TW201209020A - Diamine, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

A liquid crystal alignment agent is developed for obtaining a liquid crystal alignment film having high liquid crystal alignment and excellent black level. The liquid crystal alignment film is fabricated by polyamic acid and its derivatives obtained by reacting diamine, using diamine at least represented by general formula (I), with tetracarboxylic dianhydride. (Wherein, R is an amide group with a hydroxyl group bonded to the terminal on a nitrogen atom via a methylene group.)

Description

201209020 / /upir VI. Description of the Invention: [Technical Field] The present invention relates to a novel diamine, a liquid crystal alignment agent containing polylysine or a derivative thereof, and use thereof. [Prior Art] The liquid crystal display element is a view finder or a projection display of a video camera (note personal computer) or a desktop computer (monitor). It is used in various liquid crystal display devices such as projecti〇n display). In addition, it can also be used as an optoelectronic related component such as an optical printer head, an optical fourier transform element, and a light valve. The liquid crystal display device usually has: 1) a pair of substrates disposed opposite each other, 2) electrodes formed on one or both surfaces of the opposing faces of the pair of substrates, and 3) of the electrodes a liquid crystal alignment film formed on a surface facing each other of the substrate, and 4) a liquid crystal layer formed between the pair of substrates. The mainstream of liquid crystal display components is the display element using nematic liquid crystal, and 1) twisted 90 degree TN (Twisted, twisted nematic) type liquid crystal display element, 2) usually distorted above the stiffness STN (Super Twisted Nematic 'Super Twisted Nematic) type liquid crystal display element, 3) so-called TFT using a thin film transistor (a few Thanke T-side istor, _ transistor) bristle display element, etc. 201209020 t /υριι Use. These liquid crystal display elements have disadvantages in that the viewing angle of the image is appropriately narrowed, and when viewed from the oblique direction, a decrease in brightness or contrast and a brightness inversion of halftone are generated. In recent years, the problem of this viewing angle has been improved and put into practical use by the following techniques: 1) TN_TFT mode liquid crystal display using an optical compensation film, and 2) VA (Verdcal Alignment) using a vertical alignment and an optical compensation film. Vertical alignment mode liquid crystal display element, 3) MVA (Multi D〇 main Vertical Alignment) mode liquid crystal display element using the technique of vertical alignment and protrusion structure, or 4) & IPS (In-Plane Switching) mode liquid crystal display element, etc. The development of liquid crystal display element technology can be achieved not only by their driving method or improvement of the element structure, but also by the improvement of the constituent parts used in the element. Among the constituent members used in the liquid crystal display device, in particular, the liquid crystal alignment film is one of important materials relating to display quality, and as the quality of the liquid crystal display element is improved, the performance of the alignment film is improved. The liquid crystal alignment film is prepared by a liquid crystal alignment agent. The liquid crystal alignment agent mainly used now is a solution in which polylysine or soluble polyimine is dissolved in an organic solvent. After applying such a solution onto a substrate, a film is formed by heating or the like to form an alignment film. Although a liquid crystal alignment agent using a polymer other than polyamic acid has been studied, self-heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical properties, optical properties, display properties, and the like have been studied. Aspect considerations 'basically not put into practical use. 201209020 v»β ^ ΛΛ. Such an alignment film requires the effects of the liquid crystal display element as described below. (1) A suitable pretilt angle is imparted to the liquid crystal molecules. Moreover, the pretilt angle is hardly affected by the pressing strength at the time of friction or the temperature condition at the time of heating. (2) There is no alignment defect of liquid crystal molecules due to unevenness in friction, scratches, or reduction of the alignment film. (3) Give the liquid crystal display element an appropriate voltage holding ratio (v〇ltage

Holding Ratio : VHR ). (4) It is difficult to produce a phenomenon called "burn marks", which means that when a liquid crystal display element is displayed for a long time and then becomes another image, the previous image is in the form of an afterimage. Residual. The liquid crystal display element using the VA mode or the ips mode has good viewing angle characteristics as described above. Therefore, the liquid crystal τν developed in recent years basically uses a liquid crystal display element of a VA mode or an ips mode. When comparing the performance of the two modes, 'there are respective strengths and weaknesses due to the driving principle. For example, when the IPS mode is used, the viewing angle characteristics are particularly good'. Quickly equal strength. However, the contrast is poor compared to the VA mode. The IPS mode is not black when no voltage is applied, and this state depends on the initial alignment state of the liquid crystal due to friction, which is one of the causes of deterioration of contrast. That is, in the IPS alignment film, an alignment film having a high liquid crystal alignment property and a black display (good black level) can be strongly required. Patent Document 1 can be cited as an example of the prior art for solving such a problem. However, the technique of this document is characterized in that 6 201209020 jo i /upir uses a diamine having a triple bond at the end, and the effect is not confirmed in the liquid crystal display element of the Ips mode. [Problems to be Solved by the Invention] An object of the present invention is to develop a liquid crystal alignment having a high liquid crystal alignment property and a good black level. A liquid crystal alignment agent for the film. [Means for Solving the Problem] The present inventors have found that by using polyamic acid or a derivative thereof (in the polyamic acid or a derivative thereof, a diamine having a specific structure is used as one of raw materials) Further, the liquid crystal alignment element constituting the liquid crystal display element which satisfies the above-mentioned required characteristics is obtained, thereby completing the present invention. [Effect of the Invention] According to the present invention, a liquid crystal alignment agent having good alignment property can be obtained. Especially effective for the improvement of the black level of the IPS mode. Further, according to the present invention, it is also possible to obtain an effect of obtaining an alignment film having a small volume resistance. [Embodiment] The present invention includes the following configurations. [1] A diamine represented by the formula (I), [Chem. 24] 201209020

R (0

H2N (wherein R is an anthranyl group having a sulfhydryl group bonded to a nitrogen atom and having a hydroxyl group at the terminal). [2] The diamine according to [1], wherein R is represented by (a), (b) or (c), [Chem. 25]

(wherein, hydrazine is hydrogen or hydrazine). [3] The diamine according to [2], wherein R0 is hydrogen. [4] The diamine according to any one of [1] to [3] wherein, in the formula (I), the two amino groups are substituted for the 3-position '5', respectively, with respect to the substituent represented by R. Bit. [5] A poly-proline and a derivative thereof, which is at least one of the diamine represented by the formula (I) and the tetracarboxylic acid according to any one of [1] to [4] The anhydride is obtained by reaction. [6] A poly-proline and a derivative thereof, which is at least one of the diamine represented by the formula (I) and the other diamine 8 according to any one of [1] to [4]. A mixture of 201209020 (D2) is obtained by reacting a tetracarboxylic dianhydride. [7] The poly-proline and the derivative thereof according to [5] or [6] wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (DA-20) to formula (DA-32) More than one group, [Chem. 26]

In the formula (DA-20), G5 is a single bond, an alkylene group having a carbon number of 1 to 12, a 1,4-phenylene group or a 1,4-cyclohexylene group. (l,4-cyclohexylene); X1G is independently a single bond or CH2; moreover, G6 is independently CH or N. When G6 is N, G5 is not a single bond or CH2, and X1Q is not a single bond; 27]

201209020 38//Upit In formula (DA-21), R14 is independently hydrogen, methyl, ethyl, or phenyl; [Chem. 28]

In the formula (DA-22), the ring A6 is a cyclohexane ring or a benzene ring; [Chem. 29]

Base, i, 4, phenylene, fluorene, co, s, so2, c(ch3)2 or c(cf3)2; moreover, ring A7 is independently a cyclohexane ring or a benzene ring; [Chem. 30] 201209020 J8 //Upit

In the formula (DA-24), R15 is hydrogen or methyl; [Chem. 31]

In formula (DA-25), X1G is a single bond or CH2; XU is independently CH2, CH2CH2 or CH=CH; and, v is 1 or 2; [Chem. 32] 11 201209020 3877Upit

In the formula (DA-26), X1G is a single bond or CH2; [Chem. 33]

(DA-27) In the formula (DA-27), R14 is hydrogen, decyl, ethyl or phenyl; ring A8 is cyclohexane ring, cyclohexene ring or benzene ring; and, X12 is a single bond, CH2 or CH(CH3); [化34] 12 201209020 3877Upit

(DA-28) In the formula (DA-28), w2 and w3 are 0 or 1, and w3 = 1 when w2 = l; [Chem. 35]

13 201209020 3877ϋριί In the formula (DA-30), X13 is independently an alkyl group having 2 to 6 carbon atoms; and, Ph represents a phenyl group;

In the formula (DA-32), X14 independently represents a single bond or CH2. [8] The poly-proline and the derivative thereof according to any one of [6] to [7] wherein the other diamine (D2) is represented by the following formula (1-1) to formula (4) Diamine, [化39] 201209020 jo / /υριι

In the formula (1-1), 'b is 〇 or 1; any nitrogen in the cyclohexylene group may also be substituted by a thiol group; in the formula (1_2), 'W1 is ·CH2- or -NH-; ]

HZN

Nh2 (2) where 'X1 is a single bond or an alkylene group having a carbon number of 1 to 10; any -CHr of the alkylene group may also be -0-, -S-, -NH-, -N ( CH3)_, -C(CH3)2-, -C(CF3)2-, -CO-, -S02-, 1,3-phenylene, i,4-subunit or D guzin-1, 4-diyl (piperazine-1,4-diyl) substitution, [Chem. 41] 15 201209020 J6//Upil

In the formula (3), X2 is a single bond, 〇_, <〇〇_, _〇c〇_ or an alkylene group having a carbon number of 1 to 6; and R1 is an alkane having a carbon number of 3 to 3 Å. Or a group represented by the formula (a); in the formula (a), X3 and X4 are independently a single bond or an alkylene group having a carbon number of i to 4; and the ring B and the ring C are independently an L4-phenylene group. Or 丨, 4-cyclohexylene; R 2 and R 3 are independently fluoro or fluorenyl, and f and g are independently 〇, 丨 or 2; c, d and e are independently 〇 or 卜 and the total of c, d and e is 1 to 3; R4 is an alkyl group having a carbon number of 1 to 30, an alkoxy group having a carbon number of 丨~ buckle, an alkoxy group having a carbon number of 2 to 30, or a ch〇lesteryl group. In the alkyl, alkoxy and alkoxyalkyl groups, any hydrogen may also be substituted by fluorine; [201242] / /υριι R5

Here, X5 is independently -Ο- or an alkylene group having a carbon number of 1 to 6; j is independently 0 or 1; R5 is hydrogen, an alkyl group having 2 to 12 carbon atoms or an alkane having 2 to 12 carbon atoms Oxyl; ring T is 1,4-phenylene or 1,4-cyclohexylene; X6 is a single bond or an alkylene group having a carbon number of 1 to 3; h is 0 or 1. [9] The polyaminic acid according to any one of [6], wherein the other diamine (D2) is at least one selected from the group consisting of the following compounds, and a derivative thereof.

[化43] 17 201209020 JO / /upu

(wherein 'R is -CH2., -O- or a direct bond alkylene group having a carbon number of i~4, R12 is hydrogen or CH3, and R13 is a linear alkylene group having a carbon number of 2 to 4, and rh is The linear sub-alkyl group 'R15 with an inverse number of 1 to 8' is independently _[η2_, _(ch2)2-, 201209020 3»//υρΐΙ or -NH-, R16 is a hydrogen atom, or the carbon number is 1~ A linear alkylene group of 10, R17 is a hydrogen atom or a linear alkylene group having a carbon number of 1 to 16, and R18 is independently -CH2-, -(CH2)2- or -0-). [10] A composition comprising at least one polymer selected from the group consisting of polylysines and derivatives thereof according to any one of [5] to [9]. [11] A liquid crystal alignment agent, which is composed of a composition containing at least one polymer selected from the group consisting of polyamino acids described in [5] to [9] and derivatives thereof. [12] The liquid crystal alignment agent according to [11], which comprises the epoxy compound (E) according to [12], wherein the epoxy compound (E) is selected from the group consisting of (E1) to one or more groups of the compounds represented by the formula (E6), [E. 44] (E1) (E2) (E3)

(E5) <r^6- (wherein η is an integer of 1 to 10). [2012] The liquid crystal alignment agent according to [11], which comprises an oxazoline compound (F). [15] The liquid crystal alignment agent according to [14], wherein the oxazoline compound (F) is a compound represented by the following formula (F1), [Chem. 45]

(F1) The liquid crystal alignment agent according to [11], which comprises a bisallylndiimide compound (G). [1] The liquid crystal alignment agent according to [16], the bisallyl nadic ylidene imine compound (G) is a group selected from the group consisting of compounds represented by the following formula (G1) and formula (G2) More than one type, [Chem. 46]

[18] The liquid crystal alignment agent according to [11], which comprises a group selected from the group consisting of the compounds represented by the above (E1) to (E6), (F1), (G1), and (G2) More than one species. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of [U] to [18]. [20] A liquid crystal display element comprising the liquid crystal alignment agent according to any one of [1] to [18]. The diamine of the present invention can be represented by the following formula (1). [化47]

(wherein R is a sulfonyl group having a sulfhydryl group bonded to a nitrogen atom and having a hydroxyl group at the terminal.) In the formula (I), R is more preferably the following (a), (b) or (c) ) the diamine represented. [化48]

(wherein R0 is hydrogen or fluorenyl.) The compound represented by the formula (1) or (b) wherein R is (a) or (b) can be synthesized by the method shown in the stream. Process 1. 21 201209020 38770pif [Chem. 49]

〇2N

R.NHR1

Reverse = Brewed Chlorine and Amination 1 [Chemical 5〇J R*=:

It is synthesized by the method of R which is represented by the formula (I). Compounds of (c) can be spears.] Scheme 2. [Chem. 51]

02N^/=\^coc" N〇2 The dinitrophenyl hydrazine compound is obtained by reacting dinitrophenyl hydrazine with diethanolamine in the presence of a base such as diethylamine. The diamine of the present invention is obtained by reduction of the nitro group. 22 201209020 3877ϋριί· The liquid crystal alignment agent of the present invention is a composition containing at least one polymer selected from the group consisting of polylysine and a derivative thereof, and a solvent. Examples of the polyproline derivative include a polyimine obtained by subjecting polylysine to a complete dehydration ring-closure reaction, and a partial dehydration ring-forming reaction obtained by subjecting polylysine to a partial dehydration ring-closure reaction. a polyamic acid-polyacetamide copolymer obtained by replacing a part of the tetracarboxylic acid dianhydride with a dicarboxylic acid, or a part of the polystyrene-polyamide copolymer or The polyamine-quinone imine obtained by performing a dehydration ring closure reaction. Among these compounds, polyimine and partially ruthenium polyamine are preferred, and polyimine is more preferred. In the present invention, at least one selected from the group consisting of polylysine and a derivative thereof obtained by reacting a mixture of a diamine represented by the formula (I) and another diamine (D2) with an acid dianhydride 1 polymer. Specific examples of the diamine represented by the formula (I) used in the present invention are the following (1-1) to (1-10), and the diamines may be used in combination or only one type may be used. Further, among these compounds, a compound of (^5) or (^) is particularly preferred. [化 52] 23 201209020 3877ϋριί

In the case where a liquid crystal alignment agent is prepared by using a diamine (D2) other than the compound of the present invention, in order to further achieve the effects of the present invention, the ratio of the compound (I) of the present invention is preferably relative to the total amount of the diamine used. It is 5 mol〇/〇~100 mol%, more preferably 5 mol% to 95 mol%, and most preferably 20 mol% to 80 mol%. The diamine (D2) used in the present invention can be selected from known diamines without limitation. Preferred diamines include diamines (1-1) to diamines (1-3) shown below. Diamine (2), diamine (3) and diamine (4). It is preferred to use at least one diamine selected from the group of these diamines. 24 201209020 jo / /υριι [化53] h2n-| ^)"-ch2^H^)-nh2 (Μ) h2n^ w1 (1-2) h2n 乂fNtxH2 (1-3} in equation (1-1 In the formula, b is 0 or 1, and any hydrogen in the cyclohexylene group may be substituted by a mercapto group. In the formula (1-2), W1 is -CH2- or -NH-. These diamines (D2) In the following specific examples, from the viewpoint of further improving the alignment of the liquid crystal, the viewpoint of improving the VHR of the liquid crystal display element, and the viewpoint of improving the relaxation rate of the residual DC in the alignment film, Particularly preferred are diamines (1-2-1) and diamines (1-3). [Chem. 54] 25 201209020 >〇"υριι

(1-1-1)

(1-1-4)

(1-2-1) (1-2-2)

(1-3) [Chem. 55] Η 2Ν

Ηη2 (2) In the formula (2), X1 is a single bond or an alkylene group having a carbon number of 1 to 10, and any -CH2- of the alkylene group may also be -Ο-, -S-, -ΝΗ -, -Ν (CH3) -, -C (CH3) 2-, -C (CF3) 2-, -CO-, -S02_, 1,3-phenylene, 1,4-phenylene or pyridazine -1,4-diyl substitution. A preferred example of X1 is an alkylene group having a carbon number of 1 to 10, and any -CH2- of the alkylene group may also be -0-, •S-, -NH-, -C(CH3)2-, 1,4-phenylene or pyridazine-1,4-diyl substitution. Further, any hydrogen of the benzene ring to which the amino group is bonded may be substituted by a methyl group, but is preferably not substituted by a thiol group. Specific examples of the diamine (2) are shown below. [化56] 26 201209020 jo / /υριι

H^hQ^NQ nh2 (2-1) (2-2)

(2』) (2-10)

(2-13) (2-14) (2-15) H2H-Qr°^0/O^m2 H2N^Q^°^°O-NH2 (2-16) (2-17) H2N_QA/VV〇~ NH2 h2nh〇^^AQ~nh2 (2-18) (2-19) [化57] 27 201209020 38//Upit h2N^^nH2 H2N points, minutes (2-20) (2-21) h2n- 5nQ -nh2 (2-22) (2-23) h^-〇Sn/wSnQ~nH2 (2-24) (2-25) Me HaN^^N^^2 (2-26)

H2N h2Nh〇h〇分 (2-28) (2-29)

(2-36) [化58] 28 201209020 jo / /υριι (2-37) (248) (2-39)

(2-40)

(2-48) h2n~o/no~!_h〇/no~wh2 (2-49) [Chem. 59] 29 (240) 201209020 3877ϋριί

Me. Me

(2-51)

(2-52) [Chem. 60] R1

\

Ox"

A In the formula (3), X2 is a single bond, -O-, -COO-, -OCO- or an alkylene group having a carbon number of 30 201209020 J5//Upit of 1 to 6, preferably a single bond, -Ο- , -COO- or an alkylene group having a carbon number of 1 to 3. R1 is an alkyl group having 3 to 30 carbon atoms or a group represented by the formula (a), and is preferably a group having a carbon number of 4 to 20 or a group represented by the formula (a). In the formula (a), X3 and X4 are independently a single bond or an alkylene group having a carbon number of 1 to 4, preferably a single bond, -CH2- or -CH2CH2-. Ring B and Ring C are independently 1,4-phenylene or 1,4-cyclohexylene. R2 and R3 are independently fluorine or fluorenyl, and f and g are independently 0, 1, or 2, but preferably f and g are both 0°c, d and e are independently 0 or 1, and the total of c, d, and e For 1 to 3. R4 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms, and the alkyl group, alkoxy group and alkoxyalkyl group. Any hydrogen in the group may also be substituted by fluorine. Preferable examples of R4 are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxyalkyl group having 2 to 20 carbon atoms, and the alkyl group, alkoxy group and alkoxy group. The hydrogen in the alkyl group is not substituted by fluorine. Preferred examples of the diamine (3) are shown below. [化61] 31 201209020 38770pif

H2n h2n 0^22 (3-12) 0-O-R22 (3-13) H2i4 H2ri [Chem. 62] 32 201209020 J8//Upit

In the formula (3-1) to the formula (3-25), R20 is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably an alkyl group having 5 to 16 carbon atoms. . 33 201209020 3877ϋριί R21 is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 10 carbon atoms. R22 is an alkyl group or a cholesteryl group having 4 to 20 carbon atoms, preferably an alkyl group having 6 to 16 carbon atoms or a cholestyl group. R23 is an alkyl group having 4 to 20 carbon atoms, preferably an alkyl group having 6 to 16 carbon atoms. R24 is an alkyl group having 3 to 20 carbon atoms or an alkoxy group having 3 to 20 carbon atoms, and preferably an alkyl group having 5 to 12 carbon atoms. [化63]

In the formula (4), X5 is independently -0- or an alkylene group having a carbon number of 1 to 6, preferably --〇-, -CH2- or -CH2CH2-°j is independently 0 or l〇R5 is hydrogen The alkyl group having 1 to 20 carbon atoms or the alkoxy group having 1 to 20 carbon atoms is preferably hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, more preferably An alkyl group having a carbon number of 4 to 7. Ring T is 1,4-phenylene or 1,4-cyclohexylene. X6 is a single bond or an alkylene group having a carbon number of 1 to 3. Moreover, h is 0 or 1. Further, the bonding position of the amino group to the benzene ring is preferably para-position with respect to X5. Preferred examples of the diamine (4) are shown below. [化 64] 34 201209020 jo / /υριι

(4-3)

[化 65] 35

201209020 ·3δ / /UplI

(4.15) (4-16) In the formula (4)) to the formula (4) 6), 0 is hydrogen, the number of carbon atoms of the charcoal is argon or the alkoxy group having a carbon number of 丨~:^, preferably having a carbon number of 4~ 7 alkyl. In the specific example of the above diamine (D2), the diamine (1-2-1), the diamine (1-3), and the diamine (2-1) to diamine (2-) shown below are more preferable. 3), diamine (2-7), diamine (2-10) ~ diamine (2-27), diamine (2_29), diamine (2-37) ~ diamine (2-41), two Amine (2-43)~diamine (2-47), diamine (2-51), diamine (3-1) to diamine (3-12-1), and diamine (4-1)~ Diamine (4-12). 36 201209020 J5//Upil

(1-2-1) (1-3) [Chem. 66] Η2Ν, <ί V-NH3 1 (2-1)

H2N

(2-2) Called H2N {2.3) NH2

>-nh2 {2-7}

H2n- /! \Ps// \

If VV ^ H, nh2 HzN nh2 (2-14) {2·15)

As/V〇~NH2 (2*16)

Η2Ν々Λ^ν0-ΝΗ2 (2-18) (2-20) η^〇-\λ ^ (2-21) h2nhQ/ /~NH2 (2-22) i^O~NH2 h2nhQ^S'-/ vSn〇hnh2 h2N_^/! VV, s (2-23) (2-24) 37 201209020 •Ό / / VIJJ1 [化67] h^-〇/Sn/VX/S^Q-nh2

Me Π2Ν^νγ〇-2 (2-25) Me (2-26) Η2Ν-^^Ν^ΛίΗ〇>-ΝΗ2 (2·27) (2-29)

(2-38) h2n-< knh2 \ fl \J '『m, (2-37) η2ν^〇^〇^νη2 h2n-^s^s^-nh2 (2-39) (2-41) ( 2-43) H2NO/N0-(CH2)3-0/X0-NH2 ^ H2N~^]^/X^^iCH2)6^0/X^-NH2 t2-45>

(2-46) (2-47) [Chem. 68] 38 201209020 ^δ//υριι

[化69] 39 !; 201209020 3»//υριι

Here, R2◦ is an alkyl group having 5 to 16 carbon atoms, and R21 is an alkyl group having 3 to 10 carbon atoms. [化70] 201209020 3δ//υρη

In a specific example of the above-described more preferable diamine (D2), when the liquid crystal alignment property is further improved, diamine (1-2-1), diamine (1-3), and diamine are more preferable. (2-7), diamine (2-10)~diamine 41 II:: 201209020 JO / /υριι (2-12), diamine (2-16)~diamine (2-19), diamine ( 2-21)~Diamine (2-27), diamine (2-37)~diamine (2-41), diamine (2-43)~diamine (2-47), diamine (2- 51), diamine (3-1) to diamine (3-11) and diamine (4-1) to diamine (4-12), particularly preferably diamine (1-2-1), diamine ( 1-3), diamine (2-7), diamine (2-10) to diamine (2-12), diamine (2-26), diamine (2-44), diamine (2- 45) and diamine (3-1) to diamine (3-6). In a specific example of the above-described more preferable diamine (D2), when it is important to impart a high VHR to the liquid crystal alignment film, diamine (1-2-1), diamine (1-3), and two are more preferable. Amine (2-1) to diamine (2-3), diamine (2-26), diamine (2-29), diamine (2-37), diamine (2.43) to diamine ( 2-47), diamine (3-1) to diamine (3-11) and diamine (4-1) to diamine (4-12), particularly preferably diamine (2-1) to diamine ( 2-3), diamine (2-26), diamine (2-29), diamine (2-44), and diamine (3-1) to diamine (3-6). In a specific example of the above-described more preferable diamine (D2), when it is important to reduce the volume resistivity of the liquid crystal alignment film, diamine (1-2-1) and diamine (1-3) are more preferable. , diamine (2-1) to diamine (2-3), diamine (2·13) ~ diamine (2-15), diamine (2-20) ~ diamine (2-26), two Amine (2-29) and diamine (2-39) to diamine (2-41), particularly preferably diamine (2-1) to diamine (2-3), diamine (2-13)~2 Amines (2-15), diamines (2-26) and diamines (2-29). However, one can be divided into two types depending on the structure. That is, when the skeleton linking two amino groups is regarded as a main chain, a diamine having a branch of an autonomous chain, that is, a diamine having a side chain group, and a diamine having no side chain group. By reacting a diamine having a side chain 42 201209020 3»770 pitch group with a tetracarboxylic dianhydride, a polylysine having a plurality of side chain groups for the main chain of the polymer is obtained. When such a polyamic acid having a side chain group for the polymer main chain is used, the liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer can increase the pretilt angle in the liquid crystal display element. That is, the side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect must be a group having 3 or more carbon atoms, and specific examples thereof include an alkyl group having 3 or more carbon atoms, an &oxy group having 3 or more carbon atoms, and an inverse number of 3 or more. The base of the alkoxy group. The ring having one or more rings and having a terminal having a carbon number of 1 or more, an alkoxy group having 1 or more carbon atoms, and a pyrithion group having 2 or more carbon atoms as a substituent It has an effect as a side chain group. When a diamine having such a side chain group is used as a side chain type diamine, and a diamine having no such a side chain group is used as a non-side bond type diamine, the diamine (1) and the diamine (4) are side chain type. The diamine, the diamine ((4)-diamine (10) and the diamine (7) are non-side chain type diamines. Further, by using a side chain type diamine and a non-side chain type diamine in a suitable manner, it is compatible with each display element. The necessary pretilt angle. That is, in the longitudinal electric field mode represented by the TN mode or the VA mode, a large pretilt angle must be used, and therefore a side chain type diamine is mainly used. In this case, in order to further control the pretilt angle, it is also possible to use it in combination. The non-side chain type diamine. The ratio of the non-side bond type diamine to the side chain type diamine can be determined according to the target pretilt (four) size. Of course, by appropriately selecting the base, it is also possible to use only the side bond type amine. Correspondingly, in the transverse electric field method, a small pretilt angle and a high liquid crystal alignment property are required, and therefore at least one type of non-side chain type diamine can be used. In the present invention, in particular, in order to exhibit a degree of 2 degrees to 1 Inclination, 43 201209020 .?〇 / /uuu preferred side The diamine is used in a proportion of 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, based on the total amount of the diamine. The tetracarboxylic dianhydride used for synthesizing the polylysine of the present invention ( In the following, the acid anhydride (A-1) may be selected from the known acid anhydrides. The preferred examples include the acid anhydrides (A-1) to (A-48) shown below. At least 1. [Chem. 71] 44 201209020 jo / /υριι

Ο

[化 72] 45 I!:: 201209020 JO / /upn

(A-16) (A-17) (A-18) (Α·19) (A«20>

(A^1)

(A-22)

(A-23)

(A-24)

O O (A-31) (A-26) (A-27)

(A-32) [Chem. 73] 46 201209020 ^δ/ /υριι

(Α48> Among the above acid anhydrides, an acid anhydride (Α-1) to an acid anhydride (Α-4), an acid needle (A-ll), an acid anhydride (Α-12), an acid anhydride (Α-14), and an acid anhydride (Α-15) are more preferable. ), acid anhydride (Α-16), acid anhydride (Α-20)~anhydride (Α·23), acid anhydride (Α-30)~anhydride (Α-32), acid anhydride (Α-34), acid anhydride (Α-39) Anhydride (Α-41) ~ acid liver (Α-43) and acid needle (Α-45) ~ acid needle (Α-48). When the liquid crystal alignment is further improved, the above anhydride 47

More preferred in 201209020 J8//UP1I are an acid anhydride (Al), an anhydride (Ad), an acid anhydride (A-12), an acid anhydride (A-14), an acid anhydride (A-15), an acid anhydride (a-16), and an acid anhydride (A). -20), acid anhydride (A-22), acid anhydride (A-23), acid anhydride (A-30), acid anhydride (A-32), acid anhydride (A-39), acid anhydride (A-42), and (A-47) The acid anhydride (A-1), the acid anhydride (A-12), the S-modified anhydride (A-14), the acid anhydride (A-20), and (A-47) are particularly preferable. When attention is paid to the case where the VHR of the liquid crystal display element is increased, the acid anhydride (A-16), the acid anhydride (a-20), the acid anhydride (A-21), the acid anhydride (A-22), and the acid anhydride (A) are more preferable among the acid anhydrides. -23), acid anhydride (A-30), acid anhydride (A-31), acid anhydride (A-32), acid anhydride (A-34), acid needle (A-41), acid needle (A-42), acid anhydride ( A-43), an alicyclic compound of an acid anhydride (A-45), an acid anhydride (a-46), and an acid anhydride (A-48), particularly preferably an acid anhydride (A-16), an acid anhydride (A-22), an acid anhydride (A-23), an acid anhydride ( A-41), anhydride (a_46) and anhydride (A-48). The polyphthalic acid used in the liquid crystal alignment agent of the present invention can be obtained by reacting the above acid mixture with a diamine. The poly = other conditions of the synthesis can be directly applied. ,'condition. A preferred example of the solvent to be used, such as the latter diamine, may be at least one selected from the group consisting of monoamines. The diamine represented by 1 (15). 48 201209020 / /υρπ

Here, R3G and R31 are independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R32 is an alkylene group having 1 to 6 carbon atoms, a phenylene group or a substituted group which is substituted by an alkyl group. An integer of ~10. Specific examples of the diamine oxime 5) include the compounds or polymers described. [化75]

Me Me H2N-(CH2)3~Si-〇-Si-(CH2)3-NH2 (15-1)

Me Me

Me / Me \ Me H2N - (CH2}3 - bow 〇 卜 卜 卜 〇 淦 + 淦 ( (CH2h-NH2 (15.2)

Me \ Me / n Me (The molecular weight of the polymer of the formula (15-2) is 850 to 3,000.) When these azepine-based diamines are used, in order to exhibit the above effects and prevent deterioration of other characteristics, it is added. The amount is preferably from 0.5 mol% to 30 mol%, more preferably from 1 mol% to i〇m〇1%, based on the total amount of a private use as a raw material. The alignment agent of the present invention may further contain an organic ruthenium compound from the viewpoint of adjusting the adhesion of the alignment film to the glass substrate. An example of an organic ruthenium compound is aminopropyl three? Oxygen 11 burned, aminopropyl triethoxy 49 201209020 38//Upit decane, vinyl trimethoxy decane paper 丞 aminopropyl decyl bis oxetane, N_(2-aminoethyl)_3 Amino-bis-trimethoxydecane, vinyltriethoxydecane, 3-mercaptopropene fluorenyl; benzyl trimethoxy decane, 3-glycidoxypropyltrimethoxy decane, 3 glycidyloxy Propyl fluorenyl decyloxy decane, 2-(3,4-epoxycyclohexylamine dimethyloxypropane, etc., and dimercaptopolyoxyl=pyridoxane, polydi The eucalyptus oil such as phenyl sulfoxane is not particularly limited as long as it is in the range of obtaining the effect of the present invention. However, if a large amount of the organic radix compound is added, When the alignment film is formed, there is a phenomenon in which the alignment of the liquid crystal is poor. Therefore, when the organic ruthenium compound is added, the range of the tear ratio contained in the alignment agent is particularly preferably 〇"wt% to 3 wt%. The scope of the present invention is also considered to be an agent of the present invention from the viewpoint of deterioration of deterioration or deterioration caused by the environment. Further, a compound having two or more silky anti-fine functional groups capable of colliding with a polyterpene ship or a contact thereof, that is, a so-called cross-section, may be further included. Such a cross-over (four) ray may be exemplified by Japanese Patent No. 3049699, Japanese Patent A polyfunctional epoxy material, an isocyanate material, etc. which are described in the above-mentioned publication, etc., etc. The electrical characteristics of a 1-crystal display element deteriorate with time. One of the reasons is that due to the influence of several residues remaining in the alignment film, other components, such as a liquid crystal compound or a sealant, which are used to form the component, are attached to the alignment film to produce a mutual interaction. Alignment agent 50 201209020 3»//υριΐ : If 3 is as shown in the above (Ε1) to (Ε5), the remaining layer of the emulsion is formed in the step of forming the alignment film _ ring ring 3 = 1 heating step) Among them, polyimine is formed to form a more chemically stable group, and eight bodies are formed from the zero base, and it is possible to reduce the use of the liquid crystal display element with other parts for a long period of time. Moreover, Ding is used to maintain the initial electrical amines; use, and \^/ things, the wealth is only as above and the residuals, "_ improve the adhesion of the alignment film on the glass substrate. As a result, it is possible to prevent the alignment film from being peeled off from the glass substrate during the rubbing treatment of the alignment film which is carried out in the production step of the liquid crystal display element. Since the electrical characteristics of the liquid crystal display element have been favored for a long time, the alignment agent of the present invention may further contain a (tetra)lin compound and a oxazine compound. The oxazoline compound means a compound having an oxazoline structure in a molecule. By adding an oxazoline compound, the remaining carboxyl group in the alignment film reacts with the oxazoline compound in the step of forming an alignment film (heating step) to form a more stable group, specifically a guanamine group, thereby Make electrical properties stable for a long time. In addition, the term "stable base" as used herein does not mean the stability of the organic group itself, but means a group having little effect such as adsorption of other substances such as liquid crystal compounds in the display element. Further, by using a compound having two or more structures as a crosslinking agent, the initial alignment state can be maintained for a long period of time. As a result, the electrical characteristics of the liquid 51 201209020 38770pif crystal display element can be stabilized for a long period of time and deterioration of display quality can be prevented. Specific examples of the oxazoline compound are 2,2,-bis(2-oxazoline), L24-tris-(2-indole-2-)·benzene, 4-butan-2-yl fluorenylene. _2_phenyl_4Ηϋ_5· _, 1,4-bis(4,5-a Ι Ι-2-^β-based) benzene, 1,3_bis(4,5-dihydrooxo-based)benzene , 2,3-bis(4-isopropenyl-2_.causine-2-yl)butane, 2,2,_bis 4_benzyl-2-oxazoline, 2,6-bis (isopropyl Base 2_oxazoline-2·yl)pyridine, 2,2,_isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2,-isopropylidene bis ( 4 phenyl-2-oxazoline), 2,2,-fluorenylene bis(4-tert-butyl-2-oxazoline), and 2,2'-indenylene bis(4-phenyl -2-oxazoline). In addition to these compounds, a polymer or oligomer having a mercapto group such as EPOCR(R) (trade name, manufactured by Nippon Shokubai Co., Ltd.) can be exemplified. Among the above-mentioned nozzle compounds, in particular, if bis(4,5-diox-2 orthracene) is used (compound represented by the compound (F1)), the original characteristics of the liquid crystal alignment are not lowered. The liquid crystal display element is prevented from deteriorating over time. . The content of the sputum compound relative to the hinge of the polymer component = 吏, ° Wt% 〜 50 (4) The content of the chelating compound is preferably 1 Wt% ~ 40, more preferably 1 wt% ~ 20 wt %. The genus of the genus Mosquito refers to the special limitation of the combination of the 恶 ° ° Qin structure in the molecule, which can be exemplified by benzoxene 2, Qin 1, and the fragrant group (including condensation, such as the international public 2^ The chemical composition described in Japanese Patent Laid-Open Publication No. 2004-352670, etc. 52 201209020 387/υριί The content is 0.1 wt% based on the total amount of the polymer component. It is preferably from 1 wt% to 40 wt%, more preferably from 1 wt% to 20 wt%, and that the 'crosslinker itself reacts to form a network-like polymer for enhancing poly-proline or polyimine. The cross-linking agent of the film strength can be used in the same manner as described above. The cross-linking agent described in JP-A-H05-310608, JP-A-2004-341030, and the like can be used. a vinyl ether, a maleimide, or a bisallyl nadic ylidene derivative represented by the above compound (G1) and a compound (G2), etc. When using these crosslinking agents, the preferred ratio thereof is relatively 5 wt% to 1 〇〇wt in terms of total amount of polymer components %, more preferably from wt% to 50% by weight. It is preferred to use at least an anthraquinone polyamine in the liquid crystal alignment agent of the present invention, or a polylysine which is produced without using the diamine (1) of the present invention. The other polylysine is used in combination. The mixing ratio in the case of combining other polylysines is 10% by weight to 95% by weight of the polyglycine of the present invention based on the total amount of the polymer. The amine acid is 5 wt% to 9 wt%, and a sufficient effect can be obtained even if the proportion of the polyproline acid of the present invention is small. In the liquid crystal alignment agent of the present invention, the polyanthracene obtained by reacting an acid anhydride with a diamine can be used in combination. A polymer other than the amine acid, for example, an epoxy resin or the like. However, when such other polymer is used in combination, the ratio thereof is preferably 30% by weight or less based on the total weight of the polymer. The alignment agent is a solution obtained by dissolving polylysine in a solvent, and the solvent can be produced from a known solvent or a solvent used in the use of the solvent according to the purpose of use. Suitable for illustration, as shown below Examples of the aprotic polar organic solvent include Ν 美 美 ΝΜΡ ΝΜΡ 、 、 、 、 、 、 、 、 、 、 、 、 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基Di-tauyl hard, hydrazine, hydrazine carbamide (DMF), hydrazine, hydrazine-diethylformamide, _ _ soil (DMAc), and γ-butyrolactone (GBL), etc. Examples of preferred examples of the improvement of the coating property other than the above may be exemplified by a lactate of lactic acid, an isophorone of 3-methyl_3_j, and a monofilament of ethylene glycol (tetra) such as ethylene glycol. Top ^^, diethyl-alcohol early silk bond (such as diethylene glycol monoethyl sulphate), ethylene glycol monosodium decyl (10), propylene glycol mono (such as propylene glycol i butyl ether), dialkyl malonate ( For example, an alcohol early alkyl ether (for example, dipropylene glycol monomethyl (1) dipropylene glycol mono compound. These compounds === some of the diols of the single _ GBL, BCS, two US US preferably _, dimethyl methine side, alcohol singular. -H alcohol single top and dipropylene The alignment agent of the present invention may be as needed, for example, in the desired coating properties. The surface activity of the object can also be adjusted to include the actual amount of the antistatic agent in an appropriate amount, and the concentration of the 4% by weight/more medium polymer is preferably ο.1 when the substrate is placed on the substrate. Must be adjusted. When the alignment agent is applied to the film thickness of &, the concentration of the polymer-containing polymer can be adjusted by dilution with a solvent plus 54 201209020 / /υρΐΓ. The viscosity of the liquid crystal alignment agent of the present invention is preferably in the range of the coating method, the concentration of the polyamide and the derivative thereof, the type of the polylysine used and the derivative thereof, and the kind and ratio of the solvent. different. For example, when applied by a printing machine, it is 5 mpa · s~1 〇〇 mpa · $ (preferably 10 mPa · s~80 mPa · s). If it is less than 5 mPa · s, it becomes difficult to obtain a sufficient film thickness; if it exceeds the mpa·s, there is a case where printing unevenness becomes large. In the case of coating with a thief, 5 峨 · s 〇 mPa s (more preferably 10 mPa · s to 100 mPa · s) is suitable. In the case of applying the ink coating device, 5 mPa · 2 mPa S (more preferably 5 mPa · s to 20 mPa · s) is suitable. The viscosity of the liquid = alignment agent can be measured by the rotational viscosity measurement method, for example, using % to viscosity tf (TVE_2QL type manufactured by Toki Sangyo Co., Ltd.)

Constant temperature: 25. Hey. J The alignment film of the present invention can be applied to a substrate by the method described below. 'When necessary, the solvent is heated and removed (pre-fired) at a relatively low temperature. Secondly, the solvent is removed to enhance the polymerization. The amidation rate of proline is such that it exhibits the original hiding of the alignment film, and thus is obtained by heating at a relatively high temperature. The film obtained as above may also be subjected to a rubbing treatment as needed. * A method of applying a liquid aligning agent is generally known as a spin coating method, a printing method, a dropping method, and the like. These methods can also be applied to the liquid crystal display device of the present invention, which is a pair of substrates disposed opposite to each other on a liquid crystal display element 55 201209020 j»//Upit member having the following members, respectively facing the pair of substrates An electrode formed on one or both sides of the surface, the liquid crystal alignment film of the present invention formed on the opposite faces of the substrate, and a liquid crystal layer formed between the pair of substrates . The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include an IT crucible or a vapor deposited film 4 of metal. Further, the electrode may be formed on the entire surface of one of the faces of the substrate, and may be formed, for example, into a desired shape which is patterned. The desired shape of the electrode may be, for example, a comb type or a zigzag structure. The electrode may be formed on one of the pair of substrates or may be formed on the two substrates. The form of formation of the electrode differs depending on the type of the liquid crystal display element. For example, in the case of an IPS type liquid crystal display element, an electrode is disposed on one of the pair of substrates; in the case of another liquid crystal display element, The two upper plates of the pair of substrates are arranged on the electric plate or the electrodes to form a ship alignment film. The liquid crystal layer is formed in a form in which a liquid crystal composition is sandwiched by the pair of substrates facing the substrate on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer or a thin plate or the like may be used to form spacers at appropriate intervals between the pair of plates and the like. A known liquid crystal composition can be used without particular limitation in the liquid crystal composition. When the alignment film of the present invention forms a liquid crystal display element as a liquid crystal alignment film, properties can be improved for all known liquid crystal compositions. The film of the present invention produced by the above method is particularly effective for the improvement of the alignment defect of the large-surface display which is difficult to rub. This 56 201209020 J»//upit type of large-faced display is driven by TFT. Further, the liquid crystal composition used in such a TFT-type liquid crystal display device is disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent Laid-Open No. Hei 9-255956. There are some § in it. Therefore, the alignment film of the present invention is preferably used in combination with the liquid crystal composition contained in these documents. The liquid crystal display element of the present invention exhibits a high black level value or the like, for example, in the case of IPS, and is excellent in alignment property. The value of this black level can be measured in the following manner. That is, the assembled unit is placed on the stage of the microscope so that the rubbing direction is reversed, and the polarizing element and the analyzer are rotated so as to have the minimum brightness. The light of the fixed brightness is contacted from the back of the unit, and the light transmitted through the unit is sensed by using a photomultiplier mounted on a polarizing microscope, and the amount of the transmitted light is converted into a voltage for measurement (the magnification of the polarizing microscope is 100 times; the eyepiece) 1〇X objective lens 10 times). The smaller the obtained voltage value, the better the black level. In the invention of the present application, actually 15 〇〇μν or less is more preferable, and more preferably 9 〇〇 μν or less. The alignment film of the present invention can impart a good level of specificity and high electrical characteristics to the liquid crystal display element. Such excellent characteristics can be exhibited by using the diamine of the present invention. In this case, the divalent moiety other than the hydrazine or hydrazine 2 group of the diamine (1) of the present invention may be substituted with no characteristic 往. The liquid crystal display element of the present invention is also excellent in electrical characteristics relating to the reliability of the liquid crystal display element. Such electrical characteristics include voltage protection ratio and ion density. The voltage holding ratio (VHR) is the (four) retention rate of the frame period (frame 57 201209020 //υρπ :====== for liquid crystal display using 5 V and frequency 3 〇Η = thief temperature For the coffee% U with 5V with a == 0.3 Hz rectangular wave ' at 6〇== holding rate is one to prevent display: The ion density is generated by applying voltage to the liquid crystal display element except for liquid crystal The concentration of ions (10) contained in the liquid crystal in the display unit is driven by the phase transient current. The liquid crystal display element of the present invention preferably has an ion density of 300 pC from the viewpoint of preventing burn marks of the liquid crystal display element. [Examples] Hereinafter, the present invention will be described by way of examples and comparative examples. The evaluation method of the liquid crystal display element in the example is as follows: <Pretilt angle measurement> Measured by a crystal rotation method (Crystal rotation method). &lt;Voltage Retention Rate&gt; According to the method described in "Water Margin, The 14th Liquid Crystal Symposium Proceedings p78 (1988)", 60: (:, a rectangular wave with a peak value of ±5 V is applied to the cell) Carry out. The value of the holding ratio is an index indicating how much the applied voltage is maintained after the frame period. If the value is 100%, it means that all charges are held. &lt;Measurement of ion amount in liquid crystal (ion density)&gt; 58 201209020 / /upit According to the method described in Applied Physics, Vol. 65, No. 1 and 1065 (1996), the liquid crystal physical property measurement system 6254 manufactured by Dongyang Technology Co., Ltd. is used for measurement. The frequency of use is 〇〇1 Hz. The triangular wave is measured at a voltage range of ±10 V and a temperature of 60 ° C (the area of the electrode is 1 cm 2 ). If the ion density is large, problems such as burn marks due to ionic impurities are likely to occur. That is, the 'ion density is a physical property value which is an index for predicting the occurrence of burn marks. &lt;1H-NMR&gt; The measurement was carried out using DRX-500 manufactured by Bruker BioSpin Co., Ltd. The samples were all depleted at 1 wt%. The measurement was carried out in a gas imitation. &lt;Weight average molecular weight (Mw) &gt; The weight average molecular weight (Mw) of the polylysine in the liquid crystal alignment agent can be used as an eluent using DMF containing 0.6 wt% of phosphoric acid, using Sh〇dex the company The manufactured GF7MHQ column was measured at a column temperature of 50 (by: gel permeation chromatography (GPC) method and determined by polystyrene conversion. &lt;Viscosity&gt; Using a viscometer ( Manufactured by Toki Sangyo Co., Ltd., TV-22) '25. (Example: Synthesis of Compound (1-5) &lt;Stage 1: Synthesis of Indoleamine&gt; A commercially available 2-amino-2-hydroxymethyl 59 201209020 / /υριι -1,3-propanediol ιο.ο g (82 6 min〇l) was added to a 200 mL three-necked flask of a thermometer, a nitrogen introduction tube, and a dropping funnel. And 10.0 g (99.1 mmol) of triethylamine was dissolved in N,N-dimethylamine. The solution was cooled to 5 ° C' and a commercially available 3,5-dinitrophenyl hydrazine gas 15.2 g (66.0 mm 〇i) was slowly added thereto. Next, the reaction solution was warmed to 8 ° C and further scrambled for 12 hours. After standing to cool, the solvent was evaporated under reduced pressure to give a crude crystal. The obtained crude crystals were recrystallized from ethanol to obtain 3,5-dinitro-N-((trihydroxymethyl)decyl)benzamide. The yield was 17 7 g and the yield was 85%. &lt;Second stage: reduction of nitro group&gt; In the reaction tube for the autoclave, 3,5 dinitro^ 17.0 g (53.9 mm 〇 1) 5 / carbon powder L7 g ' Add ethanol lion mL. The inside of the system was made into a nitrogen atmosphere, and the mixture was stirred at a hydrogen pressure of 0.5 mPa for 24 hours at room temperature. The _/carbon powder in the reaction liquid was removed, and the crude crystal was obtained by taking the pressure off (iv). The obtained crude crystals were recrystallized from ethanol to obtain 35-diaminodi/:(hydroxymethylmethyl)methyl). The yield is again i25 g, rate: b-NMR (ppm): 6.89 (s, _NHC〇_, m), 6 i3 (d, 赃h, 5.91 (t, arm.Η, 1H) 4 Q1 - 4 rk 0 Λ 4.yi 4.93 (br.S5 _〇H _NH 7H) 3.58· 3.60 (d,-CH2-,6H).

[Example 2] Synthesis of Compound (1-9) &lt;Stage 1: Synthesis of Indoleamine&gt; Bucket: = Put in a fine mL three-necked flask equipped with a stirring, a thermometer, a nitrogen introduction tube, and a dropping funnel. Commercially available diethanolamine cut g (95" 201209020 ^swupit mmol) and triethylamine 11.5 g (114.1 mmol), dissolved &amp; ΝΝ 曱 曱醯 decylamine 100 mL. The solution was cooled to 5 ° C, and 21.9 g (95.1 mmol) of commercially available 3,5-dinitrophenyl hydrazine gas was slowly added thereto. Next, the temperature of the reaction liquid was raised to 8 (TC', and further stirred for 12 hours, and then cooled, the solvent was removed under reduced pressure to obtain a crude crystal. The obtained crude rhodium was recrystallized from ethanol to obtain N,N-double. (2-Hydroxyethyl)_3,5_2^ = acesulfame. The yield is 25_0g, the yield is 88%. Soil &lt; Stage 2: Reduction of nitro group&gt; The previously obtained N,N•bis(2-hydroxyethyl)·3,5-dinitrophenylguanamine 20. 〇g (66 8 mm〇1) and 5% palladium ruthenium carbon powder 2.0 g ' Add 5 〇〇mL of ethanol, make the gas in the system, and transfer it at a hydrogen pressure of 0.5 mPa at room temperature for 24 hours. In addition, the /carbon powder in the solution should be decompressed to remove the solvent. Obtained crude crystals. The crude crystals were recrystallized from ethanol to obtain the bis- 2 benzylamine. The yield was _, and the yield was 9 %. [Example 3] &lt;Polyproline Synthesis &gt; In a three-necked flask equipped with a scrambler and a thermometer, a compound (I_5) 2 2641 g synthesized in accordance with Example 1 and a decyl methane (compound (2-1)) 04396 p were added to the product. , 虱 一 a scale One (NMP) dissolved 6〇 g of cyclobutane tetracarboxylic acid would Xuan (mMDa⑷;) was added N- ^ A liquid containment in Kish.)? Then, the pyromellitic dianhydride 871 g of the reaction mixture was heated to room temperature, and spit g'^NMP 5 g was carried out. Entering 仃 for 12 hours. Add B to it

S 61 201209020 38770pit diol monobutyl ether (BC) 30 g, a solution having a polyglycine concentration of 5 wt% was obtained. The solution has a 25 ° C viscosity of 35 mPa · sec. This solution was used as varnish A. The polyamine acid in the varnish had a weight average molecular weight of 42,000. [Example 4 to Example 17] The same procedure as in Example 3 was carried out except that the diamine and the acid dianhydride were changed as shown in Table 1, and the polyamine concentration was 5 wt%, and the viscosity at 25 ° C was 35 mPa. · sec varnish. The monomer composition of the polymer contained in the prepared varnish and the measured value of the weight average molecular weight, including Example 3, are shown in Table 1 (mol% in parentheses). 62 201209020 38//Upit [Table 1] Example varnish diamine no obtained Kamakura first secret molecular weight I D2-1 D2-2 3 A 1-5 (50) 2-1 (50) - Al (50) A-16 (50) - 42,000 4 B 1-5(40) 2-1 (60) - Al (80) A-23 (20) - 38,000 5 C 1-5(20) 2-26 (40) 2-29 ( 40) Al (20) A-16 (80) - 46,000 6 D 1-9(50) 2-1 (50) - Al (40) A-23 (60) - 41,000 7 E 1-5(60) 2 -3 (40) - Al (50) A-47 (50) - 44,000 8 F 1-5(30) 2-26 (10) 2-44(60) Al (30) A-16 (70) - 39,000 9 G 1-5(30) 2-1 (50) 4-6 (20) R=-C5Hn Al (50) A-16 (50) - 35,000 10 Η 1-5(20) 2-1 (50) 3-12(30) A-23 (100) - - 33,000 11 I 1-7(50) 2-1 (50) - Al (50) A-16 (50) - 48,000 12 J 1-6(50) 2-1 (50) - Al (50) A-16 (50) - 40,000 13 K 1-9(50) 2-1 (50) - Al (50) A-16 (50) - 41,000 14 L 1- 5(20) 2-1 (40) 2-26(40) Al (60) A-48 (40) - 29,000 15 Μ 1-5(20) 2-26 (40) 2-29(40) Al ( 40) A-20 (30) A-23 (30) 43,000 16 N 1-5(20) 2-26 (40) 2-29(40) Al (50) A-20 (50) - 37,000 17 0 1 -5 (80) 2-3 (20) - Al (40) A-14 (60) - 45,000 [Example 18] &lt;Production of black level measuring unit&gt; The varnish Al.Og was weighed in a sample bottle, and NMP/BC = 1/1 (weight ratio) was added to make the total amount 1.67 g. The polyfluorene 63 was dropped on a transparent glass substrate. 201209020 j»//upn A solution having an amine acid concentration of about 3 wt% was applied by spin coating (2 〇〇 0 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then heated in a 23 (TC oven) for 2 minutes. The thickness of the crucible formed by the heat treatment was about The 7〇nm polyimine film was subjected to rubbing treatment (injection 〇3 mm, platform feed rate 60 m/sec, rotation speed l〇〇〇rpm, alignment cloth YA]8_R (rayon)). After the membrane was ultrasonically cleaned in ultrapure water for 5 minutes, it was dried in an oven of 1201 for 30 minutes, and the surface on which the alignment film was formed was made "in the direction of the parallel direction" - the alignment of the two glass substrates was carried out. After the 'sealing with a caulking (10) county hardener containing 25 μηι, 'antiparalldceii with a gap of 25 μm was fabricated. The following liquid crystal composition A was injected into the unit, and sealed with photocurability = two Next, heat treatment was performed for 3 minutes at 110 t to prepare a liquid daily display element. The measured value of the obtained unit was 1·... U+, voltage &lt;liquid crystal composition A&gt; [Chem. 76] 64 201209020 jo / /υριι

17 wt% 17 wt% 16 wt% 10 wt% 5 wt% 10 wt% Swt% 6 wt% 13 wt% [Example 19 to Example 32] Replacing varnish A with varnish B to varnish Ο, otherwise based on Example 18 The black level measuring unit was produced by the method described. Among them, the unit produced by using the varnish was not subjected to rubbing treatment on the polyimide film to inject the liquid crystal composition Β. The results of the black level measurements of these examples are shown in Table 2 together with the results of Example 18. <Liquid Crystal Composition 65> 65 201209020 _5δ&quot;υριι [化77] 03⁄4

C4H9

n-C3H7n'〇3H7~^Z)~~^^~〇Me 12.0wt°/〇11.0 wt% 15.0 wt% 15.0wt% 5.0 wt% 6.0 wt% 6.0 wt% 5.0 wt% 5.0 wt% 6.0 wt% 6.0 Wt% 4.0 wt% 4.0 wt% 66 201209020 i /υριι [Table 2]

A good black level was observed in all the cells produced [Example 33] &lt;Pre-tilt angle and fabrication of electrical characteristic measuring unit&gt; G varnish A 'addition & amount ratio was weighed in the sample bottle Make the total amount 丨·67 g. A solution having a polyamine concentration of about 3 wt% was added dropwise to a transparent glass substrate, and coating was carried out by spin coating (9 rpm, 15 seconds). After coating, the substrate was heated at 8 Torr for 3 minutes to heat the solvent to evaporate the solvent, followed by heat treatment in an oven at 230 ° C for 2 Torr. The film thickness formed by the heat treatment is about the same, and the yttrium imide film is subjected to a rubbing treatment (pressing 0.3 mm, platform 6 〇 m/s, rotating speed 10 〇〇卬 melon, alignment cloth γ Α _ ... speed ^ ^ g? x R (rayon)) After washing the material recorded in a little 5, it is worthy of money in the 咐, phase ~ shallow. On its alignment medium 67 201209020 DO / /Upll Side v: The caulk. The alignment film surface of the other substrate was placed in the opposite direction with the rubbing direction being reversed, and the epoxy resin was an anti-parallel unit having an epoxy hard distance of 7 qing. The h group A is injected into the single 7C, and the material is hardened. Next, a 3G minute entry name display element is performed under 1UTC. The voltage stability of the single it is 98 5'^, 'making liquid crystal 90·5〇/ο (0.3Hz) 'pretilt angle is 12〇, ion density ^ 0 Hz) and [example 34~example 47] 85 pC. The varnish A was replaced with the method described in the varnishes B to 33 to prepare an electrical property measurement: the unit produced by using the varnish H was not injected with respect to the treatment, and the liquid crystal composition B was not injected. The results of the measurement of the frictional tilt angle were compared with those of the example 33 and the results [Table 3] and .

68 201209020 j〇//upu The unit order made by the manufacturer, all the density. Good VHR and ions [Case 48 to Example 62] &lt;Confirmation of the effect of the epoxy compound additive&gt; The L0 g clearing surface magic weight (weight ratio) was weighed in the sample vial to make the total amount 167 §. = $0.01 g of Epoxy Additive (E1) ~ Epoxy Additive (E5) for any i = to be fully secreted. According to the method described in Example 17, the measurement unit 1 and the measurement unit for electrical characteristics were prepared. Among them, the single it produced by the lacquer is not rubbed by the sub-secret: the liquid crystal composition B is injected. Black level measurement was performed using the fabricated cell—, VHR measurement (30 Hz and 〇.3 Hz), ion density measurement, and pre-measurement. The measurement results are shown in Table 4. [Table 4]

69 201209020 j^//upir It is confirmed that by adding an epoxy compound, the VHR and the ion density are not lowered, and the pretilt angle is not changed, and the black level can be further increased. [Example 63 to Example 77] &lt;Effect of the effect of the oxazoline compound additive> = 顺 丝 丝 ag ag ag ag ag ag ag ag ag ag ag ag ag ag BC BC BC BC BC BC BC BC BC BC BC BC BC BC BC BC BC BC BC BC g. Add to it

Lilt (four) additive (F1), fully (four). According to the example, the unit for measuring/black level measurement and the electrical characteristics are determined by π, 仃 仃 仃 仃 仃 、, VHR measurement Table 5; The ion density is sighing. The result will be shown in [Table 5]

201209020 js//upir It was confirmed that by adding an oxazoline compound, the VHR and the ion density were not lowered, and the pretilt angle was not changed, and the black level was further improved. [Comparative Example 1] Synthesis of Compound C1 [Chem. 78]

&lt;Different stage 1 In a 200 mL three-necked flask equipped with a stirring device, a thermometer, a nitrogen introduction tube, and a dropping funnel, a commercially available 3-amino-3-ethyl-p-pentane l〇.〇g (86.8 mmol) was placed. And triethylamine 13·2 g (13〇2mm〇1), = solution in N,N-didecylguanamine 50 mL. The solution was cooled to 5 t, and commercially available 3,5·dinitrophenylhydrazine gas 18 〇 g (78; =_) was slowly added thereto. Next, the reaction liquid was heated to 8 (rc and stirred for 12 hours. After standing to cool, the solvent was distilled off under reduced pressure to obtain a crude crystals in toluene and recrystallized to obtain 3 hydrazine. Benzoguanamine. The yield was 19.6 g, and the yield was 81 〇: condition ((diethyl) &lt; stage 2: reduction of nitro: &gt; ° ° placed in the reaction tube of the high pressure dad with the previous _Ν·((three) Ethyl)methyl)benzamide 19.0 g (6, ,5·-nitropalladium/carbon powder, adding 500 mL of ethanol to make the system mm〇1) and 5〇/〇 at a hydrogen pressure of 0.5 mPa, The mixture was stirred at room temperature for 24 hours, and the palladium/carbon powder in the reaction solution of the reaction product of the reaction was removed. The solvent was distilled off under reduced pressure to obtain a crude crystal. Recrystallization was carried out to obtain 3,5-diamino-N-((triethyl)indenyl)benzamide. The yield was 13.6 g, and the yield was 89%. ^-NMRCppm): 7.42 (s, - NHCO-, 1H), 6.45 (d, arm.H, 2H), 5.90 (t, arm.H, 1H), 4.78 (br.s, -NH2, 4H), 1.41 - 1.45 (q, -CH2-, 6H), 1.04 (t, -CH3, 9H).

[Comparative Example 2 to Comparative Example 4] &lt;Preparation of Polylysine&gt; According to the method described in Example 2, a varnish X to varnish having a polyglycine concentration of 5 wt% and a viscosity of 35 mPa·s was obtained. Z. The prepared varnish is shown in Table 6 (mol% in brackets). [Table 6] Comparative Example Varnish Diamine Tetracarboxylic Acid dianhydride Molecular Weight (C1) D2-1 D2-2 2 X C1 (50) 2-1 (50) - A-1 (50) A-16 (50) - 40,000 3 Y C1 (40) 2-1 (60) - A-1 (80) A-23 (20) - 39,000 4 Z C1 (20) 2-26 (40) 2-28 (40) A-1 ( 20) A-16 (80) - 43,000 [Comparative Example 5 to Comparative Example 7] &lt;Black Level Measurement and Electrical Characteristics Measurement&gt; The black level measurement unit and electrical characteristics were produced by the method described in Example 17. The unit for measurement is measured. The measurement results are shown in Table 7. 72 201209020 -&gt;δ//υριι [Table 7] . Pre-tilt ion density one (.)_____ (pc) ~ 12 _ 91 _ 1.5 One 86 i 1.7 72 of the alignment agent constituted by Comparative Example 7 ' , Ί心The black display characteristics of the unit of the material are not sufficient. [Comparative Example 8 to Comparative Example 1 &] &lt;Confirmation of Effect of Additive&gt; 1.0 g of the 轫 轫 丽 卖 卖 卖 卖 ( ( 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量 重量Epoxy compound or oxazoline = Wg. In addition, one of the compounds of the compound is added, and the unit for charging and the unit for measuring electric characteristics is used. The compound to be added and the measurement results are shown in Table 8. [Table 8] Comparative Example Adding Compound Black Level VHR (%) Pretilt Ion Density (μν) 30 Hz 0.3 Hz (°) (pC) 8 (E3) 1,910 98.1 90.3 1.1 94 9 (E6) 1,620 97.8 90.2 1.5 85 10 (F1) 1,630 98.5 91.0 2.1 73 Even if various compounds were added, no improvement in black display was observed. Moreover, the fluctuation of the pretilt angle is confirmed in a part of the unit. [Simple description of the diagram] None 73 201209020 j«//upir [Key component symbol description] None

Claims (1)

201209020 ^δ//υρπ VII. Patent application scope: 1. A diamine represented by the general formula (1), [Chemical 1] Η 2Ν (wherein R is a sulfhydryl group having a sulfhydryl group and a sulfhydryl group at the end.) 2. The diamine according to claim 1, wherein r is (&amp;;) (b) or (c), [Chemical 2] (wherein F0 is hydrogen or methyl). A diamine as described in claim 2, wherein R. It is hydrogen. The amine, the substituent described in any one of items 1 to 3, wherein the mesoid is represented by the substituent &amp; a "from its derivative, which is the patent application scope 75 201209020 item 1 The at least one of the diamines represented by the formula (I) described in any one of the above items is reacted with a tetracarboxylic dianhydride. 6. A poly-proline and a derivative thereof, which are at least one of the diamines represented by the formula (I) and the other two according to any one of claims 1 to 4 A mixture of the amine (D2) is obtained by reacting with a tetracarboxylic dianhydride. 7. The poly-proline and the derivative thereof according to claim 5 or 6, wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (DA-20) to (DA-32) One or more of the groups formed, [Chem. 3] In the formula (DA-20), G5 is a single bond, an alkylene group having a carbon number of 1 to 12, a 1,4-phenylene group or a 1,4-cyclohexylene group; X1Q is independently a single bond or CH2; G6 is independently CH or N. When G6 is N, G5 is not a single bond or CH2, and X1G is not a single bond; [Chemical 4] 76 201209020 jo / /upir In the formula (DA-21), R14 is independently hydrogen, methyl, ethyl or phenyl; In the formula (DA-22), the ring A6 is a cyclohexane ring or a benzene ring; In the formula (DA-23), G7 is a single bond, an alkylene group having a carbon number of 1 to 10, 1,4-phenylene, anthracene, CO, S, S02, C(CH3)2 or C (CF3) ) 2; 77 201209020 / / ULfll Moreover, ring A7 is independently a cyclohexane ring or a benzene ring; [Chemical 7] In the formula (DA-24), R15 is hydrogen or a hydrazine group; [Chemical 8] In formula (DA-25), X10 is a single bond or CH2; XU is independently CH2, CH2CH2 or CH=CH; and, v is 1 or 2; [Chemical 9] 78 201209020 j«//upit In the formula (DA-26), X10 is a single bond or CH2; [Chemical 10] (DA-27) In the formula (DA-27), R14 is hydrogen, decyl, ethyl or phenyl; ring A8 is cyclohexane ring, cyclohexene ring or benzene ring; and, X12 is a single bond, CH2 or CH(CH3); [Chem. 11] 79 201209020 jo / /υριι In the formula (DA-28), w2 and w3 are 0 or 1, and w3 = 1 when w2 = l; [Chemical 12] 80 201209020 i»/ /upit In the formula (DA-30), X13 is independently an alkyl group having 2 to 6 carbon atoms; and, Ph represents a phenyl group; In the formula (DA-32), X14 independently represents a single bond or CH2. 8. The poly-proline and the derivative thereof according to any one of claims 5 to 7, wherein the other diamine (D2) is a formula (1-1) to (4) The diamine represented, [Chem. 16] S 81 201209020 J8//Upit (1-1) (1-2) (1-3) or 1; any hydrogen in the cyclohexylene group is also in the formula (Bu 1), and b is a hydrazine which may be substituted by a methyl group; ) 'W1 is _ch2- or -ΝΗ-; [化17] h2n (2) Here, X1 is a single bond or an alkylene group having a carbon number of 1 to 10; any -CH2- of the alkylene group may also be -Ο-, -S-, -NH-, -N ( CH3)_, -C(CH3)2-, -C(CF3)2_, -CO-, _S〇2·, 1,3-phenylene, 1,4-phenylene or pyridazine-1,4 -dibasic substitution; [Chem. 18] 82 201209020 ό6/ /vpit In the formula (3), X2 is a single bond, -Ο-, -COO-, -OCO- or an alkylene group having a carbon number of 1 to 6; R1 is an alkyl group having a carbon number of 3 to 30 or a formula (a) In the formula (a), X3 and X4 are independently a single bond or an alkylene group having a carbon number of 1 to 4; and ring B and ring C are independently a 1,4-phenylene group or 1,4 - cyclohexylene; R2 and R3 are independently fluorine or fluorenyl, and f and g are independently 0, 1 or 2; c, d and e are independently 0 or 1, and the total of c, d and e is 1 to 3 R4 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms or a cholestyl group, and the alkyl group and the alkoxy group. In the base and the alkoxy group, any hydrogen can also be substituted by fluorine; [Chem. 19] 83 201209020 JO / /upn Here, X5 is independently -O- or an alkylene group having a carbon number of 1 to 6; j is independently 0 or 1; R5 is hydrogen, an alkyl group having 2 to 12 carbon atoms or an alkyl group having 2 to 12 carbon atoms; Oxyl; ring T is 1,4-phenylene or 1,4-cyclohexylene; X6 is a single bond or an alkylene group having a carbon number of 1 to 3; h is 0 or 1. The poly-proline and the derivative thereof according to any one of claims 5 to 7, wherein the other diamine (D2) is at least one selected from the group consisting of the following compounds, [化20] 84 201209020 jo f /upir (wherein R11 is -CH2-, -O- or a linear alkylene group having a carbon number of 1 to 4, R12 is hydrogen or CH3, R13 is a linear alkylene group having 2 to 4 carbon atoms, and R14 is a linear alkylene group having 1 to 8 carbon atoms, R15 is independently -CH2-, -(CH2)2- or -NH-, and R16 is a hydrogen atom or a direct bond alkylene group having a carbon number of 1 to 1 Å. R17 is 85 201209020 A hydrogen atom or a linear alkylene group having a carbon number of 1 to 16, and R18 is independently -CH2-, -(CH2)2- or -0-). A composition comprising at least one polymer selected from the group consisting of polylysines and derivatives thereof according to any one of claims 5 to 9. A liquid crystal alignment agent which is composed of a composition containing at least one polymer selected from the polyphthalic acid and derivatives thereof according to any one of claims 5 to 9 of the patent application. . 12. The liquid crystal alignment agent according to claim 11, which comprises an epoxy compound (E). 13. The liquid crystal alignment agent according to claim 12, wherein the epoxy compound (E) is one or more selected from the group consisting of compounds represented by the following formulas (E1) to (E6). , [Chem. 21] (wherein η is an integer of 1 to 10). 86 201209020 /upir 14. The liquid crystal alignment agent according to claim 11, which comprises 11 oxalate compound (F). 15. The liquid crystal alignment agent according to claim 14, wherein the compound (F) is a compound represented by the following formula (F1), [Chem. 22] (F1) 16. The liquid crystal alignment agent according to claim 11, which comprises the bis-dip nadecridine compound (G). 17. The liquid crystal alignment agent according to claim 16, wherein the bisallyl nadic ylidene imine compound (G) is selected from the group consisting of compounds represented by the following formula (G1) and formula (G2). More than one group, [Chem. 23] 18. The liquid crystal alignment agent according to claim 11, comprising a compound selected from the group consisting of (E1) to (E6), (F1), (G1), and (G2) 87 201209020 / /υριι One or more of the groups formed. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of the above items. A liquid crystal display element comprising a liquid crystal alignment film comprising the liquid crystal alignment agent according to any one of claims 1 to 18. 88 201209020 ^δ//υριι IV. Designation of representative drawings: (1) Designation of the representative figure of the case: None (2) Simple description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please reveal the best indication of invention. Characteristic chemical formula: (I) 201209020 3«//υρΐπ is the Chinese patent scope of No. 100128743. No slash correction. Amendment date: 1 year, 1 month, amendment, supplementary day 7. Patent application scope: h A diamine, which is of the general formula ( I), said [Chemical 1] 〇 (wherein R is a sulfonyl group having a methylene group interposed on a nitrogen atom and a hydroxyl group bonded to a terminal end). - 2. The diamine of claim 1, wherein R is represented by (a), (b) or (c), [Chem. 2] (wherein R0 is hydrogen or fluorenyl). 3. The diamine as described in claim 2, wherein R0 is hydrogen. &lt;4. The diamine of any one of claims 1 to 3, wherein in the formula (I), the two amino groups are substituted for the substituent represented by r, respectively 3 digits, 5 digits. 5. Poly-proline and its derivatives, which make the patent scope 75 201209020 38770pitl the Chinese patent scope of No. 100128743 without a slash correction. Amendment date: 1st to 4th of October 5th, 1st Any one of the diamines represented by the formula (I) according to any one of the above items is obtained by reacting with a tetracarboxylic dianhydride. 6. Polylactoic acid and a derivative thereof, which are at least one of the diamines represented by the formula (I) described in any one of claims 1 to 4, and the other two A mixture of the amine (D2) is obtained by reacting with a tetracarboxylic dianhydride. 7. The poly-proline and the derivative thereof according to claim 5 or 6, wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (DA-20) to (DA-32) One or more of the groups that are formed, In the formula (DA-20), G5 is a single bond, an alkylene group having a carbon number of 1 to 12, a 1,4-phenylene group or a 1,4-cyclohexylene group; X1G is independently a single bond or CH2; G6 is independently CH or N. When G6 is N, G5 is not a single bond or CH2, and X1() is not a single bond; [Chemical 4] 76 201209020 :&gt;〇/ /υριο is the 100128743 No. Chinese patent range without a slash correction. Amendment date: ι〇〇年ι〇月5日 (DA-21) In the formula (DA-21), R14 is independently hydrogen, decyl, ethyl or phenyl; In the formula (DA-22), the ring A6 is a cyclohexane ring or a benzene ring; [Chemical 6] (DA-23) In the formula (DA-23), G7 is a single bond, an alkylene group having a carbon number of 1 to 10, 1,4-phenylene group, 0, C0, S, S02, C(CH3) 2 or C(CF3)2; 77 201209020 38770pifl is the Chinese patent scope of No. 100128743 without a slash correction. The date of this amendment is: October 5, 1 而且, and ring A7 is independently a cyclohexane ring or a benzene ring; 7] In the formula (DA-24), R15 is hydrogen or methyl; [Chemical 8] In the formula (DA-25), X10 is a single bond or CH2; Xn is independently CH2, CH2CH2 or CH=CH; and, v is 1 or 2; [Chemical 9] 78 201209020 38//UpitI is No. 100128743 Chinese Patent scope without slash correction This revision period: October 5th, 1st (DA-26) 〇 In the formula (DA-26), X1Q is a single bond or CH2; [Chemical 10] (DA-27) In the formula (DA-27), R14 is hydrogen, decyl, ethyl or phenyl; ring A8 is cyclohexane ring, cyclohexene ring or benzene ring; and, X12 is a single bond, CH2 or CH(CH3); [Chem. 11] 79 201209020 3877Upitl No. 100128743 Chinese Patent Range No Dirty Correction Revision Date: October 5, 1 In the formula (DA-28), w2 and w3 are 0 or 1, and w3 = 1 when w2 = l; [Chemical 12] 80 201209020 JO / /upui is the Chinese patent scope of No. 100128743 without a slash correction. Amendment date: October 5, 1 于 in the formula (DA-30), X13 is independently an alkyl group having a carbon number of 2 to 6. And, Ph represents a phenyl group; [Chem. 14] Q In the formula (DA-32), X14 independently represents a single bond or CH2. 8. The poly-proline and the derivative thereof according to the sixth aspect of the invention, wherein the other diamine (D2) is a diamine represented by the following formula (1-1) to formula (4). 16] 81 201209020 The Chinese patent scope of the f〇0128743 is not underlined. This revision date: October 5, 1 H2n Nh2 (1-1) (1-2) (1-3) In the formula (1-1), b is 0 or 1; any hydrogen in the cyclohexylene group may be substituted by a thiol group; 2), W1 is -CH2- or -NH-; [chemical] h2n (2) Here, X1 is a single bond or an alkylene group having a carbon number of 1 to 10; any -CH2- of the alkylene group may also be -0-, -S-, -NH-, -N ( CH3)·, _C(CH3)2-, -C(CF3)2-, -CO-, -S〇2-, 1,3-phenylene, 1,4-phenylene or pyridazine-1, 4-diyl substitution; [Chemical 18] 82 201209020 JO / /wpiil No. 100128743 Chinese patent scope without slash correction This revision date: October 5, 100 (3) (a) In the formula (3), X2 is a single bond, -Ο-, -COO-, -OCO- or an alkylene group having a carbon number of 1 to 6; and R1 is a carbon number of 3 to 30. An alkyl group or a group represented by the formula (a); wherein, in the formula (a), X3 and X4 are independently a single bond or an alkylene group having a carbon number of 1 to 4; and the ring B and the ring C are independently 1,4-arylene. Phenyl or 1,4-cyclohexylene; R2 and R3 are independently fluoro or fluorenyl, and f and g are independently 0, 1 or 2; c, d and e are independently 0 or 1, and c, d and e The total is 1 to 3; R4 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms or a cholestyl group. In some of the alkyl, alkoxy and alkoxyalkyl groups, any hydrogen may also be substituted by fluorine; [Chemical 19] 83 201209020 38770pifl is the Chinese patent scope of No. 100128743 without a slash correction. This revision date: 1 year October 5曰 Here, X5 is independently -0- or an alkylene group having a carbon number of 1 to 6; j is independently 0 or 1; R5 is hydrogen, an alkyl group having 2 to 12 carbon atoms or an alkyl group having 2 to 12 carbon atoms; Oxyl; ring T is 1,4-phenylene or 1,4-cyclohexylene; X6 is a single bond or an alkylene group having a carbon number of 1 to 3; h is 0 or 1. 9. The poly-proline and the derivative thereof according to claim 6, wherein the other diamine (D2) is at least one selected from the group consisting of the following compounds; [Chem. 20] 84 201209020 J5//Upill is the Chinese patent scope of the No. 100128743_Scoring revision. The revised period: October 5, 1 (wherein R 1 is -CH2_, -0- or a linear alkylene group having a carbon number of 1 to 4, R is hydrogen or CH3, R13 is a linear alkylene group having 2 to 4 carbon atoms, and Ri4 is A straight-chain alkylene group having a reciprocal order, R15 is independently -CH2-, -(CH2)2- or _NH_'R is a hydrogen atom or a linear alkylene group having a carbon number of 1 to 10, and R17 is 85 201209020 iJTlSl 28743 towel text touches the ugly boat and corrects the profit _ year 1G month 5 hydrogen atom or a linear alkylene group with a carbon number of 1~16, Rl8 is independently _CHr, -(ch2)2- or -〇 ·). A composition comprising at least one polymer selected from the group consisting of polylysines and derivatives thereof according to any one of claims 5 to 9. A liquid crystal alignment agent which is composed of a composition containing at least one polymer selected from the group consisting of polyamino acids and derivatives thereof according to any one of claims 5 to 9. The liquid crystal alignment agent according to claim 11, which comprises the epoxy compound (E). The liquid crystal alignment agent according to claim 12, wherein the epoxy compound (E) is one selected from the group consisting of compounds represented by the following formulas (E1) to (£6). Above, [Chem. 21] Ο (Εδ) (E6) where η is an integer from 1 to )) 86 201209020 38//Upitl Revision period: 100 years October 5曰 is the 100128743 Chinese patent range without a slash correction. 14. If applying The liquid crystal alignment agent according to item n of the patent, which comprises a compound (F). 15. The liquid crystal alignment agent according to claim 14, wherein the oxazoline compound (F) is a compound represented by the following formula (π), [Chem. 22] 16. The liquid crystal alignment agent according to claim n, which comprises a bisallyl nadic ylidene imine compound (G). 17. The liquid crystal alignment agent according to claim 16, wherein the bisallyl nadic ylidene imine compound (G) is selected from the group consisting of compounds represented by the following formula (G1) and formula (G2). More than one species of the group, [Chem. 23] 18. The liquid crystal alignment agent as recited in claim 11 which comprises a modification selected from the group consisting of (E1) to (E6), (F1), (G1), and (G2) 87 201209020 3»//UpiiJ The revised period: 1 year, 1st, 5th, and 5th, the Chinese patent range of No. 100128743 is not more than _^ indicates that the group consisting of (four) compounds is more than one type. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of the above items. A liquid crystal display element comprising a liquid crystal alignment film comprising the liquid crystal alignment agent according to any one of the above items. 88