]heptene 5, alkene, anthracene, anthracene, p-phenylene-bis(allylbiscyclo[2·2. ji % ' N'N'. Phenyl bis (propyl propyl hydrazide propyl propyl bicyclomethyl hydrazine _ m-phenylene pinned ... Geng Xi, 曱醯 imine), job - { (1_ 甲土) _2, 4· phenylene b double (dilyl propyl bicyclo [Μ 士 稀 办 醯 醯 、 、 、 、 、 、 、 、 、 、 、 亚 亚 柄 柄 柄 柄 : : : : : : : : : : : : : : : : : : : : A stupid base, propyl propyl bicyclol; Mercaptoimine), taken, m-xylylene _ bis (diluted = double coat [2.2.1] hept-5-ene-2,3 dimethylanimine), N, N, · ya Xylene^bis(dilylpropylbicyclo[2.2._5.2,3-dimethylenimine), 2,2_bis[4-{4-(allylbicyclo[2.2.1:1g] 5_妇·2,3_ 麟基]Binyuan, 2,2·double array (allylmethylbicyclo[221=2,2,3-dimethylimine]phenoxy}phenyl]propane, Propyl bicyclo (10)] Gengfu diimide) Stupid, double {4-(allyl bicyclo [2.2.^.5. olefinic xylenimide) phenyl} methane, double {4 · (red propylene Methylbicyclo[2.21]glycol-5-diluted _2,3-diennimine)phenyl}f-fired, biguanide (methylallylbicyclo[221]hept_5_#_2,3_-A Stuffed (5) phenyl, double {4_(methylpropylpropylmethylbicyclo[221]hept-5-ene-2,3-dimethylimine)phenyl}f-alkane. 200927790 and 'particularly preferred The alkenyl-substituted nadicylimine compound can be exemplified by the following double (4) (allylbicyclo[2·2.1]hept-5-return-2,3-dimethyl group represented by the (10) configuration (Ina-1). ,imino)phenyl} 曱, N,N,_m-xylylene _bis(allylbicyclo[2 21]g _5 represented by the structural formula (1 sen 2) _ olefin 2'3 monomethylimine), and N,N'-hexamethylene bis (dipropyl biscyclo[2.2.1] gh·5·dilute 2, represented by the structural formula (Ina_3), 3. Two brewed imines).

(I na-3) Further, for example, from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention can be a compound of a polymerizable unsaturated double bond. The compound having a free === and a double bond may be one compound or two or more compounds. Further, the filament-substituted nadick-bromide compound is not included in the compound having a radical polymerizable unsaturated double bond. From the viewpoint of the above, the content of the compound having a radical polymerizable unsaturated double bond is preferably 0.01 to 1.00, more preferably 0 01 to 0, based on the weight ratio of the polyglycine or the derivative thereof. 70, further preferably 65 200927790 is 0.01 ~ 〇 5 〇. Further, from the viewpoint of lowering the ion density of the liquid crystal display element, suppressing the increase of the ion density 2 with time, and suppressing the afterimage, the compound having a radical polymerizable unsaturated double bond is substituted with a dilute group of Nadick's acrylonitrile: The ratio of 匕5: is preferably 0.1 to 10' by weight. More preferably, the compound having a radical polymerizable unsaturated double bond may be (mercapto) acrylate, (mercapto) acrylamide or the like. (Mercapto) acrylic acid derivatives and bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more free radically polymerizable unsaturated double bonds. Specific examples of the (mercapto) acrylate include, for example, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid 2-methylcyclohexyl ester, and (meth)acrylic acid dicyclopentyl ester. (fluorenyl) dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth) acrylate, (benzyl) benzyl acrylate, (meth) acrylate 2-hydroxyethyl ester and (fluorenyl) acrylic acid φ 2-hydroxypropyl ester. Specific examples of the difunctional (meth)propionic acid ester include, for example, a product of AEDIX M-210, ARONIX M-240 and ARONIX M-6200.

Products of KAICRAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and Co., Ltd. Company 66 200927790's products Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA.

Specific examples of the trifunctional or trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4'-fluorenylene bis(N,N-dihydroxyethylene acrylate aniline), ARONIX M- 400, ARONIX M-405, ARONIX M-450, ARONIX Μ-Ή00, ARONIX M-8030, ARONIX M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD 〇DPCA-120 And VGPT, a product of Osaka Organic Chemical Industry Co., Ltd. Specific examples of the (meth) acrylamide derivative include, for example, N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, N-n-propyl Alkyl acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl decyl acrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl decyl acrylamide , N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl acrylamide guanamine, N-ethyl acrylamide, N-ethyl-N-mercapto acrylamide , N,N-diethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-propylene decyl acridine (N- Acryloyl piperidine), N-acryl〇yl pyrrolidine, n,n'-methylenebis acrylamide, n,N'-ethylenebis acrylamide, n, N'-dihydroxyethylene bis propylene amide, N-(4-hydroxyphenyl) decyl acrylamide, N-phenyl methacrylamide, N-butyl decyl acrylamide, N- (isobutoxymethyl)mercaptopropenylamine, N-[2-(N,N-dimethylamino)ethyl]methyl 67 200927790 , N,N-dimethylmethyl propyl melamine, n-[3-(dimethylamino)propyl]methacrylamide, N-(decyloxymethyl)methacrylamide, N-(hydroxymethyl)_2-methacrylamide, Nbenzyl·2·decyl acrylamide, and hydrazine, Ν'-methylene bis methacrylamide. Among the (meth)acrylic acid derivatives, particularly preferred are ruthenium, osmium, dimethylene bis decyl decylamine, hydrazine, Ν'-dihydroxyethylene-bis acrylamide, ethylene diacrylate, and 4 , 4, _ methylene bis (hydrazine, hydrazine - dihydroxy ethylene acrylate aniline).

® Bismaleimide can be exemplified by: bMi_7〇 and bMI_8〇 manufactured by INDUSTRY CHEMICAL INDUSTRY Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and manufactured by Daiwa Kasei Kogyo Co., Ltd. BMI-7000. Further, the liquid crystal alignment agent of the present invention may further contain a azine compound, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The β-oxazine compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the oxazine compound G is preferably 〇.丨 by weight / relative to the polyamic acid or a derivative thereof. It is preferably 50% by weight, more preferably i% by weight to 4% by weight, still more preferably 1% by weight to 20% by weight. The oxazine compound is preferably an oxazine compound which is soluble in a solvent which dissolves polyamic acid or a derivative thereof and which has ring-opening polymerizability. Further, the number of the oxazine structure in the oxazine compound is not particularly limited. Regarding the structure of the crucible, various structures are known. In the present invention, the structure of β-oxazine 68 200927790 is not particularly limited, and the oxazine structure in the oxazine compound may be exemplified by benzoxazine or naphth〇xazine. The oxazine structure of the aromatic group of the condensed polycyclic aromatic group. The oxazine compound may, for example, be a compound represented by the following formula (a) to formula (f). Further, in the following formula, the bond represented toward the center of the ring means that it is bonded to any of the carbon constituting the ring and capable of bonding the substituent.

In the above formulae (a) to (c), Ri and R2 represent an organic group having 1 to 30 carbon atoms. Further, in the above formulae (a) to (f), R3 to R6 represent hydrogen or a hydrocarbon group having a number of turns of 1 to 6. Further, in the above formula (c), formula (d) and formula (f), X represents a single bond, _〇, _s_, -S_S-, -S〇2-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, -(CH2)m-, -〇_(CH2)m_〇·, _s(CH2)m_s. Here m is an integer from 1 to 6. Moreover, in the general formula (e) and the general formula (f), 69 200927790 Υ independently represents a single bond, -Ο-, -S-, -CO-, -c(CH3)2-, -C(CF3 ) 2_ or a sub-alkyl group having a carbon number of 1 to 3. The hydrogen bonded to the benzene ring or the naphthalene ring of Y may be independently substituted into _F, -CH3, -OH, , , so3h, -ρ〇3Η2 〇 and the side chain of the oxazine compound is included. The ruthenium or the polymer having an oxazine structure, the oligomer having an oxazine structure in the main chain, or the polyfluorene. The compound represented by the formula (a) is exemplified by the following compounds.

In the formula, R is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the formula (b) may, for example, be the following oxazine compound.

70 200927790

(b-9) (b-10) In the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms. The oxazine compound represented by the following formula (I) is exemplified by the oxazine compound represented by the following formula (I). 71 (I) 200927790

Ο In the above formula (I), R1 and R2 represent an organic group having a carbon number of 1 to 30, R3 to R6 represent an anthracene or a hydrocarbon group having 1 to 6 carbon atoms, and X represents a single bond, -CH2-, - C(CH3)2-, _CO-, 0_, -S02- or -C(CF3)2-. The oxazine compound represented by the above formula (I) is exemplified by the following anthraquinone compound.

C

72 200927790

(〇13)

(014)

73 200927790 In the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. The oxazine compound represented by the formula (d) is exemplified by the following oxime compounds.

The σ-killing compound represented by the formula (e) is exemplified by the following ? 74 200927790

(e-5)

The oxazine compound represented by the formula (f) is exemplified by the following acetonide compounds.

75 200927790

More preferably, it can be exemplified by the formula (b ❹ (2a(d, 4(:r'3)(, ;V;-5), w-7), _4). -V rf_9N 4 , the oxazine compound represented by the formula (d-6), the formula (e-3), and the formula (e^~work (f~4). The V-Qin compound can be _Sakizaki-Cong Cong-tong booklet, Japan It is produced by the same method as the method described in JP-A-2004-352670. For example, the oxazine compound represented by the formula (a) can be obtained by making a compound or a primary compound. And an aldehyde reaction (refer to International Publication No. 2004/009708 pamphlet). 76 200927790 The bismuth compound represented by t(b) can be obtained by the following method. After the addition, the reaction with a hetero (naphth〇1) system is added (refer to International Publication No. 2004/009708°, Line 2:: (c), scale = can be used in the following agent' in the aliphatic secondary amine In the presence of an aliphatic tertiary amine or an intrinsic _ ring-containing compound,

The substance is reacted with respect to a mash thereof of at least 2 moles or more than 2 moles, and 1 mole of azide (refer to International Publication No. 2004/009708 pamphlet and Japanese Patent Laid-Open Publication No.). Further, the oxime compound represented by the general formulae (4) to (1) can be obtained by an organic method of having a plurality of acyclic rings and bonding benzene rings such as 4,4,-diaminodiphenyl decane. The group's diamine, formalin and other acids and benzene are in n-butanol at 9 〇. Dehydration condensation reaction is carried out at a temperature of 〇 or above 9 〇〇c (refer to Japanese Laid-Open Patent Publication No. 2004-352670). Further, the liquid crystal alignment agent of the present invention can be further contained, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. From such a viewpoint, the content of the oxazoline compound is preferably 0.1% by weight to 50% by weight, and more preferably 1% by weight to 40% by weight, based on the polyamic acid or a derivative thereof. Further 77, 200927790 is preferably from 1% by weight to 20% by weight. From the above point of view, it is preferable that the three sets of the ny U lining mouth are. When the phlegm is phlegm, it is 0.1% by weight to 4% by weight relative to the polyamic acid or the second organism.

❹ The Celine compound may have only one type of structure in one compound, or two or two types in one compound: Further, it is desirable that the compounding has a structure of one or more of the above-described structures, and it is preferable to have two or more (four) m structures. Further, the oxime compound may be a polymer having a t(tetra) ring structure on a side bond or a copolymer. The conjugated (tetra) compound on the side bond may be a homopolymer of a monomer having a shooter structure on the side chain, or a monomer having a shooter structure on the S side chain and a monomer having no oxazoline structure. Copolymer. The oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in a side chain, or two of a side chain having a odor β sitting structure. A copolymer of two or more kinds of monomers and a monomer having no oxazoline structure. The oxazoline structure is preferably a structure which is present in the oxazoline compound to allow one or both of oxygen and nitrogen in the oxazoline structure to react with the carbonyl group of the polylysine. The oxazoline compound may, for example, be 2,2'-bis(2-oxazole), 1,2,4_tri-(2-11 oxalinyl-2)-:^(1,2, 4-tris-(2-oxazolinyl-2)-benzene), 4-π-Bus-2-yl-indenyl-2-phenyl-4H- ° Evil "Sit 5- _ (4-furan-2- Ylmethylene-2-phenyl-4H-oxazole, 5-one), 1,4-78 200927790 Bis(4,5-dihydro-2-oxazolyl)benzene, ι,3-bis(4,5-dihydrogen) _2-oxazolyl)benzene, 2,3-bis(4-isopropionyl-2·»oxo-salt_2_yl) butadiene, 2,2,·double-base 2

嚼 chewed salin, 2,6-bis(isopropyl-2-oxazoline-2-yl) bite, 2,2,·iso- benzyl bis(4-tert-butyl-2-oxazoline ), 2,2,-isopropylidene bis(4_phenyl_2-oxadiline), 2,2 benzylidene bis(4.tert-butyl-2-oxazoline), and 2,2 '_Alkenylene bis(4-phenyl-2-oxazoline). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group such as EPOCROS (trade name, manufactured by Sakamoto Co., Ltd.) may be mentioned. More preferably, the oxazoline compound is exemplified by (2-charyphyrin) and dihydro-2-oxazolyl)benzene. Further, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element, the liquid crystal alignment agent of the present invention may further contain an epoxidized human. The epoxy compound may be a "species compound" or a combination of two or more kinds. From the viewpoint of the above, the content of the epoxy compound is more preferably i% by weight to 4% by weight relative to the polyamic acid or a derivative thereof. %~2〇m More important, the epoxy compound may have one or two or more epoxy groups in the molecule. The various compounds have an epoxy ring in the molecule, such as phenyl glycidyl ether and butyl. Reduced water _, 3j, methyl epoxy city (3,3,3 catch _qingyleneQxide), gas 'Benzene 0Xide, hexafluoropropylene oxide, oxidized (cydohexene oxide), 3_glycidoxy Propyl tricalcium, 2-(3,4-epoxycyclohexyl)ethyltrimethoxywei, n'glycolate 79 200927790 , phthalic acid imine, (nonafluoro_N_butyl) epoxy ((n〇nafluoro-N-butyl)ep0xicie), perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N,N• diglycidyl aniline, and 3-[2_(all Fluorohexyl)ethoxy]-1,2-epoxypropane. Examples of the compound having two epoxy rings in the molecule include ethyleneglycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol dicondensation:

Manganese, polypropylene glycol digoxime _, neopentyl glycol dimethyl condensate (tetra), hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl _, 3 , 4 epoxy ring hexenylmethyl _ 3,, 4, _ epoxy cyclohexanic acid vinegar and 3 · (Ν, Ν _ diglycidyl) aminopropyl tributary oxylate. Examples of the compound having two epoxy rings in the knives include, for example, a certain one, a propylene group, a phenyl group, and a 1-bis[4-([2,3·epoxypropoxylate J-based)]ethyl group] Phenyl]propane

"Che fox", (Mitsui Chemical) Yasushi) ECHM〇RE: Sub-compound: Compounds having four epoxy rings are exemplified by: glyceryl groups from decyl alcohol, decene, glycerol, tetraglycidyl, 1,3-double ( Ν, Ν- diglycidyl hydrazine, carbamide, n, n, n, n, _w condensed & u 4 /, basal methyl) lysine 3 ·-allyl * condensed Phenyl methane and a filament of a filament which is exemplified by the monomerization of the compound. The epoxy group has an epoxy ring such as 7 to give: (meth)acrylic acid glycidic vinegar, (methyl) 200927790 acrylic acid 3,4-epoxycyclohexyl ester and decyl glycidyl (mercapto) acrylate. Other monomers copolymerized with a monomer having an epoxy ring may, for example, be (meth)acrylic acid or (methyl) ) decyl acrylate, ethyl (meth) acrylate 'isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (曱) Cyclohexyl acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, decyl benzene Alkene, chlorodecyl styrene, (3-ethyl-3-epoxypropenyl)methyl (meth) acrylate, fluorene-cyclohexylmaleimide, and fluorenyl-phenylmaleimine. Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate, etc. Further preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include: Ν-phenylmaleimide-glycidyl methacrylate copolymer, fluorene-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-mercapto acrylic acid shrinkage Glycerin copolymer, butyl acetonate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate hydrazide hydrazide glyceride copolymer, methacrylic acid (3-ethyl- 3-glycidyl) decyl ester-glycidyl methacrylate copolymer and styrene methacrylic acid glycidyl vinegar copolymer. Among these examples, Ν, Ν, Ν', Ν'-tetraglycidyl group are particularly preferred. -m-phenylenediamine, 1,3-bis(indole, hydrazine-diglycidylaminodecyl)cyclohexane, hydrazine ,Ν,Ν,,Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "TECHMORE VG3101L", 3,4-epoxycyclohexenylindolyl-3·,4 '-Epoxycyclohexene decanoate, fluorenyl-phenylmaleimide-glycidol methacrylate 81 200927790 Ester copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxylate More specifically, the epoxy compound may, for example, be a glyceryl ether, a glycidyl glycoside, a glycidylamine, an epoxy group-containing acryl resin, a glycidol, a isocyanuric acid, or a water. Aliphatic epoxy compound, money and fat type epoxy compound. Further, the compound means a compound having an epoxy group, and the epoxy group means a resin having a ring group.

The glycidol_ can be exemplified by: Wei A type epoxidized character, double F type epoxy compound, double s type epoxy compound, double expectant diepoxide compound, hydrogenated Wei_A type Wei compound, hydrogenated Wei type Oxygen compound, i (4) _S type epoxy compound, hydrogenated bis-epoxy compound, sister (four) _A Wei oxygen compound, singular type epoxy compound, phenolnovolac type epoxy compound, aging varnish丨_lae) _Oxygen compound, benzene-promoting varnish-type epoxy compound, brominated phenolic phenolic varnish-type epoxy compound, Pan-A varnish-type epoxy compound, naphthalene-containing slag oxide, aromatic polycondensation Glycerol bismuth compound, bicyclic fluorene diene epoxy compound, alicyclic diglycidyl compound, aliphatic polyglycidyl compound, polysulfide (P〇lySulflde) type diglycidyl hydrazine compound, and biphenol type ring Oxygen compound. The glycidol vinegar may, for example, be a diglycidyl vinegar compound or a glycidyl ester epoxy compound. The glycidylamine may, for example, be a polyglycidylamine compound. The epoxy group-containing acrylic compound may, for example, be a homopolymer of a monomer having a epoxidizing group of ring 82 200927790 and a copolymer of the glycidyl amide such as a compound. The glycidylamine type epoxy compound is exemplified as the epoxy group-containing epoxy compound. For example, an epoxy group-containing compound obtained by oxidizing a carbon bond of a dilute tobacco compound can be mentioned. The cyclic aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a ring-based compound. Examples of the bisphenolphthalein type epoxy compound include 828, 1〇〇1, 1002, 1003, 1004, 1007, and 1〇1〇 (all manufactured by Japan epoxy resin), and EPOTOHTO YD-128 (Dongdu Chemical Company) Manufactured), DER 331, Ο ο DER-332, DER-324 (all manufactured by Dow Chemical Company), EPICLON 840, EPICLON 850, EPICLON 1050 (all manufactured by Dainippon Ink) ' EPOMIC R-140, EPOMIC R-301 And EPOMIC R-304 (both manufactured by Mitsui Chemicals). Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by sakamoto epoxy resin), EPOTOHTO YDF-170, EPOTOHTO YDF-175S, and EPOTOHTO YDF-2001 (all manufactured by Dongdu Chemical Co., Ltd.). ), DER-354 (manufactured by Dow Chemical Co., Ltd.), EPICLON 830 and EPICLON 835 (all manufactured by Dainippon Ink). The bisphenol type epoxy compound may, for example, be an epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. Examples of the hydrogenated bisphenol-A type epoxy compound include: SUNTOHTO ST-3000 (manufactured by Tohto Kasei Co., Ltd.), RIKARESIN HBE-100 (Nippon Chemical and Chemical Manufacturing Co., Ltd.), and DENACOL EX-252 83 200927790 (manufactured by Nagase Chemtex Co., Ltd.) The hydrogenated bis-epoxy compound may, for example, be an epoxide of 2·-phenylphenyl H,U,3,3,3-hexafluoropropane. Examples of the desertification-type A-type epoxy compound include: 5〇5〇, 5051 (all manufactured by Japanese epoxy resin), Ερ〇τ〇Ητ〇, EPOTOHTO YDB-400 (both Dongdu Chemical Company) Manufactured), DER-530, DER-538 (all manufactured by D〇w Chemical Co., Ltd.), veins: L〇N152 and EPICLONl53 (all manufactured by Dainippon Ink). ^ The phenol novolac type epoxy compound may, for example, be 152, 154 (all manufactured by Japan epoxy resin), YDpN_638 (manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (all manufactured by D〇w Chemical Co., Ltd.) ' EPICLONN -770 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EPPN-201 and EPPN-202 (both manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolac type epoxy compound include: 180S75 (manufactured by Nippon Epoxy Resin) ydcN-701, YDCN-702 (all manufactured by Dongdu Chemical Co., Ltd.), EPICLON N-665, EPICLON N-695 ( Manufactured by Otsuka Ink Chemical Industry Co., Ltd., EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.). For example, 157S70 (manufactured by Nippon Epoxy Resin Co., Ltd.) and epjclON N-880 (manufactured by Dainippon Ink Chemicals Co., Ltd.) can be cited as the varnish-type epoxy compound. 84 200927790 The epoxy compound of the 3 naphthalene matrix can be exemplified by epiclon HP-4032, EPICLON HP-4700, EPICLON HP-4770 (all manufactured by Otsuka Ink Chemical Industry Co., Ltd.), and NC-7000 ( Made by Sakamoto Chemical Co., Ltd.). The aromatic polyglycidyl ether compound may, for example, be hydroquinone diglycidyl ether (formula E101 below) or catechol diglycidyl ether (the following structural formula) E102), resorcinol diglycidyl ether

(resorcinol diglycidyl ether 'the following structural formula E103), tris(4-glycidoxyphenyl)decane (the following structural formula E105)' l〇31S, 1032H60 (all manufactured by sakamoto epoxy resin), TACTIX -742 (manufactured by D〇w Chemical Co., Ltd.), DENACOL EX-201 (manufactured by Nagase Chemex), DPPN-503, DPPN-502H, DPPN-5〇1H, NC6_ (both made by Nippon Chemical Co., Ltd.) T MGRE VG31〇1L (manufactured by Mitsui Chemicals, Inc.), a compound represented by the following structural formula *6, and a compound represented by the following structural formula Ε107

(Ε101) 0:

:0 (Ε102) Ο

(Ε103)

85 200927790

ΤΑ二述: The cyclopentane-type epoxy compound can be exemplified by, for example:

Γρ 7,ππ (D〇W ChCmiCal ^5lt^)-^EPICL0N ο

HP-7200 (Daily Ink Chemical Industry Co., Ltd. manufactures the alicyclic diglycidyl ether compound, for example, by burning dimethanol diglycidyl bond compound c as dihexyl N DME-100 (manufactured by Shin Nippon Chemical Co., Ltd.). Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula E108) and diethylene glycol dihydrate: oil scale (the following structural formula E1G9), polyethylene glycol diglycerin Propylene glycol diglycidyl ether (the following structure J), tripropylene glycol diglycidyl ether (the following structural formula El11), polypropylene glycol diglycidyl shunt, neodecanediol dihydrated _ (Bo structural formula (4)), Ding ^ 2 2 86 200927790 glyceryl ether (structure E113 below), 1,6-hexanediol diglycidolithic (the following structural formula E114), dibromo neopentyl glycol diglycidyl ether (the following structural formula) E115), DENACOL EX-810, DENACOL EX-851, DENACOL EX-8301, DENACOL EX-911, DENACOL EX-920, DENACOL EX-931, DENACOL EX-211, DENACOL EX-212, DENACOL EX-313 (all Nagase chemtex company), DD-503 (made by Asahi Kasei), RIKAR ESIN 1-100 (Nippon Chemical and Chemical Manufacturing Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediethanol (the following structural formula Ε116), glycerol polyglycidol mystery, sorbitol polymerization Hydroxide polyglycidyl ether, trimethylol propyl polyglycidyl ether, pentaerythritol polyglycidyl ether, DENACOL EX-313, DENACOL EX-611, DENACOL EX-321 and DENACOL EX-411 (both Nagase chemtex) Manufacturing)〇

(E11〇) (E111) (E112)

(E113) (E114) 87 200927790

(Ε115) (Ε116) ... I-formation type glycidol test compound can be exemplified by FLDP 50 and FLDp_6 (all manufactured by T〇ray Thiokol). Examples of the biphenol-based epoxy compound include YX-4000, Ο

YL-6121H (all manufactured by Sakamoto Epoxy Resin), NC-3000P and NC-3000S (both manufactured by Nippon Kayaku Co., Ltd.). The diglycidyl ester compound is, for example, <exemplified by: diglycidyl terephthalate (the following structural formula 117), o-dibenzoic acid diglycidyl-'-deficient formula E118), phthalic acid Bis(2- mercapto oxiranyl ester, the following structural formula E119), a compound represented by the following structural formula E121, and a compound of two. Construction E123 table’

Methyl) vinegar as a compound of the formula E122 (IV) and with the following knot

(E119) 88 (£121) 200927790 ο

(Ε123) The glycidol vinegar ring can be exemplified by: 871, 872 (all manufactured by sakamoto epoxy resin), EPlCL〇N 200, EPICLON 400 0 (all are limited by Dainippon Ink Chemical Industry Co., Ltd.) Made by the company), DENACOL EX-711 and DENACOL EX-721 (both manufactured by Nagase Chemt汊). Examples of the polyglycidylamine compound include N,N-diglycidylaniline (the following structural formula E124), n,N-diglycidyl-o-toluidine (the following structural formula E125), N, N-diglycidyl-m-toluidine (structure E126 below), N,N-diglycidyl-2,4,6-tris-aniline (the following structural formula 27), 3-(fan 1 ^Diglycidyl)aminopropyltrimethoxymethoxypropane (Structure of Formula E128 below), N,N,〇-triglycidyl-p-aminophenylphenol (Structure of Formula E129 below), N,N, 0-triglycidyl-m-aminophenol (structural formula E130 below), 1^,:^, thio-tetraglycidyl-m-diphenyl phenyl diamine (TETRAD-X (Mitsubishi Gas Chemical) , the following structural formula E132), I,]-bis(N,N-diglycidylaminomethyl)cyclohexyl (tetrad-c (Mitsubishi Gas Chemical), the following structural formula E133), 夂4-double (n,n-diglycidylaminomethyl)cyclohexan (the following structural formula El34), U-bis(indole, fluorene-diglycidyl)cyclohexane (the following structural formula: £135) , 1,4-bis(indole, fluorene-diglycidylamino)cyclohexane ( Said junction 89 billion ο

(Ε129) 200927790 Construction Ε136), double (Ν'Ν" diglycidylamino)benzene (the following structural formula Ε137), ten pairs of (Ν'Ν_-glycidylamino)benzene (the following structure) Ε138), 2,6-bis(indolyl-diglycidylaminomethyl)bicyclo[2.2.1]heptane (the following structural formula Ε139), hydrazine, hydrazine, sandpiper 'tetraglycidyl-4 In the case of diaminopurine cyclohexylmethyl (the following structural formula II' group fN^N, N,-tetraglycidyl group > 4, in diaminodiphenyl (structure described below, '£: 141), ^1^,]^,:^-tetraglycidyl-4,4,-diaminodiphenylfluorene^<the structural formula 扪42), 1,3,5-three (heart (where 沁 沁 缩) Glyceryl)aminomercapto)benzene (the following structural formula E143), 2,4,4,-three-group diglycidyloxy oxy- 1 fine (the following structural formula E144), three (4-(N,N) _ Diverted water based oxygen (described below, structural formula _, 3, 4, 3', 4' _ tetraglyconin) basic base) A (the following structural formula E146), 3, 4, 3, 4 , _ (N, 々, glycidol minus base) ^ bond (the following structural formula E147), four (7) diglycidyl milk, and the following structural formula EI49 with 卞逑 structural formula EH8 % σ II compound (Ε130) 200927790

(E136) (E137)

91 200927790

(E146)

(E148)

92 200927790 The homopolymer of the monomer having an ethylene oxide group is, for example, glycidyl methacrylate. The mono-polymer having an ethylene oxide wire may, for example, be N-phenylmaleimide _ 曱美二二 glycerin copolymer, N•cyclohexylmaramine imino acid ==

A vinegar copolymer, a methacrylic acid-methyl-acid glycidol vinegar site polymer, a methacrylic acid butyl vinegar-glycidyl methacrylate copolymer, and a propylene glycol acid 2. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Acid glycidol vinegar copolymer. The monomer having an oxyalkylene group may, for example, be: (comparable) glycidyl acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and (meth) methacrylic methyl glycidol ester. Examples of the monomer other than the monomer having an oxiranyl group in the copolymer of the precursor having a ring-emulsion group include, for example, (fluorenyl)acrylic acid or decyl (meth)acrylate. , (mercapto) ethyl acrylate, (methyl) propyl roasting isopropyl vinegar, (meth) butyl acetonate, (mercapto) isopropyl acetonate, tert-butyl (mercapto) acrylate , (cyclohexyl) (meth) acrylate, (mercapto) acrylate vinegar, (mercapto) acrylate 2-alkyl B, (mercapto) acrylate 2- propyl styrene, styrene, methyl benzene Ethylene, chloromethyl benzene, (meth)acrylic acid (3-ethyl-3-epoxypropyl) decyl ester, N-cyclohexylmaleimide and N-phenyl maleimide . The glycidyl isocyanurate may, for example, be 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1Η,3Η,5Η)-trione (l ,3,5-triglycidyl- l,3,5-triazine-2,4,6_(lH,3H,5H)-trione, 93 200927790 The following structural formula E150), ι,3_ diglycidyl _5_ Allyl 4,3,^ triazine-2,4,6-(111,311,511)-trisole (the following structural formula: £151) and an isocyanuric acid glycidyl ester type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized ruthenium polybutadiene and EPOLEAD PB3600 (manufactured by DAICEL Chemical Industry Co., Ltd.). The cyclic aliphatic epoxy compound may, for example, be 2-methyl-3,4-epoxycyclohexylfluorenyl-2,-methyl-3',4'-epoxycyclohexylcarboxylate ( The following structural formula E153), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (structure E154 below), ε-caprolactone modified 3,4-epoxy Cyclohexylmethylepoxycyclohexyl decanoate, 1,2:8,9-diepoxylimene (1,2:8,9_diepoxy limonene, CELLOXIDE 3000 (DAICEL Chemical Industry Co., Ltd.), 3,4 -Epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (CELLOXIDE 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.), the following structural formula E155), represented by the following structural formula E156 Compounds, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY Co., Ltd.), EHPD-3150 (manufactured by DAICEL Chemical Industry Co., Ltd.), and cyclic aliphatic epoxy resin. 94 200927790

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. As the various additives, for example, a polymer compound and a low molecular compound other than the derivative and the derivative thereof may be mentioned, and they may be selected and used according to their respective purposes. For example, the Tingtong Knife Compound can exemplify a horse molecule compound which is soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal alignment agent of the present invention, and to control the electrical characteristics or the alignment property of the formed liquid crystal alignment film. Examples of the polymer compound include polyamine, polyethyl phthalate, polyurea (Pdyurea), polyester, polyepoxide (p〇lyep〇xide), and polyester polyol ( Polyester polyol ), anthrone modified polyaminodecanoate is a ketone modified polyester. 7 Further, for the low molecular compound, for example, when it is desired to improve the applicability, a surfactant suitable for the purpose may be mentioned, and 2) when it is necessary to mention: "electrostatic property, an antistatic agent may be mentioned," when it is desired to improve When the substrate is neutral or nibbing, the titanium coupling agent can be coupled with a scale, and 4) # can be imidized at a low temperature. The oxime coupling agent can be used. For example, vinyl trimethoprim 95 200927790 oxindole, oxime oxime aminoethyl) _3. aminopropyl methyl decane, lutyl sulphate ethyl) aminopropyl methyl trimethoxy #,基二Γ oxy Wei, p-aminophenyl triethoxy r, meta 3-di-dimethoxydi- Wei, m-aminophenyl triethoxy stone oxime dimethoxy ♦ burn, 3 -aminopropyltriethoxy oxime,

Ο 3A1 water a propyl propyl sulfoxide, 3 缩 甘油 甘油 亡 故 故 故 故 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Residue, 3·methylpropoxypropyltrimethoxywei, 3-sulfopropyltrimethoxywei, N_(1,3-dimethylsobutyltriethoxyhydanyl H-propylamine and And bis[3_(trioxyloxywei)propyl]ethylenediamine. The ruthenium amide catalyst may, for example, be an aliphatic amine such as tridecylamine, triethylamine, tripropylamine or tributylamine. Ordinary amines such as N,N-dimercaptoaniline, N,N-diethylaniline, mercapto-substituted aniline, hydroxy-substituted aniline; ° ratio of bite, thiol-substituted n-bite, thiol-substituted π ratio Quino, quinoline, thiol-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, hydroxy-substituted saliva The quinone imidization catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-pyridine, m-hydroxypyridine, p-hydroxyl One or two or more of pyridine and isoquinoline. The amount of the decane coupling agent added is usually from 0% by weight to 20% by weight, preferably 0.1% by weight, based on the total weight of the polyamic acid or a derivative thereof. 96% by weight. 96 200927790 The amount of the ruthenium amide catalyst is usually added in an amount of 〇1〇 to 5 equivalents, preferably 〇 is equivalent to 〜3 equivalents, relative to the carbonyl group of the polyglycolic acid or its derivative. The amount of the additive to be added varies depending on the use thereof, and is usually from 〇% by weight to 1% by weight, based on the total weight of the polyamic acid or a derivative thereof, preferably from 0.1% by weight to 50% by weight. The liquid crystal alignment agent of the present invention may further contain an acrylic polymer or an acrylate polymer in a range which does not impair the effects of the present invention (preferably, the amount of the polyamic acid or a derivative thereof within 2% by weight). And other polymer components such as polyamidoximine which is a reaction product of tetracarboxylic dianhydride, dicarboxylic acid or a derivative thereof and a diamine. Further, for example, the coating property and the liquid crystal alignment agent are adjusted. The liquid crystal alignment agent of the present invention may further contain a solvent, and the solvent may be used as long as it has a solvent capable of dissolving a polymer component, and is not particularly limited. The solvent which is generally used in the production step or the use of a polymer component such as poly-aramidic acid or a soluble polyimine may be appropriately selected depending on the purpose of use. The solvent may be a solvent. The solvent may be a mixed solvent of two or more solvents. The solvent may be a good solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability. An aprotic polar organic solvent which is a good solvent for an amine acid or a derivative thereof, and examples thereof include N-methyl-2-pyrrolidone, dimethyl imidazolidinone, and N-mercaptohexyl. Endo-amine 97 200927790 (N-methyl caprolactam ), N-methyl propionamide, N,N-dimethylacetamide, dimethyl sulfoxide Internal vinegar such as sulfoxide), N,N-dimethyldecylamine, N,N-diethylformamide, diethylacetamide, γ-butyrolactone. Examples of the other solvent for the purpose of improving coatability and the like include lactic acid ester ester, 3-mercapto-3-methoxybutanol, tetraun, isophorone, and B. Ethylene glycol monoalkyl ether such as diol monobutyl ether, monoethylidene alcohol monobutyl base, ethylene glycol monoalkyl or phenylacetate, triethylene glycol monobutyl Base propylene glycol, propylene glycol monomethyl sulfonate and propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, malonic acid dialkyl acrylate such as diethyl malonate, early detection of monopropanol, etc. An ester compound such as acetaminophen or their acetate. Among these compounds, the solvent is particularly preferably N-methyl-2-pyrrolidine, J, dimethyl sulfonium ketone, γ-butyrolactone, ethylene glycol monobutylene, diethylene glycol monoethyl ether, Propylene glycol monobutyl ether, propylene glycol monoterpene test and dipropylene glycol monoterpene puzzle. In the present invention, the concentration of the polymer component containing the polyamic acid or the derivative thereof in the liquid crystal alignment agent is not particularly limited, and is preferably from 1% by weight to 40% by weight. When the liquid crystal alignment agent is applied onto a substrate, it is necessary to perform an operation of diluting the polymer component contained in advance with a solvent in order to adjust the film thickness. In this case, from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent, the concentration of the polymer component is preferably 40% by weight or less. Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted by the coating method of the crystal alignment agent of 98 200927790. When the liquid crystal alignment agent is coated, the spin coating method or the printing method, in order to maintain the film father well. Usually, the concentration of the polymer component is mostly made! . Weight % or ι〇. For other coating methods, such as the impregnation method or the inkjet method (ink_jetmethGd), it is possible to proceed to another aspect. If the concentration of the polymer component is (four) Λ 1 weight 0/0 or more, then Obtained liquid crystal alignment film

: Soil Wadi is easy to become the best thickness. Therefore, in the usual spin coating method = printing method or the like, the concentration of the molecular component is % by weight or 0.1% by weight or more, preferably 0.5% by weight to 10% by weight. However, it can also be used at a lower concentration according to the liquid crystal alignment_coating method' tree. Further, when the liquid crystal alignment agent of the present invention is used for producing a liquid crystal alignment film, the liquid_to-agent ratio of the present invention can be determined according to the mechanism or method for forming the liquid crystal alignment agent film. For example, when the liquid crystal alignment agent (10) is formed by a brush machine, the reduction of the liquid crystal alignment agent of the present invention is preferably 5 mpa·s or more, and 5 mpa·s or more, from the viewpoint of obtaining a sufficient film thickness, and From the viewpoint of the average, the viscosity of the liquid crystal alignment agent is preferably 100 mPa·s or 100 100 mPa·s or less, and more preferably 10 mPa·s to 80 mPa·s. When the liquid crystal alignment agent is applied by a spin coating method to form a liquid crystal alignment agent, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa·s to 2 μmPa·s, and more preferably 10 mPa.s ~ 100 mPa.s. The viscosity of the liquid crystal alignment agent can be reduced by dilution of the solvent or aging with stirring. 99 200927790 The liquid crystal alignment agent of the present invention may be in the form of a polyglycine or a bamboo organism thereof, or a so-called polymer blend in which two or more kinds of polyacrylic acid or a derivative thereof are mixed. form. The liquid crystal alignment agent in the form of a polymer blend may, for example, be a liquid crystal alignment agent containing polylysine or derivatives A and B thereof, and the polyamine or the derivative A thereof contains the diamine The diamine of the side chain structure, and one or both of the polyamic acid or the diamine of the bamboo organism A and B thereof contain a diamine represented by the above formula (N). Polylysine or a derivative thereof A is a poly-proline or a derivative thereof containing the amine having a side chain structure. Polylactoic acid or a derivative thereof B is a polyaminic acid or a derivative thereof containing a diamine other than a diamine having a side chain structure. The diamine represented by the above formula (N) may be contained in at least one polyphthalic acid or a derivative thereof mixed in the polymer blend, and may be contained in polylysine or a derivative thereof. Both A and b may also be included in all of the polyamines or their derivatives mixed in the polymer blend. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent, for example, a step of forming a coating film of the liquid crystal alignment agent of the present invention, and a coating film of the liquid crystal alignment film of the present invention It is obtained by the step of heating and calcining. For the liquid crystal alignment film of the present invention, the film obtained in the calcining step can be subjected to a rubbing treatment as needed. Similar to the production of a usual liquid crystal alignment film, the coating film can be formed by coating the present invention with a liquid crystal alignment agent on a 100 200927790 liquid crystal display element. The substrate may be a glass substrate in which an electrode such as an indium tin oxide (ITO) electrode or a color filter (c〇1〇rfilter) may be provided. A method of applying a liquid crystal alignment agent onto a substrate is generally known as a spinner method, a printing method, a dipping method, and a dropping method (falling-drop Ο).

Method), inkjet method, and the like. This shot method can be applied to the present invention. The calcination of the coating film can be carried out under the conditions necessary for the polyglycine or its derivative to undergo dehydration and ring closure reaction. The calcination of the coating film is generally known as a method of heat treatment in an oven (_) or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. These methods are also applicable in the present invention. It is generally preferred to carry out the enthalpy for about 3 to 3 hours at a temperature of about 15 Torr to 30 Torr C. The rubbing treatment can be carried out in the same manner as the rubbing portion which is usually used for the alignment of the liquid crystal alignment film 2, as long as the liquid crystal film of the present invention can obtain a sufficient condition (fetaniatiGn), the condition is ' The amount of capillary intrusion is 〇.2mm~. .8 position, platform 22 is 5 mm / sec ~ 250 mm / sec, the drum speed is 5 (9) 卬 ~ (10) 〇 _. The alignment treatment method of the liquid crystal alignment film usually has a photo-alignment method or a transfer material in addition to the rubbing method. These other alignment treatment methods can be used in combination in the rubbing treatment in the range in which the yarn of the present invention can be continued. The liquid crystal alignment film of the present invention can further contain other steps in addition to the above steps. Other steps recorded may be 101 200927790 or rubbing with a cleaning solution to exemplify a step of drying the coating film, a step of washing the film before and after the treatment, and the like. In the same manner as the calcining step, the drying step or the method of heat treatment in the infrared oven is performed at ===. Green surface Wei Ke Cai. Dry money is at the temperature of the range of evaporation (10) 〇

The implementation of the 'more ship' is implemented at a relatively low temperature. The cleaning method for cleaning the liquid crystal alignment film before and after the alignment treatment with a cleaning liquid may be, for example, brushing, spraying (twisting (four), steam cleaning, ultrasonic cleaning, etc. These methods may be carried out separately or in combination. The cleaning solution can be used: pure water, or various alcohols such as methanol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and xylene; dentate solvents such as methylene Chlride, acetone and hydrazine. The ketones such as ethyl ketone are not limited to these cleaning liquids. Of course, these cleaning liquids may use a cleaning liquid which is sufficiently purified and has few impurities. Such a & washing method is used to form the liquid crystal alignment film of the present invention. The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably from 1 nm to 300 nm, more preferably from 3 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be used. The liquid crystal display element of the present invention has a known thickness measurement apparatus such as a surface profiler (pr〇f|l〇meter) or an ellipsometer (ellipSometer). a plate, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage 102 200927790 to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction. The liquid crystal alignment film of the present invention is used. The substrate may use a glass substrate described above for the liquid crystal alignment film of the present invention, and the electrode may be formed using the liquid crystal alignment film described above for the present invention. An IT crucible electrode on a glass substrate. The liquid crystal layer is formed of a liquid crystal composition sealed in a gap between a pair of opposing substrates, the pair of opposing substrates being

- opposing the surface of the substrate in which the liquid crystal alignment film is formed on the substrate toward the other substrate. The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a dielectric constant and a positive or negative anisotropy can be used. The preferred liquid enthalpy of the dielectric anisotropy = (4) The liquid hydrazine composition disclosed in the following publication: Japanese Patent No. 3, 28, Japanese Patent, Japanese, Japanese, and Japanese 3rd, Taichung, No. 9-241644 (the hall manual), Japan's special material 9_Help No. 46)): Kaiping 8.199168 bulletin (__ Kaiping 9 with the 56th bulletin, Japanese patent special (EP885271A1) Manual), Japan's Hira 9 Shop No. 643 Gazette (10) Touching the Ping-Pan No. 6 Public Gazette, Japanese Patent Special Kaiping 1〇_231482 Ping 1〇-_6 No. 2000-087040, Japan's "This Patent" Japanese Patent Laid-Open Publication No. Hei. No. 20-14822. 103 ❹ Ο 200927790 Liquid crystal composition disclosed in liquid crystal group report with negative dielectric anisotropy: 曰本专利特二=列f The following public gazette, 曰本专利Kaiping 2 Marriage == Others No. 4, No. 5, No. 5, and a special patent for this patent: Special Patent: Japanese Patent Publication No. 8-104869, Japanese Journal: No. 53, Japanese Gazette, Japanese Patent Unexamined Japanese Patent Special Open Report, Japanese Patent Special Open No. 10·23_2, Japanese Patent Door: 10-2370 04 ^Gazette, Q-day HU Gazette, Japanese Patent Unexamined Patent, Special Kaiping, Pingji II = = Issue Bulletin, Japan, and _ (four)·fine] Special Opening: This patent is open to the public. 10-237448祙八如^ 9 Japanese Patent Kaiping 10_28'ti^%726=specification),

Japanese Patent No. 10_287875, Japanese Patent No. 日本, Japanese Patent Unexamined Patent, Japanese Patent Laid-Open No. Hei 10-291945, H Patent No. 11_029581, and Japanese Patent Publication No. 2: Gossip specials: (10) 965, Japanese Patent No. 0726%, Japanese Patent Unexamined M92657, and the like. A liquid crystal composition in which the electrical anisotropy of positive or negative is positive or negative is the same as that of the optically active compound of the above-mentioned type or the like: The liquid crystal display element of the present invention is obtained by the following means: 200927790 The liquid crystal alignment film of the present invention is formed on at least one of a pair of substrates, such that the liquid crystal alignment film faces inward, and the obtained pair of substrates are opposed to each other in a gap formed between the substrates via a spacer. A liquid crystal composition is sealed to form a liquid crystal layer. In the manufacturing process of the liquid crystal display element of the present invention, a step of attaching a polarizing film or the like to the substrate may be further included as needed. The liquid crystal display element of the present invention can form liquid crystal display elements for various electric field methods. The liquid crystal display element for the electric field method includes a liquid crystal display element for applying a voltage to the liquid crystal layer in a direction horizontal to the surface of the substrate, or the electrode A liquid crystal display element for a vertical electric field mode in which a voltage is applied to the liquid crystal layer in a direction perpendicular to a surface of the substrate. The liquid crystal display element for a lateral electric field method may not exhibit a large pretilt angle. Therefore, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a transverse electric field mode, wherein the liquid crystal of the present invention The alignment agent contains, as a polylactoic acid obtained from a diamine having no diamine having a side chain structure, or a derivative thereof, polyacrylic acid having no side bond structure or a derivative thereof. The liquid crystal display element for the vertical electric field method needs to exhibit a large pretilt angle. Therefore, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a vertical electric field mode, wherein the liquid crystal alignment agent of the present invention contains A poly-brenic acid having a side bond structure or a derivative thereof, such as polyacrylic acid obtained by a diamine having a diamine having a side chain structure or a derivative thereof. The liquid crystal alignment film prepared by using the liquid crystal alignment agent of the present invention as a raw material as described above can be suitably used in liquid crystal display elements of various display driving methods by appropriately selecting a polymer which is a raw material. The liquid crystal display element of the present invention may further have the elements of the above-described constituent elements. In such a liquid crystal display element of the present invention, a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, and a driving circuit-based crystallographic element sheet can be attached to the liquid crystal display element. [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited to these Examples. The compounds used in the examples are as follows. <tetracarboxylic dianhydride>

Compound (1). Pyromellitic Dianhydride: PMDA

Compound (19): 1,2,3,4-cyclobutane tetracarboxylic dianhydride: CBD A

Compound (23): 1,2,3,4-butane tetradecanoic acid dianhydride: BT compound (37): 1,3,3a,4,5,9b_hexahydro-5 (tetrahydro-2,5 -Dioxo-3-© °夫南基)Naphtho[1,2- 十夫0南-1,3_ :_(l,3,3a,4,5,9b-hexahydro-

5 (tetrahy dro-2,5 -dioxo-3 -furanyl)naphoto [ 1,2-c] furan-1,3 -di one) : TDA

Compound (49): 2,3,5-tricarboxycyclopentyl acetic anhydride dianhydride: TCMP <diamine>

Compound: 1,4-bis(4-aminophenyl)-1,4-diazacyclohexane (1,4-bis(4-aminophenyl)-l,4-diazacyclohexane) · DAC 106 200927790 Compound: 4 ,4·-(pyridazine-1,4-diyl)bis(2-methylaniline): 3MPDA Compound: 1,4-bis(3-aminopropyl)pyridazine: APP Compound: 4,4'- Diaminodiphenylmethane: DDM Compound: 1,2-bis(4-aminophenyl)ethane: DET Compound: U-bis[4-(4-aminophenoxy)phenyl]-4·[( 4-heptylcyclohexyl)ethyl]cyclohexane: 7Η2ΗΒΑ

Compound: U-bis[4-(4-aminophenoxy)phenyl-4-(trans-4-n-pentylcyclohexyl)cyclohexane (l,l-bis[4-(4-aminophenoxy)) Phenyl-4-w (trans-4-n-pentyl cyclohexyl)cyclohexane ) · 5HHBA

Compound: 1,1-bis[4-(4-aminophenyl)methylphenyl]-4-n-heptylcyclohexane: 7HBZ

Compound: 1,3-bis(3-aminopropyl)tetramethyldisiloxane: APDS compound··bis(4-amino-2-mercaptobenzene)曱): MDT Compound: Ν, Ν·-bis(4-aminophenyl)-Ν, Ν,-dimethylethylenediamine: NN2DAMe 〇 compound. 3,6-one gas-based ridge β sitting (3, 6-diaminocarbazole ):

DACZ <Additives>

Compound: bis{4-(allylbicyclopurine.21]hept-5-ene-2,3_dioxinimine)phenyl}methane: BANI-M

Compound · N,N-di-diethylidene propylene diamine: HEA compound: bis(3-phenyl-3,4-dihydro-211_13_benzoxazine-6-yl)methane 107 200927790

(t>is(3-phenyl-3,4-dihydro-2H-l,3-benzoxazine-6-yl)methan e) : PBM

Compound: 3,4-epoxycyclohexenylmethyl_3,,41_epoxycyclohexenecarboxylic acid ester: EHE

Compound: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane: EHS

Compound: 1,3_bis(4,5-dihydro-2-oxazolyl)benzene: BOB <solvent> NMP : N-methyl-2-indole ketone® GBL: y-butane Ester BC: butyl cellosolve (ethylene glycol monobutyl ether) <1. Synthesis of polyglycine> [Synthesis Example 1] 100 mL of four equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen gas inlet port Into the flask, 3.651 g of the compound DAC and 54.0 g of dehydrated NMP' were added and dissolved under a dry nitrogen stream. Next, 1.237 g of the compound (1), 1.12 g of the compound (19) hydrazine, and 15.0 g of the dehydrated GBL' were added to react at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 兀乞 or 70 ° C or lower to carry out the reaction. Then, 25.0 g of BC was added to the obtained solution to obtain a polyglycine solution having a concentration of 6% by weight. The polyglycolic acid had a weight average molecular weight of PA, PA1 of 34,800. The weight average molecular weight of polylysine is determined in such a manner that the obtained polylysine is diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF = 0.6/100: weight ratio) to make polylysine The concentration is about 1% by weight, 108 200927790, and then the 2695 separation module (separatj〇nm〇duie), 2414 differential refractometer (manufactured by Waters) is used, and the mixed solution is used as a developing solvent and measured by the GPC method. Yi Lai counts. In addition, the tube was measured using HSPgel RT MB_M (manufactured by Shirt (10)) under the conditions of a column temperature of 4 ° C and a flow rate of 〇·35 mL/min. [Synthesis Example 2 to Synthesis Example 31]

Further, the tetracarboxylic dianhydride and the diamine were changed as shown in Tables 1 and 2, and a solution (PA2) and (PA31) were prepared in accordance with Synthesis Example 1. Including Synthesis Example 1, the results are summarized in Tables i and Tables. Synthesis Example 24 to Synthesis Example 28] Since the precipitate was precipitated during the reaction, the polyamine acid could not be synthesized. 109 200927790 [Table i] Synthesis Example No. Acid dianhydride 蕈 ear compound 旲: knife compound; amine Mo J weight average molecular weight 1 PMDA 0.23 CBDA 0.23 DAC 0.54 34800 2 PMDA 0.24 CBDA 0.24 DAC 0.26 DDM 0.26 53200 3 PMDA 0.24 CBDA 0.24 DAC 0.20 DDM 0.32 46800 4 PMDA 0.24 CBDA 0.24 DAC 0.47 5HHBA 0.05 28700 5 PMDA 0.24 CBDA 0.24 DAC 0.47 7H2HBA 0.05 73200 6 PMDA 0.24 CBDA 0.24 DAC 0.47 7HBZ 0.05 40700 7 PMDA 0.35 CBDA 0.10 DAC 0.30 DET 0.10 5HHBA 0.15 56200 8 PMDA 0.10 CBDA 0.38 DAC 0.47 5HHBA 0.05 32000 9 PMDA 0.32 CBDA 0.13 DAC 0.50 5HHBA 0.05 29000 10 PMDA 0.29 CBDA 0.16 DAC 0.39 7HBZ 0.16 33000 11 PMDA 0.23 CBDA 0.23 DAC 0.50 APDS 0.04 45000 12 PMDA 0.27 CBDA 0.19 DAC 0.50 7H2HBA 0.02 5HHBA 0.02 29000 13 PMDA 0.27 CBDA 0.18 DAC 0.36 NN2DAMe 0.14 7HBZ 0.05 62000 14 PMDA 0.27 CBDA 0.19 DAC 0.45 NN2DAMe 0.09 29000 15 PMDA 0.27 CBDA 0.18 DAC 0.39 NN2DAMe 0.14 7H2HBA 0.02 35000 110 200927790

[Table 2] Synthesis Example No. Acid dianhydride compound was mixed; amine Mo J weight average molecular weight 16 PMDA 0.23 CBDA 0.23 DAC 0.32 MDT 0.18 7HBZ 0.04 27000 17 PMDA 0.23 TCMP 0.23 DAC 0.50 5HHBA 0.04 59000 18 PMDA 0.23 TDA 0.23 DAC 0.54 37000 19 PMDA 0.27 CBDA 0.14 BT 0.04 DAC 0.50 7HBZ 0.05 34000 20 PMDA 0.23 CBDA 0.23 3MPDA 0.50 5HHBA 0.04 35000 21 PMDA 0.27 CBDA 0.14 BT 0.04 DAC 0.44 NN2DAMe 0.11 25000 22 PMDA 0.24 CBDA 0.24 DAC 0.14 DACZ 0.38 41600 23 PMDA 0.23 CBDA 0.23 DAC 0.39 DACZ 0.13 5HHBA 0.02 37800 24 PMDA 0.50 APP 0.10 DDM 0.40 Unable to synthesize 25 PMDA 0.50 APP 0.05 DDM 0.45 Unable to synthesize 26 PMDA 0.25 CBDA 0.25 APP 0.50 Unable to synthesize 27 PMDA 0.25 CBDA 0.25 APP 0.25 DDM 0.25 Unable to synthesize 28 PMDA 0.25 CBDA 0.25 APP 0.05 DDM 0.45 Unable to synthesize 29 PMDA 0.25 CBDA 0.25 DDM 0.50 85300 30 PMDA 0.25 CBDA 0.25 DET 0.45 5HHBA 0.05 65400 31 PMDA 0.40 CBDA 0.10 DET 0.30 7HBZ 0.20 31800 111 200927790 , < 2. Production of liquid crystal display elements &gt [Example 1] Concentration synthesized in Synthesis Example 1 6% by weight of polyamide acid solution (PAl) was added in NMP / BC = a mixed solvent (weight ratio) 1/1, the whole was diluted to 4 wt% to prepare the liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. <Method for Producing Liquid Crystal Display Element> A liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode by a spinner to form a film having a film thickness of 70 nm. After coating the film at 80. (: heating and drying for about 5 minutes, and then heat-treating for 20 minutes to form a liquid crystal alignment film. Next, the surface of the substrate on which the liquid crystal alignment film is formed is rubbed by a rubbing device to perform alignment treatment. Then, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. A gap material of 7 was spread on one of the glass substrates to make

The surface of the liquid crystal alignment film is formed on the inner side and the rubbing direction is anti-parallel, and is disposed in the opposite direction, and then sealed with an epoxy curing agent to produce an anti-prime element (antipamlldeell). In the material 14, a liquid crystal composition is used, and a photocuring agent is used to seal the injection port. The receiver was subjected to heat treatment for 30 minutes under the boot to produce a liquid crystal display element.

17wt·% 112 200927790

F C5H11—^f iewt_ %

F

I〇wl% F

[Embodiment 2]

A mixed solvent of NMP/BC=1A (weight ratio) was added to a polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. . Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 3] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 4] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, 113 200927790, and the whole was diluted into 4% by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 5] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example S, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 6] 混合 A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA6) having a concentration of 6 wt% synthesized in Synthesis Example 6, and the whole was diluted to 4 % by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 7] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 8] A polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2 and a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7 were used. Mix 8/2 by weight. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 114 200927790 : [Example 9] A polyglycine solution (PA13) having a concentration of 6% by weight synthesized in Synthesis Example 13 and a polyglycine solution having a concentration of 6% by weight synthesized in Synthesis Example 7 (PA7) was mixed at a weight ratio of 8/2. A mixed solvent of nmp/bc = i / i (weight ratio) was added to the obtained mixture, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 10] ® A polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2 and a polyglycine solution (PA15) having a concentration of 6 wt% synthesized in Synthesis Example 15 Mix at a weight ratio of 8/2. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 11] A mixed solvent of NMP/BC = m (weight ratio) was added to a polyglycine solution (PA8) having a concentration of 6 wt% synthesized in Synthesis Example 8, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 12] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA9) having a concentration of 6 wt% synthesized in Synthesis Example 9, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 115 200927790, [Example 13] A mixed solvent of hNMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA10) having a concentration of 6 wt% synthesized in Synthesis Example 10, and the whole was diluted. At 4% by weight, a liquid crystal alignment agent was prepared. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example H] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA12) having a concentration of 6 wt% synthesized in Synthesis Example 12, and the whole was diluted to 4 % by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 15] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA13) having a concentration of 6 wt% synthesized in Synthesis Example 13, and the whole was diluted to 4 weights. ❶ / 〇, made of liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 16] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA14) having a concentration of 6 wt% synthesized in Synthesis Example 14, and the whole was diluted to 4 A liquid crystal display element was produced in the same manner as in Example 1 except that the liquid crystal alignment agent was used to form a liquid crystal alignment agent. [Example Π] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA15) having a concentration of 6 wt% synthesized in Synthesis Example 15, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent of 116 200927790. [Example 18] A mixed solvent of ~NMP/Bc = 1/1 (weight ratio) was added to a polyglycine solution (PA16) having a concentration of 6 wt% synthesized in Synthesis Example 16, and the whole was diluted to 4 % by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 19] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (ΡΑΠ) having a concentration of 6 wt% synthesized in Synthesis Example 17, and the whole was diluted into 4% by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 20] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA18) having a concentration of 6 wt% synthesized in Synthesis Example 18, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 〇 [Example 21] A mixed solvent of hNMP/Bc = 1 / l (weight ratio) was added to a polyglycine solution (PA19) having a concentration of 6 wt% synthesized in Synthesis Example 19, and the whole was diluted to 4 % by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 22] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA20) having a concentration of 6 wt% synthesized in Synthesis Example 20, 117 200927790, and the whole was diluted. 4% by weight of 'made liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 23] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA21) having a concentration of 6 wt% synthesized in Synthesis Example 21, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 24] The concentration synthesized in Synthesis Example 22 was 6 parts by weight. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the polyacrylic acid solution (PA22) of hydrazine, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 25] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA23) having a concentration of 6 wt% synthesized in Synthesis Example 23, and the whole was diluted to 4 weights. % 'made as a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 26] To a polyglycine solution (PA22) having a concentration of 6% by weight synthesized in Synthesis Example 22, bob of 2% by weight based on the weight of the polymer was added. Then, a mixed solvent of NMP/BC=i/i (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 118 200927790 [Example 27] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA11) having a concentration of 6 wt% synthesized in Synthesis Example 11, and the whole was diluted into 4% by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 28] In a polyamine solvent solution (PA19) having a concentration of 6% by weight synthesized in Synthesis Example 19, 2% by weight of © BANI-M corresponding to the weight of the polymer was added. Then, a mixed solvent of NMP/BC = (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 29] HEA of 2 〇 weight ❶ / 相当于 corresponding to the weight of the polymer was added to a polyglycine solution (PA19) having a concentration of 6% by weight synthesized in Synthesis Example 19. Then, a mixed solvent of MNMP/BC = i / i (weight ratio) Ο was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 30] In a polyamine solvent solution (PA21) having a concentration of 6% by weight synthesized in Synthesis Example 21, 20 wt% of the weight of the polymer was added. PBM. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. 119 200927790 Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 31] The concentration synthesized in Synthesis Example 21 was 6 parts by weight. 20% by weight of BANI-M equivalent to the weight of the polymer was added to the polyhydrazine solution (PA21). Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example 1. [Example 32] 20 wt% of PBM corresponding to the weight of the polymer, 10% by weight based on the weight of the polymer, was added to the polyhexylamine solution (PA21) having a concentration of 6 wt% synthesized in Synthesis Example 21. EHS. Then, a mixed solvent of NMP/BC = 1H (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 〇 [Example 33] 20% by weight of BANI-M, which corresponds to the weight of the polymer, was added to a polyglycine solution (PA9) having a concentration of 6% by weight synthesized in Synthesis Example 9. 10% by weight of EHS. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 120 200927790 [Example 34] Ehe in an amount of 1% by weight based on the weight of the polymer was added to a polyamine solvent solution (PA11) having a concentration of 6 wt% synthesized in Synthesis Example 11. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 5 wt% to prepare a liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example 。. [Comparative Example 1] A mixed solvent of mNMP/bc = 1/1 (weight ratio) was added to a polyglycine solution (PA29) having a concentration of 6 wt% synthesized in Synthesis Example 29, and the whole was diluted to 4 % by weight, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example i using the obtained liquid crystal alignment agent. [Comparative Example 2] A mixed solvent of MNMP/Bc = 1/1 (weight ratio) was added to a polyglycine solution (PA30) having a concentration of 6 wt% synthesized in Synthesis Example 30, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 3] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA31) having a concentration of 6 wt% synthesized in Synthesis Example 31, and the whole was diluted to 4 weights. %, made into a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 4] Polyhexyl acid solution 121 c 200927790 liquid (PA29) having a concentration of 6 wt% synthesized in Synthesis Example 29 and a polyglycine solution having a concentration of 6 wt% synthesized in Synthesis Example 30 were synthesized. (PA30) was mixed at a weight ratio of 8/2. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 5]

The polyamine solvent solution (PA29) having a concentration of 6% by weight synthesized in Synthesis Example 29 and the concentration synthesized in Synthesis Example 31 were 6 parts by weight. /. The polyamic acid solution (PA31) was mixed at a weight ratio of 8/2. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. <3. Evaluation of electrical characteristics> The liquid crystal display element produced in the method of Ί a 贝 〜 〜 〜 〜 、 、 、 、 、 、 、 、 、 、 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子Determination. 1) Measurement of ion density Using the liquid crystal physical property evaluation device manufactured by TOYO Technica, 0254 m ion-density (four) was lost. The measurement correction is set such that the waveform is a triangle z, the voltage is _, and the measurement temperature is set. The smaller the 疋 value is, the better the electrical characteristics are. The results are shown in Table 3. 2) Determination of the retention characteristics of ion density 122 200927790

The following method: The liquid crystal display element was placed in an environment at a temperature of 100 ° C, and the ion density [pC] was measured by taking it out over time. The smaller the increase in ion density (for example, the increase amount is less than 1 〇〇: the increase amount = the ion density after 500 hours - the ion density at the initial (0 hour)), it can be said that the ion density retention characteristic is better, and it can be said that electricity The better the long-term reliability of the characteristics. The data after 300 hours and after 500 hours are shown in Table 3. 123 200927790 >c [Table 3]

Test No. Liquid crystal alignment agent ion density (pC) increase amount 0 300 hours after 500 hours 1 Example 1 18 45 50 32 2 Example 2 18 38 44 26 3 Example 3 17 34 46 29 4 Example 4 10 28 35 25 5 Example 5 11 15 16 5 6 Example 6 43 59 61 18 7 Example 7 10 11 27 17 8 Example 8 21 38 55 34 9 Example 9 26 27 35 9 10 Example 10 39 75 96 57 11 Example 11 15 16 17 2 12 Example 12 28 51 56 28 13 Example 13 34 47 62 28 14 Example 14 33 49 53 20 15 Example 15 54 57 80 26 16 Example 16 42 95 115 73 17 Example 17 23 41 84 61 18 Example 18 21 66 91 70 19 Example 19 4 28 43 39 20 Example 20 8 43 48 40 21 Example 21 35 66 72 37 22 Example 22 15 31 36 21 23 Example 23 34 60 75 41 24 Example 24 5 17 22 17 25 Example 25 3 10 10 7 26 Example 26 4 10 10 6 27 Example 27 64 85 92 28 28 Example 28 32 49 49 17 29 Example 29 40 49 52 12 30 Example 30 32 63 66 34 31 Example 31 22 44 50 28 32 Example 32 17 31 35 18 33 Example 33 3 11 19 16 34 Example 34 5 5 70 74 19 35 Comparative Example 1 62 209 545 483 36 Comparative Example 2 14 84 125 111 37 Comparative Example 3 66 111 202 136 38 Comparative Example 4 51 155 191 140 39 Comparative Example 5 98 312 424 326 124 200927790 As shown in Table 3 The effect of increasing the liquid suppression ion density of the liquid crystal alignment film obtained by the liquid crystal alignment agent containing the polyacid containing the DAC of the single-fat has been significantly changed. Although the present invention has been disclosed in the above embodiments by way of example, it is intended to be in the art of any of the ordinary skill in the art, and is not limited to the scope of the appended claims. [Main component symbol description] None. 125

Claims (1)

200927790 VII. Patent application scope: 1♦ Liquid crystal alignment agent containing the characteristics of the reaction product of tetracarboxylic dianhydride and diamine, or its derivative 0 (In the formula, A1 independently represents a monovalent organic group, A2 independently represents a monovalent organic group, m represents an integer of 0 to 3, and n represents an integer of 〇~4). 2. The liquid crystal alignment agent according to claim 1, wherein: Α1 is independently an alkyl group having a carbon number, an alkoxy group having a carbon number of 〜 〇, acetamide, fluorine, Gas or bromine, A2 is independently a burning group having a carbon number of 1 to 3. 3. The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (N) has an amino group in the para position of the phenyl group at both ends. 4* The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (N) is selected from the group consisting of the following structural formula (N)-1, and the structural formula (N)-2 Structural formula (N) - 5 - structural formula (N) - 7, structural formula (N) - 9, structural formula (N) - 10, structural formula (N) - 14, structural formula (N) - 17, structure One or a group of the group consisting of the compound represented by the formula (N)-18, the structural formula (N)-21~ structural formula (N)-23, the structural formula (N)-26, and the structural formula (N)-28 126 200927790 and above: h2n h2n nCvn_<C^_n (N)-2 (N)-1 H3COCHN h3co' h2n Cl nh2 h2n Cl N N—^ jj—NHj (N)-6 IMHCOCHa NH2 (N)-7 ~/N-(N)-10 (N)-9 〇CH3 / \ /-NH2 H2N-h^J-N^\|-h^^-NH2 (N)-14 (N)-22 H2N-^-N^N-^-Nh2 (N)-26. The liquid crystal alignment agent according to claim 4, which is characterized by the formula (N) The amine is one or both of the compounds represented by the structural formula (N)-1 and the structural formula (N)-2. The liquid crystal alignment agent according to claim 1, wherein the -amine further comprises the following formula (vm) and formula (X): formula (XIII) A diamine having a side chain structure: 13 is called _ 〇❹ (in the formula (VIII), Α3 represents a single bond, _〇_, _c〇〇_, _〇c〇_, -CO-, -CONH- Or -(CH2)m- (m represents an integer of 1 to 6), and Ri represents a group having a sterol skeleton, a group represented by the following formula (ι), and two amino groups bonded to the benzene ring When the positional relationship is in the para position, Ri further includes an alkyl group having a carbon number of 1 to 30, and when the positional relationship is meta, R1 further includes an alkyl group having 1 to 30 carbon atoms or a phenyl group. In the alkyl group, 'any -CH2· can be independently substituted by _Cf2_, _CHF_, _〇_ (here is discontinuous), -CH=CH_ or -OC-, and -CH3 can pass through •Ci^F' Substituted by -CHF2 or _CF3, the hydrogen of the phenyl group may be independently substituted with -F, -CH3, -〇CH3, -〇CH2F, -OCHF2 or -ocf3); (In the formula (IX), a4 and A5 each independently represent a single bond, (here, discontinuous), -COO-, -OCO-, -CONH-, -CH=CH- or a carbon number of 1 to 12 The alkylene group, R2 and R3 each independently represent -F or _CH3' ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, bis-ring-2,5-diyl, Mouth pyridine 2,5·diyl, „biidine_2,5_diyl, naphthalene·1>5_yl, naphthalene·2,7-diyl or fluoren-9,10-diyl, R4 represents - H, -F, carbon number 128 200927790 is an alkyl group of 1 to 30, a fluorine-substituted alkyl group having a carbon number of 1 to 30, an alkoxy group having a carbon number of 1 to 30, -CN, -OCH2F, -OCHF2 or - OCF3, a and b respectively represent integers of 0 to 4, c, d and e respectively represent integers of 0 to 3, f and g each independently represent an integer of 0 to 2, and c + d + e ^ 1) > (In the general formulae (X) and (XI), R5 independently represents -Η or -CH3, R6 represents -Η, or an alkyl group or alkenyl group having a carbon number of 1 to 20, and A6 independently represents a single bond, -C (=0)· or -CH2-, in the general formula (XI), R7 and R8 each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group; (In the general formulae (XII) and (XIII), A7 independently represents -0- or 129 200927790. The alkylene group having a carbon number of 1 to 6, in the formula (?π), R9 represents _h or the carbon number is 1. An alkyl group of ～30, wherein any -CH2· of the alkyl group having a carbon number of 2 to 30 may be substituted by _〇- (here, discontinuous), _ch=CH- or -OC-, A8 represents a single bond or an alkylene group having a carbon number of 1 to 3, a ring T represents a 1,4-phenylene group or a 1,4-cyclohexylene group, h represents 0 or 1, and in the formula (XIII), R10 represents The alkyl group has a carbon number of 6 to 22, and R11 represents an alkyl group having 1 to 22 carbon atoms. 7. The liquid crystal alignment agent according to claim 6, wherein the diamine having a side chain structure is selected from the group consisting of the following general formula (VIII-2) and general formula (VIII_4). At least one of the compounds represented by the formula (VIII-6), the formula (XII-2), the formula (XII-4), and the formula (XII-6): 130 200927790 R30 (In the above formula, R23, R29 and R3Q each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms). 8. The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises no formula represented by the following general formula (I) to formula (VII) and formula (XV). Side chain structure of diamine H2n-x-nh2 (1) α η2ν^—^*νη2 (II) Η2Ν^~/ ^-^νη2 (111) η2ν^-5νη2 (IV) Η2νΟ-Υ^ΝΗ2 (V) η2νΟ"Υ0Υ~Ονη2 ( VI) 131 200927790 (In the formula (I), X represents -(CH2)m- (in represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), γ independently represents a single bond , -Ο-, -SS-, -S〇2_, -CO-, -CONH~, -NHCO·, -NH-, -N(CH3HCH2)mN(CH3)·, -C(CH3)2-, -C(CF3)2-, © -(CH2)m-, -〇-(CH2)m-0-, -S-(CH2)m_S- (m represents an integer from 1 to 6)' (V) Wherein, z represents a single bond or does not exist, and in the formula (χν), 'R33 and R34 each independently represent an alkyl group having a carbon number of 丨~3 or a stupid group. A3 independently represents a methylene group, a phenylene group or a a substituted subunit, wherein 1 represents an integer of 1 to 6, and m represents an integer of 1 to 1 Å, and is bonded to a cyclohexane ring or a benzene ring in the formula (π) to the formula (VII). Hydrogen may be independently substituted with -F, -CH3, -CF3, -OH, -COOH, _S03H, Ρ03Η2, and the hydrogen bonded to the benzene ring in the formula (IV) may be substituted with a benzyl group). The liquid crystal alignment agent according to claim 8, wherein the diamine having no side chain structure is selected from the following structural formula (IV-1) and structural formula (IV-2) ), structural formula (Ιν_15) ~ structural formula (IV__17), structural formula (ν-1) ~ structural formula (V-12), structural formula (V 33), structural formula (V-35) ~ structural formula (γ - 37), at least one of the compounds represented by the structural formula (2) and the structural formula (χν-1): 132 200927790 φ H2N—νη2 (IV-1) -νη2 η2ν (V-3) (V-1) (ν-2) (V-10) (V-11) (V-12) (V-33) ^^νη2 η2ν HzN_C (V.35) Η2Ν, ^\ A /Nhfc (V-37) (V-36) Ch3 9η3 H2N-C3H6-0 卜o4-c3h6-nh2 ch3 ch3 (XV-1) 10. The liquid crystal alignment agent according to claim 1, wherein the 133 200927790 is characterized in that: the acid acid two Xuan contains aroma Family of four-acid acid bismuth 1 1 JrtJ Shenqing Patent Essence® Zhe 1 Λ ^ B_ 3G? ••所> - Miyaba contains aromatic tetracarboxylic acid. 11. The wave crystal alignment agent according to the above aspect of the invention, wherein the aromatic tetracarboxylic dianhydride is the following structural formula (1), structural formula (2), and structural formula ( 5) ~ knot ^ and structural formula (14) main two & 厶S.u ^ / ; species: (14) φ Ο 〃 12. The liquid crystal alignment agent according to the above-mentioned π Patent No. U, which is characterized in that the aromatic tetracarboxylic acid is a compound represented by the structural formula (1). The liquid crystal alignment agent according to the first aspect of the invention is characterized in that: the tetradecanoic acid dixanthine comprises an alicyclic tetracarboxylic dianhydride and an aliphatic 14+tt di-coin.擞右你. The liquid crystal alignment agent according to Item 13 of the customary and profit range is characterized by the following structural formula 1 (Japanese cyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride are (35; two knots; 】, structural formula (23), structural formula (25), structural formula of the formula to the smallest, structural formula (44) and structural formula (49) table ^ a · · 134 c 200927790 0 15. The liquid crystal alignment agent according to claim [51], characterized in that: the alicyclic four-acid acid two-needle and the aliphatic four-rebel acid two-folded bundle are in the structural formula (19), At least one of the compounds represented by the structural formula (23), the structural formula (37), and the bond configuration (49). The liquid crystal alignment agent according to any one of claims 6 to 15, wherein the liquid crystal alignment agent is characterized by: The liquid crystal alignment agent contains the polyamic acid or a derivative thereof A and the polyamino acid or the derivative A thereof contains the diamine in the diamine! The diamine having a side chain structure And one or both of the polyamines of the polyaminic acid or the derivative thereof A ^ IB comprise the liquid crystal alignment agent of the formula (N), wherein the liquid crystal alignment agent of the first aspect of the invention is characterized in that The liquid crystal alignment agent further contains a compound selected from an alkenyl-substituted Nalene-free scaly $135 200927790 aminated yttrium compound having a radical polymerizable unsaturated double bond, and an oxazine. One or more of the oxazoline compound and the epoxy compound. 18. The liquid crystal alignment agent according to claim 17, wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]g _5_ene_2,3_dimethylimine imine)phenyl}methine, hydrazine, Ν'-m-phenylene-bis(allyl-bicycloindole.21]hept-5-ene-2,3 a group consisting of dimethyl hydrazine and hydrazine, hydrazine, and hexamethylene-bis(allylbicyclo[2.2.1]hept-5-eneindole-2,3-dimethylimine) One or more of them. 19. The liquid crystal alignment agent according to claim 18, wherein the alkenyl-substituted nadicilimine compound is bis{4_(allylbicyclo[2.2.1]hept-5-ene -2,3-Diimineimine)phenyl}methane. The liquid crystal alignment agent according to claim 17, wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of ruthenium, osmium-indenyl bis acrylamide, hydrazine. , hydrazine, _ dihydroxyethylene bis acrylamide, ethylene diacrylate, and 4,4,-methylene bis(indole, fluorene-dihydroxyethylene acrylate aniline) One or more. The liquid crystal alignment agent according to claim 2, wherein the compound having a radical polymerizable unsaturated double bond is hydrazine, hydrazine-monoethylidene dipropylene amide. 22. The liquid crystal alignment agent according to claim n, wherein the wicking compound is selected from the group consisting of the following formula (b-1), formula (c-1), and formula (c-3) , (c__5), (c-7), (c-9), (d-1) to (d-6), (e-3), (e-4), and 136 200927790 (f-2) One or more of the groups consisting of the compounds represented by the formula (f-4): (c-3) (iv) 137 200927790 ο μ, the liquid crystal alignment agent described in the 22nd paragraph of the patent range is as follows: τ is characterized in that the oxazine compound is a compound represented by the formula (c-1). The liquid crystal alignment agent according to claim 17, wherein the oxazoline compound is 2,2'-bis(2-oxazoline) and 1,3-double (4,5) - Two mornings - 2 ° 0 0 sitting base) One or both of benzene. The liquid crystal alignment agent according to claim 24, wherein the oxazoline compound is 1,3-bis(4,5-dioxin-2-oxazolyl)benzene. The liquid crystal alignment agent according to claim 17, wherein the epoxy compound is selected from the group consisting of ν, ν, ν', ν'-tetraglycidyl-m-dimethylamine, 1 , 3_bis(ν,Ν-diglycidylaminomethyl)cyclohexyl, fluorene, anthracene, Ν', Ν·-tetraglycidyl-4,4,-diaminodiphenylmethane, 2_[ t(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]benzene Propane, 3,4-epoxycyclohexenylfluorenyl_3,,4, ring 138 200927790 vinegar copolymerization, phenyl phenyl maleimide-glycidyl methacrylate group h 2_(3 One or more of the group of 4_epoxycyclohexyl)ethyltrimethoxylate. The liquid crystal alignment agent described in Item 26 of the π patent range, the special ring-shaped sulphur compound is 3,4-epoxycyclohexenyl fluorenyl-3, 4L hexanoic acid vinegar Or 2 epoxycyclohexyl)ethyltrimethoxy The liquid crystal alignment film is formed by heating a coating film of the liquid crystal alignment agent according to any one of the first to seventh aspects of the invention. 29. A liquid crystal display device having a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and aligning the liquid crystal molecules in a predetermined direction A liquid crystal alignment film characterized in that the liquid crystal alignment film is a liquid crystal alignment film according to claim 28 of the patent application. 139 200927790 IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (N) (In the formula (N), A1 independently represents a monovalent organic group, A2 independently represents a monovalent organic group, m represents an integer of 0 to 3, and η represents an integer of 0 to 4). 3