TWI341863B - Liquid crystal alignment agent - Google Patents

Description

15189pif.doc IX. Description of the Invention: [Technical Field] The present invention relates to a novel liquid crystal alignment agent containing polylysine and/or polyimine, and an alignment film obtained by the alignment agent. Liquid crystal display element. [Prior Art] The liquid crystal display element is required to be twisted and negated (Twisted Nematic: TN) to super-torque to 随着lj as the screen is enlarged or the display quality or reaction speed of colorization, contrast, or color development is increased. Super Twisted

Nematic: STN) has been developed to incorporate TFT-type display elements in Thin Filmed Transistors (TFTs). In recent years, improvements in the driving method of TFT-type display elements have been continued. For example, in order to expand the viewing angle, an In-Plane Switching (IPS) method or a Vertical Alignment (VA) method has been developed, and further developed. Opticically Compensated Bend (OCB) method that responds to the animation's reaction speed. The alignment film has two functions of aligning the liquid crystal molecules in a certain direction in the display element and tilting the substrate plane (giving a pretilt angle). The tilt of the liquid crystal molecules on the plane of the substrate is referred to as a pretilt angle. This name is also used after this manual. In order to minimize temporary, chemical, and thermal deterioration of molecular alignment in the alignment film, it is mainly used as a alignment film using a polyimide film having a high glass transition point (Tg), excellent chemical resistance, or heat resistance. material. The alignment film is usually coated with a polyamido acid or a polyimide solution (hereinafter also referred to as varnish) on the electrode glass base lS189ptf.doc plate by spin coating or printing method, by heating The substrate dehydrates, closes, or evaporates the solvent of the soluble polyimine solution to obtain a film of polyimine, and then passes through an alignment treatment step such as rubbing treatment to obtain an alignment film. When such an alignment film is applied to a liquid crystal display element, it is required to have the following functions. (1) A suitable pretilt angle is imparted to the liquid crystal molecules. Further, the pretilt angle is small due to the pressing strength at the time of friction or the temperature difference at the time of heating. (2) It is possible to perform alignment processing without causing alignment defects of liquid crystal display elements. (3) It is possible to impart a proper voltage holding ratio (VHR) to the liquid crystal display element. (4) When a liquid crystal display device displays an arbitrary image for a long time, it is difficult to generate a phenomenon called "burning" as a previous image residue when it is converted to another image. In particular, a high-quality alignment film for a TFT type display element is required to have a high voltage holding ratio and is less prone to cauterization. The cauterization phenomenon is caused by the relaxation of the electric double layer due to the applied voltage, and is caused by the residual charge generated by the localization of the applied voltage due to the anion or the like contained in the display element, and the low alignment normal force to the liquid crystal. Caused by it. In particular, the STN method in which the twist angle of the liquid crystal between the substrates is large or the use of the comb electrode and the electric field direction applied to the liquid crystal is almost parallel to the substrate interface, and the alignment of the liquid crystal is required. membrane. Further, in particular, the display element of the IPS type is required to have less light leakage (good black level) in the case of black display 15189plf.doc. In order to make this black level good, it is not only necessary that the alignment film material which is excellent in the liquid crystal specification as described above and whose alignment direction of the film surface can be well aligned due to friction is also necessary. Further, in recent years, liquid crystals having a large anisotropy of a dielectric constant accompanying a decrease in voltage of a driving voltage have found a problem of display disorder (luminance disorder) occurring in the display surface. In particular, in order to remove the chips generated during the rubbing treatment and to perform water washing, there is a possibility that the water washing marks are left as a residual phenomenon of display disorder, which causes a big problem. Patent Document 1 discloses that a polymer having a structural unit of the following chemical formula (A) can be used as a liquid crystal alignment agent. However, there is no description about the characteristics of the polymer when it is used as a liquid crystal alignment agent.

Further, Patent Document 2 discloses that an alignment agent obtained by mixing a polyamic acid containing a compound of the following chemical formula (B) with another polyamic acid solution can be used as an alignment film, thereby improving alignment and current consumption. , VHR and residual charge characteristics.

Further, Patent Document 3 discloses that an alignment agent obtained by mixing a polyamic acid containing a compound of the following chemical formula (C) with another polyamic acid solution is used as an alignment film, whereby the alignment property can be improved. 15189pif.doc h2n 0-(CH2)n-0 NH2 (C) [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. Japanese Patent Application No. 169062. SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal alignment agent which has a high level of liquid crystal display which satisfies a stable pretilt angle, has a high voltage holding ratio (VHR), has a small residual charge, and is less prone to display disorder. The characteristics required for the component, in particular, have been found to have excellent alignment. The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, it has been found that a liquid crystal alignment agent used as a liquid crystal display element can be obtained by using a polyaminic acid and/or a polyimide having the following composition. The desired object is achieved and the present invention has been completed based on this finding. The present invention consists of the following matters. [1] A liquid crystal alignment agent comprising: a polyamine which comprises 10 to 100 mol% of a constituent unit represented by Formula 0-1) and 90 to 0 mol% of a constituent unit represented by Formula (1-2) An acid or a polyamidene obtained by hydrazating the polyamic acid, 〇〇-HN/^1^NH-A1-X-Q-X-A2- (1-1>

Η〇2〇κ b〇2H 15189pltdoc Ο Ο

HOzC’ b〇2H

—HN (1-2) wherein R1 represents a tetravalent organic group, R2 represents a divalent organic group, and A1 and A2 each independently represent a divalent aromatic group or a polycondensed cyclic group, and the aromatic group is either One or more hydrogens on the polycondensation ring group may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or fluorine, and X represents a single bond, oxygen or sulfur, and Q is -( CH2)P- or -((CH2)20)q(CH2)2-, p is an integer from 3' to 10, q is from 1 to 3, and R1, R2, A1, A2 and X of each constituent unit may Differently, when Q is (CH2)P- and X is a single bond or oxygen, A1 and A2 are not unsubstituted phenylene at the same time. [2] The liquid crystal alignment agent according to [1], which comprises the polyamine or the polyamidamine according to [1], wherein the composition is represented by the formula (2). Polyamidoamine 1 to 99% by weight of polymer component ' Ο 〇-HnAi3/^NH-R4— (2)

HOzC^ b〇2H In the formula (2), R3 represents a tetravalent organic group, and R4 represents a divalent organic group. R3 and R4 of each constituent unit may be different, and the constituent unit represented by the formula (2) and the formula (1) -1) The constituent units indicated are different. [3] The liquid crystal alignment agent according to [1], which comprises a polysiloxane or a polyamidoamine (1 to 99% by weight) and a constituent unit represented by the formula (3) Amidoxime 1 to 99% by weight of the polymer component' (3) (3) 1341863 15189pif.doc In the formula (3), R3 is not 4, and the organic tomb R represents a divalent organic group, each of which constitutes a single The RR "" ί is not the same as the constituent unit represented by the formula (1-1). [4] The liquid crystal alignment agent according to [1], wherein in the formula (Μ), ν and Α are each a group represented by the formula (5) to the formula (7),

Wherein R6 to R31 are each independently hydrogen, fluorine, formamidine, acetamyl, propyl, butyl 1341863 15189plf.doc isopropyl, t-butyl 'methoxy, ethoxy, propoxy or butyl The oxy ' η and m are each 0 or 1. [5] The liquid crystal alignment agent according to [1], wherein in the formula (1), '8' and A2 are each a group represented by one of the formulae (5) to (7). [6] The liquid crystal alignment agent according to [1], wherein in the formula (Μ), 'A1 and A2 are each a group represented by one of the formulae (5) to (7).

[7] The liquid crystal alignment agent according to [4] or [4] wherein, in the formula (1-1) and the formula (1-2), R1 is individually represented by the formula (8) to the formula (15-2) At least one of the 4 valence groups selected by the base, r32rm

(15-2) wherein G represents a single bond, an alkylene group having a carbon number of 丨12 or 12, a 1,4-phenylene group, a 1,4-cyclohexylene group or a 1,4-cyclohexylene group, G2 is a single bond, -CH2-, -CH2CH2-, -〇-, -C〇_, _S - '-C(CH;j)2_, or -C(CF3)2_ ' 12 1341863 15189plf.doc x1 Is a single bond or -CH2- ' R32, R33, R34 and R35 respectively represent hydrogen, methyl, ethyl or phenyl, R36 represents hydrogen or methyl, and R37 represents hydrogen, methyl, ethyl or benzene. The ring A3 represents a cyclohexane ring or a benzene ring, respectively, and q represents 1 or 2, and the group represented by the formula (15-2) is composed of two groups of bonds in which the two bonds are located at the α-position. Composition.

[8] The liquid crystal alignment agent according to [2] or [5], wherein in the formula (1-1) and the formula (1-2), R1 is individually from the formula (8) to the formula (15-2) Representing at least one of the selected 4-valent groups of the base. [9] The liquid crystal alignment agent according to [3] or [6], wherein in the formula (1-1) and the formula (1-2), R1 is individually from the formula (8) to the formula (15-2) Representing at least one of the selected 4-valent groups of the base. [1] The liquid crystal alignment agent according to [2], [5] or [8], wherein in the formula (1-1), the formula (1-2), and the formula (2), R1 and R3 are each One of the groups represented by the formula (8) to the formula (1S-2).

[Claim] The liquid crystal alignment agent according to [3], [6] or [9], wherein in the formula (1-1), the formula (1-2), and the formula (3), R1 and R3 are each individually One of the groups represented by the formula (8) to the formula (15-2). [12] The liquid crystal alignment agent according to [2], [5], [8] or [10], wherein R4 is at least one of a divalent group selected from the group represented by the formula (16) to the formula (20). It

13 (16) 15189pif.doc wherein R38 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and ring A4 is 1,4-phenylene or 1,4-cyclohexylene, respectively, and Z1 and Z2 are respectively Single bond, -CH2-, -CH2CH2- or -Ο-, R is 〇~3, s is 〇~5, tl is 〇~3, and t2 is an integer of 0~3, when tl is 2 or 3 The plural Z1 may be the same or different from each other. When t2 is 2 or 3, the plural Z2 may be the same or different, and any hydrogen of 1,4-phenylene or 1,4-cyclohexylene may be used. Substituted by an alkyl group having 1 to 4 carbon atoms,

X2 - G3 - X3 - G4 - R39 wherein X2 and X3 are each a single bond, -Ο-, -COO-, -OCO-, -NH-, -CONH- or an alkylene group having a carbon number of 1 to 12 , G3 and G4 are each a single bond or a divalent group containing 1 to 3 rings selected from an aromatic group and an alicyclic group, and R39 is hydrogen, fluorine, -CN, -OH or a carbon number of 1 to 12 The alkyl 'fluoride-based or oxygen-based group, the binding position of the substituent to the benzene ring and the two free radicals may be any position, G4 is a single bond, and X3 is -〇-, -COO-, - When 0C0-, -NH- or -CONH-, where R" is hydrogen or an alkyl group, and both G3 and g4 are single bonds, the total number of carbon atoms contained in X2, X3 and R3ym is 3 or more.

Wherein 'R4() is hydrogen or a linear or branched alkyl group having a carbon number of 1 to 20, and one of the 1341863 lSl89pif.doc alkyl groups or a plurality of non-adjacent-CHr groups may be -〇 - Substituted, χ4 is a single bond or an alkylene group having 1 to 5 carbon atoms. One of the alkylene groups or a plurality of non-adjacent-CH2- may be substituted by -〇-, and t3 is 0 to 3. An integer, and t4 is an integer from 1 to 5, and the substituent of the benzene ring and the binding site of the radical are in an arbitrary position.

In the formula, X5 and X6 are each a single bond, -CH2-, -CH2CH2- or -〇-, and R41 and R42 are each hydrogen, an alkyl group having 1 to 12 carbon atoms, or a carbon number of 1 to 12 Fluorinyl group, W is an integer of 0 to 5, ul and u2 are each an integer of 0 to 3, and X5 of a complex number when ul is 2 or 3 may be the same or different, and when u2 is 2 or 3 The plural X6 may also be the same or different from each other, and any hydrogen of u3 is 〇 or 1, 1,4-phenylene may be substituted by an alkyl group having a carbon number of 1 to 4, R43 R« (2 〇) R44 R In the private formula, 'R43 and R44 are each a C 1~3 alkyl group or a phenyl group, R45 is a methylene group, a phenylene group or an alkyl group substituted phenylene group, and u4 represents 1 to 6 The integer, and u5 represents an integer from 1 to 10. []3] The liquid crystal alignment agent 'R4 as described in [3], [6], [9] or [11] is 15 1341863 15189plf.doc selected from the groups represented by the formulas (16) to (20) At least one of the two valence groups - 〇 [14] such as the liquid crystal alignment agent of one of [1] to [丨3], in the formula (1-2), R2 is from the formula (16)~ At least one of the selected divalent groups represented by the formula (20). [15] The liquid crystal alignment agent according to any one of [1] to [3] wherein R1 is one of the groups represented by the following (I) to (V),

0) O') (in) (iv) (v) A1 and A2 are each one of the following groups,

Me or F

[16] The liquid crystal alignment agent according to any one of [1] to [3] wherein R1 is one of the groups represented by the following (1) to (V),

(1) (丨丨) (Hi) (IV) (V) 16 1341863 15189pif.doc

Al and A2 together are 1,4-phenylene, X is sulfur, Q is -(CH2)P-, and p is an integer of 3 to 6. [Liquid] The liquid crystal alignment agent according to [15], wherein R3 is one of the groups represented by the following (I) to (V),

(I) (II) (III) (IV) (V) R2 is one of the following groups,

Here, BN represents a benzyl group, and R4 is one of the following groups. 17 15189 pif.doc _0/> N0~ • hO/nO~ [18] A liquid crystal alignment film obtained from a liquid crystal alignment agent described in one of [1] to [17]. [19] A liquid crystal display element using the liquid crystal alignment film according to [18]. [Embodiment] The present invention is characterized in that a polyaminic acid having a constituent unit of the chemical formula (1-1) as an essential component or a polyimine obtained by amidating the polyamidamide is used as a base polymer, and A liquid crystal alignment agent is obtained by dissolving it in an organic solvent. Such a polymer may contain a constituent unit represented by the formula (1-2) as a constituent unit, and may further be a polyglycine containing a constituent unit represented by the formula (2) or the formula (3) or a poly-polymer. A polymer mixture of quinone imine. When such a liquid crystal alignment agent is used, a liquid crystal display element having an alignment film which satisfies the above requirements can be obtained. Here, polyamic acid or polyamidomine also has a case called a polymer only. In addition, the liquid crystal alignment agent containing polyglycine which is an essential component of the chemical formula (1-1) represents only the polyamine acid represented by the chemical formula (1-1) by chemical formula number, and is simply referred to as polyfluorene. A liquid crystal alignment agent of a polyimine which is an essential component of the chemical formula (3) and which represents a polyimine represented by the chemical formula (3) and is simply referred to as a polyimine. . The polyimine in the present invention is not limited to the polymer obtained by polyamidonic acid 100% amidation, and also contains a part of 醯 1341863 lS189pif.doc aminated polymer. In the chemical formula (1-1), in order to maintain high VHR and reduce burning, the number of aromatic ring groups of A1 and A2 is preferably 3 or less. Further, it is preferably less than 2 in the case of a condensed ring. In order to further improve the VHR of the alignment film, A1 and A2 are shown.

The aromatic cyclic condensed cyclic group may also be introduced into a substituent. In this case, in order to prevent chips of the alignment film, the substituent is preferably an alkyl group having 1 to 4 carbon atoms, a carbon number of 1 to 4 alkoxy group or a fluorine atom. Further, in particular, the polyamino acid of the present invention or X of the polyimine is an oxygen atom. In order to improve the cauterization phenomenon due to the coordination of impurity ions or the like with respect to the oxygen atom, an aromatic group having a substituent at the oxime position with respect to the oxygen atom is particularly preferable. Preferred examples of the aromatic group represented by these A1 and A2 include 1,4-phenylene '1,3-phenylene group and 2-methyl-1,4-phenylene group. 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-butyl-1,4-phenylene, 2-isopropyl, -1,4- Phenylene, 2-t-butyl-1,4-phenylene '2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propene Oxy-1,4-phenylene, 2-butoxy-1,4-phenylene, 2·fluoro-1,4-phenylene, 2,3-dimethyl-1,4-Asia Phenyl, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, 2,3,5,6-tetra Methyl-indole, 4-phenylene, 4,4,-diphenylene, 2-methyl-4,4,-diphenylene, 2-ethyl-4,4'-diphenylene , 2-propyl-4,4,-diphenylene, 2-butyl-4,4'-diphenylene, 2-t-butyl-4,4,-diphenylene, 2- Methoxy-4,4'-diphenylene, 2-ethoxy-4,4, diphenylene, 2-fluoro-4,4, diphenylene, 3-methyl-4,4 '-Diphenylene, 3-ethyl-4,4,-diphenylene, 3-propyl-4,4, diphenylene, 3-butyl-4,4'-diphenylene , 3-t-butyl-4,4,- 19 1341863 15189pif.do c diphenylene, 3-methoxy-4,4'-diphenylene, 3-ethoxy-4,4'-mono-subunit, 3-fluoro-4,4,-di Phenyl, 2,2'-dimethyl-4,4'-diphenylene, 3,3'-dimethyl-4,4'-diphenylene, 3,3,-diphenylene , 5-methyl-3,3'-diphenylene, 5,5,-dimethyl-3,3'-diphenylene, 4,4''-triphenylene, 3-methyl- 4,4,,-triphenylene, 3-ethyl-4,4''-triphenylene, 3-propyl-4,4"-triphenylene, 3-butyl-4,4',- Triphenylene, 3-t-butyl-4,4''-triphenylene, 3-methoxy-4,4,'-triphenylene, 3-ethoxy-4,4"-triphenylene , 3-fluoro-4,4,'-triphenylene, 2-methyl-4,4''-diphenylene, 2-ethyl-4,4"-diphenylene, 2-propenyl 4--4'-triphenylene, 2-butyl-4,4''-triphenylene, 2-t-butyl-4,4''-triphenylene, 2-methoxy-4 , 4''-diphenylene, 2-ethoxy-4,4,'-triphenylene, 2-fluoro-4,4"-triphenylene, 2'-methyl-4,4'' -triphenylene, 2,-ethyl-4,4"-triphenylene, 2'-propyl-4,4''-triphenylene, 2'-butyl-4,4,,triphenylene base 2'-t-butyl-4,4''-triphenylene, 2'-methoxy-4,4,'-triphenylene, 2,-ethoxy-4,4''-triphenylene Base, 2'-fluoro-4,4''-triphenylene, 2,3-dimethyl-4,4''-triphenylene, 2,5-dimethyl-4,4''-three Phenyl '2', 3'-methyl-4,4''-triphenylene, 2',5'-dimethyl-4,4''-triphenylene, 1,5-naphthalene, 2, 6-naphthalene, 1-methyl-2,6-naphthalene, and the like. Further, examples of the condensed ring group include 1,5-naphthalene, 2,6-naphthalene, 1-methyl-2,6-naphthalene and the like. In the chemical formula (1-1), Q is preferably an alkylene group having a carbon number of 10 or less in order to maintain good alignment and prevent chips during rubbing. Preferred examples are, for example, 1,3-propylene '1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1J-heptylene, 1,8-octylene, 1,9-indenylene, 1,10-indenylene, and the like. In particular, in order to improve the stability of the polymer, it is preferable to prevent the chips from being rubbed, and it is preferably 1,3-butylene. Further, for example, when the surface energy of the liquid crystal alignment agent of the present invention is to be increased, for example, the structure using Q is -((CH2)20). ) an alignment agent of m (CH 2 ) 2 . In the chemical formula (1-1), X is a single bond, oxygen, or sulfur. In this case, in order to give the liquid crystal alignment agent a higher VHR, X is preferably a single bond or oxygen, and X is preferably a single bond. Further, for example, in the case of a liquid crystal alignment agent for IPS, in order to suppress the cauterization phenomenon, it is effective to use a liquid crystal alignment agent having a small volume resistivity of a polymer as described in SID International Conference, 2003, p. 1166. X is preferably oxygen or sulfur for this purpose, and X is preferably sulfur. As the tetracarboxylic dianhydride which produces the tetravalent organic group represented by R1 and R3 in the above chemical formulas (1), (2) and (3), all known tetracarboxylic dianhydrides can be used as a particularly suitable example. The compounds (NO. 1-〗 to NO. 1-40) described in the following Tables 1 and 2 are exemplified. 21 1341863 15189pif.doc [Table 1] NO Tetracarboxylic dianhydride NO Tetracarboxylic dianhydride 1-1 Ο 〇 Prison. Ο 〇 1-2 Ο 〇 °X° ο ο 1-3 1-4 〇^°y^.〇 Long time. 1-5 1-5 〇~<β>ο 〇乂ο^ο 1-6 ο 〇ο ο ο 1-7 Ο 〇1-8 ο 9 ο Ο ο 1-9 1-10 ο 1-11 Ο 〇 1-12 W M3 〇 Similar. Ο 〇 1-14 〇 4χ^〇 1-15 Ο 〇 1-16 ο ο 1-17 〇' 〇 〇 ias cut Ο 〇 1-18 icno} ο ο 1-19 o f3c Pf3 ο ο ο 1-20. 1-2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 1-31 0 1-32 . Green 1-33 —0--jo K 1-34 〇 〇 . Off. 〇0 1-35 :Material 1-36 A 1-37 1-38 0 P 0^0 1-39 0 Ο 1-40 turns [Table 2] Compounds containing isomers in these compounds may also be used. A mixture of isomers for this purpose. Further, the tetracarboxylic dianhydride used in the present invention may be other than the above compounds. The liquid crystal alignment agent of the present invention, which is obtained by using the polymer of the tetracarboxylic dianhydride of these preferred examples, can find a high VHR regardless of either, and imparts high liquid crystal alignment while preventing cauterization. ability. Therefore, as a liquid crystal composition containing a low critical voltage, an alignment film for a TFT type liquid crystal display element which is driven at a low voltage is particularly excellent. In the case where it is desired to give the liquid crystal display element a high VHR, by NO. 1-2, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1 -20, 1-21, 1-22, 1-23, 1-24, 1-28, Bra 29, 1-30, 1-31, Bu 32, 1-38 and the like having at least one of the compounds having an alicyclic skeleton One can be achieved. And especially if you want to prevent the burning phenomenon, by using NO. 1-1, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1- The compound of 10, 1-11, 1-19 can be achieved by appropriately combining with other compounds. As the diamine produced by the organic group represented by R2 of the chemical formula (1-2) and the organic group represented by R4 of the chemical formulae (2) and (3), all known diamines can be used, but as a particularly preferable example, the following table can be mentioned. The compounds described in 3 and 4 (NO. 2-1 to N0.2-52). Further, Bn of NO. 2-41 and 2-42 is benzyl. 24 1341863 15189pif.doc [Table 3]

No. Diamine No. Diamine 2-1 h2n(ch2)3nh2 2-2 h2n(ch2)4nh2 2-3 H2N(CH2)6NH2 2-4 H2N(CH2)12NH2 2-5 H^N-^ NH, 2-6 H2W—^ WH, 2-7 2-8 HzN~C~^~NH2 2-9 H2N—Jj^pnh2 2-10 ΡΛ HjN—^ 2-11 OCijH» 2-12 2-13 HiN^0 ^0~NH2 2-14 HJH NH, 2-15 2-16 2-17 2-18 2-19 2-20 2-21 O ^ζΫ'Ότ, 2-22 h^-〇/Sn〇-nh^ 2-23 hjn-0AQ.*>^\Q-nhi 2-24 h^-〇"°'〇><〇/0>©-n^ 2-25 0 h^〇/Hs〇- ^ 2-26 h^n-QA^Kq^^-nh, 2-27 NH, 0 NH, 2-28 h^nhQmQ-called 25 1341863 15189plf.doc [Table 4] 2-29 JVi„ m*n- 〇/n〇-nh* 2-30 2-31 2-32 η^^〇Ν©_^〇'©~ΝΗϊ 2-33 h2n^°^^°n©-nhj 2-34 C4H3 η2ν-^° ^^^°^-νη2 2-35 2-36 〇4Η3 2-37 2-38 C7H15 2-39 2-40 Ν〇/ ν〇-νΗι 2-41 2-42 Βη 2-43 2-44 Η, Ν 2-45 ►Μ* 2-46 Η2Ν 2-47 HjH 2-48 η2ν η2ν 2-49 Η,Ν 2-50 MjW' 2-51 Η2Ν-^^—^>-νη2 2-52 Η2Ν"^ ^5 /=\ w s-<^-nh2 26 1341863 15189pif.doc The liquid crystal alignment agent of the present invention obtained from the polymer obtained from the diamine obtained in the above preferred examples, In any case, a liquid crystal alignment film having a liquid crystal alignment ability while preventing cauterization is provided. Therefore, as a liquid crystal composition containing a low critical voltage, an alignment film for a TFT liquid crystal display element which is driven at a low voltage is particularly Excellent. The pretilt angle of the liquid crystal is generally adjusted by changing the size of the side chain of polyamic acid or polystyrene, and in most cases, by changing the size of the diamine residue. The diamine of R2 of (1-2) is represented by the preferred examples N0.2-1 to 2-33, 2-35, 2-37, and 2-40 to 2-42 of Tables 3 and 4 above. In the case of a diamine, it is particularly suitable as an alignment agent for an IPS type which requires a small pretilt angle. Further, when the diamines represented by N0.2-33 to 2-36, 2-38, 2-39, and 2-43 to 2-52 are used, they are particularly suitable for TN, OCB, and VA which are required to have a relatively large pretilt angle. Use an alignment agent. Considering the above, the preferred R2 is N0.2-8, 2-12, 2-1 3, 2-18, 2-22, 2-36, 2-37, 2-38, 2-41, 2- 42, 2-44, 2-46 ° Further, preferred R4 is ΝΟ·2-8, 2-12, 2-13, 2-18, 2-22. The polymer represented by the formula (1-1) and the composition unit represented by the formula (1-1) and (1-2) used in the present invention may be any one of the constituent units represented by the formula (1-1): 10 to 100 mol%. Alternatively, but in the case where it is desired to impart a high alignment energy to the liquid crystal alignment film, the larger the number, the better, preferably 30 to 100 mol%, more preferably 50 to 1 mol%. The liquid crystal alignment agent of the present invention may contain only one type of structural unit represented by the formula (1-1) or may optionally contain a structural unit represented by the formula (1-2), but a formula (2) may be added thereto. Or a polymer represented by the formula (3) and a mixture of two types of 27 1341863 15189plf.doc or more (the varnish in which the plural polymer is mixed is also referred to as "polymer mixed varnish"). The polymer-mixed varnish can impart desired properties to the alignment film formed using such a film. In the liquid crystal alignment agent of the present invention, the polymer having a structure represented by the chemical formulas (16) to (18) in R2 or R4 is a component having a small surface tension. Further, the polymer containing the constituent unit represented by the formula (1-1) has particularly excellent liquid crystal alignment. Therefore, in the case where the polymer is mixed according to the present invention, the structure represented by the chemical formulas (16) to (18) is contained in R2 of the constituent unit represented by the chemical formula (1-2) as the surface of the liquid crystal alignment agent. When a component having a small tension is used, a resin which exhibits good liquid crystal alignment property on the surface of the alignment film is used, and an alignment film which is effective in finding a stable liquid crystal alignment property which is one of the features of the present invention can be obtained. Polylysine represented by the chemical formulas (1-1) and (1-2) (or the polyamidene obtained by the amidation of the polyglycolic acid. Hereinafter referred to as the former polylysine (or poly (Resole)) Polyimine represented by the chemical formula (2) (or polyimide represented by the chemical formula (3). Hereinafter referred to as the latter poly-proline (or polyimide) When the above polymer is mixed, the mixing ratio may be arbitrarily selected from 1 to 99% by weight. Polyuric acid (or polyamidoamine) which is used in the former is used as a component having a low surface tension, and when it is desired to impart a high alignment energy to a liquid crystal alignment agent, the latter polyphosphoric acid (or polyamidamine) The mixing ratio of the former is preferably 〜50% by weight, more preferably 3% to 5% by weight. The method of polymer mixing is to mix a solution of the former poly-proline (or poly-liminamide) in a suitable solvent with a solution of the latter poly-proline (or polyamidamine) dissolved in a suitable solvent. Then, the mixture solution was distilled off to dissolve 28 1341863 15189 pif.doc to obtain a mixture. The alignment film is produced from the mixture, and a solution (varnish) in which the mixture is dissolved in a suitable solvent is used. The concentration of each component of the polymer can be directly used in the production of the alignment film as desired. The polyamino acid used in the present invention has a weight average molecular weight of preferably 5,000 to 500,000, more preferably 10,000 to 100,000. Further, in the case of coating by printing using the latest ink jet method, the molecular weight is preferably 5,000 to 100,000, more preferably 10,000 to 50,000. The polyamidamine of the present invention is preferably a polyamidene derived from a polyamic acid of the above molecular weight. Further, in order to find more excellent characteristics as an alignment film, the liquid crystal alignment agent of the present invention may be a varnish in which one or more types of polymers are selected from the polymer of the present invention and any known polymer. The known polymer may, for example, be another known polymer compound such as polyamidamine or polyamine. In this case, the ratio of the polymer of the present invention in the total polymer is preferably from 50 to 100% by weight in order to effectively find the effect of the present invention (including a liquid crystal display element which provides an increase in voltage holding ratio and suppresses cauterization). The range is more preferably in the range of 70 to about 1% by weight. The liquid crystal alignment agent of the present invention is preferably one in which a predetermined polymer is dissolved in a low boiling point solvent and stored or used as a varnish. The ratio of the polymer to the solvent at this time is not particularly limited, and as described below, it is preferably a varnish coating method (brush coating method, dipping method, spin coating method) selected for forming an alignment film on a ruthenium plate. , spray method, printing method, etc.), choose the best choice. Usually, in order to suppress dislocation or pinholes during coating, the ratio of the polymerization to the varnish weight is preferably 0.1 to 30 weight%. More preferably, it is 1 to 10% by weight. p The liquid crystal alignment agent of the present invention may contain any component other than the polymer. For example, by adding an organic ruthenium compound to the liquid crystal alignment agent of the present invention, the adhesion to the glass substrate and the hardness of the alignment film formed using the alignment agent can be adjusted. Further, when the formed alignment film is subjected to the alignment treatment (including the rubbing treatment), the display failure due to the alignment film chips can be improved. The organic hydrazine compound contained in the liquid crystal alignment agent of the present invention is not particularly limited, and examples thereof include exemplified aminopropyltrimethoxydecane, aminopropyltriethoxydecane, vinyltrimethoxydecane, and N. -(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, vinyl triethyl Oxydecane, 3-methacryloxypropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, a decane coupling agent such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, dimethylpolysiloxane, polydimethyl siloxane or polydiphenyl fluorene The content of the fat in the alignment agent of the organic hydrazine compound is not particularly limited, and the range of display defects can be improved without impairing the properties required for the alignment film. However, if the content of the organic ruthenium compound in the alignment agent is increased, the alignment of the liquid crystal is liable to occur in the formed alignment film. Therefore, the concentration of the organic ruthenium compound of the liquid crystal alignment agent of the present invention is preferably 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight based on the weight of the polymer contained in the alignment agent. For the preparation of the solvent for each liquid crystal alignment agent of the present invention, 30 1341863 lS189plf.doc N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), ethylene glycol monobutyl ether (BC), ethylene glycol monoethyl ether, and 7-butyrolactone may be used in combination of two or more kinds. Further, the reaction product is not limited to this as long as it can dissolve the reaction product. At least one of the polymers used in the present invention and other components are dissolved at a concentration of 0.1 to 30% by weight, preferably 1 to 0.001% by weight based on the total weight of the solvent, and the solution is applied by brush coating or impregnation. A method, a selective coating method, a spray method, a printing method, or the like is applied to the substrate. Thereafter, the solvent is evaporated at 50 to 150 ° C, preferably 80 to 120 ° C, and then heated and formed into a film at 150 to 40 (TC, preferably 180 to 280 ° C. On the surface of the substrate before coating) The decane coupling agent treatment can improve the film-substrate bondability when the film is formed thereon. Thereafter, the film surface is rubbed in a direction with a cloth or the like to obtain an alignment film. The thickness of the alignment film of the present invention is such that the alignment is satisfied. The characteristics required for the film can be variously selected in accordance with the manufacturing conditions of the display element, but it is generally preferably 〜200 /zm. The liquid crystal display element of the present invention contains the alignment film of the present invention as an alignment film. It is also possible to have the same configuration as any known liquid crystal display element. The liquid crystal display element of the present invention has advantageous characteristics such as high voltage holding ratio, improvement in smoldering, and stable liquid crystal alignment. Therefore, the liquid crystal display of the present invention The element is, for example, a liquid crystal display element for TFT. The liquid crystal display element of the present invention has high necessity for high voltage holding ratio and improved cauterization. The effect of the alignment film contained in the article 31 1341863 15189pif.doc is particularly effective. The liquid crystal composition used for the liquid crystal display element for TFT is described in Patent No. 3086228, Patent No. 2635435, and Special Table 5- In the liquid crystal display device of the present invention, the liquid crystal composition described above can also be used. The liquid crystal alignment agent of the present invention having the above constitution can be used as an alignment film or a protective film. The use of an insulating film or the like is particularly suitable for use as an alignment film for a liquid crystal display element. Further, the liquid crystal alignment agent of the present invention can be applied to various polyamine coating agents, in addition to being used as a liquid crystal alignment agent. A mercapto resin molded article or a fiber or the like. Experimental Example The following article provides a detailed description of a product obtained by using the liquid crystal alignment agent of the present invention, that is, a liquid crystal alignment agent of a polyamidamide resin. The reaction was carried out under all nitrogen atmospheres. The molecular weight was measured by GPC method, polystyrene was used as the standard polymer, and the eluate was determined by DMF. Further, the present invention is not limited to these experimental examples. Evaluation Method of Liquid Crystal Display Element The evaluation method of the liquid crystal display element used in the experimental example is described below. 1. The pretilt angle is performed by a crystal rotation method. Charge) The residual charge is measured by the method of 32 1341863 15189plf.doc described in "Miyake, Letters, EID91-U1, pl9". The measurement method is to superimpose 50mv, lkHZ alternating current and frequency 0.0036HZ for liquid crystal cells. The low-frequency triangular wave is used. This residual charge is used as an indicator of cauterization. That is, the more the residual charge is, the easier it is to burn. 3. The voltage holding ratio is recorded by the "Water Margin, the 4th Liquid Crystal Seminar Pre-Collection ρ78". The method is carried out. The measurement conditions were a gate width of 69 μs, a frequency of 60 Hz, and a wave height of ±4.5 V. 4. Liquid crystal alignment and black level are visualized by using a polarizing microscope. In particular, the black level is observed in the state of the straight Nikon (N1C〇l) state in which the incident light is in the same alignment direction as the unit cell. 5. Chips are viewed by using a microscope 0. Experimental Example 1 (Synthesis of Liquid Crystal Aligning Agent 1 Formed from Polylysine) In a 100 ml 4-necked flask provided with a stirrer, a nitrogen gas introduction port, a thermometer, and a raw material introduction port, 1,3-double (4- Amino-2-methylphenyl)propane (hereinafter referred to as DDPMD) 1.018 g (4.500 mmol) was dissolved in 10 g of NMP. There were added pyromellitic dianhydride (hereinafter referred to as PMDA) 0.4908 g (2.250 mm 〇l) and 1,2,3,4-cyclobutane tetracarboxylic dianhydride (hereinafter referred to as CBTA.) 0.4412 g. (2.25 mm 〇 l) Stir for 6 hours. Thereafter, this solution was diluted with NMP 29 g to obtain a transparent solution of about 5% by weight of polyglycine. 33 1341863 15189pUldoc This solution has a weight average molecular weight of 74,000 and a viscosity of 64 mPa·s at 25 °C. This solution is referred to as varnish 1 below. Experimental Example 2 (Synthesis of Liquid Crystal Alignment Agent 2 Formed from Polylysine)

A varnish solution was obtained according to the method of Experimental Example 1, except that DDPM was replaced by 1.2710 g (4.500 mmol) of 1,3-bis(4-amine-2-methylphenoxy)propane (hereinafter referred to as DDPMO.). . The solution had a weight average molecular weight of 75,000 and a viscosity at 25 ° C of 56 mPa·s. This solution is referred to as varnish 2 below. Experimental Example 3 (Synthesis of Liquid Crystal Aligning Agent 3 Formed from Polylysine) A mixture of DDPM 0.5092 g (2.250 mmol) and a compound of Table 4 (NO. 2-36) 1.1311 g (2.250 mmol) was used in addition to the diamine. A varnish solution was obtained according to the method of Experimental Example 1, except that PDMA 0.9815 g (4.500 mmol) was used for the tetracarboxylic dianhydride. The solution has a weight average molecular S of 68,000 and a viscosity at 25 ° C of 42 mPa·s. This solution is hereinafter referred to as varnish 3. Experimental example 4

(Synthesis of Liquid Crystal Aligning Agent 4 Formed from Polylysine) A varnish solution was obtained in accordance with the method of Experimental Example 3 except that DDPM was replaced with DDPMO 0.6354 g (2.25 Gmmol). The solution had a weight average molecular weight of 65,000 and a viscosity at 25 ° C of 36 mPa · s. This solution is referred to as varnish 4 below. Experimental Example 4-2 (Synthesis of Liquid Crystal Aligning Agent 4-2 Formed from Polylysine) Except for bis(2-(4-aminophenyl) acetamidine) (hereinafter referred to as 34 1341863 15189 pif. Doc DDEEO.) 1, 2975 g (4.5 〇〇 mm 〇 1) was replaced by a method to obtain a varnish solution according to the method of Experimental Example 1. The solution had a weight average molecular weight of 72,000 and a viscosity at 25 ° C of 37 mPa·s. This solution is hereinafter referred to as varnish 4_2. Experimental Example 5 (Liquid alignment of liquid crystal formed by poly-branched acid lj 5 $ Δ $ j except 1,3-bis(4-aminophenylaminophenylsulfonyl)propane (hereinafter referred to as DDPS.) l. 3〇7g (4.5〇0mmol) was substituted for DDpM. 'A varnish solution was obtained according to the method of Experimental Example 1. The weight average molecular weight of this solution was 82,000' and the viscosity at 25 ° C was 42 mPa · 5. The solution below is called varnish. 5. Experimental Example 5-2 (Synthesis of Liquid Crystal Alignment Agent 5-2 Formed from Polylysine) Except 1,4-bis(4-aminophenylaminophenylsulfonyl)butane (hereinafter referred to as DDBS) In addition to 1.37 Cg (4.500 mmol) instead of ddpm, a varnish solution was obtained according to the method of Experimental Example 1. The weight average molecular weight of this solution was 73,000's. The viscosity at 25 ° C was 35 mPa·s. The solution below is called varnish. 5-2. Experimental Example 5-3 (Synthesis of Liquid Crystal Aligning Agent 5-3 Formed from Polylysine) Except that 0.628 g (2.250 mmol) of the compound (N〇.l-29) (Table 2) was used instead of CBTA, A varnish solution was obtained according to the method of Experimental Example 5-2. The weight average molecular weight of this solution was 67,000, and the viscosity at 25 ° C was 3 3 mPa · s. 5-3. Experimental Example 6 (Synthesis of Liquid Crystal Aligning Agent Formed from Polyamine) To the varnish 3 prepared in accordance with Experimental Example 3, 4.6 g (45 mmol) of acetic anhydride was added to react at 1 ° C for 1 hour. After cooling, the reaction mixture was poured into 100 ml of 35 1341863 15189 pif.doc of pure water, and the resulting precipitate was filtered. The precipitate was washed with pure water (25 ml) and methanol (25 ml), and then dried under vacuum to give polyamine. The physical property evaluation was carried out by dissolving the polymer in NMP as a 5% varnish solution. According to the method of Experimental Example 1, the varnish shown in the following Tables 5 to 7 was prepared. [Table 5] Synthetic varnish test case / varnish II Amine a) (in the range of (%) in English) tetrahexanoic acid dianhydride (inward is Wuer ° /.) Viscosity (MPa · sy molecule m. (xlO · 3) 7 DDPM - 1-2 * - 68/ 98 8 DDPM(50) 2-8(50) 1-1(50) 1-2(50) - 47/56 9 DDPM(50) 2-12(50) 1-1(50) 1-2(50 ) - 50/63 10 DDPM(50) 2-14(50) 1-1(50) 1-2(50) - 37/45 11 DDPM(50) 2-16(50) 1-1(50) 1 -2(50) - 43/65 12 DDPM(50) 2-18(50) 1-1(50) 1-2(50) - 57/56 13 DDPM(50) 2-19(50) 1-1 (50) 1-2(50) - 60/87 14 DDPM(50) 2-20(50) 1-1(50) 1-2(50) - 43/53 15 DDPM(50) 2-37(50) 1-1(50) 1-2(50) - 48/53 16 DDPM(50) 241(50) 1-1( 50) 1-2(50) - 31/38 17 DDPM(50) 2-42(50) 1-1(50) 1-2(50) - 35/45 18 DDPM(50) 2-37(50) 1-1(50) 1-2(50) - 76/102 19 DDPM(50) 2-41(50) 1-1(50) 1-2(50) - 48/53 20 DDPM(50) 2^ 2(50) 1-1(50) 1-2(50) - 44/52 21 DDPM(50) 2-13(50) 1-H25) 1-2(50) 1-13(25) 40/49 22 DDPM(50) 2-13(50) 1-U25) 1-2(50) 1-20(25) 21/29 23 DDPM(50) 2-13(50) 1-H25) 1-2(50 1-21(25) 59/64 24 DDPM(50) 2-13(50) 1-1(25) 1-2(50) 1-26(25) 30/29 25 DDPM(50) 2-13 (50) 1-U25) 1-2(50) 1-29(25) 42/49 26 DDPM(50) 2-13(50) 1-U25) 1-2(50) 1-33(25) 30 /32 27 DDPM(50) 2-13(50) 1-1(25) 1-2(50) 1-35(25) 77/100 28 DDPM(50) 2-13(50) 1-H25) 1 -2(50) 1-36(25) 43/54 29 DDPM(50) 2-13(50) M(25) 1-2(50) 1-37(25) 48/55 30 DDPM(50) 2 -13(50) 1-1(25) 1-2(50) 1-33(25) 39/49 31 DDPM(50) 2-13(50) 1-1(25) 1-2(50) 1 -35(25) 51/65 32 DDPM(50) 2-13(50) 1-1(25) 1-2(50) 1-36(25) 40/52 33 DDPM(50) 2-13(50 ) 1-1(25) 1-2(50) 1-37(25) 57/62 34 DDPM(50) 2-36(50) 1-1 - - 32/45 35 DDPM(50) 2-38(50) 1-1 - - 22/39 36 DDPM(35) 2-43(75) Μ - 35/50 37 DDPM(50) 2^4(50 Μ - - 34/66 38 DDPM(85) 2-46(15) 1-1 - - 20/30 36 1341863 15189pif.doc a) ; Compound NO. is the same as described in Tables 3 and 4. b); Compound NO. is the same as described in Tables 1 and 2. [Table 6] Synthetic varnish test example / varnish diamine a) (% in the (%)) tetraresidic acid dianhydride b) (o inside is the ear %) viscosity (MPa · sy molecular weight (xi 〇 ° 39 DDPMO ~ 1-2 - - 66/86 40 DDPO(50) 2-8(50) 1-1(50) 1-2(50) 44/59 41 DDPMO(50) 2-12(50) 1 -1(50) 1-2(50) - 56/71 42 DDPMO(50) 2-14(50) 1-1(50) 1-2(50) - 51/45 43 DDPMO(50) 2-16 (50) 1-1(50) 1-2(50) - 50/52 44 DDPMO(50) 2-18(50) 1-1(50) 1-2(50) - 39/54 45 DDPMO(50 2-19(50) 1-1(50) 1-2(50) - 61/99 46 DDPMO(50) 2-10(50) M(50) 1-2(50) - 49/49 47 DDPMO (50) 2-37(50) 1-1(50) 1-2(50) - 44/50 48 DDPMO(SO) 241(50) 1-1(50) 1-2(50) - 40/47 49 DDPMO(50) 242(50) 1-1(50) 1-2(50) - 37/45 50 DDPMO(50) 2-37(50) 1-1(50) 1-2(50) - 65 /77 51 DDPMO(50) 24U50) 1-1(50) 1-2(50) - 49/60 52 DDPMO(50) 2-42(50) 1-1(50) 1-2(50) - 33 /48 53 DDPMO(50) 2-3(50) 1-H25) 1-2(50) 1-13(25) 48/56 54 DDPMO(50) 2-13(50) 1-1(25) 1 -2(50) 1-20(25) 29/32 55 DDPMO(SO) 2-13(50) 1-1(25) 1-2(50) 1-21(25) 38/59 56 DDPMO(50 ) 2-13(50) 1-1(25) 1-2(50) 1-26(25) 35/33 57 DDPMO( 50) 2-13(50) 1-1(25) 1-2(50) 1-29(25) 41/45 58 DDPMO(50) 2-13(50) 1-H25) 1-2(50) 1-33(25) 40/44 59 DDPMO(50) 2-13(50) 1-1(25) 1-2(50) 1-35(25) 55/71 60 DDPMO(50) 2-13( 50) 1-1(25) 1-2(50) 1-36(25) 29/38 61 DDPMO(50) 2-13(50) 1-1(25) 1-2(50) 1-37( 25) 55/67 62 DDPMO(50) 2-13(50) 1-1(25) 1-2(50) 1-33(25) 54/53 63 DDPMCX50) 2-13(50) 1-1( 25) 1-2(50) 1-35(25) 59/70 64 DDPMO(50) 2-13(50) 1-1(25) 1-2(50) 1-36(25) 49/58 65 DDPMO(50) 2-13(50) 1-U25) 1-2(50) 1-37(25) 56/68 66 DDPMO(50) 2-36(50) 1-1 - 33/49 67 DDPMO( 50) 2-38(50) 1-1 - 45/64 68 DDPMO(35) 243(75) 1-1 - 43/57 69 DDPMO(50) 2-45(50) 1-1 - 52/76 70 DDPMO (85) 2-46 (15) 1-1 - - 46/41 a) : Compound NO. is the same as those described in Tables 3 and 4. b); Compound NO. is the same as described in Tables 1 and 2. 37 1341863 15189pif.doc [Table 7] Synthetic varnish 寊 test sample / diamine *) acid anhydrous viscosity (MPa · sy 淸 paint (0 is the molar %) (0 is the molar %) Molecular S (xl0o) 71 DDPS 1-2 - 76/96 72 DDPS(50) 2-8(50) 1-1(50) 1-2(50) 05/89 73 DDPS(50) 2-12(50) 1-1( 50) 1-2(50) - 39/32 74 DDPS(50) 2-13(50) 1-1(50) 1-2(50) - 59/70 75 DDPS(50) 2-16(50) 1-1(50) 1-2(50) - 45/37 76 DDPS(50) 2-18(50) 1-1(50) 1-2(50) - 40/33 77 DDPS(50) 2- 19(50) 1-1(50) 1-2(50) - 84/85 78 DDPS(50) 2-10(50) 1-1(50) 1-2(50) 36/29 79 DDPS(50 ) 2-37(50) 1-1(50) 1-2(50) - 44/51 80 DDPS(50) 2-41(50) 1-1(50) 1-2(50) - 74/64 81 DDPS(50) 2-42(50) 1-1(50) 1-2(50) 53/44 82 DDPS(50) 2-37(50) 1-1(50) 1-2(50) - 58/64 83 DD?S(50) 2^1(50) 1-1(50) 1-2(50) 45/44 84 DDPS(50) 242(50) 1-1(50) 1-2( 50) - 44/45 85 DDPS(50) 2-3(50) 1-1(25) 1-2(50) 1-13(25) 68/53 86 DDPS(50) 2-13(50) 1 -1(25) 1-2(50) 1-20(25) 46/34 87 DDPS(50) 2-13(50) 1-1(25) 1-2(50) 1-21(25) 52 /38 88 DDPS(50) 2-13(50) 1-U25) 1-2(50) 1-26(25) 43/31 89 DDPS(50) 2- 13(50) M(25) 1-2(50) 1-29(25) 63/45 90 DDPS(50) 2-13(50) 1-1(25) 1-2(50) 1-33( 25) 63/44 91 DDPS(50) 2-13(50) M(25) 1-2(50) 1-35(25) 50/34 92 DDPS(50) 2-13(50) 1-1( 25) 1-2(50) 1-36(25) 60/42 93 DDPS(50) 2-13(50) 1-1(25) 1-2(50) 1-37(25) 64/41 94 DDPS(50) 2-13(50) 1-1(25) 1-2(50) 1-33(25) 53/40 95 DDPS(50) 2-)3(50) 1-H25) 1-2 (50) )-35(25) 54/42 96 DDPS(50) 2-13(50) 1-1(25) 1-2(50) 1-36(25) iim 97 DDPS(50) 2-13 (50) 1-U25) 1-2(50) 1-37(25) 54/61 98 DDPS(50) 2-36(50) 1-1 - - 37/22 99 DDPS(50) 2-38( 50) 1-1 - 41/30 100 DDPS(35) 2-43(75) 1-1 - - 36/22 101 DDPS(50) 2-45(50) 1-1 - 58/38 102 DDPS(85 ) 2-46(15) 1-1 66/43 102-1 DDPS(70) 2-22(30) 1-1(50) 1-2(50) 61/33 102-2 DDBS(70) 2- 22(30) 1-1 83/41 102-3 DDBS(70) 2-22(30) 1-1(50) 1-2(50) - 44/28 102^ DDBS(70) 2-52(30 1-1(50) 1-2(50) - 48/32 a) ; b) ; The compound NO. is the same as those described in Tables 3 and 4. The compound NO. is the same as those described in Tables 1 and 2. 38 1341863 15189pif.doc [Table 8] Synthetic varnish Π=ΓΒ*TM») Varnish diamine a> (% in the oxime) Tetracarboxylic acid diterpene b> (% in the (%) Moss ( Mpa . s) / Molecular Weight (xlO3) 103 2-8 - 1-1(50) 1 -2(50) 48/59 104 2-13 - 1-1(50) 1-2(50) 56/76 105 2-18(50) 2-36(50) 1-1(50) 1-2(50) 58/67 106 2-13(50) 2-44(50) 1-1(50) 1-2( 50) 45/84 a) ; Compound NO. is the same as described in Tables 3 and 4. b): Compound NO. is the same as described in Tables 1 and 2. Experimental Examples 108 to 114 The following compounds A to G were used as a diamine component, and a varnish was prepared in accordance with the method of Experimental Example 1. The results are shown in Table 9. [Table 9] Synthetic varnish Experimental example Compound viscosity (mPa · s) Molecular weight (xlO-3) 107 A 45 57 108 B 56 73 109 C 35 44 110 D 48 55 111 E 65 79 112 F 54 74 113 G 33 46 Compound A: 1,3-bis(4-amino-2-fluorophenyl)propane Compound B: 1,3-bis(4-(4-aminophenyl)phenyl)propane Compound C: 1,3 - bis(4-amino-3-methylphenyloxy)propane compound D: 1,4-bis(4-amino-2-methylphenyloxy)butane compound E: 1,3- Bis(4-Amino-2-methoxyphenyloxy)propane Compound F:, 3-bis(5-amino-2-methylphenyloxy)propane 39 15189 pif.doc Compound G: 1 , 3-bis(6-amino-2-naphthyloxy)propane Experimental Example 114 In a spiral vial, 2-butyl was added to 1 g of varnish 1 prepared according to the method of Experimental Example 1. Ethoxyethanol was 6.7 g to obtain a resin composition of about 3% by weight. This composition was dropped on a transparent glass substrate provided with an ITO electrode on one side, and coated by a spin coating method (2500 rpm, 15 seconds). After the application, the mixture was heated at 80 ° C for 5 minutes, and the solvent was evaporated, and then placed in an oven at 250 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 60 nm. The glass substrate on which the resin film was formed was subjected to a rubbing treatment, and two substrates were bonded in such a manner that the rubbing direction was antiparallel, and a liquid crystal cell having a cell thickness of 20 μm was assembled. A liquid crystal composition A composed of the following compound was injected into the unit cell, and subjected to an isotropic treatment at 110 ° C for 30 minutes, and cooled to room temperature to obtain a liquid crystal display element. The residual charge of this liquid crystal display element was 0.34 V at 25 ° C, and the VHR at 20, 60 and 903 C was 99.4, 98.7, and 96.5%, respectively. Moreover, as a result of measuring the pretilt angle using this display element, the pretilt angle was 1.5 degrees. Further, as a result of observation by a microscope, no alignment defect of the liquid crystal was observed, and the black level was good. Moreover, no chips were observed (hereinafter, these measurements are referred to as initial flaws). The unit cell was allowed to stand at ll〇t for 20 hours, and after cooling to room temperature, the ruthenium was measured again. As a result, the residual charge was 〇.53 V (25 ° C), VHR was 99.2 (20), 97.7 (60), 95.5% (90 ° C), and the pretilt angle was 1.4 degrees. Moreover, the alignment defect of the liquid crystal was not observed, and the black level was also good. Further, no chips were observed (hereinafter, such measurement nicknames are referred to as 加热 after heating). 1341863 15189pif.doc

Liquid crystal composition A c2Hs~^z)~Kzy~<c^~F 17 wt%

F

n-CjHy F 17 wt% F

6 wt%

F

Experimental Example l l 5 13 wt% A liquid crystal display element and measurement characteristics were produced in accordance with the method of Experimental Example 1 except that the varnish i was replaced with the varnish 2. Initial enthalpy: residual charge; 0 36v, VHR; 96·9 (20), 95 6 (60), 93. (3, pretilt angle: 1.4 degrees. Alignment defects and chips are not. Black level is good. 41 1341863 I5189pif.doc After heating 値: residual charge; 0.47V, VHR; 97.0(20), 96.1(60) ' 93.2(9 (TC)%, pretilt angle; 1.4 degrees. The alignment defect and the chip were absent. The black level was good. Experimental Example 116 In addition to the use of a mixture of varnish 2 (50% by weight) and varnish 70 (50% by weight) in place of varnish 1, A liquid crystal display element and measurement characteristics were prepared in accordance with the method of Experimental Example 114. Initial enthalpy: residual charge; 0.29 V, VHR; 97.1 (20), 95.9 (60), 94.2 (9 (TC)%, pretilt angle; 1.2 degree. Defects and chips are not. Black level is good. After heating 値: residual charge; 0.33V, VHR: 96.7 (20), 95.5 (60), 93.8 (90 ° C)%, pretilt angle; 1.1 degrees. Alignment defects and shavings The film was not obtained. The black level was good. Experimental Examples 117 to 145 The following liquid crystal display elements and measurement characteristics were produced in accordance with the method of Experimental Example 114. 42 1341863 15189pif.doc [Table 10] Orientation film characteristics Example varnish conditions Residual charge (V) VHR (%) Pretilt angle (degrees) Alignment defect m-class chip 20°C 60°C 90°C 117 7 Initial 0. 42 99.8 98.2 96.3 1.0 After no heat or 0.45 99.6 98.0 96.] 12 No good 118 8 Initial 0.12 98.3 96.5 94.2 1.3 No good after heating 0.14 98.1 95.7 93-9 1.3 No good 119 21 Initial 0.21 99.8 97.2 95.8 1.5 No good after no heating 0.20 99.5 97.1 95.0 1.4 No good 120 39 Initial 0.15 98.3 97.2 95.8 1.0 No good after heating 0.15 98.2 97.0 95-5 1.4 No good 121 40 Initial 0.10 98.0 96.6 94.5 1.0 No good after heating 0.09 98.1 96.0 94.5 1.4 无良无122 62 Initial 0.24 97.8 95.5 93.8 1.2 No good after heating 0.31 97.5 95.0 93.5 1.2 No good 123 71 Initial 0.08 96.1 95.4 92.9 1.0 No good after heating 0.09 96.1 95.2 92.7 1.0 No good 124 96 Initial 0.08 96.3 95.2 93.0 1.1 No good after no heating 0.08 96.6 95.1 92.7 1.1 No good 125 3 (90) 72 (10) Initial 0.33 97.9 95.5 93.4 1.5 No good after heating 0.37 97.5 95.5 93.7 1.4 No good 126 3(90) 73(10) Initial 0.48 97.5 95.7 93.4 5.1 No good after heating 0.51 97.6 95.4 93.7 5.4 No good 127 3(90) 74(10) Period 0.49 97.5 94.6 93.7 7.2 No good after no heating 0.49 97.1 95.0 92.9 7.0 No good 128 66 (10) 72 (90) Initial 0.21 99.0 98.2 95.4 4.3 No good after heating 0.25 98.7 98.2 95.2 4.1 No good 129 67 ( 10) 72(90) Initial 0.19 99.2 98.5 96.0 6.8 No good after no heating 0.18 99.1 98.2 95.8 6.7 No good 130 68(10) 72(90) Initial 0.10 98.9 98.2 95.6 5.3 No good without heating 0.15 99.0 98.0 95.4 5.2 Nothing no 131 4-2 Initial 0.15 98.1 97.0 95.1 0.6 No good without heating 0.15 98.0 96.7 95.1 0.7 No good no 132 5 Initial 0.08 98.3 97.1 95.2 1.6 No good after heating 0.08 98-6 97.5 94.8 1.7 No good 133 5-2 Initial 0.10 98.5 97.5 95.4 1.5 No good after no heating 0.14 98.5 97.5 95.5 1.4 No good 134 5-3 Initial 0.11 98.5 97.7 96.4 1.8 No good after no heating 0.11 97.9 97.4 95.3 1.7 No good 135 102-1 Initial 0.07 99.0 97.6 97.0 1.5 No good after no heating 0.09 99.1 98.0 95.9 1.6 No good 136 102-2 Initial 0.11 97.6 96.7 94.8 10 No good after heating 0.15 97.7 96.5 95.2 1.1 Good no 137 102-3 Initial 0.10 99.1 98.5 96.3 0.9 No good no gain 0.10 97.9 98.5 95.9 0.9 No good 138 102-4 Initial 0.10 98 8 97.8 96.6 1.0 No good after heating 0 12 98.9 98.1 96.5 1.1 No good 43 1341863 15189pif.doc [Table 11] Experimental example enamel paint (weight M%) Condition residual charge (V) VHR (° / 〇) Pretilt angle (degrees) Alignment chip swarf 20 ° C 60 ° C 90 ° C 139 107 Initial 0.47 99.0 98.1 96.4 2.0 No good after no heating 0.47 98.9 98.0 96.8 2.1 No 140 108 Initial 0.12 97.7 96.4 94 7 1.5 No heating after 0.14 97.6 96.5 93.4 1.6 No good 141 109 Initial 0.11 99.7 97.2 95.8 1.5 Unfriendly No heating after 0.20 99.4 97.2 95.0 1.4 No good 142 110 Initial 0.15 98.3 97.2 95.8 1.0 No good without heating 0.15 98.2 97.0 95.5 1.4 No good 143 111 Initial 0.23 97.4 96.5 94.0 1.4 No good after heating 0.29 97.5 96.3 94.0 1.5 Unscrupulous 144 112 Initial 0.44 99.1 98.3 96.0 2.0 No good after no heating 0.44 99.5 98.4 96.0 2.2 No good 145 113 Initial 0.10 96.8 95.2 93.0 1.0 No. No. After heating 0.11 96.2 94.9 93.0 1.0 None No. Experimental Example 146 A liquid crystal display element and measurement characteristics were produced in accordance with the method of Experimental Example 114 except that the liquid crystal composition A was replaced with the liquid crystal composition B described below. Initial enthalpy: residual charge: 0.54 V, VHR; 97.9 (20), 95.5 (60), 93.8 (90 ° C)%, pretilt angle; 1.3 degrees. There is no alignment defect. The black level is good. After heating, 値: residual charge; 0.64 V, VHR; 97.8 (20), 95.4 (60), 93.5 (90 ° C)%, pretilt angle: 1.1 degrees. There is no alignment defect. The black level is good. 44 1341863 lS189pif.doc

Liquid crystal composition B

7 wt% 7 wt% 9 wt% 10 wt% 10 wt% 12 wt% 11 wt% 5.6 wt% 4.5 wt% 9 wt% 1 Swt% Comparative Example According to Patent No. 15874 18, Compound (NO. 1-2) was used (Table 1) and Compound (NO. 2-13) (Table 3) The varnish A was prepared in accordance with the method of Experimental Example 1. A liquid crystal display element and measurement characteristics were prepared in accordance with the method of Experimental Example 114 except that the varnish 1 was replaced with the varnish A. The results are shown in Table 12. [Table 12] Alignment characteristic condition Residual charge VHR (°/〇) Pretilt angle (degrees) Alignment black (V) 20 °C 60 °C 90 °C Defect 1® Initial 0.75 98.6 97.3 95.5 1.5 h〇 0.84 after poor heating 98.4 96.6 95.5 1.4 hn defect By comparing Experimental Examples 1Π, 120 and 123 with Comparative Example 1, when the liquid crystal alignment agent of the present invention is used, it is understood that characteristics such as residual charge or VHR can be produced without deterioration, alignment, and blackness. Good display elements. Comparative Example 2 Varnish B was prepared in accordance with the method of Test Example 1 in accordance with the following composition according to the method of JP-A-2005-43. A liquid crystal display element and measurement characteristics were produced in accordance with the method of Experimental Example 114 except that varnish was replaced with varnish B. The results are shown in Table 13. Tetracarboxylic dianhydride: Compound (NO. 1-1) (Table 1), 1 Torr. /. Diamine; compound ^〇.2-8) (Table 3), 80 mol%, compound (1^〇.2-11) (Table 3), 20 mol% [Table 13] Alignment i ((V) VHR(0/〇) fi! Inclination (degrees) Alignment defect black level w piece 20°C 60°C 90°C initial 1.25 97.4 96.1 93.5 5.3 bad without heating 1.09 97.1 95.4 93.1 5.0 )) 9 Defectiveness By comparing Experimental Example 1 26 to 1 30 with Comparative Example 2, it was found that the liquid crystal alignment agent of the present invention has a small residual charge (V) and a high VHR even in an alignment agent imparting the same degree of pretilt angle. And learned that especially the alignment of the liquid crystal is good 46 1341863 15l89pif.doc. Comparative Example 3 In accordance with the method of Experimental Example, varnish C was prepared in accordance with the following composition in accordance with Patent No. 3,169,62. A liquid crystal display element 'measurement characteristic was produced in accordance with the method of Experimental Example U 4 except that varnish was replaced by varnish C. The results are shown in Table 14. - 1 ° tetracarboxylic dianhydride: compound (ΝΟ.1-1) (Table 1), 1 〇〇 mol % Η: ϊΝ - V-NH2 diamine; '100 mol. /. [Table 14] Alignment ί Characteristic condition Residual charge (V) VHR (%) Pretilt angle (degrees) Alignment - Chip 20 ° C 60 ° C 90 ° C Defect level initial 0.42 95.2 94.2 91.8 13 Unqualified _ Add 0.48 95.0 94.4 91.1 1.2 Nothing by comparison Experimental Example 11 5 and Comparative Example 3 'It is understood that the liquid crystal alignment agent of the present invention has a high VHR. INDUSTRIAL APPLICABILITY The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention has a stable pretilt angle, a high voltage holding ratio (VHR), a small residual charge, and is less likely to cause display disorder, and the liquid crystal is satisfied at a high level. The characteristics required for the display element, in particular, a liquid crystal alignment film in which excellent alignment properties are found. 47

Claims (1)

1341863 15lJ5pifI.doc The Chinese patent scope of the No. l.3132517 is not underlined. The revised period: August 4, 1999 X. Patent Application Range: 1. A liquid crystal alignment agent comprising: 10 to 100 mol% of constituent units represented by formula (1-1) and 90 to 0 mol% of constituent units represented by formula (1-2) The polylysine formed or the polyamidene obtained by amidating the polyamic acid, A2 - (1-1) - HN H-A1 - H02d 〇 2H Ο Ο - HN V NH - r2 HO〆t〇2H (1-2) In the formula, R1 individually represents at least one of the 4-valent groups selected by the group represented by the formula (8) to the formula (15-2), and 1341863 15189pifl.doc is the Chinese patent range of No. 93132517. Scribe correction This revision period: August 4, 1999 R32 R33 Wherein G represents a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group or an M-cyclohexylene group or a 1,4-cyclohexylene group, and G2 is a single bond, -CH2 -, -CH2CH2-, -〇-, -CO-, -S-, -c(ch3)2-, or -c(cf3)2-, x1 is a single bond or -CH2-, R32, R33, R34 and R35 represent hydrogen, methyl, ethyl or phenyl, respectively, R36 represents hydrogen or methyl, R37 represents hydrogen, methyl, ethyl or phenyl, and ring A3 represents cyclohexane or benzene, respectively. a ring, and q represents 1 or 2, and the base represented by the formula (15-2) is composed of two sets of bonds in which the two bonds are located at the α-position, and R2 represents a divalent organic group, Α1 and Α2. Individually expressed by one of equations (5) to (7), R7 R10 R11 R14 R15 (5) r12 RiT^R17 49 1341863 15189pifl.doc The Chinese patent scope of No. 93132517 is not underlined. Amendment date: August 4, 1999 Wherein R6 to R31 are each independently hydrogen, fluorine, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, methoxy, ethoxy, propoxy or butoxy. η and m are each 0 or 1, X represents a single bond, oxygen or sulfur, Q is -(CH2)P- or -((CH2)20)q(CH2)2-, p is 3 to 10, q is an integer from 1 to 3, and R1, R2, A1, A2, and X of each constituent unit may be different. When Q is -(CH2)P-, X is a single bond or oxygen, A1 and A2 are different. It is an unsubstituted phenylene group. 2. The liquid crystal alignment agent according to claim 1, which comprises the polyamido acid or the polyamidamine described in claim 1 and 1 to 99% by weight and represented by the formula (2) 1 to 99% by weight of the polymer component of the polyamido which constitutes the unit, 50 1341863 15189pifi.doc Date of revision: August 4, 1999 is the number of Chinese patents No. 93132517 No underline correction This NH-R4—(2) Ο ΛΑ Seven ΛΑ H02C^ b〇2H In the formula (2), R3 The tetravalent organic group, R4 represents a divalent organic group, and R3 and R4 in each constituent unit may be different, and the constituent unit represented by the formula (2) is different from the constituent unit represented by the formula (M). 3. The liquid crystal alignment agent according to claim 1, which comprises the polyamido acid or the polyamidamine described in claim 1 and 1 to 99% by weight and represented by the formula (3) a polymer component of 99% by weight of polyamidoamine constituted by a unit, In the formula (3), R3 represents a tetravalent organic group, R4 represents a divalent organic group, and R3 and R4 of each constituent unit may be different, and the constituent unit represented by the formula (3) and the formula (1-1) The constituent units are different. 4. The liquid crystal alignment agent according to claim 2, wherein in the formula (2), R3 is each one of the groups represented by the formula (8) to the formula (15-2), 51 1341863 15189pifl.doc is the Chinese patent scope of No. 93132517 without a slash correction. Amendment date: August 4, 2004 R32 R33 Wherein G represents a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group or an M-cyclohexylene group or a 1,4-cyclohexylene group, and G2 is a single bond, -CH2 -, -CH2CH2-, -〇-, -CO-, -S-, -c(ch3)2-, or -c(cf3)2-, X1 is a single bond or -CH2-, R32, R33' R34 and R35 represent hydrogen, methyl, ethyl or phenyl, respectively, R36 represents hydrogen or methyl, R37 represents hydrogen, methyl, ethyl or phenyl, and ring A3 represents cyclohexane or benzene, respectively. Ring, and q represents 1 or 2, and the base system represented by the formula (15-2) is composed of two sets of bonds in which the two bonds are located at 0: · bits. 5. The liquid crystal alignment agent according to claim 3, wherein in the formula (3), R3 is each one of the groups represented by the formula (8) to the formula (15-2), 52 15189pifl.doc is the 93132517 patent scope without a slash correction. Amendment date: August 4th of the year 〆 In the style, the game. Is 丨, 4_ ring wood single bond, alkylene group having 1 to 12 carbon atoms, I, 4-phenylene or _CH2CH, S group or M-cyclohexylene group, G2 is a single bond, -CH2- 'X1 is a single bond or, _s_, _C(CH3)2_, or -C(CF3)2_, methyl, B's 'R32, R33, R34 and R35 respectively represent hydrogen, a certain, or a phenyl group, R36 Represents hydrogen or methyl, R37 represents hydrogen, And q table axe; the base, ring eight respectively represent a cyclohexane ring or a benzene ring, the base of the mouth / work, 1 or 2 ' (5:2) is represented by two bonds It consists of two sets of keys at α_You & 1乂. 6. The liquid crystal alignment agent according to claim 4, wherein R4 is at least one selected from the group consisting of a group represented by formula (16) to formula (20), 53 1341863 15189pifl.doc No Chinese Patent No. 93132517 Amendment date: August 4, 1999, where R38 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and ring A4 is 1,4-phenylene or 1,4-cyclohexylene, Z1 and Z2. Each is a single bond, -CH2-, -CH2CH2- or -Ο-, R is 0~3, s is 0~5, tl is 0~3, and t2 is an integer of 0~3, tl is 2 or At 3 o'clock, the plural Z1s may be the same or different from each other. When t2 is 2 or 3, the plural Z2s may be the same or different, and any hydrogen of M-phenylene or 1,4-cyclohexylene. It can be substituted by an alkyl group having 1 to 4 carbon atoms. X2 - G3 - X3 - G4 - R39 wherein X2 and X3 are each a single bond, -〇-, -COO-'-OCO-, -NH-, -CONH- or an alkylene group having a carbon number of 1 to 12 , G3 and G4 are each a single bond or a divalent φ group containing 1 to 3 rings selected from an aromatic group and an alicyclic group, and R39 is hydrogen, fluorine, -CN, -OH or a carbon number of 1~ 12 alkyl, fluoroalkyl or oxyalkyl, the position of the substituent of the benzene ring and the two free radicals can be any position, G4 is a single bond, X3 is -0-, -COO-, In the case of -0C0-, -NH- or -CONH-, when R39 is hydrogen or an alkyl group, and G3 and G4 are each a single bond, the total number of carbon atoms contained in X2, X3 and R39 is 3 or more. , 54 1341863 15189pifl.doc is the Chinese patent scope of No. 93132517 without a slash correction Revision date: August 4, 1999 (18) ～20 linear or branched alkyl, one of these yards or a non-adjacent plural/out- can be replaced by _〇_, X4 is a single bond or THfe? 5 sub-hospital base, one of the sub-hospital bases or a non-adjacent plurality of -CH2- can be replaced by -Ο-, t3 is an integer of 〇~3, and Η为卜5浦数'Qinghuan _ Daiji and the attacking position are arbitrary positions, In the formula, χ5 and χ6 are single-button, CH2-, mother-ch2- or -〇-R41, and each of the occupational hydrogen, the 1/丨2, or the carbon number 12 For 〇~5 field υ 5 integers, ul and u2 are 〇, The integers of 3, ul is 2 or 3, and the complex numbers of X5 can be the same and different from each other, and the complex β of u2 is 2 or 3, and the X6 of the η row and the plural are also mutually compatible. For the same page, the difference is 'and u3 is 〇 or 丨 疋 1 丨, any hydrogen of 4-phenylene may be substituted with an alkyl group having 1 to 4 carbon atoms, wherein R43 and R44 are each a carbon number. P〇) 1 to 3 alkyl or phenyl, R45 55 1341863 15189pifl.doc Date of revision: August 4, 1999 is the number of Chinese patents No. 93132517. There is no underline correction. The individual is methylene, phenylene or alkyl substituted phenylene, U4 means 1~6. An integer, and U5 represents an integer from 1 to 10. 7. The liquid crystal alignment agent according to claim 5, wherein R4 is at least one of a divalent group selected from the group represented by the formula (16) to the formula (20), Wherein R38 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and ring A4 is 1,4-phenylene or M-cyclohexylene alone, and Z1 and Z2 are each a single bond, -CH2-, -CH2CH2 -or-Ο-, r is 0~3, s is 0~5, t1 is 0~3, and t2 is an integer of 0~3. When t1 is 2 or 3, the plural Z1s can be the same as each other. Different, when t2 is 2 or 3, the plural Z2 may be the same or different, and any hydrogen of 1,4-phenylene or 1,4-cyclohexylene may be alkyl having 1 to 4 carbon atoms. Replace, (17) X2—G3—X3—G4—R39 In the formula, X2 and X3 are each a single bond, -〇-, -COO-, -OCO-, -NH-, -CONH- or an alkylene group having a carbon number of 1 to 12, and G3 and G4 are each a single bond or Is a divalent group containing 1 to 3 rings selected from an aromatic group and an alicyclic group, and R39 is hydrogen, fluorine, -CN, -OH or an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group or The oxyalkyl group, the binding position of the substituent to the benzene ring, and the two free radicals may be any position, G4 is a single bond, and X3 is -0-, -COO-, 56 1341863 For the Chinese patent scope No. 93132517, there is no slash correction. This revision date: "August 4th - 0C0-, -NH- or -CONH- occasions 'R39 is hydrogen or yard base, G3 and g4 In the case where all are single bonds, the total number of carbons contained in X2, χ3, and r39 is 3 or more. (18) wherein r4° is hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, and one of the alkyl groups or a plurality of non-adjacent-CH2- may be -0- Substituted, χ4 is a single bond or an alkylene group having 1 to 5 carbon atoms, and one of the alkylene groups or a plurality of non-adjacent-CH2- may be substituted by -〇-, and t3 is 〇~3. An integer, and an integer of 1 to 5, wherein the substituent of the benzene ring and the bonding position of the radical are arbitrary positions, In the formula, X and X are each a single bond, _CH2_, _CH2CH2_ or 〇_, R and R are each hydrogen, a carbon number of 12~12, or a carbon number of 12 W is an integer of 0 to 5, ul and u2 are each an integer of 0 to 3, ul, and a complex number of 棘5 of 2 thorns 3 may be the same or different ' χ 6 when 'u2 is 2 or 3. They may be the same or different from each other, and any hydrogen of S U3 stomach 0 or 1, 1,4-phenylene may be substituted by an alkyl group having 1 to 4 carbon atoms, and 1341863 15189pifl.doc is No. 9M32517 Chinese patent range without slash correction. Amendment date: August 4, 1999 R43 R43 (2〇) R44 R44 where R43 and R44 are each alkyl or phenyl with 1 to 3 carbon atoms, R45 is sub- The methyl group, the subunit or the pendant group is substituted with a phenylene group, u4 represents an integer of 1 to 6, and u5 represents an integer of 1 to 10. 8. The liquid crystal alignment agent according to claim 7, wherein in the formula (1-2), R1 is at least one of a divalent group selected from the group represented by the formula (16) to the formula (20). One, Wherein R38 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and ring A4 is 1,4-phenylene or 1,4-cyclohexylene, and Z1 and Z1 are each a single bond, -CH2-, • CH2CH2- or _〇_, r is 〇~3, s is 0~5, t1 is 0~3, and U is an integer of 0~3. When tl is 2 or 3, the plurals can be the same. Alternatively, when 12 is 2 or 3, the plural Z1 may be the same or different, and any hydrogen of the M-phenylene group or the 1,4-cyclohexylene group may be an alkyl group having 1 to 4 carbon atoms. Substitute, (17) 58 1 1341863 15189pifl.doc Date of revision: August 4, 1999 is the Chinese patent scope of No. 93132517. There is no slash correction. In this formula, X and X are single keys, ..._c〇〇_, _ 〇C〇_, -NH-, -CONH- or an alkylene group having 1 to 12 carbon atoms, and G3 and G4 are each a single bond or are selected from an aromatic group and an alicyclic group to contain 丨~3 rings. a divalent group, and R39 is hydrogen, fluorine, -CN'-oh or an alkyl group having a carbon number of 1 to 12, a fluoroalkyl group or an oxyalkyl group, a binding position of a substituent to a benzene ring, and two free groups The base can be iu set by Ren Si, G4 is a single bond, and X3 is _〇_, _c〇0- In the case of '-OCO-, -NH- or -CONH-, where R39 is hydrogen or an alkyl group, and both G3 and G4 are single bonds, the total number of carbon atoms contained in X2, X3 and r39 is 3 or 3. the above, (18) wherein R4Q is hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, and one of the alkyl groups or a plurality of non-adjacent-CH2- may be substituted by -0- X4 is a single bond or an alkylene group having a carbon number of 1 to 5, which is in the alkylene group! Or a plurality of non-adjacent -CH2- may be substituted by -〇-, t3 is an integer of 〇~3, and an integer of 1 to 5 of t4 is a substituent of a benzene ring and a binding position of a radical is arbitrary s position, In the formula, X5 and X6 are each a single bond, -CH2-, -CH2CH2- or -〇-, 59 1341863 15189pifl.doc Date of revision: August 4, 1999 is the Chinese patent scope of No. 93132517 without a slash correction R41 and R42 are each hydrogen, an alkyl group having 1 to 12 carbon atoms, or a perfluoroalkyl group having 1 to 12 carbon atoms, W is an integer of 0 to 5, and ul and u2 are each an integer of 0 to 3, ul. The X5s of the plural of 2 or 3 may be the same or different, and the plural X6s when u2 is 2 or 3 may be the same or different, and are 0 or 1,1,4. Any hydrogen of the -phenylene group may be substituted by an alkyl group having 1 to 4 carbon atoms. Wherein R43 and R44 are each independently a C 1~3 alkyl group or a phenyl group, R45 is a methylene group, a phenylene group or an alkyl substituted phenylene group, u4 represents an integer of 1 to 6, and u5 Indicates an integer from 1 to 10. The liquid crystal alignment agent according to any one of the items 1 to 3, wherein R1 is one of the groups represented by the following (1) to (V), A1 and A2 are each one of the following bases Q is -(CH2)P- or -((CH2)20)q(CH2)2-, p is an integer from 3 to 6, q 1341863 15189pifl.doc Revision date: August 4, 1999 is the 93rd The liquid crystal alignment agent of the above-mentioned item (1) to (v), wherein R1 is a group represented by the following (1) to (v). Among them A1 and A2 are collectively iota, 4-phenylene, X is sulfur, q is _((:112){)_, and p is an integer of 3 to 6. 11. The liquid crystal alignment agent according to claim 9, wherein R3 is one of the groups represented by the following (1) to (V), 〇<丨丨) (III) (IV) (V) R2 is one of the following bases, 1341863 Revision date: August 4, 1999, 15189pifl.doc is the Chinese patent scope of No. 93132517. ~o/no~ ?7^15 Bn Bn T αΧ 5 Η 11 where ΒΝ represents a benzyl group, and R 4 is one of the following groups, ^Q / sO - - 〇 / N < G) " 12. The liquid crystal alignment agent of claim 10, wherein R3 is one of the groups shown in the following (1) to (V), (I) (II) (III) (IV) (V) R2 is the following base 62 1341863 Revision date: August 2014 4曰15189pifl.doc is No. 93132517 Chinese patent scope without scribe amendment - 0/PnQ_ _o/n〇_ Here, BN represents a benzyl group, and R4 is one of the following groups, 63