TW201022331A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

This invention provides a liquid crystal display device performing VHR long-term heat reliability as required, a liquid crystal alignment film thereof which performs the required VHR long-term heat reliability, and a liquid crystal alignment agent to form the liquid crystal alignment film. The liquid crystal alignment film is formed by polyamic acid or its derivative using diamine tetraacetic acid dianhydride and aromatic diamine having side chains as raw materials, and the liquid crystal alignment film is used in the liquid crystal display device.

Description

201022331 32945pif.doc VI. Description of the Invention: [Technical Field] The present invention relates to a polyamic acid obtained by reacting a diamine with a tetracarboxylic dianhydride or a liquid crystal alignment agent of the derivative thereof, a liquid crystal alignment film obtained by the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, in particular, a liquid crystal alignment agent suitable for a vertical alignment (VA) method, A liquid crystal alignment film obtained by the liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film. [Prior Art] A liquid crystal display element is used for a viewfinder or a projection type of a video camera represented by a monitor of a notebook personal computer or a desktop personal computer. Various liquid crystal display devices, such as displa>, have recently been used for television. Further, liquid crystal display elements are also used for optical printer heads and optical Fourier transform elements (optical Fourier transform elements). Photoelectric-related components such as a light valve (for valve). Various components are known in liquid crystal display elements, and the development of liquid crystal display elements can be improved not only by driving the liquid crystal display element but also by changing the structure of the liquid crystal display element. This can also be achieved by modifying the constituent members used in the liquid crystal display device. Generally, the display member has a liquid crystal alignment film in which the liquid crystal composition in the liquid crystal layer is aligned to the south. It is an important element related to the quality of liquid crystal display elements, 201022331 32945pif.doc, liquid The role of the alignment film becomes important year by year with the quality of the liquid component. ” The liquid crystal alignment film is prepared by a liquid crystal alignment agent. Currently, the liquid crystal alignment agent mainly used is polyglycine or soluble polyfluorene. A solution obtained by dissolving an imide in an organic solvent. After coating such a solution on a substrate, a film is formed by heating or the like to form a liquid crystal alignment film. ❹ For the liquid crystal alignment film, for example, A liquid crystal alignment film of diamine tetraacetic acid is used, and it is revealed that the liquid crystal alignment film can improve the voltage holding ratio in the Super Twisted Nematic (STN) mode and the active matrix display (10) to the matrix display (refer to Patent Document i) Further, crosstalk is improved by using a liquid crystal alignment film of ethylenediaminetetraacetic acid dihepatic (see Patent Document 2). Further, it is disclosed that the use of ethylenediaminetetraacetic acid has two needles. A liquid crystal alignment film of a copolymer of a polymer material and a different acid anhydride which is bonded to a light-bonded wire (see Patent Document 3). © # On the one hand, characteristics of a liquid crystal alignment element In this case, it is required to maintain the high voltage holding ratio for a long period of time. When the high voltage holding ratio cannot be maintained for a long period of time, problems such as voltage drop, driving voltage increase, power consumption increase, and contrast reduction may occur. In the literature i, although the initial value of the electrical maintenance ratio system is improved, the long-term thermal reliability of the wire-good voltage holding ratio is studied. Further, in the above-mentioned Patent Documents 2 and 3, the improvement is also not improved. The long-term thermal reliability of the voltage holding ratio was investigated. 5 201022331 32945pif.doc [Prior Art Document] [Patent Document] [Patent Document 1] U.S. Patent No. 552 845, Pro. 2, Japanese Patent Laid-Open Publication No. Hei 6-7-S229 (Korean Document 3) 〇〇6_35〇347号 [Summary of the Invention] (4) ΐ 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供A liquid crystal alignment film having a long-term thermal reliability, and a liquid crystal alignment agent capable of forming the liquid crystal alignment film. The inventors of the present invention have found that a composition containing polyamine or a derivative thereof having a specific diamine tetraacetic acid dianhydride and/or a side chain aromatic diamine as a raw material can be used for a liquid crystal alignment agent. The liquid crystal display element having the liquid crystal alignment film formed by the liquid crystal alignment agent imparts long-term thermal reliability to a desired voltage holding ratio, thereby completing the present invention. The present invention includes the following constitutions. [1] A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the tetracarboxylic dianhydride having the following formula (TC-i) a tetracarboxylic dianhydride represented by the formula (TC-14), which contains a side chain structure represented by the following formula (VIII) and formula (X) to formula (XI) amine. 201022331 32945pif.doc

7 201022331 32945pif.doc [Chemical 2]

201022331 32945pif.doc (In the general formula (TC-1), X represents -(CH2)n, and at most two -CH2- can be independently -0-(here is not continuous), -S-, -COO-, -OCO-, -CO-, -CONH,, -CnH2nN(CmH2inCOOH)CnH2n_, -CH(CmH2mOH)-, -CH(CnH2n+1)_, _CH=CH- or -OC-substitution (m means 0~30 The integer 'n independently represents an integer from 1 to 30.) In the formula (TC-4) to the formula (TC-7), Υ independently represents a single bond, -0, _s---SS-'-S02 ---CO-, -CONH-, _NHC0-, -NH-, -N(CH3HCH2)mN(CH3)-, ❹-C(CH3)2- > -C(CF3)2- ^ -(CH2) M- > -0-(CH2)m-0- '-S-(CH2)mS- (m represents an integer of 1 to 6). In the formula (TC-5), Z represents a single bond or does not exist. In the formula (TC-9), R33 and R34 each independently represent an alkyl group or a phenyl group having a carbon number of 1 to 3, and A3 independently represents a methylene group and a phenyl group (methylene group). Phenylene or a substituted subphenylene group 1 represents an integer of 1 to 6, and m represents an integer of 1 to 10. In the formula (TC-2) to formula (TC-7), the bond is in the ring. The hydrogen on the cyclohexane ring or the benzene ring can be independently _f, -CH3, -CF3, -OH, -COOH, -S03H Substituting -P〇3H2, the hydrogen bonded to the benzene ring in the formula (TC-3) may be substituted by a benzyl group. The formula (TC-2) to the formula (TC-8) R1 independently represents _(CH2)m, at most two 〇: Η2- can be independently -0-(here is not continuous), -S-, -COO-, -OCO-, -CO-, CONH-,, CH(CmH2m〇H)-, -CH(CmH2m+1)-, -CH=CH- or -OC-substitution (m independently represents an integer of 〇30). General formula (TC-8) Wherein A1 is independently an alkyl group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 1 Å, a acetamide, fluorine, gas or bromine, and A2 independently represents a carbon number of 1 to 3, the m represents an integer of 0 to 3, and η represents an integer of 201022331 32945pif.doc of 0 to 4. In the general formula (TC-10), A3 represents a single bond, -〇-, -coo-,- Oco·, -CO-, -CONH- or -(CH2)m- (m represents an integer pR1 of 1 to 6 represents a group having a steroid skeleton or a group represented by the following formula (B), when a bond When the positional relationship of two amino groups on the benzene ring is a para position, R1 further contains an alkyl group having a carbon number of 1 to 30, and when the positional relationship is meta-position, R1 further contains a carbon number of 1~ An alkyl group or a phenyl group of 30, wherein any -CH2- of the alkyl group may be independently substituted by -CF2-, -CHF-, 〇_(here not continuous), _CH=CH- or -〇C_, -CH3 may be substituted by -CH2F, -CHF2 or -cf3, which may be independently substituted by -F, -CH3, -OCH3, -OCH2F, -OCHF2 or -OCF3. [Chemical 3]

In the general formula (B), A4 and A5 each independently represent a single bond, _〇_ (here is not continuous), -COO-, -OCO-, -CONH-, -CH=CH- or a carbon number of 1~ 12 alkylene, R2 and R3 each independently represent _F or -CH3, and ring S independently represents 1,4-decyl, M-cyclohexylene, 1, 3-dioxane-2,5-diyl (l,3-dioxane-2,5-diyl), σ 密-2 - 5-yy (Pyrimidine-2,5_diyl), 唆-1,4- Bis(pyridine_14_diyl), ^ -1,5-diyl (naphthalene-l, 5-diyl), naphthalene diyl or 蒽_9,1〇_二^ (anthracene-9,10-diyl), R4 represents _ H, carbon number is: "3" base, carbon number 1~30 fluorine-substituted alkyl group, carbon number 丨~3〇, oxygen-oxygen, -(10), -〇CH2F, -〇CHF2 t〇 CF3, a and b respectively represent integers of 〇14 201022331 32945pif.doc, C, d and e respectively represent integers of 〇~3, f and g respectively represent integers of 0~2, respectively, and c + d+e^l . In the formula (TC-11) and the formula (TC-12), R5 independently represents -H or -CH3, R6 represents -H, or an alkyl group having 1 to 20 carbon atoms or a carbon number of 2 to 20 Alkenyl, A6 independently represents a single bond, -C0- or -CH2. In the formula (TC-12), R7 and R8 each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group. In the general formula (TC-13) and the general formula (TC-14), 'A7' independently represents _〇_ or an alkenyl group having a carbon number of 1 to 6 φ. In the formula (TC_13), R9 represents -H or an alkyl group having 1 to 30 carbon atoms, and any _ch2- of the alkyl group having 2 to 30 carbon atoms in the alkyl group may be -0- (here is not continuous) , -CH=CH· or -OC-substitution, A8 represents a single bond or an alkylene group having a carbon number of 1 to 3, and the ring T represents 1,4-phenylene or 1,4-cyclohexene, and h represents 〇 or 1. In the formula (TC-14), R10 represents an alkyl group having 6 to 22 carbon atoms, and R11 represents -H or a group having 1 to 22 carbon atoms. [Chemical 4]

(In the formula (VIII), 'A3 represents a single bond, -0-, _c〇〇-, -0C0-, -CO-, -CONH- or -(CH2)m- (m represents an integer of 1 to 6), R1 represents a group having a steroid skeleton or a group represented by the following formula (IX), and when the positional relationship of two amino groups bonded to the benzene ring is para-position, R1 further contains a group having 1 to 30 carbon atoms. 'When this positional relationship is meta-position, R1 further contains a burnt group or a phenyl group having a carbon number of 1 to 30, and any -CH2- of the alkyl group may be independently -CF2_, -CHF-, -〇- Is not continuous), _ch=CH- or -OC-substitution, _CH3 can be replaced by -CH2F, -CHF2 or -CF3, this stupid 201022331 32945pif.doc-based hydrogen can be independently -F, ΤΗ;, -〇CH3 , _0CH2f, _〇CHF2 or -OCF3, wherein when the tetraphthalic acid dianhydride contains only the tetracarboxylic dianhydride represented by the formula (TC-) to the formula (ΊΧΜ4), R] further The alkyl group contained has a carbon number of 23 to 30). [(5) [[f)fl [Delete - _ Ten A4 Yun c [〇j 士 5V d -R4 (IX) e (In the general formula (IX), A4 and A5 independently represent a single bond, _〇_ (This ◎ is not continuous), -COO-, -OCO-, -CONH-, -CH=CH- or an alkenyl group having a carbon number of 1 to 12, and the scales 2 and R3 independently represent -F 4_CH3, ring S independently represents 1,4-phenylene, 1,4-cyclohexene, 1,3-dioxane-2,5-yl, punctured 2,5·diyl, pyridyl-1. 4·diyl, naphthalene-1,5-diyl, naphthalene-2,7-yl or oxime-diyl' R4 represents -Η, -F, an alkyl group having a carbon number of 1 to 30, and the carbon number is a fluorine-substituted alkyl group of 1 to 30, an alkoxy group having 1 to 30 carbon atoms, _ 〇CH 2 F, -〇CHF 2 or -〇 CF 3 , a and b each represent an integer of 0 to 4 'c, d and e respectively represent An integer of 〇~3, f and g are independent of the integers of the table 2 to 2, and c + d + egb where 'when c + d+e=1' R4 represents an alkyl group having a carbon number of 1 to 30 And a fluorine-substituted yard group having a carbon number of 1 to 30 or an alkoxy group having a rear number of 1 to 30, and A3 of the formula (VIII) means a carbon number of 大于 or more. 12 201022331 32945pif.doc [Chem. 6]

(In the formulae (X) and (XI), 'R5 independently represents ·H 4_CH3, R6 represents -Η, or an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and A6 independently represents In the formula (XI), r7 and r8 each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group). [2] The liquid crystal alignment agent according to [1] characterized in that the diamine having a side chain structure is a diamine represented by the above formula (VIII) K, and R1' is the above formula The base represented by (IX). [3] The liquid crystal alignment agent according to [2], wherein the diamine having a side chain structure is a diamine represented by the formula (VIII), and R1 is a formula (Rq) a group represented by the formula (Ri-7). For example 13 201022331 32945pif.doc [Chemistry 7]

(R]-3)

❹

1-^ A~~~<)-R (r1-7) (In the formula (R^-l), R represents a postal number of 1 to 30, a fluoro-substituted alkyl group having a carbon number of 1 to 30 Or an alkoxy group having a carbon number of 1 to 30. When R of the formula (RL1) is a group having a carbon number of 1, the group A3 of the formula (VIII) represents a group having a carbon number of 1 or more, and the formula (R, 2) From the formula (R1-?), R represents -H, Q-F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, and a carbon number of 1 to 30. Alkoxy, -CsN, -〇CH2F, -OCHF2 or -OCF3, A represents -Ο- or an alkenyl group having 1 to 6 carbon atoms). [4] The liquid crystal alignment agent according to [3], wherein the diamine having a side chain structure is selected from the group consisting of compounds represented by the following formula (VIII-2) to formula (vn) At least one. 14 201022331 32945pif.doc [Chem. 8]

H2N (vm-2)

(In the above formula, R52 represents a hydrocarbon having a carbon number of 16 to 30, represents an alkyl group having a carbon number of 1 to 30, and R54 represents a radical having a carbon number of 4 to 30. R55 represents a carbon number of 2 to 30. 30 bases). [5] The liquid crystal alignment agent according to [1], wherein the diamine having a side chain structure is represented by the above formula (X) or (XI) ° 0 [6] according to [ The liquid crystal alignment agent according to any one of the above aspects, wherein the tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride. [7] The liquid crystal alignment agent according to [6], wherein the aromatic tetracarboxylic dianhydride is a structural formula (1), a structural formula (2), and a structural formula (5) to a structural formula. (7) At least one of the compounds represented by the structural formula (11), the structural formula (12) and the structural formula (14). 15 201022331 32945pif.doc

[8] The liquid crystal alignment agent according to any one of [1] to [7] wherein the tetracarboxylic dianhydride comprises an alicyclic tetracarboxylic dianhydride and an aliphatic four-reelic acid two-needle One or both of them. [9] The liquid crystal alignment agent according to [8], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the following structural formula (19), structural formula (23) At least one of the compounds represented by Structural Formula (25), Structural Formula (35) to Structural Formula (39), Structural Formula (Formula) (44) and Structural Formula (49). 16 201022331 32945pif.doc [Chem. 10]

(19) (23)

[10] The liquid crystal alignment agent according to any one of [1] to [9], wherein the diamine further comprises the following general formula (1) to general formula (VII), general formula (XV), Two of the general formula (N) and the general formula (a) having no side chain structure

Amine 0 17 201022331 32945pif.doc [化η] h2n-x-nh2 (1)

(In the formula (I), X represents -(CH2)m- (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently represents a single Key, -Ο-, -S-, -SS-, -S02-, -CO-, -CONH-, -NHCO-, -NH-, -N(CH3)-(CH2)mN(CH3)-, _C (CH3)2-, -C(CF3)2-, -(CH2)m-, 18 201022331 32945pif.doc 0_(CH2)m-〇-, _s_(CH2)m_s_(m represents an integer of J~6), In the formula (v), 'Z represents a single bond or does not exist. In the formula (??), R33 and R34 each independently represent an alkyl group or a phenyl group having a carbon number of 1 to 3, and A3 independently represents a methylene group. a phenyl group or an alkyl group-substituted phenyl group, 丨 represents an integer of 1 to 6, and represents an integer of 1 to 10. In the formula (11) to the formula (νπ), a bond is bonded to a cyclohexane ring or a benzene. The hydrogen on the ring may be independently substituted by -F, -CH3, -CF3, -OH, &lt;X)〇H, -S〇3H, -ΡΟ#2, and the bond on the benzene ring in the formula (IV) © (4) Hydrogen can be replaced by fresh base. In the formula (Ν), Α1 independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having a carbon number of 丨4, acetamidine, fluorine, chlorine or hydrazine, and Α2 independently represents a carbon number! An alkyl group of 〜3, m represents an integer of 〇~3, and η represents an integer of 〇~4. In the formula (a), L1 represents hydrogen, a carbon group of 1 to 4, and a styl group. The liquid crystal alignment agent according to [10], wherein the diamine having no side chain structure is selected from the following structural formula (IV_1}, structural formula (^2), structural formula (IV-15)~Structure Formula (IV-17), Structural Formula (vq) Q Configuration (V-13), Structural Formula (ν·33), Structural Formula (V-35)~Structure Formula (%37) °, structural formula (VII-2), structural formula (χν-i), structural formula (9)-丨, (Ν)_2, structural formula (Ν)-14, structural formula (al) and structural formula (a_2) At least one of the compounds. 19 201022331 32945pif.doc [Chem. 12-1]

H2N is called h^-Q- (IV-1.) (IV-2) (10)Η2ΝΌη〇ΝΗ2 H2NtXi&gt;NH2 (V·*1) (V-2) (V-3)

(V-10)

(V-11)

(V-13)

h2nhQ^-n-&lt;Q^nh2 h2n-^Q&gt;-n^n-^j^nh2 (V-35) (V-36) 20 201022331 32945pif.doc 12-2]

(V-37) ?H3 ?h3 H2N-C3H6-?i-〇-Si-C3H6-NH2 CH3 CH3 (XV-1)

H2n h2n (a-0 (a-2) Ο

[12] The liquid crystal alignment agent according to any one of (1) to [1], wherein the bismuth resorcinus bismuth derivative comprises a silsesquioxane dianhydride derivative. [13] The liquid crystal alignment agent according to [12], wherein the sesquiterpene dianhydride derivative is a compound represented by the following structural formula (S_1). 21 201022331 32945pif.doc [Chem. 13]

The liquid crystal alignment agent according to any one of [1] to [13] wherein the polyamic acid or a derivative thereof comprises two polylysines or derivatives thereof A and B, the polyperuric acid or derivative A thereof comprises the diamine having a side bond structure in the diamine, and the tetrahydro acid of the poly-branched acid or derivatives A and B thereof One or both of the dianhydrides include four ortho-dianhydrides represented by the general formula (TC1) to the general formula (TC-14). [15] The liquid crystal alignment agent according to any one of [1] to [14] further comprising a radically substituted nadiimide compound having a radical polymerization. A compound of a sexually unsaturated double bond, an oxazine compound, or a compound. One or more of an oxaz〇iine compound and an epoxy compound. [16] A liquid crystal alignment film which is formed by heating a coating film of the liquid crystal alignment agent according to any one of [n to [15]. [17] A liquid crystal display element having: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode applying a voltage to the liquid crystal layer; and aligning the liquid crystal molecules at a predetermined The liquid crystal display element in the direction of the liquid crystal display element is characterized in that the liquid crystal alignment film is the liquid crystal alignment film according to [16]. 201022331 32945pif.doc According to the present invention, it is possible to provide a liquid crystal display element which can exhibit voltage long-term thermal reliability. The above described features and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] The liquid crystal alignment agent of the present invention contains a polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine. The derivative of the poly-branched acid is a component which is dissolved in a solvent when a liquid crystal alignment agent described later containing a solvent is prepared, and the liquid crystal alignment film described later can be formed into a liquid crystal alignment film. The component of the liquid crystal alignment film containing the imine as a main component is a derivative of such a polyamic acid, and examples thereof include soluble polyimine, polyamic acid ester, and polyamine glycine ( Polyam^c add amide), etc., more specifically, 丨) all amino groups of poly-proline are reacted with silk (eafbGxy 1), and 2) partially undergo dehydration ring closure reaction. Part of the poly-branches 15 and 3) The poly-branched vinegar obtained by converting the filament of poly-proline to g is replaced by an organic dicarboxylic acid from a part of the acid di-hepatic contained in the tetra-acid diif compound. The polylysine-polyamine copolymer obtained by the reaction is further exemplified by 5) a polyamidoquinone obtained by subjecting a part or all of the polyamido-polyamine copolymer to a dehydration ring-closing reaction. Amine (imamide-imide). The polyamic acid or a derivative thereof may be one compound or two or more compounds. Further, the poly-proline or a derivative thereof may be a compound having a structure of a reaction product of a tetracarboxylic dianhydride and a diamine, or may be a mixture of other raw materials and may be passed through 23 201022331 32945 pif.doc. An inverse product obtained by a reaction other than the reaction of acid dianhydride with a diamine. The tetracarboxylic dianhydride used in the present invention contains tetradecanoic dianhydride represented by the above formula (tc_U to formula (TC-14). As the four represented by the formula (TC-1) In the carboxylic acid dianhydride, in the formula, χ is preferably an alkylene group as a main chain having a carbon number of 〇 20, and for example, an acid dianhydride represented by the following structural formula may be mentioned.

The tetracarboxylic dianhydride represented by the formula (TC-2) has a carbon number of 烷10 which is a main chain, and is, for example, an acid dianhydride represented by R 冓. Yak

As the tetracarboxylic dianhydride represented by the formula (TC-3), the carbon number of the broad chain as the main chain nonenyl group is G 10, and the formula 'R' is exemplified by 24 201022331 32945 pif.doc. The acid dianhydride represented by the structural formula. [Chemistry 16]

In the general formula, the number of carbon atoms of the alkenyl group as the main chain is from 0 to 10, and examples of the tetracarboxylic dianhydride represented by the formula (TC-4) include an acid represented by the following structural formula. Diacid anhydride. [Chem. 17]

25 201022331 32945pif. doc As a tetracarboxylic dianhydride represented by the formula (TC-5), in the formula, R1 is preferably an alkenyl group as a main chain having a carbon number of 0 to 10, and examples thereof include the following structures. The acid dianhydride represented by the formula. [Chem. 18-1]

ο ο ο ο 26 201022331 32945pif.doc [Chem. 18-2]

φ is a tetracarboxylic dianhydride represented by the formula (TC-6), and in the formula, R1 is preferably a carbon atom of the primary group as a primary bond, and the number of carbon atoms is 0 to 10, and examples thereof include r represented by the following structural formula. Two needles. Into [Chemistry 19]

As the tetracarboxylic dianhydride represented by the formula (TC-7), the carbon number of the alkenyl group having a main chain of the formula is 〇~1〇, for example, the acid represented by the structural formula of γ and γ Diacid anhydride. &amp; 27 201022331 32945pif.doc [Chem. 20]

The number of carbon atoms of the alkenyl group which is a main chain of the tetrazoic acid dihydrazide represented by the formula (TC-8) is 〇~1〇, and f is an acid field represented by the structural formula. Anhydride, in the formula, R1 can be exemplified by

28 201022331 32945pif.doc [化*21_1]

29 201022331 32945pif.doc [Chem. 21-2]

The tetracarboxylic dianhydride represented by the formula (TC-9) may, for example, be an acid dianhydride represented by the following structural formula.

[化22] 〇. 〇 , ? H3 ?h3 t N-Si-O-Si-C3H6-N, ch3 ch3 o 0 1 The tetracarboxylic dianhydride represented by the formula (TC-10), for example, may be exemplified by the following formula or structural formula The acid dianhydride represented.

30 201022331 32945pif.doc [Chem. 23-1]

31 201022331 32945pif.doc [Chem. 23-2]

Ο R*

❹ (In the above formula, R23, R24, R25 and R26 each represent an alkyl group having 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms). 32 201022331 32945pif.doc [Chem. 24]

The tetracarboxylic dianhydride represented by the formula (T C -11) may, for example, be an acid dianhydride represented by the following structural formula. 33 201022331 32945pif.doc [Chem. 25]

The tetracarboxylic dianhydride represented by the formula (TC-12) may, for example, be an acid dianhydride represented by the following structural formula.

34 201022331 32945pif.doc [Chem. 26]

35 201022331 32945pif.doc The tetracarboxylic dianhydride represented by the formula (TC-13) may, for example, be an acid dianhydride represented by the following formula. [化27]

36 201022331 32945pif.doc (R29 represents - an anthracene, an alkyl group having a carbon number of 1 to 30 or an alkoxy group having a carbon number of 1 to 30, more preferably an alkyl group having a carbon number of 3 to 30 or a carbon number of 3 to 30. 30 alkoxy groups). The tetracarboxylic dianhydride represented by the formula (T C -14) may, for example, be an acid dianhydride represented by the following formula. [化 28]

(R29 represents an alkyl group having 6 to 22 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms. R3Q represents an anthracene or an alkyl group having 1 to 22 carbon atoms, more preferably -H or a carbon number is 1 to 10 alkyl groups). Examples of the other tetracarboxylic dianhydride include acid dianhydride represented by the following formula. 37 201022331 32945pif.doc [Chem. 29]

The tetracarboxylic dianhydride which is particularly suitable for use in the present invention is a tetracarboxylic dianhydride represented by the general formula (TC-1) to the general formula (TC-7), and among them, a tetracarboxylic acid represented by the following structural formula is particularly preferable. Diacid anhydride. [化30]

38 201022331 32945pif.doc In addition, the polyamine which constitutes the liquid crystal alignment agent of the present invention is formed from the viewpoint of exhibiting a desired voltage holding ratio in the liquid crystal display element and achieving long-term thermal reliability of the voltage holding ratio. The acid dianhydride of the acid preferably contains 10% to 100% of the tetracarboxylic dianhydride represented by the above (Td) to the above (TO! 4) in a molar ratio, and more preferably contains 2% by weight. 1% by mass of tetracarboxylic dianhydride represented by the above (TC-1) to (TC_14). The tetracarboxylic dianhydride of the present invention preferably contains an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic acid bisphenol refers to at least one of the two anhydrides which are bonded by the aromatic compound on the two A sigma of an acid anhydride formed by a carboxyl group (carb0xy). The aromatic tetracarboxylic dianhydride may, for example, be a compound represented by the following structural formula (1) to structural formula (10). Scales 39 201022331 32945pif.doc [Chem. 31]

❹

(7) (8) (9)

40 201022331 32945pif.doc The aromatic tetra-rebel acid liver is preferably in the t configuration (1) structural formula (2), structural formula (5) - structural formula (7), structural formula ((1), structural formula (12) and structure The compound represented by the formula (14) is more preferably a compound represented by the structural formula (1), and is preferably a viewpoint that the liquid crystal display element exhibits electrical properties required for a voltage holding ratio or the like. In the acid two needles constituting the polyproline in the liquid crystal alignment agent of the present invention, the aromatic carboxylic acid dianhydride is preferably contained in an amount of from 1% to 98 to 98%, more preferably 10% by weight. 95% of the aromatic tetra-retensive acid two-needle. The four-poisonic acid two-needle of the present invention preferably contains one or both of the following alicyclic tetra-acid dianhydride and aliphatic tetracarboxylic dianhydride. The cyclic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride formed by two rebel groups bonded to an alicyclic compound having two bonds a compound of an acid anhydride formed by two carboxyl groups bonded to an aliphatic compound as the alicyclic tetracarboxylic acid Examples of the anhydride include compounds represented by the following structural formula (19) to structural formula (22), structural formula (24) to structural formula (44), and structural formula (49) to structural formula (65). 41 201022331 32945pif .doc

42 201022331 32945pif.doc

43 201022331 32945pif.doc [Chem. 32-3]

(60) (61)

Examples of the aliphatic tetracarboxylic dianhydride include compounds represented by the following structural formula (23), structural formula (45) to structural formula (48), structural formula (66), and structural formula (67).

44 201022331 32945pif.doc

[化33]

The alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride preferably have the structural formula (19), the structural formula (23), the structural formula (25), and the structural formula (35) to the structural formula. (39) The compound represented by the structural formula (44) and the structural formula (49), more preferably the compound represented by the structural formula (19) or the structural formula (23). In addition, from the viewpoint of exhibiting electrical properties required for a voltage holding ratio and the like in the liquid crystal display element, it is preferable to use a molar ratio in the acid anhydride of the poly-proline which constitutes the liquid crystal alignment agent of the present invention. Containing 1% to 98% of the alicyclic tetrahydro acid dixanthine and the lipid thief two needles, more preferably containing 〜95% of the alicyclic tetranic dianhydride and the lipid _four Wei Er liver. The invention of the invention makes the _ four ships and the second field preferably octave oxy-combustion because it is a highly cross-linked body and will not be hydrolyzed, so it can be read as a Weijing alignment agent 45 201022331 32945pif.doc stability. In addition, even if the enthalpy of the yttrium, f cattle is excessively mixed, the liquid crystal alignment film can be used. The (tetra) sesquioxin derivative used in the present invention may be, for example, a dreamy hemoxytetraacetate derivative as described in the manual of the 〇〇3 2 〇 〇 , , , , , , Expressed by the general formula. [34]

In the formula (S), R is independently selected from hydrogen, an alkyl group having a hindrance of 1 to 45, a substituted or unsubstituted aryl group, and a substituted or unsubstituted arylalkyl group. 'Y is independently represented by the following (a) or (b). [化35]

(b) In the formula (a) and the formula (b), one or two X represents an acid anhydride group. The remaining X is independently hydrogen, halogen, or hydroxyl. 46 201022331 32945pif.doc Or a monovalent organic group, Z is -ο-, -CH2- or a single bond. Wherein, in the alkyl group having a carbon number of from J to 45, any hydrogen may be substituted by fluorine, and any CH2- may be -〇·, -CH=CH-, cycloalkenyl (cyclic) or cycloalkenyl Replacement with cycloalkenylene. In the alkenyl group in the substituted or unsubstituted arylalkyl group, any hydrogen may be substituted by fluorine, and any _CH2. may be substituted by -0-'-CH=CH- or a ring-burning group.

Among the above formulas, a particularly preferred sesquinal dianhydride derivative is a compound represented by the following structural formula (S-1). (S-1) p0h-si-°〇?sr-°Ph 0) Gas additionally exhibits electrical properties such as voltage holding ratio in liquid crystal display elements, and exhibits long-term thermal reliability. In view of the above, in the acid succinic acid constituting the polyacrylic acid in the liquid crystal alignment agent of the present invention, it is preferable to contain 1% to 60% of the sesame sesquiterpoxide dianhydride derivative in terms of a molar ratio. More preferably, it contains 10% to 40% of the &gt;5 sesquioxide dianhydride derivative. The tetracarboxylic dianhydride used in the present invention may be arbitrarily used in its kind or blending amount within the range in which the effects of the present invention are achieved. Further, in the present invention, a copolymer obtained by copolymerizing a tetracarboxylic dianhydride represented by the above formula (TCM) to formula (TC-14) with one or more other tetracarboxylic dianhydrides is preferably used. . The use of tetradecanoic dianhydride improves the storage stability of the alignment agent, and therefore it is preferred to use tetradecanoic dianhydride. It is also possible to replace a part of the four resorcinic dianhydrides with a tickic acid anhydride. 47 201022331 32945pif.doc (This kind of substitution of carboxylic anhydriling can cause polymerization when polylactoic acid is formed, and should be terminated (tenninatiGn)' The polymerization reaction is prevented from proceeding. Therefore, by such substitution, the molecular weight of the obtained polymer (polyfluorene or its filament) can be easily controlled, for example, the liquid crystal alignment can be improved without extracting the effects of the present invention. The coating property of the agent. The ratio of the carboxy group to the tetra-ruthenium ratio is preferably 'as a reference' in the range of the effect of the present invention and is preferably equal to or less than 1 〇 of the total amount of the four-poisonous two-needle. As long as the effects of the present invention are not impaired, the diacids of the acid which are replaced with the tickose may be of the same type, or may be two or more. As the monoacid anhydride, for example, a maleic acid needle may be mentioned. (maleic anhydnde) . ^ (phthalic anhydride) ^ (=嶋acid anhydride), Zhengyijihuzhanxuan (4) (4) occupational acnd anhydnde), n-dodecyl succinic acid Xuan, Zheng 16 Lu Hu (4) and Cyclohexanoic acid needle. Ten silk shot 〇 = four new liver can be in the second (four) relative to the _ acid rate is less than or equal to H) Mohr% of the _, will be two needles of acid, into two acids. As long as the effects of the present invention are not impaired, the acid: ship II - is - type, or both or = 竣 The diamine used in the present invention has a side chain structure. The diamine of the side chain structure means a diamine having a substituent (display) which is an autonomous chain when the substituent linking the two amino groups is used as a main chain and can exhibit a desired pretilt angle (Pretilt ang)丨e). The side chain of the diamine having: f may be appropriately selected according to the desired pretilt angle. For example, the side chain may include a group having a hindrance of 8 or more. The above-mentioned diamine having a side chain structure may, for example, be a compound represented by the following formula (VIII) and formula (X) to formula (XI). [化37] R1

(VIII) ❹

(In the formula (VIII), A3 represents a single bond, -〇·, _c〇〇_, -OCO-, -CO-, -CONH- or -(CH2)m- (m represents an integer of 1 to 6), R! represents a group having a steroid skeleton or a group represented by the following formula (IX), and when the positional relationship of two amino groups bonded to the benzene ring is para-position, R) further contains a carbon number of 1 to 30. When the positional relationship is meta-position, r1 further contains a burning group or a phenyl group having a carbon number of 1 to 30. In this hospital base, any _〇^2_ may be independently -CF2-, -CHF· , -0-(here is not continuous), _ch=CH- or -〇C·substitution '-CH3 may be substituted by -CHyF, -chf2 or -cf3, and -ch3 may be substituted by -CHJ, -CHF2 or -CF3, The hydrogen of the phenyl group may be independently substituted by -F, -CH3, -OCH3, -OCH2F, -〇CHF2 or -〇CF3. wherein 'when the four-rebel dianhydride contains only the general formula (TC-1) When the tetracarboxylic dianhydride represented by the formula (TC-14) is used, the alkyl group further contained in R1 has a carbon number of 23 to 30). [化38]

Jd

(In the general formula (IX), '_A and A each independently represent a single bond, _〇_ (here is not continuous), -COO-, -OCO-, -CONH-, -CH=CH- or carbon 49 201022331 32945pif .doc = alkenyl group of 1 to 12, !^ and R3 each independently represent _F or seven%, and ring s independently represents M. phenylene, M_cyclohexene, and u_dioxin. Base, biting _2,5·diyl, β-biting, 4_diyl, naphthalene], 5_diyl-Cali-based, 蒽-9,10·diyl' R4 means _H, _F, a fluoro-substituted alkyl group having a carbon number of 1 to 30 and a carbon group having a carbon number of 1 to 30, ON, a secret, -〇CHF2 or _0 (^3, a And b denote 〇~: the integers 'c, d, and e respectively represent integers of 〇~3, (and § independently represent integers of 0~2, respectively, and c + d+egl. Where, when c + d + When e=l, R4 represents an alkyl group having a carbon number of 1 to 30, a fluorine-substituted alkyl group having a carbon number of 丨~sun or an alkoxy group having a carbon number of 1 to 30, and A3 of the formula (VIII) represents a carbon number. A base greater than or equal to 1.)

(In the general formulae (X) and (XI), R5 independently represents _H or ^, and R6 represents an alkyl group having a carbon number of 1 to 2 fluorene or an alkenyl group having a carbon number of 2 to 20, and the A6 site is not only A bond, -C0. or -CH2-, in the formula (XI), R7 and R8 each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group). 50 201022331 32945pif.doc The diamine used in the present invention is preferably a diamine represented by the formula (V111; 1 and wherein R) is represented by the following formula (R1-1) to (RL7). The compound represented. [Chem. 40]

❹

(In the formula (RL!), R represents an alkyl group having a carbon number of 1 to 30, a fluorine-substituted silk having a carbon number of 1 to 3 fluorene, or a fluorenyl group having a carbon number of 3G, as R of the formula (Wl) When it is a group having a carbon number of 1, the A3 of the formula (VIII) represents a group having a carbon number i in the range of 1, wherein, in the formula (Ri-2) to the formula (r1-7), R represents -H, An alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 30, -c=n, -och2f, -ochf2 or -〇CF3, not shown. • or an alkenyl group having a carbon number of 1 to 6). In the case of J&amp;, it is preferred to contain one selected from the group consisting of compounds represented by the following formula (VIIK2) to formula 51 201022331 32945 pif.doc (VIII_8). [化41]

〇 (In the above formula, R52 represents a radix of 16 to 30, and R represents a filament having a carbon number of 1 G to 30, # represents a carbon number of Μ Μ Μ, and R 55 represents a carbon number of 2 to 30. The radical 452 is preferably a halogen group of 16 to 25, R53 is preferably a graft having a carbon number of 10 to 25, R54 is preferably a group having a hindrance of 4 to 25, and R55 is preferably an alkyl group having a carbon number of 2 to 5%. The diamine represented by the above formula (VIII) can be produced by a method known in the art. As such a production method, for example, a reaction of 1,2_stanediamine and o-dibenzoic acid in an air environment is carried out, and the reactant is dissolved in / sulphuric acid and mixed with the smog. A method of reducing the compound obtained by reduction of the obtained compound to an amino group. 52 201022331 32945pif.doc The diamine represented by the formula is preferably in the general formula, one of the two "war.AA bonds at the 3 position of the steroid skeleton, and the other bond is at the 6 position, preferably the two amino groups respectively. The bond is bonded to the carbon of the benzene ring, and the bond is in the meta or para position of the bonding of A. As the diamine represented by the formula (X), for example, the following structural formula (X-1) can be cited. ) to a diamine represented by the structural formula (X_4).

"As a diamine represented by the above formula (ΧΙ), in the formula (χι), a "NH2-(R6_)ph_A6_〇_, which is bonded to the carbon on the benzene ring, respectively, but 褫The 遂 bond is in the meta or para carbon of the carbon bonded by the steroid skeleton. The σ is the outer two ke groups respectively bonded to the benzene ring, but preferably the bond is in the meta or alignment of the A bond. on. The diamine represented by the formula (XI) is, for example, a diamine represented by the structural formula (XI-1) to the structural formula (XI-8) of f逑 53 201022331 32945 pif.doc. [Chem. 43-1]

54 201022331 32945pif.doc [&gt;[匕 43-2]

55 201022331 32945pif.doc From the viewpoint of exhibiting a desired pretilt angle in the liquid crystal display element, the diamine of the polylysine which constitutes the liquid crystal alignment agent of the present invention preferably contains 1 in a molar ratio. From 0.01 to 90% of the diamine having a side chain structure, more preferably from 5% to 70% of the diamine having a side chain structure. Further, the diamine used in the present invention may further contain a diamine having no side chain structure. A diamine having no side chain structure means a diamine having no substituent (side chain) which branches autonomously when a substituent linking two amino groups is used as a main chain, and can exhibit desired Pretilt angle. The diamine having no side chain structure may, for example, be a compound represented by the following formula (1) to formula (νπ), formula (XV), formula (N) and formula (a). 56 (I) 201022331 32945pif.doc

H2N—X—NH2 η η2ν^—^·νη2Η2Ν〇-γ-〇 h2nC^nh2 νη2

Η2ν〇·ΥΌΥΌνη2

(II) (Hi) (IV) (V) (VI) (νιι) (1) m (2) η (“” 丨 νη2 (Ν) η2ν

-ΝΗ, Ν η2ν In the formula (1), X represents -(CH2)m- (m represents an integer of 1 to 6), and in the formula (III) and the formula (V) to the formula (VII), Y independently Represents a single bond, 〇-, S-, _S-S-, -S02-, -CO-, -CONH-, -NHCO-, -NH-, -N(CH3HCH2)mN(CH3)-, -C( CH3)2-, -C(CF3)2-, -(CH2)m-, 57 201022331 32945pif.doc -0-(03⁄4)^, -S-(CH2)mS-(m represents an integer of 卜6), In the general formula (v), 'Z represents a single bond or does not exist. In the general formula (χν), r33 and r34 each independently represent a carbon number of 1 to 3, and A3 independently represents a sub-f group and a benzene. A subphenyl group substituted with a base or a domain group, 丨 represents an integer of 丨~6, and m represents an integer of 1 to 10. In the general formula (11) to the general formula (νπ), the hydrogen on the alkane ring or the benzene ring may be independently substituted by _F, _CH3, Θ = == 卿2, and the benzene ring in the formula (IV) On the key. The general-purpose towel 'A1' indicates that the alkyl group, the ethylamine, the fluorine, and the n n number are 1 to 3 groups, and m represents an integer of 0 to 3 cm. In the formula (4), L! represents an anthracene, an alkyl group having a number of 1 to 4, a strepyl group or a benzyl group. The diamine represented by the formula (I) may, for example, be a diamine represented by the following structural formula (1-1) to structural formula (1_3). Ο H2N(CH2)2NH2 H2N(CH2)4NH2 H2N(CH2)eNH2 (M) d-2) (1-3) As the diamine represented by the formula (II), for example, the 锗 configuration can be described. (II-1), a diamine represented by the structural formula (11-2).化~|^ρΝΗ2 η2ν-(^)-νη2 Η2Ν~ (ΙΙ-2) (11-1) Structure 2 = can be cited as β 58 201022331 32945pif.doc [Chem. 47]

The diamine represented by the formula (IV) is, for example, a diamine represented by the following structural formula (IV-1) to structural formula (IV-17).

h2nhQ-nh2 h2n-Q-nh2

(IV-1) (IV-2)

HO

COOH

H2N, v, NH2 (!V-8)

In the case of the diamine represented by the formula (V), for example, a diamine represented by the following structural formula (V-1) to structural formula (V-37) can be mentioned. [化 49-1]

(V-13) (V-14) (V-15) ^-〇&quot;°^0Ό-νη2 η2νη〇κ°—〇λ_τνΗ2 (V-16) (V-17) h2n-^°—°^k -nh2 h2n-Qk°——o^-NH2 (V-18) (V-19) 60 201022331 32945pif.doc [化49-2] h2n Ο (V-21) (V-20) h2N~~C~ ^~s~~s~C~^~nh2 HzN~HC~^s^s&gt;'sC~^~NH2 (V-22) (V-23)

H2n^QS—s-〇-NH^ h2n-^ks—sQ-nh2 (V-24) (V-25) h2n-^Ks'-^^s^J^NH2 (V-26) h2n-〇^ S—-S^h2 (V-27)

OH OH

HQ

(V-33)

(V-34) h2n

(V-35) nh2 (V-36) 61 201022331 32945pif.doc

(V-37) [Chem. 49-3] h2n The diamine represented by the formula (VI), for example, a diamine represented by the following structural formula (VI-1) to structural formula (VI-6) . [化 50] ^ ^ -nh2

(VI-1) (v|-2) Noisy. 0 points are called Η2Ν^^〇γ々ΝΗ2 (VI-4)

ΝΗ2 (VI-5) (VI-5) η2ν (VI-5) Examples of the diamine represented by the formula (vii) include the following formula (VII-1) to (VII). -16) The diamine represented. 62 201022331 32945pif.doc [Chem. 51]

H2n

NH2 h2n (Vtl-1) h2n

Ch2

(VU-3)

(VH-5)

(VII-7)

NH2 (VH-2)

Nh2 (VIM) h2n

Nh2 (VII-6)

H2N

NH (VII-8) nh2 (VII-9) (VI MO) H2N_^^°'vC^ch2V〇k〇nC)k&quot;nh2 hzn'^C^0'vO^ch2^O^0&quot;O_nh2 (VII -11) (VII-12)

(VH-15) (Vll-ΐβ) The diamine represented by the formula (XV) is, for example, a compound represented by the following formula (XV-1). And the like. (N)-l~Structure Formula (N)-2, Structural Formula (N)-5~Structure Formula (N)-7, Structural Formula (N)-9~Structure Formula (N)-10, Structural Formula (N -14, Structural Formula (N)-17~Structure Formula (N)-18, Structural Formula (N)-21~Structure Formula (N)-23, Structural Formula (N)-26 and Structural Formula (N)- Compound represented by 28. 201022331 32945pif.doc [化53] η2ν- η2ν

/ν~0^νη2 (Ν)-1 (Ν)-2

CI η2ν

CI

Ν Ν—^ jj~~ΝΗ2 (Ν)-6 Ο

Br, Η2Ν

H3cq η2ν

(Ν)-7 Ν^~~^Ν (Ν)-10

Br H3COCHN ΗΗmC^'nh2 h2n-^^nC/n_&lt;Cj&gt;_i NHCOCH3 νη2

〇ch3 &gt;-νη2 (Ν)-9 Η2Ν—Ν'^/ν~^~&quot;^~~νη2 (Ν)-14 η2ν

Ν Ν \f (Ν)-17

ΝΗ2

Η2ν·

NHCOCH3 NHCOCH3〇-^^ΝΗ2 (Ν)-21 η2ν

(Ν)-18 och3 h3covN^fsl (Ν)-22

Ηη2

Cl η2ν

Ν Ν Ν_/ (Ν)-23

Νη2 JHL Factory ' HsN \_ν~Ν\_/Ν.

/^ΝΗ2 (Ν)-26

Hgcq η2ν

Och3 H3cq &lt;DCH3 ΝΗζ (Ν)-28 65 201022331 32945pif.doc The diamine represented by the formula (a) is, for example, represented by the following structural formula (a-Ι) and structural formula (a-2). compound of. [化54] h2n

(a-1)

Among these diamines, the diamine having no side chain structure preferably has the structural formula (IV-1) to the structural formula (IV-5), the structural formula (IV-15) to the structural formula (IV-17), Structural formula (V-1) to structural formula (V-13), structural formula (V-26), structural formula (V-27), structural formula (V-31), structural formula (V-33), structural formula (V-35)~Structure Formula (V-37), Structural Formula (VI-1), Structural Formula (VI-2), Structural Formula (VI-6), Structural Formula (VII-1)~Structure Formula (VII) -5) and the diamine represented by the structural formula (XV-1), more preferably structural formula (IV-1), structural formula (IV-2), structural formula (IV-15) - structural formula (IV-17) ), structural formula (V-1) to structural formula (V-13), structural formula (V-33), structural formula (V-35) to structural formula (V-37), structural formula (VII-2), A diamine represented by the structural formula (XV-1), the structural formula (N)-1, the structural formula (N)-2, the structural formula (N)-14, and the structural formula (a-Ι). From the viewpoint of exhibiting electrical properties required for ion density or the like in the liquid crystal display element, it is preferable to use a molar ratio in the diamine of the poly-proline which constitutes the liquid crystal alignment agent of the present invention. Contains 1〇/. ～98% of the diamine having no side chain structure, more preferably 10% to 95% of the diamine having no side chain structure. The diamine in the present invention can be used as described in the formula (1) to the formula (VIII), the formula (X) to the formula (XI), the formula (XV) and the formula (N) 201022331 32945pif.doc Other diamines other than diamines. Examples of the other diamines include naphthyl diamines having a naphthalene structure, fluorene-containing amides, diamines represented by the following general formulae (XII) and (XIII), and a diamine having a side chain structure other than Z (VIII) and formula (X) to formula (XI): [Chem. 55]

R10 r11 In the formulae (XII) and (XIII), Α7 independently represents _〇_ or an alkenyl group having a carbon number of . Further, in the formula (XII), R9 represents _H or an alkyl group having a carbon number of from 3% to 3 Å, and in the alkyl group, any _CH of an alkyl group having a carbon number of from 2 to 30 is 瘳-〇-( Here, it is not continuous), -CH=CH- or -OC-substitutes two A8^Joe single bonds or alkenyl groups having a carbon number of 1 to 3, and ring T represents fluorene, fluorenyl or i, 'cyclohexene, h Further, in the formula (ΧΙΠ), r1g&amp; shows a burnt group having a number of breaks of 6 to 22, and R11 represents a burnt ring having a carbon number of 〜22. In the diamine represented by the above formula (XII), the amino group in the rain is successively attached to the carbon of the benzene ring, but the Wei scale is in the meta position of the a7. The diamine represented by the formula (XII) is exemplified by a diamine of the formula ραι-υ to the formula (ΧΠ-8). Μ举 following 67 201022331 32945pif.doc [Chem. 56-1]

R29 R29

R30

68 201022331 32945pif.doc

[化56-2] R3〇

In the diamine represented by the above formula (xiii), in the formula (xm), :: ammonia is bonded to the carbon on the benzene ring, but is preferably bonded to the meta position relative to the octa 7 or The diamine represented by the formula (χιπ) in the para position is described in the formula (XJiJ-) to the formula (ΧΙΠ-3). Su $ can be enumerated as τ 69 201022331 32945pif.doc [ 57]

In the general formulae (XIII-1) to (XIII_3), R31 preferably represents an alkyl group having 6 to 22 carbon atoms, and more preferably an alkyl group having 6 to 20 carbon atoms. R32 preferably represents -H or an alkyl group having 1 to 22 carbon atoms, and more preferably represents an alkyl group having 1 to 10 carbon atoms. Examples of the other diamines include compounds represented by the following formula (Γ) to (8'). 201022331 32945pif.doc

[化58]

R36 independently represents the carbon number

In the formula (Γ) to the formula (8,), R35 and an alkyl group of 3 to 30 are used. In the liquid crystal alignment agent constituting the present invention, the ratio of C_ine) to diamine is less than that of the diamine in the process of not damaging the present invention (IV) for the diamine, in the monoamine The termination of the polymerization reaction when the 'partial replacement of the diamine, the equimolar range of polyamine, and the substitution of the valinate, the substitution of the species can cause the formation to no longer proceed, and the through-axis species is called a difficult reaction. The molecular weight of the polymerization (polyglycine or a derivative thereof) obtained by the method of 2010 201031 31 32945 pif. doc can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The diamine substituted with a monoamine may be one type I or two or more types as long as the effects of the present invention are not impaired. The monoamine may, for example, be a present amine (-), 4, phenylaniline (4_hydr〇xyanmne), cyclohexylamine (Cyd〇heXylamine), n-butylamine (n-butylamine), n-pentylamine, n-hexylamine, or Heptamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, N-octadecylamine and n-dodecylamine. 0. The polystamic acid or a derivative thereof, the monomeric towel, may also be improved to include a monoisocyanate compound. By including a monoisocyanate compound in the monomer, the terminal of the obtained polyacrylic acid or a derivative thereof can be modified to adjust the molecular weight. By using this terminally modified polylysine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. In view of the above, 5, the content of the monoisocyanate compound in the monomer is preferably 丨 mol% to 10 mol%/〇 with respect to the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. ~ In addition to the tetralinic acid represented by the general formula (TC-1) to the general formula (TC_14), and the diamine represented by the general formula (VIII) and the general formula (X) to the general formula (XI) The polyaminic acid or a derivative thereof can be produced in the same manner as the well-known polyaminic acid or a derivative thereof used in the formation of a film of a polyimide. The total addition amount of the four resorcinic dianhydrides is preferably equal to the total mole of the diamines, such as the molar ratio of 0.9 to 1.1. The molecular weight of the polyamic acid or a derivative thereof is preferably 10,000 to 5 GG, GGG, more preferably 2 Å, _2 to 2 (8), based on the weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyacrylic acid or its derivative can be determined by using gel permeation chromatography ((5)

The Permeation Chromatography (GPC) method was measured and determined. The polyaminic acid or a derivative thereof can be confirmed by the presence of a large amount of defects by infrared spectroscopy (Infrared spectr〇sc〇py, ir) and nuclear magnetic resonance (NMR). The solid component obtained by precipitation of the solvent was analyzed. In addition, the monomer to be used can be confirmed by decomposing the polyamic acid or a derivative thereof with an aqueous solution of a strong alkali such as KOH or NaOH and using gas chromatography (GC), which is highly efficient. High Performance Liquid Chromatography (HPLC) or Gas Chromatograph-Mass Spectrometer 'GC-MS is used to analyze the extract obtained from the decomposition mixture using an organic solvent. The liquid crystal alignment agent of the present invention may further contain the polypyridic acid or other components other than the derivative thereof. The other ingredients may be one type or two or more types. For example, the liquid crystal alignment agent of the present invention may further contain an alkenyl group-substituted nadicki-imine compound from the viewpoint of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The alkenyl-substituted nadick-yourmine compound may be one compound or two or more compounds. The content of the alkenyl-substituted nadicylimine compound is preferably 0.01 in terms of the weight ratio of the poly-proline or the derivative thereof in the liquid crystal alignment agent, from the viewpoint of the above-mentioned 73 201022331 32945 pif. 〜1.00, more preferably 0.01~〇·7〇, and step i is selected from 0.01 to 0.50. The alkenyl-substituted nadicylimine compound is preferably a compound which can be dissolved in a solvent which dissolves the poly-proline or the derivative thereof used in the present invention. Examples of such a fine group-substituted Nadick-based imine compound can be exemplified by the compound represented by the following formula (Ina). [化59]

In the general formula (Ina), L1 and L2 each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and An aryl or a benzyl group, n represents 1 or 2. When n=l, W represents an alkyl group having a carbon number of i to 12, an alkenyl group having a carbon number of 2 to 6, a cycloalkyl group having a carbon number of 5 to 8, and a merma, a carbon having a carbon number of 6 to 12. Base, with 』(〇)#〇)Name H (zl, Z2, and z3 independently represent the base of carbon tolls 2 to 6, q is 〇 or 卜 and r is the number of 卜孙), ~ (zVb_z5_h (z4 and the standing indicates that the carbon two is a ring of 1 to 4 or a ring with a carbon number of 5 to 8, and Β represents a second stupid, and the s table is not 0 or 〗)) -Τ-Β-Η(Β denotes subphenylene' and τ denotes _CH2_, _c(CH3)2_, _〇_, carry _, ^_ or SCV) (4) base, or one of the wires ~3 The hydrogen is substituted by a hydroxyl group by a group of 201022331 32945pif.doc. In this case, preferred W is a carbon group having a carbon number of 1 to 8, an alkenyl group having a carbon number of 3 to 4, a cyclohexyl group, a phenyl group, or the like. a benzyl group, a poly(ethyleneoxy)ethyl group having a carbon number of 4 to 1 Å, a phenyloxy phenyl group, a phenyl methyl phenyl group, and a benzene group. Phenyl isopropylidene phenyl, and one or two of these hydrazines are replaced by hydroxy groups Into groups.

When n=2 in the general formula (Ina), W represents an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, and an arylene group having 6 to 12 carbon atoms. ), the base represented by -Ζ^Ο-θονζ3#1 to Z3 and r as described above, and the base represented by -Z4_B-Z5- (the meaning of Z4, Z5, and B are as described above) -B-(0-B)sT-(B-0)sB-(B represents a subphenyl group, τ represents an alkenyl group having a carbon number of 1 to 3, or _S〇2_, s represents 〇 or 丨) The group represented by the group or a group in which one to three hydrogens of these groups are substituted with a hydroxyl group. ^At this time, 'the preferred one is an alkenyl group having 2 to 12 carbon atoms, cyclohexene, phenylene, tolylene, xylylene, and -C^-O-^OVO. -CKZ2 represents an alkenyl group having 2 to 6 carbon atoms, r represents a group represented by 1 or 2), _Β_Τ_Β_ (Β represents a subphenyl group, and τ represents -Ον, _〇- or ·δ〇2_) The group represented by the group represented by f-〇_B-C3H6_B-0-B-(B represents a phenyl group) and a group in which one or two hydrogens of these groups are substituted with a hydroxyl group. — such an alkenyl-substituted nadicylimine compound can be used, for example, as described in Japanese Patent No. 2729565, by maintaining a dilute quinamic acid if derivative and a diamine at a temperature of 2, 2, 2 32945 pif.doc A compound or substance obtained by synthesis in an hour to 20 hours. The compound shown below is a compound which is a substituting group of a nadic ylidene imine compound. It can be N-methyl-dilylbicyclo[2 21]hept-5-ene-2,3·diindolemethyl-propylpropylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, methyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine, benzyl-methylallylmethylbicyclo[221 Geng _5-ethylidene-amine, amide, Ν-(2-ethylhexyl)-allylbicyclo[2 21]g _ : methyl imidate, 岬乂 3 dimethyl hydrazine暴暴) _ propyl (indenyl) bicyclo [2 2a dimethyl sulfoximine, N-allyl-allyl bicyclo [2 · 21] g · 5 ·, j, 3 quinone imine, Ν · Allyl-propylpropylmethylbicyclo[2 21]g,3-^ quinone imine, Ν-propyl-decyl propyl bicyclo[2.2.1]g _5 ,, 醯imino , Ν·isopropyl County, propyl bicyclo [2·21] g _ _, 3 _ di quinone imine, Ν • isopropenyl-allyl (methyl) bicyclo [2.2.1] g _ 5: two A 曱醯 曱醯 imine, Ν · isopropyl _ methallyl bicyclo [2 secret, 3- two

Dimethyl imine, Ν-cyclohexyl, propyl bicyclo [2 2. 丨] heptanimide, Ν·cyclohexyl·allyl (indenyl) bicyclo [, '^-methionine, Ν· Cyclohexyl-methyl-propyl propyl double 21]hept='3-di-indenine, fluorenyl-phenyl-allyl bicycloalkenene 3_imine, ^2,3-dimethyl hydrazine-benzene -Allyl (methyl) bicyclo [2 imine, Ν 节 , , propyl bicyclic like W A 3 broth N-pyringyl - propyl methyl bicyclo [2.2 imine, π, Imine imine, N-76 201022331 32945pif.doc benzyl-decyl propyl bicyclo [2.2.1] g · 5 · dilute _2, 3 dimethyl anilide - hydroxyethyl) 娣 娣Bicyclo[2.2.1]hept-5-ene-2,3-diimineimine, Ν-(2-hydroxyethyl)-allyl (indolyl)bicyclo[22]]heptene·- Yttrium imine, Ν-(2-hydroxyethyl)-methylallylbicyclo[m]heptane-2,3-diindole, imine-(2,2-di-f--3- Propyl)-allylbicyclo[2 21]heptane

-2,3-dimethylimine, N-(2,2-dimethyl-3-hydroxypropyl)-allyl (methylbicyclo[2.Z1]hept-5-ene-2,3 -dimethylimine, called 2,3-dihydroxypropylpropylbicyclo[2.2.1]hept-5-ene-2,3-diindoleimine, N-(2,3-dihydroxypropyl )-allyl (indenyl)bicyclo[2.2.1]hept-5-ene-2,3·diimine imine t N-(3-hydroxy-i-propenyl)-allylbicyclo[221 G?___ene_2,3_dimethylimine, N-(4-hydroxycyclohexyl)-allyl (methyl)bicyclo[2 2丨]hept-5-ene-2,3- Diquinone imine, n-(4-phenylphenyl)-propylpropyl bicyclo [22.ηg_5_wo-2,3-dimethylenimine, anthracene-(4-hydroxyphenyl) _Allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-diimineimine, Ν-(4-hydroxyphenyl)-methylallylbicyclo[2.21]g _5_ ene-2,3-dimethylimine, Ν-(4-hydroxyphenyl)-methylallylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Imine, Ν-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, ν_(3-hydroxyphenyl)-allyl (fluorenyl)bicyclo[2.2.1]hepta-5_蝉-2,3-dimethylimine, Ν•(p-hydroxybenzyl)-propylpropylbicyclo[2.2.1]hept-5-ene- 2,3-dimethyl醯iamine, Ν·{2_(2-hydroxyethoxy)ethyl}-allylbicyclic hydrazine.2.1]gly-5-ene-2,3-dimethylanimine, Ν-{2-( 2·Hydroxyethoxy)ethyl}•allyl (methyl)bicyclo[2 21] 77 201022331 32945pif.doc Hept-5-ene-2,3-diimine, Ν·{2-( 2-hydroxyethoxy)ethyl}-mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν-{2-(2-hydroxyethoxy) Ethyl}-mercaptopropyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3·diindole imine, Ν[[2-{2-(2-ylethylethyl) Ethyl]ethyl]-dilyl bis-[2.2.1]hept-5-ene-2,3-diimine, 沁[2-{2_(2-hydroxyethoxy)B Oxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν-[2-{2-(2-hydroxyethoxy) Ethyl}ethyl]-mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine, Ν-{4-(4-hydroxyphenyl iso- Propyl)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, fluorene-{4-(4-hydroxyphenylisopropylidene)phenyl Allyl (fluorenyl)bicyclic guanidine .2.1]g-5-ene-2,3-diimine, Ν-{4-(4-hydroxyphenyl isopropylidene Phenyl}-mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-diimine, and oligomers thereof, oxime, Ν'-ethylene bis ( Allyl bicyclo [2.2.1] hept-5-ene-2,3-diimide imine), hydrazine, Ν'-ethylene-bis(allylhydrazinobicyclo[2.2.1]hept-5- Alkene-2,3-diimineimine), hydrazine, Ν'-ethylene-bis(mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), Ν,Μ-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), anthracene, Ν'-hexamethylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3·diimide), hydrazine, Ν'-hexamethylene-bis(allylhydrylbicyclo[2.2.1]g-5 -ene-2,3-diimineimine), anthracene, Ν'-dodedecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diazide Amine), 1^^-dodedecyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), anthracene, Ν'-cyclohexene Alkene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), anthracene, fluorene-cyclohexene-bis(allylhydrazinobicyclo[2.2.1 ]hept-5-ene-2,3-dioxime 201022331 32945pif.doc imine), 1.2-double {3'-( Propyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine imine) propoxy}ethane, 1,2-bis{3'-(allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-diimideimine)propoxy}ethane, 1,2-bis{3'-(nonylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine imine)propoxy}ethane, bis[2匕{3'_(allylbicyclo[2.2.1]hept-5-ene-2,3-diindole Imine)propoxy}ethyl]ether, bis[2'-{3'-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dimethylidene@amine) Propoxy}ethyl]ether, 1,4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)propoxy}butane 1,4_bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine)propoxy}butane, ]^,:^ - p-Phenyl-bis(allylbicycloindole.2.1)hept-5-ene-2,3-diimineimine), N,N'_p-phenylene-bis(allylmethyl) Bicyclo[2.2.1]hept-5-ene•2,3-dimethylimine), hydrazine, Ν'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-diimine), hydrazine, Ν'-m-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimineimine) , :^, ^'-{(1-indolyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), hydrazine, Ν'- 〇 p-Diphenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), hydrazine, Ν1ί 曱 phenyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine), hydrazine, Ν'-m-phenylenedifluoryl-bis(allylbicyclo[2.2.1] g- 5-ene-2,3-diimineimine), hydrazine, Ν'-m-xylylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-di曱醯imino), 2.2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenoxy}phenyl]propane, 2, 2-double 79 201022331 .32945pif.doc [4 曱 (mercaptopropyl double ring [2.21] g _5_ dilute _2, 3 oxy} phenyl] propyl, double {4- (dilyl bis bicyclo [ 221] Gg_5 dil 23 amine = quinone imine) phenyl} decane, bis {4_(allylmethyl bis heptane-2,3-diimideimine) phenyl} methane, Deng "double { 4-(Methylallylbicyclo[2.2.lm_52,3•Diennimine) Benki}A Hyun, Double {4-(曱Allyl fluorenylbicyclo[2 21]g _5_diluted _2,3_ diimineimine)phenyl}, bis{4_(allylbicyclo[2.21]g _5_rare-2, 3-diimineimine)phenyl}ether, bis{4_(allylmethylbicyclo[2 2 -5 ru 2,3 bis quinone imine) phenyl) ether, double bud Propylbicyclo[2_2·1]hept-5-ene-2,3-dimethylenimine)phenylhong, biguanide propyl bicyclo[2.2.1] g-5·ene-2,3-di甲 亚 ) ) 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基Methylallyl bicyclo [2·2·1] Geng 办 曱醯 phenylene] hind, 1,6 · bis (allyl bicyclo [2.2 η g · 5 _ _ _2 gt; Amine)-3-carbyl 9, ι, ΐ 2 · bis (nonylallyl biscyclo[2 21]hept-5 sulphate-2,3-diimine)-3,6·di-based Twelve &amp;, u_ bis (allyl bicyclo [2.2.1] hept-5 · dilute _2, 3 · dimethyl quinone imine) _5 · via base ring hexane, 5_ bis {34 ally Bicyclo[2.2.^-5• olefinic dimethyl quinone imine] propoxy} hydroxypentane, 1,4 bis (allylbicyclo[2.21]hept-5-ene-2,3_2曱醯imino)-2-phenylbenzene, 1,4-bis(dilylmethylbicyclo[2 .2.lm_5,_2n_amine)-2,5-dihydroxybenzene, N,N'_p-(2-hydroxy)benzodiazepine-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine), '冲_对对(2_hydroxy) 笨 曱 · · bis (allylmethylcyclo[2.2.1]hept-5-ene-2,3-dimethyl醯imine), 201022331 32945pif.doc (2-hydroxy) benzodiazepine _ bis (allylbicyclo [2 21] hept-5 ene diimide), N, N, - (2 -transmethyl) benzylidene-bis(methyl-ylbicyclo[2.2.1]hept-5-ene-2,3-dimethylanimine), N,N'_pair (2,3_2 Styrene dimethyl-bis(allylbicyclo[2.2.1]hept-5ene-2-,3-dimethylimine), 2,2-bis[4-{4-(allyl Bicyclo[2 21]hept-5-ene_2,3-dimethylimine)_2_hydroxy-phenoxy}phenyl]propane, bis(4_(allylhydrazinobicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine imine)_2_hydroxyphenyl}methane, 〇{3_(allylbicycloindole.2.1)hept-5-ene-2,3·diindole Imine)-4-hydroxyphenyl}ether, bis{3-(mercaptopropylbicyclo[2 21]hept-5-diuretic 2,3-dimethylimine)·5_ylphenyl μ wind, 1,1,1_three {4_(allylhydrazinobicyclo [221]hept-5-ene-2,3.dimethylanilide)} phenoxy Propyl propyl, hydrazine, hydrazine, hydrazine, tris(ethenylallylbicyclopurine .2.1]hept-5-ene-2,3-dimethylimine)isocyanurate, and these Oligomers, etc. Further, the alkenyl-substituted nadicil imidized human used in the present invention may be an asymmetric alkynyl group or a phenylene group-containing compound represented by the following hydrazine. , ,,°传式❹ 81 201022331 32945pif.doc [化60]

Preferred compounds among the alkenyl-substituted nadic quinone imine compounds are listed below. N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dioximine), N,N'-ethylene bis(allylhydrazinobicyclo) P.2.1]hept-5-ene-2,3-diimineimine), N,N'-ethylene-bis(nonylallylbicyclo[2.2.1]hept-5-ene-2,3 - Dimethyleneimine), hydrazine, Ν'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, Ν'- Hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), anthracene, Ν'-hexamethylene-bis(allylhydrazino) Bicyclo[2.2.1]hept-5-ene-2,3-diimineimine), fluorene, Ν'-dodedecyl-bis(allylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine), hydrazine, Ν'-taudecyl-82 201022331 32945pif.doc bis(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3 - xylenimide), ν, Ν, - cycloheximide - bis (allyl bicyclopurine .2.1] hept-5-oxime 2, 3-dimethylanimine), hydrazine, Ν'-ring Hexene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3.dimethylanilide), hydrazine, Ν'-p-phenylene-bis(allylbicyclo[ 2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, Ν'-p-phenylene-bis ( Propylmethylbicyclo[2.2.1]hept-5·lean-2,3-carboximine), hydrazine, Ν'·m-phenylene-bis(allylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), hydrazine, ϊνΓ-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-lean-2,3-dimethylhydrazine Imine), 1^,1&lt;['-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dimethyl imine), hydrazine, Ν'-p-diphenylene bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), hydrazine, hydrazine - p-Phenylphenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, &gt; fluorene-m-xylylene bis ( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine), hydrazine, hydrazine--m-xylylene-bis (dilylpropyl bicyclo [2.2.1] Geng-5-diluted-yield imine), 2,2·bis[4-{4-(l-propylbicycloindole.2.1)hept-5-ene-2,3-diimineimine)phenoxy Phenyl]propane, _ 2,2-bis[4-{4·(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3·diimide) phenoxy }phenyl]propane, 2,2-bis[4-{4-(nonylallylbicyclo[2.2.1]hept-5-ene-2,3.dimethylanilide)phenoxy}benzene Base] , bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimineimine)phenyl}decane, bis{4_(allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-carboximine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-rare-2,3- Dimethyl imine) phenyl} decane, bis{4-(mercaptoallylmethylbicyclo[2.2.1:^_5^-2,3_diimideimine)phenyl} fluorene, double {4-(Ledylbicyclo[2.2.1]hept-5·rare 83 201022331 32945pif.doc -2,3-dimethylanimine) Stupid (four), double {4_(dilylmethylbicyclo[2] 21]hept-5-ene-2,3-dimethylimine)phenyl}ether, bis{4_(methylallylbicyclo[2·2.1]hept-5-晞-2,3-dimethyl醯imino) stupid (tetra), bis(tetra)allylbicyclo[2.2y]glycol-5-diluted-2,3-dimethylimine imine) stupid μ wind, double {4_(dilylpropyl bis-% [2.2.1]Hept-5-rare-2,3-diimineimine) Stupid}飒, bis(4_(mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3 - Diimine imine) Phenyl} oxime.

More preferred alkenyl substituted nadic quinone imine compounds are listed below. ν,ν'_ethylene-bis(allylbicyclo[221]hept-5-ene-2,3_dimethylhydrazine, ΗΝ'-ethylene·bis(allyl-f-cyclobicyclo[221]hept-5 • Rare n Q = ΪΞ), Ν, Ν, 叫 ( (4) stalk base double ring yang system - rare Τ Τ Τ 、 卿 卿 卿 卿 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ -5-ene,-diimineimine), hydrazine, hydrazine, -hexamethylene fluorenyl-bis(allylbis-;-2=dimethylanilide), ·hexa-propyl pin; k bis-imine), N'NL dodecamethylene-bis (dipropyl bis-bis[2.2.1]hept-5-ene-2,3-diimine), N, N, _ Twelve bis (allyl fluorenylbicyclo[2.2.1]g _5_diluted _2,3 bis quinone imine), Nf = banister-bis(allylbicyclo[2.21]g _5_ Dilute _2,3_dimethylenimine, cyclohexene-bis(dipylmethylbicyclo[2 21]hept-5-ene-2,3_imine), τ occupation ν, ν'_ p-Phenyl-bis(allylbicycloindole.21]hept-5-eneindole 3_diimine), hydrazine, Ν'-pair: under-phenyl bis(allyl-decylbicyclo[221] Geng_5_diluted 2,3-dimethyl quinone imine), hydrazine, hydrazine, -m-phenyl bis(allylbiscyclo-5-ene-2,3-diimineimine), hydrazine , Ν, _ interstitial-bis(allyl hydrazine Bicyclo[2.2.1]hept-5-ene-2,3-diimineimine), taken.](1_methyl)_2, 4_times to 84 201022331 32945pif.doc bis(allyl) Bicyclo[2.2.1]hept-5-oxime-2,3-carboximine), N,N'-p-dimethylphenyl-bis(allylbicyclo[2.2.1]hept-5-ene _2,3-dimethylimine), n,n'-p-diphenylphenyl-bis(allylmethylbicyclo[m]hept-5-ene-2,3·diimide) , N, N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N,_ stupid _Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), +2,2-bis[4-{4-(allylbicyclo[2] 21]g-___ene_2,3_diindole φ amine)phenoxypurine phenyl]propane, 2,2_bis[4-{4-(allylmethylbicyclophene P.2.1) Hg-5-ene-2,3-diimineimine) phenyloxy}phenyl]propane, 2,2- bismethylallylbicyclo[2.2.1]hept-5-ene-2,3 _ Diimine imine) phenoxy}phenyl]propane, bis(4-(10)propylbicyclo[2 2 1;]g-5 ruthenium 2,3-diimine) , bisallylhydrazinobicyclo[221]hept-5-ene-2,3-dimethylimine)phenyl}methane, double {4-(methallyl) Bicyclo[2.2.1]hept-5-ene-2,3-diimineimine) stupid}methane, double {4_(methylallylmethylbicyclo[2.2.1]hept-5-lean_ 2,3_dimethylimine imine)phenyl}methane. Further, 'as a particularly preferred alkenyl-substituted nadicylimine compound, a double {4-(allylbicyclo[2.2.1]hept-5 represented by the structural formula (Ina-Ι) shown below can be cited. -ene-2,3-diimineimine)phenyl}methane, n,N,-m-xylylene-bis(allylbicyclo) represented by the formula (Ina-2) [2.2.1 ]hept-5-ene·2,3-dimethylimine), and N,N′·hexamethylene-bis(dipropylbicyclo[2.2.1]g, represented by the structural formula (Ina_3) -5-rare-2,3-diimine). 85 201022331 32945pif.doc [Chem. 61]

In addition, for example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond, for example, in order to stabilize the electrical properties of the liquid crystal display device for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one compound or two or more compounds. Further, the alkenyl-substituted nadic quinone imine compound is not included in the compound having a radical polymerizable unsaturated double bond. 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 0 01, based on the weight ratio of the polyglycine or a derivative thereof. ～0 70, further preferably 〇.〇1 ～0·50. Further, in terms of reducing the ion density of the liquid crystal display element, suppressing the increase in the ion density with time, and further suppressing the afterimage, the compound having a radical polymerizable unsaturated double bond is substituted with the alkenyl group in place of the nadic ylidene compound. The ratio is preferably 0.1 to 10, more preferably 0.5 to 201022331 32945 pif. doc, and the compound having a radical polymerizable unsaturated double bond may, for example, be a (meth)acrylic acid vinegar or a methyl group. a derivative such as acrylamide or a bismaleimide (10) maleimide). The compound having a self-polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more free radically polymerizable unsaturated double bonds. Specific examples of the (meth) acrylate include (fluorenyl) φ cyclohexyl acrylate, (mercapto)acrylic acid 2·methylcyclohexyl ester, and dicyclopentanyl (meth)acrylate. Mercapto)dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth) acrylate, benzyl (mercapto) acrylate (nonyl) 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Specific examples of the difunctional (meth) acrylate include, for example, Ethylene diacrylate, East Asia Synthetic Co., Ltd. products Ar〇nix M_21〇, Aromx M-240, and Aronix M-6200, Japanese chemical Products of KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd. © V260, V312 and V335HP, and products of Kyoeisha Chemical Co., Ltd.

Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA. Specific examples of the trifunctional or trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4,-methylenebis(indene, fluorene dihydroxyethylene acrylate aniline), Aronix Μ- 400, Aronix Μ-405, Aronix

M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD 87 201022331 32945pif.doc DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 and Osaka Organic Chemistry Industrial (share) product VGPT. Specific examples of the (fluorenyl) acrylamide derivative include, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, N-n-propylpropenylamine, and N-positive Propylmercapto acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl decyl acrylamide, N-ethoxyethyl acrylamide, &amp; ethoxyethyl decyl propylene oxime Amine, hydrazine, tetrahydrofurfuryl acrylamide, hydrazine, tetrahydrofurfuryl methacrylamide, hydrazine-ethyl acrylamide, hydrazine-ethyl-fluorenyl hydrazide, hydrazine, hydrazine Ethyl acrylamide, hydrazine-methyl-hydrazine-n-propyl acrylamide, 10 Ν-methyl-hydrazine-isopropyl acrylamide, hydrazine-acrylonitrile fluorene, hydrazine-acrylonitrile Pyrrolidine, anthracene, Ν'-methylenebis acrylamide, hydrazine, hydrazine, -ethylene bis acrylamide, hydrazine, hydrazine-dihydroxyethylene bis acrylamide, ν-(4-hydroxyphenyl) Mercapto acrylamide, Ν-phenylmercapto acrylamide, Ν-butyl methacrylamide, Ν-(isobutoxymethyl)methacrylamide, Ν-[2-(Ν,Ν· Dimercaptoamino)ethyl]decyl acrylamide, hydrazine, hydrazine dimethyl methacryl decylamine, hydrazine-[3-(dioxin IL-based) propyl] mercapto acrylamide, hydrazine-(decyloxy) decyl acrylamide, N-(methylidene)-2-methacrylamide, ν-benzyl-2 Methyl acrylamide is hydrazine and N, N'-methylenebismercapto acrylamide. Among the (meth)acrylic acid derivatives, particularly preferably, anthracene bis acrylamide, hydrazine, Ν'-dihydroxyethylene bis acrylamide, ethylene diacetate, and 4,4'-fluorenylene (Ν, Ν-dihydroxyethylene acrylate aniline). Examples of the bismaleimide include ΒΜΙ·7〇 and BMI-80 manufactured by INDUSTRY CHEMICAL INDUSTRY, and BMI-1000, BMI-3000, and BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. 88 201022331 32945pif.doc BMI-5000 and BMI-7000. Further, for example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound from the viewpoint of long-term stability of electrical properties in the liquid crystal display element. The oxindole compound may be one compound or two or more compounds. In view of the above, the content of the oxazine compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, based on the polyamic acid or a derivative thereof. The step is preferably from 1% by weight to 20% by weight. The oxazine compound is preferably soluble in an oxazine compound which can dissolve a solvent of poly-proline or a derivative thereof and has ring-opening polymerizability. Further, the number of the oxazine structure in the oxazine compound is not particularly limited. The structure of the oxazine is known in various structures. In the present invention, the structure of the oxindole is not particularly limited, and the oxazine structure in the oxazine compound may be exemplified by a benzoxazine or a naphthoxazine having a condensed polycyclic aromatic group. The structure of an aromatic oxazine. Examples of the oxazine compound include compounds represented by the following formula (a) to formula (f). Further, in the following formula, a bond represented toward the center of the ring means that the bond is bonded to any of the carbon constituting the ring and which may bond the substituent. w 89 201022331 32945pif.doc

In the above formula (a) to formula (c), R1 &amp; R2 represents an organic group having 1 to 30 carbon atoms. Further, in the above formula (8) to the formula (0, R3 to R6 represent hydrogen or a ketone having a carbon number of 1 to 6. Further, the above formula (c), formula (phantom and formula (f)) In the X table, the early key, _S-S-, -S〇2-, -CO-, -CONH-, _NHCO_, _C(CH3)2-, _C(CF3)2-, -(CH2)m, -0-(CH2)m〇-, -S-(CH2)mS-. Here, 'm is an integer of 1 to 6. Further, in the above formula 0) and formula (f), Y independently represents a single bond, -〇-, -S-, -CO-, -C(CH3)2-, -C(CF3)2_ or a ruthenium group having a carbon number of 1 to 3. The bond in the γ is The hydrogen of the benzene ring or the naphthalene ring may be independently substituted by _F, _CIi3, -OH, -COOH, -S03H, ·Ρ〇3Η2. In addition, the oxazine compound includes an oligomer having an oxazine structure in a side chain. In the case of the oxazine compound represented by the formula (a), for example, the oxoxine compound of 201022331 32945pif.doc can be cited.

(a-1) (a-2) In the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably a hospital group having 1 to 20 carbon atoms. Examples of the oxazine compound represented by the formula (b) include the following oxime compounds. 91 201022331 32945pif.doc [Chem. 64]

In the formula, R1 is preferably an alkyl group having a carbon number of 1 to 30, and more preferably a alkyl group having a carbon number of 1 92 201022331 32945 pif.doc 〜20. The oxazine compound represented by the following formula (c-I) is exemplified by the oxazine compound represented by the following formula (C). [Chem. 65]

(c-I)

In the above formula (cI), R1 and R2 represent an organic group having a carbon number of 1 to 30, R3 to R6 represent an anthracene or a hydrocarbon group having 1 to 6 carbon atoms, and X represents a single bond, -CH, ·, -C (CH3) 2_, -CO-, -0-, -S〇2· or _C(CF3)2_. The oxazine compound represented by the above formula (c-I) may, for example, be the following acetonide compound. 93 201022331 32945pif.doc [Chem. 66·1]

94 201022331 32945pif.doc

[Chem. 66-2]

(c-15)

(〇14) 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 oxazine compound. 95 201022331 32945pif.doc [Chem. 67]

(d-9)

(d-10)

The oxazine compound represented by the formula (e) may, for example, be the following acetonide compound. 96 201022331 32945pif.doc [Chem. 68]

Φ As the oxime compound represented by the formula (f), for example, the following oxazine compounds can be mentioned. 97 201022331 32945pif.doc [Chem. 69]

98 201022331 32945pif.doc Among these oxazine compounds, more preferably, the formula (b-1), the formula (c_i), the formula (IV), the formula (IV), the formula (IV), the formula (IV), the formula (4) to the formula (IV), the formula (Μ), An oxazine compound represented by the formula (e-4) and the formula (f-2) to the formula (f-4). The oxazine compound can be used in the same manner as 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 Laid-Open Publication No. Hei. The way to manufacture. For example, the oxazine compound represented by the formula (a) can be obtained by reacting a phenol __ηο1) compound, a primary amine, and an aldehyde (aidehyde) (refer to International Publication No. 2004/009708). Further, the oxazine compound represented by the general formula (b) can be obtained by a method in which a primary amine is slowly added to a method of adding a primary amine to a yde, and a naphth〇1 is added. The compound is reduced by reaction (refer to International Publication No. 20〇4/〇〇97〇8). Further, the oxazine compound represented by the general formula (c) can be obtained by - in the organic solvent, the sullen compound of the oxime, relative to Q, is at least 2 moles per benzene. Or 2 molars or more, reacting with a primary amine of moir in the presence of an aliphatic sec〇ndary μ es, aHphatic tertiary amines or an inert nitrogen-containing compound ( Reference is made to the International Publication No. 2004/009708 and Japanese Patent Laid-Open No. 1M2258. Further, the oxazine compound represented by the general formula (d) to the general formula (f) can be obtained by having 4, 4, diaminodiphenylmethyl having a plurality of benzenes in n-butanol. The ring and the aldehyde of the organic group of the benzene ring, the aldehyde such as Foma or the like, and the phenol are subjected to a dehydration condensation reaction of 99 201022331 32945 pif.doc at a temperature of 9 〇〇c or more (refer to Japanese Patent Laid-Open No. 2004-352670) Bulletin). Further, for example, from the viewpoint of long-term stability of electrical properties in the liquid crystal display element, the liquid crystal alignment agent of the present invention may further contain an oxalate-based compound. The oxazoline compound is a compound having an oxazoline structure. The stagnation compound may be one compound or two or more compounds. In view of the above, the content of the ruthenium compound is preferably 〇.1 heavy 〇 / 〇 〜 5 〇 wt% 'more preferably 1% by weight relative to the polyamic acid or a derivative thereof. 〜4〇% by weight, further selected as 1% by weight to 20% by weight. Alternatively, in view of the above, the content of the oxazoline compound is preferably such that when the oxindole structure in the oxazoline compound is converted to an oxazoline, the poly-proline or a derivative thereof is It is from 0.1% by weight to 40% by weight. The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more octopus structures in one compound. Further, the oxetan compound may have one oxazoline structure in one compound, but preferably has two or more oxazoline structures. Further, the oxazoline compound may be a polymer having an oxazoline ring structure on the side or a copolymer. The polymer having a smectic structure on the side chain may be a homopolymer of a monomer having a morphine structure on the side chain, or may have a wickiness on the side chain. A copolymer of a monomer of a stand-up structure and a monomer having no oxazoline structure. The copolymer having an oxazoline structure on the side chain may be a copolymer of two or more kinds of early forms having an oxazoline structure in a side chain, or may be a rain species having a sputum structure on a side bond or Copolymerization of two or more kinds of monomers with a monomer having no oxazoline structure; 201022331 32945pif.doc The preferred cavity structure towel can be inversely related to the filament of the polyamic acid (Car-) = The structure exists in the structure of the oxazoline compound. As the sputum compound, for example, it can be: =?; (2. sinensis 2 _ base) · stupid, 'biting -2- quinone quinone 嗤 5 ketone, M, (4, 5 _ Dioxane_2_Evil silk) Benzene, ^ (4,5_一虱_2' ° ° 坐 基) benzene, 2,3- bis (4-isopropyl dil _2 _ 唾 ^ ^ Shuang Na-2 - Ester (tetra), 2,6-bis(isopropyl)pyrene, 2,2-isopropylidene bis(4-tert-butyl-2-oxoline), 2 2 =ylbis(4-phenyl _2_mum), 2,2'-methylene double (4_tert-butyl oxo and 2,2-methylene bisphenyl. b: in addition to, for example, Ep_s (trade name, A polymer or oligomer having an oxazolyl group, such as manufactured by Riken Co., Ltd.: In addition, for example, in terms of long-term stability of electrical properties in a liquid crystal display element, the liquid crystal alignment agent of the present invention can be further advanced. The epoxy compound may be a compound, or may be a compound of two or more. From the viewpoint of the above, the content of the epoxy compound is relative to the poly-proline or its The derivative, σ% by weight to 5 g% by weight, more preferably 7% by weight to 4%, preferably 1% by weight to 20% by weight. There are various compounds having one or two or more epoxy rings in the molecule. As a compound having an epoxy ring in the molecule, for example, phenyl glycidyl ether can be cited (phenyi 101 201022331 32945pif.doc §1&gt; 〖611^), butyl glycidyl ether, 3,3,3-trifluoro propylene oxide, styrene oxide, hexafluoropropylene oxide, Oxycyclohexene oxide, 3-glycidoxy propyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy sulphur, N-shrinkage N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin Epichlorohydrin, epibr〇mohydrin, hydrazine, hydrazine-diglycidylaniline, and 3·[2-(perfluorohexyl)ethoxy propylene oxide. As a molecule, there are two epoxy rings. Examples of the compound include ethylene glycol diglycidyl ether: polyethylene glycol II. Glycidyl ether, propylene glycol diglycidyl ether, tripropylene = alcohol diglycidyl shunt, polypropylene glycol diglycidyl (tetra), neopentyl glycol - glycosaminoglycan (tetra), hydrazine, 6 hexanediol diglycidyl ether, glycerol condensate甘/ from ether 2,2 odor neopentyl glycol diglycidyl ether, π epoxide cyclohexane methyl oxime epoxy 5 hexamethylene broth and 3_(N,N- diglycidyl)aminopropyl Dimethoxydecane. iSi . λ r/i is a compound having two epoxy rings in the knife, for example, it can be listed as a two-epoxy two-oxyl) stupid base]-2 pieces [1,1-double [4_([2,3 _Ethylene acrylate vr^1〇1 ,]]ethyl]phenyl]propane (trade name "Techmore VG31〇1L / manufactured by Mitsui Chemicals Co., Ltd.") = compound with four epoxy rings in korai, for example Can be listed as: glycidyl · 2,4-hexanediol, n, n, military-tetraglycidyl meta-diamine, hydrazine, 3 · bis (take diglycidyl amino fluorenyl) cyclohexane 102 201022331 32945pif.doc Phenylmethane and, in addition to the compound, as an oligomer having an epoxy ring or Si in the molecule, ===: for example, (10)) acrylonitrile: alkane , condition; ^, 1 ^ tetraglycidyl _4, 4, _ diamino 3 _ (Ν · propyl propyl - Ν 'glycidyl) aminopropyl three;:: Roller insurance department, , Μ J Shi Xi Xuan's example ester (four) ddy! (meth) a Crylate), (meth) propyl _ and (meth) methacrylate methyl glycidyl ester. Nyle hexanone as a single with an epoxy ring Other examples of the copolymerization of the body include (meth)acrylic acid, (methyl) Methyl enoate, (propane N-based\propylene 5 butyl hydrazine, (methyl) propyl acetoacetate t-butyl vinegar, (¥ base} propyl _ cyclohexanol, (methyl) acrylic acid vinegar, (A Acetyl acid · 2 old ethyl vinegar, (meth) acrylic acid · 2 · thiopropyl S, styrene, methyl stupyl, chlorophenyl styrene, (meth) acrylate (3_Ethyl_3_epoxypropyl)methanil cyclohexylmaleimide and N-phenylmaleimide.

Preferable specific examples of the polymer having a monomer having an epoxy ring include polyglycidyl acrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexylmalanium. Imine-glycidyl methacrylate copolymer, benzyl methacrylate-methylpropionic acid glycidol g-copolymer, mercapto-acrylic acid butyl vinegar-glycidyl methacrylate copolymer, sulfhydryl 2-hydroxyethyl acrylate-glycidyl methacrylate copolymer, (3-ethyl-3-epoxypropyl) decyl acrylate-glycidyl methacrylate copolymer and styrene-methyl Propylene 103 201022331 32945pif.doc . Acid glycidyl ester copolymer. Among these examples, particularly preferred are ruthenium, osmium, iridium, osmium, _tetraglycidyl metaxylylenediamine, 1,3-bis(indole, fluorene-diglycidylaminomethyl)cyclohexane, hydrazine ,Ν,Ν',Ν'-tetraglycidyl_4,4,-diaminodiphenylmethane, trade name "Techmore VG3101L", 3,4-epoxycyclohexenecarboxylic acid-3,,4,- Epoxycyclohexane methyl ester, N-phenyl maleimide-methyl methacrylate glycidyl ester copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. More specifically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, acrylic resin containing epoxy 0, glycidylamine, and glycidol isocyanurate. An ester, a chain aliphatic epoxy compound, and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group. Examples of the glycidyl ethers include a double-presence A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol s type epoxy compound, a double epoxy compound, and a hydrogenated double A type epoxy compound. , hydrogenation double age F type epoxy compound, hydrogenated double expectation S type epoxy compound, hydrogenated double condensed epoxy compound, brominated bisphenol A type epoxy compound, brominated bisphenol F type epoxy compound, phenol novolac Phenol novolac type 惫彳 铷 phenol phenol novolac type epoxide, bromo phenol phenol, lacquer type epoxy compound, bromine smear varnish type epoxy compound, double scent 1 novolac Epoxy compound, epoxy compound containing naphthalene skeleton, aromatic polycondensation compound, dicyclopentadienyl epoxy compound, cyclic diglycidyl ether compound, aliphatic polyglycidyl ether compound, 9 104 201022331 32945pif.doc type dihydrated glycoside compound "and condensed water and shrinkage can be cited as diglycidyl vinegar compound. As the glycidylamine, for example, polyglycidyl amination can be mentioned.

The bupropionic acid-based compound having an epoxy group may, for example, be a homopolymer or a copolymer of a monomer having a oxiranyl group. Ring 1 = shrinkage, for example, rotten glycidylamine as the chain aliphatic epoxy compound, and examples thereof include an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound. compound of. The cyclic aliphatic epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cyclic olefin compound. Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1〇〇3, 1〇〇4, 1007, and 1010 (all of which are Japan Epoxy Resins). Manufactured, Epot〇hto yD_128 (made by Tohto Kasei Co., Ltd.) 'DER-331, DER-332, DER-324 (all manufactured by Dow Chemical Japan) 'Epiclon 840, Epiclon 85〇, Epiclon 1050 (both Manufactured for DIC, Epomic R-140, Epomic R-301 and

EpomicR-304 (all manufactured by Mitsui Chemicals Co., Ltd.). As the bisphenol F-type epoxy compound, for example, 806, 105 201022331 32945 pif. doc 807, 4004P (all manufactured by Epoxy Epoxy Co., Ltd.), Ep〇t〇ht〇YDF-170, Epotohto YDF-175S, Epotohto YDF-2〇01 (both manufactured by Tohto Kasei Co., Ltd.), DER-354 (manufactured by D0W Chemical Japan Co., Ltd.) Epiclon 830 and Epiclon 835 (both manufactured by DIC). As the bisphenol type epoxy compound, for example, an epoxide of 2,2-bis(4-diphenyl)-1,1,1,3,3,3-hexafluoropropane can be mentioned. As the hydrogenated bisphenol A type epoxy compound, for example,

Simtohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Toka Coffee HBE-100 (manufactured by Shin Sakamoto Chemical Co., Ltd.), and Denac 〇1 Θ EX_252 (manufactured by Nagase Chemtex). The hydrogenated bisphenol type epoxy compound may, for example, be an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-fluorene, iota, 3,3,3-hexafluoropropane. Examples of the brominated bisphenol A type epoxy compound include 5050 and 5051 (all manufactured by Enamel Epoxy Resin Co., Ltd.), Ep〇t〇ht〇YDB-360, and Epotohto YDB-400 (both Manufactured for Dongdu Chemical (share), DER-530, DER-538 (all manufactured by Dow Chemical Japan)

Epiclon 152 and Epiclon 153 (both manufactured by DIC). 〇 〇 N 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 152 Dow Chemical Japan (manufactured by Dow Chemical Japan), Epiclon N-770 (manufactured by DIC), EPPN-201 and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.). Examples of the nonylphenol novolak-type epoxy compound include 180S75 (manufactured by Sakamoto Epoxy Resin), YDCN-701, YDCN-702 (^106 201022331 32945pif.doc manufactured by Tohto Kasei Co., Ltd.) EpiclonN -665, Epiclon N-695 (all manufactured by DIC), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1〇25 and EOCN-1027 (both Japanese chemical companies) Manufacturing). As the bismuth A-age acid/varnish-type epoxy compound, for example, 157S70 (manufactured by Enamel Epoxy Co., Ltd.) and Epiclon N-880 (manufactured by DIC) can be listed. @ As the epoxy compound containing a naphthalene skeleton, for example,

Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (both manufactured by DIC) and NC-7000 (manufactured by Sakamoto Chemical Co., Ltd.). As the scented polyglycidyl bond compound, for example, hydroquinone diglycidyl ether (the following structural formula E101) catechol diglycidyl ether (catech〇1 diglycidyl) can be exemplified. Ether) (structure E1〇2 below), resorcinol diglycidyl ether (structure E103 below), tris(4-glycidyloxyphenyl)decane (described below) Structural Formula E105), 1031S, 豢1032H60 (all manufactured by Epoxy Epoxy Resin), TACTIX-742 (Dow)

Chemical Japan (manufactured by Chemical Japan), Denac〇i EX-20 l (manufactured by Nagase chemtex) 'DPPN_5〇3, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techm 〇re VG31〇1L (manufactured by Mitsui Chemicals Co., Ltd.), a compound represented by the following structural formula El〇6, and a compound represented by the following structural formula E107. 107 201022331 32945pif.doc [化70] (Ε101) (Ε102) (Ε103)

Examples of the biscyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by Dow Chemical Japan Co., Ltd.) and Epiclon HP_72® (manufactured by DIC Co., Ltd.). Examples of the alicyclic monoglycidyl scale compound include a cyclohexanone-glycidyl ether compound and Rikaresin DME-100 (manufactured by Shin Sakamoto Chemical Co., Ltd.). As the aliphatic polyglycidyl ether compound, for example, it can be listed as 108 201022331 32945 pif. doc: ethylene glycol diglycidyl ether (the following structural formula E108), diethylene glycol diglycidyl ether (the following structural formula E1) 〇9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (the following structural formula E110), tripropylene glycol diglycidyl ether (the following structural formula Bill), polypropylene glycol diglycidyl ether, neopentyl Alcohol diglycidyl ether (structure E112 below), 14-butanediol diglycidil scale (structure E113 below), 1,6-hexanediol diglycidyl ether (structure E114 below), Dimethylpentanediol diglycidyl ether (the following structural formula E115) ' Denacol EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX -211, Denacol EX-212, Denacol EX-313 (all manufactured by Nagase Chemtex) 'DD-503 (made by ADEKA), Rikaresin W-100 (made by New Japan Physical and Chemical Co., Ltd.), 1, 3,5,6-tetraglycidyl-2,4-hexanediol (Structure E116 below) 'Glycerol polyglyc Idyl ether) 'sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl beta ether, pentaerythritol polyglycidyl ether, denacol EX-313, Denacol EX-611, Denacol EX-321 [71]

(E108) (E109)

(E110) 109 201022331 32945pif.doc

As the polysulfide type diglycidyl ether compound, for example, FLDP-50 and FLDP-6(R) (all manufactured by T〇ray Thi〇kol (5)) can be cited. Examples of the biphenol-based epoxy compound include YX-4000 and YL-6121H (all manufactured by Japan Epoxy Resin Co., Ltd.), NC-3000P and NC-3〇OOS (all of which are Japanese chemical drugs). (share) manufacturing).

Examples of the diglycidyl ester compound include bisglycidyl benzoate (the following structural formula Π7), diglycidyl phthalate (the following structural formula E118), and phthalic acid. Bis(2-fluorenyloxiranylmethyl)ester (the following structural formula EH9), a compound represented by the following structural formula E12i, a compound represented by the following structural formula E122, and represented by the following structural formula E123 compound of. 110 201022331 32945pif.doc [Chem. 72]

(E117)

(E118)

(E119)

Ο (E123)

As the glycidol vinegar epoxy compound, for example, Wl, 872 (all manufactured by 曰本环氧树脂 epoxy resin) can be used as 'Epicl〇n200, EPicl〇n 4〇〇 (all manufactured by dic). ), Denacol EX-711 and Denacol

Ex·721 (both manufactured by Nagase Chemtex). As the polyglycidylamine compound, for example, Nn structural formula, N,N-diglycidyl group (structure described below), bipartite material base, stupid amine structure formula (127), Wxr , Ν_-glycidyl 2,4,6·tribromoaniline (lower, Ν' diglycidyl) aminopropyltrimethoxy 111 201022331 32945pif.doc montane (the following structural formula E128), Ν , hydrazine, 0_triglycidyl-p-amino (hereinafter, the structural formula E129), N,N,0-triglycidyl-m-aminophenol (the following structural formula E130), N,N,N,,N ,-tetraglycidyl metaxylylenediamine (TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.), the following structural formula E132), n bis(Ν,Ν·diglycidylaminomethyl)cyclohexane (TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.), the following structural formula Ε133), 1,4·bis(indole, fluorene-diglycidylaminomethyl)cyclohexane (the following structural formula E134), l,3-bis(indole, fluorene-diglycidylamino)cyclohexane (formula 135 below), 1,4-bis(indole, fluorene-di-glycidylamino)cyclohexane ( The following structural formula E136), l,3-bis(indole, fluorene-diglycidylamino)benzene (the following structural formula Ε137) 1,4-Bis(Ν,Ν-diglycidylamino)benzene (the following structural formula Ε138), 2,6-bis(indole, fluorene-diglycidylaminomethyl)bicycloindole.2.1] Heptane (structure Ε 139 below), hydrazine, hydrazine, hydrazine, &gt;^ tetraglycidyl-4,4·-diaminodicyclohexyldecane (structure formula Ε140 below), 2,2'- Dimercapto-(1^凡:^',:^-tetraglycidyl)-4,4,-diaminobiphenyl (the following structural formula Ε141), Ν, Ν, Ν', Ν'-four shrinkage Glyceryl-44,-aminodiphenyl ether (formula 142 below), 1,3,5·tris(4-(anthracene, Ν-diglycidyl)aminophenoxy)benzene (described below) Structural formula Ε143), 2,4,4,-tris(Ν,ν_ diglycidylamino)diphenyl ether (the following structural formula Ε144), tris(4-(Ν,Ν-diglycidyl) Aminophenyl)decane (the following structural formula Ε145), 3,4,3',4'-tetrakis(Ν,Ν-diglycidylamino)biphenyl (the following structural formula is delayed 146), 3 , 4, 3, 4, -4 (team &gt; 1- diglycidylamino) diphenyl ether (the following structural formula Ε 147), a compound represented by the following structural formula Ε 148, and the following structural formula Ε 149 Compound represented112 201022331 32945pif.doc [Chem. 73]

(E124)

(E126)

(E128) (E129)

(E136) (E137) 113 201022331 32945pif.doc [Chem. 74]

(E138)

(E141)

(E144)

Ο 114 201022331 32945pif.doc

[化75]

(E148)

As the monomer having an epoxy group, polymethyl propyl thief glycidol vinegar is used. Examples of the copolymer of the compound include a fluorene-phenylmaleimide-methyl propyl glycidyl ester copolymer, fluorene-cyclohexylmaleimine-glycidyl methacrylate copolymerization. , benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 115 201022331 32945pif.doc 2-hydroxyethyl methacrylate -Methylpropoxyethyl methacrylate -3 -epoxypropyl) methyl acetonate: Acid: Your gas path, +, mesh: styrene glycidyl ester copolymer. As the monomer having an epoxy group, for example, a certain group of decyl glycidyl acrylate.克 酉曰 酉曰 酉曰 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰Methyl acrylate, ethyl acetonate, isopropyl methacrylate, butyl acetonate, butyl acetonate, (meth) acrylate Tert-butyl vinegar, cyclomethicone (meth) acrylate, decyl (meth) acrylate: (mercapto) acrylate - 2. ethyl acetonate, (meth) acrylate _2 propyl acetonide, styrene, Methylstyrene, chloromethylstyrene, (mercapto)acrylic acid (3-ethyl-3-epoxypropyl) vinegar, cycline hexamethylene quinone imine, and n-stupyl maleimide . Examples of the isocyanuric acid and the % chloroglycerin include 1 '5_triglycidyl-1,3,5-triazine-2,4,6-(1's 3 511)-trione. (Strong formula E150 below), l,3-diglycidyl-5-allyl-indole, 3,5-triazine-2,4,6·(1Η,3Η,5Η)-trione (under The structural formula is £151) and the isocyanuric acid glycidyl ester type epoxy resin. [化76]

201022331 32945pif.doc ^ As the chain aliphatic epoxy compound, for example, epoxidized polybutadiene and Ep〇lead pB36〇〇 (manufactured by Daicd Chemical Industries Co., Ltd.) can be cited. As the cyclic aliphatic epoxy compound, for example, 2: methyl-3,4-epoxycyclohexanecarboxylic acid 2,_methyl_3,4,-epoxycyclohexylmethine ( The following structural formula E153) '2,3-epoxycyclopentyl·2,3,_epoxycyclopentyl hydrazine (the following structural formula Ε154), ε-caprolactone modified 3,4_epoxy Cyclohexanoic acid _3,,4,_epoxy oxime Cyclohexyl hydrazine, 1,2.8,9-diepoxy lemon dilute (cell 〇xide 3000 (Daicel Chemical Industry Co., Ltd.)), 3, 4_ Epoxycyclohexene decanoic acid _3,, 4, epoxycyclohexenyl methyl vinegar (Cell® xide 2021P (manufactured by Daicel Chemical Industry Co., Ltd.), the following structural formula E155), represented by the following structural formula E156 The compounds, CY-175, CY-177, CY-179 (both manufactured by CIBA-GEIGY Co., Ltd.), EHPD-3150 (manufactured by Daicel Chemical Industry Co., Ltd.), and cyclic aliphatic epoxy resins. [化77]

(E155) (E156) Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include polymeric compounds other than polyglycine and derivatives thereof, and low molecular weight compounds, which can be selected and used according to the purpose of each of 117 201022331 32945 pif.doc. For example, as the polymer compound, a quotient molecular compound which is soluble in an organic solvent can be mentioned. From the viewpoint of controlling the electrical properties or the alignment properties of the liquid crystal alignment film formed, it is preferred to add such a polymer compound to the liquid crystal alignment agent of the present invention. As the polymer compound, for example, t-amine, t-gas vinegar, polyp (p〇lyUrea), poly-S-polyester, polyepoxide (p〇iyep〇xide), polyester polyol (polyester p〇ly〇i), anthrone modified polyurethane and anthrone modified polyester. Further, as the low molecular compound, for example, 1) when it is desired to improve the coating property, an surfactant suitable for this purpose may be mentioned, 2) an antistatic agent may be mentioned when it is necessary to improve the antistatic property, and 3) when it is desired to improve The adhesion between the substrate and the rubbing resistance may be exemplified by a silane coupling agent or a titanium coupling agent, and 4) when the hydrazine imidization is carried out at a low temperature, Amination catalyst. Examples of the decane coupling agent include vinyl trimethoxysilane, vinyl triethoxy decane, and N-(2-aminoethyl)_3_aminopropyl decyl decyloxydecane. , N_(2_aminoethyl)-3-aminopropyl decyl trimethoxy sulphur, p-aminophenyl trimethyl decyl sulphate, p-aminophenyl triethoxy sulphate, m-aminophenyl triterpene Oxygen sylvestre, m-amino-p-butyl triethoxy sulphate, 3-aminopropyltrimethoxy^, 3-aminopropyltriethoxy sulphur, 3, glycidoxypropyltrimethoxy Base decane, 3-glycidoxy propyl methyl dimethoxy decane, % oxonyl hexyl) ethyl trimethoxy oxanthine, 3- chloropropyl decyl decyloxy oxime, 3-chloro Propyltrimethoxywei, 3_mercaptopropanyloxypropylpropyl 118, 201022331 32945pif.doc Oxydecane, 3-mercaptopropyltrimethoxydecane, n_(1,3-dimethylbutylene) -3-(triethoxycarbosulfanyl)-1·propylamine and bis[3_(trimethoxycarbamidyl)propyl]ethylenediamine. Examples of the brewing imidization catalyst include aliphatic compounds such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-di Aromatic amines such as ethyl aniline, methyl substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, transsubstituted 0 吼 °, quinoline, methyl substituted quinone, hydroxy substituted quinolin a cyclic amine such as an isoquinoline, a mercapto-substituted isoquinoline, a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole, or a hydroxy-substituted imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethyl phenylamine, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-aminopyrylene, and isoquine. One or two or more of them. The amount of the decane coupling agent to be added is usually 0.1% by weight to 50% by weight based on the total weight of the polyamic acid or a derivative thereof, preferably 〇丨% by weight to 2% by weight. The amount of the ruthenium imidization catalyst to be added is usually 0.01 to 5 equivalents, preferably 5 to 3 equivalents, per gram of the carbonyl group of the poly-aracine or its derivative. The amount of the other additives to be added varies depending on the use thereof, and is usually 0% by weight to 3% by weight based on the total weight of the polyaminic acid or a derivative thereof, preferably 0.1% by weight to 1% by weight. Further, for example, the liquid crystal alignment agent of the present invention can be carried out in a range which does not impair the effects of the present invention (preferably, the amount of the polyacrylic acid or a derivative thereof is 119 201022331 32945 pif. doc %) It contains a pienoic acid polymer, an acrylic vinegar polymer, and other polymer components such as polyamidoximine which is a reaction product of tetracarboxylic dianhydride, dicarboxylic acid or a derivative thereof and a diamine. Further, for example, from the viewpoint of adjusting the coatability of the liquid crystal alignment agent or the concentration of the polyamic acid or a derivative thereof, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve a polymer component. The solvent widely includes a solvent which is usually used in the production step or use of a polymer component such as polyaminic acid or soluble polyimine, and can be appropriately selected depending on the intended use. The solvent may be a solvent or a mixed solvent of two or more solvents. The solvent 'is a good solvent for the polyamic acid or a derivative thereof, or another solvent for the purpose of improving coatability.

The protonic polar organic solvent in which the polylysine or the derivative thereof is a good solvent may, for example, be N-methyl-2-pyrrolidone or dimercapto Dimethyl imidazolidinone, N-methyl Q caprolactam, N-methyl propionamide, N,N-dimercaptoamine, dimethyl Dimethyl sulfoxide, N,N-dimethylformamide, N,N-diethyl decanoic acid, diethyl acetamide, γ-butyrolactone (γ -butyrolactone) and other vinegar. Examples of the other solvent for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol (3-methyl-3-me1; hoxybutanol), tetraterpene. Tetralin, isophor 120 201022331 32945pif.doc ketone (isophorone), ethylene glycol monobutyl ether (she § 1 outer 〇 1 monobutylether) and other ethylene glycol monoalkyl ether, diethylene glycol single Ethylene glycol single-burning test, such as ethylene glycol monobutyl or phenyl acetate, triethyl alcohol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ether, A dipropylene glycol monoalkyl ester such as diethyl malonate or a dipropylene glycol monoalkyl sulfonate such as dipropanol monoterpene ether or an acetate compound such as an acetate. Among these compounds, the solvent is particularly preferably N-methyl-2-pyrrolidone, dinonylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl hydrazine, diethylene glycol monoethyl ether, propylene glycol single Butyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl bond. In the present invention, the concentration of the south molecular component containing the polyamic acid or the bamboo organism thereof in the liquid crystal alignment agent is not particularly limited, and is preferably from 0.1% by weight to 40% by weight. When the liquid crystal alignment agent is applied onto a substrate, in some cases, it is necessary to perform an operation of diluting the contained high molecular component with a solvent in advance in order to adjust the film thickness. In this case, the viscosity of the liquid crystal alignment agent is adjusted to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent. The concentration of the two molecular components is preferably 40% by weight or less. Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted depending on the method of applying the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polymer component is usually usually 10% by weight or less. For other coating methods, such as dipping or ink jetting, it is possible to further reduce the "length". On the other hand, if the concentration of the polymer component is 0.1% by weight or more, the film thickness of the obtained liquid crystal alignment film is likely to be the best. Therefore, in the usual spin coating method, printing method, or the like, the concentration of the molecular component is 大于 1% by weight or more, preferably 〇 5% by weight. However, the coating method by the liquid crystal alignment agent may be used at a lower concentration. In addition

When the liquid crystal alignment agent of the present invention is used for the production of a liquid crystal alignment, the viscosity of the liquid crystal alignment agent of the present invention can be determined according to the film forming the liquid crystal compound or the silkworm. For example, when the film is formed to form a film of a liquid crystal alignment agent, the viscosity of the liquid crystal alignment agent is preferably 5 mPa·s or more from the viewpoint of obtaining a sufficient film thickness, and the viewpoint of suppressing uneven printing is suppressed. In other words, the liquid crystal alignment agent of the present invention is selected to be 1 〇 mPa.s' or more, more preferably 1 〇 mPa.s to 8 〇 mPa s. When a liquid crystal aligning agent film is formed by a spin coating method (spin e) liquid crystal alignment agent, the liquid crystal alignment agent _ viscosity of the present invention is preferably 5 mPa·s to 200 mPa·s, and more preferably 1 〇 mPa.s~1 〇 (mPa.s. The viscosity of the liquid crystal alignment agent can be reduced by dilution of the solvent or accompanying aging of the mixture.

The liquid crystal alignment agent of the present invention may be in the form of a polyglycine or a living organism thereof, or a form of a so-called polymer blend in which two or more kinds of polyaminic acid or a derivative thereof are mixed. The liquid crystal alignment agent of the form of the polymer blend may, for example, be a liquid crystal alignment agent containing polylysine or derivatives thereof 8 and 8, and a polyamine containing polyamine or its derivative A. One or both of the diamines having a side chain structure, and the poly-branched acid or the derivatives of the derivatives A and B, the tetrahydro dianhydride 122 201022331 32945 pif.doc contains the formula (TC-1) to the formula Tetracarboxylic dianhydride represented by (TC-14). Polylysine or a derivative thereof A is a polyamine or a derivative thereof containing the diamine having a side chain structure. Polylysine or a derivative thereof B is a poly-tantoic acid or a derivative thereof containing a diamine other than a diamine having a side chain structure. The diamine represented by the above formula (TC-1) to formula (TC-14) may be contained in at least one polyphthalic acid or a derivative thereof mixed in the polymer blend. Included in the poly-proline or its derivatives φ A and B ' can also be included in all of the polyamines or derivatives of these blends in the polymer blend. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent, for example, a step of forming a coating film of the liquid crystal alignment agent of the present invention by the liquid crystal alignment film of the present invention, and a coating film therefor It is obtained by the step of heating and calcining. For the liquid crystal alignment film of the present invention, the film obtained in the calcining step can be subjected to rubbing treatment as needed. ® is the same as the usual liquid crystal alignment film which can be formed by applying the liquid crystal alignment agent of the present invention on the substrate of the liquid crystal display element. The substrate may be a glass substrate such as an electrode such as an Indium Tin Oxide ITO electrode or a color filter (c〇1〇r fllter). As a method of applying a liquid crystal alignment agent onto a substrate, a spin coating method, a printing method, a secondary collapse method, a drop method, an inkjet method, and the like are generally known. These methods are equally applicable in the present invention. 123 201022331 32945pif.doc The calcination of the coating film can be carried out under the conditions required for the polyamic acid or the dehydration and ring closure reaction. As the sinter of the coating film, a method of heat-treating in an oven or an infrared furnace, a method of heat-treating on a hot plate, and the like are generally known. This method is equally applicable in the present invention. It is usually preferably carried out at 15 (TC to 3 〇 0. (: at a temperature of about ～ minutes to 3 hours).

The rubbing treatment can be carried out in the same manner as the rubbing treatment which is usually used for the alignment treatment of the liquid crystal alignment film, as long as it can satisfy the conditions of the liquid crystal alignment of the present invention (i* etaniatiGn). Particularly preferred conditions are a brush press-in amount of 0.2 mm to 0.8 mm, a platform moving speed of 5 mm/see to 25 Gmm/see, and a roll (four) speed of · P rpm. As a method of aligning the liquid crystal alignment film, a photo-alignment method, a transfer method, and the like are often known in addition to the rubbing method. The method of obtaining the effect of the present invention can be used in the rubbing treatment method. one eight

The inventive liquid crystal alignment film can be suitably used, including the method (IV) of the other steps of the step 1 described above. As such another step, the frequency of the film (4) is used, or the film after the cleaning process 1 is used for cleaning. The procedure of h ΪΓ Wei burning is the same, and the drying step is often known as a method of heat treatment in a baking furnace, addition on a hot plate, and the like. These methods may also be carried out in the drying step, and the step is preferably carried out at a temperature lower than the temperature of the calcining step at a temperature within a range in which the solvent can evaporate. 124 201022331 32945pif.doc

The cleaning method for cleaning the liquid crystal alignment before and after the alignment treatment using the cleaning liquid may be, for example, bmshing, spraying, spuming, Wei washing or lining m, and the branches may be used in a single row or in combination. As the cleaning liquid, pure water, various alcohols such as alcohol (mehtyl alcohol), ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene may be used. Methylene chloride) is a solvent such as a dentate solvent, a propyl group, a methyl group or a methyl ketone, but is not limited to these mash liquids. Of course, these cleansing yarns can be thoroughly cleaned with a pure surface impurity. This cleaning method can also be applied in the step of forming the liquid crystal alignment film of the present invention. The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably from 10 nm to 300 nm, more preferably from 3 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a surface profiler or an ellips meter. A liquid crystal display element of the present invention has: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and aligning the liquid crystal molecules in a predetermined direction A liquid crystal alignment film; the liquid crystal alignment film is a liquid crystal alignment film of the present invention. The substrate may use the glass substrate described above for the liquid crystal alignment film of the present invention, and the electrode may use the IT germanium electrode 0 125 formed on the glass substrate described above for the liquid crystal alignment film of the present invention. 201022331 32945pif.doc The liquid crystal layer is formed of a liquid crystal composition sealed in a gap between a pair of opposing substrates, and the pair of opposing substrates is a substrate of one of the pair of substrates The surface on which the liquid crystal alignment film is formed faces the other substrate. The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. The liquid crystal composition disclosed in the following publications can be used for the liquid crystal composition disclosed in the following publication. Japanese Patent No. 3,862, 528, Japanese Patent No. 2635435, Japanese Patent Special Table Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. , Japanese Patent Laid-Open (four) Coffee No. (Fei Chuang Nen Ming Ming), Japanese Patent Laid-Open (four) Kyu, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (ΕΡ 885 271 Α 1 specification), Japanese Patent Laid-Open No. 1〇_2〇4_ (Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. No. 2, No. 2, No. 2, No. 2, No. 2, No. 231, 482, Japanese Patent Laid-Open No. Hei No. Hei No. 2000-087040 Bulletin, Japanese Patent Laid-Open No. 2882882, and the like. The dielectric constant anisotropy is 优 优 晶 57 = = = = = = = = = 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示The newspaper, the Japanese full-time Kaiping 8 · the purchase of the 69th bulletin, the day = 126 201022331 32945pif.doc 10-168076, the Japanese patent this patent special Kaiping 1〇 · 236989 ^ Thousands of No. 3 bulletin, the day - cans , Japanese patent; = Pingwen 22 = special open patents, special Kaiping 10-236993 #八四号, newspaper, Japanese 10-236994 bulletin, Japanese special two ': Japanese patent special Kaiping ^ ^ l〇-237〇t ^lt1〇-237〇〇〇;&quot;&quot;V^ ' 9 10-237024, Japanese patent ^, Japanese patent special Kaiping

Japanese Patent Laid-Open No. 10-237076, Japanese Patent No., Japanese Patent Laid-Open (EP967261A1), Japanese Patent No. _237448, 曰J曰, Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Japanese Patent Publication No. 10-287875, Japanese Patent Publication No. 10-291945, 曰太直名丨Λ± 特开平土奎咖报曰本专利公开平11-〇29581号,日 i主μ开平11_ Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2000-256. Even when an optically active compound having a positive or negative dielectric constant anisotropy is added or used, there is no effect on the silk. The liquid crystal display device of the present invention is obtained by forming a liquid crystal alignment film of the present invention on at least one of the ruthenium-based substrates, and causing the liquid yam alignment film to face inward to pass the obtained pair of substrates via the spacer. The spacers are opposed to each other, and a liquid crystal composition is sealed in a gap formed between the substrates to form a liquid helium layer. In the manufacturing process of the liquid crystal display element of the present invention, a step of attaching a polarizing film or the like to the substrate may be further included as needed. 127 201022331 32945pif.doc The liquid crystal display element of the present invention can be (10) formed into various electric field type liquid crystal display elements. In the liquid crystal display device for the electric field method, a liquid crystal display element for a lateral electric field method in which a voltage is applied to a crystal layer in a direction parallel to a surface level of the substrate, or an electrode of the household electrode is used. A liquid crystal display element for a vertical electric field method in which a voltage is applied to the liquid in a direction perpendicular to the surface of the substrate. The liquid crystal display element for the θ lateral electric field method may not exhibit a large pretilt angle. Therefore, the liquid crystal alignment film of the present invention is formed by a liquid crystal display element in which the liquid crystal alignment film is turned over to the transverse electric field mode, wherein the present invention The liquid crystal aligning agent contains a polyglycine having no side or a derivative thereof such as a miscellaneous ship obtained from a diterpene diamine having a side chain structure or a derivative thereof. The ''s liquid crystal display element for the vertical electric field method needs to exhibit a large = angle. Therefore, the liquid crystal alignment film formed by the present invention is suitable for a liquid crystal display element for a vertical electric field mode, in which the present liquid crystal alignment The agent contains citric acid or a derivative thereof such as polyacrylic acid or a derivative thereof comprising diterpenoids having a diamine having a side chain structure. As described above, the liquid crystal alignment film of the present invention can be used as a raw material to prepare a liquid crystal alignment film, and the raw material, that is, the polymer ride, can be applied to each surface (four) moving pair (four) crystal age element. The liquid crystal display element can further have the other constituent elements of the above configuration, and the liquid crystal display element of the present invention can be equipped with a bias (thinness), a wavelength plate, a light scattering film, and 128. 201022331 32945pif.doc A component commonly used in liquid crystal display devices such as driver circuits. [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited to these Examples. The compounds used in the examples are not described. &lt;tetracarboxylic dianhydride&gt; EDDA: ethylenediaminetetraacetic acid dianhydride PhDDA: 1,4-phenylenediaminetetraacetic acid dianhydride DA PMDA. PyromeiHtie Dianhydride CBDA. Cyclobutanetetracarboxylic acid Two needles (CyCi〇butane tetracarb〇xylic dianhydride) PSQ1 : 18,21-bis(3·(2,5-dioxotetrahydrofuran-3-yl)propyl)-18,21-dimethyl-1,3, 5,7,9,11,13,15-octylphenyl-pentacyclic [10.5.1·25,13.17,11·19,15] Ten Shixi Oxygen Burning NPDA: Naphthalene-1,4,5,8- Tetracarboxylic acid dianhydride NTCA: naphthalene-2,3,6,7-tetradecanoic acid dianhydride &lt;diamine&gt; 〇DDM : 4,[diaminodiphenyl decane DDET · 4,4- oxadiphenyl乙乙院DATA . 1,3,5-Diamino-1,2,4_三嗤5HHP1PDA : 5·{4-[4-(4-n-pentylcyclohexyl)]cyclohexyl}phenylmethyl- 1,3-diaminobenzene 25P1PDA : 2-(stylmethyl)-indole-diaminobenzene 5HP1PDA: 5-{4-(4-pentylcyclohexyl)}phenylindolediamino129 201022331 32945pif.doc 7H2HP1PDA : 5-{4-[2-(4-n-hexylcyclohexyl)ethyl]cyclohexyl}phenylphenyl-1,3-diaminobenzene 3HHPEPDA: benzoic acid _3,5-diaminophenyl-4 -(4,-propylbis(cyclohexane)-4-yl)酉16DAB: benzamidine_3,5 _Diaminohexadecyl ester &lt;solvent&gt; NMP : N-methylpyrrolidone BC : butyl cellosolve (ethylene glycol monobutyl ether) &lt;1. Synthesis of poly-bristine &gt; ❾ [ Synthesis Example 1 In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 0.7420 g of 5HHP1PDA, 0.7934 g of DDM, and 37.0 g of dehydrated NMP were placed, and the mixture was dissolved under a dry nitrogen stream. . Next, 1.4646 g of EDDA was added, and after reacting for 30 hours, 10.0 g of BC was added to synthesize a polyglycine solution (PA 1) having a concentration of 6% by weight. When the temperature rises due to the reaction temperature in the reaction of the raw material, the reaction temperature is suppressed to about 70 ° C or 7 (TC or less) to carry out the reaction. In addition, the weight average of the polylysine in the obtained PA1 is obtained. The molecular weight is 72,600. The weight average molecular weight of polylysine is determined in such a manner that a mixed solution of seven mf of phosphoric acid is used in such a manner that the polyglycine concentration is about 1% by weight (filling acid / DMF = 0.6/100) , the weight ratio) to dilute the obtained polyamic acid, and then use the 2695 separation module, 2414 differential refractometer (manufactured by Waters)' to use the mixed solution as a developing solvent 130 201022331 32945pif.doc and use The GPC method was used for the measurement, and the polystyrene conversion was performed. Further, the column was measured using HSPgel RTMB-M (manufactured by Waters) under the conditions of a column temperature of 40 C and a flow rate of 0.35 mL/min. Example 2 - Synthesis Example 11 A polyphthalic acid solution (PA2 to PA11) was prepared according to Synthesis Example 1 except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 1. The synthesis example 1 was included. The results are summarized in Table i. ^ [Comparative Example 1 to Comparative Synthesis Example 3 A polyglycine solution (PA12 to PA14) was prepared according to Synthesis Example 1 except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 1. The results are summarized in Table 1. 131 201022331 132 Comparative Synthesis Example 3 Comparative Synthesis Example 2 Comparative Synthesis Example 1 Synthesis Example 11 Synthesis Example 10 Synthesis Example 9 I Synthesis Example 8 Synthesis Example 7 Synthesis Example 6 Synthesis Example 5 Synthesis Example 4 Synthesis Example 3 Synthesis Example 2 Synthesis Example 1 | 5 u&gt;&gt;to涿l-&gt;^ o歹*-k SO oo On Κ) i Directional Agent o O EDD A Acid dianhydride (mol%) PhDD A 1 1—^ o (-Λ -! PMD .A j CBD A NPD A NTC A g sB Diamine without side chain (mo)%) DDE T DATA U) o 5H HP1PD A Diamine with side chain (mol%) U) 1 5H PI PDA | 7H2H P1PD A 3HH PEPDA ® ^ Os C oy\ o 47,200 o -4 oo o so oo U) oo 89,200 o 91,800 | n&gt;* 1—· cog V o 72,600 ϋ&gt; 14 ^&quot;4 *U)· ΙΦ 32945pif.doc ο 201022331 32945pif.doc [Synthesis Example 12 to Synthesis Example 16] A polyaminic acid solution (B1 to B5) was prepared according to Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 2. [Comparative Synthesis Example 4 and Comparative Synthesis Example 5] A polyaminic acid solution (B6, B7) was synthesized according to Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed in the ratio shown in Table 2. [Table 2] Two-needle (mol%) diamine (mol%) diamine (mol0/〇) Weight average molecular weight EDDA PMDA CBDA PSQ1 NTCA DDM DDET Synthesis Example 12 B1 50 50 100 70,700 Synthesis Example 13 B2 50 50 100 66,100 Synthesis Example 14 B3 20 60 20 100 32,400 Synthesis Example 15 B4 50 50 100 74,100 Synthesis Example 16 B5 50 50 100 108,000 Comparative Synthesis Example 4 B6 50 50 100 51,500 Comparative Synthesis Example 5 B7 50 50 100 83,300

[Synthesis Example 17 and Synthesis Example 18] A polyaminic acid solution (C, C2) was prepared according to Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 3. [Comparative Synthesis Example 6 and Comparative Synthesis Example 7] A polyaminic acid solution (C3, C4) was synthesized according to Synthesis Example 1, except that the tetracarboxylic dianhydride and the diamine were changed in the ratio shown in Table 3. 133 201022331 32945pif.doc Acid dianhydride (mol%;) Diamine (mol%) with side chain θ diamine (mol%) Weight average molecular weight EDDA CBDA PSQ1 25P1PDA 5HP1PDA Synthesis Example 17 C1 20 80 50 50 77,700 Synthesis Example 18 C2 20 40 40 50 50 32,200 Comparative Synthesis Example 6 C3 100 50 50 58,300 Comparative Synthesis Example 7 C4 60 40 50 50 25,600 The concentration synthesized in Synthesis Example 12 to Synthesis Example 16 and Comparative Synthesis Example 4 and Comparative Synthesis Example 5 was 6 The polyglycine solution (C1 to C7) having a concentration of 6% by weight and the polyamine solvent (C1 to C4) having a concentration of 6 wt% synthesized in Synthesis Example 17, Synthesis Example 18, Comparative Example 6, and Comparative Example 7 were used. The weight ratio of 90/10 (the former/the latter) was mixed to prepare a liquid crystal alignment agent (PA15 to PA28). The composition ratios of PA15 to PA28 are summarized in Table 4. [Table 4] Directional agent varnish varnish weight ratio PA15 B1 C3 B1/C3-9/1 PA16 B2 C3 B2/C3 = 9/l PA17 B6 C1 B6/C 1=9/1 PA18 B1 ~~ci B1/C1= 9/1 PA19 B2 B2/C 1=9/1 PA20 B3 C4 B3/C4 = 9/l PA21 B3 B3/C2 = 9/l PA22 B6 ~~cT~~^ B6/C3 = 9/l PA23 B4 ci B4/C1=9/1 PA24 B5 B5/C 1=9/1 PA25 B7 Cl B7/C 1=9/1 PA26 B4 C3 B4/C3 = 9/l PA27 B5 C3 B5/C3 = 9/l PA28 B7 C3 B7/C3 = 9/l 134 201022331 32945pif.doc To the polyglycine solution (A3, A13) having a concentration of 6% by weight synthesized in Synthesis Example 3 and Comparative Synthesis Example 2, respectively, with respect to the weight of the polymer Add 10% by weight of bis{4-(allylbicyclo[2,2,1]hept-5-thin-2,3-diimineimine) base 曱 、, 2-(3,4- Epoxycyclohexyl)ethyltrimethoxyxanthene and N,N-(1,2-divinylethene)bispropenylamine were used to prepare a liquid crystal alignment agent (PA29 to PA32). The composition of PA29 to PA32 is shown in Table 5. Additive varnish additive addition amount (wf%) PA29 PA3 double {4_(dilylbiscyclo[2,2,1]hept-5-diluted-2,3_diimideimine)phenyl}decane'- 10 PA30 PA3 2-(3,4-epoxycyclohexyl)ethyldimethoxydecane 10 PA31 PA3 N,N-(1,2-dihydroxyethylene) bispropene oxime 10 PA32 PA13 double {4_(ene Propylbicyclo[2,2,1]heptane-^^:dioxin-p-imine)phenyl}decane 10 &lt;2. Preparation of liquid crystal display element&gt; [Example 1] 0 Synthesis Example 1 A mixed solvent having a concentration of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA1) having a concentration of 6% by weight and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. &lt;Method for Producing VA Type Liquid Crystal Display Element&gt; The obtained liquid crystal alignment agent was applied onto a pair of substrates with ITO transparent electrodes by spin coating, and dried on a hot plate for 8 minutes under 8 days. The substrate was heated and calcined in an oven set at 220 ° C for 20 minutes to obtain a substrate on which a liquid crystal alignment film was formed. The surface 135 on which the liquid crystal alignment film is formed is 201022331 32945pif.doc is the inner side, and the injection hole of the liquid crystal remains on one of the substrates, and the periphery is sealed with an epoxy-based agent to spread and attach the 4 25 beer on the other substrate. Gap material. The liquid crystal composition shown in the obtained unit (edl) was vacuum-filled, and the injection hole was sealed using a light seal to seal the injection hole and =travi^Uv). Finally, I got VA in ιι〇. Management (different _ theory _) processing)

136 201022331 32945pif.doc [Chem. 78]

5wi% 7wt%

Bwf% 8wt% 14wt% 14wt% 10wi% 10wl% 12wt%

12% by weight [Example 2 to Example 26, Comparative Example 1 to Comparative Example 6] The concentration obtained by combining in Synthesis Example 2 to Synthesis Example 26 and Comparative Synthesis Example 1 to Comparative Synthesis Example 6 was carried out as needed. To a 6 wt% polyproline solution (PA2 to PA32), a mixed solvent of 137 201022331 32945 pif.doc of NMP/BC = 1/1 (weight ratio) was added, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. &lt;Evaluation of long-term thermal reliability of voltage holding ratio 'VHR&gt;&gt; The liquid crystal display elements produced in Examples 1 to 26 and Comparative Examples 1 to 6 were subjected to the following manner. Evaluation of the long-term thermal reliability of VHR. (1. Measurement of VHR) The voltage holding ratio of the VA liquid crystal display element was measured using a liquid crystal physical property evaluation device 6254 manufactured by Toyo Corporation. The measurement conditions are: gate width of 60 ps, frequency of 30 Hz, wave height of ±5 V, and measurement temperature of 60 °C. (2. Calculation of long-term thermal reliability of VHR) For the liquid crystal display elements produced in Examples 1 to 26 and Comparative Examples 1 to 6, the VHR measured within 24 hours after the fabrication of the device The value is set to VHR (initial). In addition, the liquid crystal display device after the VHR measurement was stored in an oven at TC for 5 hours, and the value of VHR measured under the conditions described above was VHR (5 hours). The VHR reduction rate is calculated from the two VHRs obtained according to the following formula. The smaller the value, the better the long-term thermal reliability of VHR. The results are shown in Table 6. VHR reduction rate = [{VHR (initial) - VHR (5 (8) hours)}xl〇0]/VHR (initial) 138 201022331

[Table 6] Excipient VHR (initial) (%) VHR (500 hours) (%) VHR reduction rate (%) Example 1 PA1 96.99 96.46 0.5 Example 2 PA2 99.02 97.17 1.9 Example 3 PA3 95.55 93.70 1.9 Example 4 PA4 98.49 95.39 3.1 Example 5 PA5 94.47 91.41 3.2 Example 6 PA6 97.02 96.21 0.8 Example 7 PA7 95.26 95.16 0.1 Example 8 PA8 97.00 96.33 0.7 Example 9 PA9 97.81 97.04 0.8 Example 10 PA10 96.20 95.11 1.1 Example 11 ΡΑ11 96.33 95.40 1.0 Comparative Example 1 ΡΑ12 98.86 91.05 7.9 Comparative Example 2 ΡΑ13 98.31 91.61 6.8 Comparative Example 3 ΡΑ14 98.05 91.73 6.4 Example 12 ΡΑ15 98.98 97.72 1.3 Example 13 ΡΑ16 98.99 94.73 4.3 Example 14 ΡΑ17 99.47 96.36 3.1 Example 15 ΡΑ18 99.18 98.96 0.2 Example 16 ΡΑ19 99.23 98.05 1.2 Example 17 ΡΑ20 99.33 94.82 4.5 Example 18 ΡΑ21 99.40 98.06 1.3 Comparative Example 4 ΡΑ22 99.26 90.83 8.5 Example 19 ΡΑ23 99.30 98.20 1.1 Example 20 ΡΑ24 99.20 98.40 0.8 Example 21 ΡΑ25 99.49 96.72 2.9 Example 22 ΡΑ26 99.06 94.98 4.1 Example 23 ΡΑ27 99.49 96. 72 2.8 Comparative Example 5 ΡΑ28 99.18 88.57 10.7 Example 24 ΡΑ29 98.78 97.59 1.2 Example 25 ΡΑ30 99.03 98.54 0.5 Example 26 ΡΑ31 99.16 98.16 1.0 Comparative Example 6 ΡΑ32 99.01 91.49 7.6 139 201022331 As shown in Table 6, the use of monomer A liquid crystal display element of a liquid crystal alignment film obtained by a liquid crystal alignment agent containing poly-lysine of edda has an effect of extremely high VHR long-term thermal reliability. The present invention has been disclosed in the above embodiments, and it is not intended to limit the invention to those of ordinary skill in the art, and the invention may be modified and exemplified without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention is defined by the scope of the appended patent application [Simple Description] / None. [Main component symbol description] None.

140

Claims (1)

201022331 VII. Patent application scope: 1. A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, wherein the tetracarboxylic dianhydride contains the following a tetracarboxylic dianhydride represented by the formula (TC-1) to the formula (TC-14), wherein the diamine is represented by the following formula (VIII) and formula (X) to formula (XI) Diamine having a side chain structure, [Chemical 1] 141 201022331 [Chemical 2] 142 201022331 In the formula (TC-1), X represents -(CH2)n-, and at most two -CH2- may be independently -0-' but here -0 is not continuous, -S-, -COO- , -OCO-, -CO-, -CONH- &gt; -CnH2nN(CmH2mCOOH)CnH2n- &gt;_CH(CmH; 2ni〇H)-, -CH(CnH2n+i)-, -CH=CH- or -C =C-substitution, in the above formula (TC-1), m of X represents an integer of 〇30, and n independently represents an integer of 1 to 30; in the formula (TC-4) to (TC-7) , Υ independently represents a single bond, -0-, -S-, -SS-, -S〇2-, -CO-, -CONH-, -NHCO-, 0-NH-, -N(CH3)-( CH2)mN(CH3)-, -C(CH3)2_, -C(CF3)2-, -(CH2)m-, -0-(CH2)m-0-, -S-(CH2)m_S-, In the above formula (TC-4) to formula (TC-7), m of Y represents an integer of 1 to 6; in the formula (TC-5), Z represents a single bond or does not exist; In the above, R33 and R34 each independently represent a decyl group or a phenyl group having a carbon number of 1 to 3, and A3 independently represents a fluorenylene group, a benzyl group or a pyridyl group substituted with a phenyl group, and 1 represents 1 to 6 The integer, m represents an integer from 1 to 10; in the formula (TC·2) to the formula (TCV7), the hydrogen bonded to the cyclohexane ring or the benzene ring may be independently _F, _CH3, -CF3 , -OH, - Substituting C00H, -S〇3H, -p〇A, the hydrogen bonded to the benzene® ring in the formula (TC-3) may be substituted by a benzyl group; the formula (TC-2) to the formula (TC_8) Where R1 independently represents -(CH2)m-, at most two _ch2- can be independently _〇_, but here 0- is not continuous, -8-, -(:00-,-0(: 0-, _(:0_, _&lt;:01^_, -CH(CmH2mOH)-, -CH(CmH2m+1)-, -CH=CH- or -OC-substitution, the above formula (TC-2) m in the general formula (TC_8) independently represents an integer of 〇~3〇; in the general formula (TC-8), A1 is independently an alkyl group having a carbon number, and the carbon number is 1 to 1 G oxy group, acetamidine Amine, gas, chlorine or chlorine, a2 independently represents an alkyl group having a carbon number of 1 to 3, m represents an integer of 0 to 3, n represents an integer of 〇143 201022331 〜4; in the formula (TC_1〇), A3 represents a single bond, ... C〇〇·, -(^CO-, -CO-, -C0NH_ or _(CH2)m_, wherein m of A in the above formula (TC1〇) is not an integer of 1 to 6, and R1 represents a group of a steroid skeleton or a group represented by the following formula (B), when the positional relationship of two amino groups bonded to the acyclic ring is para-position, Ri further contains an alkyl group having a carbon number of 丨~sun, when Positional relationship In the meta position, Ri further contains an alkyl group having a carbon number of 1 to 3 Å or a phenyl group. Any _CH2_ in this alkyl group may be independently _Cf2_, _CHF_, -Ο-, but here -〇_ is not continuous , _ch=ch- or -OC-substitution, -CH3 may be substituted by -CHsF, -CHF2 or -CF3, and the hydrogen of the phenyl group may be independently deuterated by -F, -CH3, -〇CH3, -0CH2F, -CHF2 Or -ocf3 substituted; [Chemical 3] In the general formula (B), A4 and A5 each independently represent a single bond, -〇-, but here -0- is not continuous, _C〇〇---OCO---CONH-, -CH=CH· or carbon The number is 1 to 12 alkenyl groups, R2 and R3 each independently represent -F or -CH3, and ring S independently represents fluorene, 4_phenylene, 1,4-cyclohexene, 1,3-dioxin Alkano-2,5-diyl, pyrimidine-2,5-diyl, pyridine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or 蒽·9,1 〇-diyl, R4 represents -H, -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -ON, - OCH2F, -〇CHF2 or -OCF3, a and b respectively represent integers of 0~4 'c, d and e respectively represent integers of 0~3, f and g respectively represent integers of 0~2, respectively, and c + d + e21 ; in the formula (TC-11) and the formula (TC-12), R5 independently represents -H or -CH3, and R6 represents -H, or 144 201022331, a carbon or carbon having a carbon number of 1 to 20 The number is 2 to 20 alkenyl groups, and A6 independently represents a single bond, -CO- or -CH2-; in the formula (TC-12), R7 and R8 each independently represent -H and have a carbon number of 1 to 20; Alkyl or phenyl; in the formula (TC_13) and formula (TC-14), A7 is independent The ground represents _〇_ or an alkylene group having a carbon number of 1 to 6; in the formula (TC-13), R9 represents -H or an alkyl group having a carbon number of 1 to 3 Å, and the carbon number in the alkyl group is 2 Any -CH2- of the decyl group of -30 may be -〇_, but here -0 is not continuous, -CH=CH- or -C=C.substitution, and A8 represents a single bond or a carbon number of 1-3. The alkenyl group 'ring T represents 1,4-phenylene or 1,4-cyclohexene, h represents hydrazine or 1; in the formula (TC-14), R10 represents a stimulus having a carbon number of 6 to 22 , R is not Η or a carbon number of 1 to 22, [Chemical 4] In the formula (VIII), Α3 represents a single bond, -〇-, -COO-, -OCO-, -CO-, -CONH- or -(CH2)m-, and m of Α3 in the above formula (VIII) represents In the integer of 1 to 6, R1 represents a group having a steroid skeleton or a group represented by the following formula (IX), and R1 further contains a carbon number when the positional relationship of two amino groups bonded to the benzene ring is para Is an alkyl group of 1 to 30, and when the positional relationship is meta-position, R1 further contains an alkyl group or a phenyl group having a carbon number of 1 to 30, and any -CHr· in the alkyl group may be independently -CF2-, - CHF-, -0-, but here -0- is not a continuous, -CH_CH- or -C^C-substitution, -CH3 can be replaced by -CH2F, -CHF2 or -CF3. The hydrogen of this phenyl group can be independently &gt;F, -CH3, -OCH3, -OCH2F, -OCHF2 or -〇CF3 are substituted; wherein, when 145 201022331, the tetraruthenic dianhydride comprises only the formula (TC-1) to the formula (TC-14) In the case of the tetragonal acid monoanhydride, the carbon number of the alkyl group further contained in R1 is 23 [Chemical 5] "A3" gl Ten π C 十 5V d - R4 (IX) e In the general formula (IX) 'A4 and A5 each independently represent a single bond, _〇_, but here ^ is not continuous, -COO-, -OCO- &Gt; -CONH- &gt; -CH=CH-❹ , a burnt base having a carbon number of 1 to 丨 2 ' R 2 and R 3 each independently represent -F f CH 3 'ring S independently represents ι, 4- benzene Base, i, 4_cyclohexene, anthracene, 3_dioxane^,5-diyl, pyrimidine-2,5-diyl, pyridine-1,4-diyl, naphthalene_1,5-di Earth 2'7--yl or 蒽-9,1〇-diyl, R4 represents _h, -F, carbon number is 1 to 3 〇, alkyl, fluorosubstituted alkyl having 1 to 3 carbon atoms Alkoxy group having a carbon number of 1 to 30, -〇ΞΝ, -0CH2F, -OCHF2 or -0 (^3, a and b each represent an integer of 0 to 4', c, d and e respectively represent 〇~3 Integer, f and g respectively represent the integer ' of 〇~2' and c + d+egl; where, when c Q + d + e = l ' R4 denotes the carbon number is the base of Bu Deng, the carbon number is a fluorine-substituted alkyl group of hydrazine or an alkoxy group having a carbon number of 1 to 3 Å, and a3 of the formula (vm) represents a group having a carbon number of 1 or more, 146 201022331 [Chem. 6] In the general formulae (X) and (XI), R5 independently represents -Η or -CH3, R6 represents -Η, or an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and A6 independently In the formula (XI), R7 and R8 each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group. 2. The liquid crystal alignment agent according to claim 1, wherein the diamine having a side chain structure is a diamine represented by the above formula (VIII), and R1 is the above formula (IX) ) the base represented. 3. The invention as described in claim 2, wherein the diamine having a side chain structure is a diamine represented by the formula (VIII), and R1 is a formula (RM) to a formula ( 1^-7) The base represented, 147 201022331 In the formula (R-1), R represents a group having a carbon number of ruthenium, a fluorine-substituted alkyl group having a carbon number of -30 or an alkoxy group having a carbon number, and R of the formula (rLi) is carbon. When the number is 1, the A3 of the formula (VIII) represents a group having a carbon number of 1 or more, and in the formula (R)-2 to (RL7), R represents _h, -F, and the carbon number is An alkyl group of 1 to 30, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, _〇N, -OCH2F, -OCHF2 or -OCF3, and A represents -O- or carbon. The number is 1 to 6 of the burnt base. 4. The liquid crystal alignment agent according to claim 3, wherein the diamine having a side chain structure is a compound selected from the group consisting of the following formula (VIII-2) to formula (VIII-8) At least one of: 148 201022331 [Chem. 8] In the above formula, 'R52 represents an alkyl group having a carbon number of 16 to 30, R53 represents an alkyl group having a carbon number of 1 〇 to 3 Å, R54 represents an alkyl group having a carbon number of 4 to 3 Å, and R55 represents a hindrance number. 2 to 30 bases. The liquid crystal alignment agent according to claim 1, wherein the diamine having a side chain structure is a diamine represented by the above formula. 6. The liquid crystal alignment agent according to any one of claims 1 to 5 wherein the tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride. 7. The liquid crystal alignment agent according to claim 6, wherein the aromatic tetracarboxylic acid is the following structural formula (1), structural formula (2), structural formula (5) to structural formula. (7) at least one of the compounds represented by the structural formula (11), the structural formula (12), and the structural formula (14). 149 201022331 8. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the tetracarboxylic dianhydride comprises an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. One or both parties. 9. The liquid crystal alignment agent according to claim 8, wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the following structural formula (19), structural formula (23), At least one of the compounds represented by the structural formula (25), the structural formula (35) to the structural formula (39), the structural formula (44), and the structural formula (49): ❹ 150 201022331 [Chemical] The liquid crystal alignment agent according to any one of the items 1 to 5, wherein the diamine further comprises the following general formula (1) to general formula (VII), general formula (XV), and a diamine having no side chain structure represented by the formula (N) and the formula (8), 151 201022331 [11] H2N-X-NH2 (i) H2NOy-〇NH2 (i,,) In the formula (I), X represents -(CH2)m-, and X in the above formula (1) represents an integer of 1 to 6, and in the formula (III) and the formula (V) to the formula (VII), Y Independently means a single bond, -〇-, -s-, -SS-, -S02-, -CO-, ·&lt;:ΟΝΗ-, -NHCO-, ΝΗ_, -N(CH3)-(CH2)mN( CH3)_, _C(CH3)2-, _C(CF3)2·, 152 201022331 -(CH2)m-, -0-(0^0...S_(CH2)m each, the above formula (3) and formula ( V)~ 通式 in the general formula (VII) represents an integer of hexa. In the general formula (v), Z represents a single bond or does not exist, and in the general formula (XV), R33 &amp; R34 independently represent the carbon number Is an alkyl group or a phenyl group of 1 to 3, and A3 independently represents a methylene group, a phenylene group or a sub-phenyl group substituted with an alkyl group, 丨 represents an integer of 〜6, and 2 represents an integer of 1 to 10; (Π)~ In the general formula (VII), the hydrogen bonded to the cyclohexane ring or the benzene ring may be independently _F, _CH3, _CF3, _〇H, _c〇〇I1, ❺ _S〇3H, - Substituted by p〇3H2, the hydrogen bonded to the benzene ring in the formula (IV) may be substituted by a benzyl group; in the formula (N), A represents independently an alkyl group having a carbon number of 1 to 4 and a carbon number. Is a 1 to 4 alkoxy group, acetamide, fluorine, chlorine or A2 independently represents an alkyl group having a carbon number of 1 to 3, m represents an integer of 0 to 3, and η represents an integer of 0 to 4; in the formula (8), L1 represents hydrogen, and a carbon group having a carbon number of 1 to 4, 11. A liquid crystal alignment agent according to claim 10, wherein the diamine having no side chain structure is selected from the following structural formula (IV-1), structural formula (IV) -2), structural formula (IV_15) ~ structure, structural formula (V-1) &amp;~ structural formula (V-13), structural formula (V-33), structural formula (V-35) ~ structural formula (V -37), structural formula (νπ_2), structural formula (χν_丨), structural formula (Ν)-Bu (Ν)-2, structural formula (N)-i4, structural formula (a-1) and structural formula ( At least one of the compounds represented by a-2): 153 Η2ν^〇κνη2 201022331 [Chemical 12-1] H2N~〇&quot; (IV-1) (IV-2) H2n (V-10) (V-11) HO OH (V-33) H2N-hQ-°N〇-NH2 (V-13) h2n (\Λ35) (V-36) 154 201022331 [化 12-2] (VII-2) 9H3 ?H3 Η2Ν-〇3Η6-έί—Ο-έ Bu C3H6-NH2 ch3 ch3 (XV-1) (a_l) (a_2) 12. The liquid crystal alignment agent according to any one of the preceding claims, wherein the tetracarboxylic dianhydride comprises a sesquiterpoxy dianhydride derivative. The liquid crystal alignment agent according to claim 12, wherein the sesquiterpoxy dianhydride derivative is a compound represented by the following structural formula (S-1): 155 201022331 [Chem. 13] (Sl) 14. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the fumed chiral acid or derivative thereof comprises two polylysines or derivatives thereof A and B, the polyperuric acid or derivative A thereof comprises the diamine having a side chain structure in the diamine, and the polycarboxylic acid or a derivative thereof and a tetracarboxylic acid of the derivatives A and B One or both of the dianhydrides include four needles of tetrazolium represented by the general formula (TC-1) to the general formula (TC-14). The liquid crystal alignment agent according to any one of the items 1 to 5, further comprising a compound selected from an alkenyl-substituted nadic ylidene compound and having a radical polymerizable unsaturated double bond, One or more of an oxazine compound, an oxazoline compound, and an epoxy compound. A liquid crystal alignment film which is formed by heating a coating film of a liquid crystal alignment agent according to any one of the above claims. 17. A liquid crystal display element having a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and aligning the liquid crystal molecules in a predetermined direction The liquid crystal display element is characterized in that: the liquid crystal alignment film according to claim 16 is a liquid crystal alignment film according to claim 16. 157 201022331 32945pif.doc IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the symbol of the 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: None.