TW201130889A - Liquid crystal alignment agents, liquid crystal alignment layers and liquid crystal display device - Google Patents

Abstract

This invention is related to a liquid crystal alignment agent, which includes at least a polymer selected from polyamic acid and derivative thereof obtained by reacting a diol and a mixture of tetracarboxylic dianhydride represented by formula (I) and other tetracarboxylic dianhydride. The liquid crystal alignment agent of this invention is characterized in that, based on a total amount of the mixture of the tetracarboxylic dianhydrides, a ratio of tetracarboxylic dianhydride represented by formula is 5 mol% to 95 mol%, the other tetracarboxylic dianhydride is 5 mol% to 95 mol%. A liquid crystal alignment layer having high liquid crystal alignment property and excellent black level can be obtained by using the liquid crystal alignment agent of this invention. In formula (I), X is C2-12 alkylene.

Description

201130889 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent containing polyamic acid or a derivative thereof and use thereof. [Prior Art] A liquid crystal display element is used for a viewfinder of a video camera typified by a monitor of a notebook computer or a desktop personal computer, Various liquid crystal display devices such as projection displays have recently been used for televisions. Moreover, the liquid crystal display element is also used as an optoelectronics related element such as an optical printer head, an optical opticai transform element, and an iight valve. The liquid crystal display device generally includes: 1) a pair of substrates disposed oppositely, 2) electrodes formed on one or both of the opposing faces of the pair of substrates, and 3) faces formed on the pair of substrates The liquid crystal alignment film and 4) a liquid crystal layer formed between the pair of substrates. The mainstream of the conventional liquid crystal display elements is a twisted nematic (TN) type liquid crystal display element which is twisted by 90 degrees using a nematic liquid crystal display element '1), and 2) a super twisted nematic which is normally twisted by 180 degrees or more ( A super-twisted Nematic 'STN) type liquid crystal display element and 3) a thin film transistor (TFT) liquid crystal display element using a thin film transistor for a switching element for driving a voltage of a liquid crystal are put into practical use. These liquid crystal display elements have the following disadvantages: a correct eye view 4 201130889 The image has a narrow viewing angle, and when viewed from an oblique direction, a decrease in brightness or contrast and a brightness inversion at halftone are produced. In recent years, the problem of this viewing angle is to use 1) a TN-TFT mode liquid crystal display element using an optical compensation film, and 2) a vertical alignment (VA) mode liquid crystal display element using a vertical alignment and an optically complementary negative film. 3) Multi-domain Vertical Alignment (MVA) mode liquid crystal display elements using either vertical alignment and protruding structures, or 4) In-Plane Switching 'IPS' Techniques such as a mode liquid crystal display element are improved to make each element practical. The development of the technology of the liquid crystal display element is achieved not only by the improvement of these driving methods or element structures but also by the improvement of the constituent members for the elements. Among the constituent members used for the liquid crystal display element, in particular, a liquid crystal alignment film, which is an important material related to display quality, as the quality of the liquid crystal display element is improved, it is important to improve the performance of the alignment film. The liquid crystal alignment film is prepared by using a liquid crystal alignment agent. At present, the liquid crystal alignment agent mainly used is to transfer polylysine or soluble polyimine (P = ^) to organic solvent (4) (10). Applying such a solution to the rest of the reading, Li•Fresh Green: Liquid crystal alignment agent using a polymer other than poly-aracine: Μu (liquid crystal resistance), coatability, liquid crystal alignment, electrical characteristics, optical characteristics, display It has not been put into practical use. This type of alignment film requires the effect of the 201130889 on the liquid crystal display element as described below. Ο) Appropriate pretilt angle is imparted to the liquid crystal molecules. Moreover, the pretilt is hardly affected by the crushing strength at the time of rubbing or the temperature condition at the time of heating. Or the removal of the alignment film (2) does not cause defects in the alignment of liquid crystal molecules caused by unevenness in rubbing, scratches, or the like.

(3) An appropriate voltage holding ratio (VHR) is applied to the liquid crystal display element. S (4) When the liquid crystal display element displays an arbitrary image for a long period of time, it is difficult to cause a phenomenon in which the previous image remains "burned" after the image is changed to another image. The liquid crystal display element using the VA mode or the IPS mode is a large part of the liquid crystal τν which has been developed in recent years because of the good viewing angle characteristics as described above. In the case of comparison of the test mode of the control mode, the long-short causes caused by the drive principle exist respectively. • For example, in the case of the lps mode, the viewing angle characteristics are particularly good, and the response speed under halftones is relatively fast. . However, the contrast ratio VA mode difference eIps mode shows black when no voltage is applied, and the filament state depends on the initial listening state of the liquid crystal accompanying the impurity, which is one of the causes of deterioration of contrast. That is, in the lps alignment film, an alignment film having a high liquid crystal alignment property and a black display (black level (10) level) is strongly required. An example of the prior art for the purpose of solving the above problems can be summarized as a technique of reading (4) characterized by using a diamine having a triple bond at the end. [Prior Art Document] 6 201130889 [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-300940-A SUMMARY OF THE INVENTION The object of the present invention is to develop a liquid crystal alignment which is excellent in liquid crystal alignment and has a good black level. A liquid crystal alignment agent for the film. The present inventors have found that a liquid aa display element having improved characteristics described above can be obtained by using a liquid crystal alignment agent containing a polyamine or a bamboo organism having a specific structure, thereby completing the present invention. That is, the liquid crystal alignment agent of the present invention is shown in the following item [1]. [1] A liquid crystal alignment agent comprising a poly-proline and a derivative thereof obtained by reacting a mixture of four rebel-acids represented by the formula (J) with other tetra-retoxacin and a diamine. a composition of at least one of the polymers, and based on the total amount of the mixture of the tetracarboxylic dianhydrides, the ratio of the tetracarboxylic dianhydride represented by the formula is 5 mol% (m〇l%) to 95 Mol%, the ratio of other tetracarboxylic dianhydride is 5 mol% to 95 mol%:

Wherein X is an alkylene having 2 to 12 carbon atoms. Further, an example in which a polyphthalic acid obtained by using a tetracarboxylic dianhydride of the formula (I) is used in a liquid crystal alignment agent is disclosed in Japanese Laid-Open Patent Publication No. 2001-131285. However, this prior art does not use the specific example of the mixture of the tetracarboxylic dianhydride of the formula (I) and the other tetracarboxylic dianhydride of the formula (I), and there is no description relating to the improvement of the black level. Further, examples of the diamine which becomes a reaction object are also limited. [Effects of the Invention] According to the present invention, a liquid crystal alignment agent having good alignment property can be obtained. Especially effective for improving the black level associated with the IPS mode. [Embodiment] First, the terms used in the present invention will be described. The tetrabasic liver is sometimes referred to as an acid anhydride. Therefore, the tetra-salt liver represented by the formula (1) is sometimes referred to as an acid (I). The tetracarboxylic carboxylic acid represented by other chemical formulas is also represented by the same shorthand notation. The diamine represented by the formula is sometimes referred to as an amine (2). The diamine represented by other chemical formulas may also be represented by the same simple method. The term "arbitrary" used in the definition of the chemical formula of ° ° means "not only the position but also the number can be freely selected". For example, the expression "arbitrary Α can be replaced by B, c, D or Ε", except that one Α can be replaced by Β, CD or E, any one of a plurality can pass B, c, D In addition to the meaning of any one of the substitutions in E, it is also possible to have a mixture of B-substituted a, C-substituted A, D-substituted A, and E-substituted A and E. Wherein, when any one may be substituted by another group, 'there is not a plurality of consecutive ones (Η!·substituted by the same group.) The substituent which is not explicitly bonded to any of the carbons constituting the oxime is a bonding position thereof. The chemically problem-free paradigm is free. 8 201130889 The case where the same token is used in multiple chemical formulas means that the radicals have the same defined range, but it does not mean that all the chemical formulas must be the same base at the same time. In the following, the same group may be selected among a plurality of chemical formulas, or a different group may be selected in each chemical formula. In this case, when a plurality of identical symbols are used in one chemical formula, the plurality of groups may be all in the other chemical formulas. The base may be different, and only a part may be different. Me in the chemical formula means a methyl group. The present invention is composed of the above item [1] and the following items [2] to [12]. [2] as [1] The liquid crystal alignment agent according to the above, wherein the other tetracarboxylic dianhydride is at least one of the tetracarboxylic dianhydride represented by the formula (A-1) to the formula (A-46), and the diamine is selected from the formula (1). -1) ~ (b 3), (2), (3) and (4) At least one diamine in the diamine group represented by: 201130889

10 201130889 (A-14)

IcfX^ (A-24) (A-25)

(A-29)

11 201130889

12 201130889

Any of the sounds of the sound ~ r b is 〇 or 1, Cyclohexyl (CyCl〇hexylene). Money can be substituted by methyl; 弋 (1 2), w1 is _ (^2- or _|^-: h2n

Nh2 (2) wherein 'X1 is a single bond or an alkylene group having 1 to 10 carbon atoms; any -CHr of the alkylene group may be -0, -S-, -NH-, -N(CH3)-, -C(CH3)2-, -C(CF3)r, -CO-, -S02-, 1,3-phenylene, 1,4-extension or Fox-1 , 4_diyl (piperazine-l, 4_diyl) replaced; 13 201130889

(3) (a) In the formula (3), 'X2 is a single green bond, 〇-, -COO-, -OCO- or a minus 30 alkyl group, or a formula (a) number 1 to 6 alkylene group R1 is a group represented by carbon number 3~ and stellite; (a) the towel 'X and χ4 are independently a stretching group 2; the ring is independently a stretching phenyl group or a stretching ring hexyl group, R and R Independently fluorine or methyl, f and g are independently 〇, i or 2; c, d and e are independently 〇 or! The sum of these is Bu 3; r4 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxy group having 2 to 3 carbon atoms, or a cholesteryl group. The 'arbitrary hydrogen in the burning, decyloxy and alkoxy groups can be replaced by fluorine. 201130889

Η2ν-^Χχ5 wherein 'X5 is independently -〇- or an alkylene group having 1 to 6 carbon atoms; j is hydrazine 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; Τ is 1,4-phenylene or 1,4-cyclohexylene; X6 is a single bond or a C 1 to 3 alkyl group; h is 0 or 1. [3] The liquid crystal alignment agent according to [2], wherein the other tetracarboxylic dianhydride is a formula (A-1) to (A-4), a formula (A-11), and a formula (A-12) Formula (A-14), Formula (A-18) to Formula (A-21), Formula (A-28) to Formula (A-30), Formula (A-32), Formula (A-37), At least one of the tetracarboxylic anhydrides represented by the formula (A_39) to the formula (A-41) and the formula (A-43) to the formula (A-46), and the diamine is a formula (1-2-1), a formula (1-2) 1-3), formula (2-1) to formula (2-3), formula (2-7), formula (2-10) to formula (2-27), formula (2-29), formula (2) -37)~Formula (2-39), Formula (2-41), Formula (2-43)~Formula (2-47), Formula (2-51), Formula (3-1)~Formula (3- 12) and at least one of the diamines represented by the formula (4-1) to the formula (4-12): 15 201130889

Μ H WM (Α·14) (Α-18) (Α-19) (Α-20)

16 201130889 h2n

'Vnh2 (1-2-1) H2N h2n- -nh2 (2-1) h2n

(2-2) NH2 H2N (1-3)

(2-3) NH2

(2-7)

H2N^Q

H2n- NH2 h2n nh2 (2-14) (2-15) (2-16)

(2-19) '0, (2-18) />-NH2 H2NHf VV VNH2 (2-20) H2NH〇>-Sn S -0~NH2 (2-21) (2-22) h2nhQks^sn 〇-nh2 h2nhQks^/ss/〇_NH2 (2-23) (2-24) 17 201130889

(2-27) (2·29) Η2Ν

Ηη2 Ρ-37)

(2-38)

(2-39) (2-41) Η2Ν

Ηη2 (2-43) -(CH^a

(2-44)

Me Me

(2-46) (2-47) (2-51) 18 201130889

Wherein R 2 Q is an alkyl group having 5 to 16 carbon atoms, R 21 is an alkyl group having 3 to 10 carbon atoms, and R 22 is an alkyl group having a carbon number of 6 to 16 or a cholesteryl group; 19 201130889

Wherein R26 is an alkyl group having 4 to 7 carbon atoms. [4] The liquid crystal alignment agent according to [3], wherein the other tetracarboxylic dianhydride is a formula (A-1), a formula (Α·2), a formula (A-12), and a formula (A-14). Formula (A-18), 201130889 Formula (A-20), Formula (A-21), Formula (A-28), Formula (A-30), Formula (A_37), Formula (A-40) and Formula At least one of the tetracarboxylic anhydrides represented by (A-45), the diamine is a formula (1-2-1), a formula (1-3), a formula (2-7), and a formula (2-10)-form (2-12), formula (2-16) to formula (2-19), formula (2-21) to formula (2-27), formula (2-37) to formula (2-39), formula ( 2-41), Formula (2-43)~Formula (2_47), Formula (2-51), Formula (3-1)~Formula (3_12), and Formula (4-1)~Formula (4-12) At least one of the diamines indicated. [5] The liquid crystal alignment agent according to [4], wherein the other four resorcinic dianhydrides are the formula (A-1), the formula (A-12), the formula (A-14), and the formula (A-18) And at least one of the tetracarboxylic anhydrides represented by the formula (A-45), wherein the diamine is a formula (1-2-1), a formula (1-3), a formula (2-7), and a formula (2-10) At least one of the diamines represented by the formula (2-12), the formula (2-26), the formula (2-44), the formula (2-45), and the formula (3-1) to the formula (3-6) One. [6] The liquid crystal alignment agent according to [3], wherein the other four acid dianhydrides are the formula (A-14), the formula (A-18), the formula (A-19), and the formula (A-20). , formula (A-21), formula (A-28), formula (A-29), formula (A-30), formula (A-32), formula (Α·39), formula (Α-40), At least one of the tetracarboxylic anhydrides represented by the formula (Α: 41), the formula (Α-43), the formula (Α-44), and the formula (Α_46), and the diamine is a formula (1_2-1), a formula (1- 3), formula (2-1) to formula (2-3), formula (2-26), formula (2-29), formula (2-37), formula (2-43) to formula (2-47) At least one of the diamines represented by the formula (3-1) to the formula (3-12) and the formula (4-1) to the formula (4-12). [7] The liquid crystal alignment agent according to [6], wherein the other tetracarboxylic dianhydride is a formula (Α-14), a formula (Α-20), a formula (Α-21), a formula (Α-39) At least one of the tetracarboxylic anhydrides represented by the formula (Α-44) and the formula (Α-46), the diamine is of the formula 21 201130889 (1-2-1), the formula (1_3), the formula (2-1) At least one of the diamines represented by the formula (2_3), the formula (2-26), the formula (2-29), the formula (2-44), and the formula (3-1) to the formula (3-6). [8] The liquid crystal alignment agent according to [3], wherein the other four rebel acids are a formula (A-1), a formula (A-2), a formula (A-3), and a formula (A-4). At least one of the tetracarboxylic anhydrides represented by the formula (A-11), the formula (A-12) and the formula (A-45), and the diamine is a formula (1-2-1) or a formula (1-3) , formula (2-1) to formula (2-3), formula (2-13) to formula (2-15), formula (2-20) to formula (2-26), formula (2-29), At least one of the diamines represented by the formula (2-39) and the formula (2-41). [9] The liquid crystal alignment agent according to [8], wherein the other four acid-lowering needles are the formula (A-1), the formula (A-2), the formula (Α·4), and the formula (A-12). At least one of the four resorcinic acids represented by the formula (A-45), the diamine is a formula (1-2-1), a formula (1-3), a formula (2-1) to a formula (2-3) At least one of the diamines represented by the formula (2-13) to the formula (2-15), the formula (2-26), and the formula (2-29). [10] The liquid crystal alignment agent according to any one of [1] to [9], further comprising another polyamic acid selected from the group consisting of not using the tetracarboxylic dianhydride represented by the formula (I) At least one polymer of its derivatives. [11] A liquid crystal alignment film which is formed by heating a coating film of a liquid crystal alignment agent as described in any one of [!] to [?]. [12] A liquid crystal display element 'includes: a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film according to [U]. 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 derivatives thereof, and a solvent. Polyamide derivative 22 201130889 A polyimine obtained by completely performing a dehydration ring-closure reaction of polylysine, and a partially enzymatic amination obtained by partially performing a dehydration ring-closure reaction of polyamic acid. A lysine-polyamide copolymer obtained by substituting a part of a tetra-retensive dianhydride into a dicarboxylic acid, and the poly-proline-polyamide A polyamide which is obtained by subjecting a part or all of the copolymer to a dehydration ring-closure reaction. Among these derivatives of polylysine, polyimine and partial ruthenium polyamine are preferable, and polyimine is more preferable. In the present invention, at least one polymer selected from the group consisting of polylysine obtained by reacting a mixture of an acid anhydride (I) with another acid anhydride and a diamine and a derivative thereof is used. Ο 〇

X in the formula (I) is an alkylene group having 2 to 12 carbon atoms. The alkylene group is a linear alkyl group and has a carbon number of 5 to 12, which is preferred because it imparts a large liquid crystal orientation to the alignment film. The polymer may be used singly or in combination of at least two kinds of the above-mentioned polyamic acids, or may be used in combination with the above-mentioned polyglycine. Further, as described below, at least one polymer selected from the group consisting of polylysines and derivatives thereof, and other polyphthalic acid 23 201130889 and derivatives thereof selected from the group consisting of without using the acid anhydride (I) may be used. At least one polymer is used in combination. In addition, in the following description except the example, the "poly-proline" used without an annotation has a general term for poly-aracine and its derivatives obtained by reacting an acid anhydride (I) with a mixture of other acid anhydrides and a diamine. The meaning. The other acid anhydride used in combination with the acid field (I) can be selected from the known acid anhydride without limitation. A preferred example is the acid anhydride (A-1) k anhydride (Α·46) shown below. It is preferred to use at least one of these acid anhydrides. 24 201130889

25 201130889 〇· .0 0·

Μ (Α-14) (Α-15) (Α-16)

Me

(Α-19) (Α-20) (Α-21) (Α-22)

(Α-23) (Α-24) (Α-25)

26 201130889

ο

= other _ 'the above fine' is more preferably an acid anhydride (A-) to an acid anhydride (A_4), an acid anhydride (Α_ιυ, an acid anhydride (A-12), an acid anhydride (Α·14), an acid anhydride (A-) 18) ~ Anhydride (A-21), Anhydride (A-28) ~ Anhydride (Α-30), Anhydride (Α-32), Anhydride (Α-37), Anhydride (Α-39) ~ Anhydride (Α-41 ), and anhydride (Α-43) ~ acid needle CA-46). 27 201130889

28 201130889 In the case of further improving the alignment of the liquid crystal, it is more preferable to use _(called, _(^2), acid Xuan (^2), sour liver (A·14), acid anhydride (W8). ), acid anhydride (A-20), acid Xuan (A_21), acid anhydride (A 8 ), _ (A_3G), acid anhydride (Α·37), acid field (A_40), and anhydride (A*45)' are particularly good Acid Xuan (A-1), acid if (Α·12), sour liver (Α-14), acid ▲ (Α_18), and sour liver (Α_45). In the case of paying attention to the VHR of liquid crystal display elements, the above Among the dianic anhydrides, it is more preferably acid field (A_14), acid needle (Α·18), _(Μ), sour liver (A-20), acid anhydride (A_21), acid Xuan (A_28), sour liver (A_(9) , sour liver (Α·30), acid anhydride (Α·32), acid Xuan (Α·39), acid anhydride (a_4〇), acid field (A-41), g-reagent (A_43), _ (-) and Oxan (A_46) alicyclic compound, especially _ (A14), riding (a_2〇), acid Xuan (A-21), anhydride (Α·39), acid needle (A_44) and sour (α 46) By reducing the volume resistance value of the liquid crystal alignment film, the relaxation speed of the charge (residual DC) in the alignment film is improved, which is an The method of the shochu is effective - in view of the purpose of the above, the other acid liver is more preferably an acid anhydride (A-1), an acid anhydride (A_2), an acid anhydride (A_3), an acid anhydride (A-4), or an acid anhydride (A_U). And an acid anhydride (A_12) and an acid anhydride (A·#), particularly preferably an acid anhydride (A-1), an acid anhydride (Α·2), an acid anhydride (A_4), an acid anhydride (A_12), and an acid anhydride (A-45). It is not limited to these acid anhydrides, and other known compounds can be used within the scope of achieving the object of the present invention. The mixing ratio of these acid anhydrides in the mixture of acid if (I) and other acid livers is based on the total amount of the mixture. The acid anhydride (1) is 5 mol% to 95 m〇1%, and the other acid anhydride is 5 m〇i% to % m〇i%. The ratio of the mixture 29 201130889 is preferably 'anhydride (D is 15 m〇i) %〜85 mol%, other acid needles are 15 to 85 mol%. The diamine used in the present invention can be selected from the known diamines without limitation. The preferred diamines can be exemplified by the following diamines (1_1). }~Diamine (1-3), diamine (2), diamine (3), and diamine (4). It is preferred to use at least one diamine selected from the group consisting of these diamines.

In the formula (li), b is hydrazine or 1, and any hydrogen in the cyclohexyl group may be substituted with a methyl group. :2- or -NH-. < Medium 'W1 is -CH2- or 4 Specific examples of these diamines are listed below. 201130889

In the formula (2), χ1 is a single bond or a stretching group having a carbon number of 1 to 1 Å, and any -CH2- of the stretching group may be -0-, -S-, -NH-, -N (CH3) )-, -C(CH3)2---c(CF3)2-, -CO·, -S02-, 1,3-phenylene, 1,4_phenylene or pyridazine-1,4- Substituted by the second base. A preferred example of oxime 1 is an alkylene group having a carbon number of 10, in which case any _CHr_ of an alkyl group may be via _〇_, _s, -NH-, -C(CH3)2-, ι,4- Substituted by phenyl or oxime. Further, any hydrogen of the benzene ring to which the amino group is bonded may be substituted with a mercapto group, but it is preferably not substituted with a methyl group. "" Specific examples of the diamine (2) are listed below. 31 201130889 H2N-0/N0-NH2 H2N- NH2 h2n~ nh2 (2-3) (2-1) P-2)

P-7)

Ρ·8>

(2-9) H2N nh2 (2-10)

(2-14) (2-15)

H2N η〇ΛΛ/〇"ΝΗ2 h2n〇〇v^AQh (2-17) (2-16) NH, h2n-(\ // vv 'σ ^ NHz h2n^〇/〇s/n^〇n〇 ~ (2-18) P-19}

NH, 32 201130889 h2n- -NH, H2NH〇^Sn (2-20) S-〇~NH2 (2-21) h2n to small, h2n-^W^_ (2-23) NH, (2-22 ) Η2ΝΗ〇/ O' S\/\/^sA /)~NH2 (2-24) H2NH〇^, vv V '\ /"H2 (2-25)

Me

(2-28) (2-29)

(2-36) 33 201130889

(2-38) (2-39) (2-40)

Me Me Me Me h^n-hQ/Sn0^v〇-nh^ λι ' Bu ~ (2-41) (2-42)

CH2)3 (2_44) H2N-0/S^~<CH2)6-^/N^-NH2 (2-45)

Me Me

H2 ^2·46)

F3cv .CF

(2-47) (248) (2-49) 34 201130889 (2·5.)

(2-53) R1

In the formula (3), 'X2 is a single bond, _〇_, _c〇〇_, _〇C〇_ or an alkylene group having a carbon number of 1 to 6, preferably a single bond, _〇_, _€〇〇 _ or an alkylene group having a carbon number of 1 to 3, R1 is an alkyl group having 3 to 3 carbon atoms, or a group represented by the formula (a), preferably an alkyl group having 4 to 20 carbon atoms or a formula (a) The base represented. In the formula (a), X3 and X4 are independently a single bond or a C1-alkylene group, preferably a single bond, _CH2. or _CH2CHr. Ring B and ring c 35 201130889 independently 1,4-phenyl or fluorene, ‘extension of cyclohexyl. R2 and R3 are independently fluorine or fluorenyl, and f and g are independently 〇, i or 2, preferably f and g are 〇°c, d and e are independently 〇 or 1, and the total of these is 1 ～3eR4 is a decyl group having a carbon number of 1 to 3 Å, an alkoxy group having a carbon number of 丨~, an alkoxy group having a carbon number of 2 to 3 Å, or a thiol group, and these alkyl groups, alkoxy groups, and alkoxy groups. In the alkyl group, any hydrogen may be substituted by fluorine. Preferred examples of R4 are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and an alkyl group, an alkoxy group and an alkyl group having a cholesteryl group. The hydrogen in the oxyalkyl group is not substituted by fluorine. Preferred examples of the diamine (3) are listed below. 36 201130889

(3-6)

(3-13) 37 201130889

_

(3-15)

(3-21)

In the formula (3-1) to the formula (3-25), R20 is an alkyl group having a carbon number of 1 to 20, 38 201130889 or an alkoxy group having 1 to 20 carbon atoms, preferably an alkyl group having 5 to 16 carbon atoms. R21 is a burnt group having 1 to 20 carbon atoms or an alkyloxy group having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 1 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 cholesteryl group. R23 is a carbon group having 4 to 2 carbon atoms, preferably a carbon group having 6 to 16 carbon atoms. R24 is a carbon group having 3 to 2 carbon atoms or an alkoxy group having 3 to 20 carbon atoms, and is preferably an alkyl group having 5 to 12 carbon atoms. R5

(4) Preferably, both -〇-, -CH2. or -CH2CH2- are 〇 or 1. R5 is a gas, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, 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 4 to 7 carbon atoms. Ring T is 1,4·phenyl or i,4·cyclohexylene. Χ6 is a single bond or an alkylene group having 1 to 3 carbon atoms. Further, h is ruthenium or osmium. Further, the bonding position of the amino-p-phenylene ring is preferably aligned with respect to χ5. Preferred examples of the diamine (4) are listed below. 39 201130889

40 201130889

In the formula (4-U to (4-16), R26 is a hydrogen group, a carbon number] to 12, and a hospital base having a slave number of 1 to 12, preferably a carbon number of 4 to 7. In the specific example of the diamine, the diamine (1-2-1), the diamine (1-3), the diamine (2-1) to the diamine (2-3), and the diamine shown below are more preferred. (2-7), diamine (2-10) to diamine (2-27), diamine (2-29), diamine (2-37) ~ diamine (2-39), diamine (2 -41 ), diamine (2-43) to diamine (2-47), diamine (2-51), diamine (3-1) to diamine (3-12), and diamine (4- 1) ~Diamine (4-12) 〇201130889

H2N'/XJrVNH2 (1-2-1) H2N h2n- -nh2 (2-1) h2n

(2-2) Called H2N (1-3)

(2-3) NH2

/)-nh2 (2-7)

(2-12) (2-13) H2N- Η2Ν·^ν〇ν'σ NH2 h2n nh2 (2-14) (2-15) // v V w zrm2 (2-16)

H2N-^^-S,

2 H2N

I

(2-18) S s~〇~NH2 (2-21) h2n_^3/ n^3_nHz (2-20) η2ΝΗ〇Λ/^〇·νη: (2-22) H2N_〇^ N0~NH2 H2N -^ /X vv S (2-23) (2-24) X3~NH2 42 201130889

(2-25)

Me h2n-^/N^n Me 'Or' P-26) -NH, H2N^0_0_0_nH2 H2N^〇-nwn^〇-NH2 P-27) (2-29)

(2-43) (2-M) (2-45) (2-46) (2-47) (2-51) 43 201130889

Here, R2G is an alkyl group having 5 to 16 carbon atoms, R21 is an alkyl group having 3 to 10 carbon atoms, and R22 is an alkyl group having 6 to 16 carbon atoms or a cholesteryl group. 44 201130889

In the specific example of the above-mentioned more preferable diamine, in order to further improve the alignment property of the liquid crystal, it is more preferred to be a diamine (1-2-1), a diamine (1-3), or a bis-45 201130889 amine (2- 7), diamine (2-10) ~ diamine (2 · 12), diamine (2-16) ~ diamine (2-19), diamine (2-21) ~ diamine (2-27) , diamine (2-37) ~ diamine (2-39), diamine (2-41), diamine (2-43) ~ diamine (2-47), diamine (2-51), two Amine (3-1) to diamine (3-11), and diamine (4-1) to diamine (4-12) ' Particularly preferred are diamines (1-2-1), diamines (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-mentioned preferred diamine, it is preferable to impart a high VHR to the liquid crystal alignment film, and more preferably a diamine (1_2-1), a diamine (1-3), or a diamine (2-1) to two. Amine (2-3), diamine (2-26), diamine (2-29), diamine (2-37), a fe·(2-43)~monoamine (2-47), diamine (3·1)~Diamine (3-11), and diamine (4-1)~diamine (4-12) 'Specially preferred as 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 the specific example of the above-described preferred diamine, it is more preferable to reduce the volume resistivity of the liquid crystal alignment film, preferably diamine (丨-2-i), diamine (丨_3), diamine (2- 1) ~Diamine (2-3), diamine (2-13) ~ diamine (2-15), monoamine (2-20) ~ diamine (2-26), diamine (2-29) , diamine (2-39) and diamine (2-41), particularly preferably diamine (2-1) to diamine (2 3), diamine (2-13) to diamine (2-15) , diamine (2·26) and diamine (2-29). However, diamines can be classified into two types depending on their structures. That is, when the skeleton linking two amino groups is regarded as a main chain, the diamine is a diamine having a side chain group which is a branch of an autonomous chain, and a diamine having no fiber group. By reacting a di-branched tetra-dianhydride having a side chain group, a polylysine having a plurality of side chain groups for the main chain of the polymer 46 201130889 is called. When such a polyamic acid having a side chain group to 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 of 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 alkoxy group having 3 or more carbon atoms, and an alkoxy group having a carbon number of 3 or more. Base. 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 an alkoxy 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 side chain group is used as a non-side chain type diamine, the above diamine (3) and diamine (4) ) is a side chain type diamine, a diamine (U1) to a diamine (1-3), and a diamine (2) is a non-side chain type diamine. Further, by appropriately separating the side chain type diamine from the non-side chain type diamine, the pretilt angle necessary for each of the display elements can be used. That is, a relatively large pretilt angle is required in the longitudinal electric field mode represented by the TN mode or the VA mode, and therefore a side chain type diamine is mainly used. At this time, in order to further control the pretilt angle, a non-side chain type diamine can be used at the same time. The blend ratio of the non-side chain type diamine to the side chain and the monoamine may be determined by the ratio of the pretilt angle as the target. By appropriately selecting the side chain group, it is also possible to use only the side and the type of amine. . In the transverse electric field mode, since the pretilt angle is small and high liquid crystal alignment is required, at least one of non-side chain type diamines can be used. In the present invention, in particular, in order to exhibit a pretilt angle of 2 degrees or more, it is preferred to use the side bond type diamine to be more than 5 mol% to 70 47 201130889 mol% in the total amount of the diamine. Mol%~50 mol%. The polyphthalic acid used in the liquid crystal alignment agent of the present invention is obtained by reacting a mixture of the above acid anhydride and a diamine in a solvent. In the synthesis reaction, other than the selection of the raw materials, the conditions in the usual polyaminic acid synthesis can be directly applied without special conditions. The solvent used is as described later. In the liquid crystal alignment agent of the present invention, in order to prevent the removal by friction, it is preferable to use at least one type of silylene (silGxane) diamine. A preferred example of the divalent amine diamine is a diamine represented by the formula (15).

In R32^, 'R and ^31 are independently an alkyl group or a stupid group having a number of 1 to 3, and an alkyl group or a phenyl group substituted with an alkyl group. y is an integer of 1 to 1 。. Specific examples of the monoamine (15) include the following compounds or polymers. H2N-(CH2)3-Si-〇_^|_(CH2)3_NH2 (151)

Me Me

Me H2N-(CH2)3-si_ Me

(CH2)3-NH2 (15-2) (The molecular weight of the polymer of the formula (15-2) is 85 〇 to 3 〇〇〇.) 48 201130889 When these dioxane-based diamines are used, the amount of addition is relatively The total amount of the diamine used as the raw material is preferably from 0.5 mol% to 30 mol%, more preferably from 1 mol% to 10 mol%. 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. Examples of the organic ruthenium compound are amino propyl trimethoxysilane, amino pr〇pyl triethoxysilane, vinyl vinyi trimethoxysilane, and N. -(2-Aminoethyl)-3-aminoethyl-3-methyl propyl methyl dimethoxysilane, N-(2-aminoethyl)- N-(2-aminoethyl)-3-amino propyl trimethoxysilane, vinyl triethoxysilane, 3-mercaptopropyl ethoxylate 3-methacryloxy propyl trimethoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxypropyl decyl dimethoxysilane Oleane coupling agent (3-glycidoxy propyl methyl dimethoxysilane), 2-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane Coupling agent ), as well as dimethyl polysiloxane, poly Polydimethyl siloxane, polydiphenyl siloxane, etc., silicone oil. The addition ratio of the organic ruthenium compound in the alignment agent is not particularly limited as long as it is in the range of the effect of the invention of the present invention, and the concentration of the enthalpy is relative to the polymer contained in the alignment agent t = ^•0 ! Weight % * (Wt%) ~ 5 wt 〇 / 〇 range. If it is 5 _ cho, the possibility of misalignment of the liquid crystal caused by the raw material of the test material is 0.1. The addition of _ special H wt% ~ 3 wt% range. From the viewpoint of preventing deterioration of characteristics over time or deterioration caused by environment, the alignment agent of the month may further contain a compound having two or more functional groups reactive with the carboxyl group of the polyamide I or its emitter, that is, a so-called crosslinking agent . Examples of such a crosslinking agent include a polyfunctional epoxy group as described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. , isocyanate materials, etc. Further, a cross-linking polymer which reacts by itself to form a network structure, such as a cross-linking agent which increases the (tetra) degree of the heteroamino acid or the polyimine, can also be used for the same purpose as described above. In the above-mentioned Japanese Patent Application Laid-Open No. Hei 10-310608, Japanese Patent Application Laid-Open No. Hei No. Hei. Maleimide), or bisallyl-resistant quinone imine ((5) such as coffee) derivatives. When these crosslinking agents are used, a preferred ratio of these parenting agents is from 5 wt% to wt%, more preferably from 10 wt% to 50 wt%, based on the total amount of the polymer component. The liquid crystal alignment agent of the present invention preferably uses at least one of polyamic acid, and may also be used in combination with other poly 50 201130889 proline which is produced by using no acid anhydride. The mixing ratio of the case of combining other poly-proline is based on the total amount of the polymer, the poly-proline is iOwt% to 95 wt%, and the other poly-proline is 5 wt% to 90 wt%, even if the polyamine A sufficient effect can be obtained by a small proportion of acid. In the liquid crystal alignment agent of the present invention, a polymer other than polyamic acid obtained by the reaction of an acid anhydride with a diamine, such as a polyester or an epoxy resin, can be used at the same time. However, when such other polymers are used at the same time, the proportion of the polymer is preferably 30% by weight or less based on the total weight of the polymer. The alignment agent of the present invention is a solution obtained by dissolving polylysine in a solvent. The solvent can be appropriately selected from the solvents used in the production or use of the known polyamic acid, depending on the purpose of use. These solvents are exemplified as follows. Examples of the aprotic polar organic solvent include N-methyl-2-pyrrolidone (NMP), dimethyl imidazolidinone, and N-mercapto N-methyl caprolactam, N-methyl propionamide, N,N-dimethyl acetamide, dimercapto ilamide Dimethyl sulfoxide ), N,N-dimethyl formamide (DMF), N,N-diethyl formamide, N,N-diethyl a solvent such as a solvent such as N, N-diethyl acetamide (DMAc) or γ-butyrolactone (GBL) and a solvent other than the above-mentioned solvent and improving the coating property. Preferred examples thereof include alkyl lactate, 3-methyl-3-methoxy butanol, tetrahydronaphthalene 51 201130889 (tetralin ), and isophor. Ketone (iSOphorone), ethylene glycol monoalkyl bond (for example, ethylene glycol monobutyl ether (BSS)), ethylene glycol early burnt puzzle (for example: diethylene glycol) Single E), Ethyl Alcohol Monophenyl, Triethylene Glycol Monoether Ether, Propylene Glycol Monoalkyl Ether (eg Propylene Glycol Monobutyl Ether), Dialkyl Malonate (eg: Diethyl Malonate) Diethyl malonate, dipropylene glycol monoalkyl group (for example: dipropylene glycol monoterpene), and ester diol monoester ester compounds. Among these solvents, NMP, dinonyl imidazolidinone, GBL , BCS, diethylene glycol monoethyl _, propylene glycol monobutyl ether, and dipropylene glycol singular. The alignment agent of the present invention may further contain various additives as needed. For example, when it is desired to further improve the coatability, an appropriate amount may be contained. The surfactant suitable for the purpose may contain an appropriate amount of an antistatic agent when it is necessary to further improve the antistatic property. The concentration of the polymer in the alignment agent of the present invention is preferably from 〇1 wt% to 40 wt%, more preferably It is necessary to adjust the film thickness when the alignment agent is applied onto the substrate, and it is possible to adjust the concentration of the polymer to be contained by previously diluting with a solvent. The alignment film of the present invention is obtained by Obtained as follows: The method described below applies the above-mentioned alignment agent to the substrate, and if necessary, the solvent is heated and removed at a relatively low temperature (prepared for calcination); then, in order to further promote solvent removal, the ruthenium imidization of the poly-proline is improved. Rate, in order to express the original characteristics of the alignment film, and to heat at a relatively high temperature (formally burnt). For the film obtained in the above manner, a rubbing treatment can be carried out as needed. The liquid crystal display device of the present invention includes: a pair of bases 52 201130889 which are disposed oppositely, and electrodes formed on one or both of the faces of the pair of substrates, which are formed on the opposite faces of the pair of substrates The liquid crystal alignment film of the present invention 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 indium tin oxide Oxide 'ITO) or a metal vaporized II film. Alternatively, the electrodes may be formed on the entire surface of one of the faces of the substrate, for example, may be formed into a desired shape that is patterned. The electrode is made up of a comb or a tooth structure. The electrode (10) may be formed on the wafer substrate in the counter substrate or on the germanium substrate. The formation form of the f-pole differs depending on the type of the crystal display element. For example, in the case of an lps-type liquid crystal display element, electrodes are disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, Electrodes are disposed on two of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode. The liquid crystal layer is formed by the above-mentioned pair of substrates which are opposed to each other by the surface on which the liquid crystal alignment film is formed. When the liquid crystal layer is formed, fine particles or a resin sheet or the like may be inserted between the pair of substrates as needed to form an appropriate spacer. 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, it can be improved for all known H-like objects. The alignment film of the present invention produced by the above method is particularly effective for the improvement of alignment defects of the display, which is difficult for the rubbing treatment. This large-faced display is a TFT-to-H motion control. In addition, this type of TFT type liquid crystal display 53 201130889 = the liquid crystal composition used in the article is described in Japanese special (4) = newspaper: Japanese Patent No. 2635435, Japanese Patent Special Table is 5, and it is Japanese patent. Japanese Laid-Open Patent Publication No. Hei 9-255956. Therefore, the alignment of the invention is preferably used in combination with the liquid crystal composition described in these publications. The liquid crystal display element of the present invention exhibits a high test when used for, for example, lps, and is excellent in alignment properties such as level values. The value of this black level can be adjusted in the following manner. That is, the liquid crystal cell assembled in the anti-parallel direction of the rubbing direction is disposed on the stage of the micromirror, and the polarizer and the analyzer are rotated to be the minimum bright light; the power take-up multiplier is defeated to minimize the minimum The magnification of the silk micromirror is 100 times '10 times X times the X-connector 10 times). The smaller the value of the brightness, the better the black level. The system is set up to have a minimum brightness of · μν and a lower part of preferably less than 900 μν. In the present application, the value of the minimum luminance is used as the value of the black level. The liquid crystal display element of the present invention is also excellent in electrical compatibility with respect to the reliability of the liquid crystal display element. Such t gas characteristics include voltage holding ratio and ion density. The voltage holding ratio (VHR) means that the ratio of the voltage applied to the liquid crystal display element to the liquid crystal display element during the frame period is maintained in the liquid crystal element + to indicate the display characteristics of the liquid crystal display element. The liquid crystal display element 4 of the present invention has a voltage holding ratio of 97.0% or more measured under a temperature condition of 5 V and 3 GHz, and is measured at a temperature of 6 Gt using a rectangular wave of 5 v and a frequency of 〇 3 Hz. The voltage holding ratio is 85 〇% or more, which is preferable from the viewpoint of preventing display failure. The ion density is a transient current other than the driving of the liquid 54 201130889 crystal generated by applying a voltage to the liquid crystal display element, and indicates the concentration of the ionic impurities contained in the liquid crystal in the liquid crystal display element. The liquid crystal display element of the present invention preferably has an ion density of 300 pC or less from the viewpoint of preventing the burning of the liquid crystal display element. The pretilt angle in the liquid crystal display device of the present invention can be, for example, a liquid crystal characteristic evaluation apparatus OMS-CA3 type manufactured by Central Seiki, and is described in Journal 〇f Applied Physics, Vol. 48, No. 5, p. 1783-1792 (1977). Determined by crystal rotation method. [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 examples is as follows. <Delay of the alignment film, film thickness, and pretilt angle measurement> It was determined using an ellipsometer spectrometer M-2000U (manufactured by J. A. Woollam Co., Inc.). In the case of this example, the retardation value of the film increases in proportion to the degree of alignment of the polymer backbone. That is, a film having a large retardation value has a large degree of orientation. <Voltage Retention Rate> Using the "Shuishouhe" 14th LCD Symposium Prep Draft p78 (1988)" The measurement was carried out by applying a rectangular wave having a wave height of ±5 V to the liquid crystal cell. It is done under the thief. Honest is an indication of how much the applied voltage remains after the frame period. If the value is 1%, it means that all charges are maintained. <Measurement of Ion Amount in Liquid Crystal (Ion Density)> According to the method of Applied Physics, Vol. U) No. 65 (1996), the method of 'liquid crystal measurement system 6254, manufactured by Toyo Technica Co., Ltd.' The measurement was carried out. Use a triangular wave with a frequency of 〇.〇1 Hz at a voltage range of ±10 V and a temperature of 6 (measured at TC (the area of the electrode is 1 cm2). If the ion density is large, it is likely to cause burning due to ionic impurities. Poor condition, that is, the ion density is a physical property value which is an index for predicting the occurrence of burning. <Weight average molecular weight (Mw)> The weight average molecular weight (Mw) of polyglycine in the liquid crystal alignment agent is by gel permeation chromatography (Gel Permeation Chromatography, GPC, manufactured by Shodex Co., Ltd., GF7MHQ), using DMF containing 0.6 wt% phosphoric acid as the eluate, and the column temperature was 5 〇. (:, using polystyrene as a standard solution. <viscosity> Use Viscometer (manufactured by Toki Sangyo Co., Ltd., TV-22), measured at 25 ° C. The compounds used in the examples and comparative examples are listed below.

56 201130889 Carbon number of acid Sf No. X Reference or physical property Il 4 Melting point 195.8 ~ 196.8 ° C 1-2 8 Melting point 109.7~111.2 °C 1-3 10 曰本专利特开2001-131285号 Acid Sf ( Al ): pyromellitic dianhydride (PMDA) acid needle (A-2) : 3,3',4,4'-biphenyltetradecanoic acid liver (3,3',4,4' -biphenyl tetracarboxylic dianhydride &gt; BPDA) Anhydride (A-12) : 2,3,6,7-naphthalene tetracarboxylic dianhydride (NPDA) Anhydride (A-14 ) : 1,2,3,4-cyclobutane tetracarboxylic dianhydride ( CBDA) acid needle (A-18) : 1,2,3,4- Dicarboxylic acid dianhydride (1,2,3,4-butane tetracarboxylic dianhydride &gt; BDA) anhydride (A-20 ) : 1,2,4,5-cyclohexanetetradecanoic acid dianhydride (1,2 ,4,5-cyclohexane tetracarboxylic dianhydride » CHDA) acid needle (A-30): RikacidTDA-l〇〇 (New 曰 Physicochemical (stock)) acid needle (A-45). Ethylenediaminetetraacetic acid two needle (ethylene Diamine tetraacetic dianhydride * EDTAD ) The above anhydride is an anhydride at a commercially available compound. And then dried in vacuo to add used. The acetic anhydride treatment is carried out in the following manner. First, 10 times the amount of acetic anhydride and optionally the same amount of fluorene benzene were used for each compound' to heat at 80 ° C for 2 hours. It was then cooled to room temperature and the precipitate was filtered. 57 201130889 Anhydride (A-21) : 2,3,5-tricarboxycyclopentyl acetic dianhydride (TCMP) Anhydride (A-44): 2,4,6 , 8-tetracarboxy-bicyclo[3_3.0]octane dianhydride (2,4,6,8-tetracarboxy_bicyclo[3.3.0]octane dianhydride, BODA) The above anhydrides are respectively based on Japanese Patent Laid-Open No. 58-109479 No. Bulletin, J. Am. Chem. Soc., Vol. 82, 6342 (1960) for synthesis. Diamine (2-1): 4,4'-diaminodiphenyl methane &gt; DDM Diamine (2-7) : 1,2-bis(4-amino Phenyl) ethane (1,2-bis(4-aminophenyl)ethane 5 DD2) The above diamine is a commercially available compound used directly in the experiment. Diamine (2-11) : 1,4-bis(4-aminophenyl)butane (1,4-bis(4-aminophenyl)butane, DD4) Diamine (2-26) : Ν,Ν'- N,N,-bis(4-aminophenyl)ethylenediamine (N,N'-dimet;hyl-N,N'-bis(4-aminophenyl)ethylene diamine,MPED) Diamine (2 -29 ) : 1,4-bis(4-aminophenyl)piperazine (APPD) Diamine (2-44): 1,3-bis(4-( 4-, 4-bis(4-(4-aminophenylmethyl)phenyl)propane (APMPP) The above diamines are based on J. Appl. Polym. Sci., Vol. 8,

No.l, 533 (1964), J. Polym. Sci., Part A, Polym. Chem" V〇1.30, N〇.6, 1099 (1992), 曰本专利专开昭 51-136917号 58 201130889 The method described in Japanese Patent Laid-Open No. 193346 discloses the synthesis of 0 diamine (3-5-1): R21 = pentyldiamine (4-6-1): R26 = heptyldiamine (4-9) -1) : The diamines of R26=propyl or more are synthesized by reference to the methods described in Japanese Patent Publication (10) 4 3 Side No. E ^ 贿 813 813 、 、 、 、 、 、 、 、 、 、 日本 Q 聪 聪 聪 聪 聪 , , , , N) is abbreviated as Compound (N). It is a Japanese-made monolith (combined with the square wire described in the bulletin. The specialty is 2〇()2·162630. In addition, the polymer material is all in the money flow. get on.

(3-5-1) (4-6-1) (4-9-1) 59 201130889

(N) [Synthesis Example 1] <Preparation of polyamic acid varnish A> DDM (2.2611 g, 11.405 mmol) was dissolved in NMP (22.5 g) to give an acid anhydride (1-1) (0.9988 g, 2.851 mmol) PMDA (0.6219 g, 2.851 mmol) and CBDA (1.1183, 5.702 mmol) were added while remaining below room temperature. After 2 hours of mixing, NMP (10.0 g) and BC (12.5 g) were added. The viscosity of this solution was 83 mPa.s. The solution was stirred at 7 °t: for about 4 hours to obtain a varnish A having a viscosity of 34 mPa.s. The polyamido acid of the varnish has a weight average molecular weight of 52, 〇〇〇. [Synthesis Example 2 to Synthesis Example 23] <Preparation of Polyamic Acid Varnishes B to W> Using the same raw material compositions as shown in Tables 1 and 2, a polyamic acid varnish was prepared by the same method as in Synthesis Example 1. B to w, physical properties were measured in the same manner as in Synthesis Example 1. In addition, the percentage of moles is indicated in brackets. 201130889 <Table 1> Synthesis Example No. Varnish name anhydride (abbreviation / formula No.) Diamine (abbreviation / formula No.) Viscosity (mPa-s) Weight average molecular weight 1 A Μ (25) PMDA (25) CBDA (50 DDM 34 48,000 2 B 1-1 (50) CBDA (50) DDM 35 52,000 3 C 1-2 (50) CBDA (50) DDM 35 56,000 4 D 1-3 (50) CBDA (50) DDM 32 50,000 5 E 1-2 (25) CBDA (50) BPDA (25) DDM 37 63,000 6 F 1-2 (25) CBDA (50) NPDA (25) DDM 33 55,000 7 G 1-2 (25) CBDA (50) BDA (25) DDM 33 50,000 8 Η 1-2 (50) CHDA (50) DDM 36 64,000 9 I 1-2 (50) TCMP (50) DDM 35 57,000 10 J 1-2 (25) CBDA (50) DDM 31 68,000 61 201130889 TDA-100 (25) 11 K 1-2 (25) CBDA (50) EDTA (25) DDM 35 54,000 12 L 1-2 (50) CBDA (50) DD2 (80) MPED (20) 31 50,000 13 Μ 1-2 (50) CBDA (50) DD2 (80) APPD (20) 33 67,000 14 Ν 1-2 (50) CBDA (50) DD4 (50) APPD (50) 35 58,000 15 0 1-1 ( 50) CBDA (50) APMPP (50) MPED (50) 35 58,000 62 201130889 <Table 2> Synthesis Example No. Varnish name anhydride (abbreviation / formula No.) Diamine (abbreviation / formula No.) Viscosity (mPa.s ) Weight average molecular weight 16 P 1-2 (25 PMDA (25) TCMP (50) DDM (70) 3-5-1 (30) 33 69,000 17 Q 1-2 (25) CHDA (75) DDM (70) 3-5-1 (30) 30 67,000 18 R 1-2 (25) PMDA (25) CBDA (50) DDM (85) 4-6-1 (15) 31 59,000 19 S 1-2 (25) PMDA (25) CBDA (25) BODA (25) DDM (90) 4-9-1 (10) 32 63,000 20 T PMDA (20) MMDA (80) DDM 34 57,000 21 U PMDA DD4 35 70,000 22 V PMDA (50) CBDA (50) DDM (85) 4-6- 1 (15) 36 73,000 23 W CHDA DDM (70) 3-5-1 (30) 37 78,000 [Example 1] <Preparation of liquid crystal cell for black level measurement> Weigh 1.0 g of varnish A in a sample vial A mixed solvent of NMP/BC = 1/1 63 201130889 (weight ratio) was added to become 1.67 g. Next, a polyglycine solution having a polymer of about 3 wt% of the polymer was dropped on a transparent glass substrate, and coating was carried out by a spinner method (2, rpm rpm) for 15 seconds. After coating, the substrate was heated at 80 C for 3 minutes, the solvent was evaporated, and then 23 Torr in an oven.加热 Heat treatment for 20 minutes. The polyimide film with a thickness of about 70 nm was rubbed (extrusion: 0.3 mm, platform feed rate: 60 m/s, rotation speed: 1000 i: pm 'rubbing cloth: YA_18_R (man-made fiber)) . Then, the glass substrate on which the alignment film was formed was subjected to ultrasonic cleaning in ultrapure water for 5 minutes' and then dried in an oven at 12 ° C for 30 minutes. The surface on which the alignment film was formed was placed on the inner side, and the rubbing direction was opposed to each other, and then the anti-parallel liquid crystal having a gap of 25 μm was formed by sealing with an epoxy curing agent containing a gap agent of 25 μm. ^ntiparalld ceU ). Then, the liquid b 曰 composition A shown below was injected into the liquid crystal cell, and the injection port was sealed with a light hardener. Next, heat treatment was performed for 30 minutes on uyc I to prepare a liquid crystal display element. The black level of the liquid crystal cell was measured and found to be 1,25 〇 μν. <Preparation of Pretilt Angle and Liquid Crystal Cell for Measuring Electrical Characteristics> Using the glass substrate on which the alignment film was formed in the same manner as described above, the agent was dispersed on the alignment film. This is sealed with the other substrate = the film surface is inwardly - the anti-parallel liquid is sealed in such a manner that the rubbing direction is anti-parallel, and the anti-parallel liquid Γ α having a gap of 7 μm is injected into the liquid crystal in the same manner as described above. Sealed with a mouthing agent. Next, a liquid crystal display element was produced by performing a knife knives at 110 °C. The solar cell unit's 64 201130889 VHR (30 Hz and 0.3 Hz) and ion density were measured and found to be 98.3%, 88.8 Å/〇, and 157 pC. <Liquid crystal composition A>

17 wt% 17 wt% 16 wt% 10 wt% 5 wt% 10 wt% 6 wt% 6 wt ° / 〇 13 wt% [Example 2 to Example 15] Using the varnish B to varnish shown in Table 1, the same as in Example 1. The way to obtain the liquid crystal display element. The values of the black level, VHR, and ion density at this time are shown in Table 3 together with the results of Example 1. 65 201130889 <Table 3> Example No. Varnish name Black level VHR (%) Ion density Uv) 30 Hz 0.3 Hz (pC) 1 A 1,250 98.5 87.4 157 2 B 1,180 99.3 92.1 67 3 C 1,230 99.2 92.3 51 4 D 1,110 99.0 90.7 85 5 E 1,040 98.7 89.3 123 6 F 1,200 98.6 86.8 133 7 G 1,360 99.0 90.5 92 8 Η 1,250 99.4 95.3 32 9 I 1,430 99.5 94.8 25 10 J 1,170 97.9 89.4 230 11 K 1,100 98.4 89.9 167 12 L 970 99.2 90.7 88 13 Μ 990 99.1 91.0 72 14 N 960 99.2 91.1 65 15 0 950 99.0 90.2 73 [Comparative Example 1] A liquid crystal display element was produced in the same manner as in Example 1 except that varnish T was used instead of varnish A. The black level, VHR (301^ and 0.31^) and ion density of the liquid crystal cell were measured, and the result was 2,81 (^¥, 99.0〇/〇, 91.5%, and 46卩0 [Comparative Example 2]

A liquid crystal display element was produced in the same manner as in Example 1 except that varnish U was used instead of varnish A. The black level of the liquid crystal cell, VHR 66 201130889 (30 edges and 0.3 edge), and ion density were measured, and found to be 2, 13 (^, 95.0%, 79.8%, and 421 pC. [Example 16] In addition to using varnish R instead of varnish A liquid crystal display element was produced in the same manner as in Example 1. The pretilt angle, VHR (30 Hz and 0.3 Hz), and ion density of the liquid crystal cell were measured and found to be 5.8, 98.7%, 90.0%, and 101 pC. The retardation of the glass substrate attached to the film before assembly of the liquid crystal cell was measured and found to be 0.23 nm. [Example 17 to Example 19] A liquid crystal display element was obtained in the same manner as in Example 1 using varnish S. In addition, used in varnish T A mixture of varnish R and varnish S was separately added, and liquid crystal display elements were obtained in the same manner as in Example 1. The results of measuring the pretilt angle, VHR (30 Hz and 0.3 Hz), and ion density values for these liquid crystal display elements, and The retardation measurement value of the glass substrate attached to the film before assembly of the liquid crystal cell is shown in Table 4. In addition, the weight percentage is shown in parentheses. 67 201130889 <Table 4> Example No. Varnish name Pretilt angle VHR (%) Delay (.) 30 Hz 0.3 Hz (pc) (nm) 16 R 5.8 98.7 90.0 ΙοΓ--~~~ 0.23 17 S 5.4 98.5 88.6 153'~~~~~ 0.27 R (20) ----- 18 T (80) 4.7 99.4 91.1 56 0.15 S (20) ---~~~· 19 T (80) 4.6 99.5 91.2 64 0.19 [Example 20] In addition to adding a compound of eucalyptus to the varnish R relative to the polymer component In addition to (N), a liquid crystal display was produced in the same manner as the example. The pretilt angle, VHR (3〇112 and 〇3 Hz), and ion density of the liquid crystal cell were measured and found to be 5 3 . 2%, % 3%, and 63. In addition, 'the retardation of the surface substrate attached to the film before the liquid crystal cell is measured' is 0.17 nm. [Example 21] In addition to adding 3 wt to the varnish R relative to the polymer component % 3-aminopropyldimethoxy group; a liquid crystal display was produced in the same manner as in Example 16. The pretilt angle, VHR (30 Hz and 0.3 Hz), and ion density of the liquid crystal cell were measured. As a result, it was 5 5, 99 〇%, 91 2%, and 96 pO. Further, the retardation of the glass substrate attached to the film before assembly of the liquid crystal cell was measured, and the result was 1818 nm. [Comparative Example 3] 68 201130889 A liquid crystal display element was produced in the same manner as in Example 16 except that varnish V was used instead of varnish R. The pre-dip of the liquid crystal cell was measured for VHR (30 Hz and 0.3 Hz) and ion density, and the result was 6.0. , 97 5〇/' 84.8% and 248 pC. Further, the retardation value of the attached film to the glass substrate before assembly of the liquid crystal cell was 0.13 nm. [Example 23] A liquid crystal display element was produced in the same manner as in Example 1 except that varnish P was used instead of varnish A. At this time, instead of the liquid crystal composition A, the liquid crystal composition B is sealed in the liquid crystal cell. The pre-angle, VHR (30 Hz and 〇.3 Hz) and ion density of the liquid crystal cell were measured and found to be 98 2 . 99.3%, 92.1%, and 52 pO. The liquid crystal cell was observed under a polarized microscope under crossed nicols. As a result, although some light leakage streaks caused by friction were observed, it was still in a good alignment state. . <Liquid Crystal Composition B> 69 201130889

_n_C4H9 "MX>n.C5H" n-C3H7-^^--^y.〇Me η^Ο〇〇π.〇3Η7

e 12.0 wt% 11.0 wt% 15.0 wt% 15.0 wt% 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% [Example 24] The square ϊ I used varnish Q A liquid crystal display element was produced in the same manner as in Example 20 except for the varnish P. The pretilt angle of the liquid crystal cell, 201130889 98.0 (VHR (30 Hz and 0.3 Hz), and ion density, &quot;·〇%, 90.6%, and 89 π were measured. The polarized light was observed under the microscope, and the light leakage was observed. Stripe, but still in a good alignment state. ', [Comparative Example 4] &quot; In addition to using varnish W instead of varnish!&gt;, a liquid crystal display element was produced in the same manner as in Example 23. The pretilt angle of the liquid crystal cell was measured. , VHR (30 Hz and 0.3 Hz) and ion density, the results were 98 3 〇, 98.5%, 87.3%, and 186 pC. The liquid crystal cell was observed under a polarizing microscope under crossed Nicols, and the results were compared with Example 23 or In the case of the example 24, the liquid crystal alignment agent of the present invention can be used as an alignment film for a liquid crystal display element. The liquid crystal alignment of the present invention is inferior to that of the light leakage caused by friction. [Industrial Applicability] Since the alignment film obtained by the agent has high liquid crystal alignment property, it is particularly useful as an IPS mode, a TN mode, and a VA mode used for rubbing the alignment film. [Simplified Explanation] No. [Main components Explanation of symbols] None 0 71

Claims (1)

201130889 VII. Patent application scope: 1. A liquid crystal alignment agent which is obtained by reacting a divalent acid dianhydride represented by a magical formula with other tetradecanoic acid dianhydride and a diamine. a composition of at least one of a polyamic acid and a derivative thereof, and the ratio of the tetracarboxylic dianhydride represented by the formula (I) is 5 based on the total amount of the mixture of the tetracarboxylic dianhydride M〇i%~95 mol% 'The ratio of other tetracarboxylic dianhydride is 5 m〇l%~95 m〇l〇/〇: Wherein X is an alkylene group having 2 to 12 carbon atoms. 12 of the base. And at least one of at least one of the diamine groups represented by the formula (4), (2), formula (3) and formula (72 201130889) (A-4) (A-5) (A-6) (A-7) (A-8) (A-9) (A-10) (A-11) (A-12) (A-13) 73 201130889 (A-29) 74 201130889 75 201130889 h2n h2n -(〇-^ Nh7 (1-1) (1-2) (1-3) In the formula C 1-1 ), h ·* is substituted by a methyl group; 4 any hydrogen of the Q or n-cyclohexene M can be in the formula (1_2) 'W1 Any damage of -CH2- or _ΝΗ-: (2) 2 -X1-^^ΝΗ2 may be an extension of m to 1 ig; the extension base -C(CF3),. -CO-, ^- 〇-''s--NH-'-N(CH3)--c(CH3),^ Substituting bismuth from diyl, 3. stretching phenyl, hydrazine, stretching or material 76 (3) 201130889 d (a) In the formula 〇), x2 is a single bond, ·〇, c〇〇·, seven (7) numbers 1 to 6 of the wire; R1 is a carbon number of 3 to 3. The base represented by the rabbit; (a) In the formula U), 'X3 and X4 are independently a single bond: silk 2; ring f and ring C are independently prepared or ^=&quot; and, independently, gas or Methyl, ... independently: 〇i Art 'c and e are independently (^ or ), the total of these is w~3; r4 is a fluorenyl group having a carbon number of 1 to 3 G, a thiol group having a carbon number of 1 to 3 G, and carbon The number 2i3〇 of the alkoxy group or the cholyl group, which can be substituted by fluorine in the acetyl group, the silk group and the methoxy group: 77 201130889 (4) wherein X5 is independently -〇- or an alkylene group having 1 to 6 carbon atoms; j is 0 or 1; R5 is hydrogen, an alkyl group having 2 to 12 carbon atoms or an alkoxy group having 2 to 12 carbon atoms The ring T is 1,4-phenylene or ι,4-cyclohexylene; X6 is a single bond or an alkylene group having a carbon number of 1 to 3; h is hydrazine or 1. 3. The liquid crystal alignment agent according to claim 2, wherein the other tetracarboxylic dianhydride is of the formula (A-1) to the formula (A-4), the formula (A-ll), the formula (A-12), Formula (A-14), Formula (A-18) to Formula (A-21), Formula (A-28) to Formula (A-30), Formula (A-32), Formula (A-37), Formula (A-39) at least one of the tetracarboxylic anhydrides represented by the formula (A-41) and the formula (A-43) to the formula (A-46), and the diamine is a formula (1-2-1), a formula (1-3), Formula (2-1) to Formula (2-3), Formula (2-7), Formula (2-10) to Formula (2-27), Formula (2-29), Formula ( 2-37)~Formula (2-39), Formula (2-41), Formula (2-43)~Formula (2-47), Formula (2-51), Formula (3-1)~Formula (3) -12) and at least one of the diamines represented by the formula (4-1) to the formula (4-12): 78 201130889 79 201130889 h2N^AQ H2N nh2 (2-15) ΝΗ, (2-14) H2n~〇·% min NH2 (2-21) η2νη〇Λ^Α〇·νη2 (2-23) η2νη〇Λ/^ (2-22) h2n^W (2-24) 80 201130889 (2-27) (2-29) Η2Ν-〇/Ν〇^_3^/Ν0ΗΝΗ2 H2N^/NQ^iCH2)6-〇/N0^NH2 (2-43) (2&lt;44) (2-45) Me Me (2-46) (2-47) (2-51) 81 201130889 Wherein R 2 Q is an alkyl group having 5 to 16 carbon atoms, R 21 is an alkyl group having 3 to 10 carbon atoms, and R 22 is an alkyl group having 6 to 16 carbon atoms or a cholesteryl group; 82 201130889 Wherein R26 is an alkyl group having 4 to 7 carbon atoms. 4. The liquid crystal alignment agent according to claim 3, wherein 83 201130889, the tetracarboxylic dianhydride is of the formula (Al), the formula (A-2), the formula (A-12), the formula (A- 14), Formula (A-18), Formula (A-20), Formula (A-21), Formula (A-28), Formula (A-30), Formula (A-37), Formula (A-40) And at least one of the four hydrocarbon anhydrides represented by the formula (A-45), the diamine is a formula (1-2-1), a formula (1-3), a formula (2-7), and a formula (2-10) )~ (2-12), (2-16) to (2-19), (2-21) to (2-27), and (2-37) to (2-39) , formula (2-41), formula (2-43) ~ formula (2-47), formula (2-51), formula (3-1) - formula (3-12) and formula (4-1) ~ At least one of the diamines represented by the formula (4-12). 5. The liquid crystal alignment agent according to claim 4, wherein the other tetracarboxylic dianhydride is of the formula (A-1), the formula (A-12), the formula (A-14), and the formula (A-18). And at least one of tetracarboxylic anhydrides represented by the formula (Α·45), wherein the diamine is a formula (1-2-1), a formula (1-3), a formula (2-7), and a formula (2·10) Among the diamines represented by formula (2-12), formula (2-26), formula (2-44), formula (2-45), and formula (3-1) to formula (3-6) At least one. 6. The liquid crystal alignment agent according to claim 3, wherein the other tetracarboxylic dianhydride is of the formula (Α-14), the formula (Α-18), the formula (Α-19), and the formula (Α-20) ), (α·21), (Α-28), (Α-29), (Α-30), (Α-32), (Α-39), (Α-40) At least one of a tetracarboxylic anhydride represented by the formula (Α-41), the formula (Α-43), the formula (Α-44), and the formula (Α-46), and the diamine is a formula (1-2-1) , formula (1-3), formula (2-1) to formula (2-3), formula (2-26), formula (2-29), formula (2-37), formula (2-43)~ At least one of the diamines represented by the formula (2-47), the formula 0-1) to the formula (3-12), and the formula (4-1) to the formula (4-12). 7. The liquid crystal alignment agent according to claim 6, wherein 84 201130889, the tetracarboxylic dianhydride is a formula (A-14), a formula (A-20), a formula (A-21), a formula (A) A-39), at least one of the tetracarboxylic anhydrides represented by the formula (A-44) and the formula (A-46), and the diamine is a formula (1_2-1), a formula (1-3), and a formula (2- 1) The diamine represented by the formula (2-3), the formula (2-26), the formula (2-29), the formula (2-44), and the formula (3-1) to the formula (3-6) At least one of them. 8. The liquid crystal alignment agent according to claim 3, wherein the other tetracarboxylic dianhydride is of the formula (A-1), the formula (A-2), the formula (A-3), and the formula (A-4). At least one of the tetracarboxylic anhydride represented by the formula (A-11), the formula (α·12), and the formula (A-45), and the diamine is a formula (1-2-1) or a formula (1-3) ), formula (2-1) to formula (2-3), formula (2-13) to formula (2-15), formula (2-20) to formula (2-26), and formula (2-29) At least one of the diamines represented by the formula (2-39) and the formula (2_41). The liquid crystal alignment agent according to claim 8, wherein the other tetracarboxylic dianhydride is of the formula (Α- 1), at least one of the four rebel needles represented by the formula (Α-2), the formula (Α-4), the formula (Α·12), and the formula (Α-45), the diamine is a formula (1-2) -1), formula (1_3), formula (2-1) to formula (2-3), formula (2-13) to formula (2-15), formula (2-26), and formula (2-29) At least one of the diamines indicated. The liquid crystal alignment agent according to any one of the items 1 to 9, which further comprises other polyfluorenes selected from the group consisting of not using the four resorcinic dianhydride represented by the formula (I). At least one polymer of an amine acid and a derivative thereof. A liquid crystal alignment film which is formed by heating a coating film of the liquid crystal alignment agent according to any one of the above-mentioned items (i) to claim 9 201130889. A film formed by heating a coating film of the liquid crystal alignment agent according to claim 10 of the patent application. A liquid crystal display element 'includes a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film according to claim 11 of the patent application. A liquid crystal display element comprising: a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film according to claim 12 of the patent application. 86 201130889 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Ο 〇 3 201130889 Amendment date: April 19, 100 - This is the method described in the Japanese version of the Japanese Patent Laid-Open No. (1), No. 46, No. 100105832. Diamine (3-5-1) : R21 = pentyldiamine (4-6-1): R26 = heptyldiamine (4-9-1) : R26 = propyl oxime: diamine is separately The compound represented by the formula (8) is synthesized by reference to the publication of Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 4-341030, Japanese Patent No. 4, No. 3, No. 3, No. 3, No. 2-3, -frk · Sst A “ 〇 (4-6-1) C5H11 (3-5-1) C3H7 (4-9-1) 59 201130889 Revision date: April 19, 1 No Chinese line specification for the ί〇0105832 [Synthesis Example 1] <Preparation of polyamic acid varnish 〉> DDM (2.2611 g '11 4〇5 mm〇i) was dissolved in nmp (22.5 g), and anhydride (1-1) (0.9988 g, 2.851) Mm), PMDA (0.6219 g, 2.851 mmol), and CBDA (i 1183 g, 5 7〇2 _〇1) are kept at room temperature below - added. After 2 hours, add NMp (1〇·〇 g) and BC (12.5 g). The solution has a viscosity of 83 mpa s. The liquid was aged for about 4 hours to obtain a varnish with a viscosity of 34 mPa s = lacquer _ _ weight average molecular weight of 52 〇〇〇. [Synthesis Example 2 to Synthesis Example 23] <Polyproline varnish Preparation of poly-acid 4 into ' by the same method as shown in Table 1 and Table 2 The lacquers B to W were deleted, and the physical properties were measured in the same manner as in Synthesis Example 1. In addition, the percentage of moles is indicated in brackets.