TW200930760A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display - Google Patents

Abstract

This invention provides a liquid crystal display device which has lower ion density and good long-term reliability of the ion density, and can apply to various drive manners. A liquid crystal aligning agent containing a polyamic acid or its derivatives, and an epoxide compound are used to form a liquid crystal alignment film, and to a liquid crystal display device with the liquid crystal alignment film. The polyamic acid and its derivatives are a reaction product of a diamine and tetracarboxylic dianhydride, and the epoxide compound has an average number of function groups larger than 1.

Description

200930760 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent comprising polyamic acid or a derivative thereof and an epoxy compound, and a liquid crystal alignment formed by the liquid crystal alignment agent A film, and a liquid crystal display element including the liquid crystal alignment film. [Prior Art] ^ The liquid crystal display element is used in a monitor of a note personal computer or a desktop computer, and a view finder of a video camera. Various liquid crystal display devices such as a projection display have recently been used in televisions. Further, the liquid crystal display element can also be used as an optoelectr〇nics-related element such as an optical print head (oppticai printer head), an optical Fourier transform device, and a light valve.

The liquid crystal display element generally has: 1) a pair of substrates disposed oppositely; 2) 电极 electrodes formed on one or both of the faces of the pair of substrates; 3) formed on the pair of substrates a liquid crystal alignment film on the surface facing each other; and 4) a liquid crystal layer formed between the pair of substrates. M In the previous liquid crystal display elements, display elements using nematic liquid crystals were in the mainstream'. At present, tn (Twisted Nematic 'twisted nematic) type liquid crystal display elements, which are twisted by 9 degrees, 2) A STN (Super Twisted Nematic) liquid crystal display device having a twist of 180 degrees or more, and a so-called τρτ 4 200930760 (Thin Film Transistor) liquid crystal display device using a thin film transistor. However, these liquid crystal display elements have the following drawbacks: the image can be accurately recognized, and the brightness or contrast is lowered when viewing from an oblique direction and the brightness inverse is halftone. In recent years, this The viewing angle problem has been passed through T) TN-TFT type liquid crystal display elements using optical compensation films, 2) Vertical Alignment (VA) type liquid crystal display elements using vertical alignment and optical compensation films, 3) and vertical alignment and protrusion structures MVA (Multi Domain Vertical Alignment) liquid crystal display device, or 4) IPS (In-Plane Switching) liquid crystal display device with lateral electric field method, 5) ECB ( Electrically Controlled Birefringence) , electronically controlled birefringence type liquid crystal display elements, 6) optically compensated bending (Optically Compensated Bend or 〇pticaiiy self-Compensated Birefringence: OCB) type liquid crystal display elements have been improved, and the improved technology is being practically applied, or research.发展 The development of liquid crystal display device technology is not only achieved by improving these driving methods or device structures, but also by improving the constituent members used in liquid crystal display elements. Among the constituent members used for the liquid crystal display element, in particular, the liquid crystal alignment film is one of important factors related to the display quality of the liquid crystal display element. 'As the quality of the liquid crystal display element continues to increase, the role of the liquid crystal alignment film becomes more and more The more important. The liquid crystal alignment film can be prepared by using a liquid crystal alignment agent. The liquid crystal alignment agent mainly used at present is a solution obtained by dissolving polyglycine or soluble polyimine 5 200930760 (polyimide) in an organic solvent. After this solution is applied onto a substrate, film formation is carried out by heating or the like to form a polyimide film. Such a liquid crystal alignment agent is known, for example, as a raw material of polyphthalic acid or a derivative thereof, tetracarb® xylic dianhydride and diamine, and a pretnt angle expressed. A liquid crystal alignment agent which is prescribed (for example, refer to Japanese Laid-Open Patent Publication No. 2002-62537). At present, various liquid crystal matching agents other than polyglycolic acid have also been studied, but heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties, and the like are considered. On the one hand, these liquid crystal alignment agents are hardly practical. In order to improve the display quality of the liquid crystal display element, an important characteristic of the liquid crystal alignment film is required, and an ion density can be cited. If the ion density is high, the voltage applied to the liquid crystal during the frame time is lowered, resulting in a decrease in luminance and hindering the normal gray scale display. In addition, even if the initial ion density is low, the ion density (long-term reliability) after the south temperature acceleration test is increased, and the like is also a problem. ® An attempt to solve the problem is known as a liquid crystal alignment agent containing a poly-proline or a derivative thereof and a predetermined amount of a compound having an oxazine structure (for example, refer to Japanese Patent Laid-Open Publication No. 2007-286597 However, with the development of the technology of liquid crystal display elements, the industry is increasingly demanding to provide liquid crystal alignment agents that can solve the problems. SUMMARY OF THE INVENTION In view of the above circumstances, the industry is expected to develop a liquid crystal alignment agent for liquid crystal display elements having improved ion density and long-term reliability, 200930760, and a liquid crystal alignment film formed using the liquid crystal alignment agent, and having the liquid crystal A liquid crystal display element of an alignment film. The present inventors conducted intensive studies in order to solve the above problems. As a result, it has been found that a liquid crystal display element containing a polyisamic acid or a derivative thereof and a predetermined epoxy compound can have a good ion density and long-term reliability of a liquid crystal display element having a liquid crystal alignment film produced using the liquid crystal alignment agent. Thus, the present invention has been completed. Ο The present invention includes the following constitution. [1] A liquid crystal alignment agent comprising, as a reaction product of a diamine and a tetracarboxylic dianhydride, a polyaminic acid or a derivative thereof, and an epoxy compound having an epoxy group having an average functional group number of more than 1, characterized by In the case where the diamine is a diamine represented by the following formula (1)

◎ (In the general formula (1), X1 and X2 respectively represent or _CH2_, γι represents -Η, the following structural formula (Η-1), general formula (Π-2) or general formula (ΙΙ-3), Ζ1 indicates that An alkylene group having a fluorenyl group having a carbon number of 1 to 12, a 4-substituted-1, 1_cyclohexylene group represented by the following formula (ΙΙΙ-1) or the formula (ΙΙΙ-2), m, η And ρ denotes 〇 or 1. respectively, wherein m + n + p is 〇, 1 or 3, and when m + n + p is 〇, Y1 represents a general formula (仏丨), a general formula (π_2) or a general formula ( ΙΙ-3), 7 200930760 When m + n + p is i, m and n represent 〇, and χ2 represents ·, and the amino group of the aminophenyl group bonded by X2 is bonded to the meta position of X2, ^ ι When m + n + p is 3, X1 and X2 represent _〇_ or _CIV, respectively, Y represents not-Η, and zl represents a sub-alkyl group or a group having a carbon number of 1 to U. m]) or 4_-1,1-cyclohexylene of the formula (m_2).)

(1Μ) (Π-2) (In the formula (Π-2) and the formula (ΙΙ-3), γ2 and γ3 each represent a group having a carbon number of 1 to 30.)

(川-1) (ΙΙΙ-2) ❹ (In the formula (ΙΙΙ-1) and the formula (ΙΙΙ-2), γ4 and γ5 each represent an alkyl group having a carbon number of 1 to 30.) [2] According to [ 1] The liquid crystal alignment agent according to the above formula, wherein the diamine represented by the formula (I) is m + n + p is 3, and X1 and χ2 represent -0- or -CHr, respectively, and Υ1 represents - Η, and Ζ1 represents a 4-substituted-1,1-cyclohexylene diamine represented by the above formula (ΠΙ_ι) or the formula (ΙΙΙ-2). [3] The wave crystal alignment agent according to the above formula, wherein the diamine represented by the formula (I) is one or both of the diamines represented by the structural formula A1 and the structural formula Α2. ° 8 200930760

The acid stalk is a square or both of the following structural formula (1) and structural formula (Μ).

[5] The liquid crystal alignment agent according to [1], wherein the diamine represented by the formula 0 (1) is m + n + p is 3, and X1 and X2 respectively represent -0- or -CHr· ' Y1 represents -H, and Z1 represents a diamine which may have an alkylene group having a methyl group of 1 to 12 carbon atoms. [6] The liquid crystal alignment agent according to [5], wherein the diamine represented by the formula (I) is such that X1 and X2 each represent -CH2-, and Z1 represents a carbon which may have a methyl group. A number of 1 to 10 alkylene diamines. [7] The liquid crystal alignment agent according to [6], wherein the diamine represented by the above formula (I) is a diamine represented by the following structural formula B1. 9 200930760,

[8] The liquid crystal alignment agent according to any one of [7], wherein the diamine further comprises a diamine represented by the following structural formula (νπι_ΐ3), the tetracarboxylic acid The anhydride is one or both of the following structural formula (丨) and structural formula (14).

(14) The liquid crystal alignment agent according to [1], wherein the diamine represented by (I) is m+n + p is 〇, and the Y1 expression is (11-1), a diamine of the formula (II-2) or the formula (II-3). .

[10] The liquid crystal alignment agent according to [9] characterized in that the diamine represented by the formula (I) is the above formula (Π-2) and Y2 in the formula (11) And Y3 represent a diamine of an alkyl group having a carbon number of 1 to 20, respectively.

[11] The liquid crystal alignment agent according to [9] or [10] characterized in that the diamine represented by the formula (I) is selected from the following structural formula C: More than one of diamines. 200930760

[12] The liquid crystal alignment agent according to any one of [9] to [11] wherein the diamine further comprises the following structural formula (VIII-1) and structural formula (VIII-7); One or both of the diamines represented by the following structural formula (1) and structural formula (14) or

Both sides.

[13] The liquid crystal alignment agent according to [1], wherein the diamine represented by the formula (I) is m + n + p is 1, m and η are 0, and 11 200930760 X The amino group of the aminophenyl group to which -Ο-'X is bonded is bonded to the diamine of the meta position of X2. [14] The liquid crystal alignment agent according to [13], wherein the diamine represented by the formula (I) is one or both of the following formula D1 and the diamine represented by the formula D2. square.

The liquid crystal alignment agent according to [13] or [14], wherein the tetracarboxylic dianhydride is in the following structural formula (1) and structural formula (14) One or both parties.

The liquid crystal alignment agent according to [1], wherein the diamine includes m + n + p in the general formula (I) of 3, and X1 and X2 respectively represent -0- or - CH2-'γΐ represents _H, and ζι denotes a diamine having an alkylene group having a fluorenyl group of 1 to 12, and one or more selected from the following four diamines: (1) m+n + p in the formula (I) is 3, X1 and $ respectively represent -0- or <:Η2·, γ1 represents _H, and 2 represents the general formula (III-1) or a diamine of a 4-substituted-u•cyclohexylene group represented by the formula (III-2); 12 200930760 (2) m + n + p in the formula (I) is 0, and Y1 represents the formula (11-1), a diamine of the formula (ΙΙ-2) or of the formula (ΙΙ-3); (3) m + n + p in the formula (I) is 1, m and η are 0 And X2 represents -0-, the amino group of the aminophenyl group to which X2 is bonded is bonded to the diamine of the meta position of X2; (4) m + n + p in the above formula (I) is 0, Υ1 A diamine of the formula (II-4) is represented.

(11-4) In the formula (II-4), Y6 represents an alkyl group having a carbon number of 1 to 30. The liquid crystal alignment agent according to [16], wherein the formula The diamine represented by the above (I) includes a diamine represented by the following structural formula B1 and one or more selected from the group consisting of the following four kinds of diamines: (1) Two represented by the following structural formula A1 or structural formula A2 (2) a diamine represented by the following structural formula C1 or structural formula C2; (3) a diamine represented by the following structural formula D1 or structural formula D2; (4) the following structural formula (XI-47) The diamine represented.

Nh2 (B1) h2n 13 200930760

[18] The liquid crystal alignment agent according to any one of [1] to [17] which is characterized in that it contains two or more kinds of polyaminic acid or a derivative thereof. [19] The liquid crystal alignment agent according to [17] characterized by containing m + n + p in the general formula (I) as 3'X and X respectively representing or -CH2-, Y1 represents - H, and Z1 represents a polylysine or a derivative thereof which can have a reaction product of a dialkyl group having a methyl group having 1 to 12 carbon atoms and a tetracarboxylic dianhydride, and the following three polylysines Or one of the derivatives of its derivatives: 200930760 or both: (1) as m + n + p in the above formula U) is 3, X1 and χ2 respectively represent -CH2-, Y1 represents -H, and Z1 a polylysine which represents a reaction product of a 4-substituted-1,1-cyclohexylene diamine represented by the above formula (III-1) or ((-2)) and a tetradecanoic acid dianhydride Or a derivative thereof; (2) m + n + p in the general formula (I) is O 'Y1 represents a general formula (Π-1), a general formula (Π-2) or a general formula (ΙΙ-3) a polyaminic acid or a derivative thereof, which is a reaction product of a diamine and a tetracarboxylic acid; (3) as 111 + 11 + 1) in the above formula (I): l, m and η are 0 'And X2 represents _〇_, the amino group of the bonded aminophenyl group is bonded to the meta-diamine of X2 and the reaction of tetracarboxylic dianhydride The polylysine of the product or its derivative. [20] The liquid crystal alignment agent according to any one of [1] to [19] wherein the epoxy compound is selected from the group consisting of glycidyl ether, glycidol vinegar, glycidylamine, and epoxy group-containing One or more of the group consisting of acrylic resin, glycidylamine, glycidyl isocyanurate, chain aliphatic epoxide, and cyclic aliphatic epoxide. [21] The liquid crystal alignment agent according to [20], wherein the epoxy compound is selected from the group consisting of ruthenium, osmium, iridium, Ν'-tetraglycidyl-m-xylenediamine, bis(Ν, Ν-diglycidylaminoindenyl)cyclohexane, ν,ν,ν,,ν,, glycidyl-4,4'-diaminodiphenyl decane, 2_[4-(2,3- Epoxypropoxy)phenyl]-2_[4-[1,1·bis[4_([2,3·epoxypropoxy]phenyl)]ethyl]phenyl]propane, 3,4- Epoxycyclohexene fluorenyl 3,4'-epoxycyclohexenylcarboxylate, fluorenylphenylmaleimide-glycidyl methacrylate copolymer, bisphenol indophenol 15 200930760 One or more of an epoxy compound, a fused epoxy compound, and N n 〇_triglycidyl p-aminophenol. [22] A liquid crystal alignment film which is formed by pseudo-firing a film of the liquid crystal alignment agent according to any one of [1] to [21]. P3] a liquid crystal display device comprising: a pair of substrates arranged in opposite directions; and electrodes formed on one or both of the surfaces facing each of the pair of substrates, formed on each of the pair of substrates The liquid crystal alignment film on the opposite surface, and the liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to [22]. Further, in the present specification, when referring to "descent base,", "dilute base," and "block base", these groups may be linear or branched. [Effect of the Invention] The present invention can provide a liquid crystal display element of various driving methods with low ion density and long-term reliability. The above described features and advantages of the present invention will become more apparent from the following description. [Embodiment] The liquid crystal alignment agent of the present invention contains a polyamine or a derivative thereof, and an epoxy compound having an epoxy group having a number average functional group of more than 1. The polyamic acid or a derivative thereof may be used singly or in combination of two or more. The content of the polyamic acid or a derivative thereof is preferably from 1% by weight/〇: 50% by weight', more preferably from 7% by weight to 3% by weight, based on the liquid crystal alignment agent. . Further, the content of the epoxy compound is preferably 0.1 parts by weight to 100 parts by weight, more preferably 0.5 parts by weight to 8 parts by weight, based on the weight of the polyphthalic acid or its derivative. The polyaminic acid or a derivative thereof is a reaction product of a diamine and a tetracarboxylic dianhydride. The poly-proline derivative is a component in which the poly-proline derivative is in a form dissolved in a solvent when the liquid crystal alignment agent described below is formed, and the liquid crystal alignment agent is made into the following In the case of a liquid crystal alignment film, a liquid crystal alignment film containing, as a main component, polyacrylimide can be formed. Examples of such poly-proline derivatives include soluble polyimine, polyphthalamide, and polyamidamine, and more specifically, all of the amino and enradyl groups of the polyamine. Polyimine which is obtained by dehydration ring closure reaction; 2) partial polyimine which is obtained by dehydration ring closure reaction of a part of amino and carboxyl groups of polyproline; 3) conversion of thiol group of polyproline to ester Polyacetamide; 4) a poly-proline-polyamine copolymer obtained by replacing a part of a dianhydride contained in a tetra-retensive dianhydride compound with an organic dicarboxylic acid; further 5) A polyamidoquinone imine obtained by subjecting a part or all of the polyamic acid-polyamine copolymer to a dehydration ring-closure reaction. In the polyamic acid or a derivative thereof, the tetracarboxylic dianhydride and the diamine are preferably 0.8: 1.2 to 1.2 in terms of a molar ratio: 〇·8, more preferably 〇9: 丨1 to 1 a : 0.9. The diamine may be used in combination of two or more kinds, and the diamine includes a diamine represented by the following formula (I). The diamine of the formula (1) may be used in combination of two or more kinds. In the diamine, the diamine represented by the formula (I) is preferably 0. 5 mol% to 1 mol%, more preferably 1 mol% to ιοο mol%. 17 200930760

In the general formula (i), x1 and x2 each represent -〇- or -ch2-, and γ1 represents -Η, the following structural formula (11-1), general formula (ΙΙ-2) or general formula (ΙΙ- 3), Ζ1 represents an alkylene group having a fluorenyl group having a carbon number of 1 to 12, a 4-substituted-1,1-Asia represented by the following formula (ΙΙΙ-1) or a formula (ΙΙΙ-2) The cyclohexyl group, m, η and ρ represent 0 or 1, respectively.

However, in the general formula (I), m + n + p is 0, 1 or 3, and when m + n + p is 0, Y1 represents a general formula (11-1) and a general formula (Π-2). Or the general formula (11_3); when m + n + p is 1, m and η represent 0, and X2 0 represents -Ο-, and the amino group of the aminophenyl group to which X2 is bonded is bonded to the meta position of X2; When m + n + p is 3, X1 and X2 represent -0- or -CH2-, respectively, Y1 represents -Η, and Z1 represents an alkylene group having a methyl group of 1 to 12, or a general formula (ΙΙΙ-1) or 4-substituted-U-cyclohexylene represented by the formula (ΙΠ_2). The diamine represented by the above formula (I) is, for example, m + n + p is 3, X1 and X2 represent -Ο- or -CH2-, Y1 represents -H, and Z1 represents the formula (III). -1) or a 4-substituted-1,1-cyclohexylene 200930760-based A-type diamine represented by the formula (III-2). The type A diamine can be mainly applied to a TN type liquid crystal display element. Examples of the quinone diamine include diamines represented by the following structural formulae Α1 and Α2.

Further, the diamine represented by the above formula (I) is, for example, m + n + p is 3, X1 and X2 represent -Ο- or -CH2-, respectively, Y1 represents _H, and Z1 represents a fluorenyl group. The alkylene type B diamine having a carbon number of 1 to 12 is used. The type B diamine can be mainly applied to IPS and VA type liquid crystal display elements. Preferably, the B-type diamines X1 and X2 represent -CH2-, respectively, and Z1 represents a diamine having an alkylene group having 1 to 10 carbon atoms which may have a mercapto group. Examples of such B-type diamines include the following The diamine represented by the structural formula B1.

(B1)

Further, the diamine represented by the above formula (I) is, for example, m + n + p is 0, and Y1 represents the above formula (II-1), formula (II-2) or formula (Π) The -3) diamine C-type diamine 〇C-type diamine can be mainly applied to the VA 200930760 type liquid crystal display element. The C-type diamine is preferably a diamine of the formula (II-2) and the formula (II-3) wherein Y2 and Y3 each represent an alkyl group having 1 to 20 carbon atoms. Examples of such a C-type diamine include diamines represented by the following structural formula C1 to structural formula C4.

Further, the diamine represented by the above formula (I) is, for example, m + n + p is 1, m and η are 0, and X2 represents -Ο-, the amino bond of the aminophenyl group to which X2 is bonded D-diamine in the meta position of X2. The D-type diamine can be mainly applied to an IPS type liquid crystal display element. Examples of the D-type diamine include a diamine represented by the following structural formula D1 and structural formula D2.

20 c 200930760 The diamine may further comprise other diamines other than the pass. The linear diamine diamine represented by the diamine (IV) to the general formula (X) represented by the other two:) may be one of the following formulas, or two or more of them may be used. Amine A chain diamine

HaN-A1—NH2

m (V) (VI) (VII) mi) (IX) (X) In the formula (IV), A1 represents -(CH2)m-. Here, m represents an integer of 1 to ❹12. Further, in the general formula (VI) and the general formula (VIII), A1 independently represents an early bond, -0, -S-, -SS-, -S〇2_, -CO-, -CONH-, -NHCO-, _C(CH3)2-, _C(CF3)2-, -(CH2)m-, -0-(CH2)m-0-, -N(CH3HCH2)mN(CH3)-, -S-(CH2)mS -. Here, m represents an integer of 1 to 12. Further, in the formula (IX), A2 independently represents -S-, -CO-, -C(CH3)2-, -C(CF3)2- or an alkylene group having 1 to 3 carbon atoms. Further, in the general formula (X), A1 independently represents -S-, -SS-, -S〇2-, 21 200930760: -CO-, -CONH-, -NHCO-, -C(CF3)2·, -0-(CH2)m-0-, -S-(CH2)mS-. Here, m represents an integer of 1 to 12. Further, in the general formula (X), A2 represents a single bond, -Ο-, -S-, -CO-, -C(CH3)2-, -C(CF3)2- or a carbon number of 1 to 3 Alkylene. Further, the hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulae (V) to (X) may be independently -F, -Cl, -CH3, -OH, -COOH, -S03H, -Ρ03Η2 Or 4-hydroxybenzyl substitution. The linear diamine represented by the formula (IV) is, for example, a diamine represented by the structural formula (IV-1) to the structural formula (IV-3). H2N~nh2 H2N~^nh2 H2Na^^^nh2 (!V-1) {丨V-2) (IV-3) The linear diamine represented by the formula (V) is exemplified by a structural formula (V- 1) and a diamine represented by the structural formula (V-2).

(V-1)

HgN (V-2) The linear diamine represented by the formula (VI) may, for example, be a diamine represented by the structural formula (VI-1) to the structural formula (VI-3).

Nh2 h2n (VI-1)

NHa H2N (VI-2)

(VI-3) The linear diamine represented by the formula (VII) may, for example, be a diamine represented by the structural formula 22 200930760 (VII-1) to the structural formula (VII-14). 〇 H2N called (VIM)

(VII-2) OHHzNJ^XNH2

(VI1-6) so3H

v NH2 (VII-10)

(VII-14) NHz

COOH

HO

(VM-8) P〇3H2

H2 "v nh2 (VII-12) The linear diamine represented by the formula (VIII) may, for example, be a diamine represented by the structural formula (VIII-1) to the structural formula (VIII-31). 〇

Ηη2 η2ν-\ Η2Ν (vm-2)

(Vll^3) (VIIH)

η2νΆ // \\ Η2Ν-^ ^ ΝΗ2 Η2Ν—^~ΝΗ2 (VIII-4) (VIIi-5) (VIII-6) 23 200930760

H2N-^ ^-NHz HzN-^ />-NH2 HsN-i HNH2 (VUi-7) (VIII-8) (VIIi-9>

❹ H2N,,~0NQj-NHa H2NH0KOW〆, /"1Η2 (V»l-14) (VIIH5) (Vllt-16) (Vllt-17) h2n

Nh2 h2n~^^s'v^3>-nh2 hzn'~^3^sss'^ nhz (VIII-18) (Vili-19)

HzN

,s -nh2 nh2

(VIII-20) 〇

H2N

VA (VIII-21) Ss

HzN~^y^ Λ

NH2 (VIII-22) (Vltl-23)

24 200930760

OH OH

NH2

The linear diamine represented by the formula (ix) may, for example, be a diamine represented by the structural formula (IX-1) to the structural formula (IX-6).

(IX-1)

(IX-2)

The linear diamine represented by the formula (X) may, for example, be a diamine represented by the structural formula (X-1) to the structural formula (X-6).

(X-1)

NHa (X-2)

HZN

〇

(Χ-4)

(X-6) 25 c 200930760 The more preferred direct bond type diamines of these direct bond type monoamines include structural formula (VII-1) to structural formula (VII-5) and structural formula (vm-1)~ i configuration (νΠΙ-13), structural formula (VIII-24), structural formula (νηι·25), structural formula (VIII-29), structural formula (VIII-31), structural formula αχ·!), structural formula (1X4), a structural formula (ιχ_6), and a diamine represented by the structural formula (χ_ι), and further preferred linear diamines include structural formula (VII-1), structural formula (VII_2), structural formula to structural formula. (VIII-13), a structural formula (VIII_29), and a diamine represented by β in the structural formula (vm_3i). From the viewpoint of obtaining an appropriate alignment property when a liquid crystal display element is produced, 5, in the ruthenium and IPS type liquid crystal display device, the molar ratio of the linear diamine in the diamine is preferably 1% to 90. %, more preferably 5% to 80%.

In applications in which a large pretilt angle is required, such as a VA liquid crystal display device, a 〇CB liquid crystal display device, or an STN liquid crystal display device, the diamine preferably includes a diamine having a side chain structure, so the general formula (1) The diamine represented by the above may be used. Examples of the diamine having a side chain structure include a side chain type diamine represented by the following formula (XI) to formula (XV). The side chain type diamine may be used singly or in combination of two or more.

26 200930760 In the general formula (XI), A3 represents a single bond, -ο-, -coo-, -OCO-, -CO-, -CONH-, or -(CH2)m-. Here, χη represents an integer of 1 to 6. R represents a group having a ster〇id skeleton, a group represented by the following formula (XVI) or a leuco group having a hindrance of 1 to 30. In this syllabary, Rensi '-CH2- can be independently replaced with -CF2·, -CHF-, -Ο-, -CH=CH- or -CH3 can be independently replaced with -CH2F, -CHF2 or _cf3. Wherein, _〇_ in the alkyl group is not adjacent.

In the general formula (XVI), 'A4 and A5 each independently represent a single bond, -〇_, -COO_, -0C0_, _c〇NH_, _CH=CH_ or a subunit having a carbon number of Bu. R8 and R9 independently represent -F or -CH3, respectively. Ring s represents 1,4-phenylene, 1>4-cyclohexylene, dioxane-2,5-diyl, pyrimidine_2,5-diyl, fluorene 1:2,5-, yl, Naphthalene_1,5-diyl, naphthalene_2,7-diyl or onion _9,1〇_ Ο II. R represents -F, an alkyl group having 1 to 30 carbon atoms, a halogenated group having a carbon number of 丨~Deng, and an alkoxy group '_cn, _〇cH2F, -OCHF2 or _OCF3 having a carbon number of 30. Further, a and b respectively indicate that the jingle & or b is 2 to 4, respectively, and the adjacent A4 or the adjacent A5 are different =:, d and e are independently represented. An integer of 〜3, when e is 2 or 3, a plurality of rings 8 may be the same group, and the groups independently represent an integer of 〇~2, and wherein 'w when m in the formula (5) is 丨'C-, c, d and e are respectively! The situation, or exclude a4 and other) 27 200930760 Single-key or the case of a sub-base with a carbon number of 2.

(XH)

(XIH) In the formula (XII), the hydrogen bonded to the carbon forming the steroid skeleton may be independently substituted by -CH3. In the formula (XII) and the formula (XIII), R11 each independently represents -H or -CH3, and R12 represents -H or an alkyl group or alkenyl group having 1 to 20 carbon atoms. A6 independently represents a single bond, -C(=0)- or -CH2-. In the formula (XIII), R13 and R14 each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group. 28 200930760

nice. In (XIV), Rl5 indicates _H or a product with a carbon number of 1 to 30: it is set to 1^. Any mother with an alkyl group with a carbon number of 2 to 30 - can be independent: do not compare t H = CH shouter _ Lang. However, this is not the case. In the formula (XIV) and the formula (??), a7 is independently 1 or a calcined group having 1 to 6 carbon atoms. In the formula (XIV), A8 ❹ ^ single bond or a filament having a carbon number of 1 to 3. Ring T represents 1,4-phenylene^,4,4,5-hexyl. h means 〇 or 1. In the formula (χν), the ruler 16 has a number of 6 to 22 filaments, and Rl7 represents _H or a carbon number of 1 to 22. However, in the general formula (XIV), when r is Q, Rl5 is seven, when the field 'excludes A8 is a single bond' or R5 is 〇, the side chain type diamine represented by the general formula (XI) In the bonding, the bonding position relationship of the two amino groups bonded to the benzene ring is preferably meta or para. The bonding positional relationship of the two Jins is more preferably as follows: when ΙΑ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The diamine represented by the following formula (XI-1) to the formula (XI-9) may, for example, be a diamine represented by the following formula (XI-1).

In the above formula (XI-1), formula (XI-2), formula (XI-5) and formula (XI-6), R18 preferably has an alkyl group having a carbon number of from 1 to 30 or a carbon number of The alkoxy group of 1 to 30. is more preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms or a carbon number of 5 to 25 Alkoxy group. Further, in the above formula (XI-3), formula (XI-4) and formula (XI-7) to formula (XI-9), R19 is preferably an alkyl group having 1 to 30 carbon atoms or carbon. The alkoxy group having a number of 1 to 30 is more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. Further, the side chain type diamine represented by the above formula (XI) may, for example, be a diamine represented by the following formula (XI-10) to formula (XI-15) in 200930760.

R25 o=cf b xS (XI-12)

(Xi-13)

(XI-14) (XM5) In the above formula (XI-10) to formula (XI-13), R20 is preferably an alkyl group having 4 to 30 carbon atoms, more preferably an alkyl group having 6 to 25 carbon atoms. . In the above formula (XI-14) and formula (XI-15), R21 is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 25 carbon atoms. Further, the side chain type diamine represented by the above formula (XI) may, for example, be a diamine represented by the following formula (XI-16) to formula (XI-36).

31 200930760

(Xl-35) — (ΧΙ-36) The formula (ΧΙ-16), the formula (ΧΙ-17), the formula (χι_2〇), the formula (ΧΙ-22), the formula (ΧΙ-23) , general formula (ΧΙ-26), general formula (xi-28), 32 200930760, general formula (ΧΙ·29), general formula (XI-34), and general formula (XI-35), R22 preferably has a carbon number of The alkyl group of 1 to 30 and the alkoxy group having 1 to 30 carbon atoms are more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. The general formula (XI-18), the general formula (XI-19), the general formula (XI-21), the general formula (XI-24), the general formula (XI-25), the general formula (XI-27), In the general formula (XI-30) to the general formula (XI-33) and the general formula (XI-36), R23 is preferably -H, -F, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 1 to 30. The alkoxy group, -CN, -OCH2F, -OCHF2 or -OCF3, more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. In the above formula (XI-31) and formula (XI-32), A9 represents an alkylene group having 1 to 20 carbon atoms. Further, the side chain type diamine represented by the above formula (XI) may, for example, be a diamine represented by the following structural formula (XI-37) to (XI-46).

33 200930760

〇

The diamine represented by the formula (χι_ι) of the side chain type diamine represented by the general formula (Γ) is more preferably a diamine represented by the formula (ΧΙ-2) or the formula (ΧΙ.4). . 3 A bond is in the 1st position of the steroid nucleus, and the other bond is in the 6th position of the nucleus. In addition, each of the _-Nanweiwei County a6 乂 乂 on the phenyl group is represented by two side chain type diamines represented by the above formula (XII) (XII-1) to the structural formula. (XII_4) The spears can be listed as 34 200930760

The side chain type diamine represented by the formula (XIII), preferably two "NH2-(R14-)Ph-A6-0-", respectively, are bonded to the carbon of the phenyl group, and the two "NH2- (R14-)Ph-A6-0-" is bonded to the phenyl group on the phenyl group with the inter- or meta-position of the carbon of the deuteron. In addition, two amino groups bonded to the two phenyl groups, respectively, are preferably bonded to the meta or para position of A6. The side chain type diamine represented by the above formula (XIII) may, for example, be a diamine represented by the following structural formula (XIII-1) to structural formula (XIII-8). 35 200930760

The side chain type diamine represented by the above formula (XIV) preferably has two amino groups bonded to each of the two phenyl groups bonded to the meta or para position of A7. The side chain type diamine represented by the above formula (XIV) may, for example, be a diamine represented by the following formula (XIV_1) to (XIV-9).

Ru ^

37 200930760 In the above formula (XIV-1) and formula (XIV-2), R24 is -H, and in the formula (XIV-4) and formula (XIV-5), R25 is ruthenium. Further, in the above formula (XIV-3), R24 is preferably -Η or an alkyl group having a carbon number, and in the formula (XIV-6) to formula (XIV-9), R25 is preferably -H or carbon. The number is 1 to 20. The side chain type diamine represented by the above formula (XV) preferably has two amino groups bonded to each other on the two phenyl groups, respectively, at the meta position of the A7 or the para position of the above formula (XV). The side chain type diamine represented by the above may be used. The formula (χν·ι) ~ general formula (χν_3) is represented by J * amine 0

(XV»3) In the above formula, R26 is preferably a burnt group having a carbon number of 6 to 2 Å or a carbon number of 1 to 10. The alkyl group, R27 is preferably obtained in the case of a liquid crystal display element, and the molar ratio of the side chain type diamine in the viewpoint of the pretilt angle of ΤΝ and VA type liquid crystal display is preferably 1% to ' 80% in the diamine. ° ° / ° ' more preferably 5% ~ other than the illustrated diamine having a fluorene structure or having the diamine may further comprise the other diamine of the formula (I), such as naphthalene based on a naphthalene structure A lanthanide diamine, a diarrhea oxygenated system having a diarrhea bond, a diarrhea, 38 200930760, a diamine having a side bond structure other than the side chain structure represented by the formula (XI) to the formula (XV), If the other diamine has a side chain structure, then: the B component of the amine; if the other two materials are tender, it can be used as the A component of the amine. For example, the above-mentioned diamine represented by the following (XVII) can be mentioned. %

Q ΗζΝ—(-Α10-

R29 Jj ^29 R28 Si-^-Α10-^τ-ΝΗ3 (XVII) In the above formula (XVII), R28 and R29 independently represent an alkyl group having a carbon number of 3 or the group 'AIG independently represents a methylene group, A phenylene group or a pyrene substituted phenylene group. i represents an integer of 1 to 6 and represents an integer of 1 to 1 。. The diamine represented by the above formula (XVII) may, for example, be a diamine represented by the following structural formula (XVII-1) to structural formula (XVII-7).

Ch3 ch3 ii-CHg-SI-O-Si-ch2-nh2 CH« CHa (XVU-1) CH3 CH3 HaN-c^-ao-si-c3h6-nh2 CH3 CH3 (XVII-3) ch3 ch3 H2N-C2H4- 〒- CH, ch3 PCVII-2) CH3 CH3 HiN-C^e^Si-Osc^-NHa CH3 ch3 (XVIM) C^HS H2N**C3He-Si-〇-S{—CgHg-NHg Q2H5 (m\ s) CH3 CH3 CH3 H2N~C^H6-Si-〇~SrC>-S»--C3He--NH2 CH3 CH3 CH3 (XVli-S) 39 200930760 c3h7 C3Ht

HgN-QjHg - Si -0" S-Kan-NH2 C3H7 C3H7_f-7) The other diamine is not particularly limited, and examples thereof include those represented by the following formula (Γ) to (8'). Diamine.

In the above formula, R3G independently represents an alkyl group having a carbon number of 3 to 30, and in the formula (4'), the formula (6') and the formula (8'), R31 represents a carbon number of 3 ~30 alkyl. Further, the other diamine is not limited to the above-described diamine, and it is of course possible to use various forms of diamines other than the other diamines within the range in which the object of the present invention can be attained. 200930760 A portion of the diamine may also be substituted with a monoamine. If a part of the diamine is substituted with a monoamine, the polymerization reaction to form the polyamic acid or its derivative can be terminated, and the further reaction can be inhibited, whereby the molecular weight of the amine amine or its derivative can be easily determined. In this view, the ratio "1" should be in the form of the silk _ effect _: the molar content of the amine is less than or equal to the molar content of the amine. The tetracarboxylic dianhydride is only fixed. The second liver, H is particularly limited to the use of the polyglycine species of the present invention. It is also possible to use two or more types. In terms of the form, it is preferably an appropriate one: the organism is formed to be soluble in a solvent, and the tetradecanoic acid can be used. List the field - select the tetraacid dianhydride. The four rebel acid inx and the rider = face four fine two Xuan, the aliphatic said aromatic tetracarboxylic acid diacid ~ anhydride. ~ ((1) represented by the compound = For example, the following structural formula (1) can be cited

41 200930760

ο ο (12) (1 3) ❹ The aromatic tetracarboxylic dianhydride is preferably the following structural formula (1), structural formula (2), structural formula (5), structural formula (6), and structural formula ( 7) The compound represented by the formula (1) is more preferably a pyromellitic dianhydride represented by the formula (1). The aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride, 〇, for example, a compound represented by the following structural formula (14) to structure S (62). 42 200930760

(18) (19) (2 0)

43 200930760

44 200930760

The aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are preferably compounds represented by the structural formula (14) to the structural formula (29) and the structural formula (6〇), more preferably Io, 2, 3, 4-cyclobutane tetracarboxylic dianhydride represented by the formula (14). Further, in view of making the polyaminic acid of the present invention or a derivative thereof into a polyimine which can dissolve Q in a solvent, the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic acid The anhydride is preferably a compound represented by the structural formula (19), the structural formula (20), the structural formula (27) to the structural formula (29), and the structural formula (60). Further, the tetracarboxylic dianhydride is also a tetrabasic acid dihepatic having a side chain structure. Four having a side chain structure - increasing the pretilt angle of the liquid crystal display element. The acid having a side chain structure, for example, may be exemplified by the following structural formula (63) and a compound having the fluorene skeleton 45 200930760 represented by the structural formula (64).

〇 Make the liquid crystal components have good: The two delete the aromatic four thief::; the four-week two _ and the four-parent two-parent-square or two.

The acid reading two needles also include various forms of four thief dianhydrides, and are not limited to the four remedies. The dilute acid liver may use other various forms of tetracarboxylic dianhydride within the scope that can be achieved by the object of the present invention. A part of the tetracarboxylic dianhydride may be replaced with a carboxylic acid liver. If a part of the tetra-retensive dianhydride is replaced with a slow anhydride, the polymerization reaction for producing the poly-aracine or its derivative can be terminated, and further reaction can be suppressed, whereby the obtained polyamine can be easily controlled. From the viewpoint of the molecular weight of the acid or its derivative, it is preferred to replace a part of the tetracarboxylic dianhydride with a carboxylic anhydride. The ratio of the carboxylic anhydride to the tetracarboxylic dianhydride may be within the range of the effect of the present invention, and the standard is 10 mol% or less of the tetracarboxylic dianhydride. With respect to the combination of the diamine and the tetracarboxylic dianhydride described above, more specifically, from the viewpoint of a decrease in ion density and an improvement in the alignment property, it is preferred that the diamine contains the A-type II. And an amine and one or more of the diamine represented by the ν, σ configuration (VIII-3), the structural formula (VIII-7), and the structural formula (), and the tetracarboxylic dianhydride comprises the structural formula (1) One or both of the structural formulas (14). Further, in view of reduction in ion density, improvement in orientation, and prevention of sticking, it is preferred that the diamine comprises the B-type diamine and the diamine represented by the structural formula (VIII-13), and The tetracarboxylic dianhydride includes one or both of the structural formula (1) and the structural formula (14). Further, from the viewpoint of a decrease in ion density and an improvement in the alignment property, the diamine preferably contains the C-type diamine and the diamine represented by the structural formula (VIII-1) and the structural formula (VIII-7). One or both of the tetracarboxylic dianhydrides include one or both of the structural formula (1) and structural formula (14). Moreover, it is preferable that the diamine includes one or both of the D-type diamines represented by the structural formula D1 and the structural formula D2 from the viewpoint of a decrease in ion density, an improved alignment, and prevention of sticking. And the tetracarboxylic dianhydride includes one or both of the structural formula (1) and the structural formula (14). The weight average molecular weight of the polyaminic acid or a derivative thereof is not particularly limited, and when it is used as a component of a liquid crystal alignment agent, in the step of calcining the film with a liquid crystal compound 47 200930760, the polymerization is carried out. The proline or its derivative does not evaporate. The weight average molecular weight is preferably 5xl〇3 or more, more preferably 1xl〇, in terms of obtaining good physical properties of the component as a liquid crystal alignment agent. 4. Further, from the viewpoint of facilitating the operation of aligning the liquid crystals having viscosity or the like, the weight average molecular weight is preferably equal to or less than lxl〇6. The weight average molecular weight of the polyamic acid or a derivative thereof can be measured by a gel permeation chromatography (GPC) method. For example, the obtained polyaminic acid or a derivative thereof is diluted with dimethylformamide (DMF) to a concentration of polyglycine or a derivative thereof of about 1% by weight, using Chromatopac C-R7A, The product was measured by a gel permeation chromatography (GPC) method using DMF as a developing solvent, and converted to polystyrene to determine the weight average of the polyaminic acid or its derivative. Molecular weight. Further, from the viewpoint of improving the accuracy of the Gpc measurement, it is also possible to use a mineral acid such as phosphoric acid, hydrochloric acid, nitric acid or sulfuric acid, lithium bromide or lithium chloride, etc., in the DMF towel. The polylysine or its derivative can be produced by a well-known method. For example, the diamine may be introduced into a reaction vessel having a raw material inlet, a nitrogen inlet, a thermometer, a stirrer, and a condenser, and a required amount of monoamine may be charged as needed. Then, a solvent (e.g., a guanamine-based polar solvent N-methyl-2-pyrrolidone or dimethylguanamine) and the tetracarboxylic dianhydride are added, and a desired amount of a carboxylic anhydride is added as needed. At this time, it is preferred that the total amount of the tetracarboxylic dianhydride is substantially equal to the total number of moles of the diamine (the molar ratio is about). The reaction can be carried out for 1 hour to 48 hours under stirring at 〇 ° C to 7 〇 t: whereby a polyaminic acid solution can be preferably obtained. Further, it is also possible to increase the reaction temperature by heating (for example, 5 〇 ° c to 8 〇 〇 to obtain a polyglycine having a small molecular weight. The resulting polylysine is precipitated with a large amount of a poor solvent, and filtered. The solid component and the solvent are completely separated, whereby polylysine can be obtained. As the polyamidamine derivative, a soluble polyimine can be usually obtained by: a polylysine solution, and An acid anhydride needle such as acetic acid needle, propionic acid or difluoroacetic anhydride, and a tertiary amine such as triethylamine, pyridine or collidine as a dehydration ring-closing catalyst together at 20 ° C to 150 ° C The hydrazine imidization reaction is carried out at a temperature. Further, the soluble polyimine may be obtained by using a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a glycol solvent). The polyaminic acid is precipitated from the polyaminic acid solution, and the precipitated polylysine is combined with the same dehydrating agent and dehydration ring-closing catalyst in a solvent such as toluene or xylene. t The hydrazine imidization reaction is carried out at a temperature of 〜. In the hydrazine imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closure catalyst is preferably 0.1 to 10 (mole ratio). Both the dehydrating agent and the dehydration ring-closing catalyst are used. The total amount used is preferably 1.5 times by mole to 10 times the molar amount of the acid dianhydride contained in the tetraphthalic acid dianhydride used by adjusting the chemical hydrazide dehydrating agent, The amount of the catalyst, the reaction temperature, and the time of the reaction, the amount of the imine can be controlled to obtain a part of the polyimine. In addition, if the part of the tetracarboxylic dianhydride is replaced by the organic two, then A poly-proline-polyamine copolymer can be obtained. Among them, the ratio of dimethane to _acid dianhydride can be within the range of the effect of the present invention, and the standard is the carboxylic acid of the tetracarboxylic dianhydride. Less than or equal to the ear. Further, polyamidoquinone imine can be obtained by chemically hydrazating a poly-proline-polyamine copolymer.

The polylysine or a derivative thereof can be determined by analysis by infrared spectroscopy (IR) or nuclear magnetic resonance (NMR). Alternatively, the solid polyamic acid or its derivative can be decomposed with an aqueous solution of a strong base such as K〇H or NaOH. Then the polylysine is extracted with an organic solvent and passed through Gc, high performance liquid chromatography (High Performance Liquid). Chromatography, HPLC), gas chromatography-mass spectrometry (Gas Chromatography-Mass sPectr〇metry 'GC-MS) analysis, thereby identifying the polyamine or its derivative obtained by diluting with a solvent. Adjust it to the desired viscosity before using it. Further, the obtained polyaminic acid or a derivative thereof may be separated from the solvent and then re-dissolved in the following solvent together with the epoxy compound described below to prepare a liquid crystal alignment agent; or may be separated from the solvent. An epoxy compound is added to prepare a liquid crystal alignment agent. With respect to the poly-proline or a derivative thereof, it is possible to adjust the surface of the liquid crystal component by appropriately using the diamine or tetracarboxylic dianhydride having a side chain structure such as the side chain type diamine, and shouting The material (IV) aminic acid or its organism can be applied to any type of liquid crystal display element. As the pretilt angle, most of the VA liquid crystal display elements require 8 turns. ~9〇. For large pre-tilt angles on the left and right, OCB type liquid crystal display elements mostly require 7. ~2〇. The left and right corners of the TN type liquid crystal display element or the STN type liquid crystal display element often require a pretilt angle of about 3 to 10 degrees, and most of the lps type liquid crystal display elements require germanium. A small pretilt angle of ~ 3°. ~

Q The properties exhibited by polyacrylic acid or a derivative thereof such as the pretilt angle can be obtained by using a monomeric polyamic acid or a derivative thereof having such a property. The properties exhibited by the monomer, = the polyamine obtained by the monomer having such characteristics, or any organism thereof, and may also be obtained by using a plurality of monomers. In view of the fact that the liquid crystal alignment agent of the present invention has excellent characteristics, it is preferred that the liquid crystal alignment agent contains two or more kinds of heteroamino acids which are partially or wholly of the monomer. Or its touch. The mixing ratio of two or more kinds of diamino acids or derivatives thereof may be such a degree as to obtain the desired characteristics corresponding to the use of the Weijing alignment agent. More specifically, by appropriately selecting the diamine or tetrawei species and the combination of the diamine and the tetranucleus, the =3=requires S to add a good ion density or a more uniform = pre-collar angle, etc. The required features, and can improve these features. The combination of the two or more kinds of polystyrenes or their derivatives &s can be exemplified by, for example, 200930760: (1) poly-tyranamic acid containing the B-type diamine or a derivative thereof, and blood containing the poly-guanidine of the type A diamine An amine acid or a derivative thereof, a polyaminic acid or a derivative thereof comprising the c-type diamine, or a combination comprising the d-type diamine tyrosine acid or a derivative thereof; (7) comprising the amine acid or a combination of a touch, a poly-assay or a straight-line containing the type A diamine, and a poly-proline or a derivative thereof comprising the C-type diamine, and (3) comprising the B-type diamine a poly-acid or a derivative thereof, comprising the D-type di-branche or a derivative thereof, and the poly-fluorene comprising the A-type diamine (tetra)-acid or a derivative thereof or comprising the c-type diamine A combination of an amine acid or a derivative thereof. The epoxy compound is a compound having two or more epoxy groups, such as a (tetra) epoxy group having an average number of functional groups greater than 1. The epoxy compound may be in the form of - or both of them. In the liquid crystal alignment agent, the type and content of the epoxy compound and the content of the solution which can form the epoxy compound and the polyaminic acid or its derivative are used. Further, the epoxy resin means a resin having an epoxy group. Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidylamine, glycidyl isocyanurate, and chain aliphatic epoxy. Compounds and cyclic aliphatic epoxy compounds. Examples of the glycidyl ether include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol s type epoxy compound, a bisphenol type epoxy compound, a hydrogenated bisphenol A type epoxy compound, and hydrogenation. Bisphenol F type epoxy compound, hydrogenated bisphenol S type epoxy compound, hydrogenated bisphenol type epoxidation 52 200930760 ^ Object: desertification (four) oxime type epoxy compound, galvanic substance, benzene type epoxy compound, cresol _ Type epoxidation 2; benzene cleavage type compound, enthalpy __ ring epoxy compound, epoxidation containing naphthalene skeleton: substance: fragrant sulphate sweet compound, dicyclopentadiene _ benzene _ ring An oxygen compound, an alicyclic diglycidyl (10) compound, an aliphatic polyglycidol mystery compound, a polysulfide (10) ySulflde) type diglycidyl epoxy compound.

Ο The glycidol vinegar may, for example, be a diglycidyl vinegar compound or a glycidyl ester epoxy compound. Examples of the glycidylamine include a polyglycidylamine compound and a glycidylamine type epoxy resin. The epoxy group-containing acrylic acid compound may, for example, be a homopolymer or a copolymer of a monomer having an oximnyl group. The glycidylamine can be exemplified by a glycidylamine type epoxy compound. The chain aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound. The cyclic aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cycloolefin compound. Examples of the bisphenol A type epoxy compound include 828, 1〇〇1, 1002, 1003, 1004, 1007, and 1〇1〇 (all made of Japanese epoxy resin).

Epo Tohto YD-128 (manufactured by Dongdu Chemical Co., Ltd.), der_331, DER-332, DER-324 (both manufactured by Dow Chemical Co., Ltd., 2009, 200930760) 'Epiclon 840, Epiclon 850, Epiclon 1050 (both Made by Dainippon Ink), Epomik R-140, Epomik R-301, and EpomikR-304 (both manufactured by Mitsui Chemicals). Examples of the bisphenol F-type epoxy compound include 806, 807, and 4004P (all manufactured by Japanese epoxy resin), EpoTohto YDF-170, Epo Tohto YDF-175S, and Epo Tohto YDF-2001 (all manufactured by Dongdu Chemical Co., Ltd.). ), DER-354 (manufactured by The Dow Chemical Company), Epicl〇n 830 and Epiclon 835 (both manufactured by Dainippon Ink).

The bismuth epoxy compound may, for example, be an epoxy compound of 2,2-bis(4-pyridylphenyl)-1,1,1,3,3,3-hexafluoropropene. Examples of the hydrogenated bisphenol A type epoxy compound include Sun Tohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rikaresin HBE1 (manufactured by Nippon Chemical and Chemical Co., Ltd.), and Denacol EX-252 (manufactured by Nagase Chemical Co., Ltd.). The deuterated double-prone type ring-like emulsion compound may, for example, be an epoxy compound hydrogenated with 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. Examples of the brominated bisphenol A type epoxy compound include: 5〇5〇' 5〇M (all manufactured by Japanese epoxy resin), Ep〇T〇ht〇YDB_36〇, Ep〇Tohto YDB-400 (both Made by Dongdu Chemical Co., Ltd., Dirty _53〇, DER-538 (all manufactured by The Dow Chemical Company), Epici〇n i52 and Epiclon 153 (both manufactured by Otsuka Ink). Examples of the benzene-based epoxy compound include: i52, 154 (all manufactured by Nippon Epoxy Resin), YDpn, manufactured by Lizhou (both manufactured by Dow Chemical Co., Ltd. 54 200930760 N_770 (Daily Ink Chemistry) Industrial Co., Ltd.), EPPN-201 and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.). The cresol novolac type epoxy compound is exemplified by 180S75 (manufactured by 曰本 epoxy resin), YDCN -701, YDCN-702 (both manufactured by Dongdu Chemical Co., Ltd.), Epiclon N_665, Epiclon N-695 (all manufactured by Otsuka Ink Chemical Industry Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 EOCN-1025 and 〇EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.). The bisphenol A phenolic epoxy compound is exemplified by 157S70 (manufactured by Sakamoto Epoxy Co., Ltd.) and Epiclon N. -880 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) The epoxy compound containing a naphthalene skeleton may, for example, be Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (both from Japan) Manufactured by Ink Chemical Industry Co., Ltd., and NC-7000 (manufactured by Sakamoto Chemical Co., Ltd.) 0 The aromatic polyglycidyl ether compound is exemplified by p-benzoic diglycidyl (the following structural formula 101) ) 'Niaoben two diglycidyl ether (the following structural formula 102), resorcinol diglycidyl ether (the following structural formula 103) '2-[4-(2,3-epoxypropoxy) Phenyl]-2-[4-[1,1-bis((2,3-epoxypropoxy)phenyl)]ethyl]phenyl]propan (hereinafter, structural formula 104), three (4-glycidoxyphenyl)methane (the following structural formula 1〇5) ' 1〇3lS, 1032Η60 (all manufactured by Japanese epoxy resin), TACTIX-742 (manufactured by The Dow Chemical Company)' Denacol EX- 201 (made by Changchun Chemical Co., Ltd. 55 200930760), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.) 'TeCm〇re VG3101L (manufactured by Mitsui Chemicals, Inc.), the following The compound represented by Structural Formula 〇6 and the following

Compound of formula 107

56 200930760

_ _ Dicyclopentadiene Benzene epoxide compound: TACTIX-556 (manufactured by The Dow Chemical Company), Epicl〇n Hp_72〇〇 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.). Examples of the alicyclic diglycidyl compound include a cyclohexanedimethanol diglycidyl ether compound and Rikaresin DME_1® (manufactured by Shin Sakamoto Chemical Co., Ltd.). Examples of the aliphatic polyglycidol mystery compound include ethylene glycol diglycidyl ether (the following structural formula 108), diethylene glycol diglycidyl eight mystery (the following structural formula 109) 'polyethylene glycol II Glycidic acid, propylene glycol diglycidyl ether (the following structural formula 110) 'tripropylene glycol diglycidyl ether (the following structural formula 111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following structure) Formula I12), 1,4-butanediol diglycidyl ether (structure 113 below), 1,6-hexanediol diglycidyl ether (structure 114 below), dibromo neopentyl glycol condensate Glycerol ether (Structure 115 below), Denacol EX, 810, Denacol EX-851, Denacol EX-8301, Denacol EX_911 x Dcnacol EX-920 'D6ii3.col EX-931 '

Denacol EX-211, Denacol EX-212, Denacol EX-313 (both manufactured by 57 200930760 Nagase Chemical Co., Ltd.), DD-503 (manufactured by Asahi Kasei Co., Ltd.) Rikaresin H〇〇 (Nippon Chemical and Chemical Co., Ltd.) tetraglycidyl group - 2,4-hexanediol (Structure 116 below), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX- 313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all manufactured by Changchun Chemical Company).

(110)

(112) ❹ (111)

(113)

(114}

5g 200930760 The double-type epoxy compound can be exemplified by: π·, YL-6121 are all made of Japanese epoxy resin, NC_3〇〇〇p, NC_3〇〇〇s (all manufactured by Nippon Kayaku Co., Ltd.) ). ❹ The mono-glycidyl vinegar compound may, for example, be diglycidyl terephthalate (the following structural formula I17), diglycidyl phthalate (the following structural formula 118), ortho-dicarboxylic acid Bis(2- mercapto oxiranyl methyl vinegar) (the following structural formula 119), hexahydro-o-p-diformate diglycidyl ester (the following structural formula 120), a compound represented by the following structural formula 121, The compound represented by the following structure ^ 122 and the compound represented by the following structural formula 123 °

(118)

(119) (117)

CH3 〇22) 59 200930760

It can be exemplified by 871, 872 ιη 2〇〇, Epiclon 400 (manufactured by 1 company), and manufactured by Denacol ϊ Changhua Chemical Co., Ltd.). The glycidyl ester epoxy compound such as ^ (all manufactured by 曰 环氧树脂 epoxy resin), Epicli 〇 n2 (by Dainippon Ink Chemical Industry Co., Ltd. EX-711 and Denacol EX-721 (both by Chang, Lai Diamine (TETRAD-X (Mitsubishi Gas Chemical)' following structural formula 132), & bis(indole, hydrazine-diglycidylaminomethyl)cyclohexane (TETRAD-C; two-labeled 1Ls chemistry), The following structural formula 133), i, 4-bis (N, dimethyl condensed water, the polyglycidylamine compound, for example, n, n-di (glycidyl) aniline (the following structural formula 124), hydrazine, Ν-diglycidyl o-toluidine (structural formula 125 below), hydrazine, hydrazine-glycidyl m-toluidine (structure 126 below), hydrazine, hydrazine-diglycidyl-2,4,6 -Tribromoaniline (Structure 127 below), 3-(anthracene, fluorene-diglycidyl)aminopropyltrimethoxy oxet (the following structural formula 128), hydrazine, hydrazine, 0-triglycidyl P-aminophenol (formula 129 below), hydrazine, hydrazine, hydrazine-diglycidyl-m-aminobenzene (described below, structural formula 130), hydrazine, hydrazine, hydrazine, hydrazine, tetraglycidyl Aminodiphenylmethyl The following formula 131), Ν, Ν, Ν, Ν - tetraglycidyl-dimethoxy present

200930760 Hydroglycidylaminof group) = 9)) 222 g-glycidyl Μ Ό Ό ) 141 141 141, χ Μ Μ Μ Ν Ν - - - ( ( ( ( ( ( ( ( ( ( ( ( ), hydrazine, hydrazine, hydrazine 4,4,-diaminodiphenyl ether (structure formula 142 below), 1,3,5_tri(4_(Ν,Ν_ diglycidyl)aminophenoxy)benzene (Structural formula Μ3 below), 2,4,4'-tris(Ν,Ν-diglycidylamino)diphenyl ether (structure 144 below), tris(4-(Ν,Ν-bi-shrink) Glyceryl)aminophenyl)methylxanthine (the following structural formula 145), 3,4,3,,4,-tetrakis(Ν,Ν-diglycidylamino)biphenyl (described below, mouthwash configuration 146) , 3,4,3,,4,-tetrakis(Ν,Ν-diglycidylamino)diphenyl bond (the following structural formula 147), a compound represented by the following structural formula 148, and the following structural formula 149 compounds of the system. ❹

(128}

(126) (129)

(130)

Ν^Νϊ^ρ (131) 61 200930760

(136) (137}

62 (142) 200930760

The homopolymer of the monomer having an oxiranyl group may, for example, be poly 63 200930760 ❹ 缩 glycidyl methacrylate. The copolymer of the monomer having an oxiranyl group may, for example, be N-phenylmaleimide-methyl hydrazide ruthenium oil vinegar copolymer, Ν_cyclohexylmaleimide-acrylic acid shrinkage Glycerin copolymer, methacrylic acid (tetra) fluorenyl-acid glycidol vinegar copolymer, methyl acetoin butyl methacrylate methacrylic acid glycidyl vinegar copolymer, methyl propyl benzoate-2-hydroxyethyl _ Glycidyl acrylate copolymer, (3 ethyl-3- oxypropyl) decyl methacrylate - glycidyl methacrylate urethane and styrene - glycidyl methacrylate copolymer. Further, the monomer having an oxiranyl group may, for example, be a dilute acid glycidol, or a (fluorenyl) propylene scale _3,4_epoxycyclohexane from methyl methacrylate.丫丞) In the copolymer of the monomer having an epoxy group, the monomer other than the monomer is, for example, (methyl: , (methyl) oleate, Methyl) propyl acrylate, (methyl isopropyl vinegar, (meth) acrylic acid TS, (f) acrylic acid isobutyl § 2 butyl acrylate, (meth) acrylate ring Hex vinegar, (meth)acrylic acid) (methyl)propionic acid-2-ethylidene vinegar, (meth)acrylic acid _2 _ propyl propyl hydrazine, ^ ethyl methyl styrene, chloromethyl Benzene, (曱基) = _3_ propylene propylene) f vinegar, N_cyclohexylmaleimine, and ruthenium imine. Yan·1 ^ ^ a) L3--glycidyl-5-allyl_丨3 5 = Gong Na satire 3H, chat three _ (the following structural formula 151) and heterogeneous two ^ 64 200930760 glycidyl ester type Epoxy resin.

Ο ❹ The chain-like aliphatic epoxy compound is exemplified by epoxidized polybutadiene and Epolead PB3600 (manufactured by Daicel Chemical Industry Co., Ltd.). The cyclic aliphatic epoxy compound is exemplified by the following: 3,4-epoxycyclohexene methyl epoxy cyclohexenyl decanoate (Celloxide 2021 (manufactured by Daicel Chemical Industry Co., Ltd.), the following structural formula 152), 2_mercapto-3,4-ring Oxycyclohexylmethyl 2'-mercapto_3', 4'-epoxycyclohexylformate (Structure 153 below), 2,3-epoxycyclopentyl 2', 3'-ring Oxycyclocyclopentyl ether (Structure 154 below), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3,4,-epoxycyclohexyl decanoate, 1,2:8 IX-epoxy limonene (Celloxide 3000 (manufactured by Daicel Chemical Industry Co., Ltd.), the following structural formula 155), a compound represented by the following structural formula 156, CY-175, CY-177, CY-179 (both It is manufactured by CIBA-GEIGY Co., Ltd., EHPD-3150 (manufactured by Daicel Chemical Industry Co., Ltd.) and a cyclic aliphatic epoxy resin.

65 200930760

(156) (155) Ο The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A phenolic gas compound, a cresol novolak type epoxy compound, and a cyclic aliphatic type oxygen compound, more preferably Ν,Ν,Ν,,Ν,-tetraglycidyl-m-xylenediamine, L3-bis(Ν,Ν-diglycidylaminomethyl)cyclohexane, 'wind: ^', 1^ four shrinkage Glyceryl-4,4,-diaminodiphenyl"methyst, trade name "Tecmore VG3101L", 3,4-epoxycyclohexenemethyl_3,,4,_ ring-rolled cyclohexenyl fluorene Acid ester, N-phenylmaleimide-mercapto-acrylic acid glycidyl vinegar copolymer, hydrazine, hydrazine, 0-triglycidyl-p-carbyl benzene, double phenolic epoxy compound and One or more of phenol novolac type epoxy compounds. The liquid crystal alignment agent of the present invention may further comprise the polyamic acid or a derivative thereof, and a component other than the epoxy compound. The components further contained in the solvent include various solvents and various additives contained in ordinary liquid crystal alignment agents. The solvent widely includes a solvent which is usually used in a production step or use of a polymer component, such as polyamic acid, soluble polyimine, and polyamine amine, and the solvent can be appropriately selected depending on the purpose of use. For example, the solvent can be used from the viewpoints of adjusting physical properties such as viscosity of the liquid crystal alignment agent, ease of handling, and simplification of steps. The solvent may be used singly or in combination of two or more. The solvent may, for example, be a protic polar organic solvent which is readily soluble in polylysine or a derivative thereof, and a coating property improving solvent which changes the surface tension of Table 66 200930760 to improve coatability, etc., and the solvent preferably contains these. A solvent mixture of solvents. Examples of the aprotic polar organic solvent include N-methyl-pyrrolidone (N-methyl-2-pyrr〇lid〇ne), hydrazine, hydrazine, and dimethylimidazoline _ (Ν,Ν'- Dimethyl imidazolidincme ), N-methyl Capr〇lactam , N,N-dimethyl proPi〇namide , Ν,Ν-dimercaptoacetamide, Dimethylsulf〇xide, N,N-dimethyldecylamine, ν,ν^ethylformamide, hydrazine, hydrazine-diethylacetamidine, n, n, n, n,-tetramethylurea, monobutyrolactone, and gamma-valerate. One or more of the aprotic polar organic solvent "di-anthracene-methyl-2-pyrrolidone, anthracene, fluorene--di-decyl imidazolidinone, butyl lactone, and γ-valerolactone. Examples of the improving solvent include ethylene glycol lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and ethylene glycol monobutyl ether. Diethylene glycol monoalkyl ether such as alkyl ether, diethylene glycol monoethyl ether, monoalkyl glycol glycol acetate or monophenyl ester of ethylene glycol acetate, triethylene glycol monoalkyl ether, propylene glycol An alkyl ester such as propylene glycol monoalkyl ether such as butyl ether or malonyl malonate such as diethyl malonate or dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, or an ester compound such as these. The improving solvent is preferably one or more selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. The types and ratios of the aprotic polar solvent and the coating improving solvent, It is possible to consider the printability, coatability, solubility, and storage stability of the liquid crystal alignment agent. The solubility of the aprotic polar solvent and the storage stability of the solvent are improved, and the coating property is improved by the printing of the solvent. The raw material and the coating property are relatively superior to the aprotic polar solvent, and the additive is used to improve the liquid crystal alignment property. However, the above-mentioned added sword may be a molecular compound or a low molecular compound other than polyglycine or a derivative thereof used depending on the purpose.

> From the viewpoint of controlling the liquid crystal to be formed to the electrical property or the alignment property of the agent, the polymer compound is preferably a polymer compound soluble in an organic solvent. Examples of such a polymer compound include polyamine, polyurethane, polypyrene, polyester, polyepoxide, and polyacetate (p〇lyesterp〇ly〇1). , silicone modified polyurethane, polyoxymethylene modified polyester. Examples of the low molecular compound include a surfactant, an antistatic agent, a silane coupling agent, a titanium coupling agent, and a ruthenium amide catalyst. From the viewpoint of improving the coatability of the liquid crystal alignment agent, a surfactant is preferred. From the viewpoint of improving the antistatic property of the liquid crystal alignment agent and the liquid crystal alignment film, an antistatic agent is preferred. From the viewpoint of improving the adhesion between the liquid crystal alignment film and the substrate or the abrasion resistance, a decane coupling agent and a titanium coupling agent are preferable. In the case of forming a liquid crystal alignment film, a ruthenium imidization catalyst is preferred from the viewpoint of performing ruthenium imidization at a low temperature. The decane coupling agent may, for example, be vinyltrimethoxy oxacyclohexane, vinyltriethoxy decane, N-(2-aminoethyl)-3-aminopropyl decyl decyloxydecane, N -(2-aminoethyl)-3-aminopropylmethyltrimethoxy 68 200930760 〇❹ decyl decane, p-aminophenyl trimethoxy decane, p-aminophenyl triethoxy decane, m-aminophenyl trimethoxy Base decane, m-aminophenyl triethoxy decane, 3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxy decane, 3-glycidoxypropyltrimethoxy decane, glycidol Oxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3·chloropropylmethyldimethoxydecane, 3-chloropropyltrimethyl Oxydecane, 3-(methacryloxy)propyltrimethoxydecane, 3-mercaptopropyltrimethoxysulfonium, N-(l,3-dimethylbutylidene)_3_(triethyl) Oxymethoxine)]-propylamine and hydrazine, hydrazine, -bis[3-(trimethoxyindolyl)propyl]ethylenediamine. The ruthenium amide catalyst may, for example, be an aliphatic amine such as tridecylamine, triethylamine, tripropylamine or tributylamine; hydrazine, hydrazine: methylaniline, yebethylene aniline , f-substituted aniline, hydroxy-substituted aniline and other aromatic surface K, methyl silk substitute H substituted (four), 喧 ( (qmn〇 line), methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted disinfectant , admission and storage, material (imida her), Jiamei = Daimi saliva, secret replacement of the rice ring surface. The lysine soil is preferably one or more selected from the group consisting of hydrazine, hydrazine dimethyl phenylamine, o-, m-, p-aniline, o-, m-, p-hydroxypyridine and isoquinoline. ^Coupling_Addition amount (IV) Polyamine or its touch substance Reset G weight ~ 1G wt% 'preferably Q" wt% to 3 wt%. Or its derivative (10) hanging (1) Tian! ~5 when 1, preferably 0.05 equivalents ~ 3 ♦ amount. The amount of other additives added is according to the use; &« or its derivative _ weight ❹ weight% ~ 3 two amount ^ ^ 69 200930760 0.1% by weight ~ 10% by weight.

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 may further contain a gyion-substituted nadiimide compound. The dilute group-substituted nadicki-imine compound may be one compound or two or more compounds. From the viewpoint of the above, the content of the rare-base substituted nadic ylidene compound is 'preferably 〇.〇1 with respect to the weight ratio of the poly-proline or the derivative thereof in the liquid crystal alignment agent. 〜1·〇〇' is more preferably 0.01 to 0.70, still more preferably 〇01 to 0 5〇. 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. Examples of such an alkenyl-substituted nadicylimine compound include compounds represented by the following formula (Ina).

In the formula (Ina), Li and L2 each independently represent hydrogen, an alkyl group of 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a calcined aryl group having a carbon number of 5 to 8 or The base, η represents 1 or 2. When 1 is 1, I represents a carbon group having a carbon number of 1 to 12, an alkenyl group having a carbon number of two, a cycloalkyl group having a number of turns of 5 to 8, and an aryl group having a carbon number of 6 to 12. _(〇ν(Ζ2〇νζ3·Η (Zl, ζ2, and ζ3 independently represent ♦, ～6 alkylene, q represents 0 or 1, and ^表方200930760 1厂30 integer) The group, _(z4)s_b_z5_h a and z5 independently represent an alkylene group having a carbon number of 丨~4 or a cycloalkylene group having a carbon number of 5 to 8, B represents a phenylene group, and s represents hydrazine or 1) The group represented by -BTBH (B represents phenylene group and τ represents -CH2-, -C(CH3)2-, -〇_, _C0_, -s- or s〇2_) a group or a group in which one to three hydrogens of these groups are substituted by a hydroxyl group. At this time, 'preferred W is an alkyl group having a carbon number of 1 to 8, and a carbon number of 3 to 4 Alkenyl, cyclohexyl, phenyl, benzyl, poly(ethyleneoxy)ethyl having a carbon number of 4 to 1 fluorene, phenyloxyphenyl, phenylmethylphenyl, phenylisopropylidenephenyl, and One or two argon groups of these groups are substituted by a hydroxyl group. When the formula (Ina) When n=2, 'W represents an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, an arylene group having a carbon number of 6 to 12, and -Z^O-^OVZ3- (Z1 to Z3 and r have the meanings as described above), a group represented by -Z4-B-Z5- (Z4, Z5, and B, as described above), and -B-(〇 -B) sT-(B-〇)sB- (B represents a phenylene group, T represents an alkylene group having a carbon number of 1 to 3, or _s〇2_, s represents a group represented by hydrazine or 1), Or one to three hydrogens of these groups are substituted with a hydroxy group to form a substituted group. At this time, 'preferred W is an alkylene group having a carbon number of 2 to 12, a cyclohexylene group, a phenylene group, and a benzene group. Methylene, diphenylene phenyl, represented by _C3H6-0-(Z2-0)r-0-C3H6- (Z2 represents an alkylene group having 2 to 6 carbon atoms, and r represents 1 or 2) a group to represent a phenylene group, and T represents a group represented by -CH2-, -〇- or _s〇2_), and -B-〇-B-C3H6-B-0-B- (Table B 71 200930760, a group represented by the 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 described in Japanese Patent No. 2729565, by replacing an alkenyl group with a nadic anhydride derivative and a diamine at a temperature of 80 ° C to 22 (rc). The compound obtained by the synthesis is maintained for 5 hours to 20 hours; or a commercially available compound. Specific examples of the alkenyl-substituted Nadick-based imine compound include the compound shown below: N-methyl-propylpropyl bicyclo [2.2.1]hept-5-ene-2,3-dimethylimine, N-methyl-allylmethyl-cyclo[2.2.1]hept-5-lean·2,3-dimethylhydrazine Amine, methyl-methallyl-cyclo[2.2.1]hept-5-ene-2,3-dimethylimine, n-methyl-methylallylmethylbicyclo-P.2.1] -5-ene-2,3-dimethylimine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-dihydro-2,3-dimethylimine , N-(2-ethylhexyl)-allyl (indenyl)bicyclo[22 1:|gly-5_埽_2,3_diimide, allyl-allyl bicyclo [ 221]hept-5-ene-2,3-dimethylhydrazine quinone imine, allyl-dipylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine , propyl-methylallyl bicyclo [2.2.1] g- 5-ene-2,3-dimethylimine, N-isopropenyl-allyl bicyclo [221]hept-5-ene-2,3-dimethylanimine, N-isopropenyl- Allyl (fluorenyl) bicyclo[2.2.1]g _5_women·2,3_: formamidine, Ν_isopropenyl-methylallyl bicyclo[2·2.1]g-5 - 归 · 2 3_ Diimine, Ν-cyclohexyl allyl bicyclo [221] G _5 _ _2, 3- dimethyl imimine, Ν-cyclohexyl-allyl (A Bi)[2.2.1]hept-5-female-2,3_dimethylimine imine, Ν-cyclohexyl-mercaptopropyl bicycloindole. 2 g·54_23_ 72 200930760 = brewed imine _ propyl propyl υ υ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Second ring [2.21] G.5_women_2,3_dimethylya

^ ^ ψ ^m2.2Am-5^2^ Ψ ' N = propyl propyl ring 〇

Q soil ethyl), propyl bicyclo [2 21] g · 5 _ _2, 3 dimethyl hydrazide = yl ethyl) allyl (methyl) bicyclo [2 2 ^ _ 5_m == = base (10) A scales shout: ring _ (four) N-(2,2_dimethyl_3_ propyl propyl) _ propyl propyl ring [such as] heptylamine H propylene _) keji bicyclo [2.2 .1] Geng_5 marriage, 3-dimethyl ring W-based (methyl) bicyclo-g, transphenyl) dipropyl bicyclo [2.2.1] hept-5-ene_2,3 -Metformin H-phenyl)- propyl (?)-bicyclo[2.2.1]heptane--2,3-discriminate 2, N<4-hydroxyphenyl)-methylallyl Bicyclo[2.2.1]g _5_ ring [2.2. ed. 2,3-dicarboxylic acid imine, post-经:=: 73 200930760 (methyl)bicyclic P.2.1]hept-5-ene- 2,3-dimethylimine, N-(p-branched)-dilylbicyclo[2.2.1]hept-5-lean-2,3-dimethylimine, trans-ethoxy Ethyl}-allyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylanimine, N-{2-(2-hydroxyethoxy)ethyl}-ene Propyl (indenyl)bicyclo[2 2 ^hept-5-ene-2,3-diindoleimine, N-{2-(2-hydroxyethoxy)ethyl hydrazine-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-diindoleimine, n_{2_(2,ylethoxy)ethyl}-methylpropylpropylmethylbicyclic P.2.1 ]Geng-5· Alkene 2,3-dimethyl hydrazine, imine, NPd ethoxylated) ethoxy}ethyl]-dilylbicyclo[2.2.1]hept-5-rare-2,3-dimethyl Imineimine, 1^-[2-{2-(2-carbylethoxy)ethoxy}ethyl]-allyl (indenyl)bicyclo[2.2.1]hept-5-rare- 2,3-dimethylimine imine, N-[2-{2-(2·transethoxyethoxy)ethoxy}ethyl]-mercaptopropyl bicyclic P.2.1]g-5- Rare-2,3-dimethylimine, Ν-{4-(4·p-phenylphenylisopropylidene) benzyl}-dilute-soil [2.2.1]g-5-slung-2 , 3-di-branched imine, Ν-{4-(4._hydroxyphenylisopropylidene) phenyl [dilyl (methyl) bicyclo [2 2 1:) g _5 a woman - 2,3-dimethylimine, Ν-{4-(4-hydroxyphenylisopropylidene)phenylmmethyl 0 propylbicyclo[2.2.1]hept-5-浠-2,3- Dimethylimine, and oligomers (oligomer) of these compounds, N,N'-ethylene-bis(allylbicyclo[221]hept-5-ene-2,3-dimethylhydrazine Amine, N,N'-ethylidene-bis(dilylmethylbicyclo[2 2 ge _5_dil _2,3-dimethylanilide], N,N'-ethylidene- Bis(methylallylbicyclo[2 21]hept-5-ene-2,3-carboximine), N,N'-trimethylene·bis(ene) Bicyclo[2 2"]hept-5-ene-2,3-dimethylimine), N,N'_hexamethylene-bis(allylbicyclo-P.2.1]hept-5- Women-2,3-dimethylimine), N,N,·hexamethylene double (propyl propyl 74 200930760 methyl one ring [2·2.1] hept_5_ene_2,3_dimethyl Imine), _,_dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-oxime-2,3-dimethylenimine), N,N,-dtsubsia Methyl-bis(allylmethylbicyclo[2 2 hept·5_diluted_2,3·diennimine), N,N,_cyclohexylene·bis(dipropylbicyclo[2.2 .1]hept-5-rare-2,3-dimethylenimine), N,N'-cyclohexylene. bis(dilylmethylbicyclo[2 2 dilute-2,3-dimethylhydrazine Imine), _ U-double {3'-(dipropylbicyclo ρ.2.1]hepta-5-ene-2,3 diterpene imine) 〇propoxy}Ethylene, I2-double (3 '_(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)propoxy}ethane, hydrazine, _(methallyl) Bicyclo[2.2.1]hept-5-ene·2,3-dimethylimine imine)propoxy}ethane, double ρ, _{3,_(allylbicyclo[2.2.1]g -5·ene-2,3-dimethylimine imine)propoxy}ethyl] bis, bis[2,-{3,-(allylmethyltricyclo[ 2.2.lm_5ene_2,3-dimethylanilinium)propoxy}ethyl]ether, 1,4-double {3,-(allylbicyclo[2.2 qiao ng ^ ene_2,3 - Diimine imine) propoxy}butane, 1>4_bis(allyl-decylbicyclo[2.2.1]hept-5-ene-2,3-dimethylanilide)propoxy Butane, N, N'_p-phenylene-bis(allylbicyclo-P.2.1]hept-5-ene-2 3-di-W-diamine), n, n,--- Phenyl-bis(allyl-decylbicyclo[221]hept-5-ene-2,3-diimineimine), N,N'-m-phenylene-bis(allylbicyclo[ twenty two. Gh-5-cono-2,3-diimineimine), hydrazine, hydrazine--m-phenylene-bis(allyl-decylbicyclo[2·2·1]hept-5-ene-2 , 3· diimine imine), hydrazine, hydrazine, -{(1-methyl>2, diphenylene bis(dipropylbicyclo[2.2.1]hept-5-ene_2,3 _ dimethyl quinone imine) ', νν, _ p-xylylene-bis (allyl bicyclo [2.2.1] hept-5-diluted _2, 3- dimethylanimine), ν, ν ,-p-p-phenylene-bis(allyl-decylbicyclo[2'21]hept-5-dimethylanilide), N,Nl meta-diphenylene-bis(allyl Base two rings 75 200930760 [2.2.1] hept-5·ene·2,3-dimethylanimine), taken, xylylene-bis(dilylpropyl bicyclo[2.2.1]g Rarely, dimethyl iodide), Λ2·shuangpu (allyl bicyclo [2·2.1] g _5 · dilute · 2,3 · dimethyl quinone imine) this milk base} phenyl] propyl, 2,2_double [Μ4 propyl methyl bicyclo [2.2 qiaoh-5-ene-2,3-dimethyl quinone imine) phenoxy} phenyl] propane 9, 2, 2 bis methyl Dilyl propyl bicyclo [2.21] ng. 5 nucleus 2,3 dimethyl anilide) phenoxy} benzyl] propane, double {4-(dilylbicyclo[2 2 〇Ο 〇Ο 胺 imine) phenyl} methyl, double {4 propyl methyl ring Geng-2,3-dimethylimine imine)phenyl}methane, double {4-(methylallylbicyclo[2.21]g-5 ru 2,3-dimethyl phenylene}methyl 6 , double {4_(methyl-dipylmethylbicyclo[2 21]hepta-5, dilute _2,3-dimethylimine) phenyl}metholone, bis 2,3-dimethylanimine) Phenyl}_, bis... (allylmethylbicyclic-like-5-ene-2,3-dimethylimine) phenyl}, more, double {4_(methyl-propyl bicyclo [2.2 .1]Hept-5-rare-2,3-dimethylanimine)phenyl}ether, bis{4_(allylbicyclo[=1]hept-5-ene-2,3-dimethylhydrazine Imine)phenyl), double {4_(propyl propylmethyl-%[2.2.1]hept-5-ene-2,3-diindoleimine)phenyl)hard, #双{4- (Methylallyl bicyclo [2.2.lm_5-ene-2,3-dimethylimine) phenyl} fluorene, 1,6-bis(allyl bicyclo[2 21]hept-5]-ene _2,3_dimethylimine imine)_3-pyrrolidone, 1,12·bis (methallylbicyclo[2 2 ^hept-5·lean-2,3-dimethylimine] )_3,6-dihydroxydodecane,-bis(allylbicycloP.2.1]hept-5-ene-2,3-dimethylimine imine)_5-hydroxycyclohexane, y-double P ·-(allyl bicyclo ρ·2.1]hept-5-ene-2,3_diimide imine) propoxydihydroxy pentane, ι,4-bis (ene) Base bicyclic p2丨]hept-5_ene_2,3_dimethylhydrazine 76 200930760 Amine)-2-hydroxybenzene, amine) yl J-bicyclo[2.2.1]g-5- 2,3 - dimethyl yam 2 5 ^ ^ tolyl - bis (allyl methine, take, - p-dip) sub-two NN, complete: dimethyl ring [Ζ 2 · 1] hept-5-ene 43- two Mercaptoimine), -Μ 'di-tolyl. bis(dipropylbicyclic)heptyl I 埽=-methylimine), hydrazine, hydrazine, |(10)yl) xylylene bis(methyl)二亚^亚-甲本基-jing propyl 2 ie 2 im_5wu U• skill brew 2,2·double [4_{4_(dipropyl bicyclo [221] g 3 2 ί ί 甲 & & > 2, phenyl-phenyl}methyst, double base ice, brewed imine > 4 marriage _ benzene: ? {3_(methallyl bicyclo [221] g _ 5, 2, 3 _ di -phenyl} stone wind, hydrazine, 1·3 {4_(晞propylmethylbicyclo[2 2 11-glycol-5.2,3-dimethylanimine]}phenoxymethyl, Ν, Ν, , Ν, · allyl-propyl term 2.2., 5-ene, 2,3-dimethylenimine}iso (air urethane & ester, and oligomers of these, and the like. Further, the alkenyl-substituted nadicylimine compound used in the present invention may be a compound which does not have a carbaryl group or a silk group. 77 200930760

Preferred compounds among the alkenyl substituted nadic quinone imine compounds are listed below. Ν,Ν'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3.dimethylhydrazine 0 imine), hydrazine, Ν'-ethylene-bis ( Allyl decylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), hydrazine, Ν'-ethylene-bis(methylallylbicyclo[2.2. 1]hept-5-ene-2,3-diimineimine), hydrazine, Ν'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethyl imine), hydrazine, Ν'·hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3·diimide), hydrazine, Ν' -hexa-indenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), hydrazine, Ν'-docamethylene-double ( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine), hydrazine, Ν'-docamethylene-bis(allylhydrazylbicyclo[2.2. 1]hept-5-ene-2,3-dimethylhydrazide 78 200930760 Amine), ν, ν·-cyclohexylene-bis(allyl bicyclo[2.2 ^heptene], N , N'-cyclohexylene-bis (allyl fluorenyl bicyclic waste: -2,3-dimethylimine), .J ana-ene fluorene, Ν'-p-phenylene-bis(ene) Propylbicyclo[2 21]hept-5-ene_2 3_animine), hydrazine, hydrazine, p-phenylene bis(allylmethyl) Ring [2 2丨]g; ^ · 2,3-dimethylenimine), yttrium, -m-phenylene, (weld propyl bismuth^-5-ene-2,3-dimethylimine) ), ν, Ν, · m-phenylene-bis(allylhydryl hydrazide·2.1]hept-5-ene-2,3_diimine), hydrazine, hydrazine, -{(1_曱基)_2,4_亚笨^基}-bis (propyl propyl bicyclo [2·2.1]heptene 2,3-dimethyl quinone imine) ', _' p-xylylene-bis (10) Propyl work 卯geng-5 sound 2,3•dimethyl imipenem), hydrazine, Ν'-p-xylylene-bis(allyl-decylbicyclo[221]hept-5-ene-2 , 3·dimethylimine imine), hydrazine, hydrazine, _ m-diphenylene bis(allylbicycloindole 2.6]hept-5-ene-2,3·dimethylanimine), hydrazine , Ν, m-xylylene bis(dipylmethylbicyclo ρ.2· ηg _5_ene_2,3_diimide), 2,2_double [4_{4_(lean Propylbicyclo[2.21]hept-5-ene-2,3-dimethylenimine)phenoxy}phenyl]propane, 2,2 bis[4-{4-(allylhydrylbicyclic) [221] Geng _5 〇 〇 _2, 3 _ dimethyl imidate imine) phenoxy} phenyl] propyl, 2, 2- bis [4-{4- (decylallyl bicyclo fluorene. 2.1]hept-5-ene·2,3-dimethylimine imine)phenoxy}phenyl]propane, double {4·(dipropyl bicyclic) [2.2.1] Geng _5_ dilute _2,3_dimethyl quinone imine) phenyl} brothel, double {4-(l-propyl decyl bicyclo [221] g _5 _ _ _ _ Listen to imine) phenyl} decane, double {4-(methylallyl bicyclo[2·2·ηh_5_lean-2,3-di-f-imine) phenyl}-methyl, Double {4·(methyl propyl propyl bicyclo [2 2 qiao GJ 2,3 bis quinone imine) phenyl} methane, double {4_(allyl bicyclo [2 21] g _ 5_ene 79 200930760 _2,3·dimethylimine) stupid, (tetra) _ (dilylmethyl bicyclo [2.2.1] hept 5|2,3-dimethylenimine) phenyl} mystery, Double {4_(decylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylenimine)phenyl}indole, double {4_(allylbicyclo[2.2^] Geng-5-rare-2,3-dimethylanimine)phenyl} stone wind, double {4_(allylmethylbicyclo[2.2.1]heptene_2,3-dimethylimine Phenyl}hard, bis(tetra)methylallylbicyclo[2.2.1]glycol 2,3-dimethylimine)phenyl}hard. More preferred dilute-substituted Nadicki-imine compounds are listed below. Ν'Ν'_Ethylene·bis(allyl bicyclo[2.2.1]g·5^_2,3—dimethylene]imine, anthracene, ethylene-bis(allyl fluorenyl) Bicyclo[2.2.1]g _5_diluted_2,3_dimethylimine imine), hydrazine, hydrazine, - sub-[yl-bis(methylallylbicyclo[2 21]heptene-2 , 3-diimine imine), hydrazine, hydrazine, _trimethylene hydrazine _ bis (allyl bicyclo [2 bis hep-5-ene-2,3-diimine), hydrazine, hydrazine , _ hexa-indenyl-bis(allyldi-cyclo[2.2.1]hept-5-ene-2,3-carboximine), ν,Ν'-hexamethylene] bis(ene Propylmethylbicyclo[2.2.1]hept-5-rare-2,3-dimethylimine), wind]^'-twwthylene-bis(dipropylbicyclo[2.2.1 ]hept-5-ene-2,3-dimethylimine imine), hydrazine, _12-fluorenyl-bis(allylmethylbicycloindole.2.1)g-5-ene-2,3_曱醯^ 0 amine, Ν, Ν '_cyclohexylene-bis (allyl bicyclo [2.2.1] g _5_埽_2, 3 bis diimide imine), Ν, Ν ' - cyclohexylene-bis (l-propyl decylbicyclo[2 gh. 2,3-dimethyl quinone imine), hydrazine, Ν'-p-phenylene-bis(allyldicycloalkenene-2, 3-diimineimine), hydrazine, hydrazine, p-phenylene-bis(allylmethylbicyclo[221] 1-1ene-2,3-diimineimine), hydrazine, hydrazine, _m-phenylene bis(allylbicyclo ρ2ι)hept-5-ene-2,3-dimethylimine), ν,Ν'-m-phenylene_bis(f-propyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), ν,Ν'-{(1_甲甲Base)_2,4_亚笨200930760 基}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylenimine), Ν Ν, _ p-xylylene ·Double (dilute propyl work, Geng 5, ^ ^ amine), hydrazine, hydrazine, - p-xylylene-bis (l-propylmethylbicyclo[2 2..5-female-2,3 - dimethyl quinone imine), hydrazine, hydrazine, m-xylylene _ bis ( allymethylene ring [2.2.1] hept-5-thin-2,3-dimethyl ruthenium), hydrazine, Ν, _ m-xylylene propyl propyl bicyclo [2.2.1] hept·5-ene-2,3-dimethyl carbamide), hydrazine

二义双卜(四)埽propyl bicyclo-like Qiao Gengshi^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Ring [2 2 1]hept-5-ene-2,3-carboximine)phenoxy}phenyl]propyl^, 2,2_bis[4 {4-(methyl晞propyl-cyclo[ 2.2.1] hept-5-rare-2,3-dimethylimine imine) phenyloxy}phenyl]propane, bis{4-(allylbicyclo ρ.2.1]hept-5-ene_2 , 3_dimethylimine imine) phenyl}methane, bis{4_(allylmethylbicyclopj丨)hept-5-ene-2,3-dimethylenimine)phenyl}methane, double (Methylallyl bicyclo[2 21]hept-5-ene-2,3-dimethylimine)phenyl}methane, bis{4·(methylallylmethylbicyclo[2 ·1·1]hept-5-ene-2,3_diimineimine) stupid}}. And a particularly preferred dilute-substituted nadic ylidene compound may be exemplified by the following formula (Ina-Ι): bis{4-(allylbicyclo[2.2.1]hept-5-ene _2,3_diimine)phenyl}methane, n,Ν'-m-xylylene-bis(allylbicycloindole.2.1)g, represented by the formula (Ina-2) 5-sweet-2,3-diimineimine), and N,N,_hexamethylene-bis(allylbicyclo[2·2·1]g, represented by the structural formula (Ina_3) -5-ene-2,3-dimethylimine). 200930760

Further, for example, in terms of electrical characteristics of the liquid crystal display element, the liquid crystal alignment agent of the present invention can also be a compound which further polymerizes the unsaturated double bond. The compound having a ^ free 饱和 saturated double bond may be used as a compound or two or more compounds. In addition, the said has a free-saturated double-combination, and does not include a substitute for a satin compound. In view of the above, the content of the compound having a radical polymerizable unsaturated double bond is preferably 0.01 to 1.00, more preferably 001 to 〇7, based on the weight ratio of the polyglycine or a derivative thereof. Further, it is more preferably 0.01 to 0.50. In addition, from the viewpoint of reducing the ion density of the liquid crystal display element, suppressing the increase of the ion density with time, and suppressing the afterimage, the compound having a radical polymerizable unsaturated double bond is substituted with the alkenyl group to the nadic pyrimine. The ratio of the compound ' is preferably (1) 丨 to (7), more preferably 〇. 5 to the weight ratio, and the compound having a radical polymerizable unsaturated double bond can be exemplified by 82 200930760 (mercapto) acryl vinegar, (meth) propyl (meth)acrylic acid derivatives such as dilute amines, and bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically unsaturated double bonds. Specific examples of the (fluorenyl) acrylate include, for example, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (methyl) Dicyclopentyloxyethyl acrylate, is〇b〇rnyl (meth)acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (methyl) 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate. Specific examples of the difunctional (fluorenyl) acrylate include, for example, ethylene diacrylate, products of East Asian Synthetic Chemical Co., Ltd., ARONIX M-210, ARONIX M-240, and ARONIX M-6200, Nippon Chemical Co., Ltd. Products of the company KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684 'products of Osaka Organic Chemical Industry Co., Ltd. V260, 〇V312 and V335HP, and products of Kyoeisha Oil Chemical Industry Co., Ltd. Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA 〇

Specific examples of the trifunctional or higher polyfunctional (fluorenyl) acrylate include, for example, linalyl bis(N,N-dihydroxy acrylate phenyl aniline), ARONIX M-400, ARONIX M- 405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD 83 200930760 DPCA-30 > KAYARAD DPCA-60 > KAYARAD 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 propyl amide, N-isopropylmethyl propyl amide, n-propyl acrylamide, N-n-propyl Methyl propylene decylamine, N-cyclopropyl acrylamide, N_cyclopropyl decyl acrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl decyl decylamine , N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl propylene phthalamide, N-ethyl acrylamide, N-ethyl propyl amide , n, N-diethyl acrylamide, N-fluorenyl-N-n-propyl acrylamide, N-fluorenyl-N-isopropyl acrylamide, N-propylene nitrite N-acryloyl piperidine), N-acryl〇yl pyrrolidine, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, n ,N,-dihydroxyethylidene bis acrylamide, N-(4-hydroxyphenyl)methacrylamide, N-phenylmercapto amide, N-butyl methacrylamide, (different Butoxymethyl)mercaptopropenylamine, N-[2-(N,N-dimethylamino)ethyl]methyl benzyl amide, N,N- Methylmercapto acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-(methoxymethyl)decyl acrylamide, N-(by fluorenyl) 2-methylpropenylamine, N-benzyl-2-propenyl acrylamide, and N,N'-fluorenylene bis(methacrylamide). Among the (meth)acrylic acid derivatives, 'particular preference is given to N,N,-ylidene bis acrylamide, hydrazine, Ν'-diethyleneethylene propylene amide, ethylene glycol diacetate. And 4,4'-methylenebis(indole, anthracene-di-diethyl acrylate).

Examples of the bismaleimide include: BMI-70 and BMI-80 manufactured by CHEMICAL 84 200930760 INDUSTRY Co., Ltd. and BMI-1000, BMI-3000, BMI-4000, and BMI manufactured by Daiwa Kasei Kogyo Co., Ltd. -5000 and BMI-7000.

Further, for example, the liquid crystal alignment agent of the present invention may further contain 11 a caller compound from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The compound of the ° can be a compound or two or more compounds. In view of the above, the content of the oxazine compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, even more preferably 1%, based on the polyaminic acid or a derivative thereof. Weight%~2〇% by weight. The oxazine compound ' is preferably soluble in a solvent which dissolves poly-proline or a derivative thereof, and has a ring-opening polymerizable oxazine compound. Further, the amount of the oxazine structure in the oxazine compound is not particularly limited. Regarding the structure of the oxazine, various structures are known. In the present invention, the structure of the oxazine is not particularly limited, and the oxoxazine in the chewing compound may include a benzoxazine or a naphthoxazine having a condensed polycyclic aromatic group. The oxazine structure of the group-based group. For each knee, the stimulating compound can be, for example, a compound of the formula (a) to exemplified. Further, in the following formula, a bond toward the center of the ring, Read the knot in the ring and can take the wire -^ 85 200930760

In the above formula (a) to formula (C), R1 and R2 represent an organic group having 1 to 30 carbon atoms. Further, in the above formula (a) to the formula, R3 to R6 represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. Further, in the above formula (c), formula (d) and formula (f), X represents a single bond, -0_, -S_, -SS- ' -S〇2- '-CO- ' -CONH - '-NHCO- ' -C(CH3)2- ' -C(CF3)2-, -(CH2)m-, -0-((:Η2)πΓ〇, -S-(CH2)mS-. Where ο m is an integer from 1 to 6. In addition, in the general formula (e) and the general formula (f), 'Y independently represents a single bond, -0-, -S-, _CO-, _C(CH3) 2_, -C(CF3)2_ or an alkylene group having a carbon number of 1 to 3. The hydrogen bonded to the benzene ring and the naphthalene ring of the Y may be independently -F, -CH3, -OH, -COOH Further, the -S 03Η, -Ρ〇3Η2 is substituted. In addition, the oxazine compound includes an oligomer or polymer having a oxazin structure in a side chain, an oligomer or a polymer having an oxazine structure in the main chain. The chewing compound represented by the formula (a) is exemplified by the following chewing 86 200930760 compound.

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 formula (b) is exemplified by the following oxazine compound.

(b-3> (b-4) (b-5) 87 200930760

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).

In the above formula (I), R1 and R2 represent an organic group having a carbon number of 1 to 30, R3 to R6 represent hydrogen 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) may, for example, be the following acetonide compound. 88 200930760

(c-11) (〇-12) · 89 200930760

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 formula (d) may, for example, be the following acetonide compound.

90 200930760

The oxazine compound represented by the formula (f) is exemplified by the following oxime compounds. 91 200930760

(M1) 92 200930760 Among these oxazine compounds, a more preferable oxazine compound may be exemplified by the formula (bl), the formula (〇1), the formula 〇3), the formula (c-5), the formula (c-7), and the formula (c-9). And a pyridazine compound represented by the formula (d-Ι)~formula (d-6), the formula (e_3), the formula (e_4), and the formula (f-2) to the formula (f-4). The oxazine compound can be produced by the same method as the method described in the International Publication No. 4〇〇4/〇〇97〇8, the Japanese Patent Laid-Open No. Hei No. 12-258, and the Japanese Patent Publication No. 2004-352670. . For example, the oxazine compound represented by the formula (a) can be obtained by reacting a phenol compound, a primary amine, and an aldehyde (refer to International Publication No. 2004/009708). Further, the oxazine compound represented by the formula (b) can be obtained by reacting a primary amine into a formaldehyde slowly, and then adding a compound having a naphthol (naphth〇1)-based hydroxyl group. The reaction was carried out (refer to the International Publication No. 2004/009708 manual). Further, the oxime compound represented by the formula (c) can be obtained by the following formula: in the presence of an organic solvent towel in the presence of a secondary secondary amine, an aliphatic tertiary amine or a surface nitrogen-containing heterocyclic compound. The oxime benzoin compound is reacted with respect to an acid having at least 2 moles or more, and i-moleamide (refer to International Publication No. 2004/009708 and Japanese Patent Laid-Open No. 11-12258 Bulletin). Further, the compound of the formula (d) to the formula (f) can be obtained by the following formula: in the n-T-alcohol, at 4 (Tt above the temperature I i to make 4,4 L of diaminodiphenyl) A diamine having a plurality of benzene rings and an organic group bonded to these benzene rings, a vine such as formicin, and benzene are subjected to a dehydration condensation reaction of 93 200930760 (refer to Japanese Patent Laid-Open No. Hei 2 _35267 No. 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 a sedative compound. The chewing compound is a compound having a sputum structure. The cylindrical compound may be one compound or two or more compounds. From the above viewpoint, the content of the chewing compound is preferably relative to the polyamic acid or a derivative thereof. 〇1 ^ %% to 50% by weight, more preferably 1% by weight to 4% by weight, more preferably 1% by weight to 20% by weight. Alternatively, from the above viewpoint, the content of the oxazoline compound is preferably Oxazoline When the oxazoline structure in the compound is converted to oxazoline, it is 0.1% by weight to 4% by weight based on the polyamic acid or a derivative thereof. A compound has only one oxazoline structure, and may have two or more kinds of oxalate structures in one compound. In addition, the 嗤 嗤 嗤 compound has only one sin in one compound. The oxazoline structure may be preferably two or more oxazoline structures. Further, the oxazole oxime compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. The polymer of the spurt structure may be a homopolymer of a monomer having an oxazoline structure in a side chain, or may be a copolymer of a monomer having an oxazoline structure in a side chain and a monomer having no oxime structure. The copolymer having an oxazoline structure on the side chain may be a copolymer of two or more kinds of monomers having a ruthenium structure on the side chain, or may be two having an oxazoline structure on the side chain. Kind or more Copolymerization of a monomer with a monomer having no oxazoline structure 94 200930760 : The reaction of the oxygen in the oxoporphyrin structure and the carbonyl group of the nitrogen acid is carried out in such a manner that the oxazoline structure is preferably one or two The structure may be related to the oxazoline compound in which the polyamine is contained. 〇Ο The above-mentioned radiant compound may, for example, be: 2, 2, _ bis (tetra) salicin), tris-(2·β oxa salinyl _2 -) stupid, 4 · pyran-2-ylmethylene 2 -phenyl-4H-t-pro-5-one, anthracene-bis (4,5-dihydro-2_ 〇 〇) benzene, u bis(4,5-dihydro-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4 -m oxa salin, 2,6 bis(isopropyl-2·nosin-2-enyl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2,-isopropylidene bis(4-styl-2+), 2,2,_indenyl bis(tert-butyl·2_βoxazoline) and 2,2'-arylene Bis(4-phenyl_2-oxazoline). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group such as EP〇CR〇s (trade name, manufactured by Nippon Shokubai Co., Ltd.) may be mentioned. More preferably, the U sputum compound is exemplified by 2, bis (2 oxazoline) and 1,3-bis (4,5-dihydro 2 -oxazolyl) benzene. The content of polyphthalic acid or a derivative thereof in the liquid crystal alignment agent of the present invention can be selected according to a coating method in which a liquid crystal alignment agent is applied onto a substrate. For example, if it is a printing machine used for a manufacturing step of a general liquid crystal display element (including an offset printer or an inkjet printer), the liquid crystal alignment which is sometimes simply referred to as "printer". The content of polyamic acid or a derivative thereof is preferably 0.5% by weight to 30% by weight, more preferably 1% by weight to 15% by weight, and the content of the polyglycine 95 200930760 or a derivative thereof may be The relationship between the viscosity of the liquid crystal alignment agent (described below) is appropriately adjusted. The viscosity of the liquid crystal alignment agent of the present invention varies depending on the coating method, the concentration of polyglycolic acid or a derivative thereof, the kind of polyglycine or a derivative thereof used, and the kind and ratio of the solvent. For example, when coating is carried out using a printing machine, the viscosity of the liquid crystal alignment agent is preferably 5 mPa·s to 100 mPa's, more preferably 1 〇 mPa.s to 80 mPa.s. If the viscosity of the liquid crystal alignment agent 0 is less than 5 mPa.s, it is difficult to obtain a sufficient film thickness for the liquid crystal alignment film; if the viscosity of the liquid crystal alignment agent is more than 1 μmPa.s, the unevenness of printing increases. When the liquid crystal alignment agent is applied by a spin coating method, the viscosity of the liquid crystal alignment agent is preferably 5 mPa·s to 200 mPa·s, more preferably 1 μmpa.s to 1 μmPa-s. The viscosity of the liquid crystal alignment agent can be rotated. For measurement, for example, a rotational viscometer (TVE-20L plastic manufactured by Toki Sangyo Co., Ltd.) can be used for measurement (measurement temperature: 25. (3). The liquid crystal alignment film of the present invention is the liquid crystal of the present invention. The ruthenium film of the alignment agent is formed by calcination. The formation of the film of the liquid crystal alignment agent and the calcination can be carried out by a usual method of photoresist. The liquid crystal alignment film can be, for example, by the present invention. The liquid crystal alignment agent is applied onto a substrate for a liquid crystal display element or a measurement substrate such as calcium fluoride or ruthenium, and the film of the liquid crystal alignment agent is heated to, for example, 15 Å. 〇~WC, preferably 18 (TC~) The film thickness of the liquid crystal alignment agent is preferably 10 nm to 300 nm, more preferably 3 〇 nm to 1 〇〇 nm. Further, when the liquid crystal alignment film is used, it is used in a liquid crystal display device such as an IPS type liquid crystal display device. display In the case of a member, it is preferable to subject the liquid crystal alignment film to a rubbing treatment. The film thickness of the liquid crystal alignment film can be adjusted according to the viscosity of the liquid crystal alignment agent or the method of applying the liquid crystal alignment agent. It is measured by a well-known film thickness measuring device such as a differential meter or an index meter. The liquid crystal alignment film may be subjected to hydrolysis or the like as needed, and may be subjected to IR or mass spectrometry (MS). A commonly used analytical method for analyzing components in a liquid crystal alignment film, for example, 'Performance improvement of polybenzoxazine by alloying with polyamide: effect of preparation method on the properties" (Tsutomu Takeichi et. al., polymer, 2005, 46, ρ. 4909· In 4916), a method of analyzing a oxazine compound in a film obtained by imidating polyphosphonium hydrazide by hydrazine is described. The liquid crystal display device of the present invention has a pair of substrates arranged in opposite directions and is formed in A tantalum electrode on one or both of the opposing faces of the pair of substrates is formed on the pair of bases a liquid crystal alignment film on a surface facing each of the plates, and a liquid crystal layer formed between the pair of substrates. The pair of substrates with electrodes disposed opposite to each other is preferably a transparent substrate (for example, a glass substrate). At least one or both of the pair of substrates are provided with electrodes in accordance with the form of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Such an electrode may, for example, be an indium tin oxide (ITO) or a metal 97 200930760 vapor film. The electrode may be formed on the entire surface of the substrate, or the electrode may be formed into a patterned predetermined shape. Further, an electrode may be provided only on one of a pair of substrates, or an electrode may be provided on both of the substrates. For example, for a substrate on which no electrode is provided, the liquid crystal alignment film of the invention can be formed on the surface of the substrate, and the liquid crystal alignment film of the present invention can be formed on the electrode on the substrate on which the electrode is provided. The formation of the liquid crystal alignment film of the present invention is as described above.

The liquid crystal layer sandwiched between the pair of substrates contains a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and any one of the liquid crystal composition X having a positive dielectric anisotropy (dieleetrie anisGtropy) and a negative liquid crystal composition can be used depending on the driving mode. . Preferred examples of the liquid crystal composition having positive electrical anisotropy are disclosed in the following publications: Japanese Patent Laid-Open No. 3, 862, 862, Japanese Patent Application No. 263, Japanese Patent Publication No. 5 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 8-199168 (ΕΡ722998Α1), Japanese Patent Special Kaiping (four) Plus Bulletin, Japanese Patent No. 9·255956, Japanese Special Material Μ4 Purchase Bulletin (Li 527, Japanese Patent Special Kaiping) 1〇•纲〇1 Newspaper (10) Yuanli), Japanese Patent Special Kaiping ο44% Bulletin, 曰本专利专开平职1482号, 曰本专利公开98 200930760 2_·〇87_号, Japanese Patent The liquid crystal composition of the open type liquid crystal display element may be various liquid crystal compositions of dielectric constant + negative. A preferred example of the liquid crystal composition: "Under the following publication: Japanese Laid-Open Patent Publication No. SHO 57-U4532, No. 4, No. 4-4725, Japanese Patent Laid-Open No. A-A, Japanese Patent Laid-Open No. Hei 8-40953,曰太〇❹ 2ΠίΓ 869, Japanese Patent Special Opened Coffee 6 曰 曰 = No. Bulletin '曰 专利 Patent Special Phase α 4 * Japanese Patent Special Open No. 10-236990 No = 9t3 Lit ^ Ping 1 〇 % % No. Gazette, 曰本专利专开平本 ^ t本料咖平 (4) No. 6994 Bulletin, Japanese 57=yGGG Bulletin, Japan __+ This special Japanese Patent Unexamined Patent No. 10-237024, Japanese 237〇75 ma Japanese Patent Unexamined Japanese Unexamined Ships Japanese Patent Laid-Open No. 1 & 237G76, Japanese Patent Laid-Open Patent Publication No. 1G_237448 (10) = Gazette No. 1,74, and Sakamoto Patent Special Kaiping = = two = flat; The liquid crystal display element of the present invention may of course have other members. For example, in a color display TFT type liquid crystal element using a thin film transistor, in the case of the patent publication No. 1__, Japanese Patent Laid-Open Publication No. 99 200930760 Opening on the first substrate; forming a thin film crystal The insulating film, the protective film, the signal electrode, and the pixel are electrically rotated, and the second flip substrate may have a black matrix (blaek gift &), a color filter, a planarization film, and a pixel that shields light outside the pixel region. Electrodes, etc. ' ❹

Further, in the VA type liquid crystal display element, particularly the MVA type liquid crystal display element, a micro protrusion called a region (d_in) is formed on the first transparent substrate. Further, in order to adjust the cell gap Udi gap between the substrates, a spacer may be formed on the first transparent substrate. The liquid crystal display device of the present invention may be fabricated by any method, for example, by including the following steps. Production: 1) a step of applying a liquid crystal alignment agent on the two transparent substrates; 2) a step of drying the applied liquid crystal alignment agent; 3) performing the dehydration and ring closure reaction for drying the liquid crystal alignment agent a step of heat treatment; 4) a step of performing an alignment treatment on the obtained liquid crystal alignment film; 5) after laminating the two substrates, sealing the liquid helium a composition between the substrates, or dropping the liquid crystal composition dropwise The step of bonding the substrate to another substrate after the block substrate. The coating method used in the step of applying the liquid crystal alignment agent is generally known by a spin coating method, a printing method, a dipping method, a dropping method, a spray method, or the like. These methods can also be applied to the present invention. Further, a method of performing the drying step and the step of heat treatment necessary for the dehydration reaction is generally known as a method of performing heat treatment in an oven or an infrared furnace, and feeding on a hot plate. 200930760 The method of heat treatment, etc. These methods can also be made in the present invention. The drying step is preferably carried out at a lower temperature (5. 0 (: ~ 140 C) of the solvent which can be evaporated. The heat treatment step is usually preferably carried out at a temperature of from about 150 ° C to about 300 ° C. Ο About IPS Weijing display element, 0CB type liquid crystal display element, ΤΝ type liquid crystal display element, STN Weijing display element, the alignment treatment of the liquid crystal alignment film is usually performed by rubbing treatment. Most of the VA Weijing display elements are not subjected to rubbing treatment. However, it is also possible to carry out the rubbing treatment. Then, after applying the adhesive on one of the substrates, the substrate is bonded to the other substrate', and the liquid crystal is injected in a vacuum. When using the drop-injection method, before the bonding, The liquid crystal composition is dropped onto one of the substrates, and then the substrate is bonded to the other substrate. The bonding agent is cured by heat or ultraviolet rays, thereby producing the liquid crystal display element of the present invention. In the liquid crystal display element of the invention, a polarizing plate (polarizing film), a wave plate, a light-scattering film, a driving circuit, etc. may be attached. [Embodiment] Hereinafter, by way of example The present invention, but the present invention is not limited to these examples given compounds used in the examples are as follows embodiment < tetracarboxylic dianhydride > compound: Yue pyromellitic dianhydride (Pyromellitic Dianhydride): pmda

Compound: 1,2,3,4-cyclobutane tetracarboxylic dianhydride: CBDA 101 200930760 <Diamine>

Compound: 4,4'-diaminodiphenylpyrene: ddM

Compound. 4,4-A-methoxy-phenylethene: DDET Compound: U-bis[4-(4-aminophenoxy)phenyl]_4·(anti-4·n-pentylcyclohexyl)cyclohexane :5HHBA ^ Compound: U-bis[4-(4-aminophenoxy)phenyl]_4_[(4-n-heptylcyclohexyl)ethyl]cyclohexane: 7H2HBA^^ Compound.1,1-Doub [4-(4-Aminophenylfluorenyl)phenyl]_4_n-heptylcyclohexane: 7HBZ ^ Compound: I,3-bis[4-(4-aminophenylmethyl)phenyl]propane: BABZP3 Compound: 2,2_bis[4-(4-Aminophenoxy)phenyl]propane: BApp

Compound: 1-phenylmercapto-2,5-diaminobenzene: 2,5-PlPDA

Compound: 1-phenylmethyl-3,5-diaminobenzene: 3,5-PlPDA

Compound: 5-[4-(4-N-pentylcyclohexyl)cyclohexyl]phenylmethyl]}diaminobenzene: 5HHP1PDA

Compound: 5_{[4_(4-n-heptylcyclohexyl)ethyl]cyclohexylhydrazine phenylmethyl-1,3-diaminobenzene: 7H2HP1PDA

Compound: 5_[4_(n-hexadecyl)phenylmethyl-diaminobenzene: 16P1PDA

Compound: 3,3'-diaminodiphenyl ether: 3,3,-DDE Compound: 3,4,-diaminodiphenyl ether: 3,4,_dde Compound: 4,4,-diaminodiphenyl Ether ether: 4, 4, _dde <epoxy compound> 102 200930760 ,

Compound.N,N,N,N'-tetraglycidyl_4,4,-diaminodiphenylmethane: TGDDM Compound: bisphenol A phenolic epoxy compound M57S7〇 (trade name, 曰本epoxide) Co., Ltd.) Compound: 3,4-epoxycyclohexenemethyl_3,, 4'-epoxycyclohexenylcarboxylic acid vinegar. Celloxide 2021 (trade name, manufactured by Daicel Chemical Industry Co., Ltd.) Compound: 曱Phenolic novolac type epoxy compound: EOCN-104S (commercially known as 'Nippon Chemical Co., Ltd.), and an epoxy group-containing compound having an average functional group number of 2 or more) <Solvent> NMP. N-fluorenyl- 2_〇比嘻炫嗣GBL : Butyrolactone BC : Butyl cellosolve (ethylene glycol monobutyl ether) <1·Polymeric acid synthesis > [Synthesis Example 1] 0 With thermometer, mixer, raw material Into a 100 mL four-necked flask with a gas inlet and a nitrogen inlet, 2.426 g of DDM and 54.0 g of dehydrated NMP were added, and the mixture was stirred and dissolved under a dry nitrogen stream. Then, 1.735 g of PMDA, 0.840 g of CBDA, and 15.0 g of dehydrated GBL were added and reacted at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 7 (TC or less), and 25.0 g of BC is added to the obtained solution to obtain a polyglycine solution having a concentration of 6% by weight. The proline solution was set to PA1 ^ 103 200930760 [Synthesis Examples 2 to 19] In addition to the modification of the tetracarboxylic dianhydride and the diamine according to Table 1, the polyaminic acid solutions PA2 to PA19 were prepared according to Synthesis Example 1. The results in Example 1 are summarized in Table 1. Table 1

Synthesis Example No. Tetracarboxylate acid dianhydride Molar fraction II compound ► Molar fraction 1. PA1 PMDA CBDA 0.33 0.17 DDM 0.50 2. PA2 PMDA CBDA 0.40 0.10 DDET 5HHBA 7H2HBA 0.40 0.05 0.05 3. PA3 PMDA CBDA 0.40 0.10 DDET 7HBZ 0.35 0.15 4. PA4 PMDA CBDA 0.24 0.24 DDET 5HHBA 0.47 0.05 5. PA5 PMDA CBDA 0.24 0.24 DDET 7HBZ 0.47 0.05 6. PA6 PMDA CBDA 0.10 0.40 BABZP3 0.50 7. PA7 PMDA CBDA 0.25 0.25 3,4'-DDE 0.50 8. PA8 PMDA CBDA 0.25 0.25 3,3'-DDE 0.50 9. PA9 PMDA CBDA 0.25 0.25 4,4'-DDE 0.50 10. ΡΑΙΟ PMDA CBDA 0.25 0.25 BAPP 0.50 11. ΡΑ11 PMDA CBDA 0.10 0.40 BAPP 0.50 12. PA 12 CBDA 0.50 2,5-PlPDA 5HHP1PDA 0.25 0.25 13. PA13 PMDA CBDA 0.10 0.40 2,5-PlPDA 16P1PDA 0.15 0.35 14. PA14 PMDA CBDA 0.10 0.40 2,5-PlPDA 5HHBA 0.25 0.25 15. PA15 PMDA 0.25 DDM 0.50 104 200930760 CBDA 0.25 16. PA16 CBDA 0.50 3,5-PlPDA 0.25 5HHP1PDA 0.25 17. PA17 2,5-PlPDA 0.11 CBDA 0.49 5HHP1PDA 0.20 7H2HP1PDA 0.20 18. PA18 PMDA 0.10 DDM 0.45 CBDA 0.40 5HHP1PDA 0.05 19. PA19 PMDA 0.5 0 16P1PDA 0.50 <2. Production of liquid crystal display element> [Comparative Example 1] PA1 and pa2 were 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 of the solution was diluted in such a manner that the concentration of the polyamic acid was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. <Production Method of Liquid Crystal Display Element> (Example 丨 to Example 12, Comparative Example 1 to Comparative Example 13) A liquid crystal alignment agent was applied onto two glass substrates with IT 〇 electrodes using a spin coater to form A film with a film thickness of 70 nm. After coating to form a film, it was dried by heating at 80 ° C for about 5 minutes, at 210. (: A liquid crystal alignment film was formed by performing heat treatment for 20 minutes. Then, the surface of the substrate on which the liquid crystal alignment film was formed was subjected to a rubbing treatment using a rubbing device, and the film was subjected to a treatment. Then, the liquid crystal was treated in ultrapure water. The alignment film was ultrasonically cleaned for 5 minutes, and then dried in an oven at 3 ° C for 3 minutes. A 7 μm gap material was spread on one of the glass substrates to form a surface on which the liquid crystal alignment film was formed. Inside, and rubbing 105 200930760 The direction of the two glass substrates is opposite to each other, and then sealed with an epoxy hardener to make an antiparallel cell with a gap of 7 μm. The liquid crystal composition shown below was injected, and the injection port was sealed with a light hardener, and then heat-treated at ll ° C for 30 minutes to prepare a liquid crystal display element.

17wt. %

I8wt.%

Butt%

1〇wt %

6wt% 106 200930760 C3H7

Ewt.%

[Example 1] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 1, 20 parts by weight of TGDDM was dissolved with respect to 10 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 2] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 1, 20 parts by weight of 157S70 was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above.比较 [Comparative Example 2] PA1 and PA3 were mixed at a weight ratio of 8/2. To the obtained mixture, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the whole of the solution was diluted to a concentration of 4% by weight of polyglycine to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 3] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 2, a liquid crystal alignment agent was obtained by dissolving 2 parts by weight of TGDDM' with respect to 1 part by weight of polyglycolic acid. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 4] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 2, 20 parts by weight of Celloxide 2021P was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 3] A mixed solvent of nmp/BC = 1/1 (weight ratio) was added to PA4, and the entire solution was diluted with a concentration of t-bramic acid of 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 5] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 3, TGDDM dissolved in 2 parts by weight with respect to 100 parts by weight of polylysine was dissolved to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 6] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 3, e〇cn_104S was dissolved in an amount of 2 parts by weight based on 1 part by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 4] A mixed solvent of NMP/BC = 1 A (weight ratio) was added to PA5, and 108 200930760 was diluted with the entire solution so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 7] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 4, dissolved = 2 parts by weight of TGDDM per 1 part by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 8] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 4, E〇CN_1〇4S was dissolved in an amount of 2 parts by weight based on 1 part by weight of polyacrylic acid to obtain a liquid crystal alignment agent. . Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 5] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA6, and Q was diluted with the concentration of polyacrylic acid to 4% by weight to obtain a liquid crystal alignment agent. . Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 9] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 5, a liquid crystal alignment agent was obtained by dissolving 20 parts by weight of TGDDM per 100 parts by weight of polyglycolic acid. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 10] 109 200930760 〆 In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 5, E〇CN_1〇4S was dissolved in 2 parts by weight relative to 1 part by weight of polyglycine. Liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 6] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA7, and the entire solution was subjected to release by a concentration of poly-aracine to 4% by weight to obtain a liquid crystal alignment agent. . Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Example 11] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 6, it was dissolved, and 20 parts by weight of TGDDM was obtained for 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 7] A liquid crystal alignment agent was obtained by adding a mixed solvent of NMP/BC = 1/1 (weight ratio) to PA8 and dilute the entire solution so that the concentration of polyamine was 4% by weight. Using the obtained liquid crystal alignment agent, Red Heco was produced as described above. [Example 12] In 4% by weight of the liquid crystal alignment agent obtained in h» compared with Example 7, 20 g parts of TGDDM was dissolved for 100 parts by weight of polyglycolic acid to obtain a crystal alignment agent. The liquid crystal display element was produced by using the obtained liquid crystal in the manner as described above. 110 200930760 [Comparative Example 8] A mixed solvent of NMP/BC = 1 A (weight ratio) was added to PA9, and the entire solution was diluted so that the concentration of polyproline was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 9] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 8, 20 parts by weight of TGDDM with respect to 100 parts by weight of polyglycolic acid was dissolved to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 10] A mixed solvent of nmp/bc = "i (weight ratio) was added to PA10, and the entire solution was diluted with a concentration of polyglycolic acid of 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described above. [Comparative Example 11] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 10, 20 parts by weight of TGDDM for 1 part by weight of polyglycolic acid was dissolved to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. [Comparative Example 12] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA11. The whole of the solution was subjected to release by a concentration of polyglycolic acid of 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the manner as described in 111 200930760. [Comparative Example 13] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 12, TGDDM was dissolved in an amount of 2 parts by weight based on 1 part by weight of the polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. [Comparative Example 14] PA PA6 and PA12 were mixed at a weight ratio of 9/1. To the obtained mixture, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to give a weight of 4 parts by weight of polyglycine. /. The solution is diluted as a whole to obtain a liquid aa aligning agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. <Production Method of Liquid Crystal Display Element> (Example 13 to Example 20, Comparative Example 14 to Comparative Example 21) A liquid crystal alignment agent was applied onto two glass substrates with IT 〇Q electrodes using a spin coater. A film having a film thickness of 70 nm was formed. After coating to form a film, it was dried by heating at 80 ° C for about 5 minutes, at 210. (: The heat treatment was performed for 20 minutes to form a liquid crystal alignment film. Thereafter, the liquid crystal alignment film was ultrasonically washed in ultrapure water for 5 minutes, and then dried in an oven at 12 Torr for 30 minutes. 4 μm of the gap material was spread on the inside so that the surface on which the liquid crystal alignment film was formed was placed inside, and then sealed with an epoxy curing agent to prepare a liquid crystal cell having a gap of 4 μm. The liquid crystal composition shown below was injected with a light hardener to seal the inlet of 112 200930760. Then, heat treatment was performed for 30 minutes at ll ° C to prepare a liquid crystal display element.

C3H7 〇

CgHn

5wt. % 7wt. % Swt % 8wt % 14wt%

14wt % 10wt% 10wt%

12wt.%

12 wt% [Example 13] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 14, a liquid crystal alignment agent was obtained by dissolving 113 200930760 with 2 parts by weight of TGDDM per 100 parts by weight of polyacrylic acid. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Comparative Example 1. [Comparative Example 15] pA6 and pA13 were mixed at a weight ratio of 9/1. To the obtained mixture, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the whole of the solution was diluted in such a manner that the mobility of the polyamic acid reached 4% by weight to obtain a ruthenium liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Example 14] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 15, dissolution = 2 g parts by weight of tgddm for 1 part by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Comparative Example 16] Q PA6 and PA14 were mixed at a weight ratio of 9/1. Adding a mixed solvent of NMP/BC=l/l (weight ratio) to the obtained mixture, and diluting the whole solution in a manner that the degree of polyglycine is 4% by weight, thereby obtaining a hydrating agent . A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Example 15] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 16, 20 parts by weight of 157S70 was dissolved for 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Comparative Example 114 200930760 14. [Comparative Example 17] pA15 and pA16 were mixed at a weight ratio of 9/1. To the obtained mixture, a mixed solvent of NMP/BC = 1 / 1 (weight ratio) was added, and the whole of the solution was diluted with a mass ratio of polyamine to 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Example 16] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 17, 20 parts by weight of TGDDM was dissolved with respect to 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Example 17] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 17, Cen〇xide 2〇21P was dissolved in an amount of 2 parts by weight based on 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, 液晶 a liquid crystal display element was produced in the same manner as in Comparative Example 14. [Comparative Example 18] pAl5 and ρΑ17 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole of the solution was diluted so that the concentration of polyglycolic acid reached 4% by weight to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Example 18] 115 200930760 In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 18, E〇CN_1〇4S was dissolved in an amount of 2 parts by weight based on 1 part by weight of polyglycolic acid to obtain a liquid crystal. An aligning agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Comparative Example 14. [Comparative Example 19] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to PA18, and the whole solution was subjected to a dilute zero release so that the concentration of polyglycine reached 4% by weight to obtain a liquid crystal alignment. Agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Example 19] In 4% by weight of the liquid crystal alignment agent obtained in Comparative Example 19, dissolved = 2 parts by weight of TGDDM per 100 parts by weight of polyglycolic acid to obtain a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Example 20] Q 4 weight ❶/ obtained in Comparative Example 19. In the liquid crystal alignment agent, a liquid crystal alignment agent was obtained by dissolving 100% by weight of E〇CN_1〇4S in an amount of 100 parts by weight of polyamic acid. A liquid crystal display element was produced in the same manner as in Comparative Example 14 using the obtained liquid crystal alignment agent. [Comparative Example 20] pA15 and pA19 were mixed at a weight ratio of 9/1. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixing =, and the entire solution was diluted in such a manner that the concentration of the polyamidamine was 4% by weight to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a light crystal display element was produced in the same manner as in Comparative Example 14 116 200930760. [Comparative Example 21] In 4% by weight of the liquid crystal alignment agent obtained by the phase deviation 20, 20 parts by weight of TGDDM was dissolved in the amount of poly-proline, and the evaluation of < 3. Electrical characteristics was obtained. In the example, the first embodiment to the second embodiment are compared with the comparative example 1 to the ratio. The ion density and long-term reliability of the components are shown. Device 6254 type 〇.01 Hz; under electric condition J: the waveform is a triangular wave; the smaller the value of the frequency is, the electrical characteristic is the thief. The measured ion density is better. The results are shown in Table 2 and Table 3. Measurement of retention characteristics of the density The liquid crystal display element of the density was evaluated for the ionicity test over time. The temperature is maintained as follows: τ method: The liquid crystal display element is placed on the display element and the liquid crystal display value is taken out midway through the removal time. The smaller the value [pc]. The period reliability of the ion density after 200 hours is better. The better, and the long electrical characteristics are shown in Table 2, Table 3, and after 200 hours, as shown in 117 200930760.

Table 2 Test-off-f density (p(:) Polydecylamine epoxy compound Example No. The amount of acid solution compound added after 200 hours after the initial value of 100 hours (% by weight) 1. Comparative Example 1 67 68 77 PA1/PA2 - 0 2. Example 1 24 23 25 PA1/PA2 TGDDM 20 3. Example 2 42 27 30 PA1/PA2 157S70 20 4. Comparative Example 2 50 54 57 PA1/PA3 - 0 5. Example 3 36 41 37 PA1/ PA3 TGDDM 20 6. Example 4 32 35 38 PA1/PA3 Celloxide 2021P 20 7. Comparative Example 3 82 84 98 PA4 - 0 8. Example 5 7 14 15 PA4 TGDDM 20 9. Example 6 43 54 65 PA4 EOCN- 104S 20 10. Comparative Example 4 101 105 113 PA5 - 0 11. Example 7 16 27 31 PA5 TGDDM 20 12. Example 8 59 69 80 PA5 EOCN-104S 20 13. Comparative Example 5 63 83 77 PA6 - 0 14. Example 9 19 38 44 PA6 TGDDM 20 15. Example 10 43 55 65 PA6 EOCN-104S 20 16. Comparative Example 6 473 617 644 PA7 0 17. Example 11 17 25 31 PA7 TGDDM 20 18. Comparative Example 7 502 608 601 PA8 - 0 19. Example 12 20 23 27 PA8 TGDDM 20 20. Comparative Example 8 501 828 853 PA9 - 0 21. Comparative Example 9 70 109 137 PA9 TGDDM 20 22. Comparative Example 10 170 191 211 PA10 - 0 23. Comparative Example 11 24 30 32 ΡΑΙΟ TGDDM 20 24. Comparative Example 12 108 153 232 ΡΑ11 - 0 25. Comparative Example 13 17 35 81 PA11 TGDDM 20 118 200930760 Table 3

ο ο 〜 As shown in Table 2 and Table 3, the liquid crystal display element using the liquid crystal alignment agents of Examples i to 20 in which the epoxy compound was added can suppress the increase in the ion density with the passage of time. <4. Evaluation of alignment characteristics> For the liquid crystal display elements produced in Examples 3, 5, 7, 9, 11, 12 and Comparative Examples to Comparative Example 13, after the liquid crystal composition was injected, 119 was added. 200930760 This component before heat treatment is sandwiched between two deflections _), observe the alignment of the liquid crystal _ ^, and mount the backlight (back table 4 ❹

::Γ二价:向特:二===: The condition can be considered to be good in orientation. The results are shown in Table 4. Test Example No. Liquid crystal alignment agent flow alignment 42. Comparative Example 1 43. Example 1 44. Comparative Example 2 No. 45. Example 3 46. __ " _ Comparative Example 3 47. Example 5 48. Comparative Example 4 49. Example 7 50. '5 51. Example 9 52. —---- Comparative Example 6 53. Example u 54. Comparative Example 7 None 55. Example 12 No 56. - —-- Comparison Example 8 57. Comparative Example 9 58. Comparative Example 1〇59. Comparative Example 11 60. Comparative Example 61. ' 1--------- Than the drum example 13 '·' ^^^1 12〇200930760 As shown in Table 4, the liquid crystal alignment agent to which the epoxy compound was added, which was developed this time, did not confirm the flow alignment even when an epoxy compound was added, and the high alignment property was maintained. Although the present invention has been disclosed in the above embodiments, the present invention is not intended to be used in the scope of the present invention. When the patent application and the retouching are attached, the [simplified description of the schema] is defined as the quasi-definite reason. [Main component symbol description] None 0 0 121

Claims (1)

200930760 VII. Patent application scope: 1. A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a diamine and a tetracarboxylic dianhydride, and an epoxy group having a hydrazine functional group of more than 1. The epoxy compound, the liquid crystal alignment agent is characterized in that the diamine is a diamine represented by the following formula (I): (In the general formula (I), X1 and X2 each represent -0 or _CH2_', and γ1 represents -Η, the following structural formula (11-1), general formula (ΙΙ-2) or general formula (Η-3) Ζ1 represents an alkylene group having 1 to 12 carbon atoms which may have a mercapto group, a 1-substituted-1,1·cyclohexylene group represented by the following formula (ΙΙΙ-1) or the formula (ΙΙΙ-2) m, η, and ρ respectively represent 〇 or 1; where 'm+n + p is 〇, 1 or 3 ' When m + n + p is 〇, γ1 represents the general formula (11_1), general formula (11-2) Or formula (II-3), when m + ii+p is 1, the melon and !1 are 〇 2' and $ represents the amino group of the aminophenyl group to which X2 is bonded, which is bonded to the meta position of χ2 When m + n + p is 3, X1 and X2 represent -0ΚΗ2_, Υ1 represents -Η, and Ζ1 represents an alkylene group having a methyl group of 1 to 12, or a formula (ΙΙΙ-1) Or 4·substituted-1,1-cyclohexylene) represented by the formula (IIP2), 122 200930760 («-2) (II-3) (H-1) (In the formula (II-2) and the formula (Π-3), Y2 and Y3 are respectively shown in the group of -30), (ΪΙΙ-1) (Chuan-2) _ * (In the general formula (III-1) and the general formula (III-2), Y4 and Y5 each represent an alkyl group having a carbon number of 1 to 3 Å). 2. The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (J) is m + n + p is 3, and X represents or And -H, and Z1 represents a 4-substituted-1,1-cyclohexylene diamine represented by the above formula (111-1) or (III-2). 3. The liquid crystal alignment agent according to the second aspect of the invention, wherein the diamine represented by the formula (1) is one of the following formula A1 and the diamine represented by the formula A2. Or two parties, 4. The liquid crystal alignment 123 200930760 agent according to the second or third aspect of the patent application, characterized in that the H amine is in the first step (vm_3) and the structural formula (VIII_7) is from the Lai type (νπι·3ΐ). One or both of the above-mentioned t-acids and the structural formula (14) of the above-mentioned one amine, which is called ^ 5. The liquid crystal alignment agent 所述 according to the scope of the patent application, characterized in that: the diamine represented by the formula (1) is a smear; I: m + n + p is 3, X and X respectively represent -〇_ or <-, Y1 represents _H, and Ζι denotes a diamine having a methyl group having a carbon number of 1 to 12. 6. The liquid crystal alignment agent according to claim 5, wherein the diamine represented by the formula (1) is X1 and X2 respectively represent -2' and Z1 represents a carbon which may have a methyl group. The number of 1 to 1 Å of an alkylene diamine. 7. The liquid crystal alignment agent as described in claim 6 is characterized in that the diamine represented by the above formula (I) is a diamine represented by the following structural formula B1, 124 200930760 h2n (B1) The liquid "曰 aligning agent" according to any one of claims 5 to 7, wherein the diamine further includes a diamine represented by the following structural formula (VIIM3) The tetracarboxylic dianhydride is / or both of the following structural formula (1) and structural formula (14), h2m, eight PQ (VitUi3) 9. The liquid crystal alignment agent according to claim 1, which is characterized in that the diamine represented by the general formula (I) is m+n+p is 0' and Y The diamines of the formula (11-1), the formula (II-2) or the formula (II-3) are not shown. 1. The liquid crystal alignment agent according to claim 9, wherein the diamine represented by the formula (1) is the γ2 and Y3 in the formula (2) i (11-3) The liquid crystal according to claim 9 is characterized in that the diamine represented by the formula (1) is selected from the following structural formula C1 to structural formula C4. Derived diamine (four) - above, 125 200930760 12. The liquid crystal alignment agent according to claim 9, wherein the diamine further comprises a diamine represented by the following structural formula (VIII-1) and structural formula (VIII-7); One or both of the tetracarboxylic dianhydrides are one or both of the following structural formula (1) and structural formula (14). The liquid crystal alignment agent according to the first aspect of the invention, wherein the diamine represented by the formula (I) is m + η + p is 1, m and η are 0, and X 2 An amino group 126 which represents an aminophenyl group to which X2 is bonded. 126 200930760 A monoamine M which is a meta position of x2. The liquid crystal alignment agent according to claim 13 is characterized in that: The formula (1) &_form D1 and the structural formula D2 show the side or both sides of the amine towel ' HaN (D1) The liquid crystal alignment agent according to claim 13 or claim 14, wherein the tetracarboxylic acid is one or both of the following structural formula (1) and structural formula (14). (1) 16. The liquid crystal alignment agent according to claim 1, wherein the diamine comprises m + n + p in the formula (I) is 3, and X1 and X2 represent -0, respectively. - or CH2, γ1 represents _H, and zl represents a diamine having a pure group having a methyl group of 1 to 12, and one or more selected from the group consisting of the following four kinds of diamines: (1) m + n + p in (/) is 3, X1 and X2 represent or -CH2-, Y represents, H, and zl represents the formula (heart) or formula (IH-2) (4) a diamine of the _u_cyclohexylene group; (2) m + n + p in the formula (1) is 〇, and γι denotes 127 200930760, a formula (Π-1), a formula (II) -2) or a diamine of the formula (II-3); (3) m + n + p in the formula (I) is 1, m and η are 0, and X2 represents -0-, X2 The amino group of the bonded aminophenyl group is bonded to the diamine of the meta position of X2; (4) m + n + p in the formula (I) is 0, and Υ1 represents the formula II (II-4) amine, (11-4) (In the formula (II-4), Y6 represents an alkyl group having 1 to 30 carbon atoms). 17. The liquid crystal alignment agent according to claim 16, wherein the diamine represented by the formula (I) includes a diamine represented by the following structural formula B1, and is selected from the following four One or more kinds of the diamines: (1) a diamine represented by the following structural formula A1 or structural formula A2; (2) a diamine represented by the following structural formula C1 or structural formula C2; © (3) a diamine represented by the structural formula D1 or the structural formula D2; (4) a diamine represented by the following structural formula (XI-47), <B1) 128 200930760 18. The liquid crystal alignment agent according to claim 1, which comprises two or more kinds of polyaminic acid or a derivative thereof. 19. The liquid crystal alignment agent according to claim 18, wherein m + n + p in the general formula (I) is 3, and X1 and X respectively represent _0- or - CH〗-, Y is not, and the Z table may not have a mercapto group of 1 to 12 alkylene diamines and tetracarboxylic dianhydrides of the anti-129 200930760 ' and the following three poly-aracines Or 2 ( 1 ) as m + n + p in the general formula (I) is 3, :1 and X2 respectively represent or _, γ1, and z1 represents the general formula (III-1) Or polylysine or a derivative thereof, which is a reaction product of a 4-substituted-1,1-cyclohexylene group represented by the formula (ΙΠ-2) with a tetrasulphuric acid anhydride; ❹ (2) As the m + n + p in the above formula (I) is 〇, and γ ΐ represents a diamine of the formula (ΙΜ), a formula (π_2) or a formula (π_3) and a tetrahydro acid a polyamic acid or a derivative thereof as a reaction product of an anhydride; (3) m + n + p in the general formula (I) is 1, m and η are 20 ' and χ 2 represents -〇-, X2 The amino group of the bonded aminophenyl group is a polyamine or a derivative thereof which is a reaction product of a diamine and a tetracarboxylic dianhydride at the meta position of X2. The liquid crystal alignment agent according to claim 1, wherein the epoxy compound is selected from the group consisting of glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, and shrinkage. One or more of the group consisting of glycerin amide, glycidyl isocyanurate, a chain aliphatic epoxide, and a cyclic aliphatic epoxide. 21. The liquid crystal alignment agent according to claim 20, wherein the epoxy compound is selected from the group consisting of ruthenium, osmium, iridium, Ν'-tetraglycidyl-diphenylene diamine, 1 , 3-bis(indole, fluorene-bisglycidylaminomethyl) cyclohexene, 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, 3,4-epoxycyclohexenyl-3,4,-epoxy 130 200930760 Cyclohexenylcarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymerization And a bisphenol A phenolic epoxy compound, a cresol novolac epoxy compound, and one or more of hydrazine, hydrazine, and 0-triglycidyl p-aminophenol. The liquid crystal alignment film is formed by calcining a film of the liquid crystal alignment agent according to any one of claims 1 to 21. A liquid crystal display device comprising: a pair of substrates arranged in opposite directions, ◎ electrodes formed on a surface or both surfaces of a surface facing each of the pair of substrates, formed on each of the pair of substrates The liquid crystal alignment film on the opposite surface, and the liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to the above-mentioned item. 131 200930760 IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (In the general formula (1), X1 and X2 respectively represent -0_ or _〇12-, Y1 represents _H, the following structural formula (Π-1), general formula (II-2) or general formula (ιι·3) Ζ1 represents an alkylene group having a methyl group having a carbon number of 1 to 12, a 4-substituted-pyrene ring represented by the following formula (III-1) or (III-2), m, n and Ρ represent 〇 or 1 respectively; ([M) 阙 (In the formula (Π-2) and the formula (II-3), γ2 and γ3 each represent a group having a carbon number of 1 to 30), (In the general formula (III_1) and the general formula (ΙΠ·2), 'Y4 and Y5 respectively represent a burnt group having a number of stones of 1 to 30). Ί 3