TW200923012A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device - Google Patents

Abstract

This invention provides a liquid crystal alignment agent for a liquid crystal display device to improve long-term reliability and image sticking. The liquid crystal alignment agent includes alkenyl substituted nadimide compound, radical polymerization compound having unsaturated double bond, and polyamic acid and its derivatives, wherein the alkenyl substituted nadimide compound is represented as formula (Ina). The amount of alkenyl substituted nadimide compound is 0.01 to 1.00 weight parts according to that of the polyamic acid and its derivatives. The amount of radical polymerization compound having unsaturated double bond is 0.01 to 1.00 weight parts according to that of the polyamic acid and its derivatives. The amount of polyamic acid and its derivatives is 0.5 to 30 weight percents among the above-mentioned composition.

Description

200923012 IX. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent which combines an alkenyl-substituted nadiimide compound in polyamic acid And a compound having a radical polymerizable unsaturated double bond. [Prior Art] The liquid crystal display element is used for a viewfinder of a video camera (vide〇camera) typified by a note personal computer or a desktop personal computer monitor. Various liquid crystal display devices such as projection displays have recently been used as televisions. Further, the liquid crystal display element is also used as an optoelectronic related element such as an optical printer head, a Fourptical Fourier transform device, or a light valve. The liquid crystal display device usually has: 1) a pair of substrates disposed oppositely, 2) electrodes formed on one or both of the opposing faces of the pair of substrates, and 3) respective pairs of the substrates a liquid crystal alignment film formed on the opposite surface, and 4) a liquid crystal layer formed between the pair of substrates. The mainstream of the conventional liquid crystal display elements is a display element using a nematic liquid crystal, which has been twisted by a twisted nematic (Twisted Nemati C 'TN) type liquid crystal display element of 9 turns 200923012, 2) usually twisted by 180 degrees. Or a super-twisted nematic (STN) type liquid crystal display element of 180 degrees or more, and 3) a thin film transistor (TFT) type liquid crystal display element using a thin film transistor is put into practical use. These liquid crystal display elements have a drawback in that the angle of view where the image can be properly seen is narrow, and when viewed from the oblique direction, a decrease in brightness or contrast and a brightness inversion at halftone are generated. In recent years, the above-mentioned viewing angle problems have been improved by the following techniques: 1) a TN-TFT type liquid crystal display element using an optical compensation film, 2) a vertical alignment (VA) type liquid crystal display element using a vertical alignment and an optical compensation film. And 3) multi-domain vertical alignment (MVA) type liquid crystal display elements using vertical alignment and protrusion structure technology, or 4) lateral field electric field conversion (hl_plane Switching 'IPS) type liquid crystal display elements, 5) Electronically controlled birefringence (ECB) type liquid crystal display element, 6) Optically Compensated Bend or Optically sdf-Compensated Birefringence (OCB) type liquid crystal display element. Moreover, the improved technology is put into practical use, or research is being carried out to put these technologies into practice. The technical development of the liquid crystal display element is realized not only by improving these driving modes or element structures, but also by modifying the constituent members used for the liquid crystal display element. Among the constituent members used in the liquid crystal display device, in particular, the liquid crystal alignment film is an important factor relating to the display quality of the liquid crystal display device, and the function of the liquid crystal alignment film 200923012 is gradually increasing as the quality of the liquid crystal display device is improved. important. The liquid crystal alignment crucible is prepared from a liquid crystal alignment agent. At present (liquid helium alignment agent is a solution of polylysine or soluble ruthenium in an organic solvent. The solution of such a solution of the earth plate is smuggled to form a poly-alignment film. Various liquid crystal alignment agents other than the liquid crystal alignment agent were also subjected to the heat resistance, chemical property (liquid crystal resistance), coatability, liquid helium alignment, electrical properties, optical properties, and most of them were not put into practice. In order to improve the display quality of the liquid crystal display device, the LCD has a wide density of lions. If the ion density is high, ==% of money (f delete e) _ towel is applied to the age of the crystal, the degree of decline is impeded Normal gray age. And ^ low density but high temperature accelerated ion density after the test (long-term reliable 2 is a problem. On the other hand, if the residual charge is large, then the voltage is turned off after the voltage is applied (〇ff) There is also a so-called afterimage, that is, a residual image that should disappear. The decrease in long-term reliability or the generation of afterimages may degrade the display quality of the liquid crystal, which is a problem. Recently, some methods have been proposed to solve the problem. Long-term reliability problem. 1) Known as a kind of aminic acid composition for forming a liquid crystal alignment film, and combining two or more kinds of poly-brenic acid having different physical properties (for example, Japanese Patent Laid-Open) U.S 3) A varnish composition containing two or more kinds of polyaminic acid having different physical properties, and polyamine and a solvent (for example, International Publication 01/000733 pamphlet) is known. 4) A varnish composition containing a polymer material containing a polyamine acid or the like synthesized using a diamine compound having a specific structure (for example, Japanese Patent Laid-Open No. 2〇〇2_16263) is known. The nickname bulletin). I) A technique of adding a low molecular weight oxime resin to a polyimide and a polyamid varnish is known (for example, Japanese Patent Laid-Open Publication No. Hei. No. Hei. Further, a technique for solving the problem of improving the performance of a liquid crystal display element by adding an additive to polyamic acid has been proposed. Such a technique can be exemplified by a liquid crystal alignment agent containing poly-aracine and a hardening accelerator having a structure of (Mi·): a structure or a material (for example, Japanese Patent Laid-Open Publication No. Hei 9-302225) a liquid crystal alignment agent containing a lysine and a dilute group substituted Nadicki-imine compound = such as the 'Japanese Patent Laid-Open No. _34 horn and the Japanese Patent No. 2 ΓΓΓ 91 A liquid crystal alignment agent of an oxonium compound (for example, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-323701). However, the use of these prior art techniques does not adequately address ion density and the long-term reliability of 200923012. For example, in the report A of Japanese Patent Laid-Open No. Hei 9-302225, the hardening accelerator evaporates, sublimes, and decomposes during the imidization process in the production of a liquid crystal alignment film, and liquid crystals produced by using the liquid crystal alignment agent. In the alignment film, the influence of hardening on the electrical characteristics of the liquid crystal alignment film has not been studied. Further, for example, in the Japanese Patent Laid-Open Publication No. 2002-323701, (4) of the ionic impurities is included in the subject, and the voltage holding ratio of the manufactured liquid crystal display member is described in the examples. However, although the voltage holding ratio and the ion # degree are sometimes related, the initial voltage holding ratio may not be related to the ion money at any time. It is generally considered that the ionic impurities are contained not only in the production of the liquid crystal display element but also, for example, by decomposition of the liquid crystal accompanying the operation of the liquid crystal display element, and vary with time. Therefore, the technique of Japanese Laid-Open Patent Publication No. 2002-323701, which is an ionic impurity, is considered to be a technique for effectively reducing the ionic impurities contained in the element when the liquid crystal display element is produced, but

From the point of view of suppressing the generation of ionic impurities over time, there is still room for research. Recently, some methods have been proposed to try to solve the "after-images, problems." 1) A poly-proline composition is known which is used to form a liquid crystal alignment film, and the combination contains two or two kinds of physical properties. The above-mentioned polyacrylic acid (Japanese Patent Laid-Open No. Hei 11-193345 and Japanese Patent Laid-Open No. Hei No. Hei 11-193347). 2) A varnish composition containing polyglycine and polyamine Polymer composition and solvent (International Publication No. 00/61684 pamphlet) 200923012 Two kinds of two or two 〇_0733 booklets with different physical properties. Polyamide and solvent. (International publication of sub-materials The lacquer silk, the high-molecular acid, etc. (the polyamine acid synthesized by the diamine compound of the present two specific structure = Japanese Patent No. 162 (10)). The second-child residual technique cannot be sufficiently solved by the residue. The long-term reliability of the charge (4) secret $-m-shirt degree and the electrical characteristics associated with the change of the 离, Β 问 j 1 1 ! · · · · · 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶Forming agent A liquid crystal display element and a liquid crystal display element including the liquid crystal alignment film. [Invention] The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, it has been found that an alkenyl group substituted with a nadic ylidene compound is used. When a compound having a free f-polymerizable unsaturated double bond is used as a modifier and a liquid crystal alignment agent combined with arginine, the liquid crystal display element having the produced liquid crystal alignment film can be provided with good ion density and long-term reliability. The present invention has been completed, and the liquid crystal alignment agent of the present invention is as shown in the following item [1]. Π] - a liquid crystal alignment agent which is an alkenyl-substituted nadic pyrimine a compound, a compound having a radically polymerizable unsaturated double bond, and a composition of polyacrylic acid or a derivative thereof, and an alkenyl group substituted with Nadickium 11 200923012 The amine compound is a compound represented by the formula (Ina), an alkene The ratio of the substituted Nadick-based imine compound is 0.01 to 1.00 by weight relative to the polyglycine or a derivative thereof, and has a radical polymerization The ratio of the compound of the unsaturated double bond is from 0.01 to 1.00 by weight based on the weight ratio of the poly-aracine or its derivative, and the ratio of the poly-proline or the derivative thereof is 0.5 wt0 / in the composition. ~30 wt°/〇 (% by weight):

Wherein 'L1 and L2 are each independently hydrogen, an alkyl group having a carbon number of 2, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or Benzyl; n is hydrazine or 2; when n==1, w is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, carbon a group of 6 to 12 aryl, benzyl, and zi_(〇)q_(z2〇)r_z3_H (in this group, ζι, ζ2*ζ3 are independently 2 to 6 carbon atoms, and burned The group J q is 〇 or 卜 and r is an integer of j 〜 3 )), a group represented by -(z4)sb-z5-h (in the group, 24 and 25 are independently a carbon number of 1 to 4) An alkylene group or a cycloalkylene group having a carbon number of 5 to 8, B is a phenylene group, and or a group represented by Β) or ~Β_Τ·Β_Η (in the group, 'Β is a phenylene group, and τ For even, c (ch, do, :co_, -s-, or -so2-), one to three hydrogens in such w can be substituted by a radical 'when ~2' W is the carbon number a sub-alkyl group of 2 to 20, a cycloalkylene group having a carbon number of 5 to 8, an arylene group having a carbon number of 6 to 12, represented by 12 200923012 _Z _(〇)q-(Z2〇)rZ3- Group The zl~r of the group, described above, the group represented by _(zVb_z5_ (the meaning of the group: !* S is as described above), or the shot-B-table card = group (The meaning of 基 and τ of the base money is as described above), and one to three hydrogens in this may be substituted by a radical. [Effect of the invention] According to the present invention, the density of the lion is low, and the lion is low.

Corresponding long-term reliability is good, and afterimage characteristics; the problem is to improve the liquid crystal display element. J [Embodiment] First, the terms used in the present invention will be described first. "Nadick is an imine compound, which refers to a compound β with the following Nadik 醯

0 Ν- ο Moreover, the "alkenyl substituted nadic ylidene compound refers to a compound in which the hydrogen of the nadic amide group is substituted with an alkenyl group. The substitution position of the alkenyl group is 5, 6 or 7 A compound having a radically polymerizable unsaturated double bond, which is defined as a compound excluding an alkenyl-substituted nadic ylidene compound. (Mercapto) acrylic acid is used as a general term for acrylic acid and methacrylic acid. The compound represented by the formula (1) is referred to as the compound (1), and the compound represented by the other formula is also the same. Regarding the side chain type diamine and the non-side chain type diamine, a description will be given of the diamine used in the present invention. The definition of these terms is described at the outset. 13 200923012 The present invention is constituted by the above item [1] and the following items [2] to [22]. [2] The liquid crystal according to [1] An alignment agent which is a composition containing an alkenyl-substituted nadic ylidene imine compound, poly-proline or a derivative thereof, and a compound having a radically polymerizable unsaturated double bond, and an alkenyl group substituted with nadic ylide The compound is of the formula (lna-1)~ Ina -3) a compound represented by at least one of:

[3] The liquid crystal alignment agent according to [1] or [2], which is a compound containing a silk-substituted Nadick light-weight compound, having a free silk & and a double bond, and a poly-acid or The composition of the derivative, the compound of the ΐΪίί radical polymerizable unsaturated double bond is (meth)propanoid [4] The liquid crystal alignment agent according to [1] or [2], which has a gynecological substitution a Nadick light amine compound, a compound having a free silk compound and a double bond, and a composition of polyglycine or a derivative thereof, and a compound having a radical polymerizable unsaturated double bond has two or A compound having two or more radically polymerizable unsaturated double bonds or a mixture containing the compounds. [5] The liquid crystal alignment agent according to [4], which is an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable unsaturated double bond, and a poly-proline or a derivative thereof The composition, and the compound having a radical polymerizable unsaturated double bond is N,N,N'-methylene bisacrylamide, N,N'-dihydroxyethylene- N,N'-dihydroethylenebisacrylamide, ethylene bisacrylate, and 4,4,-methylenebis(N,K[-monoethylidenepropionate) At least one of 4,4'-methylene bis (N, N-dihydroethylene acrylate aniline). [6] The liquid crystal alignment agent according to [1], wherein the polystyrene is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). a polymer obtained by reacting at least one of aromatic tetracarboxylic dianhydrides with a diamine, and the diamine is selected from the group consisting of non-side chain type diamines represented by formula (I) to formula (νπ) At least one of the following: 15 200923012

H2n-x1-nh2 H2N N~^ nh2 H2N^~' N^NH;

NH2

(I) (II) (III) (IV) (V) (VI)

(VII) wherein X1 is a linear alkylene group having a carbon number of 2 to 12; X2 is a linear alkylene group having a carbon number of 1 to 12; and X3 is independently a single bond, -0-, -CO-, - CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, -0-(CH2)t-0-, -S-, -SS-, -S02-, each as - Or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen on the cyclohexane ring or the benzene ring may be -F, 16 200923012 -CH3 or -OH, -COOH, - S03H, or -Ρ03Η2, benzyl or hydroxy-based group substitution. [7] The liquid crystal alignment agent according to [1], wherein the polyamic acid is a polymer obtained by reacting an aromatic tetracarboxylic dianhydride represented by the formula (1) with a diamine, and the The diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), formula (IV_16), formula (V-1) to formula (V-12), formula (V- 33) and at least one of the non-side chain type diamines represented by the formula (W-2).

17 200923012 H2N-^^-NH2 H2N-j^jpNH2

NH2

(IV-1) (IV-2) nh2 nh2 (IV-15) (IV_16)

NH,

H2N

[8] The liquid crystal alignment agent according to [1], wherein the polylysine is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14) At least one of the aromatic tetracarboxylic dianhydrides and the tetrasocene (tetra) compound other than the aromatic compound are reacted with a diamine to obtain a (tetra) compound, and the 18 200923012 diamine is selected from the formula (i) At least one of the group of non-side chain type diamines represented by the formula (w).

Wherein X1 is a linear alkylene group having a carbon number of 2 to 12; X2 is a linear alkylene group having a carbon number of 1 to 12; and X3 is independently a single bond, -〇-, -CO-, -CONH-, -NHCO-, -C(CH3)2·, -C(CF3)2-, -〇-(CH2) wide 0-, -S·, -SS-, 19 200923012 • SCV, -S-(CH2)rS Or a linear alkylene group having a carbon number of 1 to 12, and t is an integer of 1 to 12; any hydrogen on the cyclohexane ring or the benzene ring may be -F, -CH3 or -OH, -COOH, - SO3H, or -P〇3h2, a nodal group or substituted with a benzyl group. [9] The liquid crystal alignment agent according to [8], wherein the tetracarboxylic dianhydride other than aromatic is a formula (19), a formula (23), a formula (25), and a formula (35) to a formula (37). At least one of the compounds represented by the formula (39), the formula (44), and the formula (49).

(10) The liquid crystal alignment agent according to [1], wherein the polyβ is a mixture of the aromatic tetracarboxylic dianhydride represented by the formula (1) and the aromatic bismuth phthalate tetraphthalic acid dianhydride. The diamine which is obtained by reacting with a diamine is selected from the group consisting of the formula (IV-1), the formula (IV-2), the formula 'and the formula (^-16), and the formula (another one) At least one of the non-side chain type diamine represented by the formula (¥-12), 々广' J ^ (V-33) 20 200923012 and the formula (YU-2).

21 200923012 \

NH2

HO

(V-33)

[11] The liquid crystal alignment agent according to [10], wherein the tetracarboxylic dianhydride other than the aromatic compound is a formula (19), a formula (23), a formula (25), or a formula (35). At least one of the compounds represented by the formula (37), the formula (39), the formula (44), and the formula (49). 22 200923012

〇 CH3

Ο

(twenty three)

[12] The liquid crystal alignment agent according to [1], wherein the tetracarboxylic dianhydride other than the aromatic compound is a compound represented by the formula (19). [13] The liquid crystal alignment agent according to [1], wherein the polyamine is obtained by formulating the formula (1), the formula (2), the formula (5) to the formula (7), and the aromatic four of the formula a polyfluorene obtained by reacting at least one of a carboxylic acid dianhydride with a diamine, and the diamine is a mixture of at least one non-side chain type diamine and to a small: = type diamine wherein the non-side chain The diamine is a non-side chain type diamine represented by the formula (the formula). The side chain type diamine has a carbon number of 3 or more, and the number of carbon atoms is 23 200923012. 3 or more or more alkoxy groups, alkoxyalkyl groups having 3 or more carbon atoms, a group having a steroid skeleton, and an alkyl group having a carbon number of 1 or more and a carbon number of 1 or a side chain group in the group of a ring having 1 or more alkoxy groups or an alkoxyalkyl group having 2 or more carbon atoms:

(丨)

(II) (Hi) (IV) nh2

(V)

24 200923012 wherein X1 is a linear alkylene group having a carbon number of 2 to 12; χ2 is a linear alkylene group having a carbon number of 1 to 12; and X3 is independently a single bond, _〇_, ..., -NHCO-' -C(CH3)2-'-C(CF3)2- > -〇-(CH2)rO- ^ -S- > -SS- ' -S〇2_, or a linear chain with a carbon number of 1~12 An alkylene group, and t is an integer from 1 to 12; any chlorine on the benzene ring or on the benzene ring may be via _F, -CH3 or -OH, -COOH, -S〇3H, or -Ρ〇3η2 'The beauty is replaced by hydroxybenzyl. [14] The liquid crystal alignment agent according to [13], wherein the side chain type II is a group selected from the group consisting of compounds represented by the formula (vm) to the formula (ΧΙΙ);

(VIII) (wherein R1 is a single bond ' _C0-, -C〇〇, _〇(7) \ -C〇NH-, -CH2〇_, _CF2〇_, or an alkylene with a carbon number of 1 to 6: And any _ch2- in the sub-alkyl group may be substituted by 〇_, ,; r2 is a group having a _ time frame, a carbon number of 2 = a group, a group having a carbon number of 3 to 3 Å or a phenyl group having a carbon number of 3 to oxy group as a substituent, or a group of the formula (D-i and any -CH2- of the alkyl group which may be via hydrazine); gamma CH- or 25 200923012

Wherein 'R, R14 and R 5 are independently a single bond, _〇_, _C〇〇_, _〇c〇, -CONH-, an alkylene group having a carbon number of 1 to 4, and an oxygen having a carbon number of 丨~3 a sub-alkyl group or a sulfoxy group having a carbon number of 1 to 3; ring B and ring C are independently iota, 4-subunit or 1,4-cyclohexylene; and R16 and R17 are independently a fluorine or a fluorenyl group and M1 and m2 are independently 〇, 1 or 2; e, f and g are independently an integer of 〇~3, and their total value is 1 or more; R!8 is an alkyl group having 1 to 30 carbon atoms, carbon An alkoxy group having a number of 1 to 30 or an alkoxyalkyl group having a carbon number of 2 to 3 Å. Among these alkyl groups, alkoxy groups and alkoxyalkyl groups, any hydrogen may be substituted by fluorine, and any -CH2 · may be substituted with a difluoromethylene group or a group represented by ^ (D-2);

(D-2) wherein R HP and f are independently a carbon group or a phenyl group, and η is an integer of from 1 to 100. )

26 (IX) 200923012 (wherein R3 is independently hydrogen or 30 alkyl, or carbon number is 9 soil, is 11, carbon number is 1~ bond, Lu or · ϊ _ Γ base m5 is independent, etc.

/ R (, R in the R 疋 carbon number of 1 to 30, and the alkyl, think - can _a, _CH = CH" Ge CsC substitution; R9 independent _ 〇 _ ΐ ΐ carbon number is a filament of 1 to 6; ring A is 1,4 phenylene or M_ Λ 己 hexyl, a is 0 or 1; b is 〇, 1 or 2; and c is independently 27 200923012

(wherein R1() is an alkyl group having a carbon number of 3 to 30 or a fluorinated alkyl group having a carbon number of 3 to 30; and R11 is hydrogen, an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30. a fluorinated alkyl group; R12 is independently -0- or an alkylene group having a carbon number of 1 to 6; and d is independently 0 or 1. [15] The liquid crystal alignment agent according to [13], wherein the side bond The diamine is selected from the group consisting of formula (VIII-2), formula (VIII-4), formula (VIII-5), formula (VIII-6), formula (X-2), and formula (X-4). a diamine in the compound. 28 200923012 h2n

R23 HzN (VIII-2)

R24 h2n (VIII-4)

(wherein R23 and R24 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 3 carbon atoms, R29 and an alkyl group independently having a carbon number of 丨~, or a carbon number of 1 to 30 The liquid crystal alignment agent according to the item [13], wherein the non-side chain type diamine is selected from the group consisting of formula (IV-1), formula (IV-2), and formula (IV). 15), a diamine in the compound represented by the formula (IV to 16), the formula (V-1) to the formula (V-12), the formula (v_33), and the formula (VII-2), and the side chain type diamine is selected a diamine in a compound represented by the formula (Cong Yi 2), formula (Hand 1), Formula (5), Formula (6), Formula (χΙ~2), and Formula (XI-4) . 29 200923012 H2N—^ ^~nh2 (iv-1)

(IV-15) (IV-16) ί

3

ChU

Nh2

Nh2

(VII-2) 30 200923012

(VIII-2)

R24 R29

NH 2 (wherein R 23 and R 24 are independently a carbon group having a carbon number of 3 3 Å or a carbon having a carbon number of 1 to 3 Å, a number of alkoxy groups of 3 to 30, R29 and R 3 fluorenyl groups or carbon The alkoxy group having a number of from 1 to 30. [17] The liquid crystal alignment agent according to [1], wherein the polyglycolic acid is selected from at least one of a fragrant four-acid dianhydride and at least a polymer obtained by reacting a mixture of four ortho-acid dianhydrides other than aromatic with at least one non-side chain type diamine, and by reacting a mixture of said tetracarboxylic dianhydride with at least one side chain type diamine At least one of the polymers obtained by reacting at least one of the mixture of the non-side chain plastic diamines, wherein the aromatic 31 200923012 tetracarboxylic dianhydride is represented by the formula (14), "Formula (2), Formula (5) The four-acid-low-needle other than the formula (7) and the formula are the formula (19), the formula (23), the formula ((5), the S (35) to the formula (37), the formula (39), and the formula. (44) and formula (49), wherein the non-side chain type diamine is of the formula (IV-2), the formula (IV-15), the formula 〇ν~ΐ6, U, ^, and the formula (V-1) ~ (V - 12) Formula (V -33) and formula (νπ, 2), V U said

The side chain type diamine is represented by the formula (2), the formula (Μ~4), the formula Y (Μ-6), the formula (XI-2), and the formula (Χι~: (Qing-5) Said.

(14) 32 200923012

33 200923012 h2N—^ nh2 (IV-1)

(IV-15) (IV-16)

(V-1)

(V-2)

(V-3)

NH2

(VII-2) 34 200923012

(VI11-2)

(Vlll-5) (VIM)

(VIII-6) R29

Nh2 i teach a hi'R #r24 independently for a carbon number of 3 to 3g of stimuli or carbon = alkoxy groups, r29 and ^ the number of rides for the 〇3〇 burnt or the number of turns is 1~3〇 Alkoxy. [18] The liquid crystal alignment agent according to [17], wherein the polyproline is a mixture of at least one aromatic tetracarboxylic dianhydride and at least one aromatic tetracarboxylic dianhydride and at least A polymer obtained by reacting a non-side chain type diamine. [19] The liquid crystal alignment agent according to [17J, wherein the polyproline is a mixture of at least one aromatic tetraphthalic acid dianhydride and at least one aromatic 35 200923012 = tetracarboxylic dianhydride and at least a polymer obtained by reacting a non-side chain type diamine, and a polymerization obtained by reacting a mixture of the tetracarboxylic dianhydride with a mixture of at least one non-side chain type diamine and at least one side chain type diamine a mixture of things. [20] The liquid crystal alignment agent according to [17] wherein the polyproline is at least one selected from the group consisting of at least one aromatic tetracarboxylic dianhydride and at least one A mixture of two needles of tetracarboxylic acid other than aromatic is obtained by reacting a mixture of at least one non-side chain type diamine and at least one side chain type diamine. [21] A liquid crystal alignment film which is formed by applying a liquid crystal alignment agent according to [1] to a substrate and baking it in a state of a film. [22] A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one or both of opposing surfaces of the pair of substrates, and each of the pair of substrates A liquid crystal alignment film formed on a surface facing each other and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film described in the above. Hereinafter, the liquid crystal alignment agent of the present invention will be described in detail. The liquid crystal alignment agent of the present invention is a composition containing an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable property and a double bond, and a polyglycolic acid. First, the first description of the rare-substituted Nadick-waking imine compound is given. The alkenyl-substituted nadicylimine compound is preferably a compound which can be dissolved in a solvent which dissolves the polyamine or its derivative used in the present invention. An example of such an alkenyl-substituted nadicylimine compound is a compound represented by the formula (Ina).

And l2 are each independently hydrogen, a carbon number of 1 to 12 \ alkenyl group having a carbon number of 5 to 8, a cycloalkyl group, an aryl group or a benzyl group η of 1 or 2. When η=1, W is a dilute base having a carbon number of (Ina), a cyclone having a carbon number of 5 to 8 = a sub-alkyl group having a base of 2 to 6 to 6 or less, and q is 〇 or i is independently a group of 2, a sub-alkyl group or a nucleus of _(zVb_z5 2 is an integer of 1 to 3 )), a 5 to a single carbon number of 1 to 4 s is 0 or 1) a spear, a garment, a radical, B is a phenylene group, and T is a group, such as a group (B is a phenylene group, and a group shown, or such a C-, or each -S〇2-) group . a group substituted with ~3 hydrogen brityl groups. At this time, the preferred alkenyl 3 3 *, alkenyl group, cyclohexyl group, and alkyl group are 1 to 8 alkyl groups, and the carbon number is 3 to 4 ethyl groups. a phenoxyphenyl group, a poly(ethylene oxide) having a number of 4 to 1 fluorene, and a group having a methyl group, a benzylidene phenyl group, or a hydrogen group substituted by a radical. group. 37 200923012 *When n=2 in the formula (ha), 'W is an alkylene group having a carbon number of 2 to 2 fluorene, a cycloalkylene group having a carbon number of 5 to 8, and an aromatic group having a carbon number of 6 to 12. a group represented by a Ϊ _α (Ζ 2 〇) name (the meanings of Z1 〜 Z3 and r are as described above), a group represented by -Z4-B_Z5- (the meaning of z4, Z5, and B are as described above). 〇-B) s_T_(B_0)s_B_ (B is a phenylene group, and τ is a group having a carbon number of 13 and an alkylene group, _〇· or _S〇2·' s is 〇 or g, One to three hydrogen radicals of these groups are substituted by a radical. In this case, preferred W is an alkylene group having a carbon number of 2 to 12, a cyclohexylene group, an subunit, and a phenylene benzene. Tolylene, xylene, a group represented by -C3H6_0-(匕0>0_cation 6_ (22 is an alkylene group having 2 to 6 carbon atoms, ^ is 1 or 2), a group represented by (B is a phenylene group and is CHr, -〇_ or _s〇2_), a group represented by B QHe-BOB- (B is a phenylene group), and a group of this group a group in which one or two hydrogens are substituted by a hydroxyl group. Such a dilute group-substituted nadicylimine compound can be used, for example, as in Japanese Patent No. 565 As described, the obtained compound is synthesized by subjecting a dilute group to a nadic anhydride derivative and a triamine at a temperature of 8 (rc to 22 G. (10) for 5 hours to 20 hours, or a commercially available person. Specific examples of the nadic ruthenium compound include the following compounds: Ν·Methyl-allyl bicyclo [2.2. ηg·5|2,3-dimethylanilide C N'methyl.allylbicycl〇[2.2 .1]hept.5.ene-2,3-dicarboximide ), N-methyl-allylmethylbicyclo[2 21]hepta-5|2,3-dimethylimine, N.methylmethyl Allylbicyclo[2 21]g _5_women_2,3_dimethyl styrene 38 200923012 amine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene -2,3-dimethylimine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2 -ethylhexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-allyl-allyl bicyclo [2.2.1] Hg-5-ene-2,3. Diimine, N-allyl-allylhydrazylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N -allyl-mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropene -Allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-isopropenyl-allyl (fluorenyl)bicycloindole.2.1]hept-5-ene -2,3-dimethylimine, N-isopropenyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-diimide, N-cyclohexyl-allyl Bis-ring 卩 ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] ] Diquinone imine, N-cyclohexyl-mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine, N-phenyl-allyl bicyclo [2.2. 1]hept-5-ene-2,3-dimethylimine, N-phenyl-allyl (indenyl)bicyclo[2.2.1]hept-5-ene-2,3_diimine , N-benzyl-allylbicyclo[2.2.1]hept-5-ene-2,3-diindoleimine, N-benzyl-allylhydrylbicyclo P.2.1]hept-5- Alkene-2,3-diimineimine, N-benzylmercaptopropylbicyclic P.2.1]hept-5-ene-2,3-diindoleimine, N-(2-hydroxyethyl )-allyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1] Hg-5-ene-2,3-diindoleimine, N-(2-hydroxyethyl)-mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Asian ,^-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclic P.2.1]hept-5-ene-2,3-diindoleimine, N-(2,2 -Dimercapto-3-hydroxypropyl)-allyl (indenyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν-(2,3-dihydroxy Propyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-diindole 39 200923012 : Κ(2'3-dipropylpropylpropyl (methyl)bicyclic P. 2.1] Geng-5-, Rong\', j", brewing imine, N_(3_glycosyl-1-propanyl)-allylbicyclo[2.2.1] 雔声 r”2,3"&quot ; 甲亚亚胺, N_(4_ 经cyclohexylallyl (methyl) clothing.. 1]hept-5-ene-2,3-dimethylimine, N-(4-hydroxybenzene Base) _ propyl bicyclo [2.2.1] g _ 5 _ _2, 3 dimethyl dimethyl imimine, N _ (4 _ phenyl) _ ,, yl (methyl) bicyclo P.2.1] -5-ene-2,3-dimethylanimine, N♦ylphenyl)methallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine N_(4-Alanylphenyl)-methylallylhydrazinobicyclo[2.2.1]hept-5u 2,3-dimethylimine, N-(3-hydroxyphenyl)-allyl bicyclo [2.2.1]hept-5-ene-2,3-dimethylanimine, N-(3-disylphenyl)-allyl(methyl)bicyclo[HI]hept-5-rare-2 , 3-曱Yttrium, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-diimide, N-{2-(2-hydroxyethoxy) Ethyl}-allylbicyclo[2.2.1]heptane;5-diluted 2,3-diimineimine;;^{2-(2-carbylethoxy)ethylbupropene (Methyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-{2-(2-hydroxyethoxy)ethyl}•decylallyl bicyclo [2.2.1] H--5-ene-2,3-dimethylimine imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylhydrazinobicyclo[2.2.1 Hept-5-ene-2,3.diimide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1] Hg-5-ene-2,3-diindoleimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl (indenyl)bicyclo[2.2 .1]hept-5-ene-2,3-diimineimine, :^-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]·methallyl bicyclo [2.2.1]hept-5-ene-2,3-diimideimine, N-{4-(4-hydroxyphenylisopropylidene)phenylbuallylbicyclo[2.2.1]g -5-retributed-2,3-diphenyl iodide, anthracene {4-(4-p-phenylphenylisopropylidene) phenylbuallyl (indenyl)bicyclo[H1]hept-5- Alkene-2,3-diindole Amine, 200923012 N_{4-(4-Phenylphenylisopropylidene)phenyl}-methylallylbicyclo[2 21]hept-5-ene-2,3-diimineimine, and Their oligomers (〇lig〇mer); N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-consin-2-,3-dimethylimine) (N , N,-ethylene-bis (allylbicyclo[2.2. l]hept-5-ene-2,3-dicarb oximide), Ν,Ν'-ethylene-bis(allylmethylbicyclo ρ2 ηg· 5_ene-2,3-diimineimine), hydrazine, Ν'·ethylene-bis(indenyl propyl bicyclic pH) hept-5-ene-2,3-diimine) , Ν, Ν'-triamyl bis-(dipropylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), hydrazine, hydrazine, hexamethylene-bis ( Propyl propyl bicyclo [2.2.1] hept-5 · dilute -2,3-dimethylanimine), hydrazine, hydrazine - hexamethylene hydrazine _ bis (dilyl propyl bicyclo [2.2.1] g -5-浠-2,3-dimethylimine), ν,Ν,-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diindole Yttrium imine), hydrazine, hydrazine, _ 12-mercapto bis (allyl fluorenylbicyclo [2.2.1] hept-5-thin-2,3-dimethyl quinone imine), hydrazine, Ν '- Cyclohexylene·bis(allylbicyclo[2.2.1]hept-5-rare-2, 3-dimethylimine), hydrazine, Ν'-cyclohexylene-bis(allylmethylbicyclic hydrazine.21]hept-5-ene-2,3-dimethylimine), 1,2- Double {3·-(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine)propoxy}ethane, 1,2-double {3'-(allyl Methylbicyclo ρ.2.1]hepta-5-ene-2,3-·monomethanolimine) propyl acrylate}, Ethylene, 1,2-double {3'-(decyl propyl bicyclo [2.2 .1] Hept-5-ene-2,3-diindoleimine)propoxy}benzine, bis-dipropylbicyclo[2.2.1]hept-5-ene-2,3·dimethylhydrazine Amine)propoxy}ethyl]ether, bis[2'-{3.-(allylmethylbicyclo[2.2.1]hept-5-ene·2,3-dimethylamine]propoxy Ethyl]ether, 1,4-bis{3'-(allylbicyclo ρ.2·ΐ]hept-5-diluted 2,3·diimine)propoxy}butane, 1,4-Bis{3,-(allylmethylbicyclo41 200923012 [2.2.1]hept-5-ene-2,3-diimineimine)propoxy}butane, N,N' - p-phenylene bis(allylbicyclo[221]hept-5-ene-2,3-dimethylimine), N,N,-p-phenylene-bis(allylmethylbicyclo[ 2.21] Hg-5-ene-2,3-dimethylimine imine), N, N1 m-phenylene-bis(allylbicyclopurine 21]hept-5- -2,3-diimine), n,N'.m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diimine , n, N'-{(1-methyl)-2,4-phenylene}•bis (propylpropyl bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine ), N, N, _ 亚 曱 - - - bis (allyl bicyclo [2.2.1] hept-5 - dilute 2,3-dimethyl quinone imine), N, N '- Phenyl-bis(allylhydrazinobicyclo[2 21]hept-5-lean-2,3-carboximine), n,N'-m-diphenylene phenyl-bis(allyl Bicyclo[2.2.1]hept-5-ene·2,3-dimethylimine), n,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine imine), upper 2-bis[4_{4_(propylpropylbicyclo[2.2^_5•ene-Μ·dimethylimine]phenoxy}phenyl]propane 2,2-bis[4-{4-(allylmethylbicyclo[2 2 ηhept-5-ene-2,3-diimideimine)phenoxy}phenyl]propane, 2, 2_bis[4-{4-(methylallylbicyclo[221]hept-5-diluted 2,3-dimethylanilide)phenyl(oxy}phenyl]propanoid, double {4- (Allyl bicyclo [2.2.1] hept-5-ene-2,3-diimine imine) phenyl} oxime, bis{4_(l-propyl fluorenylbicyclo[2 2 ^Geng^•rare-2,3-dimethylimine imine)phenyl}methane, *double {4-(mercaptopropylidene bicyclo[221]hept-5,2,3-dimethylenimine) Phenyl}曱9, bis{4_(methallylhydrazinobicyclo[221]hept-5-diluted_2,3_-formimine)phenyl}^, biguanide 4_(allylbicyclo[ 2: 2 sessile _2,3 bis quinone imine) phenyl > ether, bis {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di曱醯imino)phenyl} bond, double {4_(mercaptopropyl bicyclo42 200923012 [2.2.1]hept-5-ene-2,3-diimideimine)phenyl}ether, double { 4-(allylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine)phenyl}sulfone, bis{4-(allylhydrylbicyclo[2.2.1]g -5-ene-2,3-diimineimine)phenyl}sulfone, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylhydrazine Amine) phenyl} hydrazine, 1,6-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)-3 hydroxy-hexane, 1,12- Bis(decylallylbiscyclo[2.2.1]hept-5-ene-2,3-carboximine)-3,6-dihydroxydodecane, 1,3-bis(allyl bicyclol [2.2.1] Hept-5-ene-2,3-dimethylimine)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dimethylimine imine)propoxy}hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene_2,3 -dimethylimine imine)-2-lightyl-benzene' M-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimineimine)-2,5 -dihydroxy-benzene, N,N'-p-(2-hydroxy)pyridinylene•bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimine , N, NH(2-hydroxy) xylylene-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,N'- M-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), hydrazine, Ν·-m-(2- Hydroxy) xylylene-bis(mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, Ν'-pair-(2,3·2 Hydroxy) xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), 2,2-bis[4-{4-(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-carboximine)-2-hydroxyphenoxy}phenyl]propane, bis{4-(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-diimineimine)-2-hydroxy-phenyl}decane, bis{3-(allylbicyclo[2.2.1]hept-5-ene-2, 3-dio Amine)-4_hydroxybenzene 43 200923012 base ether, double {3_(methylallylbicyclo[2.2 巧 士 士 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义 义,1_3{4-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-diimineimine)}phenoxymethylpropane, N,N,,N" _Tris(ethylene methallyl bicyclo [2.2.1] hept-5-ene-2,3-dimethylimine) isocyanurate, and oligomers thereof and the like. Further, the alkenyl-substituted nadicylimine compound ' used in the present invention' may also be a compound represented by an asymmetric alkylene group. The following arrest structure of Abenki

Yt5^a^itrr In the present invention, these alkenyl groups may be used alone in place of the Nadick Acrylic Compound, or a mixture of two or more of them may be used. The compound of the above-mentioned alkenyl substituted nadic quinone imine compound is listed below. N,N'-ethylene bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), N,N'-trimethylene·bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimine ), N, N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), N,N'-hexamethylene double (allylmethylbicyclic P.2.1]hept-5-ene_2,3-dimethylimine), hydrazine, fluorene-dodecyl-bis(allylbicyclo[2.2.1] Hg-5-ene-2,3-diimineimine), hydrazine, Ν'·docamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -dimethylimine), hydrazine, hydrazine--cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), hydrazine, Ν'- Cyclohexylene-bis(allylmethylbicyclic guanidine 2.6]hept-5-ene-2,3-carboximine), fluorene, Ν'-p-phenylene-bis(allylbicyclo[ 2.2.1] hept-5-ene-2,3-dimethylimine), hydrazine, Ν'-p-phenylene-bis(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine), hydrazine, Ν'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene -2,3-diimine), hydrazine, Ν'-m-phenylene-bis(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-diimine ), N, IsT-{(l-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) , N,N'-p-diphenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine), N,N'-p-difluorene Phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), hydrazine, Ν'-m-xylylene-bis(allyl bicyclol) [2.2.1]hept-5-ene-2,3-diimineimine), anthracene, Ν'-m-diphenylene bis-allyl (allyl fluorenylbicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine Phenyloxy 45 200923012 yl}phenyl] propyl, 2,2 bis [4-{4-(mercaptopropylmethylbicyclo[221]hept-5-ene-2,3·diennimine)benzene Oxy}phenyl] propyl, bis (methallyl double bad [2.2.1] hept-5-thin-2,3-dimethylimine) phenoxy} stupid] Burning, double {4-(allylbicyclo[2.2.lm_5-2,3-dimethylanilinide)phenyl}methyst, double {4-(mercaptopropylmethylwei[2 2]]g 5_rare-2,3 diimine)phenyl}methane 'double {4-(methylallylbicyclo[2 2"]hept-5-ene_2,3_dimethylimine)benzene曱 曱, { {4-(methylallyl fluorenylbicyclo[2 21]hept-5-ene-2,3-dimethylimine)phenyl}methane, double imitation _(allyl Bicyclo[2.2.1]hept-5-female-2,3-carboximineimine)phenyl}ether, bis{4_(allylhydrazinobicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine) phenyl, bis 4-(methyl dipropylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}ether, double {4 -(allylbicycloP.2.1]hept-5-ene-2,3-diimineimine)phenyl}sulfone, bis{4-(allylhydrazinobicyclo[2.2.1]hept-5 - dilute-2,3-diimine imine)phenyl}sulfone, bis{4_(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) benzene Base} Hard. More preferred alkenyl substituted nadic quinone imine compounds are listed below. N,N'·Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-diimineimine), N,N,-ethylene-bis(nonylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dimethylimine), N,N,-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine ), N,N,-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-carboximine), N,N'-hexamethylene-based Bis(allylhydrazinobicyclo[2·2·1]hept-5-ene·2,3-diimineimine), N,N,-dodedecyl-bis(dipropylbicyclo[ 2.2.1]Hept-5-rare-2,3-diimineimine), hydrazine, hydrazine, -12 46 200923012 methylene-bis(mercaptopropylmethylbicyclo-like genomic-5-subring Hexyl bis(allylbicyclo[2.21]heptane::21^=amine), N,N'·cyclohexylene·double (salvation methyl bis-2,3-dimethyl quinone imine) J/KJ对 亚 · · bis ( 蝉 propyl bicyclo [2.2.1] ng, do - A. imine), Ν, Ν, _ on the silk bis (_ yl methyl bicyclo [221] ng j 2, 3 _ dimethyl quinone imine), N, N' _, phenyl bis (dilyl propyl double = -5- -2,3·di-branched imine), yeah, m-phenylene_bis(succinylmethyl cone), [2.2.1]g·5|2,3_dimethylimine), N, N, ♦ methyl) group}_ bis (propyl propyl bicyclic P.2.1] heptane i 2,3-dimethyl quinone imine) ', p-diphenylene bis (allyl bicyclo [2.2 .1]g _5·ene-2,3·dimethylanimine), N,N′,$diphenylene bis(10)propylmethylbicyclop.2”]g··2,3- Dimethyl imidate), N, N'-m-xylylene _ bis (allyl bicyclo guanidine · 2 · 1) hept · 5 - ene - 2, 3 - dimethyl quinone imine), N, N , _ m-xylylene phenylmethyl bicyclo [2.2.1] hept-5-indole-2,3-dicarboxylic acid imine), —2^2-bis[4-{4-(allyl) Bicyclo[2 2 j]hept-5•ene_2,3-dimethylimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[ 2.2 hept-5-ene-2,3·dimethylimine imine)phenoxy}phenyl]propane, 2,2-bis[,{4-(nonylallylbicyclodimethylimidazolyloxyl }Phenyl]propane, bis{4_(dipropylbicyclop-imine)phenyl}methane, bis{4-(allylmethylbicyclic P.2.1]hept-5-ene-2,3-di Formamidine)phenyl)methane, bis-mercaptopropylbicyclo[221]hept-5- -2,3-dimethylimine)phenyl}methane, bis{4_(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine) benzene Base} methane. 47 200923012 Further, a particularly preferred alkenyl-substituted nadicylimine compound can be exemplified by the following double {4-(allylbicyclo[2·2.1]hept-5-oxime represented by the formula (Ina-1). _2,3-dimethylimine)phenyl}methane, N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5- represented by formula (Ina-2) Alkene-2,3-dimethylenimine), and N,N'-hexaindolyl-bis(allylbicyclo[2.2.1]hept-5-thin- represented by formula (Ina-3) 2,3-dimethylimine).

(Inna-1) (I na-2) (I na-3) Next, a description will be given of a compound having a radical polymerizable unsaturated double bond used in the present invention, although an alkenyl-substituted nadic ylidene compound also has The radical polymerizable unsaturated double bond, but as described above, the alkenyl-substituted nadicilimine compound is not included in the compound having a radical polymerizable unsaturated double bond used in the present invention. Such a compound having a radical polymerizable unsaturated double bond is preferably a (meth) acrylate, a (meth) acrylamide derivative or the like, and a bismaleimide 48 200923012 (bismaleimide). Further, a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds is more preferable. Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-nonylcyclohexyl (meth)acrylate, dicyclopentanyl (meth) acrylate, and (methyl) Dicyclopentyloxyethyl acrylate, isobornyl (meta) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Ester, and 2-hydroxypropyl (meth)acrylate.

Specific examples of the difunctional (meth) acrylate include ethylene diacrylate, products of ARONIX M_210, ARONIX M-240, and ARONIX M-6200, manufactured by Nippon Kayaku Co., Ltd. KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and products of Kuraei Oil & Fat Chemical Industry Co., Ltd. Light Acrylate BA-4EA ' Light Acrylate BP-4PA Light Acrylate BP-2PA. Specific examples of the trifunctional or trifunctional or higher polyfunctional (meth) acrylate include 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline), ARONIX M-400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Osaka Products of Organic Chemical Industry Co., Ltd. 49 200923012 VGPT. Specific examples of the (indenyl)-glycidylamine derivative include N-isopropylacrylamide, N-isopropylmethylpropenylamine, N-n-propylpropenylamine, and N-n-propyl group. Methyl acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl decyl acrylamide 'N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylamide, N-tetrahydrofurfUryl acrylamide, N-tetrahydrofurfuryl methacrylamide, ethyl acrylamide, N-ethyl-N-mercapto acrylamide, N, N -Diethyl acrylamide, N-methyl-propyl propyl amide, Ν'-mercapto-N-isopropyl propylene amide, Ν-acryl hydrazine 11 N-acryloyl piperidine ) 'N-acryloyl pyrrolidine, Ν, Ν·-methylene bis acrylamide, N, N'-ethylene bis acrylamide, hydrazine, Ν ·- Dihydroxyethylidene bis decylamine, N-(4-hydroxyphenyl)decyl acrylamide, N-phenylmercapto acrylamide, N-butyl decyl acrylamide, N-(isobutyl) Oxymethylmethyl)methacrylamide, N-[2-(N,N-didecylamino)ethyl]methacrylamide, hydrazine, hydrazine-dioxin Methyl acrylamide, Ν-[3-(didecylamino)propyl]decyl acrylamide, Ν-(decyloxy) methacrylamide, Ν-(hydroxymethyl)-2 Methyl acrylamide, hydrazine-benzyl-2-methyl acrylamide, and N,N'-methylene bis methacrylamide. Among the above (mercapto)acrylic acid derivatives, fluorene, fluorenyl-fluorenyl bis decyl decylamine, hydrazine, Ν'-dihydroxyethylene-bis acrylamide, ethylene diacrylate, and 4 are particularly preferable. , 4'-methylenebis(anthracene, fluorene-dihydroxyethylene acrylate aniline). Specific examples of the bismaleimide include BMI-70 and BMI-80 manufactured by Pharma Chemical Co., Ltd., and 50 200923012 bmi-iooo, BMI-3000, and BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. , BMI-5000 and BMI-7000. Next, the poly-proline and the derivative thereof used in the present invention will be described. Polylysine is a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine, which is dissolved in a solvent and coated on a substrate, followed by heating, thereby being formed on the surface of the substrate. A liquid crystal alignment film formed of a polyimide film. Examples of such derivatives of poly-proline are soluble polyienimine, polyamidomate and polyamidamine. More specifically, a polyimine which is obtained by completely dehydrating and ring-closing a guanamine bond and a carboxyl group of polyproline, a part in which a guanamine bond and a carboxyl group of a polyglycolic acid are partially dehydrated and closed are exemplified. Polyimine, a polyphthalate obtained by converting a carboxyl group of a polyamic acid into an ester, and a polycondensation obtained by replacing a part of a tetracarboxylic dianhydride with a dicarboxylic acid (or a toothing or an acid anhydride thereof) Proline _polyamine copolymerization

And when the poly-proline-polyamine copolymer is partially or completely dehydrated and closed as an acid component; f can only obtain poly-glycolic acid/polyamide copolymerization and it is possible to obtain a mixture And/or a mixture of poly-aragic acid in the present invention, which is called polylactoic acid on the premise of this possibility.

A mixture of polymers is used. Acid dianhydride can be selected as a condition: use the four

Carboxylic acid II 51 200923012 agent. Further, among such tetracarboxylic dianhydrides, it is preferred to use at least one aromatic tetracarboxylic dianhydride. Preferred examples of the aromatic tetracarboxylic dianhydride are listed below. 0 200923012

F3Q PF3

53 200923012 Among the above aromatic tetrazoic acid dianhydrides, compound (1), compound (2), compound (5), compound (6), compound (7) and compound (14) are more preferable, and compound (1) is particularly preferable. (pyromellitic dianhydride). In the present invention, at least one of the aromatic tetracarboxylic dianhydride and at least one tetracarboxylic dianhydride other than aromatic may be used in combination. Preferred examples of the tetracarboxylic dianhydride other than aromatic are listed below. 54 200923012

55 200923012

56 200923012

Among the tetrazoic acid dianhydrides other than the above aromatic compounds, the compound (19) to the compound (39) and the compound (49) are more preferable, and the compound (19), the compound (23), the compound (25), and the compound (35) are more preferable. - Compound (37), Compound (39), Compound (44), and Compound (49). Further, the compound (19) (1,2,3,4·cyclobutane tetraphthalic acid dianhydride) is particularly preferred. On the other hand, in order to form the polyaminic acid of the present invention or a derivative thereof into a solvent-soluble polyimine, it is preferred to use the formula (24), the formula (35) to the formula (44), and the formula ( 49) A tetracarboxylic dianhydride represented by the formula (50), the formula (53), and the formula (60). Further, in the present invention, it is preferred to use at least one of the aromatic tetracarboxylic dianhydride and at least one aromatic tetracarboxylic dianhydride in combination, and in particular, it is preferable to use the compound (1) in combination (2009). Pyromellitic dianhydride) and compound (19) (1,2,3,4-cyclobutanetetracarboxylic dianhydride). When a liquid crystal alignment film is formed by using a liquid crystal alignment agent containing the polyamic acid and the compound (A) thus obtained, a liquid crystal display element containing the liquid crystal alignment film can be provided with good long-term reliability in relation to a voltage holding ratio. Further, as the tetracarboxylic dianhydride in the present invention, other tetracarboxylic dianhydrides other than the compound (i) to the compound (67) can be used. Other tetracarboxylic dianhydrides may be arbitrarily selected as long as the object of the present invention is achieved, and various forms of tetra-baric acid dianhydride may be used. For example, tetracarboxylic acid dianhydride having a side chain structure may also be used. When a poly-tantoic acid obtained by using a tetra-orthoacid dianhydride having a side chain structure is used in a liquid crystal alignment agent, a liquid crystal alignment film formed of the liquid crystal alignment agent can increase a liquid crystal display element containing the liquid crystal alignment film. Pretilt angle. The tetracarboxylic dianhydride having a side chain structure is not particularly limited, and a preferred example thereof is a compound (68) having a steroid skeleton and a compound (69). 58 200923012

In the present invention, a part of the tetracarboxylic dianhydride may be used instead of phthalic anhydride. By replacing a part of the tetracarboxylic dianhydride with a carboxylic acid anhydride, the polymerization reaction can be terminated, whereby the reaction can be further inhibited, so that the molecular weight of the obtained polyamic acid can be easily controlled. The ratio of the carboxylic acid field to the tetracarboxylic dianhydride is preferably 10 mol% (mol%) or 10 mol% or less based on the total amount of the tetracarboxylic dianhydride as long as it does not impair the effects of the present invention. Any diamine can be used in the present invention. However, in the case of a VA type liquid display element, 80 is often required. ~90. Large pre-tilt angles on the left and right, in the case of 〇CB type liquid crystal display elements, are mostly required to be 7. ~2〇. The left and right = angles are mostly required to be 3 in the TN Wei Jingling component or the STN Weijing display component. ~1〇. The left and right pretilt angles, and in the case of a 1PS liquid helium display element, require Q. ~3. Small pre-dip on the left and right 59 200923012 Corner. Therefore, the adjustment of the pretilt angle must be considered. Further, diamines can be classified into two types depending on the difference in their structures. In other words, when the skeleton linking two amino groups is regarded as the main chain, the diamine is divided into a diamine having a group branched from the main chain, that is, a side chain group, and a group having no side chain group. Diamine. By reacting a diamine having a side chain group with a tetracarboxylic dianhydride, polylysine or polyimine having a plurality of side chain groups with respect to the polymer main chain can be obtained. When such a polyamic acid or a polyimine having a side chain group with respect to a polymer main chain is used, a liquid crystal alignment film formed of a liquid crystal alignment agent containing the polymer can increase a liquid crystal display element. Pretilt angle. That is, the above-mentioned side chain group is a group having an effect of increasing the pretilt angle 'is selected from alkoxy groups having a carbon number of 3 or more, a carbon number of 3 or more, and a carbon number of 3 Or a 3 or more alkoxyalkyl group, a group having a _ time frame, and a terminal having a filament having a carbon number of i or more, a carbon number of 丨 or more, or a carbon number of 2 or more In the group of the alkoxyalkyl ring. The diamine having such a side chain group is referred to as a side chain type diamine in the present invention. An amine which does not have such a side bond group is referred to as a non-side chain type diamine. The mouth and the 'by appropriately combining the side chain type diamine and the non-side chain type diamine, 5 correspond to the pretilt angle required for each of the above-mentioned respective surface display elements. Also, when a large pretilt angle is not required, it is sufficient to use at least one type of non-side chain. In the case of the above-described use of a VA liquid crystal display device, an OCB liquid crystal display 5 or a second STN liquid crystal display device, a non-side chain type monoamine and at least one type of side chain type diamine may be used in combination. The ratio of the chain-type amine to the side-bonded diamine can be determined according to the pre-tilt angle of the target 60 200923012. Of course, it is also possible to use only the side chain type diamine to correspond to the desired pretilt angle by appropriately selecting the side chain group. Thus, the liquid crystal alignment agent of the present invention can be applied to any kind of liquid crystal display element. In addition, the effect of such a side chain group is also the same for the tetracarboxylic acid dianhydride. Specific examples of the side chain groups are as follows. First, the first one can be exemplified: alkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl , a dilute carbonyloxy group, a diloxy oxo group, a bake aminocarbonyl 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 a carbon number of 3 or more. However, the alkoxy group may be 3 or more in terms of the total carbon number. Further, these groups may be linear or branched. Next, the terminal ring has a group having a carbon number of 丨 or 丨 or more, an alkoxy group having 1 or more carbon atoms, or an alkoxy group having 2 or more carbon atoms as a substituent. There may be mentioned a phenyl group, a phenylalkyl group, a phenyl alkoxy group, a phenoxy group, a phenylcarbonyl group, a phenylcarbonyloxy group, a phenoxycarbonyl group, a phenylcarbonyl group, a phenylcyclohexyloxy group, a carbon group. a number of 3 or more cycloalkyl, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexyl oxy-bis(cyclohexyl) Oxyl, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenoxycarbonyl, and ring A group having a ring structure of a hexyl bis(phenyl)oxycarbonyl group or the like. In addition, bis(cyclohexyl) 200923012 and bis(phenyl) may also be bonded via an alkylene group instead of a single bond. In addition, the following ring group may also be mentioned: two or two benzene rings or a cyclohexane ring through a single bond, -〇-, -COO·, seven c〇_, -CONH- or a carbon number 1 to 3 of an alkylene group to be bonded, and the terminal ring has an alkyl group having 3 or more carbon atoms, a fluorine having 3 or more carbon atoms, an alkyl group, and a carbon number of 3 or more. An alkoxy group or an alkoxyalkyl group having a carbon number of 3 or 3 is used as a substituent. Of course, the group having a steroid skeleton is also an effective side chain group. i Preferred examples of the non-side chain type diamine are listed below. H2n-x1-nh2

Wherein 'X1 is a linear alkylene group having a carbon number of 2 to 12; X2 is a linear alkylene group having a carbon number of 1 to 12; \3 is independently a single bond, _〇, _〇〇-, _(3 :〇;^11-, -NHCO·, -C(CH3)2-, -C(CF3)2-, ·0-(0Η2χ·0-, -S-, -SS-, 62 200923012 -S〇2 -, -S-(CH2)tS· or carbon number is 〜12 t is an integer of 1 to 12; any hydrogen of a cyclohexane ring or a benzene ring may be via _f, _CH3 or -OH, -COOH, -S03H Or -P〇3h2, benzyl or hydroxybenzyl group. Preferred examples of the diamine represented by the formula (I) are listed below. H2N(CH2)2NH2 H2N(CH2)4NH2 H2N(CH2)eNH2 H2N(CH2)« NH2 (1-1) (I-2) (I-3) (^) The following is a preferred example of the diamine represented by the formula (?): H2N-|^J-NH2 (H-2) Preferred examples of the diamine represented by (dish)

(111-1)

Preferred examples of the diamine represented by the formula (IV) are listed below. 200923012 h2n-^^-nh2 H2N-j^jpNH2 Me h2n~^~~^~ni- (IV-1) (IV-2) (IV- 3) Me Me M OH 丄HO \ _ H2N—^ ^~nh2 XX H2N—f \-NH Me' Me h2n^^^nh2 \=/ (IV-5) (IV-6) (IV-7)

COOH

H2N v, NH2 (IV-8)

HOOC H2N-nh2 (IV-9)

H03S h2n—v nh2 (IV-11) po3h2

H2N ^ 'NH2 (IV-12)

Preferred examples of the diamine represented by the formula (V) are listed below. 2009 200912 12 ΗζΝ r~HH2 Η2Ν_λ (V-1)

(V-7)

NH 丨2

(V-14)

NH. 2 (\M7) H2N_H〇"〇V〇-NH2 H2N-〇X〇'^Q-NH2 (V-13) H2N^〇X〇^〇V〇-NH2 (V-16) h^n -〇^0%^0"〇-nh2 (V-18)

Nh2 (V-15)

(V-19) 65 200923012

NH 2 (V-21) (V-20) H2N~C~^~S~S~C~~^~NH2 H2N-[^SvS^O-NH2 (V-22) (V-23)

H2N 〇-h2 _分3一s分NH2 (V-25) (V-24) H2N ~^ys^^s^y~m2 _ s^q_NH2 (V-27) (V-26)

ChU

F3c cf3

(V-30) /^nh2

O H2N—^ ^ ^V_/~NH2 H2N~^~^~S02~C~^~NH2 (V-31) (V-32) HO OH (V-33) OH OH H2N^y^^-NH2 ( V-34) Preferred examples of the diamine represented by the formula (VI) are listed below.

(VI-3) (VI-4)

(VI-5) (VI-6) A preferred example of the diamine represented by the formula (YU) is shown below. 67 200923012

(VII-3)

(VII-8) H2N—^

H2N

H2N i. <r<y^Or points. Repair. (VIM 2) Plant nh2 ^~nh2 H2N-^ One (VII-16) (Vll-9) (VII-11)

Me Me H2N—^

(VII-15) -nh5 -nh7 (VI Bu 10) NH〇 NH2 (VII-14)

68 200923012 Among these diamines, more preferred compounds (ιν-5), compounds (IV are compounds (] γ 〜1) ~ compounds (V-1) ~ compounds (v, compound compounds (V-27), compounds (v, compound (V-26), compound (VI-1), compound (νι~2) = compound (V~33), compounding and brewing. ~Compound (dicarboxylic: Qin 6), and Ον -D, compound (= Preferred examples are compounds (IV-(6), compound ("): =, (V-33), and (VII-2). ° V (1), the side chain type used in the present invention Specific examples of the diamine include diamines represented by (M) to (XII). h2n R2

NH2 (VIII) Formula (VID) towel 'R1 is a single bond, -O-, -COO-, -oco-, (-C0NH-, -ch2〇-, -cf2o-, or a carbon number of 〜6) Any alkyl group in the alkylene group may be substituted by -0_, _CH=CH_ or substituted; R2 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 a phenyl group having 3 to 30 alkyl groups or an alkoxy group having a carbon number of 3 to 3 Å as a substituent or a group represented by the formula (D-1), and any -CH2- in the alkyl group may be _〇_, _CH=CH_ or _CsC_ replaced. 69 200923012

(D-1) Among them, H_13 and R14 know that R 15 is derived from -CONHm , and is independently a single bond, 〇-, (00·, _〇〇>, or carbon number Γ, burning base, carbon number is 1 to 3 of oxyarlenylene, benzoquinone deuterium #魏氧; ring Β and ring C are independently 1,4-亚

It f cyclohexyl; Rl6 and R" are independently fluorine or methyl, and m2 is independently 〇, 1 or 2; e, f and g are independently positive numbers of 0 to 3, and their total value is i or more; Rls is an alkoxy group having a carbon number of 3 Å, an alkyl group, a carbon number of 丨~, or an alkoxyalkyl group having a carbon number of 2 to 3 Å, such an alkyl group, an alkoxy group and an alkoxyalkyl group. In the group, any oxygen may be substituted by fluorine ' and any -CH2 may be substituted with a difluoromethylene group or a group represented by the formula (D-2). R19 I Si- I R20

(D-2) wherein R19, R20, R21 and R22 are independently a carbon number of 1 to 10 or a phenyl group, and n is an integer of 1 to 100.

70 200923012 wherein R3 is independently hydrogen or methyl; r4 is a carbonyl group or a carbon number of 2 to 3G; and r5 is: or even. Excellent _ is that the two minus filaments are also key == 3 positions of the alcohol skeleton, and the other bond is at: position:. The bonding position of the two fluorene groups on the stupid ring is preferably meta or para position in the bonding position. In addition, := Any hydrogen that can be bonded to the carbon on the moon frame can be replaced by a methyl group.

(X) wherein R3 is independently hydrogen or methyl; R4 is hydrogen, an alkyl group of 碜 to ～, or an alkenyl group having a carbon number of 2 to 30; R5 is independently a single bond, or -CHr; and, and R7 Independently hydrogen, an alkyl group having a carbon number of 丨~兕, or a stupid base. The bonding positions on the = ring of the two R7-substituted amino styryl groups are preferably each a meta or para position relative to the carbon to which the steroid skeleton is bonded. Further, it is preferred that the bonding positions of the two amino groups on the benzene ring are each a meta or a para position with respect to R5. 71 (XI) (XI) 200923012

Wherein R 8 is an alkyl group having a carbon number of 1 to 30, and any -CH 2 - of the alkyl group may be _ 〇 _, _ch = CH - or substituted; R 9 is independently / ^ or ^ carbon number is 1 to 6 An alkylene group; ring a is a fluorene phenylene group or a ι 4 · ^ ring group; a is 0 or 1 · 'b is 0, 1 or 2; and, c is independently selected for each of the knot lines,

a fluorinated alkyl group; an alkyl group having 3 to 30 carbon atoms or a fluorine atomic group having a carbon number of 3 to 3 to 3 Å = 2, a carbon number of 1 to 3 G or a carbon number; and d is a number For the 〖~6 (4) position excellent _ is, the respective subtraction on the benzene ring as the formula (na) table _ _ sub-R to " brother is meta or para. ~Formula (10), Table:::: Examples can be enumerated by the formula (er, 〗) 200923012

(VIJI-6)

(VIIM1) In the formula (Μ-1) to the formula (Μ-11), R23 and R24 are each preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably having a carbon number of An alkyl group of 5 to 25 or an alkoxy group having a carbon number of 5 to 25. 73 200923012 R25 R25 R25

(VIII-12) (VIII-13) (VIII-14) (VIII-15)

In the formula (VIII-12) to the formula (M-15), R25 is preferably an alkyl group having 4 to 30 carbon atoms, more preferably an alkyl group having 6 to 25 carbon atoms. In the formulae (Μ-16) and (Μ-17), R26 is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 25 carbon atoms. 74 200923012

H2n h2n (VIII-20)

H2N h2n (VIII-22) H2N h2n (VIII-21)

H2N 〇 h2n

(YIII-24)

(VIII-27) (VIII-28) 75 200923012

H2n

(VIII-31)

(VIH*35) (ν"|_3β) ch3 ch3 i.

(VIII-37)

Si-〇-Si-R27 II ch3 ch3 In the formula (Μ-18)~(M-37), R27 and R28 are each preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. More preferably, it is an alkyl group having 5 to 25 carbon atoms or an alkoxy group having 5 to 25 carbon atoms. 76 200923012

Among the above diamines, a diamine represented by the formula (M-1) to the formula (Μ-11) is preferable, and a formula (Μ-2), a formula (Μ-4), a formula (Μ-5), and a formula (Μ) are more preferable. — A diamine represented by any one of 6). Examples of the diamine represented by the formula (IX) include a diamine represented by the formula (κ_ι) to the formula (ΙΧ-4). 77 200923012

Examples of the diamine represented by the formula (x) include a diamine represented by the formula (χ - i) to the formula (X-8). 78 200923012

79 200923012

80 200923012 Examples of the diamine represented by the formula (□) include a diamine represented by the formula (χΐ-J) to the formula (XI_8).

R30

81 200923012 R30

R3〇

In the formula (XI-1) to the formula (XI-3), R29 is preferably an alkyl group having a carbon number of from 1 to 30, and in the formula (XI-4) to the formula (XI-8), R30 preferably has a carbon number of 1 ~20 alkyl. Examples of the diamine represented by the formula (XII) include a diamine represented by the formula (XII-1) to the formula (XII-3). 82 200923012

R32 is preferably hydrogen. In the formula, 'R31 is preferably a burnt group having a carbon number of 6 to 2 Å or a burnt group having a carbon number of 1 to 10. In the present invention, other diamines other than the formula (1) may also be used in combination. Examples of such other diamines may be a naphthalene diamine having a structure of 2 =: hthalene), a diamine having a fluorene (fluoride structure, and a diterpenoid diamine having a Wei burning bond). A preferred example of the fluorene-based diamine is a compound represented by the following formula (xv): H2N-X4-R33 I-Si-O-I R34 R33-Si-X4-NH-R34 (XV) In the formula (XV), R33 and K34 are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and X4 is independently an alkylene group having 1 to 6 carbon atoms or a phenylene group, and m is 1 to 1 Å. In addition, any hydrogen of the substitutable group may be substituted with an alkyl group having 1 to 4 carbon atoms. Preferred examples of other diamines include, in addition to the monoxane-based diamine, the following formula (1,)~ Compound represented by formula (8'). 83 200923012

nH2 h2N

NH2 Hi\

base. \ Use a single amine, so that: two r easy two: ==== into the tree of the day (four) miscellaneous 13⁄4 of its domain shot secret weight average on the sub-quantity. The weight average molecular weight of the polyamic acid or a derivative thereof is not particularly limited. When used as a liquid crystal alignment component, it is increased by 5 or more, and more preferably 1χ1〇4 or _4 or more. 200923012 Polyammonic acid or a derivative thereof having a weight average molecular weight of 5xl 〇 3 or 5x10 or more does not evaporate in the step of firing the liquid crystal alignment film, and has excellent physical properties as a component of the liquid crystal alignment agent. The poly-aracine acid or a derivative thereof in the present invention may have any weight average molecular weight. The weight average molecular weight of the polyamic acid or a derivative thereof is not particularly limited, and when it is used as a component of the liquid crystal alignment agent, it is preferably 5 x 13 or more, or more preferably 1 x 10 or more. The polyglycine having a weight average molecular weight of 5xl〇3 or 5χ103 or more or a derivative thereof does not evaporate in the step of firing the liquid crystal alignment film, and has excellent physical properties as a component of the liquid crystal alignment agent. The weight average molecular weight is by gel permeation chromatography (Gd)

Permeation Chromatography, GPC) method. For example, the obtained polyaminic acid or its derivative is diluted with a monomethylformamide (DMF) to a polymer concentration of about 1 wt4 and then a 2695 separation module (separatj〇nm〇) Duie) and 2414 differential refractometer (differential she (10) for example) (made by gamma (10) company) 'DMF is used as a developing solvent and measured by gel permeation chromatography (GPC) method, and then obtained by polystyrene conversion Weight average molecular weight. In addition, in order to accurately perform GPC measurement of polyacrylic acid or polyacrylic acid, a mineral acid such as phosphoric acid, test, nitric acid or sulfuric acid or a brominated clock (leg um blOmide) may be prepared. Cong cWoride) is the same as the line-age solution in DMF. The polyamidoxime or a derivative thereof in the present invention can be produced by a known method. For example, 'with raw material addition port, gas inlet port, 85 200923012

The thermometer, one less amount of the required amount of dry amine. Next, adding a solvent (for example, a guanamine-based polar solvent N_methyl_2_pyrrole: (she is like Qingfu (4)) or dimethylmethamine, etc.) and a species or two or more of the four ships, and Add Rui Xuan as needed. At this time, the total number of moles of the total amount of the four ships is approximately equimolar (the molar ratio is about 〜9~u/). You can order it in the (TO ~ 耽 temperature reaction! Hou ~ 48 ^], to obtain a solution of poly-proline. In addition, you can also heat the 'Tennan reaction temperature (for example, 5 〇. 〇 ~ 8〇.〇To obtain a polyamic acid having a small molecular weight. The obtained poly-acid solution can be diluted with a solvent and used to adjust to the desired degree of dryness. The acid is precipitated, and the solid component and the solvent are completely separated by filtration or the like, and the polyamic acid is identified by infrared spectroscopy (IR) and nuclear magnetic resonance (Magnetic Resonance 'NMR) analysis. After decomposing the solid polyamic acid in an aqueous solution of a strong alkali such as KOH or NaOH, extraction is carried out with an organic solvent, and gas chromatography (eas) is performed.

Chromatograph ' GC ), liquid chromatography (HPLC) or gas chromatography-mass spectrometry (Gas)

Chromatography-Mass Spectrometry, GC-MS) analysis, whereby the monomers used can be identified. 86 200923012 性聚=:明;==: It is soluble for poly-acid derivatives. Γ 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏A tertiary amine such as collidine is obtained by carrying out a hydrazine imidation reaction at a temperature of ~150 C. * A large amount of poor solvent (P, solvent) (methanol, 3 ^ t solvent or a glycol-based solvent, which precipitates the poly-aracine from the poly-complex and the liquid mixture, and causes the precipitated poly-proline to be sprayed in the indole:=nei, or a stupid (_η〇), and the same as above The dehydrating agent and the dehydration ring-closing catalyst are obtained together in a ruthenium imidation reaction at a temperature of 2 (rc~15 。). In the hydrazine imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount of the dehydrating agent and the dehydration ring-closure catalyst is preferably from 5 times to 1 times the total amount of the acid dianhydride contained in the tetrazoic acid dianhydride to be used. Molar. By adjusting the chemical hydrazide dehydrating agent, the amount of catalyst, the reaction temperature, and the reaction time The degree of ruthenium iodization can be controlled to obtain a partial polyimine. The obtained polyimine can be separated from the solvent and then redissolved in a solvent to be described later together with the modifier to be used as a liquid crystal alignment agent, wherein The modifier is a combination of at least one selected from the group consisting of the alkenyl-substituted nadic quinone imine compound strontium selected from the heterocyclic compound, or 'the modifier may be added without being separated from the solvent to be used as a liquid crystal. Further, as described above, a part of the acid dioxane used in the tetracarboxylic dianhydride of the present invention may be replaced with an organic dicarboxylic acid. If the organic dicarboxylic acid 87 200923012 and the tetracarboxylic dianhydride are used, the present invention is used. In the poly-proline acid of the invention, a poly-proline-polyamine copolymer can be obtained. Here, the ratio of the organic dicarboxylic acid to the tetracarboxylic acid-hepatic can be within a range that does not impair the effects of the present invention. The basis thereof is preferably 10 mol% or less, or 10 mol% or less. Further, polyamidoquinone imine can be produced by chemically imidating the polyamic acid-polyamide copolymer. Various additives. The liquid crystal alignment agent of the present invention is described. The liquid crystal alignment agent of the present invention is a composition containing an alkenyl-substituted nadic ylidene imine compound, a compound having a radical polymerizable unsaturated double bond, and a polyglycine or a derivative thereof. From the viewpoints of adjustment of physical properties such as viscosity, ease of use, simplification of steps, and the like, the liquid crystal § & agent of the present invention may contain a solvent in one step, or may contain a liquid crystal alignment device containing (4) in a stepwise manner. From the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the heterocrystal alignment of the present invention is a sinusoidal imine compound.

U.UI^U.DU °

From the viewpoints of the decrease of the ion density, the suppression of the ion density with the increase of the time of 88 200923012, and the suppression of the afterimage, the compound having a radical polymerizable unsaturated double bond is substituted with the alkenyl group to the nadic ylidene compound. The ratio is preferably 0.1 to 10, more preferably 0.5 to 5 by weight. The content of poly-proline or a derivative thereof in the liquid crystal alignment agent of the present invention can be appropriately selected depending on the coating method in which the liquid crystal alignment agent is applied onto the substrate. For example, a printing machine used in a manufacturing step of a general liquid crystal display element (including an offset printer and an inkjet printer), which is sometimes referred to simply as a "printing machine," The content of the polyaminic acid or a derivative thereof in the agent is preferably 篁 十 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' However, it is appropriately adjusted in consideration of the relationship with the viscosity of the liquid crystal alignment agent. The solvent used in the present invention broadly includes a production step of a polymer component such as polylysine, soluble polyimine, and polyamidoximine. Or a solvent which is usually used in the use, and is appropriately selected depending on the purpose of use. The solvent is preferably 'containing 1' an aprotic polar organic solvent which is soluble in polylysine or soluble polyimine, and 2) A mixed solvent which changes the surface tension to improve the solvent of coating properties, etc. These solvents are exemplified below. 1) An aprotic polar organic solvent which is a good solvent for polyaminic acid or soluble polyimine (hereinafter referred to as Aprotic polar organic solvents): for example N-methyl-2-pyrrolidone, dimethyl imidazolidinone, N-methyl caprolactam, N-A N_methyi pr〇pi〇namide, N,N-methylacetamide, dimethyi suifoxide, ν,Ν- 89 200923012 dimethylformamide, N,N - diethylformamide, diethylacetamide, γ-butyrolactone, and γ-valer〇iactone. Among these solvents, N-methyl-2-oxime is preferred. Anthraquinone, dimethyl sigma sulphonone, γ-butyrolactone, and γ-pentane y. 2) A solvent (hereinafter referred to as another solvent) that changes surface tension to improve coatability, etc.: for example, lactic acid alkyl g, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl, etc. ethylene glycol monoalkyl ether, diethylene glycol single Diethylene glycol monoalkyl ether such as diethyl ether, ethanediol monoalkyl ether or phenyl ether acetate, triethylene glycol monoalkyl hydrazine, propylene glycol monobutyl ether and other propylene glycol monoalkyl ether, malonic acid II Ethyl ester (m An alonate monoalkyl ether such as a dialkyl malonate or a dipropylene glycol monomethyl ether; or an ester compound such as an acetate thereof; among these solvents, ethylene glycol monobutyl ether and diethylene glycol monosaccharide are preferred. Ethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monoterpene ether. The type and ratio of the aprotic polar solvent and other solvents can be considered in terms of printability, coating properties, solubility, and storage stability of the liquid crystal alignment agent. Purpose. The aprotic polar solvent is relatively excellent in storage stability as compared with other solvent groups, and the printability and coating of other solvents are as described above. The liquid crystal alignment agent of the present invention may contain various types. The various additives may be based on a polymer compound other than the derivative: or a compound. The polymer which is soluble in the organic solvent may be used as g 1 by adding these additives, and the formed liquid crystal 酉 200923012 may be controlled to the film. Electrical properties or alignment. Examples of such a polymer include polystyrene, polyurethane, polyurea, polyester, polyepoxide, and p〇lyester polyol. , anthrone modified polyurethane and anthrone modified polyester. Further, for the low molecular compound additive, for example, 1) an interfacial agent may be used in accordance with the purpose when it is desired to improve the coatability, 2) an antistatic agent may be used when it is necessary to improve the antistatic property, and 3) when it is desired to improve the substrate A decane coupling agent or a titanium coupling agent may be used for the adhesion or the abrasion resistance, and the ruthenium amide catalyst may be used when the oxime imidization is carried out at a low temperature. Examples of the sulphur coupling agent include ethylene trimethoxy oxalate, vinyl triethoxy decane, and N-(2-aminoethyl)-3-aminopropyl decyl dimethoxy.矽, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxy sinter, p-aminophenyltrimethoxy sylvestre, p-aminophenyltriethoxy oxane, m-aminophenyl Trimethoxy decane, m-aminophenyl triethoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, guanidal glyceryloxypropyl tributary oxylate Alkane, 3-glycidoxypropylmethyl-methoxymethoxy, 2-(3,4-epoxycyclohexyl)ethyltrimethoxycranane, 3-chloropropyldecyldimethoxy Decane, 3-chloropropyltrimethoxy decane, 3-methylpropenyloxypropyltrimethoxy oxysulfonate, 3-mercaptopropyltrimethoxy decane, N-(l,3-di Methylbutylene)_3_(triethoxydecylalkylamine, N,N,-bis[3-(trimethoxydecyl)propyl]ethylenediamine, etc. Examples of the imidization catalyst are preferably added ··Trimethylamine, triethylamine, dipropylamine, dibutylamine, etc. Aliphatic amines; dinonylaniline, n, N_ 91 200923012 Alkyl aniline, methyl aniline, brinic substituted aniline and other aromatic amines; bite, methyl substitution (four), substitution (four), surface, methyl Replacing 啥 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Ν, Ν _: mercapto aniline, o- phenyl aniline, guanamine, p-hydroxyaniline, o-ring, meridian bite, bismuth, isophthalocyanine, etc. The weight ratio of polyamic acid or a derivative thereof is 0 to 〇·1 〇, preferably 0.001 to 0 〇 3. The amount of the octa-imidization catalyst is usually added relative to the poly-proline or its derivative. The number of the base is 0.01 to 5 equivalents, preferably 5 to 3 equivalents. The addition of the other additives 1 varies depending on the use, and is usually 〇~0.30, preferably 〇〇, based on the weight ratio of the 1 amino acid or the derivative thereof. 〇1 to 0.10. Another preferred embodiment of the liquid crystal alignment agent of the present invention contains two or more kinds of poly The composition of the proline is, for example, a liquid crystal alignment agent containing a second polyamic acid and a second polyamic acid, wherein the first polyamic acid is not used for the tetracarboxylic dianhydride or the diamine. The 'second poly-proline acid obtained by the compound having a side chain group is obtained by using one or both of a tetracarboxylic dianhydride and a diamine using a compound having a side chain group. More specifically, the One of polylysines is at least one aromatic tetracarboxylic dianhydride (preferably the compound (1) to the compound (18)) and at least one aromatic tetracarboxylic dianhydride (preferably the compound) (19) ~ Poly(amino acid) or a derivative thereof obtained by reacting one or both of the compound (67)) with at least one non-side chain type diamine (preferably 92 200923012 compound (I) to compound (YU)) (hereinafter sometimes referred to as "polyamido acid I,"), and another poly-aramidic acid is one or both of the aromatic tetracarboxylic dianhydride and the four solubilized acid needles other than the aromatic 'and at least a side chain type diamine (preferably compound (view) ~ compound (XII), or The reaction mixture of at least one side-chain diamine and at least one non-side chain type diamines obtained polyamide acid or a derivative (hereinafter referred to as "polyamide acid Π ,,). The composition containing poly-proline I and bismuth citrate of the present invention is prepared by mixing the poly-proline I and poly-proline π. The weight ratio of the mixed polyaminic acid I to polypyridic acid π is preferably 1/11::=99/1 to 50/50 Å, more preferably Ι/Π = 95/5 to 80/20. The weight ratio may be appropriately adjusted according to the required pretilt angle, and if the ratio of the polyaminic acid is increased, the pretilt angle can be increased. Further, the liquid crystal alignment agent of the present invention may contain only polyamic acid I and ruthenium polyamide, or may further contain poly-aramid acid other than poly-proline acid J and polyglycine η or a derivative thereof. On the other hand, the polystyrene π has an effect of imparting a suitable pretilt angle to a liquid crystal display element containing a liquid crystal alignment film which is a liquid crystal alignment film containing [the liquid crystal alignment] Formed by the agent. A diamine other than the diamine having a side chain may also be used in combination in synthesizing the polyacrylic acid π. Examples of the diamine which can be used in combination include the above-mentioned compound (I) to the compound (\1), a diamine, and a decane-based diamine. By combining (blending) the polyamic acid I and polyphthalic acid π, excellent characteristics as a liquid crystal alignment agent of the present invention can be imparted. Specifically, it is possible to impart a liquid crystal alignment film formed using the composition of the present invention by appropriately selecting the kind of the diamine to be used and a combination thereof for the diamine which is a raw material of polylysine. Better long-term reliability and a suitable pretilt angle. The liquid crystal alignment film of the present invention can be formed, for example, by applying the liquid crystal alignment agent of the present invention to a substrate for a liquid crystal display element or a substrate for measurement such as calcium fluoride or ruthenium, and then applying the liquid crystal alignment agent. The film is heated to, for example, 150. (: ~400 ° C, preferably 18 〇 t 280 ° C. In this morning, the film thickness of the liquid crystal alignment film is preferably from 1 〇 nm to 3 〇〇 nm, more preferably from 3 〇 nm to 150 nm. Further, the liquid crystal alignment film Preferably, the film thickness of the liquid crystal alignment film can be adjusted according to the viscosity of the liquid crystal alignment agent or the coating method of the liquid crystal alignment agent. In addition, the film thickness of the liquid crystal alignment film can be adjusted by a profilometer or a polarizing ellipticity. The composition of the liquid crystal alignment film can be measured by hydrolysis or the like as needed, and can be analyzed by an ordinary analytical method such as IR or MS. The liquid crystal display element includes: a) a pair of substrates disposed oppositely, 2) a liquid crystal alignment film of the present invention formed on an opposing surface of each of the pair of substrates, and 3) sandwiching the pair of substrates The liquid crystal layer between. The pair of electrode-attached substrates disposed opposite each other is preferably a transparent substrate (e.g., a glass substrate). Electrodes are provided on the surface of at least one or both of the pair of substrates in correspondence with the form of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. 94 200923012 Examples of such an electrode include indium tin oxide (Indium Ή 〇 ,, 湘) or metal evaporation. The electrodes may be formed either on the entire surface of the substrate or in a specific shape such as patterned. The substrate 疋 without the electrode is formed on the surface of the substrate to form the liquid crystal alignment f ′ of the present invention, and the substrate on which the electrode is provided is the liquid crystal alignment film of the above (4). The formation of the liquid crystal alignment film of the present invention is as described above. The liquid crystal layer sandwiched between the pair of substrates contains a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and may be any composition in a liquid crystal composition having a negative dielectric constant anisotropy according to a driving mode of ^ tf ^ ^ ( dielectric constant anisotropy ) ^. . An example of a preferred liquid crystal composition having a positive dielectric anisotropy is disclosed in Japanese Patent No. 3,862, 528, Japanese Patent No. (4) No. 5, Japanese Patent Publication No. 5-5, No. 5, Japanese Patent Laid-Open Japanese Patent Laid-Open No. Hei 9-241644 (EP885272A1), Japanese Patent Laid-Open No. Hei 9-302346 (cut 06466A1), Japanese Patent Laid-Open/ Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (Which (4)), Japanese Patent No. _16 (Front 4229A1), Japan Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2000-087040, Japanese Patent Laid-Open No. 2000-087040, and Japanese Patent Laid-Open No. Hei.寻刿特开95 200923012 The liquid crystal composition used in each of the electric constants, the example of the butterfly is disclosed in the Japanese crystal composition 4^8S5 tt 8-104869 bulletin = 胄 、, Japanese patent special open patent M_# bulletin, daily newspaper = bulletin, 曰本 patent special open patents special open flat == 10_237〇〇4 bulletin, this patent special open patent, special open flat = 5 Li 1G_237G24 bulletin, 曰 (10) 7075 bulletin, , Japanese patent special open flat patent system flat 1G marriage 23 attack bulletin, 曰利特开平 H) marriage 74 t^mP96726, 曰本号号 bulletin, Japan ln%% patent this flat 1 () · 287875 Kaiping 2 = 945 Gazette, 曰本 Patent Special Report, Japanese Patent Special Open Vision 9th Publication No. 2001-019965, Japanese Soul Newspaper, Japanese Patent Unexamined Japanese Patent Laid-Open No. 192657, _=_72626 and Two different: used for positive or negative liquid crystal composition. _ Above optically active compound 96 200923012 The liquid crystal display element of the present invention may of course contain other members. For example, in a TFT-type liquid crystal element using a color display of a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like can be formed on the first transparent substrate, and in the second through plate There is a black matrix, a color filter, a planarization film, a halogen electrode, and the like which shield light outside the primitive region. Further, in the VA type liquid crystal display element, particularly the MVA type liquid crystal display element, a microprotrusion called a field (d〇main) is formed on the first transparent substrate. Further, a spacer for adjusting the cell gap of the liquid crystal cell between the substrates may be formed. The liquid crystal display element of the present invention is produced by any method, for example, by a method including the following steps. Applying a liquid crystal alignment agent to the two transparent substrates, 2) drying the applied liquid crystal alignment agent, and 3) performing necessary heat treatment on the dried liquid crystal alignment agent to perform dehydration and ring closure reaction; 4) Aligning the obtained peaches with the ship; and 5) sealing the two substrates with the special gap, sealing the liquid crystal in the gap between the substrates, or dropping the liquid crystal on one substrate and attaching to the other substrate Hehe. The coating method in the step of coating the liquid crystal alignment agent is generally known as a spinner method, a printing method, a dipping method, a falling-drop method, an inkjet method, and the like. These methods can also be used in the present invention. Further, the drying step and the method of carrying out the step of the twisting treatment necessary for the dehydration reaction are generally known in an oven (_) or an infrared furnace 97 200923012. ί method, heating on a hot plate (hGt plate). These methods can also be used in the present invention. Drying step 140. 〇疋, it is carried out at a lower temperature (5〇.0~i) in the range in which the solvent can be evaporated. The heat treatment step is usually preferably carried out at a temperature of about 15 (TC~3〇〇C). Usually, the rubbing treatment is performed. There are many VA liquid crystal display elements, and the rubbing treatment is performed, but the rubbing treatment may be performed. Next, 'the coating agent is applied to one of the substrates and bonded together: in the case of the drop casting method' Before the bonding, the liquid is attached to the substrate, and then bonded to the other substrate. The heat or ultraviolet light is used to harden the contact agent used for the bonding, thereby producing the liquid-displaying liquid crystal display element of the present invention. 〇CB type liquid crystal display element, TN liquid crystal display element, and STN Wei crystal display element, liquid display element film) == element = electricity: C polarizing plate (polarized light) [Embodiment] Hereinafter, the present embodiment will be described by way of examples. The invention is set forth in the examples. The compounds used in the examples are as follows: 丨艮<tetracarboxylic dianhydride> Compound (1): pyromellitic acid di-hepatic compound (19): 1,2,3 , 4-cyclobutanetetracarboxylic acid diammonium compound (23): l, 2 , 3,4-butadiene tetracarboxylic acid di-sodium _ <diamine> 98 200923012 Compound (V-1) : 4,4,-diaminodiphenyl decane compound (V-7): 1,2- Bis(4-aminophenyl)ethane compound (by-2): 1,3-bis(4-(4-aminobenzyl)phenyl)propane compound (XI-6-1) : l,l-double [4-(4-Aminophenoxy)phenyl H-[(4-heptylcyclohexyl)ethyl]cyclohexane compound (XI-4-1): 1,1_bis[4-(4- Aminophenoxy)phenyl-4-(trans-4-n-pentylcyclohexyl)cyclohexane compound (XI-6-2): 1,1-bis[4-(4-aminophenyloxy) Phenyl]-4-[(4-ethylcyclohexyl)ethyl]cyclohexane compound (XI-2-1)··1,1_bis[4_(4•aminophenyl)methylphenyl] 4-n-pentylcyclohexane < alkenyl-substituted nadic quinone imine compound> Compound (Ina-1): bis{4-(allylbicyclo[2.2.1]hept-5-ene-2 ,3·diimine)phenyl}methane

<Compound having a radical polymerizable unsaturated double bond> ΕΒΑ: ethylenediacetate NEBA: Ν, Ν'-ethylenebis propylene amide ΗΕΑ : Ν, Ν'-work hydroxyethylidene bispropene Amidoxime: 4,4,-arylene di(Ν,Ν-dihydroxyethylene acrylate stupid 99 200923012 <solvent > NMP : N_methyl-2-° than metholone GfiL : γ - Butyrolactone BC: butyl cellosolve (ethylene glycol monobutyl ether) [Synthesis Example 1] (synthesis of poly-proline) In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material addition port, and a nitrogen inlet Add compound (V — i ) (2.91 g), dehydrated NMP ( 54 g) # GBL ( 15 g), and mix and dissolve under dry Wei air flow. Then, add compound (19) (1.01 g) and compound ( 1) (2.08 g) 'reacts at room temperature for 3 hours. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 7 〇〇C or 7 Torr. The reaction is then obtained. The solution towel was added with BC (25, a poly-aramidic acid solution having a cerium concentration of 6 wt/〇; Α1). The obtained polyglycine had a weight average molecular weight of 57,0. 00. \ The weight average molecular weight of poly-aracine is determined by the following method: using a solution of phosphoric acid-D1VH (by weight ratio, DMf === 00) for the aged _-acid, = - ' Then use the 2695 separation module and 2414 difference = ======= column temperature" so that [Synthesis Example 2 to Synthesis Example 8] were changed except for the four-nano and diamines as shown in Table 1. 100 200923012 Synthesis Example 1 As a reference, a polylysine solution (PA2) to a polyaminic acid solution (PA8) was prepared, including Synthesis Example 1 'Preparation ratio of raw materials and weight average molecular weight of polyamine obtained It is summarized in Table 1. <Table 1> Synthesis Example PA acid solution 4CA-dihepatic diamine-rate weight average molecular weight No. No. Compound No. Molar fraction compound No. 1 PA1 (1) (19) 0.30 0.20 ( V-1) 0.50 57,000 2 PA2 (1) (19) 0.40 0.10 (V-7) (XI-4-1) 0.40 0.10 36,000 3 PA3 (1) (19) 0.40 0.10 (V-7) (XI-6 -1) 0.40 0.10 33,000 4 PA4 (1) (19) 0.10 0.40 (W-2) 0.50 52,000 5 PA5 (1) (19) 0.25 0.25 (V-1) 0.50 51,500 6 PA6 (1) (19) 0.40 0.10 (V -7) (XI-6- 2) 0.40 0.10 50,000 7 PA7 ( 1) (19) 0.40 0.10 (V-7) (XI-2- 1) 0.30 0.20 53,600 8 PA8 (1) (19) (23) 0.30 0.10 0.10 (VII-2) (V-1) 0.25 0.25 59,000 ( Note) PA acid refers to polyamic acid, and 4CA refers to tetracarboxylic acid. [Example 1] (Production of liquid crystal display element) A polyamine acid solution (PA1) having a concentration of 6 wt/min prepared in Synthesis Example 1 and a concentration prepared in Synthesis Example 2 were used in a weight ratio of 8/2. It was mixed with a 6 wt ° / 醯 polyglycine solution (PA2). Next, in the obtained mixture, a ratio of 101 parts per 100 parts by weight of polyglycolic acid per 100 parts by weight of 2009 20091212, respectively, an alkenyl-substituted nadic ylidene imine compound (ina-1) and A compound having a radical polymerizable unsaturated double bond, that is, MHA. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. A liquid crystal display element was produced using the obtained liquid crystal alignment agent, and the production method was as follows. A liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode by a spinner to form a film having a film thickness of 70 nm. After the film is applied, it is 8 〇. The crucible was heated and dried for about 5 minutes, and then subjected to a heat treatment at 210 ° C for 20 minutes. Then, rubbing treatment was carried out to form a liquid crystal alignment film. After ultrasonic cleaning of the substrate in ultrapure water for 5 minutes, it was 12 Torr in an oven. Dry under 30 for 30 minutes. A gap material of 7 μm is spread on one of the glass substrates, and another glass substrate is disposed opposite to the inner side of the surface on which the liquid crystal alignment film is formed so that the rubbing direction is antiparallel. . Then, an epoxy hardener was used to seal the periphery of the liquid crystal alignment film, and an antiparallel cell having a gap of 7 μm was formed. The liquid crystal composition shown below was injected into this liquid crystal cell, and an injection port for the liquid crystal composition was sealed with a light hardener. Then, heat treatment was performed at 110 ° C for 30 minutes to prepare a liquid crystal display element. <Liquid crystal composition> 102 200923012

17wt. %

17wt. %

16wt. % 1〇wt. % C3H7-{^)-C2H4

5wt. % 1〇wt. % c5Hi 1-^ C2H4·

6 wt. % 6 wt. % 13 wt. % [Example 2] A polyglycine solution (PA1) having a concentration of 6 ^ Q / prepared in Synthesis Example 1 and a synthesis ratio of 3 were prepared in a weight ratio of 8/2. The concentration is 6. The polyamic acid solution (PA3) is mixed. This is then in the mixture obtained. The compound (: (10) and the compound having a radical polymerizable unsaturated double bond, that is, HEA, are added to the ratio of π by weight of each of the poly-acids in an amount of 1 G by weight. 103 200923012 Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. Using the obtained liquid crystal alignment agent, and Example 1 A liquid crystal display element was produced in the same manner. [Example 3] A polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and a concentration prepared in Synthesis Example 2 were used in a weight ratio of 8/2. Mixing 6 polyamic acid solution (ΡΑ2), then adding alkenyl-substituted nadicylimine to the obtained mixture in a ratio of 10 parts by weight per 100 parts by weight of polyglycolic acid. The compound is a compound (Ina monoterpene and a compound having a radically polymerizable unsaturated double bond, that is, Neba. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) is added and diluted to prepare a polyglycine concentration. 4 wt% of liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 by using a liquid crystal alignment agent. [Example 4] A polyacrylic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example i and a weight ratio of 8/2 were used. The polyglycine solution (PA2) having a concentration of 6 wt% prepared in Synthesis Example 2 was mixed, and then in the obtained mixture, in a ratio of 1 part by weight per 100 parts by weight of the polyglycolic acid. 'Addition of an alkenyl-substituted nadic ylidene compound, that is, a compound (Ina-1) and a compound having a radically polymerizable unsaturated double bond, MHA, respectively, and the total amount of the modifier composed of these compounds is 2 parts by weight. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added to dilute polylysine to 4 wt% with respect to the whole solution to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent' In the same manner as in Example 1, a liquid crystal display element 104 200923012 was produced. [Example 5] In a polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 4, 'in terms of 100 parts by weight per 100 parts by weight Alkenyl substitution by a ratio of 10 parts by weight of proline The dick ylidene compound is a compound (Ina-1) and a compound having a radical polymerizable unsaturated double bond, that is, MHA, and then 'diluted with a mixed solvent of NMP/BC=1/1 (weight ratio) to make a poly A liquid crystal display element having a lysine concentration of 4 wt% was used. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 6] The concentration prepared in Synthesis Example 4 was 6 wt%. In the polyamic acid solution (PA4), an alkenyl-substituted nadic ylidene imine compound (Ina-1) is added in a ratio of 1 part by weight per 1 part by weight of polyglycolic acid. And a compound having a radical polymerizable unsaturated double bond, that is, EBA. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 7] A polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and a polyglycine having a concentration of 6 wt% prepared in Synthesis Example 6 were added in a weight ratio of 8/2. The solution (PA6) was mixed. Next, in the obtained mixture, an alkenyl-substituted nadic ylidene compound, that is, a compound (Ina-1) 105 200923012 and a compound having a radical polymerizable unsaturated double bond, that is, HEA, are added, respectively, per 100 parts by weight. Polyglycolic acid '20 parts by weight of the compound (Ina-1) was added, and 5 parts by weight of HEA was added. Then, a mixed solvent of nmp/bcsIA (weight ratio) was added, and polyglycine was diluted to 4 wt% with respect to the entire solution to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 8] A polyglycine solution (PA5) having a concentration of 6 wt〇/0 prepared in Synthesis Example 5 and a polycondensate having a concentration of 6 wt% prepared in Synthesis Example 6 were prepared in a weight ratio of 8/2. The amine acid solution (M6) was mixed. Next, in the obtained mixture, an alkenyl-substituted nadic ylidene compound, that is, a compound (Ina-i) and a compound having a radically polymerizable unsaturated double bond, that is, HEA, respectively, are added, respectively, with respect to 100 parts by weight of polyfluorene. Amino acid, 20 parts by weight of a compound (Ina-1) was added, and 5 parts by weight of HEA was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyglycine was diluted to 4 wt% with respect to the entire solution to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 9] A polyglycine solution (PA5) having a concentration of 6 wt% prepared in Synthesis Example 5 and a polyglycolic acid having a concentration of 6 wt% prepared in Synthesis Example 7 were added in a weight ratio of 8/2. The solution (PA7) was mixed. Next, in the obtained mixture, an alkenyl group is substituted with a nadic substituted imide compound, that is, a compound and a compound having a radical polymerizable unsaturated double bond, that is, HEA, wherein 30 is added per 100 parts by weight of the polyglycolic acid. Parts by weight of compound (Ina 106 200923012 - 1 ) ' and 20 parts by weight of HEA were added. Then, a mixed solvent of nmp/bc = 1/1 (weight ratio) was added, and polyglycine was diluted to 4 wt% with respect to the entire solution to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 10] A polyglycine solution (PA5) having a concentration of 6 wt% prepared in Synthesis Example 5 and a polyglycine having a concentration of 6 wt% prepared in Synthesis Example 7 were added in a weight ratio of 8/2. The solution (PA7) was mixed. Next, in the obtained mixture, ί ' is respectively added with an alkenyl-substituted nadic ylidene compound, that is, a compound (lna-1) and a compound having a radical polymerizable unsaturated double bond, that is, HEA, wherein the polymer is polymerized per 100 parts by weight. For the proline, 20 parts by weight of the compound Gna-1) was added, and 10 parts by weight of HEA was added. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polyglycine was diluted to 4 wt% with respect to the entire solution to prepare a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Example 11] (In a polyglycine solution (PA8) having a concentration of 6 wt% prepared in Synthesis Example 8, an alkenyl-substituted nadic ylidene compound, a compound (Ina-oxime), was added and freely added. The compound of the polymerizable unsaturated double bond, that is, HEA', wherein 2 parts by weight of the compound (Ina-1) is added per 1 part by weight of the polyamic acid, and 1 part by weight of HEA is added. Then, A mixed solvent of NMP/BC=m (weight ratio) was added, and polyglycine was diluted to 4 wt% with respect to the whole solution to prepare a liquid crystal alignment agent. The liquid crystal alignment agent obtained was used in the same manner as in Example 1. A liquid crystal display element 107 200923012 was produced. [Comparative Example 1] A polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and a concentration prepared in Synthesis Example 2 were used in a weight ratio of 8/2. It is mixed with a 6 wt% polyproline solution (PA2), and then diluted in a mixed solvent of NMP/BC = 1/1 (weight ratio) in the obtained mixture to prepare a polyglycine concentration. 4 wt% of a liquid crystal alignment agent. Liquid crystals were produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 2] A polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 1 and a concentration of 6 wt0/〇 prepared in Synthesis Example 2 were prepared in a weight ratio of 8/2. a polyaminic acid solution (PA2) is mixed. Then, in the obtained mixture, a compound having a radical polymerizable unsaturated double bond is added in a ratio of 10 parts by weight per 100 parts by weight of the polyglycolic acid. MHA was then added to the obtained mixture by adding a mixed solvent of NMP/BC = 1/1 (weight ratio) to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. The obtained liquid crystal alignment agent was used. A liquid crystal display element was produced in the same manner as in Example 1. [Comparative Example 3] In a polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 4, 'NMP/BC = 1/1 was added. The mixed solvent of (weight ratio) was diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 108 200923012 [Comparative Example 4] In a polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 4 For the ratio of 1 part by weight per 100 parts by weight of polyamic acid, an alkenyl-substituted nadic ylidene compound (Ina-indole) is added, and then NMp/BC=1/ is added to the obtained mixture. A mixed solvent of 1 (weight ratio) was diluted to prepare a liquid crystal alignment agent having a polyglycine concentration of 4 wt%, and a liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. 1 to test example 15] (Evaluation of electrical characteristics) The liquid crystal display elements produced in Examples 1 to Π and Comparative Examples ～ to 4 were measured for ion density (long-term reliability of electrical characteristics), and flicker-free was used. The residual Dc was determined by the (fliekerfree) method, and the measurement method was as follows. 1) Measurement of ion density The liquid crystal property evaluation device manufactured by Toyo Technica 6254 type H ion measurement unit is a pico-coulomb (pico piece: the waveform is a triangular wave, the frequency is (10) m _ The measurement temperature is set to 60 °C. The smaller the measured value, the better the electrical characteristics. The results are shown in Table 2. 2) The measurement of the retention property of the ion density The measured liquid crystal display element has an ion density with time, and 呷 = retention characteristics The test method is to take out the liquid crystal display element over time and determine: sub;; = 109 200923012 The smaller the increase in density (after the ion timbre, if it is placed under the conditions of 500 small to say that the ion density is 100pC*100pc or less), the reliability can be long-term. Good, the department can say that the electrical characteristics of the data = will be placed after 245 hours and after 500 hours 3) The residual dc measurement by the flicker-free method using FG-11 制造 manufactured by Yokogawa Electric Co., Ltd., 3 v The DC voltage overlaps with a rectangular wave of 30 Hz and 1.64 V and is applied for 3 minutes. The flicker elimination voltage was measured for 30 minutes from the end of the application. The table shows the flicker elimination voltage 5 minutes after the end of application. In addition, the measured temperature is set to 253⁄4. The closer the measured value is to 〇, the better the electrical characteristics can be said. The results are shown in Table 2. <Table 2> \Test Example No. Liquid crystal display element ion density (pc) Residual DC (mV) 0 After 245 hours, 500 hours later __ 5 minutes later 1 Example 1 1 22 49 77 -19 2 Example 2 18 33 47 -57 3 Example 3 47 82 101 _ -41 4 Example 4 22 69 91 -4 5 Example 5 27 49 65 -10 -------- 6 Example 6 84 123 158 - 3 7 Tube 'Example 7 13 40 40 -67 8 Paste Example 8 7 51 75 -75 —— -9 Example 9 13 19 25 -88 10 ΫExample 1〇12 33 41 r -98 11 fExample I1 9 39 61 -97 12 Comparative Example 1 72 112 139 L -666 ~~--- 13 th Comparative Example 2 36 104 198 -64 14 Comparative Example 3 112 201 244 -144 15 Comparative Example 4 41 53 63 "-131 110 200923012 As shown in Table 2, when a liquid crystal alignment agent is prepared by mixing a modified agent obtained by combining an alkenyl-substituted nadicylimine compound and a compound having a radical polymerizable unsaturated double bond in polyamic acid, The liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment agent can be seen to suppress the effect of increasing the ion density with time, and the afterimage characteristics are also remarkably improved. Although the present invention has been disclosed as an example, It is not intended to limit the present invention, and any technical lying towel has the usual knowledge, spirit and scope, and when some changes can be made, the scope of protection of the Ming Dynasty is attached to the "Simplified Perimeter [Simplified Description] The latter is subject to [main symbol description] No 111

Claims (1)

200923012 VII. Application for Patent Park: 1. A liquid crystal alignment agent, which is a compound containing an alkenyl-substituted nadic ylidene compound, a compound having a radical polymerizable unsaturated double bond, and a poly-proline or a derivative thereof. The composition, the liquid crystal alignment agent is characterized in that the alkenyl-substituted nadic ylidene compound is a ratio of the compound 'alkenyl substituted Nadick-based imine compound represented by the formula (Ina) to the poly-proline or The weight ratio of the derivative is 00, and the ratio of the compound having a radical polymerizable unsaturated double bond is G.G1~1.GG' and the weight ratio of the polyamine or the organism is The ratio of the proline or the derivative is 〇5 wt% to 3 wt% in the composition. N-(I η: carbon number it is independently hydrogen, carbon number 1 to 12, base group, 5 to 8 12 square or turn; n is * money base, carbon number is 丄~U When the number of filaments and carbon is 2 or 2, it is a radiant group, and the number of aryl groups of 6 to 12 is 5 to 8: sub-regional basis, and q is a bite independent of the number of turns represented by 叱Η. The integer is 1 to 4 of the filament or gamma (in the group ''4* Ζ5 alone j base, and sAn:l the number of rabbits 5 to 8 is m ^ and 8 is 〇 or D, or = base? u represents the base 112 200923012 In this group, B is a phenylene group, and τ is _CH2-, _c(CH3)r, -Ο, -CO-, or -S〇2·' 1 to 3 hydrogen-cholines are substituted; when η = 2, W is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, and a carbon number of 6~ The arylene of 12, the group represented by the group, the meaning of 卩 and r in the group, as described above, the group represented by -(z4)s_B_z5_, Z4, Z5 in the group, The meanings of B and s are as described above, or a group represented by _3-butyl$-, and the meanings of B and τ in the group are as described above, and one of the sulfones is ~3 2. The liquid hydrogen aligning agent according to claim 1, wherein the liquid aei aligning agent contains a rare-substituted nadic ylidene compound, poly-proline or a derivative thereof. And a composition of a compound having a radical polymerizable unsaturated double bond and the alkenyl-substituted nadic ylidene compound is at least one of the compounds represented by the formula (Ina-1) to (Ina-3): (I na-2) (I na-3) 113 200923012 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the liquid crystal alignment agent is an alkenyl-substituted nadic pyrimine A compound, a compound having a radically polymerizable unsaturated double bond, and a composition of polyglycine or a derivative thereof, and a compound having a radical polymerizable unsaturated double bond is an acrylic acid derivative or a mercaptoacrylic acid derivative. 4. The liquid crystal alignment agent according to claim 1 or 2, wherein the liquid crystal alignment agent is a compound having an alkenyl-substituted nadic ylidene compound and having a radical polymerizable unsaturated double bond, And a composition of a poly-proline or a derivative thereof, and a compound having a radically polymerizable unsaturated double bond is a compound having two or more radically polymerizable unsaturated double bonds, or contains the compound mixture. 5. The liquid crystal alignment agent according to claim 4, wherein the liquid crystal alignment agent is a compound containing an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, and a polydecylamine. A composition of an acid or a derivative thereof, and a compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-methylenebis propylene amide, ^^^ dihydroxyethylene _ At least one of an amine, ethylene diacrylate, and 4,4,-methylenebis(N,N-diethyleneethyl acrylate aniline). 6. The liquid crystal alignment agent according to the above aspect of the invention, wherein the polyamic acid is an aromatic tetra-retensive dianhydride represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). At least one of the reaction with a diamine to obtain a (tetra) compound, and the diamine is at least one selected from the group consisting of a phase chain type diamine represented by the formula (1) to the formula (vir): 114 200923012 Wherein X1 is a linear alkylene group having a carbon number of 2 to 12; X2 is a linear alkylene group having a carbon number of 1 to 12; and X3 is independently a single bond, -0-, -CO-, -CONH-, -NHCO-, -C(CH3)2_, -C(CF3)2-, -0-(CH2)t-0_, 115 200923012 200923012 -S- , — -i > -PU thiol or face, _C〇〇H 'H t ring or Benzene ring -S〇3H, or deductor: cyclohexane ring or benzene ring. As in the scope of claim 1 The liquid crystal alignment agent, wherein the polyamic acid is a polymer obtained by reacting an aromatic tetracarboxylic dianhydride represented by the formula (1) with a diamine, and the diamine is selected from the formula (jV) 1), (IV-2), (IV-15), (jy_16), (V-1)~ (V-12), (V-33) and (γυ-2) At least one of the non-side chain type diamines indicated: 116 200923012 (V-3) Nh2 (VII-2) 8. The liquid crystal alignment agent according to claim i, wherein the polylysine is obtained by formula (1), formula (2), formula (5) to formula (7) 117 200923012 A polymer obtained by reacting a mixture of at least one tetracarboxylic acid monoanhydride represented by the formula (14) with a diamine, and the diamine is selected from the group consisting of At least one of the group of non-side chain type diamines represented by formula (I) to formula (vir): 118 200923012 wherein X1 is a linear alkylene group having a carbon number of 2 to 12; χ2 is a linear alkylene group having a carbon number of 1 to 12; X3 is independently a single bond, _〇_, _c〇_, -CONH_ , -NHCO·, -C(CH3)2-, -C(CF3)2-, -0-(CH2)t-0-, -s-, -SS-, -S〇2-, _S_(CH2) t_S_ or a linear subfamily having a carbon number of 12, t is an integer from 1 to 12; any hydrogen of a cyclohexane ring or a benzene ring may be via _F, _CH3 or -OH, -COOH, -S03H, or -P〇3H2, benzyl or hydroxy-based group taken & 9. The liquid crystal alignment agent according to claim 8, wherein the tetracarboxylic dianhydride other than aromatic is a formula (19), a formula (23), a formula (25), and a formula (35) to (a) 37), at least one of the compounds represented by formula (39), formula (44), and formula (49): The liquid crystal alignment agent according to the first aspect of the invention, wherein the polyphthalic acid is an aromatic tetracarboxylic dianhydride represented by the formula (1) and a tetracarboxylic dianhydride other than the aromatic 119 200923012. a polymer obtained by reacting a mixture with a diamine, and the diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula ( V - 1) at least one of the non-side chain type diamine represented by the formula (V-12), the formula (V-33), and the formula (W-2): Ο 0 120 200923012 (V-1) (V-2) (V-3) NH2 Ii. The liquid crystal alignment agent according to claim io, wherein the tetracarboxylic dianhydride other than aromatic is a formula (19), a formula (23), a formula (25), a 121 200923012, a formula (35). At least one of the compounds represented by the formula (37), the formula (39), the formula (44), and the formula (49): 12. The liquid crystal alignment agent according to claim 10, wherein the tetracarboxylic dianhydride other than the aromatic compound is a compound represented by the formula (19): V (19) The liquid crystal alignment agent according to claim 1, wherein the polyamic acid is obtained by formula (1), formula (2), formula (5) to formula (7), and 14) a polymer obtained by reacting at least one of the aromatic tetracarboxylic dianhydrides with a diamine, and the diamine is a mixture of at least one non-side chain 122 200923012 amine and at least one side chain type diamine, Wherein the non-side chain amine is a non-side chain type diamine selected from the group consisting of formula (I) to formula (YU): in the group, the side chain type diamine has a carbon number of 3 or 3 The above-mentioned alkoxy group having a carbon number of 3 or more, an alkoxyalkyl group having 3 or more carbon atoms, a group having a steroid skeleton, and a terminal having a carbon number of 1 or more. a side chain group in the group of a ring having an alkyl group, a carbon number of fluorene or more, or an alkoxy group having 2 or more carbon atoms: 123 200923012 h2n-x1-nh; Wherein x1 is a linear alkylene group having a carbon number of 2 to 12; x2 is a linear sub-group having a carbon number of 1 to 12; and X3 is independently a single bond, _〇_, _c〇_, _c〇NH- -NHCO-, -C(CH3)2-, -C(CF3)2-, -〇_(CH2)t-0·, -S-, -SS-, -S〇2---S-( CH2)tS- or a linear alkylene group having a carbon number of 1 to 12, t is an integer of 1 to 12; any hydrogen of a cyclohexane ring or a benzene ring may be subjected to _F, _CI^f-OH, -COOH, -S03H, or -P〇3h2, benzyl or hydroxy-benzyl group substitution. 14. The liquid crystal alignment agent according to claim 13, wherein the side chain type diamine is a diamine selected from the group consisting of hydrazines represented by the formula (Cong) to (式π): 124 200923012 f Wherein 'Rl is a single bond, CO-, -COO., -〇CO_, CH2〇·Ρ2〇_ or a sub-alkyl group having a carbon number of 丨~6, and any -CHr of the sub-1 group It may be via _Q_, _CH=CH or substituted; ^ is a group having a steroid skeleton, a burning group having a carbon number of 3 to 30, a filament having a carbon number of 3 to 3 G or a slit having a carbon number of 3 to SG. a phenyl group of a substituent, or a group represented by the formula (D-U, and any -CH2· in the alkyl group may be substituted by _〇_, _CH=CH_ or _c=c_; Wherein 'R13, R14 and R15 are independently a single bond, _〇...c〇〇, _〇c〇, -CONH-, an alkylene group having a carbon number of 1 to 4, and an oxyalkylene group having a carbon number of 丨~3 Or an alkyleneoxy group having a carbon number of 1 to 3; ring B and ring c are independently 丨4 diphenylene or 1,4-cyclohexylene; π* Rn is independently fluorine or methyl, and ml and m2 Independently 〇] or 2; e, ^g are independently an integer of 〇~3, and their total value is 1 or more; is an alkyl group having a carbon number of 30, an alkoxy group having a carbon number of 1 to 30, Or a decyloxy group having a carbon number of 2 to rt 3 Å. Among these alkyl groups, alkoxy groups and alkoxy groups, any nitrogen may be substituted by fluorine, and any -CH 2 · may be difluoromethylene or a group represented by the formula "'(D - 2); 125 200923012 R19 I Si- I R20 R21 IO-Si-I R22 (D-2) It: '...^... and kg are independently an integer having a carbon number of (7) or a base and n is an integer of 1 to iq; (IX) Commonly (A) is a hydrogen such as horse hydrogen or m; r4; or a carbon number of 2 to 3, a number of 1 to " or -CH2-; and a base of 6 and 7; R is independently a single bond, CC Or phenyl, · and Yi Liqian, Wei for 1~3G base 126 (XI) 200923012 NH, NH, r8~{<SHch2^· 'a wherein R8 is an alkyl group having a carbon number of 1 to 30, and any tCH2 of the alkyl group may be replaced by _〇·, _CH=CH_ or -CsC R9 is independently or a calcined group having a carbon number of 1 to 6; ring A is 1,4-phenylene or M_, cyclohexyl; a is 0 or 1; b is 〇, 1 or 2; and, e Independently 0 or 1; Qr^ (XII) Fluorine 3 group ^= is a filament of Λ~3G or a flammable group having a fluorinated number of 1 to 3G of k30 to 30 or an i group of a scorpion; 立立为4,为·〇_ or The carbon number is 卜~" The side chain type diamine is the liquid crystal alignment agent described in it:: (Xiao-6), Formula 2 (Qing-2), Formula (5)-4), Formula, 5 Diamine in the formula: (ΧΙ~2) and the compound represented by 纟(ΧΙ-4) 127 200923012 R23 R24 (VIII-5) (VIII-6) R29 °^h2 Wherein R23 and R24 are independently an alkyl group having a carbon number of 3 to 3 fluorene or an alkoxy group having a carbon number of 3 to 30, and R30 and R30 are independently an alkyl group having a carbon number of 丨% or a carbon number of 1 to 30. Alkoxy group. 16. The liquid crystal alignment agent according to claim 13, wherein the non-side chain type diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (iv-15), formula ( IV-1), a diamine in the compound represented by the formula (V-1) to the formula (V-12), the formula (v-3), and the formula (pass-2), wherein the side chain type diamine is selected from the formula (M-2), Formula (View 4), Formula (Shan-5), Formula (Li-6), Formula (XI-2), and a compound represented by Formula (XI-4) 2009 20091212 Amine: (V-7) (VI1-2) 129 200923012 h2n R23 (VI11-2) R24 H2N h2n (Vlll-5) (VIII-4) R24 H2N (VIII-6) f Nh2 % V , wherein R 23 and R 24 are independently an alkyl group having a carbon number of 3 to 3 fluorene or an alkoxy group having a carbon number of 3 30, and the quaternary 29 and R 3 〇 are independently an alkyl group having a carbon number of 1 to 3 Å or Alkoxy groups having a carbon number of 1 to 1. 17. The liquid crystal alignment agent according to claim 1, wherein the polystyrene acid is selected from the group consisting of at least one aromatic tetracarboxylic dianhydride and at least one tetracarboxylic acid dianhydride other than the scented group. a polymer obtained by reacting at least one non-side chain type diamine, and reacting a mixture of the tetradecanoic acid dianhydride with a mixture of at least one side chain type diamine and at least one of said non-side chain type diamines And at least one of the obtained polymers, wherein the aromatic tetracarboxylic dianhydride of 130 200923012 is represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (H). The tetracarboxylic dianhydride other than the aromatic is a formula (19), a formula (23), a formula (25), a formula (35) to a formula (37), a formula (39), a formula (44), and a formula ( 49) indicates that the non-side chain type diamine is of the formula (jy-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (v-1) (V-12), formula (V-33), and formula (YU-2) indicate that the side chain type diamine is of the formula (M-2), formula (M-4), formula 5), \1~6), formula (XI-2) and XI-4) represented; 131 200923012 (49) 132 200923012 Nh2 (VII-2) 133 200923012 R 23 Wherein R23 and R24 are independently an alkyl group having a carbon number of 3 to 30 or an alkoxy group having a carbon number of 3 to 30, and R29 and R3G are independently an alkyl group having a carbon number of 1 to 30 or a carbon number of 1 to 30. Alkoxy. 18. The liquid crystal alignment agent according to claim 17, wherein the polystyrene is a mixture of at least one aromatic tetraphthalic acid diif and at least one aromatic tetracarboxylic dianhydride and at least one A polymer obtained by reacting a non-side chain type diamine. 19. The liquid crystal alignment agent according to claim 17, wherein the polyproline is a mixture of at least one aromatic tetracarboxylic dianhydride and at least one tetracarboxylic dianhydride other than 134 200923012 a polymer obtained by reacting at least one non-side chain type two fee, and reacting a mixture of the tetradecanoic acid dianhydride with at least one non-side chain type diamine and at least one side chain type diamine A mixture of polymers obtained. The liquid crystal alignment agent according to claim 17, wherein the polystyrene acid is at least one selected from the group consisting of at least one aromatic tetracarboxylic dianhydride and A mixture of at least one aromatic tetraretaic dianhydride other than aromatic is obtained by reacting a mixture of at least one non-side chain type diamine and at least one side chain type diamine. A liquid crystal alignment film formed by coating the liquid crystal alignment agent according to claim 1 on a substrate and firing it in a state of a film. A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one or both of opposite surfaces of the pair of substrates; and a relative orientation of each of the pair of substrates A liquid crystal alignment film formed on the surface of the liquid crystal alignment film and a liquid crystal alignment layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to claim 21. 135 200923012 VII. Designated representative map: (1) Designated representative figure of the case: None (2) Simple description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: