TW201100463A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

A liquid crystal alignment film demands important properties, such as ion density, to enhance display quality of a liquid crystal display device. If the ion density is high, a voltage applied to the liquid crystal in a frame cycle is decreased, with a result that the brightness is decreased and an obstacle to displaying a gray scale normally occurs. Besides, even an initial density is low, the result caused by ion density increase after a high temperature accelerate test (long period stability) is bad. The ion density of the liquid crystal device formed by using the liquid crystal alignment agent of this invention is low, and the long period stability is excellent. The liquid crystal alignment agent includes a polyamic acid obtained by reacting a specific diamine including a piperazine ring in its molecular or a mixture of the specific diamine and other diamine with at least two of tetracarboxylic dianhydrides at 70 to 200 DEG C.

Description

201100463 6. DISCLOSURE OF THE INVENTION: TECHNICAL FIELD The present invention relates to a liquid crystal alignment agent comprising polyamic acid obtained by reacting a diamine and a tetracarboxylic dianhydride. ). Further, the present invention relates to a liquid crystal alignment film obtained from the liquid crystal alignment agent and a liquid crystal display element comprising the liquid crystal alignment film. [Prior Art] The liquid crystal display element is used for a viewfinder of a video camera typified by a monitor (n〇teb〇〇k personal computer) and a desktop computer (monitor) ( Among various liquid crystal display devices such as a view finder and a projection display, they have recently been used for televisions. Further, the liquid crystal element is also used for an optical optical head (optical printer head), an optical F〇urier transf〇rm element, and an optoelectronic (Pt〇electr〇nics) related element such as an electric bulb. Various elements are known in the liquid crystal display element, and the development of the liquid crystal display element is achieved not only by the driving method of the liquid crystal display element and the structure of the liquid crystal display element but also by the improvement of the constituent members used in the liquid crystal display element. The liquid crystal display element generally includes a liquid crystal alignment film for aligning the liquid crystal composition in the liquid crystal layer to 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. As the liquid B display element is still quality, the role of the liquid crystal alignment film becomes important year by year. The liquid crystal alignment film is formed using a liquid crystal alignment agent. At present, a liquid a 曰 alignment agent mainly used is a solution obtained by dissolving polyglycine or soluble polyimine 201100463 (J^lyimide) in an organic solvent. The liquid crystal alignment film is formed by applying such a solution onto a substrate and then forming a film by heating or the like. The important characteristics required for the liquid crystal alignment film in order to improve the display quality of the liquid crystal display element include an ion density. If the ion density is high, the voltage applied to the liquid crystal in the frame period is lowered, and as a result, the brightness is lowered to cause an obstacle to the normal gradation display. In addition, even if the initial zero ion mobility is low, the ion density (long-term reliability) after the accelerated temperature test is not good. Attempts to solve the above problems, for example, a polyphthalic acid composition containing two or more polylysines having different physical properties in combination for forming a liquid crystal alignment film is known (for example, refer to Japanese Patent Laid-Open Publication No. U-i93345 and Japanese Patent No. Japanese Patent Laid-Open No. Hei 11-193347). On the other hand, a liquid crystal alignment agent for forming a film having a high imidization ratio even at a low temperature is known to contain a diamine having a divalent organic group containing a basic nitrogen atom such as pyridazine and A liquid crystal alignment agent obtained by reacting tetrakisperic acid dianhydride to obtain a chitosan acid (for example, refer to Japanese Laid-Open Patent Publication No. Hei 9-194725). Further, poly-proline which is obtained by reacting an aromatic diamine containing a nitrogen atom with a tetra-retensive dianhydride and its thermal properties are known (for example, see j〇urnal of Polymer Science: Part A: Polymer Chemistry, vol. 30, pl099-1102 (1992)). However, in the liquid crystal alignment agent obtained by these prior art, there is still room for further research on the problem of reduction in ion density. [Exposure of the Invention] An object of the present invention is to provide a liquid crystal display element having low ion density and excellent long-term reliability, and a liquid crystal alignment film imparting characteristics to the liquid crystal display element, and a liquid crystal for forming the liquid crystal alignment film. An alignment agent, a polymer used in the liquid crystal alignment agent, and a diamine which is a raw material of the polymer. The present inventors used a composition containing poly-aracine for a liquid crystal alignment agent, which is an aliphatic diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group, and two types. The above tetrazoic acid dianhydride is used as a raw material. As a result, it was found that the liquid crystal display element including the liquid crystal alignment film formed of the liquid crystal alignment agent exhibits a low ion density and is excellent in long-term reliability. Further, it has been found that the liquid crystal alignment agent has excellent storage stability, thereby completing the present invention. The liquid crystal alignment agent of the present invention is shown in the following item [1]. [1] A liquid crystal alignment agent comprising polylysine, which is a diamine represented by the formula (N) or a mixture of the diamine and another diamine, and at least two tetracarboxylic dianhydrides. Polylysine obtained by carrying out a reaction at 70 to 20 (TC).

H2N - γ1 - N N - Y2 - NH (N) In the formula (N), Y1 and Y2 are independently a single bond or a linear alkyl group having 1 to 7 carbon atoms. [Effect of the Invention] 201100463 It is possible to obtain a composition of polylysine or a derivative thereof obtained by reacting a diamine and a tetracarboxylic dianhydride which are preferred embodiments of the present invention for a liquid crystal alignment agent. A liquid crystal alignment agent with high stability is stored. The liquid crystal display element including the liquid crystal alignment film which is aligned with the liquid 曰 sa exhibits a low ion density and is excellent in long-term reliability. The above and other objects, features and advantages of the present invention will become more <RTIgt; ® [Embodiment] The terms used in this manual are explained. The diamine represented by the formula may be simply referred to as a diamine (N) t &gt; the diamine represented by another chemical formula may be abbreviated as such. The tetracarboxylic acid two needle represented by the formula (丨) is sometimes simply referred to as an acid anhydride (1). The tetracarboxylic acid bismuth represented by other chemical formulas is sometimes abbreviated as such. "(Meth)acryloxy" is a general term for acryloxy and decyl propylene oxime. "(Mercapto) acrylate" is a generic term for acrylate and methacrylate, "(meth)acrylic acid." It is a general term for acrylic acid and mercaptopropionate. 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. Further, for example, the expression "arbitrary A may be replaced by B, C or D" means that at least one A may be replaced by B, at least one a may be replaced by c, at least one A may be replaced by D, and a plurality of a It can be replaced by at least two of b~D. Among them, the case where a plurality of consecutive -CH2· is substituted by the same group is not included. The substituent having an unclear bonding position with the carbon constituting the ring means that the bonding 7 201100463 position is free in the range of chemically no problem. In the chemical structural formula, a group in which a character (for example, D) is surrounded by a hexagon means a group of a ring structure (ring D). The case where the same symbols are used in a plurality of chemical formulas means that the groups have the same definition range, but it does not mean that they must be the same group in all chemical formulas at the same time. It may be the same group in a plurality of chemical formulas, or may be a different group in each chemical formula. The present invention is composed of the above item [1] and the following items [2] to [17]. [2] The liquid crystal alignment agent according to [1], wherein the Y1 and Y2 are a triacene group. [3] The liquid crystal alignment agent according to [1] or [2] wherein the other diamine is a diamine having a side chain group selected from the group consisting of formula (VIII) and formula (X) to formula (XIII) At least one of the diamine groups represented.

In the formula (VIII), A3 is a single bond, _〇_, -CO-, -COO-, -OCO-, _CONH·, -CH2〇-, _CF2〇-, or an alkylene group having 1 to 6 carbon atoms. Any of the -CH2- in the group can be substituted by 〇---CH=CH- or -CeC-; R1 is a group having a ster〇id skeleton, an alkyl group having a carbon number of 3 to 30, Any of a phenyl group having an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms as a substituent, or a group represented by the formula (IX), and an alkyl group having a carbon number of 3 to 30, which is 201100463 - CH2· may be replaced by -Ο-, -CH=CH- or _ς:Ξ〇;

In the formula (IX), 'A4 and A5 are independently a single bond, COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, or a carbon number. 1 to 3 of alkoxy; ring b and ring c are independently 1,4-phenyl or 1,4-cyclohexylene; R 2 and R 3 are independently fluoro or fluorenyl, and f and g are independently 0, 1 or 2; c, d and e are independently an integer of 0 to 3, and their total is 1 or more; R4 is a carbon number of 1 to %, an alkoxy group having 1 to 30 carbon atoms, or Alkoxyalkyl group 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· may be substituted by a di-i-methyl group;

9 (XI) 201100463

R7 奋〇_a6^^NH2 R8 In the formula (X) and formula (XI), R5 is independently hydrogen or methyl; R6 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms R7 and R8 are independently an alkyl group having 1 to 20 carbon atoms or a phenyl group; A6 is independently a single bond, -CO- or -CH2-;

(XII) (XMI) In the formula (XII) and the formula (XIII), R9 is a methyl group or an alkyl group having 2 to 30 carbon atoms, and any -CH2- of the alkyl group may be -0-, -CH=CH- Or -CeC-substituted; R1g is an alkyl group having 6 to 22 carbon atoms; R11 is an alkyl group having 1 to 22 carbon atoms; 10 201100463 A7 is independently -Ο- or a carbon number of 1 to 6; a single bond or an alkyl group having a hindrance of 1 to 3; the ring T is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is hydrazine or 1. [4] The liquid crystal alignment agent according to [3], wherein the other diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4) to formula (VIII-6), and formula (ΧΠ-2) And at least one of the diamines represented by the formula (XII-4) and the formula (ΧΠ-6).

H2n

R23 (VIII-4) h2n

(XII-2) (XIW) 201100463 R30

In the above formula, R23, R29 and r30 are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. [5] The liquid crystal alignment agent according to [1] or [2] wherein the other diamine is a diamine having a side chain group selected from the group consisting of formula (VIII) and formula (X) to formula (XIII) At least one of the diamine group represented by the group and the diamine having no side chain group, that is, at least one selected from the group consisting of the diamine groups represented by the formulae (I) to (VII) and (XV) mixture.

In the formula (VIII), A3 is a single bond, -〇-, -CO-, _COO-, -OCO-, •CONH·, -CH20-, -CF2〇-, or an alkylene group having a carbon number of 1 to 6, Any -CH2- in the alkylene group may be substituted by -〇-, -CHCH- or -CeC-; R1 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 3 fluorene, and having a carbon number of 1 to 30. An alkyl group or a phenyl group having 1 to 30 carbon atoms and a phenyl group as a substituent, 12 201100463 or a group represented by the formula (IX), and any -CH 2 - in the alkyl group having 3 to 3 Å carbon atoms may be - 〇-, _CH=CH4_CsC substituted;

In the formula (IX), 'A4 and A5 are independently a single bond, -〇-, -COO-, -OCO-, -CONH-, an alkylene group having a carbon number of 1 to 4, and an alkylene oxide having a carbon number of 丨3. a radical or an alkylene group having 1 to 3 carbon atoms; the ring b and the ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R2&amp;R3 is independently a fluorine or a methyl group, f And g is 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 1 to 3 carbon atoms and a carbon number of 1 to 30; An alkoxy group or an alkoxyalkyl group having 2 to 30 carbon atoms, wherein any of the alkyl, alkoxy and alkoxyalkyl groups may be substituted by fluorine, and any -CH 2 may be difluoro Substituted by thiol;

13 (XI) 201100463

R7^)~〇-a6^JNH2 R8 In the formula (X) and formula (XI), R5 is independently hydrogen or a fluorenyl group; R6 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms; R7 and R8 are independently an alkyl group having 1 to 20 carbon atoms or a phenyl group; A6 is independently a single bond, -CO- or -CH2-;

Nh2 (XII) (XIII) In the formula (XII) and formula (XIII), R9 is a methyl group or an alkyl group having 2 to 30 carbon atoms, and any -CH2- of the alkyl group may be -0-, -CH=CH - or -CeC-substituted; R1g is an alkyl group having 6 to 22 carbon atoms; R11 is an alkyl group having 1 to 22 carbon atoms; 14 201100463 A7 is independently -Ο- or an alkylene group having 1 to 6 carbon atoms; A8 a single bond or a C 1 to 3 alkyl group; ring T is 1,4-phenyl or 1,4-cyclohexylene; h is 0 or 1;

H2n (I) (II) (III)

Nh2 (IV)

In the formulae (I) to (VII) and (XV), X is a linear alkylene group having 2 to 12 carbon atoms; Y is independently a 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)t_S- or a linear alkylene group having a carbon number of 1 to 12, t is an integer from 1 to 12; when Z1 and Z2 are 氲, 15 201100463 and Y is -NH-, -N(CH3) When -, -CH2-, -C(CH3)2- or -C(CF3)2-, they may be bonded to each other to form a single bond; ring D is a phenyl or piperazine-1,4-diyl group; R33 and R34 are independently an alkyl group having 1 to 3 carbon atoms or a phenyl group; and A3 is independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group-substituted phenyl group; m is 1 to 1 An integer of hydrazine; any hydrogen of the cyclohexane ring or the benzene ring may be substituted by fluorine, fluorenyl, trifluoromethyl, -OH, -COOH, -S〇3h, _p〇3h2, a benzyl group or a hydroxybenzyl group. Α [6] The liquid crystal alignment agent according to [5], wherein the straight female __ bite is selected from the group consisting of (vm-2), (vm-4)~ (vm_6; ! (XII-) 4) and at least one of the diamines represented by formula (XII-6), and selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15) to formula (IV_17; /, Formula (V-1) to Formula (V-12), Formula (V-33), Formula (V_35) to Formula (v_37), Formula (VI-7), Formula (VII-2), and Formula (XV-1) a mixture of at least one of the diamines represented.

16 201100463

R23 h2n (VIII-6)

R30

(XII-6)

NH2 H2N-j^jpNH2 (IV-2)

(IV-17)

17 201100463

CHq

CH 丨 3 (VII-2) H2N—〇3Ηρ-Si_0_S Bu C3H6—NHg CH3 ch3 (XV-1) »29 • 30 In these formulas, R23, Rzy and R3U are independently alkane with a carbon number of 1 to 30. . Base, or a methoxy group having a carbon number of 1 to 30. [7] The liquid crystal alignment agent according to [1], wherein the poly-aramidic acid is a mixture of two polyamic acids: at least one selected from the group consisting of diamines represented by formula (N) a mixture of at least one selected from the group consisting of a diamine having a side chain group according to the item [3], which is selected from the group consisting of the formula (VIII) and the diamine group represented by the formula (X) to the formula (XIII), and a polylysine obtained by reacting four retinic dianhydrides; and the diamine having no side chain group according to [5] is selected from the group consisting of formula (I) to formula (VII) and formula (XV) a mixture of at least one of the represented diamine groups, or at least one of the diamines having no side chain groups, and at least one selected from the group consisting of diamines represented by formula (N), and tetracarboxylic acid The polyamic acid obtained by the reaction of the dianhydride. [8] The liquid crystal alignment agent according to [1], wherein the polyamic acid is a mixture of two polylysines: a group of diamines selected from the group consisting of formula (N) The at least one diamine having a side chain group according to [3], which is at least one selected from the group consisting of formula (VIII) and formula (X) to formula (XIII), and according to [ The quinone diamine having no side chain group described in 5 item, that is, a mixture selected from at least one of the group consisting of the diamine groups represented by the formulae (I) to (VII) and (XV), and four a polylysine obtained by reacting a carboxylic acid dianhydride; at least one of at least one of the diamine having no side chain group or the diamine having no side chain group and at least one selected from the group consisting of formula (N) A mixture of at least one of the indicated diamine groups and a polylysine obtained by reacting tetrahydrogen di liver. [9] The liquid crystal alignment agent according to [1], wherein the polyamic acid is a mixture of two polylysines selected from the group consisting of 201100463 diamine represented by the formula (N) a mixture of at least one selected from the group consisting of a diamine having no side chain group according to [5], that is, at least one selected from the group consisting of formula (I) to formula (νπ) and formula (XV) a polylysine obtained by reacting with a tetrakis acid group; the diamine having a side chain group according to [3], which is selected from the group consisting of formula (VIII) and formula (X) to formula (XIII) a mixture of at least one of the diamine groups represented by the group or at least one of the diamines having a side chain group and at least one of the diamines having no pendant group, and four resorcinic acid A mixture of polylysines obtained by the reaction of an anhydride. [10] The liquid crystal alignment agent according to any one of [1], wherein the at least two tetracarboxylic dianhydrides are aromatic tetracarboxylic dianhydrides and tetrazoic acid other than aromatic a mixture of anhydrides. [11] The liquid crystal alignment agent according to [10], wherein the aromatic tetracarboxylic dianhydride is a formula (1), a formula (2), a formula (5) to a formula (7), and a formula (17) At least one of the compounds represented. ο ο η λ 〇

[12] The liquid crystal alignment sword according to [11], wherein the compound is a compound represented by the formula (1). The liquid crystal alignment agent according to any one of [1] to [9], wherein the at least two of the four genus are of the formula (1), the formula (2), the formula (5) 4 (7), and the formula (1) 17) at least one of the aromatic tetranuclear anhydrides represented,

Four enemies other than the aromatics represented by the formula (19), the formula (23), the formula (25), the formula (35) to the formula (39), the formula (44), the formula (49), and the formula (68) a mixture of at least one of acid di livers.

(17) ❹

(38) (39) 21 201100463

[14] The liquid crystal alignment agent according to [13], wherein the tetracarboxylic dianhydride other than the aromatic is a formula (19), a formula (23), a formula (37), a formula (49), and a formula (49) 68) At least one of the compounds represented.

[15] The liquid crystal alignment agent according to [13], wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (1), and the tetrahydro acid dianhydride other than the aromatic compound is the formula (19). The compound represented. [16] A liquid crystal alignment film which is formed by heating a coating film of the liquid crystal alignment agent according to any one of [1] to [15].

[17] A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer formed between the substrates; an electrode for applying a voltage to the liquid crystal layer; and a liquid crystal alignment film according to [16]. 22 201100463 A polylysine obtained by reacting a mixture of the diamine (these) with another diamine not represented by the formula (N) and two or more kinds of tetracarboxylic dianhydride. The polyamic acid may be a derivative of polylysine or a mixture of polyamine and its derivative. The derivative of poly-proline can be exemplified by: a poly-imine obtained by completely performing a defoaming ring-closing reaction of poly-proline, and 2) a partial brewing obtained by partially performing a closed-loop reaction of poly-aracine. Imidized poly-aracine, 3) polyamine, 4) poly-proline-polyamine copolymer obtained by substituting a part of tetracarboxylic dianhydride into a dicarboxylic acid, 5) The polyamido-polyamine copolymer = a polyamidoguanamine obtained by subjecting a part or all of the dehydration ring-closure reaction. Preferred among these derivatives are polyiminimide and a part of the ruthenium iodide, ruthenium, and more preferably polyimine. In the present specification, "polyproline" is used as a general term for poly-proline and its derivatives, in addition to the examples. The diamine used in the present invention is a compound having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group represented by the following formula (N). H2N—Y1—^—Y2—NH 2 ( N ) In the formula (N), Y 1 and Y 2 are independently a single bond or a linear alkyl group having a carbon number of 7. Examples of the diamine (N) are listed below. 23 201100463 H2M'~|sj--nh2 H2N-H2C-NN-CH2-NH2 (N-1) (N-2) H2N-~~(-ch2]^-nh2 h2n-(-h2c^-(-CH2 -)^—NH2 (N-3) (N-4) H2N--|h2C-)--N^^n_|CH2^_Nh2 H2N-fH2C^-N^^N-(cH2)j-NH2 (N -5) (N-6) h2n-(-h2c-)~-_^n-(-ch2)^-nh2 h2n-{-h2c·}^-^n-^-CHz-)^-NH2 ◎ ( N-8) (N-7) Among these diamines, 'diamines (N-3) and (N-4) are preferred, and diamines (N-4) are more preferred. The raw material diamine in the case of producing the polyamic acid used in the liquid crystal alignment agent of the present invention may be at least one diamine selected from the group consisting of diamine (N), and may further contain other than the diamine. At least one of the other diamines. That is, the ratio of the use of the diamine in the diamine (N) group as the proportion of the diamine raw material used for the tyrosine acid is i mole % ~ brother %: preferably i Ear %~50 mol%, more preferably 5 mol%~ buckle = , % ° By making the diamine (8) the said use ratio, the ion density of the page can be reduced, and can be maintained for a long time. Low ions; Moreover, the liquid crystal alignment agent exhibits high storage stability. When other diamines can be divided into two types according to their structures, the skeleton linking the two amino groups is regarded as the main chain, and the i-diamine will be the base of the autonomous chain branching, ie, the diamine of the side chain group. And a diamine having no side chain groups. By reacting a diamine having a side chain group and a tetracarboxylic dianhydride, a polylysine having a plurality of side chain groups in the main chain of the polymer is obtained. When such a polyamic acid having a side chain group to the polymer main chain is used, the liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer can enlarge the pretilt angle in the liquid crystal display element. Namely, the side chain group is a group having an effect of expanding 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 thereof include an alkyl group having 3 or more carbon atoms and a carbon number of 3

The above alkoxy group, an alkoxyalkyl group having 3 or more carbon atoms, and a group having a steroid skeleton. A group having one or more rings and having a ring having a carbon number of 丨 or more, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as a substituent may also have Effect of side chain groups = The side chain groups in the present invention are selected from these groups. In the following description, the diamine having a side chain group may be referred to as a side chain type diamine. Further, the diamine having no side chain group may be referred to as a non-side chain type diamine. Moreover, by appropriately using the side chain type diamine and the non-side chain type diamine, it is possible to give a pre-dip, which is necessary for each of the surface elements, in a twisted nematic (Twisted Nematic ' The TN) method and the Vertical Alignment (VA) method are necessary to represent the larger angles of the 'should'. Therefore, the side chain type is mainly used. At this time, in order to control the angle of the turn, it can be used in combination. Non-side chain type. The blending ratio of the non-side chain type diamine to the side chain type diamine can be determined according to the angle of the angle. Of course, by appropriately selecting the side chain group, it is also possible to use a side chain type diamine. Such as horizontal electric field switching 25 201100463

In the transverse electric field method such as the Switching 'IPS) method, since the pretilt angle is small and high liquid crystal alignment is necessary, at least one of non-side chain 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 side chain groups are as follows. First, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, an alkenylcarbonyl group, an alkenyl group may be mentioned. A carbonyloxy group, an alkenyloxycarbonyl group, an alkenylaminocarbonyl group, an alkynyl group, an alkynyloxy group, an alkynylcarbonyl group, an alkynylcarbonyloxy group, an alkynyloxycarbonyl group, an alkynylaminocarbonyl group or the like. Further, the alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having 3 or more carbon atoms. However, the alkoxyalkyl group may have a carbon number of 3 or more as a whole. Further, these groups may be linear or branched. Next, the terminal ring has an alkyl group having a carbon number of 丨 or more, an alkoxy group having a carbon number of j or more, or an alkoxyalkyl group having a carbon number of 2 or more as a substituent, and examples thereof include a phenyl group and a phenylalkyl group. , phenylalkoxy, phenoxy, phenylcarbonyl, phenylcarbonyloxy, phenoxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexyl , cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexyloxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis( Cyclohexyl) phenyl (1⁄4 hexyl)phenyl phenyl, bis(cyclohexyl)oxy, bis(cyclohexyl) phenoxy, and cyclohexyl bis(phenyl)oxy (10) base. Further, a ring assembly group which is a group having two or more cyclohexane rings having two or more benzene rings, or a group based on the above, and the bonding group is independently a single bond,伸_, -COO-, ·〇〇)_, _C〇NH_ or a carbon number of 3, and the terminal ring has a carbon number of 1 or more, a fluorine number-substituted alkyl group having a carbon number of 丨 or more, A carbon number of 1 or more, or a fluorene-containing oxy-methyl group as a substituent. Of course, a group having a steroid skeleton is also effective as a side chain group. Preferred examples of the side chain type diamine are the diamines represented by the formula (VIII) and the formula (x) to the formula (XIII).

In the formula (VIII), A3 is a single bond, 〇, _c〇-, _C00-, -OCO-, -CONH-, -CH2〇-, -CF2〇-, or an alkylene group having a carbon number of 1 to 6, Any -CH2· in the extended alkyl group may be substituted by -Ο-, -CH=CH- or -C=C-. Preferred examples of Ο A3 are a single bond, -〇-, -COO-, -OCO-, -CH20-, and an alkylene group having a carbon number of 1 to 3, and a particularly preferable example is a single bond, _〇_, _CC ) a&gt;, -OCO-, -CH20-, -CH2-, and -CH2CH2-. The rule 1 is a group having a steroid skeleton, an alkyl group having 3 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms as a substituent, or a formula (IX) The group represented by the above-mentioned -CH2- of the alkyl group having 3 to 30 carbon atoms may be substituted by -〇-, -CH=CH- or -C-C-. Preferable examples of R1 are a carbon group having a carbon number of 3 to 30, a alkyl group having a carbon number of 1 to 30 or an alkoxy group having a carbon number of 1 to 30 as a phenyl group having a substituent of 27 201100463, and a formula (ι) The base of the representation. The bonding position between the two amino groups and the benzene ring is preferably 3 bits =, a bit or 2 positions and 5 positions when the bonding position of A3 is set to 1 position. 〃 5

In the formula (IX), A4 and A5 are independently a single bond, _〇_, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, an alkyloxy group having a carbon number of 丨3, or The alkyleneoxy group having 1 to 3 carbon atoms is preferably a single bond or a stretching group having a carbon number of 〜4. Ring B and Ring C are independently 1,4 to phenyl or hexyl. R2 and R3 are independently fluorine or methyl. f and g are independently 〇, ^ or 2, preferably 〇. c, d &amp; e are independently integers of 〇 〜 3, and their total is 1 or more. R4 is an alkyl group having a carbon number, an alkoxy group having a carbon number of 丨~邛, or a green nucleus having a carbon number of 2 to 3 G, and (4) a silk, an alkoxy group; a methoxy group, and any hydrogen may be substituted by fluorine. And, any _&amp; can be substituted by a difluoro-subunit. A preferred example of r4 is the carbon number. A mercapto group and an alkoxy group having 1 to 30 carbon atoms. U's sink

28 201100463 (XI) ❹ CX) and ι ’ "" are independently hydrogen or methyl. It is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Han 7 and R 8 are independently an alkyl group or a phenyl group having a ratio of 1 to 20 carbon atoms. A6 is independently two-CO- or _ch2·. In the formula (X), it is preferred that one of the two "NH2_phA6" bonds to the 3 position of the steroid skeleton, and the other is bonded to the 6-position, and the positions of the two amino groups and the benzene ring are preferably relative to The bonding position of a6 is a meta or para position. In the formula (5), the two "called a bond between A and the ring are better."

For the meta or alignment. In addition, the two stupid lugs are better than the combined positions.

(ΧΠ) 29 201100463

(XIH) 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 substituted by -0, -CHCH- or -CeC-. R1G is an alkyl group having 6 to 22 carbon atoms, and R11 is an alkyl group having 1 to 22 carbon atoms. A7 is independently -0- or an alkylene group having 1 to 6 carbon atoms. A8 is a single bond or an alkylene group having 1 to 3 carbon atoms. Ring T is 1,4-phenylene or 1,4-cyclohexylene. h is 0 or 1. In the formula (XII), the bonding positions of the two amino groups and the benzene ring are preferably in the meta or para position with respect to the bonding position of A7. In the formula (XIII), the bonding positions of the two amino groups and the benzene ring are preferably in the meta or para position with respect to the bonding position of A7. Specific examples of the diamine (VIII) are listed below. 30 201100463

In the formula (VIII-1) to the formula (VIII-ll), 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 a carbon number. 5 to 25 alkoxy groups. 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. 31 201100463

H2n

(VIIM6) (VIIM7)

In the formula (VIII-12) to the formula (VIII-17), R25 is an alkyl group having 4 to 30 carbon atoms, 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. ϋ 32 201100463 h2n&gt;. Servant 27 h2n h2n h2n (VIII-18) H2N H2N H2N h2n (VIII-20) (VIII-21) 〇 h2n h2n h2n h2n (VIII-22) (Vlli-23) H2N 〇 Servant 27 h2n (VIII-24) H2N 〇 M ,c 〇 ,0

R27 h2n (VIII-25) H2N 〇 h2n

R27 (VIII-26) H2N o 0 heat 28 h2n (Vlll-27) H2N 〇 f, h2n o

R27 (VIII-28) 33 201100463 H2N 0 h2n k h2n h2n (VIII-29) h2n 0 \ ο

(VHI-30)

H2N h2n (VIII-31) »28 (VIII-32)

H2n h2n (VIII-33) (VIII-34) H2N 〇 h2n H2N o 27 &gt;=\^ /^_f h2n

»28 (VIII-36) (VIII.35)

Ch3 ch3 SKO-Si-R27 CH3 ch3 (VIII-37) 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. It is preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. R28 is hydrogen, fluorine, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -C3N, -OCH2F, -OCHF2 or -OCF3, preferably an alkyl group having 3 to 25 carbon atoms. Or an alkoxy group having a carbon number of 3 to 25. 34 201100463

Among the diamines (VIII-1) to diamines (VIII-43), preferred are diamines (VIII-1) to diamines (VIII-11), more preferably diamines (VIII-2) and Amine (VIII-4) to diamine (VIII-6). Specific examples of the diamine (X) are listed below. 35 201100463

Specific examples of the diamine (χι) are listed below. ❹ 36 201100463

37 201100463

38 201100463

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

39 201100463

40 201100463 R30

R30

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 a carbon number. 3 to 30 alkoxy groups. 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 a carbon number. 3 to 30 alkoxy groups. Specific examples of the diamine (XIII) are listed below. 41 201100463

(XIII-3) In the formula (XIII-1) to the formula (XIII-3), R31 is an alkyl group having 6 to 22 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms. R32 is an alkyl group having 1 to 22 carbon atoms, and preferably an alkyl group having 1 to 10 carbon atoms. In a specific example of the side chain type diamine, preferred are diamine (VIII-2), diamine (VIII-4) to diamine (VIII-6), diamine (XII-2), and diamine ( ΧΠ-4) and diamine (XII-6). The side chain type diamine as described above is for the purpose of exhibiting a large pretilt angle in the liquid crystal display element, and when the polymer used for the liquid crystal alignment agent of the present invention is produced, the side chain type II is preferably used. The ratio of the amine in the total amount of the diamine is set to 1 mol% to 9 mol%, more preferably 5 mol% to 7 mol%, as described above, the diamine having no side chain group as described above is Preferable examples of the non-side chain type diamine include compounds represented by the formulae (1) to (VII) and (XV). 42 201100463

〇 In these formulas, hydrazine is a linear alkylene group having 2 to 12 carbon atoms. γ is independently a single bond, ·0, -CO-, -ΝΗ-, -N(CH3)-, -CONH-, -NHCO-, -C(CH3)2-, _C(CF3)2-,-0 -(CH2)r0-, -S-, -SS-, -S02-, -S-(CH2)tS- or a linear stretching group having a carbon number of 1 to 12, and t is an integer of 1 to 12. When Z1 and Z2 are hydrogen and Y is -NH-, -N(CH3)-, -CHr, -C(CH3)2- or -C(CF3)2-, they may be bonded to each other to form a single bond. Ring D is a phenyl or 1,4-diaza heterocyclohexyl group. 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, a strepto group or a phenyl group substituted by an alkyl group. m is an integer of 1 to 10. 43 201100463 Any hydrogen of the cyclohexane ring or the benzene ring may be substituted by fluorine, sulfhydryl, -OH, -COOH, -S03H, -Ρ03Η2, benzyl or hydroxybenzyl. Examples of the diamine (I) are listed below. H2n(ch2)2nh2 h2n(ch2)4nh2 h2n(ch2)6nh2 (1-1) (I-2) (I-3) Specific examples of the diamine (II) are listed below. h2N^_NH2 h2n^-nh2 (11-1) (II-2) Specific examples of the diamine (III) are listed below.

Specific examples of the diamine (IV) are listed below. 44 201100463 H2N~〇~' NH, H2N^QpNH2 ch3 h2n NH2 CH:

2 H3C (IV-4)

H2N—^ NH (IV-1) (IV-2) (IV-3)

OH

COOH h2n-^-nh2 Λ H2N,v, NH: (IV-6) H2N ^ 'NH7 (IV-8)

HOOC H2N- —NH2 (IV-9)

SO3H

h2nT nh2 JL h2n

(IV-7) H03S

Nh2 (IV-11) (IV-10)

Cf3

(IV-17) h2n nh2

Specific examples of the diamine (V) are listed below. 45 201100463

(V-10) (V-11)

(V-12)

46 201100463 h2n

Nh2 (V-13) H2N^^|QpNH2

(V-15) (V-14)

(V-16) (V-17) H2NHQr〇'^^〇O^NH2 H2N^Qk°--^—0-0^^ (V-18) (V-19)

H2N^Q&quot;°^^0x&lt;Q-NH2 H2N-QrS-&lt;Q^NH2 (V-20) (V-21) Η2Ν_ΗΟ_δ~8_&lt;0^ΝΗ2 h2N_h〇/S^s'O&gt;_nh2 (V -twenty three)

(V-22)

H2N

(V-26) \&lt;r I, (V-25) -NH2 (V-27) 47 201100463

H2N

(V-31) H2N_^〇^s〇2H0&gt;_ NH2 ch3 _/ J H2N-〇-〇^NH2 H3C CH3 f3c cf3 /=\ \/ /=\ h3c Η2ΝΛ_/^υ^ΝΗ2 H2NAJkyJ&gt;~nh: (V-28) (V-29) (V-30) (V-32) H0V /0H OH I OH h2nH0h ^Knh2 h〇-nh2 (V-33) (V-34) The following lists the diamines (VI) Specific examples.

(VI-1) (VI-2)

(VI-3)

(VI-4)

(VI-6) (VI-5) h2n

(V-35)

(V-36)

2 (V-37) 48 201100463 Specific examples of the diamine (VII) are listed below.冲~\_1 (V!M) (VII-2) h2n_〇^s^^ch2V〇^v〇~nh2 η2ν_〇^{^·〇η2^3^χ{Ι}~νΗ2 Ο ❹ (νΐΙ ·3) (VM-4) h3c ch3 Ν2Ν_^3^0^^κ^0&quot;'νη2 h2N^0^v0~0/x0~nh2 (Vll-S) (VII-6) f3c cf3 o ^rO^ QrQr—&lt;Y^y\^y^y^ (VII-7) (VII-8) Η2Ν~〇κ〇Ν{3^νζ^0χ{3-ΝΗ2 h2n_C^〇v^O^ch2^3C^ 0'^3~nh2 (Vlf-9) (VIMO) H2N~0^〇4CH2^Q^Q^NH2 H2N^Q^^fCH2^^^^~NH2 (VII-11) (VH-12) H3C CH3 2 jj h2n_〇^°'s〇^\^〇vGknH2 H2N~O^0n^jk^vO^°^O_nh2 ( VII-15) (VII-16) Specific examples of the diamine (XV) are listed below. 49 201100463 9h3 ch3 H2N-C3H6-Si-0-Si-C3H6-NH2 CH3 CH3 (xv-1) Among the non-side chain type diamines, diamines (IV-1) to diamines (IV- are preferred. 5), diamine (IV-15)~diamine (Iv_17), diamine (γ^)~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) , diamine (νπ-l)~diamine (VII-5) and diamine (XV-1), more preferably diamine (ΙλΜ), diamine (IV_2), diamine (IV-15)~2 Amine (ιν-17), diamine (VJ)~diamine (ν-12), diamine (V-33), diamine (γ·35)~diamine (ν_37), diamine (νΙ·7) , Diamine (VII-2) and diamine (XV-1). The non-side chain type diamine as described above preferably has a lower ion density in the liquid crystal display element. It is preferably a molar ratio in the total amount of the diamine which is a raw material of the polyamic acid in the liquid crystal alignment agent of the present invention. It contains 1% to 98%, more preferably 10% to 95%. As the diamine used in the present invention, a diamine other than the diamine to diamine (VIII), a diamine (X) to a diamine (xm), and a diamine (??) 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). Examples of the side chain type diamine other than the diamine (VIII) to diamine (?π) are diamine (oxime) to diamine (81). 201100463

In these formulas, R35 and R36 are each independently a calcined carbon of 3 to 3 Å. In the production of polyamic acid in the liquid crystal alignment agent of the present invention, these diamines can be used within the range which does not impair the effects of the present invention. In the production of poly-proline, substantially the molar amount of the tetracarboxylic dianhydride component and the diamine component are mixed in an organic solvent. At this time, the salt precipitates, but the reaction temperature is usually set to 70 ° c ~ 200 ° C, preferably 7 〇 t ~ 15 〇 t, more preferably 70 ° C ~ l 〇〇 ° C, the precipitate in the mixture will Dissolve and react straight

The reaction was continued until it became a homogeneous solution and then the temperature of the solution was lowered to room temperature. ^ V 51 201100463 When producing poly-proline, a monoamine can be added to the diamine. By adding a monoamine, it is possible to cause termination of the polymerization reaction in the formation of poly-proline, and it is possible to suppress the polymerization of the above polymerization reaction. Namely, the molecular weight of the obtained polymer (polyglycine or a derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The addition ratio of the monoamine may be appropriately adjusted in consideration of the molecular weight of the target poly(A). 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-thiolamine, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadesamine, n-heptadecane, ten people Base amine = and n-icosylamine. In the present invention, when a diamine and a tetracarboxylic dianhydride are reacted to obtain a valine acid, a mixture of 1 amine and another diamine selected from the group consisting of diamine (N) as described above may be used. In this case, one of the preferable examples of the other diamine is at least one of a side chain type diamine selected from the group consisting of diamine (VIII) and diamine (χ) to diamine (ΧΙΠ). Another preferred example of the other diamine is at least one selected from the group consisting of a diamine (VIII) and a diamine (χ) to diamine (ΧΠΙ) group, and a diamine (I). a mixture of at least one of the non-side chain type diamines in the diamine (VII) and diamine (XV) groups, wherein the items [3] to [6] are selected from the group consisting of diamines (Ν) Preferred examples of the combination of a diamine, a side chain type diamine, and a non-side chain type diamine. In the present invention, a polyaminic acid obtained by reacting a mixed diamine and a tetracarboxylic acid with 52 201100463 as a polymer component as described above may be used, and a mixture of polylysines having different raw materials may be used as a polymer component. One of the preferred examples of the mixture of polylysines is a mixture of two polylysines: at least one selected from the group consisting of diamines (N) and diamines (VIII) and two a mixture of at least ~ of the side chain type diamines in the amine (X) to diamine (XIII) group, or further added to the diamine mixture selected from the group consisting of two knees (I) to diamines (VII) and two a mixture of at least one of a non-side chain type dioxin in an amine (XV) group, and a poly-tantoic acid obtained by reacting a tetracarboxylic dianhydride; at least one of the non-side chain type diamines, Or a polylysine obtained by reacting at least one of the non-side chain type diamines with a mixture of at least one selected from the group consisting of diamines in the diamine (N) group and tetracarboxylic dianhydride. Another preferred example of the mixture of polylysines is a mixture of two polylysines: at least one selected from the group consisting of diamines in the diamine (N) group, and selected from the group consisting of diamines (I)~ a mixture of at least one of a diamine (VII) and a non-side chain type diamine in a diamine (XV) group, and a polyphthalic acid obtained by reacting a tetracarboxylic dianhydride; (VIII) and at least one of a side chain type diamine in the diamine (X) to diamine (XIII) group, or at least one of the side chain type one amine and at least one of the non-side chain type diamine The mixture is reacted with a tetracarboxylic dianhydride to obtain a polylysine. The above [7] to [9] describe a preferred example of a mixture of a polymer component of polyamic acid. At least two tetracarboxylic dianhydrides are used in the present invention. A preferred example of the tetracarboxylic dianhydride is a mixture of aromatic tetraphthalic dianhydride and a tetracarboxylic dianhydride other than aromatic. Examples of the tetracarboxylic dianhydride other than the aromatic compound are an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. Further, the aromatic tetracarboxylic acid in the present invention is a tetracarboxylic acid in which four carboxyl groups are directly bonded to one or more aromatic rings. Examples of the aromatic tetracarboxylic dianhydride are listed below.

54 201100463

Among the aromatic tetracarboxylic dianhydrides, preferred are an acid anhydride (1), an acid anhydride (2), an acid anhydride (5) to an acid anhydride (7), an acid anhydride (11), and an acid anhydride (17)', particularly preferably an acid anhydride ( 1).

Examples of the alicyclic tetracarboxylic dianhydride are listed below.

(21) (22) (19)

(20)

55 201100463

Ο 0 0 0 0 ο (29) (30) (31)

0 J 0 II 0 J 1 i . Rushing. At 0 (38) U 0 (39) 1 (40) 1 ϊ (41) 1 56 201100463

Among the alicyclic tetracarboxylic dianhydrides, preferred are an acid anhydride (19), an acid anhydride 57 201100463 (25), an acid anhydride (35) to an acid anhydride (37), an acid anhydride (39), an acid anhydride (44), and an acid anhydride (49). More preferably, it is an acid anhydride (19). Examples of aliphatic tetracarboxylic dianhydrides are listed below. Preferred in the following examples are the acid anhydride (23) and the acid anhydride (68).

(67) (68) In the present invention, tetracarboxylic dianhydride other than the acid anhydride (1) to the acid anhydride (68) may be used. Examples thereof include tetracarboxylic dianhydride having a side chain group. By using a tetracarboxylic dianhydride having a side chain group, the pretilt angle in the liquid crystal display element can be enlarged. Examples of the tetracarboxylic dianhydride having a side chain group include an acid anhydride (69) having a steroid skeleton and an acid anhydride (70). 58 201100463

In the case of producing polyamic acid, a dicarboxylic acid anhydride can be added to the tetracarboxylic dianhydride. By the above, the termination of the polymerization reaction in the formation of polyamic acid can be caused, and the progress of the polymerization reaction can be suppressed. That is, in order to easily control the molecular weight of the obtained polymer (polyglycine), for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The addition and subtraction of the second ship if can be appropriately adjusted by considering the molecular weight of the target polyamine. Further, the addition of the dianic anhydride may be two or more kinds as long as the effects of the present invention are not impaired. Er Weixuan's example f cis acid liver, phthalate _, sulfonium succinate needle, 癸 癸 十二 十二 十二 τ τ τ τ τ τ τ τ τ τ τ τ τ τ /, alkyl succinic anhydride and cyclohexanic anhydride. In the present invention, an acid vinegar compound is produced when producing polyamic acid. By adding the "mu", the end of the early isocyanide is added to the endo-acidic compound, and the molecular weight of the obtained poly-proline is modified. By using the terminal-type 59 201100463 type polyacrylic acid, for example, the coating characteristics of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From the above (4), the amount of the monoisocyanate compound to be added is preferably from 1 mol% to 1 mol% based on the total amount of the diamine and the tetradecanoic acid. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The polylysine used in the present invention can be produced in the same manner as the known polylysine used for forming a film of polyimine. The total addition amount of the tetracarboxylic dianhydride is preferably set to be approximately equal to the total number of moles of the diamine (mole ratio 〇9 to 1.1 or so). The molecular weight of the polyamic acid is preferably 10,000 to 5 Torr, more preferably 2 〇 200 to 200,000, in terms of polystyrene-equivalent weight average molecular weight (Mw). Gel permeation chromatography

The measured value of the Permeation Chromatography, GPC) method was determined. The polyglycolic acid can be confirmed by infrared (Infrared, IR) or nuclear magnetic resonance (NMR) analysis of a solid component obtained by sinking a large amount of a poor solvent. The polylysine is decomposed by using a strong alkali aqueous solution such as KOH or NaOH, and an extract obtained by using an organic solvent for the decomposed product is subjected to gas chromatography (Gas Chromatography 'GC), high performance liquid chromatography (High Perf). 〇rmance Liquid Chromatography, HPLC) or gas chromatography _ mass spectrometry (Gas

Chromatography-Mass Spectroscopy (GC-MS) was performed to confirm the raw materials used. The liquid crystal alignment agent of the present invention may further contain other components than the polyamic acid. For example, from the viewpoint of stabilizing the electrical properties of the liquid crystal display element for a long period of time 201100463, the liquid crystal alignment agent of the present invention may further contain an alkenyl substituted nadimide compound. Preferred examples of the gynecologically substituted nadic ylidene compound are listed below.

For example, from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the invention may further contain a compound having a radical polymerizable bond. A base having a radical polymerizable unsaturated double bond, acrylic acid, (meth)acrylic amine, etc. (methyl) two ==::= two _; more preferably having two 丞 clothes σ steeply unsaturated double A (meth)acrylic acid derivative of a bond. Sexuality 2: Long-term stability of electrical properties such as 2-crystal display elements. The side-by-side liquid crystal compound (4) may further contain a oxoxazine compound. The Qin δ group may, for example, be a compound represented by the formula (4) to the formula (7).

In the formulae (a) to (f), R1 and R2 are an organic group having 1 to 30 carbon atoms; R3 to R6 are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; and X is a single bond, 0-, s-, and SS. -, -S02-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, _c(CF3)2-, _(CH2)m-,-0-(CH2)m-0- , -S-(CH2)mS-'m is an integer from 1 to 6; Y is independently a single bond, -Ο-, -S-, -CO-, -C(CH3)2-, _C(CF3)2 - or an alkyl group having a carbon number of 1 to 3. For example, from the viewpoint of long-term stability of electrical characteristics in 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 epoxy compound may be a monomer, an oligomer or a dimer having a morning oxygen 5 coat. The liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives, such as polyacetic acid and its derivatives, and low molecular weight compounds can be selected and used for various purposes. The polymer may be a polymer which is soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics and 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. The polymer may, for example, be a polyamide, a polyureaane, a polyurea, a polyester, a polyepoxide, or a polyphenol (p〇). Iyester p〇ly〇l), silicone modified polyurethane, and oxime modified polyester. The low molecular compound is, for example: 1) a surfactant suitable for the purpose when it is desired to improve the coating property; 2) an antistatic agent when it is necessary to improve the antistatic property; and 3) when it is desired to adhere to the substrate. When the rubbing resistance is improved, a decane coupling agent and a titanium coupling agent are mentioned. Further, 4) When the hydrazine imidization is carried out at a low temperature, a ruthenium amide catalyst can be mentioned. Examples of the decane coupling agent include vinyl trimethoxy decane, ethylene glycol diethoxy pulverization, and N-(2-cycloethyl)-3-aminopropylmethyl dimethyl methoxy decane. N-(2-Aminoethyl)-3-aminopropylmethyltrimethoxydecane, a gas-based base dimethoxyoxymethane, a p-hydroxyphenyltriethoxy group, and a basic Dimethoxyoxymethane, m-aminophenyl triethoxy fever, 3-aminopropyl dimethoxy dream, 3-apropylpropyl triethoxy fever, chloropropyl fluorenyl-1曱 珍 珍 珍 , 3 - propyl propyl di methoxy fever, comparable to propylene methoxy propyl trimethoxy decane, 3-mercaptopropyl trimethoxy sulphur, N- (l, 3- Mercaptobutylene)-3-(diethoxyhydrazone)-propylamine, and N,N'-bis[3-(trimethoxymethylalkyl)propyl]ethylenediamine. 63 201100463 The ruthenium amide catalyst may, for example, be an aliphatic amine such as tridecylamine, triethylamine, tripropylamine or tributylamine; N,N-dimethylaniline, anthracene, fluorene-diethylaniline, An aromatic amine such as a mercapto-substituted aniline or a hydroxy-substituted aniline; a pyridine, a mercapto-substituted pyridine, a hydroxy-substituted pyridine, a quinoline, a mercapto-substituted quinoline, Hydroxy-substituted quinoline, isoquinoline, mercapto-substituted isoquinoline, trans-substituted isoindole, imidazole, mercapto-substituted m-b sitting, substituted with hydroxy Acyclic amines such as imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimercaptoaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine and isoquine. One or two or more. 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 and 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 steps and uses of a polymer component such as polyglycolic acid or soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be one solvent or a mixture of two or more kinds. Such a solvent may be exemplified by a lyophilic solvent of the polyaminic acid and another solvent which is intended to improve coatability. The aprotic polar organic solvent which is a solvating solvent for polyglycine is exemplified by N-methyl-2-pyrrolidone and dimethyl methalin (N-methyl-2-pyrrolidone). Dimethyl imidazolidinone ), N-methyl caprolactam, N-mercaptopropionamide, hydrazine, hydrazine-dimethyl bromide 64 201100463 Amine, dimethylsulfoxide, Lactones such as N,N-dimethylformamide, N,N-diethylguanamine, diethylacetamide, γ-butyrolactone. Examples of other solvents for improving coatability and the like include lactic acid sulfonate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and ethylene glycol. Alkyl ether (such as ethylene glycol monobutyl ether), diethylene glycol single-burning test (such as diethylene glycol monoethyl ether), ethylene glycol monoalkyl base acetate, ethylene glycol monophenyl ether Acid ester, triethylene glycol monoalkyl ether, propylene glycol monoalkyl hydrazine (such as propylene glycol monomethyl sulfonate, propylene glycol monobutyl ether), dialkyl malonate (such as diethyl malonate), dipropylene glycol single An alkyl ether (for example, dipropylene glycol monomethyl ether) and an acetate obtained by esterifying a terminal thiol group of these compounds. Particularly preferred solvents among these solvents are Ν-methyl-2-pyrrolidine steel, ν, ν-dimercaptoacetamide, dimethyl imidazolidinone, butyrolactone, ethylene glycol monobutyl ether, and Ethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoterpene, and dipropylene glycol monoterpene 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 0.1% by weight to 4% by weight. When the liquid crystal alignment agent is applied onto a substrate, it is necessary to perform an operation of diluting the polymer component contained in order to adjust the film thickness 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 viscosity of the solvent. Further, the concentration of the polymer component in the liquid crystal alignment agent is also a factor of 65 201100463, which is adjusted according to 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 maintain the film thickness to be good, the concentration of the polymer component is usually usually 9% by weight or less. The concentration can be further lowered by other coating methods such as dipping or inkjet. On the other hand, when the concentration of the polymer component is 〇·1% by weight or more, the film thickness of the obtained liquid crystal alignment film is easily optimized. Therefore, the concentration of the polymer component is 01% by weight or more, preferably 0.5% by weight to 1% by weight, based on a usual rotator method or printing method. However, in some coating methods of liquid crystal alignment agents, the polymer components can also be used at a lower concentration. Further, in the case of producing a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined depending on 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 is preferably 5 mPa·s or more from the viewpoint of obtaining a sufficient film thickness, and the printing unevenness is suppressed. The viscosity of the liquid crystal alignment agent of σ ' is preferably mPa.s or less, more preferably 10 mPa.s to 80 mPa.s. In the case where a liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, from the same viewpoint, the viscosity of the liquid crystal alignment agent is preferably 5 mpa·s to 2 μmpa.s. Good for mPa's ~ 1〇〇mpa's. The viscosity of the liquid crystal alignment agent can be reduced by aging with the dilution or stirring of the solvent. 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 66 201100463 crystal alignment agent, for example, the liquid crystal alignment film of the present invention can be formed by the coating film of the liquid crystal alignment agent of the present invention, and The step of heating the calcination of the coating film is obtained. For the liquid crystal alignment film of the present invention, the film obtained in the hatching step may be subjected to a rubbing treatment as needed. The coating film can be formed by applying the liquid crystal alignment agent 本 of the present invention to a substrate in a liquid crystal display device in the same manner as in the production of a usual liquid crystal alignment film. The substrate may be exemplified by indium tin oxide (Indium Tin)

Oxide, ITO) Electrode such as an electrode or a glass substrate such as a color filter (c〇1〇rmter). 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 dropping 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 polyhydric acid to exhibit dehydration or ring closure reaction. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared oven, a method of heat treatment on a hot plate, and the like. These methods are equally applicable in the present invention. It is usually preferably 15 inches. (:~3〇〇. (: 1 minute to 3 hours at the left and right temperatures. The rubbing treatment can be carried out in the same manner as the alignment treatment which is usually used for the liquid crystal alignment film, as long as it is the liquid crystal alignment film of the present invention. It is sufficient to obtain a condition of sufficient delay (coffee (10)). The preferred conditions are: 压.2 mm~0.8 mm, the moving speed of the platform is 5 mm/sec to 250 mm/sec, and the roll is rotated. The speed is 5 〇〇 瓜 ～ ～ ～ 67 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 The step includes the coating film other than the step == rubbing at the step of cleaning the step; the film after the film is added to the tidy solution by the cleaning liquid can also be applied to the drying step as an example. It is carried out at a temperature within the range of evaporation, and more preferably = in the case of a temperature lower than that of (4) Lai Bucai's temperature, the cleaning method of the liquid crystal alignment film using the cleaning liquid Z2=brushing), (jetspray) , steam cleaning or jiU washing, etc. These methods may be used singly or in combination. The liquid is used to purify water, or various alcohols such as methanol, ethanol, and isopropanol, and aromatic smog such as hexamidine, meth, and toluene. Chlorhexidine and other dentate are propyl I methyl ethyl _ or the like; but it is not limited to these cleaning = 3⁄4, and some cleaning solutions are used to form the liquid crystal of the present invention by using a sufficiently cleaned impurity. The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably from 30 nm to more than 30 nm. More preferably, it is 30 nm to 15 Å. The liquid crystal of the present invention 68 201100463 can be used as a film for each film. The liquid crystal display device of the present invention comprises: a pair of substrates, liquid crystal molecules, and formed between the pair of substrates, and a known film thickness measuring device. a liquid crystal layer, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film of the present invention which has a liquid crystal molecule in a predetermined direction. The substrate may be a glass substrate based on the liquid crystal alignment film of the present invention. An ITO electrode formed on a glass-made substrate as described in the liquid crystal alignment film of the present invention, wherein the liquid crystal layer is formed of a liquid crystal composition sealed between substrates which are inside the liquid crystal alignment film surface. The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having positive dielectric anisotropy include liquid crystal groups disclosed in the following patent documents. Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 8- No. Hei. Japanese Laid-Open Patent Publication No. Hei 9-302346 (E. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. s. Japanese Patent Laid-Open No. Hei 9 255956, Japanese Patent Laid-Open No. 9_24 No. (EP885271A1 Specification), Japanese Patent Special Kaiping No. 1〇_2〇娜号 (E Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Silk;=::==: The following patents can be cited. The patents of this patent are open to the public. 2_报开 = Special 1:: Patent special Kaiping &amp; i_9 n 二^953遽 Gazette, 曰本号公告, 日太直船, the patent application special Kaiping 10·16嶋初Q ^ ^ 曰 专利 专利 专利 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 The purchase of the tactile bulletin, the Japanese patent m, the Japanese special publication (4) No. 7024, the Sakamoto special to the special Kaikai 1〇_237035, the bulletin, the Japanese patent special offer: This patent is open to the public. (Public W_2_ Bulletin, Japanese Gazette 029581, Japanese Patent Special Zone 1 Deputy 〇〇 虎 公报 、, Japanese Patent Special Open _2563 This patent is open. __019965, 曰本专' In the liquid crystal composition in which the dielectric anisotropy is positive or negative, one or more optically active compounds may be used in the liquid crystal composition of the above-mentioned Japanese Patent Publication No. 2001-192657. The liquid crystal display element of the invention can form liquid crystal display elements for various electric field modes In the liquid crystal display device for the electric field method, a liquid crystal display element for a transverse electric field method in which a voltage is applied to the liquid crystal layer in a direction horizontal to the surface of the substrate; and A liquid crystal display element for a vertical electric field type in which a voltage is applied to the liquid crystal layer in a direction perpendicular to a surface of the substrate. The liquid crystal display element for a transverse electric field method may also have a pretilt angle. In the liquid crystal display device for a lateral electric field method, a liquid crystal alignment film formed of a liquid crystal alignment agent containing a non-side-chain type polyacrylic acid obtained by using a non-side chain type diamine is preferably used. The element needs to exhibit a relatively large pretilt angle. Therefore, it is preferable to use a side chain type polycondensation obtained by using a diamine mixture containing a side bond type diamine or a side chain type diamine in a liquid crystal display element for a longitudinal electric field mode. Liquid crystal alignment film formed by a liquid crystal alignment agent of valine acid. 14-type liquid crystal matching prepared by using the liquid crystal alignment agent of the present invention as a raw material The diatom film can be applied to liquid crystal display elements of various display driving methods by appropriately selecting a polymer as a raw material thereof. The liquid (four)* element of the present invention may further include elements other than the elements to be formed. In the liquid crystal display device, one of the liquid crystal display elements such as a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, and a driving circuit is used as the other constituent elements described above. The present invention will be described by way of examples. Further, the compound used in the example 201100463 is as follows. <Four acid dianhydride> Anhydride (1)·all stearic acid anhydride anhydride (19): i, 2, 3, 4_ Cyclobutane tetracarboxylic acid dianhydride acid acid (23): 1,2,3,4-butadienic acid dianhydride anhydride (68): ethylenediaminetetraacetic acid dianhydride <diamine> diamine (N-3 ): 1,4_bis(2-aminoethyl)pyridazinediamine (N-4): 1,4_bis(3-aminopropyl-carbazinamide (V-1): 4,4' -diaminodiphenylmethanediamine (V-7) : 4,4'-diamino-1,2-diphenylethanediamine (V-35) : 4,4'-diamino-diphenylamine Diamine (VII-13) : 2,2-bis(4_(4_amino) Oxy)phenyl)propanediamine (VIII-5-1) : 5-[[4-(4,-pentyl[1,1,-bicyclohexyl]-4-yl)phenyl]methyl] -1,3·diaminophenylenediamine (ΧΙΙ-2-1): 1,1-bis[4-(4-aminophenyl)nonylphenyl]-4-n-heptylcyclohexanediamine ( ΧΙΙ-4-1): 1,1_bis[4-(4-aminophenoxy)phenyl_4-(trans-4-n-pentylcyclohexyl)cyclohexane [alkenyl substituted by sodium Dickylimine compound] A compound represented by the following structural formula (Ina-1): ΒΑΝΙ-Μ 72 201100463

[cyclohexyl ethane compound] DGA : 4,4'-fluorenylene bis(N,N-diglycidylaniline) ECS : 2_(3,4-epoxycyclohexyl)ethyltrimethoxydecane 0 〈 Compounds having a radical polymerizable unsaturated double bond> HEA : N, N'-dihydroxyethylidene bis decylamine <solvent> NMP : N-mercapto-2-pyryl ketone ketone BC : butyl cellosolve (Ethylene Glycol Monobutyl Ether) <1. Synthesis of Polylactam> [Synthesis Example 1] 0.8242 g of a compound was added to a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen introduction port. Hydrazine (XII_4_1), 23686 g of the compound (V-1), 0.2739 g of the compound (N-4), and 2 〇·〇g of dehydrated NMP were stirred and dissolved under a dry nitrogen stream. Next, 0.4473 g of the compound (1), 1.6088 g of the compound (19), 0.6772 g of the compound (23), and 5 μg of the dehydrated NMP were added, and reacted at 75 ° C for 8 hours, and then at room temperature. Reaction for 15 hours. 24.0 g of the obtained solution was added to obtain a polyglycine solution having a polymer solid content (hereinafter abbreviated as a polymer solid content) containing unreacted monomers and by-products at a concentration of 6 wt%. The poly 73 201100463 tyrosine was used as PA1. PA1 has a weight average molecular weight of 25, ι. The weight average molecular weight of polylysine is determined by diluting the obtained polyaminic acid in a phosphoric acid-DMF mixed solution (acidity/DMF = 0.6/100: weight ratio) to make polyfluorene The concentration of the amine acid reached about 2% by weight' and then the measurement was carried out by the Gpc method using a 2695 separation module. 2414 differential refractometer (manufactured by Waters), and the polystyrene conversion was carried out. In addition, the column is used

HSPgel RT

MB_M (Waters was produced under the conditions that the column temperature was thief and the flow rate was mL/min. [Synthesis Examples 2 to 17] In addition to the (PA17), including the combination of the four bribes and the diamine The results are summarized in Table 1 for Synthesis Example 1 to prepare (iv) (iv) solution (pA2)~ to Example 1, and the results are summarized in Table 丄.

74 201100463 Table 1

Synthesis Example No. Polyammonic acid solution No. Acid dianhydride 2 ί Reaction conditions Weight average molecular weight No. Mo Jun 1% No. Moer % Temperature (°c) Time (hr) 1 15 N-4 10 1 PA1 19 60 XII-4-1 10 75 8 25,100 23 25 Vl .80 1 50 N-4 10 2 PA2 19 50 XII-4-1 10 75 7.5 22,700 V-7 80 1 20 N-4 10 3 PA3 19 80 XII -4-1 10 75 7 32,800 Vl 80 1 50 N-4 20 4 PA4 19 50 XII-4-1 10 80 5 27,400 Vl 70 1 50 N-4 10 5 PA5 19 50 XII-4-1 10 70 7.5 30,400 Vl 80 1 80 N-4 10 6 PA6 19 20 XII-4-1 10 70 5.5 24,000 Vl 80 1 50 N-4 10 7 PA7 70 7 27,600 19 50 Vl 90 1 50 N-4 10 8 PA8 19 50 XII- 2-1 20 70 7 38,900 Vl 70 1 100 N-4 20 9 PA9 VIII-5-1 10 70 6 34,500 VII-13 35 Vl 35 10 ΡΑΙΟ 1 100 N-4 10 75 6 36,500 Vl 90 75 201100463 Table 1 ( Continued) Synthesis Example No. Polyproline solution No. Acid dianhydride diamine Reaction conditions Weight average molecular weight No. Molar% No. Molar% Temperature (°c) Small (hr) 1 60 N-4 10 11 PA11 19 40 V-1 80 75 7 42,300 XII-4-1 10 1 70 N-4 10 12 PA12 19 30 V-1 80 70 5 39,200 XII-4-1 10 1 30 N-4 10 13 PA13 19 40 V-1 90 75 4 42,400 68 30 1 50 N-4 10 14 PA14 19 50 V-1 70 75 4 41,500 V-35 20 1 80 N-3 10 15 PA15 19 20 V -7 70 70 3.5 51,300 XII-2-1 20 16 PA16 1 80 V-7 80 39,600 19 20 X1I-4-1 20 17 PA17 1 50 V-1 100 _ 45,000 <Evaluation of storage stability of liquid crystal alignment agent> The liquid crystal alignment agent was allowed to stand in a freezer at -20 ° C for one month. At this time, the case where the polymer was precipitated was judged as "poor", and the case where the polymer was not observed was judged as "good". 76 201100463 Table 2

Ο [Example 1] <2. Production of liquid crystal display element> ο, a mixed solvent of NMP/BC-4/1 (weight ratio) was added, and the concentration of σ in the synthesis example was 6% by weight of poly-acid. The solution (ρΑι) was diluted 'to make the polymer_component concentration _ 4% by weight to prepare a liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. <Method for Producing Liquid Crystal Display Element> A liquid crystal alignment agent was applied to a glass substrate with two electrodes attached thereto by a spinner to form a film having a film thickness of 70 nm. After coating, it is dried by heating at 8 ° C for about 1 minute, and then heat treated at 210 ° C for 15 minutes, thereby ^ 77 201100463 U·' v'lt Θ 3Crr Ώϋ . ΛΛ. *4-

The liquid crystal alignment film was dried at 120 ° C for 30 minutes after ultrasonic cleaning for 5 minutes in an ultrapure water towel. . Then, the gap material of 4 yn! is spread on one of the glass substrates in the oven to form the surface of the liquid crystal alignment film as the inner side, and the rubbing direction is antiparallel in the opposite direction, and then hardened by the atmosphere. The agent was sealed to produce an antiparallel unit (antiparaiiei ceii) with a gap of 4 /zm. A liquid crystal composition as shown below was injected into the unit, and the injection port was sealed with a light hardener. Subsequently, heat treatment was carried out for 30 minutes at ll 〇 ° C to prepare a liquid crystal display element. 78 201100463

CzHs

17wt. % C3H7

C5Hh

16wt. % ❹ c2h5-^)-c2H4

F 10wt. % c3h7-(^)-c2H4

F 5wt. % C5H11—^ y~C2H4·

F 10wt. % c2h5

6wt. % 〇 C3H7 CsHn

6 wt. % 13 wt.% [Example 2] A mixed solvent of NMP/BC = 4/1 (weight ratio) was added, and a polyglycine solution (PA2) having a concentration of 6% by weight synthesized in Synthesis Example 2 was diluted. The solid content of the polymer was 4% by weight to prepare a liquid 79 201100463 crystal alignment agent. Then, 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 = 4/1 (weight ratio) was added, and a polyglycine solution (pA3) having a concentration of 6% by weight synthesized in Synthesis Example 3 was diluted 'to make a polymer solid content The concentration reached 4% by weight to prepare a liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example 1. [Example 4] A mixed solvent of NMP/BC = 4/1 (weight ratio) was added, and a polyglycine solution (pA4) having a porphyrity of 6 wt% synthesized in Synthesis Example 4 was diluted to make a polymer solid. The concentration of the component was 4% by weight to prepare a liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example i. [Example 5] A mixed solvent of NMP/B04/1 (weight ratio) was added, and a polyglycine solution (pA5) having a concentration of 6% by weight synthesized in Synthesis Example 5 was diluted 'to make a polymer m body component concentration The phase was 4% by weight to prepare a liquid helium alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example i. [Example 6] A mixed solvent of NMP/BC = 4/1 (weight ratio) was added, and a polyglycine solution (pA6) having a concentration of 6% by weight synthesized in Synthesis Example 6 was diluted to make a polymer solid component. The concentration reached 4% by weight to prepare a liquid 201100463 to form a phase alignment agent with Example 1. New Zealand makes the liquid crystal display element in the same way. [Example 7] A mixed solvent of NMP/BC = 4/1 (weight ratio) was added, and a concentration of 6% by weight of poly-aracine solution (pA7) was synthesized in 7 to achieve a polymer solid concentration of 4 % by weight, from the crystal alignment agent. Then using the obtained liquid crystal alignment agent to

G

The liquid crystal display element was produced in the same manner. , _1 phase [Example 8] Add a mixed solvent of NMP/BC = 4/1 (weight ratio), and a poly-proline solution (pA and release) of the concentration of ό/〇 synthesized in 8-8 to polymerize The concentration of the SI body component was 4% by 4% from the = crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in &lt; ^ 'phase [Example 9] Adding NMP/BC = 4/1 (by weight) of a mixed solvent, a concentration of 6% by weight of a polyamine solution (PAH) synthesized in 11 is diluted and diluted to a polymer solid content of 4% by weight, thereby making ' Liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in the real form. [Example 10] A mixed solvent of NMP/BC = 4/1 (weight ratio) was added, and 12 was synthesized. The synthesized concentration of hexanic acid solution (pAl2) of 6% by weight is diluted to make the solid content of the polymer reach 4% by weight to prepare 201100463 liquid crystal alignment agent. Then, the obtained liquid crystal alignment agent is used to Example 1 A liquid crystal display element was fabricated in the same manner. [Example 11] Adding NM A mixed solvent of P/BC==4/1 (weight ratio), and a polyglycine solution (PA13) having a concentration of 6% by weight synthesized in Synthesis Example 13 was diluted to have a polymer solid concentration of 4% by weight. ❶/〇, thereby preparing a liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example j. [Example 12] A mixture of NMP/BC = 4/1 (weight ratio) was added. The solvent was mixed with a polyglycine solution (PA.) having a concentration of 6% by weight synthesized in Synthesis Example 15 to have a polymer solid content concentration of 4% by weight to prepare a liquid hydrazine 3 complexing agent. The liquid crystal alignment element was obtained in the same manner as in Example 1. [Example 13] A polyglycine solution (PA17) having a concentration of 6 wt% prepared in Synthesis Example 17 was prepared in Synthesis Example 5. The polyglycine solution (PA5) having a concentration of 6% by weight is mixed at a weight ratio of 8/2, and then diluted with a mixed solvent of NMp/BC = 18 (by weight) to prepare a solid concentration of the polymer. 4% by weight of liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example [. [Example 14] A polyglycine solution (PA14) having a concentration of 6 wt% prepared in Synthesis Example 14 and a preparation prepared in Synthesis Example 5 were prepared. The phthalic acid solution 82 201100463 liquid (M5) having a concentration of 6 wt% was mixed at a weight ratio of 8/2, and then diluted with a mixed solvent of NMp/Bc -= (weight ratio) to prepare a polymer solid. A liquid crystal alignment agent having a knife/degree of 4% by weight was used, and then a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 15]

A polyhexillary acid solution (PA14) having a concentration of 6% by weight prepared in the synthesis of m4 and a poly-tantoic acid solution (PA16) having a concentration of 6% by weight prepared in Synthesis Example 16 were mixed at a weight ratio of 8/2. Then, a mixed solution dilution of NMp/Bc = 1/1 (weight ratio) was added to prepare a liquid crystal alignment agent having a polymer solid concentration of 4% by weight. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example 1. [Example 16] To a polyglycine solution (PA15) having a concentration of 6 wt% prepared in Synthesis Example 15, 2 parts by weight was added as an alkenyl group-substituted portion with respect to 1 part by weight of the polymer solid content. A compound of Nadickimine compound (ΒΑΝΙ·Μ). Then, NMP/BC = 1/1 (weight ratio) of &amp; solvent was added and diluted to obtain a polymer solid concentration of 4% by weight of a crystal alignment agent. Next, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in the example. [Example 17] To a polyglycine solution (PA15) having a concentration of 6 wt% prepared in Synthesis Example 15, 1 part by weight as an ethylene oxide was added to 1 part by weight of the polymer solid content. Compound of compound (ECS). Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a solid concentration of 4, 2011% by mass. Next, a liquid crystal display element 0 was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 18] To a concentration of 6% by weight of a polylysine solution (PA15) prepared in Synthesis Example 15 The polymer solid component was added in an amount by weight, and a compound (BANI_M) as an alkenyl substituted imidazoline compound and 10 parts by weight of a compound (ECS) as an oxirane compound were added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to obtain a liquid crystal alignment agent having a polymer oxime component concentration of 4% by weight. Then, a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent'. [Example 19] A compound (DGA) as an epoxy icy compound was added in an amount of 1 part by weight relative to 100 parts by weight of the polymer solid content in a concentration of 6% by weight of an amino acid solution prepared in Example 15. Then, the mixed solvent of the Bian Nong 1 production ratio was diluted: and made; = the liquid crystal with a concentration of 4% by weight of the liquid crystal. Next, a liquid crystal display was produced in the same manner as in Example ' using a liquid crystal alignment agent of the composition [Example 20] In a concentration of 6 wt% of ruthenium 15) prepared in Synthesis Example 15 'relative to the polymer solid content i 〇 f =重量份作秘县械_迪_魏化^:力^ 84 201100463 (ΒΑΝΙ-Μ), 20 parts by weight of a compound (ΗΕΑ) as a compound having a radical polymerizable unsaturated double bond. Then, a mixed solvent of NMP/BC = 1 A (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polymer solid content concentration of 4% by weight. Next, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example 1. [Comparative Example 1] Ο Ο A mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and a polyglycine solution (ραπ) having a concentration of 6 wt% synthesized in Synthesis Example 17 was diluted to polymerize. The solid content of the solid matter was 4% by weight to prepare a liquid crystal alignment agent. Then, using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in Example i. <3. Evaluation of electrical characteristics> The liquid crystal display elements produced in Examples 1 to 2G and Comparative Example i were subjected to measurement of ion density and measurement of long-term reliability in the following manner. 1) Measurement of ion density The liquid crystal physical property evaluation device 6254 manufactured by T〇y〇 Technica was used. The 2-row ion density [pC] was determined. The measurement conditions are the waveform f Hz, the voltage: that is, the measurement temperature is set to be the case. The results are shown in Tables 3 and 4 as initial (〇 hour) values. 2) The measurement of the retention characteristics of the ion density is as follows: The test method of the = characteristic/maintaining characteristic is to use the day-to-day display of 7L pieces in an environment of temperature 1〇〇°c, 85 201100463 Take out and measure the ion density [pC]. The smaller the increase in ion density (for example, the increase amount is less than 100: the amount of increase = the ion density after 500 hours - the initial ion density), the better the retention characteristic of ion density can be said. The better the long-term reliability of the characteristics. The data after 300 hours and 500 hours are shown in Table 3 and Table 3.

The so-called PA acid solution in the table is an abbreviation for polylysine solution. 86 201100463 Table 4 Mixing ratio by weight of additive with respect to polymer solid content)...................1〇〇Test PA acid solution ion density (pC) 500 Small example No. (Additive) Initial (0 hours) After 300 hours, after 500 hours, increase 16 Example 16 A PA15 (ΒΑΜ-Μ)... ΡΑ15 】 112 Addition — __ 2d 143 149 37 - 17 Example 17 ( ECS) 100 —Η_ 1〇〇6 32 51 AC ΡΑ15 ' 18 Example 18 (ΒΑΝΙ-Μ) __ 20 19 19 32 — Example 19 (ECS) ΡΑ15 __10 __100 13 (DGA) '~ΡΑ15 ~~~~—1° ... 100 38 51 56 18 20 (ΒΑΝΪ-Μ) .......20 29 (ΗΕΑ) _ 20 94 106 77 ο As shown in Tables 2 and 3, the use of diamines in the raw materials ( Ν _3) and with the two sides of the four-sided two-axis yarn acid, the liquid crystal alignment of the tyrosine acid _ preservation stability can be improved, ^ including the liquid crystal alignment obtained by the liquid crystal alignment agent _ liquid ,, = The effect of increasing the density of germanium over time is significantly improved. Although the present invention has been disclosed in the preferred embodiment as above, the limitation = the invention 'anyone skilled in the art, in the field; In the protection and scope, when you can make some changes and retouching, because of the scope of the gods, please consult the shi _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Claims (1)

201100463 VII. Patent application scope: And a liquid crystal alignment agent comprising polylysine, which is a diamine represented by the formula jN) or a mixture of the diamine and other diamines, and &gt; —_ , in 7 generations ~ 2 (10). The reaction is carried out to obtain: In the formula (N), γΐ and γ2 are independently a single bond or a linear alkylene group having 1 to 7 carbon atoms. The liquid crystal alignment agent according to claim 1, wherein Y and Y2 are a trimethylene group. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the other diamine is a diamine having a side chain group selected from the group consisting of formula (VIII) and formula (X) to formula (xm). At least one of the indicated diamine groups: In the formula (Vm), 'Α3 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- in the exudyl group may be substituted by -〇-, _CH=CH- or -CeC-; R1 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 3 fluorene, having a carbon number of 1 to 30. a phenyl group having a decyl group or a carbon number of 1 to 3 fluorene as a substituent or a group represented by the formula (IX), and any _CH 2 · of the alkyl group having a number of 3 to 30 may be - -, -CH=CH- or -CEC-substitution; 88 201100463 In the formula (IX), A4 and A5 are independently a single bond, -Ο-, -C〇〇_, -OCO-, _CONH-, a stretching group having a carbon number of 1 to 4, and an alkyl group having a carbon number of 1 to 3. An alkyl group or an alkylene group having 1 to 3 carbon atoms; the ring B and the 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 methyl group. f and g are independently 0, 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 1 to 30 carbon atoms and a carbon number of 1 to 30; An alkoxy group, or an alkoxyalkyl group having 2 to 30 carbon atoms; in the alkyl group, the alkoxy group and the alkoxy group, any hydrogen may be substituted by fluorine, and any -CHr may be difluorinated. Base substitution Hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; and 7 and R 8 are independently an alkyl group having 1 to 20 carbon atoms or a phenyl group; A6 is independently a single bond, -C〇_ 89 201100463 or -ch2-; R9 An alkyl group, any -CH2- of the alkyl group may be substituted by -0, -CH=CH- or -C tri C-; R1G is an alkyl group having 6 to 22 carbon atoms; and R11 is an alkyl group having 1 to 22 carbon atoms. A7 is independently -Ο- or an alkylene group having a carbon number of 1 to 6; A8 is a single bond or an alkylene group having a carbon number of 1 to 3; and ring T is a 1,4-phenylene group or a 1,4-stretched ring. Cyclohexyl; h is 0 or 1. 4. The liquid crystal alignment agent according to claim 3, wherein the other diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4) to formula (VIII-6), and formula (XII-). 2) in the diamine represented by the formula (XII-4) and the formula (XII-6) »23 h2n (VIII-2) .23 (VIII-4) 201100463 (VII1-6) A group or an alkoxy group having 1 to 30 carbon atoms. 5. The liquid crystal alignment agent according to claim 1 or 2, wherein the other diamine is a diamine having a side chain group selected from the group consisting of formula (VIII) and formula (X) to formula (XIII). At least one of the diamine group represented by the group and the diamine having no side chain group, that is, at least one selected from the group consisting of the diamine groups represented by the formulae (I) to (VII) and (XV) Mixture: 91 201100463 In formula (VIII), A3 is a single bond, -0-, -(:0-, -(:00-, -0(:0-, -CONH-, -CH^O-, -CF2O-, or charcoal) a stretching group of 1 to 6 in which any -CHr in the alkyl group may be substituted by -〇-, -CH=CH- or -CeC-; R1 is a group having a steroid skeleton, and an alkane having a carbon number of 3 to 30 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 a group represented by the formula (IX), wherein the carbon number is 3130 Any •CH2- may be replaced by -0, -CH^CH- or -CEC-; In the formula (IX), 'A4 and A5 are independently a single bond, -〇-, -COO-, -OCO-, -CONH-, an alkylene group having a carbon number of 1 to 4, and an alkyl group having a carbon number of 丨3. a base or an alkylene group having 1 to 3 carbon atoms; the ring b and the ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; the rule 2 and the anaesthetic 3 are independently a fluorine or a methyl group. , f and g are independently 0, 1 or 2; c'd and e are independently an integer of 〇~3, and their total is 1 or more; R4 is an alkyl group having a carbon number, and an alkoxy group having a carbon number of -30 a group, or an alkoxyalkyl group having 2 to 30 carbon atoms; in the alkyl group, the alkoxy group and the alkoxyalkyl group, any hydrogen may be substituted by fluorine, and any -CH 2 · may be difluoroindenylene group Replaced; 92 201100463 In the formula (X) and the formula (XI), r5 is independently nitrogen or methyl; ^ is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 2 carbon atoms; and R7 and R8 are independently carbon. a filament of 1 to 2 G; a6 is independently a single bond, _c〇_ or -CH2-; R9 (XII) (XIII) 2 to 30 of 93 201100463 alkyl, any -CH2- of the alkyl group may be substituted by -Ο-, -CH=CH- or -C=C-; R1G is a carbon number of 6-22 Alkyl; R11 is an alkyl group having 1 to 22 carbon atoms; A7 is independently -Ο- or an alkylene group having 1 to 6 carbon atoms; A8 is a single bond or an alkylene group having a carbon number of 1 to 3; 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1; (I) h2n h2n-X-nh2 H2n nh2 Nh2 h2n (II) (III) (IV) h2n nh2 Nh2 (V) (VI) h2n In the formulae (I) to (VII) and (XV), X is a linear alkylene group having 2 to 12 carbon atoms; 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)t-S_ or a linear alkyl group having a carbon number of 1 to 12, t is an integer from 1 to 12; when Z1 and Z2 are 氲, 94 201100463 and γ is -ΝΗ_, -N( When CH3)-, _CH2-, -C(CH3)2- or -C(CF3)2-, they may be bonded to each other to form a single bond; ring D is a phenyl group or a mother _14•diyl group and R independent The ground is a carbon number of 1 to 3 or a phenyl group; A3 is independently an alkylene group having a tens 1~6 alkyl group, a phenyl group or an alkyl group-substituted phenyl group; an integer of 1 to 10; cyclohexane Any hydrogen of the ring or benzene ring may be substituted by fluorine, methyl, trifluoromethyl, -OH, -COOH, -S03H, -Ρ03Η2, benzyl or hydroxybenzyl. Ο 6. The liquid crystal alignment agent according to claim 5, wherein the other diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4) to formula (VIII-6), and formula (XlI- 2), at least one of the diamines represented by the formula (χΠ_4) and the formula (XII-6) and selected from the group consisting of the formula QV-D, the formula (IV-2), and the formula (ιν-15) to (IV) -17), formula (ν") to formula (ν_12), formula (ν-33), formula (V-35) to formula (V-37), formula (VI_7), formula (VII-2) and formula ( a mixture of at least one of the diamines represented by XV-1): 95 201100463 (XII-2) (Xll-4) R30 (XII-6) (»V-1) (4) (V-2) (V-3) (V-10) (V-11) (V-12) HO OH (V-33) 96 201100463 _ (XV-1) Ο In the above formula, R23, R29 and R30 are each independently a C number of alkyl groups or an alkoxy group having 1 to 30 carbon atoms. 7. The liquid crystal alignment agent according to claim 1, wherein the poly-aramidic acid is a mixture of two polyamic acids: selected from the group consisting of diamines represented by formula (N) a mixture of at least one selected from the group consisting of a diamine having a side chain group as described in claim 3, that is, at least one selected from the group consisting of formula (VIII) and a diamine group represented by formula (X) to formula (XIII), a polyamic acid obtained by reacting with a tetracarboxylic dianhydride; and the diamine having no side chain group as described in Claim 5 is selected from the group consisting of Formula (I) to Formula (VII) and Formula (XV) a mixture of at least one of the represented diamine groups, or at least one of the diamines having no side chain groups, and at least one selected from the group consisting of diamines represented by formula (N), and tetracarboxylic acid The poly-amic acid obtained by the reaction of the dianhydride. 8. The liquid crystal alignment agent according to claim 1, wherein the poly-aramidic acid is a mixture of two polylysines: a diamine group selected from the group consisting of formula (N) At least one of the diamine having a side chain group as described in Patent Application No. 3 97 201100463, that is, at least one selected from the group consisting of the diamine group represented by the formula (VIII) and the formula (X) to the formula (XIII), a diamine having no side chain group as described in Patent Application No. 5, that is, a mixture of at least one selected from the group consisting of formula (〗) to formula (VII) and formula (XV). Polylysine obtained by reacting with a tetracarboxylic dianhydride; at least one of at least one of the diamine having no side chain group or the diamine having no side chain group and at least one selected from the group consisting of a poly-proline which is obtained by reacting a mixture of at least one of the diamine groups represented by the tetracarboxylic dianhydride. 9. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid is a mixture of two polylysines selected from the group consisting of diamines represented by formula (N) At least one of the diamines having no side chain groups as described in Patent Application No. 5, that is, at least one selected from the group consisting of the diamine groups represented by the formulae (I) to (VII) and (XV). And a polyamine obtained by reacting a mixture with a tetracarboxylic dianhydride; and the diamine having a side chain group as described in claim 3 is selected from the group consisting of formula (VIII) and formula (X) to formula (XIII). a mixture of at least one of the diamine groups represented, or at least one of the diamines having a side chain group and at least one of the diamines having no side chain groups, and a tetrapionic acid dianhydride And the poly-aracine obtained. 10. The liquid crystal alignment agent according to any one of the invention, wherein the at least two tetracarboxylic dianhydrides are aromatic tetraphthalic dianhydrides and tetracarboxylic acids other than aromatics. a mixture of acid dianhydrides. 11. The liquid crystal alignment agent according to claim 1, wherein the aromatic tetracarboxylic dianhydride is of the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (7) 17) At least one of the compounds indicated: 98 201100463 The liquid crystal alignment agent according to Item 11, wherein the Fangxiangzu New Zealand liver is a compound of the formula (1). The liquid crystal alignment agent according to any one of the preceding claims, wherein the at least two tetracarboxylic dianhydrides are of the formula (丨), formula (2), and formula (5) At least one of aromatic tetrazoic acid dianhydride represented by formula (7) and formula (Π), and formula (19), formula (23), formula (25), formula (35) to formula (39), a mixture of at least one of tetracarboxylic dianhydrides other than aromatics represented by formula (44), formula (49), and formula (68): 99 201100463 • The liquid crystal alignment agent according to item 3 of the patent application, wherein the four-new two-next family other than the family is represented by the formula (19), the formula (23), the formula (37), the formula ^ and the formula (68) At least one of the compounds: The liquid crystal alignment agent according to the above-mentioned patent application, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (1), and the tetraphthalic acid dianhydride other than the aromatic compound is the formula (19). The compound represented. A liquid crystal alignment film which is heated by a coating film of the liquid crystal alignment agent according to any one of the above claims. And formed. A liquid crystal display device comprising: a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film according to item 16 of the patent application. 101 201100463 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 3 201100463 ^Baiweidi 99116797 Chinese manual without underline invention patent specification (this specification format, order 'Do not change any more' ※Do not fill in the mark) ※Application number, II mk&quot;% (2006„01) ※ Application曰: ※IP c classification: one father one, invention name··(Chinese/English) Qing Songfei U006D liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID 〇CRYSTAL DISPLAY DEVICE II. Abstract of Chinese invention: The important characteristics required for the liquid crystal alignment film in order to improve the quality of the liquid B. The ion density is high. If the ion density is high, the voltage applied to the liquid crystal during the frame period is When the brightness is lowered, the brightness is lowered to cause an obstacle to normal gradation display. Further, even if the initial ion density is low, the ion density (long-term reliability) after the high-temperature acceleration test is not improved. The liquid crystal alignment of the present invention is used. The liquid crystal display element formed by the agent has a low ion density' and is excellent in long-term stability, The liquid crystal aligning agent comprises a polydiamine obtained by reacting a specific diamine having a azine ring in the molecule or a mixture of the diamine and another diamine and at least two tetracarboxylic dianhydrides at 70 to 200. 201100463 Table 4 Test Example No. PA acid solution (additive) Relative to polymer solid ο ο The indicated PA acid solution in the table is an abbreviation for polylysine solution - as shown in Tables 2 and 3, using a diamine (then) in the raw material and two or more tetrazoric acid livers to produce a poly Amino acid, when preparing a liquid crystal alignment agent containing ') proline, the material is significantly improved, and the other includes the liquid crystal display element of the liquid crystal alignment film obtained by the liquid crystal alignment agent, and the suppression of the ion density is increased. The effect is improved. Although the present invention has been disclosed in the above preferred embodiments, it is intended to be limited to the present invention, and may be modified and retouched without departing from the spirit of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. [Simple description of the diagram] No [Main component symbol description] No 87 201100463 ^Baiweidi 99116797 Chinese manual without underline invention patent specification (This manual format, order 'Do not change any more' ※Do not fill in the mark) ※ Application No., II mk&quot;% (2006„01) ※Application曰: ※IP c classification: one father one, invention name··(Chinese/English) Qing Songfei U006D liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID 〇CRYSTAL DISPLAY DEVICE II. Abstract of Chinese Abstract: The ion density is important for the important characteristics required for the liquid crystal alignment film in order to improve the quality of the liquid B. If the ion density is high, the voltage applied to the liquid crystal in the frame period is lowered, and as a result, the brightness is lowered to cause an obstacle to normal gradation display. Further, even if the initial ion density is low, the ion density after the high-temperature acceleration test (long-term reliability) The increase is also not good. The liquid crystal formed by using the liquid crystal alignment agent of the present invention The element has a low ion density and is excellent in long-term stability, and the liquid crystal alignment agent comprises a specific diamine containing a pyrazine ring in the molecule or a mixture of the diamine and other diamines and at least two tetracarboxylic dianhydrides. The polylysine obtained by the reaction under 70~200. 201100463 For the younger yyi 16797 Chinese manual no line correction page Revision date: 99 years g month 20th three, English invention summary: A liquid crystal alignment film demand If the ion density is high, a voltage applied to the liquid crystal in a frame cycle is decreased, with a result that the brightness is decreased and an The impedance caused by a high-temperature acceleration test (long period stability) is bad. The liquid crystal alignment agent of this inv The liquid crystal alignment agent includes a polyamic acid obtained by reacting a specific diamine including a piperazine ring in its molecular or a mixture of the specific diamine and other diamine with at least two of tetracarboxylic Dianhydrides at 70 to 200°C. Amendment date: August 20, 2011, 201100463 for the younger brother, yyi丨0/97, Chinese patent scope, no underline correction. 7. Patent application scope: 1. A liquid crystal alignment agent containing polyfluorene Aminic acid, the polyamine represented by the formula (N) or a mixture of the diamine and other diamines and at least two tetracarboxylic dianhydrides are reacted at 7 (TC~20 (TC) And obtained: (N) H2N—Y1—NN—Y2—NH5 In the formula (N), γ1 and Y2 are independently a single bond or a straight bond stretching group having a carbon number of 1 to 7. 2. The liquid crystal alignment agent according to claim 1, wherein the Υ1 and Υ2 are a triamethylene group. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the other diamine is a diamine having a side chain group selected from the group consisting of formula (VIII) and formula (X) to formula (XIII). At least one of the diamine groups represented: (VIII) In the formula (VIII), Α3 is a single bond, -0-, -(:0-, -〇: 00-, -0 (:0-CONH-, -CH2O-, -CF2O-, or carbon number) The stretching group of 1 to 6 'any -CH in the stretching group- may be substituted by -0-, -CH=CH- or -C tri-C-; R1 is a group having a steroid skeleton, carbon number 3~ a 30-alkyl group, 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 a group represented by the formula (IX), and an alkyl group having 3 to 30 carbon atoms Any -CH2- may be replaced by -0, _CH=CH- or -CeC-; 88 201100463 Amendment date: August 20, 1999 (IX) 0 is the yin 16797 Chinese patent range without secant revision In the formula (IX), A4 and A5 are independently a single bond, -0-, _c〇〇_, -OCO-, -CONH-, a carbon number of 1 to 4, and an alkyl group having a carbon number of 丨3. An alkyl group or an alkylene group having 1 to 3 carbon atoms; the ring b and the ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; the ruler 2 and the ruler 3 are independently fluorine or a The bases, 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 1 to 3 carbon atoms and a carbon number of 1 An alkoxy group of ～30 or an alkoxyalkyl group having a carbon number of 2 to 30. In the alkyl group, the alkoxy group and the alkoxy group, any hydrogen may be substituted by fluorine, and any -CH:2- Can be substituted by difluoromethylene; r5R6 R5 wide (X) h2n- (XI) In the formula (X) and the formula (XI), R5 is independently hydrogen or methyl; Han 6 is hydrogen, a carbon number of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms; r7 and the site are Alkyl group or phenyl group having a carbon number of 1 to 20; A6 is independently a single bond, _c〇89 201100463 is the Chinese patent scope of No. 99116797 without a slash correction. The revision period: 99 years δ month 20 曰 or -CH2-; Nh2 nh2 (XII) (Xlil) In the formula (XII) and formula (XIII), R9 is a methyl group or an alkyl group having 2 to 30 carbon atoms, and any -CH2- of the alkyl group may be -0-, -CH= CH- or _CeC-substituted; R1g is an alkyl group having 6 to 22 carbon atoms; R11 is an alkyl group having 1 to 22 carbon atoms; A7 is independently -0- or alkylene group having 1 to 6 carbon atoms; 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. 4. The liquid crystal alignment agent according to claim 3, wherein the other diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4) to formula (VIII-6), and formula (XII-). 2) at least one of the diamines represented by the formula (XII4) and the formula (XII-6): R23 (VIII-2) , 23 h2n (VI11-4) 201100463 For the Chinese patent scope No. 99116797, there is no slash correction. This revision date: August 20, 1999 Among these formulas, R23, R29 and R3. It is independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. 5. The liquid crystal alignment agent according to claim 1 or 2, wherein the other diamine is a diamine having a side chain group selected from the group consisting of formula (VIII) and formula (X) to formula (XIII). At least one of the diamine group represented by the group and the diamine having no side chain group, that is, at least one selected from the group consisting of the diamine groups represented by the formulae (I) to (VII) and (XV) Mixture: 91 201100463 Revision date: August 20, 1999 h2n is the Chinese patent scope No. 99116797 without a slash correction of this R1 (VIII) nh2 In the formula (VIII), a3 is a single bond, 〇...c〇, _c〇〇_, _〇c〇-CONH-, -CH20·, -CF20-, or carbon number i~6 Any of -CH2- in the extended alkyl group may be substituted by -〇~CH=CH_ or (Ξc; R1 is a group having an _ alcohol skeleton, a Wei 3~armarm group, having a carbon number of 1 to 30 or Any one of a phenyl group having a carbon number of % to 8% by oxy group as a substituent or a group of a group represented by the formula (IX) having a carbon number of 3 to 3 Å -CH=CH- or &lt;:Ξ〇·substitution; (IX) In the formula (IX), '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 a carbon number of 丨3. An oxyalkylene group or an alkyleneoxy group having a carbon number of 1 to 3; the ring B and the ring c are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R2 and R3 are independently fluorine or fluorene. The bases, f and g are independently 0, 1 or 2; c, d and e are independently an integer of 〇 〜 3, and their total is 1 or more; R 4 is an alkyl group having 1 to 30 carbon atoms; An alkoxy group or an alkoxyalkyl group having 2 to 30 carbon atoms; in the alkyl group, the methoxy group and the alkoxy group, any hydrogen may be substituted by a gas, and any -CH2- may be difluoro Methyl substitution; 92 201100463 The Chinese patent scope of the poetry yy i i〇797 is not underlined. This revision period: August 20, 1999 In the formula (X) and the formula (XI), R5 is independently hydrazine or a methyl group; R6 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; and R7 and R8 are independently a carbon number. 1 to 20 alkyl or phenyl; A6 is independently a single bond, -CO- (XII) (XIII) In the formula (XII) and the formula (XIII), R9 is a fluorenyl group or a carbon number of 2 to 30. 93 201100463 is a Chinese patent range of No. 99116797. No slash correction. Amendment date: Aug. 20, 1999 Any -CH2- of the alkyl group may be substituted by -0, -CH=CH- or -CEC-; R1g is an alkyl group having 6 to 22 carbon atoms; R11 is an alkyl group having 1 to 22 carbon atoms; The ground is -0- or an alkylene group having a carbon number of 1 to 6; A8 is a single bond or an alkylene group having a carbon number of 1 to 3; and the ring T is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1; (I) h2n H2N——X-nh2 H2n nh2 Nh2 h2n (II) (III) (IV) h2n nh2 (V) h2n NH: Nh2 (VI) (VII) nh2 h2n p33 / 7 \ R33 H2N A3 f τ bucket 1 - Si - A3 - NH; 1 \ R34 / " 1 R34 (XV) Formula (I) ~ Formula (VII) and Formula (XV Wherein X is a linear alkylene group having 2 to 12 carbon atoms; Y is independently a single bond, -〇·, -CO-, -NH_, -N(CH3)-, -CONH-, -NHCO, - C(CH3)2-, -C(CF3)2-, 0-(CH2V〇-, -S·, -SS·, -S02-, _S-(CH2)tS- or a linear chain of 1 to 12 carbon atoms Alkyl, t is an integer from 1 to 12; when Z1 and Z2 are hydrogen, 94 201100463 Chinese Patent No. 10797 of Qidi State has no underline correction. The revised period: August 20, 1999 and Y is -NH - ', -N(CH3)-, -CH2-, -C(CH3)2- or -C(CF3)2-, may be bonded to each other to form a single bond; ring D is a phenyl or piperazine 1,4-diyl; R33 and R34 are independently alkyl or phenyl having 1 to 3 carbons; Α3 is independently alkyl, phenyl or alkyl substituted benzene having a carbon number of 1 to 6. m; m is an integer of 1 to 10; any hydrogen of a cyclohexane ring or a benzene ring may be a gas, a methyl group, a trifluoromethyl group, -OH, -COOH, _S03H, Ρ03Η2, a benzyl group or a hydroxy group group. Replace. 6. As described in claim 5 a crystal alignment agent wherein the other diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4) to formula (VIII-6), formula (ΧΙΙ-2), formula (χη_4), and formula (ΧΙΙ- 6) at least one of the diamines represented by the formula (IV_1), the formula (IV-2), the formula (IV-15) to the formula (IV-17), the formula (V_i2), and the formula (( V-33), a mixture of at least one of the diamines represented by the formula (V-35) to the formula (V-37), the formula (VI-7), the formula (VII-2) and the formula (XV-1): 95 201100463 For the Chinese patent scope No. 99116797, there is no slash correction. Amendment date: August 20, 1999 R30 (XII-2) (ΧΠ4) R30 (ΧΙΙ-6) η2ν-τ^]τνη2 Η2Ν-Λ\ //-nh2 - ^1) (1V-1) (IV-2) (IV-15) CF3 -NH2 h2n· Nh2 h2n h2n^ )&gt;-nh2 nh2 (iV-16) (V-3) (V-1) (V-2) (V-10) (V-12) 96 .201100463 _ ’ 〇 797 Chinese Patent 鞠 no scribe corrections Date of revision: August 20, 1999 CH3 CH3 ^11'2) (XV-1) In the formulas, R23, R29 and R30 are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. 7. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid is a mixture of two polylysines selected from the group consisting of diamines represented by formula (N). a mixture of at least one selected from the group consisting of a diamine having a side chain group as described in claim 3, that is, at least one selected from the group consisting of formula (VIII) and a diamine group represented by formula (X) to formula (XIII), a polyaminic acid obtained by reacting with a tetrazoic acid dianhydride; and the diamine having no side chain group as described in Patent Application No. 5 is selected from the group consisting of formula (I) to formula (νπ) and formula (XV) a mixture of at least one of the represented diamine groups, or at least one of the diamines having no side chain groups, and at least one selected from the group consisting of diamines represented by the formula (Ν), and a tetracarboxylic acid The poly-amic acid obtained by the reaction of the dianhydride. 8. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid is a mixture of two polylysines: a diamine group selected from the group consisting of formula (Ν) At least one, such as the scope of application for patents ^ 97 201100463 for the brother (10) No. 7 Chinese patent fan ugly correction This amendment date: August 2, 1999, the side chain based diamine is selected from the formula (Vm And at least one of the diamine groups represented by the formula (χ) to the formula (XIII), and the diamine having no side chain group as described in the scope of claim 5, which is selected from the formula (〗 〖) VII) and a mixture of at least one of the diamine groups represented by the formula (XV), and a polyamic acid obtained by reacting a tetracarboxylic dianhydride; and the diamine having no side chain group a mixture of at least one of the species, or the diamine having no side chain group, and at least one selected from the group consisting of diamines represented by the formula (Ν), and a tetracarboxylic dianhydride Polylysine. 9. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid is a mixture of two polylysines selected from the group consisting of diamines represented by the formula (Ν) And a mixture of at least one selected from the group consisting of a diamine having no side chain group as described in Patent Application No. 5, which is at least one selected from the group consisting of formula (I) to formula (νπ) and diamine group represented by formula (XV). And a polyamine obtained by reacting with a tetracarboxylic dianhydride; and the diamine having a side chain group as described in Claim 3 is selected from the group consisting of Formula (VIII) and Formula (X) to Formula (XIII) a mixture of at least one of the represented diamine groups, or at least one of the diamine having a side chain group and at least one of the diamines having no side chain groups, and a tetracarboxylic dianhydride The polylysine obtained. 10. The liquid crystal alignment agent according to claim 1 or 2, wherein the at least two tetracarboxylic dianhydrides are aromatic tetracarboxylic dianhydrides and tetracarboxylic dianhydrides other than aromatics. mixture. 11. The liquid crystal alignment agent according to claim </ RTI> wherein the aromatic tetracarboxylic dianhydride is of the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (17) At least one of the compounds indicated. 98 _ 丄 0797 Chinese patent range without sizing correction date: August 20, 1999 The liquid crystal alignment agent according to Item [n], wherein the sulphuric acid dianhydride is a compound represented by the formula (1). The liquid crystal alignment agent according to claim 1 or 2, wherein the mixture of at least two of the at least two kinds of the four-component two formula (1), the formula (2), and the carboxylic acid dianhydride is: (5) at least one of the aromatic tetracarboxylic dianhydrides represented by the formulas (7) and (17) and the formula (19), the formula (23), the formula (25), and the formula (35) to the formula (35). 39), 499 (17) 97 other than the aromatics represented by the formula (44), the formula (49), and the formula (68). The scope of the Chinese patent is not slashed. The date of revision: August 20, 1999 201100463 Μ%フフ丄丄υ/ The liquid crystal alignment agent according to claim 13, wherein the tetracarboxylic dianhydride other than the aromatic compound is a formula (19), a formula (23), a formula (37), a formula (49), and At least one of the compounds represented by formula (68): Ο (19) 0· The liquid crystal alignment agent according to claim 13, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (1), and the tetraphthalic acid dianhydride other than the aromatic compound is A compound represented by the formula (19). A liquid crystal alignment film which is heated by a coating film of a liquid crystal alignment agent according to any one of the above claims, wherein the Chinese patent range of πηυ797 is not included. Line correction This revision period: formed on August 20, 1999. A liquid crystal display device comprising: a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film according to item 16 of the patent application. 101