TW201016751A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device - Google Patents

Abstract

A purpose of this invention is developing an useful liquid crystal aligning agent for providing a liquid crystal display device which shows a required voltage retention rate and realizes a long-term stability of the voltage retention rate. The liquid crystal aligning agent a composition containing at least one polymer choosing from a group consisting of polyamic acid and its derivatives. The polymer is polyamic acid and its derivatives obtained by reacting at least one of diamine represented by formula (N) or a mixture of at least one of diamine represented by formula (N) and at least one of other diamine not represented by formula (N) with tetracarboxylic dianhydride. A1 is independently alkyl having 1 to 20 carbon atoms, alkoxyl having 1 ot 20 carbon atoms, hydroxyl, trifluoromethyl, fluorine, chlorine or bromine, m is an integer of 0 to 3 and A2 is independently -O-, -NH-, -N(CH3)- or -S-.

Description

201016751. / i /pii VI. Description of the Invention: [Technical Field] The present invention mainly relates to a liquid crystal alignment agent containing a diamine containing naphthalene on a primary bond and a tetrahydro acid (diamine) Tetracarboxylic dianhydride) A polyamic acid obtained by carrying out a reaction. [Prior Art] A monitor (noter) or a projection display (projecti〇) represented by a notebook computer or a desktop computer as a representative of a liquid crystal display element used for a video camera (video camera) n display ) and other liquid crystal display devices have recently been used for televisions. Further, the liquid crystal display element is also used for optoelectronics related elements such as an optical printer head, an optical fourier transform element, and a light valve. • Various components are known in liquid crystal display elements, and the development of liquid crystal display element technology is not only achieved by improving the driving method of the liquid crystal display element or the structure of the liquid crystal display element, but also by improving the constituent members used in the liquid crystal display element. achieve. The liquid crystal display element usually has a liquid crystal alignment film for aligning a liquid crystal composition having a wide liquid crystal in a specific direction. The liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element. With the improvement of the quality of the liquid crystal display element, the role of the liquid crystal alignment film has become important year by year. 5 201016751 Liquid crystal alignment film is prepared by using a liquid crystal alignment agent. At present, a liquid crystal alignment agent which is mainly used is a solution obtained by dissolving polylysine or soluble polyimine jpolyimide in an organic solvent. The liquid crystal alignment film is formed by applying the solution as described above onto a substrate and then forming a film by heating or the like. In order to improve the display quality of the liquid crystal display element, the important characteristics required for the liquid crystal alignment film can be maintained. If the money retention rate is low, then the voltage applied to the liquid crystal in the frame time is repeatedly lowered. As a result, there is a case where the brightness is lowered to cause an obstacle to the normal gradient display (upward (10) display). Further, even if the initial voltage holding ratio is high, the voltage holding ratio (long-term reliability) after the high-temperature acceleration test is lowered. As an attempt to solve the above problems, for example, a polyaminic acid composition for forming a liquid crystal alignment film containing two or more kinds of polylysines having different physical properties is known (for example, In addition, a method of synthesizing polylysine obtained by reacting an aromatic diamine having naphthalene and a tetracarboxylic dianhydride is known (see, for example, Patent Document 3). The liquid crystal alignment film is required to be further improved, and in order to obtain the desired electrical characteristics of the obtained liquid crystal alignment film, there is still room for further research on the liquid crystal alignment agent which is the liquid BB alignment film. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A liquid crystal display element in which long-term stability is achieved, performance of a desired voltage holding ratio in the liquid crystal display element, and long-term stability of the voltage holding ratio A liquid crystal alignment film and a liquid crystal alignment agent capable of forming the liquid crystal alignment film. The present inventors have found that a composition containing polyacrylic acid having a naphthalene aromatic diamine or a derivative thereof is used as a liquid crystal. In the case of the alignment agent, the liquid crystal display element having the liquid crystal alignment film formed using the liquid crystal alignment agent exhibits a desired voltage holding ratio and imparts good long-term reliability to the voltage holding ratio, thereby completing the present invention. The liquid crystal alignment agent of the invention is not in the following item [1]. [1] A liquid crystal alignment agent which is a composition containing at least one polymer selected from the group consisting of polylysine and a derivative thereof Wherein the polymer is at least one of a diamine represented by the formula (N) or at least one of the diamine represented by the formula (N) and a diamine not represented by the formula (N). a mixture of at least one of the other diamines, and a polyamic acid obtained by reacting the tetracarboxylic dianhydride or a derivative thereof, and the concentration of the polymer component in the composition is 0 gt; 1% by weight 40% by weight.

7 201016751 (Where "A1 is independently a carbon number of 1 to 10, and the carbon number is 1

Any value other than the bonding position of A2 is set. )? The invention can provide a driving method that can be applied to various driving modes, A is independently NH·, _N(CH3)_, and the bonding position of two amino groups to the stupid ring is higher than A1 and its voltage holding ratio, and is maintained for the voltage. The long-term reliability of the liquid crystal display element with a change with time is good. [Embodiment] First, the terms used in the present invention will be described. The term "liquid crystal alignment agent" refers to a composition for forming a liquid crystal alignment film. The diamine represented by the formula (N) may be referred to as a diamine (N). The same applies to a diamine represented by another chemical formula. The tetrazoic acid dianhydride represented by the formula (1) is sometimes referred to as a carboxylic acid (1). The same applies to tetrahydro acid dianhydride represented by other chemical formulas. Other diamines refer to diamines (N). The diamine other than the term "arbitrary" as used in the description of the chemical structural formula means that not only the position is arbitrary, but also the number is arbitrary. Moreover, for example, "arbitrary A can be B, C or D. The expression "substituted" means that in addition to the case where any A is substituted by B, the case where arbitrary A is substituted by C, and the case where arbitrary A is substituted by D, 'a plurality of A's are included in B to D. In the case of two substitutions, however, the case where any -CH2- may be substituted by -Ο- does not include a plurality of consecutive -CH2·----substitutions. There is no explicit bonding with the atoms constituting the ring. Substitute is available 201016751

I Λ. I Freely determine the substituent at the bonding position within the chemical range of 5. A symbol in which a character such as A is surrounded by a hexagon is a ring A. The present invention is constituted by the above item [1] and the items [2] to [20] shown below. [2] The liquid crystal alignment agent according to [1], wherein the bonding positions of the two amino groups in the formula (n) are both aligned with respect to A2. [3] The liquid crystal alignment agent according to [1], wherein the diamine is selected from the group consisting of formula (N-1) to formula (N-5), formula (N-7), and formula (N-8). And a mixture of at least one diamine of the compound group represented by the formula (N-13), the formula (N-15) and the formula (N-16) or the diamine or the other diamine. 201016751

(N-1)

(N-2)

(N-3)

(N-4)

(N-13)

(In the above formula, Me is a sulfhydryl group.) [4] The liquid crystal alignment agent according to [3] wherein the diamine is represented by the formula (N-1) and the formula (N-3) At least one of the diamines or a mixture of the diamines and other diamines. [5] The liquid crystal alignment agent according to [1], wherein the diamine is a mixture of at least one of the diamine represented by the formula (N) and another diamine, 201016751 jz. / l / μιι The other diamine is at least one selected from the group consisting of diamines having a side chain group in the cypress/amine group of the formula (vm) and the formula (χι). Α3

(wherein Α is a single bond, -0-, -CO-, _c〇〇-, -OCO-, 罾, CONH·, _CH2〇~CF2〇_, or an alkylene group having a carbon number of 6 ''any _Ch2· in the alkylene group may be substituted by _〇, -CH=CH· or; Ri is a group having a ster〇id skeleton, an alkyl group having a carbon number of 3 to 30, and having a phenyl group having a carbon number of 丨~, such as an alkyl group or an alkoxy group having a carbon number of 1 to 30, or a group represented by the formula (IX), having a carbon number of 3 to 3 Å Any -CHr in the base can be replaced by ·〇_, -CH=CH- or -OC-.)

(wherein 'A4 and A5 are independently a single bond, -〇_, _c〇〇, -OCO-, -CONH-, an alkylene group having a carbon number of 1 to 4, and an alkylene group having a carbon number of 〜3) a base or an alkyleneoxy group having a carbon number of 1 to 3; the ring b and the ring c are independently 1,4-phenylene or cyclohexylidene; R2 and R3 are independently Fluorine or methyl, f and g 11 201016751 are independently Ο, 1 or 2; c, d and e are independently an integer of 〇~3, and their total is greater than or equal to 1; R4 is a carbon number of 1 to 3〇 An alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 3 carbon atoms, and any of these alkyl groups, alkoxy groups and alkoxyalkyl groups may be used. Substituted by fluorine 'and any -CHr can be substituted by difluoromethylene.)

12

201016751 J I L· I MAX

(In the formula (XII) and formula (XIII), R9 is an alkyl group having a number of turns of 1 to 30', and any _CH2- of the alkyl group may be -0-, -CH=CH- or -OC- Substituting; R1Q is an alkyl group having a carbon number of 6 to 22; R11 is a burning group having a carbon number of 1 to 22, and A is independently -〇- or a calcining group having a number of 1 to 6; A8 is a single bond or An alkylene group having a carbon number of 1 to 3; a ring T of 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1. [6] Liquid crystal alignment according to [3] And the diamine is selected from the group consisting of formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), formula (N- 15) and a mixture of at least one diamine and another diamine in the compound group represented by the formula (N-16), wherein the other diamine is selected from the group consisting of formula (VIII-2) and formula (VIII-4) At least one of the diamines having a side chain group in the diamine represented by the formula (VIII-6), the formula (χΙΙ-2), the formula (ΧΙΙ-4), and the formula (ΧΙΙ-6). 13 201016751

(Vlll-θ) R30

(In these chemical formulas, R23, R29 and R3() are each an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms.) [7] According to [1] to [6] The liquid crystal alignment agent according to any one of the preceding claims, wherein 201016751 / X / the monoamine oxime further contains a mixture of diamines having no side chain groups. The diamine having no side chain group is selected from the group consisting of At least one of the compound groups represented by the formula (νπ) and the formula (XV). ❹

Z1 z2 (I) (II) (III)

(IV)

(In these formulas, X is a linear alkylene group having a carbon number of 2 to 12; Y is independently a single bond, -〇-, -CO-, -NH_, -N(CH3;)-, _(: ΟΝΙΙ_, NHCO-, -C(CH3)2-,, C(CF3)2-, _〇_(CH2)t-0-, -S·, -SS-, _S〇2_, -S-(CH2) rS- or a linear alkylene group having a carbon number of 1 to 12, t is an integer of 1 to 12, Z1 and Z2 are hydrogen, and when γ is 仏, _n(CH3)_, -CHr, -C(CH3) 2_ or _c(CF3)2-, Z1 and z2 may bond to each other 15 201016751 to form a single bond; ring D is phenylene or 1,4-diazacyclohexylidene; R33 and R34 Each independently is an alkyl group having a carbon number of 1 to 3 or a phenyl group; and A3 is independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a phenylene group substituted by an alkyl group; m is 1 to 10 An integer of the cyclohexane or benzene ring may be substituted by fluorine, methyl, -OH, -COOH, -S03H, -Ρ03Η2, benzyl or hydroxybenzyl.) '[8] according to [7] The liquid crystal alignment agent, wherein the diamine having no side-chain group is a formula (IV-1), a formula (IV-2), a formula (IV-15) to a formula (IV-17), Formula (V-1) to (V-12), At least one of the diamines represented by the formula (V-33), the formula (V-35), the formula (V-37), the formula (VI-7), the formula (VII-2), and the formula (XV-1) .

16

201016751, / 1 / J/1-L

H2n^〇_nOn_hO~nH2 (VI-7) (VII-2) ch3 ch3 H2N-C3H6-SBu O-S1-C3H6-NH2 ch3 ch3 (XV-1) [9] According to [1] a liquid crystal alignment agent, wherein the polymer is a mixture of the following polyaminic acid or a derivative thereof, which is at least one selected from the group consisting of the formula (VIII) and the formula (VIII) and the formula (X) a mixture of one of the diamine groups having a side chain group represented by the formula (XIII) to 17 201016751, or at least one selected from the diamine represented by the formula (N) At least one of a diamine having a side bond group in the amine group represented by the formula (vm) and the formula (X) to the formula (XIII), and at least one selected from the group consisting of the formula (I) to the formula (VII) And a mixture of at least one of the diamines having no side chain groups in the diamine group represented by the formula (xv), and the polyamic acid obtained by reacting the tetracarboxylic dianhydride or a derivative thereof, and a mixture of at least one of the diamine having no side chain group or the diamine having no side chain group and at least one of the diamine represented by the formula (N) and a tetracarboxylic acid Acid II A mixture of polyamido acids or derivatives thereof obtained by the reaction of an anhydride.

(wherein 'A3 is a single bond, -0-, -CO-, _c〇〇_, -CONH-, even 〇·, _CF2〇_, or an alkylene group having a carbon number of j 6 , 10 said alkylene group Any -CH2_ may be substituted by -〇_, _ch=ch_戍-OC-; R1 is a steroid having a steroid skeleton, an alkyl group having a carbon number of 〜3〇, having a carbon number of 1 to 30 An alkyl group or a phenyl group having a carbon number of 丨~chuan alkoxy group as a substituent or a group represented by the formula (IX), and any -CH2- of the alkyl group having a carbon number of 3 to 30 Can be replaced by _〇_, -CH=CH- or _c=C-.) 18 201016751 ^ ΛβΛ β Λ t

(wherein Α4 and Α5 are independently a single bond, -Ο-, -COO-, -OCO-, •CONH-, an alkylene group having a carbon number of 1 to 4, and an oxyalkylene having a carbon number of 1 to 3) a group or an alkyleneoxy group having a carbon number of 1 to 3; ring B and ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R2 and R3 are independently a fluorine or a fluorenyl group. , f and g are independently 〇, 1 or 2; c, d and e are independently an integer of 0 to 3, and their total is 1 or more; R4 is an alkyl group having a carbon number of 1 to 30, and the carbon number is 1 to 30 alkoxy groups or alkoxyalkyl groups having 2 to 30 carbon atoms; in these alkyl groups, alkoxy groups and alkoxyalkyl groups, any hydrogen may be substituted by fluorine, and any - CH2- can be substituted by difluoromethylene.) 19 201016751

(In the formula (X) and the formula (XI), R5 is independently hydrogen or a methyl group, R6 is hydrogen or an alkyl group or an alkenyl group having a carbon number of 1 to 20, and R7 and R8 are each independently a carbon number of 1 ～20 alkyl or phenyl, A6 is independently a single bond, -CO- or -CH2-.)

20 201016751

(XII) (XIII) (In the formula (XII) and the formula (XIII), R9 is an alkyl group having 1 to 30 carbon atoms, and any -CHr in the alkyl group may be -0-, -CH=CH Or -C=C-substituted; R1() is an alkyl group having a carbon number of 6 to 22; R11 is an alkyl group having a carbon number of 1 to 22; and A7 is independently -Ο- or a carbon number of 1 to 6 Alkylene; A8 is a single bond or an alkylene group having a carbon number of 1 to 3; ring T is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1.

21 201016751 h2n—x—nh2

(In these formulas, X is a linear alkylene group having a carbon number of 2 to 12; Y is independently a single bond, -0-, -CO-, -NH-, _CONH_, -NHCO-, -C ( CH3)2·, -C(CF3)2-, -0-(CH2)r0-, -S-, -SS-, -S〇2-, _S-(CH2)rS· or carbon number 1~12 Linear alkylene group, t is an integer from 1 to 12; Z1 and Z2 are hydrogen, and when Y is _νη_, -N(CH3)-, ch2-, -c(ch3)2- or _C(CF3) When 2_, Ζι and Z2 may be bonded to each other to form a single bond; ring D is phenylene or ι,4-diazacyclohexylene; 33 34 R and R are each independently a carbon number of 1 to 3; Alkyl or phenyl; A3 is independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a phenylene group substituted by an alkyl group 22 201016751 / A /; m is an integer of 1 to 10; cyclohexane Any hydrogen of the ring or benzene ring may be substituted by fluorine, fluorenyl, -OH, -COOH, -S03H, -Ρ03Η2, benzyl or via a benzyl group. [10] The liquid crystal alignment agent according to [1] Wherein the polymer is a mixture of the following polyaminic acid or a derivative thereof, wherein at least one of the diamine represented by the formula (N) is selected from the group consisting of the formula (X) and the formula (VII) (X a mixture of at least one of diamines having no side chain groups in the diamine group represented by V), polylysine obtained by reacting with tetracarboxylic dianhydride or a derivative thereof, and selected from At least one of a diamine having a side chain group or a diamine having a side chain group in the diamine group represented by the formula (vm) and the formula (X) to the formula (XIII) A mixture of at least one of the diamines having no side chain groups, and a polyamic acid obtained by reacting the tetracarboxylic dianhydride or a mixture thereof.

(VIII) (wherein A is a single bond, _〇_, _c〇〇(7) = two or a sub-alkyl group having a carbon number of 1 to 6, and the base is taken to correct the phase of the material; A phenol having a carbon number of 1 to 3 G or a carbon number of 30, and a carbon number of 3, 30, 30, 16, 16, 751, a phenyl group having an oxy group as a substituent, or a group represented by the formula (ι), the alkyl group having 3 to 30 carbon atoms Any / out · can be replaced by _〇_, -CH=CH- or _〇C-.)

(wherein 'A and A5 are independently a single bond, _〇_, _c〇〇_, _〇c〇_, -CONH-, an alkylene group having a carbon number of 丨~4 and having an alkyl group number of 丨~3 An anthracenyl group or a pyridyloxy group having a carbon number of 1 to 3; a ring B and a ring C are independently a phenylene group or a 1,4-cyclohexylene group; and R2 and R3 are independently a fluorine or a methyl group f. And g is independently 〇, 1 or 2; c, d&e are independently an integer of 0 to 3 'the total of them is 1 or more; r4 is a carbon number of 1 to 30, carbon number 4 1~ % of an alkoxy group, or an alkoxy group having a carbon number of 2 to 3 Å. In this ship-based, silk-based alkoxy group, any hydrogen can be substituted by fluorine, and any -CH2. Can be replaced by difluoromethylene.) 24 (X) 201016751

(XI) (In formula (X) and formula (XI), R5 is independently hydrogen or methyl, R6 is hydrogen or an alkyl or alkenyl group having 1 to 20 carbon atoms, and R7 and R8 are each independently carbon. The number is 1 to 20 alkyl or phenyl, and A6 is independently a single bond, -CO- or -CH2-.) 25 201016751

(In the formula (XII) and the formula (XIII), R9 is an alkyl group having 1 to 30 carbon atoms, and any -CH2- in the alkyl group may be -Ο-, -CH=CH- or -C= C-substituted; R1() is an alkyl group having a carbon number of 6 to 22; R11 is an alkyl group having a carbon number of 1 to 22; and A7 is independently -Ο- or an alkylene group having a carbon number of 1 to 6; It is a single bond or an alkylene group having a carbon number of 1 to 3; the ring T is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1.)

26 201016751

(I) (II) (III) (ιν) (V) (νι) (VII) (XV) (In these formulas, X is a linear alkylene group having a carbon number of 2 to 12; Y is independently Single bond, -0·, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-,-0-( CH2)t-0-, _S-, -SS-, -S〇2-, -S-(CH2)tS- or a direct bond sub-alkyl group having a carbon number of 1 to 12 is an integer of 1 to 12 Z1 and Z2 are hydrogen, and when Y is -ΝΗ·, -N(CH3)-, -CH2---C(CH3)2- or _c(cf3)2·, Z1 and Z2 can be bonded to each other. Forming a single bond; ring D is a phenylene group or a 1,4-diazacyclohexylene group; R33 and R34 are each independently an alkyl group having a carbon number of i 3 or a phenyl group; and A 3 is independently a carbon number of 1 〜6 alkylene, phenylene or alkyl substituted 27 201016751 phenylene; m is an integer from 1 to 10; cyclohexane ring or a ring of any hydrogen can be fluorine, methyl, -OH, The liquid crystal alignment agent according to [9] or [10], wherein the liquid crystal alignment agent is represented by the formula (N), wherein the liquid crystal alignment agent is a compound of the formula (N). The diamine is of the formula (N-1) to the formula (N-5), the formula (N-7), the formula (N-8), the formula (N-13), (N-15) or a diamine represented by the formula (N-16), wherein the diamine having a side chain group is a formula (VIII-2), a formula (VIII-4) to a formula (VIII-6) a diamine represented by the formula (XII_2), the formula (XII-4) or the formula (?π_6), and the diamine having no side chain group is a formula (IV-1), a formula (IV-2) Equation (ΙλΜ5)~Formula (IV-17), Formula (ν·1)~Formula (V-12), Formula (V-33), Formula (V-35)~Formula (V-37), Formula ( Νΐ·7), a diamine represented by the formula (VII-2) or the formula (XV-1).

28

201016751 I Λ. I

(In these chemical formulas, Me means sulfhydryl.)

29 201016751

(VIII-6) R30

(In these chemical formulas, r23, r29 and r3G are each an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms.)

(iv-1) h2n

30 201016751

(V-1)

(V-2)

(V-3)

(V-10) to ·11)

31 201016751

(V-37) (VI-7) ΗζΝ-Ο/ΛνΚΙΧ0Η2^Ο^χ〇-ΝΗ: (VII-2)

The liquid crystal alignment agent of any one of [1] to [11], wherein the four The carboxylic acid dianhydride is a mixture of an aromatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride and a tetracarboxylic dianhydride other than an aromatic. [13] The liquid crystal alignment agent according to [12], which is fascinated by

The tetracarboxylic dianhydride is at least one selected from the group consisting of compounds represented by the formula (1), the formula (2), the formula (5) to the formula (11) and the formula (14). 32 201016751

(14) The liquid crystal alignment agent according to [13], wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (1). [15] The liquid crystal alignment agent according to [12], wherein the tetracarboxylic dianhydride other than the aromatic compound is an alicyclic tetracarboxylic dianhydride and/or an aliphatic tetracarboxylic dianhydride. [16] The liquid crystal alignment agent according to [12], wherein the aromatic tetracarboxylic dianhydride is selected from the group consisting of formula (2), formula (2), formula (5) to formula (7), (11) and the compound group represented by the formula (14) have one less group, and the tetracarboxylic dianhydride other than the aromatic group is selected from the group consisting of the formula (19), the formula (23), and the formula (25). At least one of the compound groups represented by the formulae (35) to (39), (44) and (49). 33 201016751

η Ο η η η

η η

The liquid crystal alignment agent according to [16], wherein the aromatic 34 201016751 I Λ / tetracarboxylic dianhydride is a compound represented by the formula ,), and the tetracarboxylic acid other than the aromatic The anhydride is a compound represented by the formula (19). [18] The liquid crystal alignment agent according to any one of [1], wherein the liquid crystal alignment agent further contains a nadiimide compound selected from the group consisting of an alkenyl group, and has freedom A compound of a polymerizable unsaturated double bond, an oxazine compound, a > an oxazoline compound, and an epoxy compound. [19] A liquid crystal alignment film, wherein the liquid crystal alignment film is formed by heating a coating film of the liquid crystal alignment agent according to any one of [1] to [18]. [20] A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and aligning the liquid crystal molecules in a predetermined direction The liquid crystal alignment film is characterized in that the liquid crystal alignment film is the liquid crystal alignment film according to [19]. The liquid crystal alignment agent of the present invention contains a reaction product of a tetracarboxylic dianhydride and a diamine, a polyglycine or a derivative thereof. Examples of the derivative of the polyproline are soluble polyimine, polyphthalate, polyamidamine and the like. More specifically, it may be exemplified by: 1) polydecyl imine which is completely subjected to dehydration cyclization, and which is obtained by partial dehydration and cyclization. 3) a polyphthalic acid ester obtained by reacting a carboxyl group of a polyproline with an ester of a transester, 4) a reaction of a mixture of tetradecanoic dianhydride and an organic dicarboxylic acid, And 5) a polyamidoquinone imine of 35 201016751, which is obtained by dehydrating and cyclizing a part or all of the poly-proline-polyamide copolymer. Further, a preferred example of the derivative of polyproline is polyimine. The liquid crystal alignment agent of the present invention is a composition containing at least one polymer selected from the group consisting of polyproline and a derivative of such polyamic acid. At least one of the diamines represented by the formula (N) is used in the present invention.

In the formula (N), A1 is independently an alkyl group having a carbon number of 丨~1〇, an alkoxy group having a carbon number of 1 ', a hydroxyl group, a trifluoromethyl group, a fluorine, a gas or a bromine. Preferable examples of A are a filament having a carbon number of 3, an alkoxy group having a carbon number of 3, an It group, and a trifluoromethane. Further preferred examples are a methyl group, a methoxy group, a trans group, and a trifluoromethyl group. . The melons are independently integers of 〇~3, preferably all 0 or A2 independently _〇·, _NH_, N(CH3), or

-S-. Both A are preferably the same coordinating group. The bonding position of the two amino groups to the benzene ring is any position other than the bonding position of Αι and A2, and is preferably bonded to the alignment with respect to A2. Preferred examples of the diamine (N) are listed below. 36 201016751

Me

p3C (N-12)

Me

Me

Me

(N-14)

Me

Me Me /=in (N-16) (Me in these formulas refers to a mercapto group.) Among the diamines, diamines (N-1) to diamines (N-5) and diamines (N-) are preferred. 7), diamine (N-8), diamine (N-13), diamine (N-15), and 37 201016751 monoamine (N-16) 'more preferably diamine (Nl) and diamine (n_3) ). When the polymer in the liquid crystal alignment agent of the present invention is produced, only the diamine (N) may be used, or the diamine may be used by mixing with another diamine, that is, a diamine not represented by the formula (n). The total amount of diamine (N) used in the production of the polymer is considered from the viewpoint of exhibiting a desired ion density in the liquid crystal display element and achieving long-term stability of the ion density. The use ratio is preferably 5 mol% to 1 mol%, more preferably 5 mol% to 50 mol%. In addition, other monoamines can be classified into two types depending on their structures. When the backbone of the two amino groups of the bond is regarded as the main chain, the other diamine is a diamine having a group branched from the main chain, that is, a side chain group, and a group having no side chain group. Diamine. By reacting a diamine having a side chain group and a tetracarboxylic dianhydride, polyamic acid or polyimine having a plurality of side chain groups in the main chain of the polymer is obtained. When such a polyamic acid or a polyimine having a side chain group in a polymer main chain is used, a liquid crystal alignment film formed of a liquid crystal alignment agent containing the polymer can increase a pretilt angle of the liquid crystal display element. (pretilt angle). 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 a carbon number of 3 or more, and specific examples of the side chain group include an alkyl group having a carbon number of 3 or more and an alkoxy group having a carbon number of 3 or more. An alkoxyalkyl group having a carbon number of 3 or more, and a group having a steroid skeleton. Any one having one or more rings and having a ring at the end thereof having a carbon number of 1 or more, an alkoxy group having a carbon number of 1 or more, and an alkoxyalkyl group having a hindrance of 2 or more as a substituent The group also has the effect of a side chain 38 201016751 / J. / group. The side chain groups in the present invention are selected from these groups. In the following description, such a diamine having a side chain group is sometimes referred to as a side chain type monoamine. Further, an amine which does not have a side chain group having a carbon number of 3 or more is sometimes referred to as a non-side bond type diamine. Moreover, the respective required pretilt angles of the various display elements can be dealt with by appropriately separating the side chain type diamine and the non-side chain type diamine. Namely, in the longitudinal electric field method represented by the Twisted Nematic (TN) method or the vertical alignment (VA) method, a side chain type diamine is mainly used because a relatively large pretilt angle is required. At this time, in order to further control the pretilt angle, a non-side chain type diamine may be used in combination. The blending ratio of the non-side chain type diamine to the side bond type diamine can be determined according to the target pretilt angle. Of course, it is also possible to cope with only the side chain type diamine by appropriately selecting the side chain group. In the transverse electric field mode, since the pretilt angle is small and a more souther liquid crystal alignment property is required, at least one of non-side bond type diamines can be used. Thus, the liquid crystal alignment agent of the present invention can be applied to any type of liquid crystal display element. Specific examples of the φ side chain group are as follows. First, it may be exemplified by a group, a decyloxy group, a decyloxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an alkylaminocarbonylalkenyl group, an alkenyloxy group, an alkenyl group. Carbonyl, alkenylcarbonyloxy, decyloxy, fluorenylaminocarbonyl, alkynyl, alkynyloxy, alkynyl, alkoxy, alkynyloxycarbonyl, alkynylaminocarbonyl Wait. Further, the radical group, the dilute group and the fast group in the group are all groups having a carbon number of 3 or more. Among them, in the alkyloxyalkyl group, the total carbon number is preferably 3 or more. This 39 201016751 outer 'these groups may be straight or branched. Next, the term "the alkyl group having a carbon number of 1 or more, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent is exemplified as a phenyl group. Phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, carbon number greater than or equal to 3 Cycloalkyl, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyloxybis(cyclohexyl)oxy, bis(cyclo) Hexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenyloxycarbonyl, and cyclohexyl bis(phenyl) a group having a cyclic structure such as an oxycarbonyl group. Further, examples thereof include a ring-forming group which is a group having two or more benzene rings, a group having two or more cyclohexane rings, or a benzene ring and a cyclohexane ring. The two or more ring groups formed, the ligand groups of the set ring group are independently a single bond, _〇, •COO-, -OCO_, _CONH_ or a carbon number of 3 The base of the base and the ring at the end have a sulfhydryl group with a carbon number greater than or equal to i, and the carbon number is greater than or equal to! A fluorine-substituted courtyard group, an alkoxy group having a carbon number of i or more, or an alkoxy group having a carbon number of 2 or more is used as a substituent. Of course, groups having a steroid backbone are also effective as side chain groups. Preferable examples of the side chain type diamine are a diamine represented by the formula (νπι) and the formula (χ (XIII). ~ (VIII) 201016751 f l / jjlf* R1 I A3

NH2 ❹

In the formula (VIII), A3 is a single bond, -〇-, -CO-, -COO·, -OCO-, -CONH-, -CH20-, -CF20-, or an alkylene group having a carbon number of 1 to 6. Any -CH in the sub-alkyl group - a preferred example of a β A3 which may be substituted by -Ο-, _CH=CH- or -CeC- is a single bond, _〇-, -COO-, _〇CO-, - Particularly preferred examples of CH20-, and an alkylene group having a carbon number of 1 to 3 are a single bond, ??, -COO-, -OCO-, -CH20-, -CH2-, and -CH2CH2-. Ri is a group having a steroid skeleton, an alkyl group having 3 to 30 carbon atoms, a phenyl group having a carbon number of 1 to 30 or an alkoxy group having 1 to 30 carbon atoms as a substituent, or The group represented by (Ix), any -CHr of the alkyl group having a carbon number of 3 to 3 Å may be substituted by _〇_, _CH=CH_ or.

Preferable examples of R1 are an alkyl group having a carbon number of 3 to 30, a phenyl group having a carbon number of 1 to 3 fluorene or an alkoxy group having a carbon number of 1 to 30 as a substituent, and a The bonding position of the amino group and the benzene ring is preferably 3 positions and 5 positions or 2 positions and 5 positions.

And a group represented by the formula (IX). When the bonding position of A3 is 1 (IX) In the formula (IX), A4 and A5 are independently a single bond, _〇_, c〇〇, 201016751 -OCO---CONH-, carbon number A 1 paper The oxyalkylene group of Merma 1 to 4 or the alkylene group having 1 to 3 carbon atoms of 1 j is preferably an early bond or a ketone having 1 to 4 carbon atoms. The ring and ring C are independently a fluorene-phenylene woven-cyclohexylene group. The site is fluorine or methyl. f and g are independently G, 1 or 2, and preferably e d and e are independently an integer of 0 to 3, and their total is 1:1. R4 is the carbon number!

An alkyl group of ～30, a decyloxy group having a carbon number of 1 to 30, or an alkoxyalkyl group having a carbon number of 2 to 3 Å, and any of these alkyl groups, alkoxy groups and alkoxyalkyl groups Hydrogen can be substituted by fluorine 'and any -CH2- can be substituted by a difluoroindenylene group. Preferable examples of R4 are a burnt group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

(XI) In the formula (X) and the formula (XI), R 5 is independently hydrogen or methyl. 201016751

y χ / k/AX R6 is hydrogen, Wei is WO攸 R7 and the site is Wei 2~_ women base. Independently a single bond, _C(). or an even alkyl or phenyl group. A6 "ΝΗ2|Α6_α,, 卜^(8), preferably two on the other, the other bond on the 6 position. In addition, the position of the 3-position of the steroid skeleton is preferably relative to Α6 = 'two amino groups and benzene The bond of the ring Λ' (Υΐλ;, bond, "° position is meta or para. In the ❿2矣 in 'two 'NHHR6-) Ph-A6-〇_” and the bonding position of the benzene ring : Selection: The carbon bonded to the steroid skeleton is meta or the position of the two amino groups and the benzene ring is preferably meta or para position relative to the bonding position of A.

(XII) 'R9 is a calcined group having a carbon number of 1 to 30'. Any -CH2- in the alkyl group may be substituted by _〇_, _CH=CH- or -C=C-. R10 is an alkyl group having 6 to 22 carbon atoms, and Rii is an alkyl group having a carbon number of from i to 22. A7 is independently _〇_ or an alkylene group having a carbon number of i~6. 43 201016751 A8 is a single bond or an alkylene group having a carbon number of 1 to 3. ^ or 1,4-cyclohexylene. h is 0 or i. In the bonding position of the 1 > 4 subunit amino group and the benzene ring, it is preferred that the bonding position of the relative A A7 is a meta position or a para position. In the formula (XIII), the bonding positions of the two amino groups and the benzene ring are preferably meta or para positions with respect to the bonding position of A7. Specific examples of the diamine () are listed below.

44 201016751

In the formula (VIII-1) to the formula (VIII-11), R23 is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 5 to 25 carbon atoms. Or an alkoxy group having a carbon number of 5 to 25. R24 is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In the formula (VIII-12) to the formula (VIII-17), R25 is an alkyl group having 4 to 30 carbon atoms, and preferably an alkyl group having 6 to 25 carbon atoms. R26 is an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms. 45 201016751

H2n 0^o^r28 h2n (VIII-21) h2n h2n (vm-20)

H2n h2n (VIII-22) H2N h2n (VIII-23) H2N 〇 R27 h2n (VIII-24)

46 201016751. DL· / 1 /pil

H2N

(VIII-31) 0^^R28 h2n

(VIII-32)

In the formula (VIII-18) to the formula (VIII-37), r27 is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkane having 3 to 25 carbon atoms. A group or an alkoxy group having a carbon number of 3 to 25. R28 is hydrogen, 47 201016751 fluorine, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH2F, -OCHF2 or -OCF3, preferably having a carbon number of 3 to 25. An alkyl group or an alkoxy group having a carbon number of 3 to 25.

Among the diamines (VIII-1) to diamines (VIII-43), preferred are diamines (VIII-1) to diamines (VIII-11), more preferably diamines (VIII-2) and 48 201016751. DZ.fl / pil Diamine (VIII-4) ~ Diamine (VIII-6). Specific examples of the diamine (X) are listed below.

Specific examples of the diamine (XI) are listed below.

49 201016751

50 201016751 «/知 r a #士士

Specific examples of the diamine (XII) are listed below. 51 201016751

R29

R30

(XH-4)

R30

(XII-5)

52 201016751, / 1 /pii

R30

R3〇

In the formula (XII-1) to the formula (XII-3), R29 is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 30 carbon atoms. Or an alkoxy group having a carbon number of 3 to 30. In the formula (XII-4) to the formula (XII-8), R30 is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 30 carbon atoms. Or an alkoxy group having a carbon number of 3 to 30. 53 201016751 Specific examples of the diamine (XIII) are listed below.

Ραιι-1)

Η2

ΝΗ2 (ΧΙΙΙ-3) In the formula (ΧΙΙΙ-1) to the formula (ΧΙΙΙ_3), r31 is an alkyl group having 6 to 22 carbon atoms, preferably an alkyl group having 6 to 2 carbon atoms. R32 is an alkyl group having a carbon number of from j to 22, and is preferably an alkyl group having a carbon number of from 1 to 1 Torr. In a specific example of the side chain type diamine, a diamine (νπι_2), a diamine (νΐΙΙ·4 ) to a diamine (VIII_6 ), a diamine (χπ·2 ), a diamine (χπ_4 ), and a diamine (preferably) are preferable. ΧΙΙ-6). When the polymer used in the liquid crystal alignment agent of the present invention is produced in order to cause the liquid crystal display element to exhibit a large pretilt angle, it is preferred to use the side chain type diamine as described above in the total amount of the diamine. The ratio is set to i mol% to 90 mol%, and more preferably set to 5 mol% to 7 mol%. Preferable examples of the diamine having no side bond group, i.e., the non-side bond type diamine, as described above, include compounds represented by the formula (I) to the formula (VII) and the formula (??). 54 201016751 f 1 /ριΓ h2n—x—nh2

In these formulas, x is a linear alkylene group having a carbon number of 2 to 12. Y is independently a single bond, _〇_, _c〇_, _NH_, MCH, _c〇NH_, -NHCO- ^ -C(CH3)2- λ -C(CF3)2-' -0-(CH2) T-0- > -S- > -SS- ^ _S〇2_ '|(CH2)tS- or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12. Z1 and Z2 are hydrogen, and when Y is -NH-, -N(CH3)-, ?ch2-, -c(ch3)2- or _C(CF3)2_, ζι and Z2 may be bonded to each other to form single bond. Ring D is a phenylene group or a 1,4-diazacyclohexylene group. R and R are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group. A3 is independently an alkylene group having 1 to 6 carbon atoms, a substitutable group or an alkyl group substituted 55 201016751 =^ is an integer of 乂~1〇. Any oxime of the cyclohexane ring or the benzene ring is substituted by a gas, a methyl group, a hydrazine, a hydrazine, a hydrazine, a hydrazine, a hydrazine, a hydrazine or a hydroxy group. 33⁄4Benzyl The following is an example of the diamine (I). H2N(CH2)2NH2H2N(CH2)4NH2H2N(CH2)6NH2 (M> (1-2) (1-3) Specific examples of the diamine (II) are listed below.

Η2Ν-^〇ΚΝΗ2 Η2Νη^]-ΝΗ2 (H-1) (ΙΙ-2) Specific examples of the diamine (III) are listed below.

Specific examples of the diamine (IV) are listed below.

H2n^-NH2 h2n^nh2 (IV-1) (ΐν·2)

(IV-7) (IV-8) 56 201016751

(IV-9)

(IV-17) Specific examples of the diamine (V) are listed below.

(V-1)

(V-2)

(V-3)

57 201016751

H2n

Nh2 (V-12)

(V-16) ^'17)

〇/-22) (V-23) h2n-^KS^s^U^NH2 (V-24)

(V-25) 58 201016751

Specific examples of diamines (VI) are listed below.

Nh2 h2n (VI-1)

(VI-2) 59 201016751

(Vi-3) (VI-4) nh2

Specific examples of the diamine (VII) are listed below.

(VII-2) (νπ·1) Η2Ν·

ΝΗ2 h2n-^^n(^(-ch2- (VII-4)

(VII-5) (VII-6)

(VII-7) (VII-8) 201016751. OZ/1/pu

(VII-9) (VIMO) (VIM2) (VIM1)

H C CH (VII-13) (VIM4>

make. Tiller 〇ίι*15) (νιμιβ) Specific examples of diamines (XV) are listed below. 9h3 ch3 H2N-C3He-S 卜 OS 〇 3〇6-ΝΗ2 ch3 ch3 (XV-1) 中 Among the non-side chain type diamines, diamines (IV-1) to diamines (IV-5), preferably Amine (IV-15) to diamine (IV-17), diamine (V-1) to diamine (V-12), diamine (V-26), diamine (V-27), diamine ( V-31), diamine (V-33), diamine (V-35)~diamine (V-37), diamine (VI-1), diamine (VI-2), diamine (VI_6) More preferably, the diamine (VII-1) to the diamine (VII-5) and the diamine (XV-1) are diamines (iv-1), diamines (IV-2), and diamines (IV-15). ~Diamine (IV-17), diamine (V-1) ~ diamine (V-12), diamine (V-33), diamine (V-35) ~ diamine (V-37), two Amine (VI-7), 61 201016751 Diamine (VII-2) and diamine (xv-1). From the viewpoint of exhibiting desired electrical characteristics such as ion density in the liquid crystal display element, the non-side chain type diamine is preferably a total amount of the diamine which is a raw material of polylysine in the liquid crystal alignment agent of the present invention. The molar ratio is from 1% to 98%, more preferably from 10% to 95% per hydrazine. In the diamine used in the present invention, a diamine other than the diamine (I) to diamine (VIII), a diamine (X) to a diamine (oxime), and a diamine (XV) can be used. Examples of such a diamine include an oxime diamine having a fluorene ring and a side chain diamine other than the diamine (VIII) to diamine (XII). An example of the side-bonding diamine other than the diamine (VIII) to the diamine (XII) is a diamine (hydrazine) to a diamine (8f). __/

HaN^Q^Q^-N^ NH2 (1.) (2·) (3"

62 201016751 / χ ιγι, ί.

In these chemical formulas, R35 and R36 are each independently an alkyl group having a carbon number of 3 to 30", and in the case of producing a polyphosphonium amide in the liquid crystal alignment agent of the present invention, these diamines can be used without impairing the effects of the present invention. The extent of the use is within the scope. When polylysine is produced, a monoamine can be added to the diamine. By the addition of the monoamine, the termination of the polymerization reaction when the polyamic acid is formed can be caused, and the progress of the polymerization reaction can be suppressed. Namely, the molecular weight of the obtained polymer (polylactoic acid or a derivative thereof) can be easily controlled, and for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The addition ratio of the monoamine can be appropriately adjusted in consideration of the molecular weight of the target poly-acid. Two or more kinds of monoamines may be added as long as the effects of the present invention are not impaired. Examples of monoamines are aniline, 4-phenylaniline, cyclohexylamine, n-butylamine, n-decylamine, n-hexylamine, f-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-decylamine, N-dodecylamine, tetradecylamine, tetra-tetralinamine, n-pentadecaneamine, f-hexadesamine, n-heptylamine, n-dosamine, and ruthenium amine. In the following descriptions other than the examples, unless otherwise specified, 63 201016751, the general term for poly-proline and its derivatives is "poly-proline". In the present invention, when a diamine and a tetracarboxylic dianhydride are reacted to obtain a polyamic acid, a mixture of a diamine (N) and another diamine can be used as described above. In this case, one of the preferable examples of the other diamine is at least one selected from the group consisting of a diamine (VIII) and a side chain type diamine of a diamine (X) to diamine (oxime). Another preferred example of the other diamine is at least one selected from the group consisting of diamines (VIII) and diamines (X) to diamines (XIII), and at least one selected from the group consisting of diamines (I)~ Diamine (VII) and diamine (XV)

A mixture of at least one of the non-side chain type diamines in the group. The above items [5] to [8] are preferred examples of the combination of the diamine (N), the side chain type diamine, and the non-side chain type diamine. In the present invention, a polyamic acid obtained by reacting a mixed diamine and a tetracarboxylic acid as described above may be used as a polymer component, or a mixture of polyamic acids having different raw materials may be used as a polymer component. One of the preferred examples of the mixture of poly-proline is a mixture of polyamines: at least one of the diamines (N) and a selected from the group consisting of diamines (VIII) and diamines (X) to diamines (ΧΙΠ) a mixture of at least one of the side chain type diamines in the group or further added to the diamine mixture in a group selected from the group consisting of diamines (I) to diamines (VII) to ® and diamines (XV) a mixture of at least one of a non-side chain type diamine and a polyphthalic acid obtained by reacting a tetracarboxylic dianhydride; at least one of the non-side chain type diamine or at least one of the non-side chain type diamines A polyglycine obtained by reacting a mixture with at least one of a diamine (oxime) and a dicarboxylic acid. Another preferred example of a mixture of polylysines is a mixture of polylactoic acid 64 201016751 I Λ. t: at least one of the diamines (N) and a selected from the group consisting of diamines (i) to diamines (VII) and a polyamic acid obtained by reacting a mixture of at least one of a non-side chain type diamine in a group of diamines (χν) with a tetracarboxylic dianhydride; and selecting a diamine (VIII) and a diamine ( At least one of a side chain type diamine in the group of X) to diamine (oxime) or a mixture of at least one of the side chain type diamines and at least one of the non-side chain type diamines, and a tetracarboxylic acid The polyamic acid obtained by the reaction of the dianhydride. Preferred examples of the mixture of the polymer component being polyglycine are described in the above [9] to [11]. The tetracarboxylic dianhydride used in the present invention may be one compound or two or more compounds. The tetracarboxylic dianhydride may be exemplified by aromatic four-rebel acid, wild, four-rebel, and aliphatic four-rebel dianhydride. Examples of the aromatic tetracarboxylic dianhydride are listed below.

65 201016751

Among the aromatic tetracarboxylic dianhydrides, a carboxylic acid (1), a carboxylic acid (2), a carboxylic acid (5) to a carboxylic acid (7), a carboxylic acid (11), and a carboxylic acid (14) are preferred, and particularly preferred. Carboxylic acid (1). Examples of the alicyclic tetracarboxylic dianhydride are listed below. 66

201016751 ΛΛ I Λ. I

67 201016751

Ο

η

(49)

68 201016751. jz, /1 /pii

Among the alicyclic tetracarboxylic dianhydrides, preferred are carboxylic acid (19), carboxylic acid (25), carboxylic acid (35) to carboxylic acid (37), carboxylic acid (39), carboxylic acid (44) and carboxylic acid. Acid (49), more preferably carboxylic acid (19). Examples of aliphatic tetracarboxylic dianhydrides are listed below. The carboxylic acid (23) is preferred in the following examples.

69 201016751

In the present invention, tetracarboxylic dianhydride other than the above-described niobic acid (1) to several acid (67) may also be used. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydride having a side chain group. The pretilt angle of the liquid crystal display element can be increased by using a tetrabasic acid dianhydride having a side chain group. The tetracarboxylic dianhydride having a side chain group may, for example, be a carboxylic acid (68) having a steroid skeleton and a carboxylic acid (69).

In the production of polyamic acid, a dicarboxylic acid anhydride can be added to a tetracarboxylic dianhydride for use. In this way, the termination of the polymerization reaction 201016751 when the polyamic acid is formed can be caused, so that the progress of the polymerization reaction can be suppressed. Namely, it is possible to easily control the molecular weight of the obtained polymer (polylactoic acid), for example, to improve the coating properties of the liquid crystal alignment agent without impairing the effects of the present invention. The ratio of the addition of the acid-lowering needle can be taken into consideration for the appropriate amount of polyglycine. Further, as long as *the effect of the present invention is impaired, the type of the dicarboxylic anhydride to be added may be two or more kinds. Examples of the dicarboxylic anhydride are maleic anhydride, phtlialic anhydride, methylene succinic anhydride, n-decyl succinic anhydride, ortho- 12 Sega sorrel, sulphate, hexadecyl succinic anhydride and cyclohexanoic anhydride. In the present invention, a monoisocyanate (m〇n〇isocyanate) compound may be further added in the production of polyamic acid. By adding a monoisocyanate compound, the end of the obtained polyglycolic acid is modified and the molecular weight is adjusted. By using the terminal-modified polyglycine, for example, the coating properties of the liquid crystal alignment agent are improved by the effects of the present invention. The amount of the monoisocyanate compound to be added is preferably from 1 mol% to 1 mol% of the total amount of the diamine and the tetracarboxylic dianhydride. Phenyl cyanate and isocyanate are intended. The poly-aramidic acid used in the present invention can be produced in the same manner as the known polylysine used in the formation of a film of poly 9-bromoimine. The amount of multi-electrolytic addition of the four-acid-lower liver is preferably about the same as the total number of moles of the diamine (about 0.9 to 1.1). The molecular weight of h, poly-proline is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, based on the weight-average molecular weight (Mw) in terms of polystyrene. The molecular weight of polylysine can be determined from the measured value by a Gel Permeation Chromatography (GPC) method. The polyglycolic acid can be confirmed by analyzing the solid component obtained by sinking a large amount of poor solvent with infrared rays (Infrared, IR) or Nuclear Magnetic Resonance (NMR). By using a strong alkaline aqueous solution such as KOH or NaOH to decompose polylysine, and then extracting the organic solvent of the decomposed product, gas chromatography (Gas Chromatography, GC), high performance liquid chromatography (High) Analysis by Performance Liquid Chromatography (HPLC) or Gas Chromatograph-Mass Spectrometer (GC-MS) confirmed the raw materials used. The liquid crystal alignment agent of the present invention may further contain other components than the polyamic acid. For example, 'the liquid crystal alignment agent of the present invention may further contain an alkenyl substituted imidide compound from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. Preferred examples of the alkenyl substituted nadic ylidene compound are listed below. ®

72 201016751 I L· / ^/ΐί

For example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The compound 'having a radically polymerizable unsaturated double bond' may, for example, be a (meth)acrylic acid derivative such as (meth)propionate or (meth)acrylamide or a dim-butylene diimide. A (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds. In addition, the liquid crystal alignment agent of the present invention may further contain an oxazine compound, for example, a compound represented by the formula (a) to the formula (f), for example, from the viewpoint of the long-term stability of the electrical properties of the liquid crystal display device. Compound.

73 201016751

·(')~ί(1)_ HR2 is a hydrocarbon having a carbon number of 1 to 3 ' 'RR is hydrogen or a carbon number is 1 to 6; χ is a single 1 2, j, each S~S〇2_, C〇...CONH •, -NHC0_, c(ch3)2-, _C(CF3)2_, _(CH2)m, 〇(cH2)m〇_, -S-(CH2)mS-'m are integers of i~6; Independently, it is a single bond, _〇, S CO_, _C(CH 3 ) 2 ·, - (: 3) 2 _ or a sub-alkyl group having a carbon number of i 3 . For example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element, the liquid crystal alignment agent of the present invention may further contain an epoxy compound having one or two or more epoxy rings in the molecule. The epoxide is a monomer, an oligomer or a polymer having a ring-ring ring. The liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include polyacetamide and polymers other than the derivatives thereof, and low molecular compounds, which can be selected and used according to various purposes. The polymer may be exemplified by a polymer soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics or the alignment property of the liquid crystal alignment film formed, it is preferred to add such a polymer to the liquid crystal alignment agent of the present invention. Examples of the polymerization 201016751 include polyamine, poly(ethane), polyurea, polyester, polyepoxide, and polyacetate (p〇iyester p). 〇iy〇i), silicone modified polyurethane, and silicone modified polyester. The low molecular compound 'for example: 1) when it is desired to improve the coatability, a surfactant compatible with the purpose can be cited; 2) when it is necessary to improve the antistatic property, an antistatic agent can be cited; 3) when it is desired to improve In the case of adhesion or rubbing resistance of the substrate, a decane coupling agent or a titanium coupling agent may be mentioned; and '4) When hydrazine imidization is carried out at a low temperature, a ruthenium amide catalyst may be mentioned. Examples of the dream-burning coupling agent include vinyl trimethoxy decane, ethylene triethoxy decane, : ( 2 - aminoethyl) _ 3 aminopropyl decyl dimethoxy ketone, N- ( 2-aminoethyl)_3_aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxy decane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxy decane, m-amino Phenyltriethoxy oxime • Burning, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-apropylpropyldimethoxydecane, 3-cyclopropyltrimethoxy Baseline, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxyoxydecane, N-(l,3-dimethylbutylidene)·3 (triethoxydecane) Base) propylamine, and hydrazine, hydrazine, bis(trimethoxydecyl)propyl]ethylenediamine. Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and dibutylamine; hydrazine, hydrazine, dimethylaniline, hydrazine, hydrazine-diethylaniline, and methyl substitution. Aromatic amines such as aniline and phenylamine substituted by a base; 201016751 amines; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, Hydroxyl-substituted quinoline, isoquinoline, methyl-substituted isoquineline, trans-substituted isoindole, imidazole, methyl-substituted imidazole, hydroxy-substituted imidazole Isocyclic amines. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxyl ratio, and isoindole One or two or more of them. The liquid crystal alignment agent of the present invention may further contain a solvent from the viewpoint of applicability of the liquid crystal alignment agent or adjustment of the concentration of the polyamic acid. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve the polymer component. The solvent widely includes a solvent which is usually used in the production step or use of a polymer component such as polyamic acid or a soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be a solvent or a mixed solvent of two or more solvents. Such a solvent may, for example, be a lyophilic solvent of the polyaminic acid or another solvent which is intended to improve coatability. For the aprotic polar organic solvent in which the polylysine is a solvophilic solvent, N-methyl-2-pyrrolidone, monomethyl-pyralidone, and dimethyl Imidazolidinone), N-methyl caprolactam, N-methyl propionamide, N, N-dimethyl acetamide , dimethyl sulfoxide, ,, ,-dimethyl formamide, Ν, Ν-diethyl amide amine 201016751, /1 /pii (N,N -diethyl formamide), diethyl acetamide, γ-butyrolactone, etc. Internal vinegar. The purpose of improving other coatings such as coating properties is exemplified by: lactic acid-based vinegar, 3-methyl-3 - ethylene glycol monoalkyl ether such as decyloxybutanol, tetraun, isophorone, ethylene glycol monobutyl ether, etc., diethylene glycol monofilament such as diethylene glycol monoethyl ether Ethylene glycol monodisperse or propylene glycol monoalkyl ketone, malonate monoacetate, propylene glycol monomethyl ether and propylene glycol, etc. Base ester An ester compound such as dipropylene glycol monoalkyl ether such as dipropylene glycol monoterpene ether or an acetate thereof. Particularly preferred solvents among these solvents are: N-mercapto-2-pyrrolidone, N,N-dimethylacetamide, dimethylimidazoline, gamma-butyrolactone, ethyl ketone monobutyl ether, and one Glycol mono-mystery, propylene glycol monobutylene, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. In the present invention, the concentration of the polymer component containing the polyamic acid in the liquid crystal alignment agent is not particularly limited, but is preferably from 01% by weight to 4% by weight. When the liquid crystal alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the polymer component contained in advance with a solvent. In this case, the concentration of the polymer component is preferably 40% by weight or less from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to be suitable for the liquid crystal alignment agent to easily mix the solvent. Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted depending on the method of applying the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spinner method or a printing method, in order to keep the film thickness 77 201016751 good, the concentration of the polymer component is usually usually less than or equal to 9% by weight. When other coating methods such as dipping or ink jet are used, it is also possible to further reduce the concentration. On the other hand, if the concentration of the polymer component is 大于1% by weight or more, the film thickness of the resulting liquid crystal alignment film tends to be optimum. Therefore, the concentration of the polymer component is 0.1% by weight or more in a usual rotator method, printing method, or the like, and is preferably 〇5 weight ❶/❶ 1010% by weight. However, it can also be used at a lower concentration depending on the method of applying the liquid crystal alignment agent. Further, in the case where the liquid crystal alignment agent is used for producing a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined according to the mechanism or method of forming the film of the liquid crystal alignment agent. For example, when a film of a liquid crystal alignment agent is formed by using a printing machine, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mpa·s or more from the viewpoint of obtaining a sufficient film thickness, and from the viewpoint of suppressing printing unevenness. It is considered that the viscosity of the liquid crystal alignment agent of the present invention is preferably 100 mPa·s or less, more preferably mPa*s to 8 μmPa·s. When a liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, the viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa, s to 200 mPa*s, from the same viewpoint. It is preferably 10 mPa*s to 100 mPa«s. The viscosity of the liquid crystal alignment agent can be reduced by dilution with a solvent or aging with stirring. The liquid crystal alignment film of the present invention is a film formed by heating a coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent, for example, 201016751

The liquid crystal alignment film of the invention may be obtained by a step of forming a coating film of the liquid crystal alignment agent of the present invention and a step of heating the coating film to perform calcination. For the liquid crystal alignment film of the present invention, a film obtained by the calcining step can be subjected to a rubbing process as needed. The coating film may be formed by applying the liquid crystal alignment agent of the present invention to a substrate of a liquid crystal display element, similarly to the production of a usual liquid crystal alignment film. The substrate may be a glass substrate on which an electrode such as an indium tin oxide (ITO) electrode or a color filter (c〇1〇rfllter) ® may be provided. A method of applying a liquid crystal alignment agent onto a substrate is generally known as a spinner method, a printing method, a dipping method, a falling-drop method, an ink jet method, or the like. These methods are equally applicable in the present invention. The calcination of the coating film can be carried out under the conditions necessary for the polyglycolic acid to exhibit a dehydration/cyclization reaction. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like. These methods are also applicable in the present invention. It is usually preferably carried out at a temperature of about 150 Torr to 3 Torr for 1 minute to 3 hours. The rubbing treatment can be carried out in the same manner as the rubbing treatment which is usually used for the alignment treatment of the liquid crystal alignment film, as long as the conditions of the filling retardation are obtained in the liquid crystal alignment film of the present invention. Particularly preferred conditions are: a capillary intrusion of 0.2 mm to 0.8 mm, a platform moving speed of 5 mm/sec to 250 mm/sec, and a drum rotation speed of 5 〇〇 ^^^2 000 rpm. In the alignment treatment method of the liquid crystal alignment film, in addition to the rubbing method, it is generally possible to obtain a liquid crystal alignment film of these stages, which can be suitably obtained by the method of the step ▲ and the step thereof. Such other steps, or sputum-to-friction treatment drying step and the above-mentioned step (4), are generally known as a method of heat treatment in a supplier infrared furnace, a method of performing a teaching on a hot plate, and the like. It can be made in the material drying step. The drying step is preferably carried out at a temperature within a range in which the solvent can evaporate

More preferably, it is carried out at a relatively low temperature compared to the temperature of the calcining step. X A cleaning method for cleaning the liquid crystal alignment film before and after the alignment treatment by the cleaning liquid may be exemplified by brushing, jet spraying, vapor cleaning, or ultrasonic cleaning. These methods can be used alone or in combination. The cleaning solution can be used: pure water, or various alcohols such as methanol, ethanol, and isopropanol, aromatic fumes such as Ben, A, and 1-toluene, and halogen solvents such as methylene chloride. Anthraquinones such as ethyl ethyl ketone are not limited to these cleaning solutions. Of course, this green liquid is a cleaning liquid which is sufficiently purified and has less impurities. Such a clear &amp; method can also be applied to the cleaning step of forming the liquid crystal alignment film of the present invention. The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 201016751. 10 nm to 300 nm, and more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a profilometer or an ellipsometer. The liquid crystal display device of the present invention has a pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal of the present invention for aligning liquid crystal molecules in a predetermined direction. Orientation film. As the substrate, the glass substrate described in the liquid crystal alignment film of the present invention can be used, and the electrode can be an ITO electrode formed on a glass substrate as described in the liquid crystal alignment film of the present invention. The liquid crystal layer is formed of a liquid crystal composition sealed between the substrates, which is an inner side of the liquid crystal alignment film surface. The liquid crystal composition to be used is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A preferred liquid crystal composition having a positive dielectric anisotropy is exemplified by the liquid crystal composition disclosed in the following publication: Japanese Patent No. 3,862,828, Japanese Patent No. 2,635,435, and Japanese Patent Laid-Open No. 5-5 Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 8199168, No. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. No. Publication No. 2000-087040, Japanese Patent Publication No. 2001-48822, and the like. ^Japanese Patent Special Dielectric Anisotropy is (4) Excellent Crystal Composition Composition = = Liquid Crystal Composition: 曰本专利专开昭57 Side: ^ Newspaper, Japanese Patent Special Open 2-4725, Japanese Special Gazette, Japan Patent special Kaiping 8·_53 public “ ❹ Japanese patent special (four) 1G 2=m_453 bulletin, 10-236990 bulletin, ^ newspaper, Japanese patent special open weekday too dilute oil 1 special j special Kaiping 1G_236 &quot; No. 2 bulletin,曰本专利专开平号: r〇-2曰平i_24号曰本本平10.237075 ❹ 10-237070号, 日太直制奴报a不不扪特开平(EP967261A1手册)日太皇开平1〇- Japanese Patent Laid-open No. 237448, Japanese Patent Laid-Open No. 1^^1, Unopened 1〇_287874, No. 10-291945, No. 5, Japanese Patent Special Open, Japanese Patent, Special Kaiping (10), Rev. τ 曰 专利 专利 专利 专利 〇 〇 〇 〇 〇〇 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 019 019 019 019 019 019 019 019 019 019 019 019 019 019 019 019 019 019 Adding one or a liquid crystal composition having a positive or negative dielectric anisotropy The liquid crystal display element of the present invention can form various liquid crystal display elements for electric field mode. The electric field type liquid crystal display element can be exemplified by the surface of the electrode relative to the substrate. A transverse electric field method for applying a voltage to the liquid crystal layer in a horizontal direction, or a vertical electric field method for applying a voltage to the liquid crystal layer in a direction perpendicular to the surface of the substrate Liquid crystal display element The liquid crystal display element for a lateral electric field method does not exhibit a relatively large pretilt angle. Therefore, a liquid crystal display element containing a non-side chain type polyamic acid is preferably used in the liquid crystal display element for a transverse electric field method. The liquid crystal alignment film formed is obtained by using a non-side chain type diamine. The liquid crystal display element for a longitudinal electric field method needs to exhibit a relatively large yaw pretilt angle. A liquid crystal alignment agent containing a side chain type polyaminic acid is suitably used in the display element. a liquid crystal alignment film formed by using a side chain type diamine or a diamine mixture containing the side chain type diamine. Thus, the liquid crystal alignment agent of the present invention is used as a raw material. The liquid crystal alignment film to be produced can be applied to liquid crystal display elements of various display driving methods by appropriately selecting a polymer as the raw material. The liquid crystal display element of the present invention may further have elements other than the elements of the configuration 83 201016751. In the liquid crystal display device of the present invention, a constituent element which is generally used for a liquid crystal display element such as a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, and a driving circuit can be mounted. [Examples] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples. The compounds used in the examples are as follows. <tetracarboxylic dianhydride> slow acid (1): pyromellitic dianhydride 10 carboxylic acid (19): 1,2,3,4-cyclobutanetetracarboxylic dianhydride <diamine> II Amine (VI-7): 1,4-bis(4-aminophenyl)-1,4-diazacyclohexanediamine (Vl): 4,4·-diaminodiphenylmethanediamine ( V-7): 1,2-bis(4-aminophenyl)ethanediamine (ΧΙΙ-4-1): 1,1-bis[4-(4-aminophenoxy)phenyl-4- (trans-4-n-pentylcyclohexyl)cyclohexanediamine (XII-2-1) : U-bis[4-(4-aminophenylmethyl)phenyl]-4-n-heptyl ring Hexanediamine (Nl): 1,4-bis(4-aminophenoxy)naphthalenediamine (V-36): N,N'-bis(4-aminophenyl)-N,N'-di Mercaptoethylenediamine <solvent> NMP : N-mercapto-2-pyrrolidone BC : butyl cellosolve (ethylene glycol monobutyl ether) 84 201016751. DL·! \ /pil <1. Synthesis of poly-branched acid> [Synthesis Example 1] 2.42 g of a diamine (VI-7) and 1.072 g of a diamine (Nl) were placed in a 1 mL-neck four-necked flask equipped with a thermometer, a mixer, a raw material input port, and a nitrogen gas inlet. ), 569 g of diamine (χΙΙ 21), and dehydrated 〇 of 8〇.Gg For cake was dissolved in a dry gas stream track. Next, 683683 g of a carboxylic acid (1) and 1.434 g of a carboxylic acid (19) were added, and the mixture was allowed to react at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to 7 〇 ° C or less to cause a reaction. Then, 14.0 g of BC was added to the obtained solution to obtain a polyglycine solution having a concentration of 6 wt. The polyaminic acid was designated as pA1. The weight average molecular weight of pA1 is 40,100. The weight average molecular weight of poly-aracine is determined by the following method: the obtained polyamic acid is diluted with a scallic acid-DMF mixed solution (disc acid/DMF = 〇6/1 〇〇: weight ratio), In order to bring the polyaminic acid concentration to about 1% by weight', the mixed solution was used as a developing solvent by a GPC method using a 2695 separation module (manufacturing Water m〇dule), a 2414 differential refractometer (manufactured by Waters). The measurement was carried out in terms of polystyrene. Further, the column was measured using HSPgelRTMB-M (manufactured by Waters) at a column temperature of 40 C and a flow rate of 0.35 mL/min. [Synthesis Examples 2 to 7] Polyamic acid solutions (PA2) to (PA7) were prepared in accordance with Synthesis Example 1 except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 1. 85 201016751 The synthesis example 1 is included, and the results are summarized in Table 1. <Table 1> Synthesis Example No. Polyamine solution name Carboxylic acid diamine Weight average molecular weight No. Mohr fraction No. Molar fraction 1 PA-1 (1) (19) 0.14 0.32 (VI-7) (N-1) (XII-2-1) 0.36 0.14 0.04 40100 2 PA-2 (1) (19) 0.23 0.23 (VI-7) (N-1) (XII-4-1) 0.36 0.14 0.04 44200 3 PA-3 (1) (19) 0.27 0.18 (VI-7) (N-1) (ΧΠ-4-1) 0.39 0.14 0.02 33000 4 PA-4 (1) (19) 0.25 0.25 (Vl) 0.50 85300 5 PA-5 (1) (19) 0.25 0.25 (V-7) (XII-4-1) 0.45 0.05 65400 6 PA-6 "(1) (19) 0.40 0.10 (V-7) (XII-2-1) 0.30 0.20 31800 7 PA-7 (1) (19) 0.14 0.32 r (VI-7) (V-36) (XII-4-1) 0.36 0.14 0.04 36700 <2. Production of liquid crystal display device>

[Example 1] Q A mixed solvent of NMP/BC = l/i (weight ratio) was added to a polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1, and the whole was diluted to 4 A liquid crystal alignment agent was prepared in % by weight. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. <Method of Manufacturing Liquid Crystal Display Element>

The liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode by a spinner to form a film having a film thickness of 7 Å. After coating, it is dried by heating at 8 (TC 86 201016751 / 1 /pif for about 5 minutes, and then heat treated at 2103⁄4 to form a liquid crystal alignment film. Then, the surface of the substrate of the liquid crystal alignment film is rubbed to = H Then 'Put the liquid crystal alignment film in ultrapure water for 5 minutes^ and then dry in an oven at 120t for 30 minutes. Shuttering ❿ 7 7 7 片 片 片 7 7 7 7 7 7 7 7 7 7 7 7 7 7 The surface of the alignment film is inside and the opposite direction of the rubbing direction is anti-parallel, and the opposite ge* is placed, and the Qianliqi oxygen hardening is sealed to form an antiparallel cell having a gap of 7 μm. The liquid crystal composition shown below was injected, and the injection port was sealed with a light hardener. Then, heat treatment was performed at 110 ° C for 3 minutes to prepare a liquid crystal display element. <Liquid crystal composition>

87 201016751

F 17wt. %

17wt. % 16wt. % 10wt. % F C3H7-^-y~C2H4-^-, -F 5wt. %

10wt. %

C5h” F

6wt. % 6wt. % 13wt. %

[Example 2] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2, and the whole was diluted to 4 weights. % is made into a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 3] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution 88 201016751 liquid (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3, and the whole was diluted. A liquid crystal alignment agent was prepared at 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 1] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, and the whole was diluted to 4 weights. % is made into a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. © [Comparative Example 2] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, and the whole was diluted to 4 A liquid crystal alignment agent was prepared in % by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 3] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA6) having a concentration of 6 wt% synthesized in Synthesis Example 6, and 整体 was diluted to 4 as a whole. A liquid crystal alignment agent was prepared in % by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 4] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7, and the whole was diluted to 4 weights. % is made into a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. <3. Evaluation of electrical characteristics> 89 201016751 袢, 二实::匕3, Liquid crystal display elements produced in Comparative Examples 1 to 4 were measured for county retention rate and long-term reliability. 1) Measurement of voltage holding ratio TOY is used. Liquid day and day physical property evaluation device made by Teehniea milk 4

Idtht electric hardship rate test ^. The measurement conditions are gate width. 60 μ8, frequency: 3 Hz, pulse height: ± The higher the value of 丨 v rate, the electrical characteristic result is not shown in Table 2. 2) Measurement of retention characteristics of electric enthalpy retention rate The produced liquid crystal display element was evaluated for its voltage retention during the passage of time and evaluated for its retention characteristics. The tester's ring gas production method to maintain the characteristics ί, · The liquid crystal display element is placed at a temperature of i 〇 (rc: the decrease of the second = the smaller (for example, 二 = = 〇 = 1〇 / 0), then it can be said The better the retention characteristics of the voltage holding ratio, the better the long-term reliability of the electrical characteristics. /&gt;hour==%)=(initial (G hour) county retention rate _500 After 300 hours and after 500 hours The data shown in Table 2 is 90. The measurement is performed. 1 95^ 2 Example 2 94.2 ~9λΓ 88.2 0 ! Λ 86.3 9 8 3 Example 3 95.2 93.9 4 4 Comparative Example 1 91.9 72.0 70.5 23 5 Comparative Example 2 95.1 77.9 77.0 19 6 Comparative Example 3 95.3 h 85.3 81.6 14 7 Comparative Example 4 94.2 86.7 83.5 11 ❹ As shown in Table 2, when a polyamine is produced using a raw material diamine containing a diamine (n), a liquid crystal alignment film is formed by using a liquid crystal alignment agent containing the polymer. In the liquid crystal display element, the effect of suppressing the decrease in the voltage holding ratio with time is remarkably improved. Brief Description of main elements] [helmet ❹ None REFERENCE SIGNS

Claims (1)

201016751 VII. Patent application: L, a liquid crystal alignment agent, which is a composition containing at least one polymer selected from the group consisting of polylysine and its derivatives, wherein the polymer is At least one of the diamine represented by the formula (N) or at least one of the diamine represented by the formula (N) and at least one of the other diamines not represented by the formula (N) = a polyamic acid or a derivative thereof obtained by reacting a mixture with a tetracarboxylic acid monoanhydride, and the concentration of the polymer component in the composition is from Q1% by weight to 4% by weight, Wherein 'A independently is a carbon number of 1 to 10 linyl, a carbon number of 1: η alkoxy, hydroxy, trifluoromethyl, fluorine, gas or bromine; m alone f, α~3 _ number; A2 is independently _〇, _nh, _n(ch3), I2二社Γΐ 'The bonding position of the two amino groups to the benzene ring is any position other than the bonding position of A1 and A❶ 专利 ΤΙ 专利 专利 专利 专利The liquid crystal alignment agent according to Item 1, wherein in the formula (N): the oxime positions of the amino groups are all aligned with respect to 8-2. The liquid crystal alignment agent according to the first item of the second aspect of the invention, wherein the enthalpy is selected from the group consisting of: (1) and (10), and the formula (inter), the formula '(Ν-13), the formula (N l5) and the formula (ν_ι6) a mixture of at least one diamine or a mixture of the diamines and other diamines in the 201016751. (N-1) (N-2) (N-3) (N-4) In these formulas, Me means a fluorenyl group. 4. The liquid crystal alignment agent according to claim 3, wherein the monoamine is at least 二 or the (di) of the diamine represented by the formula (N-1) and the formula (N-3) A mixture of a diamine and other diamines. The liquid crystal alignment agent according to claim 1, wherein the diamine is a mixture of at least one of the diamine represented by the formula (N) and another diamine. At least one selected from the group consisting of diamines having a side chain group in the diamine group represented by the formula (VIII) and the formula (X) to the formula (XIII), H2N R1 I A3 (VIII) nh2 Wherein 'A is a single bond, -〇·, -CO-, -COO-, -OCO- -CONH-, -CH20-, -CF20-, or an alkylene group having a carbon number of 1 to 6; Any -CH2- may be substituted by -〇_, _CH=eH_ or ^-OC-; R1 is a group having a steroid skeleton, a carbon group having a carbon number of 3 to ^, and having a carbon number of 1 to 3? Any of the alkyl groups having a carbon number of 3 to 30, or a group represented by the formula (Ιχ), may be 〇 _ •CH=CH· or _〇C-, (IX) wherein 'A4 and A5 are independently a single bond, ·α, C(X)-CONH-, a fluorenylene group having a carbon number of 4, and an oxyethylene group having a carbon number of 3: 201016751. 11 /pii An alkyl group, or an alkyleneoxy group having a carbon number of 1 to 3; a ring 8 and a ring c are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; the rule 2 and R 3 are independently fluorine or The fluorenyl groups 'f and g are independently 0, 1 or 2; 〇, (| and 6 are independently an integer of 〇~3, and their total is greater than or equal to i; R4 is an alkyl group having a carbon number of i to 30, An alkoxy group having a carbon number of 1 to 30 or an alkoxy group having a carbon number of 2 to 3 Å. In these filaments, an anthraceneoxy group and an alkoxyalkyl group, any hydrogen may be substituted by fluorine, and any /Η: · can be replaced by difluoromethylene, (XI) In the formula: (XI), in the formula (XI), the site is hydrogen or methyl, the R7 and R8 are 1 to 2G or the dilute is 2 to 2°, and the carbon number is It is a 1~2G base or a phenyl group, and A6 stands for a single bond, -CO- or -CH2_, 95 201016751 (XII) In the formulae (XII) and (XIII), R9 is a leuco group having a number of 1 to 3 Å. Any of the alkyl groups described above may be _〇, -CH=CH- or •C=C -Substitution; R1Q is an alkyl group having a carbon number of 6 to 22; R&quot; is a alkyl group having a carbon number of 1 to 22; a7 is independently a ortho-alkyl group having a carbon number of 1 to 6; and A8 is a single bond or carbon The number is i~3 alkylene; 瓖T is I,4-phenylene or 1,4-cyclohexylene; h is hydrazine or 1. 6. The liquid crystal alignment agent according to claim 3, wherein the diamine is selected from the group consisting of a formula (NU~ formula (N-5), a formula (N_7), a tris(N-8), a formula (Ν·13), formula (N_15) and formula (N_16) describe a mixture of at least one diamine and other diamines in the compound group, wherein the other diamine is selected from the formula (VIII-2) And at least one of the diamines having a side chain group of the indoleamine represented by the formula (VI11·4) to the formula (XII-2), the formula (χπ·4), and the formula (ΧΠ-6) One, 96 201016751 / 1 / JJijf R30 (XII-6) In these chemical formulas, R23, R29 and R3G are each an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. The liquid crystal alignment agent of claim 1, wherein the diamine is a mixture further containing a diamine having no side chain group, and the diamine having no side chain group is It is at least one selected from the group consisting of compounds represented by formula ()[) to formula (vii) and formula (XV), H2N-X-NH2 η2ν'~^ νη2 (1) (II) (HI) οΝΗ. Η2ν (IV) z1 z2 In these formulas, 'X is a linear alkylene group having a carbon number of 2 to 12; Y is independently a single bond, -Ο·, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-' -C(CH3)2-' -C(CF3)2- &gt; -0-(CH2)t-0-' -S- &gt; -SS- ' -S〇2·, -S- (CH2)tS- or a linear alkylene group having a carbon number of i~12, t is an integer of 1 to 12; Z1 and Z2 are hydrogen, and when γ is _NH_, _N(CH3)_, 98 201016751, D£.l Y / pil : into a single: ^:: carbon number: 1 to 6 alkylene, sub-phenyl or alkyl substituted τ u 备 111 111 is an integer from 1 to 10; Any hydrogen of the burned ring or the benzene ring may be substituted by fluorine, methyl, .0, ·(10)H, H, _p〇3H2, or a benzyl group. The liquid crystal alignment agent according to Item 7, wherein the side chain group is not represented by the formula (ινι, formula (Μ), formula (IV&quot; 15)~ (IV·17), Formula (V-1) to Formula (ν-12), Formula (V-33), Formula (V: 35) to Formula (V-37), Formula (VI-7), Formula ( At least one of the diamines represented by VII-2) and (XV-1), 99 201016751 /-NH2 (V-10) (V-11) (V-12) h2n NH2 pH (V-33) CHq H2N-^^N-^y-NH2 H2N-^^-N^^N—^^-NH2 CH3 (V-35) (V-36) H2N~0^0^CH2t0^0&quot;NH2 (VII-2) CH3 ch3 C3H6-Si-〇-S Bu C3H6-NH2 CH3 ch3 (XV-1) 〇9. Liquid crystal as described in claim 1 An alignment agent, wherein the polymer is a mixture of the following polyaminic acid or a derivative thereof, which is 100 201016751 # j. At least one of the diamine represented by the formula (N) and a diamine having a side chain group selected from the group consisting of the formula (vill) and the diamine group represented by the formula (X) to the formula (XIII) a mixture of at least one, or at least one selected from the group consisting of diamines represented by formula (N), having a side chain group selected from the group consisting of diamines represented by formula () and formula (X) to formula (XIII) a mixture of at least one of the diamines of the group and at least one selected from the group consisting of diamines having no side chain groups in the diamine group represented by the formula (I) to the formula (VII) and the formula (χν), a polyaminic acid obtained by reacting with a tetracarboxylic dianhydride or a derivative thereof, and at least one of the diamine having no side chain group or at least the diamine having no side bond group a mixture of a polyaminic acid or a derivative thereof obtained by reacting a mixture of at least one of the diamines represented by the formula (N) with four tetrahydrous dianhydrides, R1 Wherein 'A3 is a single bond, _〇_, _c〇_, _c〇〇_, _〇c〇-, CONH·, -CH20-, -CF20-, or a sub-alkyl group having a carbon number of 1 to 6, Any _CH2_ in the sub-alkyl group may be substituted by _〇_, _CH=CH or _C=C-; R1 is a group having a steroid skeleton, a burning group having a carbon number of 3 to 3 Å, and having a carbon number Any of the alkyl groups of the alkyl group having a number of carbon atoms of 3 to 30 or the group of the formula (IX) may be any of the groups of the alkyl group having a carbon number of exemplified by the formula (IX). ·〇, 101 201016751 -CH=CH- or -oc-, Wherein, A4 and A5 are independently a single bond, -Ο-, -COO-, -0C0-, -CONH-, a mercapto group having a carbon number of 1 to 4, and an oxyalkylene group having a carbon number of 1 to 3. Or an alkyleneoxy group having a carbon number of 1 to 3; ring B and ring C are independently M-phenylene or anthracene, 4·cyclohexylene; R 2 and R 3 are independently fluorine or methyl, f and g is independently 〇, 1 or 2; c, 4 and e are independently an integer of 〇~3, and their total is 1 or more; r4 is a burning group having a carbon number of 1 to 30, and the number of breaks is 1 to An alkoxy group or a calcined oxynonyl group having a carbon number of 2 to 3 Å, in the #丝, the alkoxy group, and the acyl group, any hydrogen may be substituted by fluorine, and any _CH2- may be difluorinated. Substituted by sulfhydryl, 102 (X) 201016751 / j. / kz-iX (XI) In the formula (X) and the formula (XI), R5 is independently hydrogen or methyl, R6 is hydrogen or an alkyl or alkenyl group having 1 to 20 carbon atoms, and R7 and R8 are each independently a carbon number. Is an alkyl group or a phenyl group of 1 to 20, and A6 is independently a single bond, -CO· or -CH2-, 103 201016751 (XII) (XIII) In the formula (XII) and the formula (XIII), R9 is an alkyl group having 1 to 30 carbon atoms, and any -CH2- of the alkyl group may be -Ο-, -CH=CH - or -C=C-substitution; R1() is an alkyl group having a carbon number of from 6 to 22; R11 is an alkyl group having a carbon number of from 1 to 22; and A7 is independently -Ο- or a carbon number of from 1 to 6 Alkylene; A8 is a single bond or an alkylene group having a carbon number of 1 to 3; ring T is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1, 201016751 t L·I H2n—x—nh2 (I) H2N N~^ NH; In the formulae (I) to (VII) and (XV), X is a linear alkylene group having a carbon number of 2 ❹ to 12; Y is independently a single bond, -Ο-, -CO-, -NH -, -N(CH3)-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, -0-(CH2)t-0-, -S-, -SS -, -S02-, -S-(CH2)tS- or a linear alkylene group having a carbon number of 1 to 12, t is an integer of 1 to 12; Z1 and Z2 are hydrogen, and when Y is -NH-, - When N(CH3)-, -CH2., -C(CH3)2- or -C(CF3)2·, Z1 and Z2 may be bonded to each other to form a single bond; ring D is phenylene or 1,4- Diazacyclohexylene; R33 and R34 are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group; A3 is independently an alkylene group having 1 to 6 carbon atoms, 105 201016751 - j. Or an alkyl-substituted phenylene group; m is an integer from 1 to 10; any hydrogen of a cyclohexane ring or a benzene ring may be fluorine, methyl, -OH, -COOH, -so3h, -Ρ03Η2, benzyl or Hydroxybenzyl substituted. 10. The liquid crystal alignment agent according to claim 1, wherein the polymer is a mixture of the following polyaminic acid or a derivative thereof, which is at least one kind of a diamine represented by the formula (N) Reacting with a mixture of at least one selected from the group consisting of diamines having no side chain groups in the diamine group represented by formula (I) to formula (VII) and formula (XV) And the obtained poly-amic acid or a derivative thereof, and a diamine having a side chain group selected from the group consisting of the formula (νπι) and the diamine group represented by the formula (X) to the formula (XIII) a polyamic acid obtained by reacting at least one or a mixture of at least one of the diamine having a side chain group and at least one of the diamine having no side chain group, and a tetracarboxylic dianhydride or a mixture of its derivatives, ~ R1 I A3 Wherein 'A is a single bond, _〇_, _c〇_, ——, · 〇 "〇, _C〇NH, even f2o_, or a sub-shape having a carbon number of i~6, any of the alkylene groups -ch2_ may be substituted by -〇-, _CH==土•OC-; R1 4 has a steroid skeleton of the group s, has a money of 3 (four) pro-=3=106 201016751, / 1 / pii substituent The phenyl group, or the group represented by the formula (IX), has a slave number of 3 to 3 G, and a CH-CH- or CsC_ substitution. (IX) Wherein, A4 and A5 are independently a single bond, _〇_, &lt;〇〇_, _〇c〇_, -CONH·, an alkylene group having a carbon number of 丨~4, and an oxygen having a carbon number of 丨~3 Alkylene group, or a fluorenyleneoxy group having a carbon number of 1 to 3; ring b and ring c are independently 1,4-phenylene or iota, cyclohexylene; R2 and R3 are independently fluorine Or methyl 'f and g are independently 〇, 1 or 2; c, d and e are independently an integer of 0 to 3, and their total is 大于 or more; R4 is an alkyl group having a carbon number of from 〜30, An alkoxy group having a carbon number of 1 to 3 Å or an alkoxyalkyl group having a carbon number of 2 to Deng, and among these alkyl groups, alkoxy groups and alkoxyalkyl groups, any hydrogen may be substituted by fluorine. And any -CH2· can be used by the second gas 107 (X) 201016751 Nh2 (χι) Ο In the formula (X) and formula (XI), R5 is independently hydrogen or methyl, R6 is hydrogen or an alkyl or alkenyl group having a carbon number of 1 to 20, and R7 and R8 are each independently An alkyl group having a carbon number of 1 to 20 or a phenyl group, and A6 is independently a single bond, -CO- or -CH2-, ❹ 108 201016751 /xi MAX (XII) (XIII) In the formula (XII) and the formula (XIII), R9 is an alkyl group having 1 to 30 carbon atoms, and any -CH2- in the alkyl group may be _0-, -CH=CH _ or -C=C-substituted; R1() is an alkyl group having a carbon number of 6 to 22; R11 is an alkyl group having a carbon number of 1 to 22; and A7 is independently -Ο- or a carbon number of 1 to 6 Alkylene; A8 is a single bond or an alkylene group having a carbon number of 1 to 3; ring T is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1, 109 201016751 h2n—χ—nh2 h2n id h2n nh2 Nh2 h2n (I) (II) (HI) (IV) h2n Nh2 h2n H2n / R33 H2N—A3—h-Si—O l I \ R34 —NH, (V) (VI) (VII) R33 Si—A3- I R34 (XV) In the formulae (I) to (VII) and (xv), x is a linear alkylene group having a carbon number of 2 to 12; Y is independently a single bond, _ 〇_, _c〇_,, , N(CH3)_, -CONH·, -NHCO-, ·〇(〇:Η3)2-, -C(CF3)r, -0-(CH2)t-〇-, _S-, -SS-, -S02-, -S-(CH2)rS- or a linear alkylene group having a carbon number of 1 to 12, t is an integer of 1 to π; z1 and z2 are hydrogen, and when Y is -NH-, -N ( When CH3)-, -CH2-, -C(CH3)2- or _C(CF3)2_, Z1 and z2 may be bonded to each other to form a single bond; ring D is a phenylene group or a 1,4-aza-a hybrid Cyclohexyl, R33 and R34 are each independently a C 1 to 3 alkyl group or the group 'A is independently a carbene group having a carbon number of 1 &lt; 5 , a phenylene group of 110 201016751 or an alkyl group substituted a phenylene group; m is an integer of 1 to 10; any hydrogen of a cyclohexane ring or a benzene ring may be fluorine, methyl, _〇H, -COOH, -SOsH, -P〇3H2, benzyl or hydroxybenzyl Substituted. Φ 11. The liquid crystal alignment agent according to claim 9, wherein the diamine represented by the formula (N) is a formula (N-1) to a formula (N-5), and a formula (N- 7) a diamine represented by the formula (8), formula (N_13), formula (n-15) or formula (n-16), wherein the diamine having a side chain group is a formula (VIII_2)' (VIII4) a diamine represented by the formula (VIII_6), the formula (XII-2), the formula (XII-4) or the formula (?π_6), and the second saddle having no side bond group is a formula (Γ/· 1), Formula (Ιν·2), Formula (IV-15)~Formula (IV_17), Formula (V-1)~Formula (V_12), Formula (ν·33), Formula (V-35)~Formula (10) ), formula (4), formula (VII: VII: the diamine represented by _, ❹ 111 201016751 (N-1) (N-2) (N-3) In these formulas, Me means methyl, 112 201016751 «Ά / i / ^ΛΙ·£ (VHI-6) R30 In these formulas, R23, R29 and R3G are each an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. (iv-1) 113 201016751 _ _ . - A--- (4) (V-2) (V^3) (V-10) Hz NH2 (V-11) (\M2) (V-33) 114 201016751 / 1 / JjAlf servant H: CH3 (V-36) H2N (V-35) I (V-37) H2nK3 points (VI-7) NH2 (VII-2) nh2 ch3 ch3 H2N-C3H6-A-〇-Si-c3H6-NH2 ch3 ch3 (XV-1) 〇 12. The liquid crystal alignment agent according to claim 10, wherein the diamine represented by the formula (N) is a formula (N-1) to a formula (N-5), and a formula (N-7) a diamine represented by the formula (Ν8), a formula (Ν·13), a formula (N-15) or a formula (N-16), wherein the diamine having a side chain group is a formula (VIII-2), a diamine represented by the formula (viii-4) to the formula (VIII-6), the formula (XII-2), the formula (XII-4) or the formula (XII-6), and the diamine having no side chain group It is a formula (IV-1), a formula (ιν-2), a formula (IV-15) to a formula (IV-17), a formula (V-1) to a formula (V-12), and a formula (V-33). , a diamine represented by the formula (V-35) to the formula (V-37), the formula (VI-7), the formula (VII-2) or the formula (XV-1), 115 201016751 ± In these formulas, Me means methyl, 116 201016751 / 1 /pi/ Φ (νΐΙΙ-5) (VIII-6) R30 R30 In these formulas, R23, R29 and R3Q are each an alkyl group having 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, H2N-Q&gt;-NH2 (IV-1) 117 201016751 (V-1) (V-2) (V-3) (V-10) H2 Nh2 (V-11) (V-12) (V-33) 118 201016751 / 1 /pij[ (V-37) h2n^^〇-〇-叫(VI-7) 参h2n^0x^0^ch2^0^0_nh2 (VII-2) ch3 ch3 H2N-C3H6-Si-〇-Si-C3H6-NH2 The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride and an aromatic A mixture of tetracarboxylic dianhydrides other than the ones. The liquid crystal alignment agent according to claim 13, wherein the aromatic tetracarboxylic dianhydride is selected from the group consisting of formula (1), formula (2), formula (5) to formula (7). At least one of the group of compounds represented by the formula (11) and the formula (14), 119 201016751 ο 15= The liquid crystal alignment agent according to the item [51] of the patent application, wherein two of the tauic acid compounds are represented by the formula (1). The liquid crystal aligning agent according to claim 13, wherein the aliquot of the alicyclic alicyclic acid and/or the aliphatic tetracarboxylic dianhydride. 17. The liquid crystal alignment agent according to the invention, wherein the aromatic tetracarboxylic dianhydride is selected from the group consisting of formula (1), formula (2), and formula (5). The compound group represented by the formula (11) and the formula (14) has a small amount/species, and the tetracarboxylic dianhydride other than the aromatic group is selected from the formula (19), the formula (23), and the formula. (25), at least one of the group of compounds represented by the formula (35) to the formula (39), the formula (44), and the formula (49), 120 201016751 18. The liquid crystal alignment agent according to claim 17, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula ,), and the tetradecanoic acid other than the aromatic The dianhydride is a compound represented by the formula (19). The liquid crystal alignment agent according to claim 1, wherein the liquid crystal alignment agent further contains a compound selected from the group consisting of an alkenyl-substituted nadic ylidene compound and a radical polymerizable unsaturated double bond, At least one compound of an anthracene compound, an oxazoline compound, and an epoxy compound. A liquid crystal alignment film which is formed by heating a coating film of a liquid crystal alignment agent according to any one of claims 1 to 19. 21. A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and aligning the liquid crystal molecules in a predetermined direction A liquid crystal alignment film characterized in that the liquid crystal alignment film is a liquid crystal alignment film according to claim 20 of the patent application. 122 201016751 IV. Designated representative circle: (1) Designated representative figure of the case: None (2) Simple description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best describes the characteristics of the invention: 4