TWI361324B - Liquid crystal aligning agent,liquid crystal alignment film and liquid crystal display device - Google Patents

Description

</ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; And a liquid crystal alignment agent of at least one selected from the group consisting of polyacrylic acid (p〇iyamicacjd) and a derivative of the polyamic acid, a liquid crystal alignment film formed by the liquid crystal alignment agent, and a liquid crystal having the liquid crystal alignment film Display component. [Prior Art] The liquid crystal display element is used for a screen view of a notebook computer or a desktop computer (desktop PC), and a viewfinder (view fmder) of a video camera (vide〇camera). Among various liquid crystal display devices such as projection displays, they have recently been used for televisions. Further, it can also be used as an optoelectronic related element such as an optical print head, an optical F 〇 er transform transform element, or a light valve. The liquid crystal display device usually includes: 1) a pair of substrates disposed oppositely, 2) electrodes formed on one or both of the surfaces facing the pair of substrates, and 3) opposing pairs of the pair of substrates A liquid crystal alignment film formed on the surface, and 4) a liquid crystal layer formed between the pair of substrates. 25623pif The previous liquid crystal display element, which is mainly used as a display element using a nematic liquid crystal, twisted 90-degree twisted nematic (TN) type liquid crystal display element, usually with a twist of ΓδΟ or more A super TTwisted Nematic (STN) type liquid crystal display element and a so-called thin film transistor (TFT) type liquid crystal display element using a thin film transistor are being used. These liquid crystal display elements have a drawback in that the angle of view of the image can be normally visually observed 'when viewed from an oblique direction' to produce a decrease in brightness or contrast and a brightness inversion of halftone. In recent years, the problem of the above-mentioned viewing angle is being improved by the technique of the following liquid crystal display element: a TN-TFT type liquid crystal display element using an optical compensation film, and a vertical alignment using a vertical alignment and an optical compensation film (Vertical Alig nment 'VA) A liquid crystal display device, a multi-domain vertical alignment (MVA) liquid crystal display device using a vertical alignment and a large structure, and an in-plane switching (IPS) type in a lateral electric field system Liquid crystal display element, electrically controlled birefringence (ECB) type liquid crystal display element, optically compensated bending (0ptically c〇mpensated

Bend or Optically self-Compensated Birefringence: OCB) type liquid crystal display elements, etc., and improved techniques are being put into practical use or research. The technical development of the liquid crystal display element is realized not only by improving the above-described driving method or element structure but also by using the constituent members used in the liquid crystal display element. Among the constituent members used in the liquid crystal display device, in particular, a liquid crystal alignment film which is a high-quality liquid crystal display element which is related to the display quality of the liquid crystal display element, and which is used for a liquid crystal alignment film. At present, it is mainly prepared by dissolving (-imide) in an organic solvent on a liquid substrate, by heating, etc. ==, === =. It is also studied to use, for example, alkanoic acid for each polymerization (liquid crystal resistance), coating ===3 heat resistance, chemical resistance, dryness, sexual orientation, electrical properties, optical properties, I don’t know if I’m looking for it, it’s almost not practical. In order to improve the liquid crystal display element, the liquid crystal display element is "represented", and the voltage retention rate is mentioned. If the voltage holding ratio is low, the frame time + the voltage applied to the liquid crystal is lowered. As a result, there is a case where the degree of the party is 7^ and the normal grayscale display is faulty. In addition, the problem is that even if the initial charge retention rate is high, there is a decrease in the surface retention rate (long-term reliability) after the high-temperature acceleration test. The case of the class. In order to solve the above problems, several methods have recently been proposed. 1) A polyamine which is used for forming a liquid crystal alignment film and combining two or more kinds of polylysines having different physical properties is known. The acid composition is known, for example, from Japanese Laid-Open Patent Publication No. Hei 11-193345, and JP-A-H11-193347. 2) A polymerization containing a polyglycine and a polypamine is known. Varnish composition of the composition and solvent (for example, refer to International Publication No. WO 00/61684) / 1361324 25623pif Φ Two or more polyamine plants with different physical properties 1 and / valley The varnish is composed of WO0l/_733 manual.), such as the varnish composition of the molecular material of the first (four) two-opening shirt, the polyamine compound synthesized by the diamine compound of the polymer structure, and the Japanese patent special--(6)(4) Bulletin). The sub-species are added to the poly-bromide and the poly-branched varnish to add a low score == W technique (for example, refer to Japanese Patent Laid-Open). 9 26^4) ^ t ′X The invention similar to the present invention is disclosed in Japanese Patent Laid-Open Publication No. Hei. #b公告, Japanese Patent Laid-Open No. 2-34, and the former technology cannot fully solve the voltage holding ratio. [Description of the invention] It is expected to develop a voltage holding ratio and long-term use of the liquid crystal display (9) display element. A liquid crystal alignment film, a liquid crystal alignment film formed by using a liquid crystal alignment agent for a component, and a liquid crystal display element having the liquid crystal alignment film.

In order to solve the above problems, the inventors of the present invention conducted a preliminary study to find that a liquid crystal alignment agent containing a Nadick-imidized octa- 2-amino acid or a derivative thereof is formed to form a liquid crystal alignment i. The liquid crystal display element having this liquid crystal alignment film has a good I retention ratio and long-term reliability, thereby completing the present invention. I 1361324 25623pif

Further, it has been found that a liquid crystal alignment film which can be suitably applied to liquid crystal display elements of various display driving methods can be obtained by appropriately selecting the above polyamic acid. ......... The liquid crystal alignment agent of the present invention is represented by the following item [1].

[1] A liquid crystal alignment agent comprising a polymer component selected from an alkenyl-substituted nadic acid ruthenium imide compound, a derivative selected from poly-proline and poly-proline, and a solvent. The polymer component is at least one of a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine, and the tetracarboxylic dianhydride is at least one of the compounds represented by the formulae (1) to (17), The ratio of the polymer component based on the total amount of the composition is from 0.5 wt% to 30 wt%, and the ratio of the above alkenyl-substituted nadic acid ruthenium imide compound is relative to the polymer component. The weight ratio is 0.01 to 2

〇

〇

〇 〇 C

〇 ch2)^o. 〇

.〇 r\ 0 η η

(5)

ο

.〇 1361324 25623pif

Wherein Ph represents phenyl (phenyl) and Me represents methyl (methyl). According to the present invention, it is possible to provide a liquid crystal display element of various driving methods having a high voltage holding ratio and a long-term reliability of 12 25623 pif. The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the invention. ........................... [Embodiment] First, the words are explained. "Arbitrary" means not only freely selectable but also free to return. Choose a number. Further, "arbitrary a may be replaced by B, C, or 」" means that 'except for any substitution =, any A is replaced by C, and any A is replaced by D. Including a plurality of A substituted by at least two of b to D, for example, a thiol group ((fkyl) substituted by -〇- or _CH=CH- in the group, contains an alkyl group, Alkenyl, alkoxy (alk〇xy), alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl, etc. Further, in the present invention, it is preferred that two are connected The product represented by the formula (1) is abbreviated as a compound of the formula (1), and the compound represented by the formula (1) is also the same. The chemical structural formula in the present specification does not In the case of a substituent or a bonding position of a ligand to a ring, it means that the bonding position can be freely selected. Regarding the side chain type diamine and the non-side chain type diamine, the related description of the diamine used in the present invention The definition of these terms is explained at the outset. The present invention consists of the above [丨] term and the following items [2] to [14]. [2] The liquid crystal according to [1] An agent comprising a composition of a polymer component selected from the group consisting of an alkenyl-substituted nadic acid ylide imine compound and a derivative of poly-arachilic acid and the polyamic acid derivative, wherein the polymer component is 13 25 1324 25623pif tetracarboxylic acid, a needle obtained by reacting a diamine with a compound represented by the formula (16) and at least one of the compounds represented by the formula (I?), or a mixture of at least one of the compound represented by the formula (16) and the compound represented by the formula (17) and at least two of the compounds represented by the formula (1) to the formula (ls). [3] The liquid crystal alignment agent according to the item [1], wherein the dipic-substituted nadic acid ylide imide compound is a compound represented by the formula (a), h2c=c

(a) In the mountains, R1 and R2 are independently hydrogen, an alkyl group having a carbon number, an alkenyl group having 3 to 6 turns, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or η being 1 or 2. Soil _ η ♦ 1 when R. It is a burnt group having a carbon number of benzene, a cycloalkyl group having a carbon number of μ, an aryl group (aryi) having a carbon number of 6 to 12, a benzyl group, and -LL(0)q_(L2〇). rR4 (L) and B2 are independently carbon, ~6 alkylene, R4 is 2 to 6 carbon atoms or 1 'and Γ is an integer of 1 to 30), -(LW- R5 α3 soil is a Wei group with carbon=1~4, s is 〇 or 丨, Β2 is any hydrogen which can be substituted by phenylene, and r5 is the appearance of carbon number b, or BTB] (B2 is an arbitrary hydrogen which can be substituted by a collar, τ is he_, -c(CHi, -c〇-ms〇2-, and B) 14 1361324 25623pif is a phenyl group in which any hydrogen can be replaced by ·〇H ), when ^ is 2, 'R·3 is an alkylene group having 2 to 20 carbon atoms, an alkylene group having 5 to 8 carbon atoms, and an arylene group having 6 to 12 carbon atoms. 4 -(〇V(L2〇)rLt(Lr: L2 and y are independently subunits with a carbon number of 2 to 6, q^〇 or 〗, and Γ is an integer from 1 to 30), _(l3)s -B2-L5- and L5 are independently alkylene groups having a carbon number of 〜4, s is 〇 or j, B is a phenylene group in which any hydrogen can be replaced by -OH), -B2-T-B2· (B2 Independent • Established as an arbitrary hydrogen -OH substituted phenylene group, and T is _〇^_, &lt;2((:Η3)2-, _C0_, _〇_, -s• or _s〇2_), or seven 2-0-B2 -C(CH3)2_B2-〇-B2_ (B2 is independently a phenylene group in which any hydrogen may be substituted by _〇H). [4] The liquid crystal alignment agent according to [1], wherein the alkenyl group is substituted by an alkenyl group. The dick oxime imine compound is at least one of the compounds represented by the formula (a__i) to the formula (a-3). 1361324 25623pif

[5] The liquid crystal alignment agent according to any one of [1] to [4] wherein the diamine is selected from the group of non-side chain type diamines represented by formula (I) to formula (W). At least one of, 16 (I) 1361324 25623pif

H2N-A1-NH2

(II) h2n nh2

(111)

(IV) h2n nh2

(V)

H2n (VI)

(VII) nh2 wherein A1 is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; and A3 is independently a single bond, -0-, -CO-, -CONH-, -NHC0-, -C(CH3)2-, -C(CF3)2-, -0-A2-0-, -S-, -SS-, -S0:r, -S-A2- S-, or a linear alkylene group having a carbon number of 1 to 12; any hydrogen of the cyclohexane ring and the benzene ring may be fluorine, -03⁄4, -OH, -C00H, -S03H, Ρ03Η2, benzyl or hydroxybenzyl Substituted. [6] The liquid crystal alignment agent according to any one of [1] to [4] wherein the diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), (IV-16), at least one of the group of the non-side chain type diamine represented by the formula (V-1) to the formula (V-13), and the formula (W-2), 17 1361324

25623pif

(V-1) (V-2)

(V-3)

(V-12) (V-13)

The liquid crystal alignment agent according to any one of [1] to [4] wherein the diamine is a non-side chain type selected from the group consisting of formula (I) to formula (W). a mixture of at least one of an amine group and at least one of a side chain type diamine having a side chain group, 18 1361324 25623 pif, the side chain group being a sulfhydryl group having a carbon number of 3 or more and a carbon number of 3 Base, Wei Daqi in the 3 gorge, the sterol (S_d) skeleton group, and the terminal has an alkyl group having a carbon number greater than or equal to a burning group, a carbon number of 3 or more, or an alkyl group having a carbon number of 3 or more Selected group in the group, &amp; h2n-a1-nh2

(I) (II) (HI) (IV) (V) (VI) (VII) where 'A is a direct bond sub-alkyl group with a number of 2 to 12; A2 is a direct bond with a carbon number of 1 to 12. The base 'A is independently a single bond, _〇_, -CO-, -CCXNj&quot;j, -NHCO-, -C(CH3)2-, -C(CF3)2_, -〇-A2-0-,- S-, -SS·, -S〇2·, •S-A2-S-, or a linear alkylene group having a carbon number of 1 to 12; any hydrogen of the cyclohexane ring and the benzene ring may be fluorine, CH3, _〇H, _C00H, ·8〇3Ή, Ρ〇3Η2, benzyl or hydroxybenzyl substituted. [8] The liquid crystal alignment agent according to [7], wherein the side chain type diamine is a diamine selected from the group consisting of a compound represented by the formula (M) to the formula (XU) of 19 1361324 25623pif,

(VIII) (wherein R6 is a single bond, -0-, -CO-, -COO-, -0C0-, -C0NH-, -CH20-, -CF20-, or an alkylene group having a carbon number of 1 to 6 Any -CH2- in the alkylene group may be substituted by -0-, -CH=CH- or -CeC-; R7 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having a carbon number of An alkyl group having 3 to 30 carbon atoms or an alkoxy group having a carbon number of 3 to 30 as a substituent or a group represented by the formula (D-1), and any -CH2- of the alkyl group may be _〇 _, _CH = CH- or -C=C-,

Wherein R]8, R]9 and R20 are independently a single bond, -〇-, -COO·, -OCO-, -CONH-, an alkylene group having a carbon number of 1 to 4, and a carbon number of 1 to 3; Oxyalkylene, or alkyleneoxy having 1 to 3 carbon atoms; ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R21 And R22 is independently a fluorine or a fluorenyl group, and ml and m2 are independently 0, 1 or 2; e, f and g are independently an integer of 0 to 3, and the total of e, f and g is greater than or equal to 1; R23 is a carbon number of 3 An alkyl group of ～30, an alkoxy group having a carbon number of 3 to 30, or an alkoxyalkyl group having a carbon number of 3 to 30, and an alkyl group, an alkoxy 20 1361324 25623 pif group, and an alkoxyalkyl group. The hydrogen may be substituted by fluorine, and any -CH2_ may be substituted by a difluoromethylene or a group represented by the formula (D-2), R26 I 〇-Si- I R27

(D-2) R24

I

Si-

I R25

Wherein R24, r25 are a base or a phenyl group, and η, R26 and R27 are independently an integer having a carbon number of from 1 to 100) 1 to 10

(wherein ' R8 is independently hydrogen or a fluorenyl group; a sulphide having a size of 9 or a fluorenyl group having a charcoal number of 2 to 30;

Hydrogen, carbon number is 1~30 r1g is independent of single bond, -CO· or -CHy) 12

A h2n R11 R8 p9 &gt;w-7-R10~o

(X) (in the middle of R8 is independently a hydrogen or a methyl 9 alkyl group, or a carbon number 匕 is 虱, a carbon number is a singularity of 2 30; R is independently a single bond, _co_ 2] 1361324 25623pif

(XI) (wherein 'Rlj> is a p-mother with a carbon number of 3 to 3 - - can be _Q_, _CH=CH4 base'. Any arbitrary carbon number of this f-group is 1 to 6 sub-W Λ, R independent The filament of A or anti-horse 16 is phenylene, a is 0 or l; b is 0, 1 is 9. and 'Aya is 2, and c is independent 〇H霄^7^ 2 w (wherein R15 is a fluorinated group having a carbon number of 3 to 3; W is hydrogen, and the number of carbon atoms is 3 to 30 30; R]? is independently _〇· 0 pit base or carbon number is 1~ and ', d is independently 〇 or 1;) ', ', ~ 6 alkylene; [9] liquid crystal alignment agent as described in item m, which makes the side (view 2), formula (5) —4), Formula (known as a diamine selected from the group of compounds shown, x (Qing~6) 22 U01324

25623pif

(VIII-5) (VIII-6)

Further, R28 and R29 are independently a calcined group having a carbon number of 3 to 30 or an alkoxy group having a carbon number of 3 to 30. [1] The liquid crystal alignment agent according to item m, wherein the non-side chain type diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), and formula (IV). 16), ^-13~ Formula (V-13) and the diamine 'side chain type diamine in the group of the compound represented by the formula (V1I-2) are selected from the group consisting of a formula (circa-2) and a formula (^4). a diamine of the formula (H-5) and a compound of the formula (\1~6),

23 1361324 25623pif

(V-1) (V-2)

(V-3)

(V-12) (V-13)

(VII-2) 24 1361324

25623pif

(VI11-2)

Here, R28 and R29 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. [11] The liquid crystal alignment agent according to [1], wherein the polymer component is at least two selected from the group consisting of at least one of the compounds represented by the formulae (1) to (17). The polyamic acid or derivative thereof obtained by reacting at least one selected from the group consisting of the non-side chain type diamines represented by the formula (I) to the formula (I) to the tetracarboxylic dianhydride, by the above four a polyamic acid or a derivative thereof obtained by reacting at least one selected from the group consisting of a side chain type diamine represented by the formula (M) to the formula (M) with a tetracarboxylic dianhydride, and 'Polyamic acid or a derivative thereof obtained by reacting the above tetracarboxylic dianhydride with a mixture of the above-mentioned non-side chain type diamine and side chain type diamine, 25 1361324 25623pif

26 1361324 25623pif

ο (17) (where Ph is not a stupid base, Me means a methyl hydrazine polymer as a mixture of at least two polymers) and

(I) (II) (III) (IV) (V) Η2Νο-Α3-ο-&quot;-α ΝΗ 2

(VI) «· (VII) (where 'A1 is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; a3 is independently a single bond, _〇_ , _c〇_, -CONH-, -NHCO-, · ί:((:Η3)2-, -C(CF3)r, -〇_A2_〇_, each, -SS·, -S02-,- S-A2-S-, or a linear alkylene group having a carbon number; a cyclohexane ring and any hydrogen of a stupid ring may be fluorine, 27 1361324 25623pif

-COOH, -S03H, P03H2, benzyl or hydroxybenzyl substituted)

(VIII) (wherein R6 is a single bond, -〇-, -CO-, -COO-, -OCO-, -CONH-, -CH2O-, .-CF2O-, or a charcoal number of 1 to 6 An alkyl group, any -CH2. in the alkylene group may be substituted by -〇---CH=CH- or -OC-; R7 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having carbon a group of 3 to 30 or a group of a group having a carbon number of 3 to 30 and an alkoxy group as a substituent, or a group represented by the formula (D-1), wherein any of the groups may be _ch2- -Ο-, -CH=CH- or -OC-substitution,

Among them, 18, R19 and R20 are independently single bonds, -〇_, ._C〇〇... -OCO-, -CONH-, sub-hospital based on carbon number 1~4, carbon floes are 1~3 oxygen An alkylene group or an alkyleneoxy group having a carbon number of 1 to 3; a ring b and a ring C are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; and R21 and R22 are independently a ruthenium or a fluorenyl group. , ml and m2 are independently 〇, 1 or 2; e, f and g are independent integers of 0~3, and the total of e, f and g is greater than or equal to! R23 is an alkyl group having a carbon number of 3 to 30, an alkoxy group having a carbon number of 3 to 3 Å, or an alkoxy group having a carbon number of 3 to 30 Å, and an alkyl group, an alkoxy group and an alkoxy group. In the alkyl group, any hydrogen may be substituted by fluorine, and any ϋΗ2_ may be substituted by a group represented by the difluoroantimony 28 1361324 25623pif group or the formula (D-2) by f4 / @Si-(-Ο-Si- I , \ I R25 - - R.27 (D-2) wherein R24, R25, R26 and R27 are independently 哝 or 笨 ' and n is an integer from 1 to 100) &gt;8 R9 10

(IX) (wherein R8 is independently hydrogen or a fluorenyl group; R9 is hydrogen, an alkyl group, or an alkenyl group having a carbon number of 2 to 30; and, r]g is 1 to 30-CO- or -CH2-) Stand for a single key, h2n*

R12 A

NH, (X)'s it! Independently hydrogen or methyl; R9 is hydrogen, carbon number is 1~30^2~3G; independently is single bond, -CO-alkyl, or phenyl) independently 虱, carbon number is 1~30 29 1361324 25623pif

(wherein R3 is a sulphur group having a hindrance of 3 to 3 Å or a fluorinated group having a carbon number of 3 to fluorene; R] 6 is hydrogen, a carbon number is %%, or a carbon number is 3030. The base is R; 7 is independently _ 〇 or an alkylene group having a carbon number of 6; and d is independently 〇 or 1). [12] The liquid crystal alignment agent according to [11] wherein the polymer component is at least two selected from the group consisting of a compound represented by the formula (16) and a formula (17) a tetracarboxylic acid of at least one of the compounds or a mixture of at least one of the compound of the formula (16) and at least one compound selected from the formula (1) to the formula (15). The acid dianhydride 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-13), and formula ( Viewing the polylactoic acid or a derivative thereof obtained by reacting at least one of the group of non-side chain type diamines shown by _2), by using the above tetracarboxylic dianhydride and the selected formula (2) (Μ-4), formula (VHI-5), and polyglycine or a derivative thereof obtained by reacting at least one of the group of side chain type 30 1361324 25623pif diamine represented by formula (6) Polylysine or a derivative thereof obtained by reacting the above tetracarboxylic dianhydride oxime with a mixture of the above-mentioned non-side chain type diamine and side chain type diamine,

(V-12) (V-13)

H2N

Nh2 (VII-2) 1361324

25623pif

R29 (VIII-5) (VIII-6) 30 alkyl group or carbon wherein 'R28 and R29 are independently alkoxy groups having 3 to 30 carbon atoms. [13] The liquid crystal alignment agent disclosed in any one of the above [1] to [12], which is formed by baking in a state of a film. [14] A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; and a surface on which one or both of the surfaces facing the pair of substrates face each other, and a surface facing each of the pair of substrates A liquid crystal alignment film formed as described above, wherein a liquid crystal layer is formed between the pair of substrates.

The liquid crystal alignment agent of the present invention is a composition containing an alkenyl-substituted nadic acid ruthenium imide compound and a polymer component selected from the group consisting of poly-proline and a derivative of the poly-proline. Polylysine is a polymer obtained by reacting a tetracarboxylic dianhydride with a monoamine, dissolved in a solvent, coated on a substrate, and heated to form a polymer on the surface of the substrate. A liquid crystal composed of bismuth imide and a hard film. Examples of such derivatives of polyamic acid are soluble P〇lyimide 'p〇iyamicester', 乂 and 焉, and polyamic acid amide. More specifically, a polystyrene which is obtained by completely dehydrating a guanamine bond of a poly-proline and a carboxyl group, a partial polyimine which is partially dehydrated, and a 32 25623 pif group of poly-proline are listed. Polylysine-polyamine copolymer obtained by converting a part of a tetracarboxylic dianhydride into a dicarboxylic acid (or a halide or an acid anhydride thereof) and reacting it And making the poly-proline-polyamine copolymer part into a completely ' 兰 兰 兰 兰 兰 兰 兰 兰 兰 醯 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : In the case of an acid as an acid component, it is possible to obtain not only a polyamino acid polyamine copolymer but also a mixture comprising polyamine and/or polyglycolic acid, which is possible in the present invention. It is premise that it is a polyamidoxime-polyamine copolymer. In the present invention, at least one polymer selected from such polyamic acid and derivatives thereof is used. Further, at least two of such polymers are preferably used in combination. A preferred example of the alkenyl-substituted nadic acid ruthenium imide compound used in the present invention is a compound represented by the formula (a).

An alkyl group having a carbon number of 1 to 12, a cycloalkyl group, an aryl group or a benzyl group, wherein R1 and R2 are independently hydrogen, an alkenyl group having a number of 3 to 6 carbon atoms, and a carbon number of 5 to 8 η is 1 or 2. A cycloalkyl group, an aryl group having a carbon number of 6 to 12, a benzyl group, a ·Ll ^ an upper S-B2_R5, or a #. At this time, 'L, and an alkylene group of 2 to 6, L3 is an alkylene group having a carbon number of 1 to 4, and R4 is an alkyl group of 2 to 6 of the rock mountain. R5 is an alkyl group having a carbon number of 1 to 4. , β1 is any = 33 1361324 25623pif phenyl substituted by -OH, B2 is any hydrogen. Phenylene substituted by -OH, T is -CH2-, -C(CH3)2-, -CO-, - 0-, -S- or -S02-, q is 0 or 1, r is an integer from 1 to 30, and s is 0 or 1. When η is 2, R3 is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -L]-(0)q. - (L20)r-L4-, -(L3)s-B2-L5-, -B2-T-B2-, or -B2-0-B2-C(CH3)2-B2-0-B2_. In this case, L], L2 and L4 are independently a pyridylene group having a carbon number of 2 to 6, 1/ and L5 are independently an alkylene group having a carbon number of 1 to 4, and B2 is independently an arbitrary hydrogen: Substituted phenylene., T is -CH2-, -C(CH3)2-, -CO-, -0-, -S- or -S02-, q is 0 or 1, i• is 1~30 An integer and s is Ο or 1. Specific examples of the dimethic acid-substituted imine compound substituted with a dilute group include the following compounds and oligomers of the following compounds: 〇N-mercapto-allyl bicyclo [2.2. 1] H-methyl-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxy imide, ' 'N-mercapto-ene Propylmercaptobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, _N-mercapto-mercaptopropylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, N-fluorenyl-mercaptopropyl propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(2-ethyl Hexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy; 34 1361324 25623pif quinone imine, N-(2-ethylhexyl)·allylhydrylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, propyl allyl i-bicycloindole 2:2:1]hept-5-ene-2,3-dicarboxy quinone , N-allyl-allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide,

N-allyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-allyl bicyclo [2.2.1] g- 5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyanimine, N-iso Propenyl-mercaptopropylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine,

N-cyclohexyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, ' 'N-cyclohexyl·allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-cyclohexyldecylallyl bicyclo[2 21]hept-5-ene-2,3-dicarboxy quinone imine, N_phenyl-fluorene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N_styl-allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, 35 1361324 25623pif N-benzyl allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allyl fluorenyl bicyclo [2.2.1] H--5-ene-2,3-dicarboxy quinone imine, N-benzyl-mercaptopropyl bicyclop, 2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-(2'-hydroxyethyl)-allylbicyclo[221]hept-5-ene-2,3-dicarboxyindolimine, N-(2'-hydroxyethyl)-allyl Indenylbicyclo[2 21]hept-5-ene-2,3-dicarboxyarmine, N-(2'-hydroxyethyl)-mercaptopropylbicyclo[2 21]hept-5-ene 2,3·dicarboxyl with imine, N-(2y-dimethyl-3'-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3·dicarboxyfluorene Amine, Ν-(2',2'-dimethyl-31-propylidenepropyl)-allyl fluorenyl Ring [2.2.1] hept-5-rare-2,3-diyl-anthracene, N-(2',H-propyl)-dilylbicyclo[2 21]g_5_rare 2,3_: carboxy quinone imine, &lt; Ν-(2',3'-dipropylpropyl)-allylhydrylbicyclo[2 21]hept-5-ene-2,3-dicarboxyindole Imine, ν-(3'-propylidene)-bromopropylbicyclo[2 2hept-5-ene-2,3-dicarboxyarminemine, ν-(4'-yl-cyclohexyl) _Allyl fluorenylbicyclo[22 ηhept_5_lean-2,3-dicarboxy quinone imine, Ν-(4'-hydroxyphenyl)-allylbicyclo[2 2 hept-5-ene 2,3·dicarboxyl 36 1361324 25623pif acid imine, N-(4'-phenylphenyl)-allylmethylbicyclo[2.2·1]hept-5-ene-2,3-dicarboxyfluorene Amine, N-(4'-hydroxyl-yl)-methylallyl tombed bicyclo[i:2.1]-hept-5-ene-2,3-dicarboxyarmine, N-(4'-hydroxy stupid ))Allylallylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(3'-phenylphenyl)-allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy-indenine, N-(3'-hydroxyphenyl)-mercaptopropylbicyclo[2.2.1]hept-5-rare-2, 3-dicarboxy quinone imine, N-(p-trans-f-yl)-allyl bicyclo[2.2,1]hept-5-lean-2,3-dicarboxyl Imine, N-{2'-(2'-carbylethoxy)ethyl}-allylbicyclo[2 21]hept-5-ene-2,3-dicarboxyindenine, N-{2 '-(21-Pentylethoxy)ethyl}-allylhydrazinobicyclo[2 21]hept-5-ene'-2,3-dicarboxyindenine, 'N-{2'- (2'-Pentylethoxy)ethyldidecylallylbiscyclo[2 21]hept-5-lean-2,3-di-recommended imine, N-{2'-(2'-hydroxyethyl Oxy)ethyldidecylallylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-[2_{2_(2-carbylethoxy)ethoxy] Ethyl]-dilylbicyclo[2.2.1]hept-5-lean-2,3-dicarboxyarminemine, N-[2I-{2L(21'-hydroxyethoxy)ethoxy}B ]]-allyl fluorenyl 37 1361324 25623pif bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-[2'-{2i-(2&quot;-hydroxyethoxy Ethoxy}ethyl]-mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, Ν: {4Ι-(4,-hydroxyphenyl iso-Asia Propyl)phenyl}-allyl; ibicyclo[2:2.1]hept-5-ene-2,3-dicarboxyindenine, N-{4'-(4'-hydroxyphenylisopropylidene Phenyl}-allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene , N-{4'-(4'-Hydroxyphenylisopropylidene)phenyl}-mercaptopropylbicyclo[2.2·1]hept-5-fine-2,3-di-regiving imine , 1(1)-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindoleimine), hydrazine, Ν'-ethylene-bis(ene) Propylmercaptobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), NW-ethylidene-bis(nonylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), hydrazine, Ν1-triindolyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline), ' Ν,Ν'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), hydrazine, Ν'-hexamethylene-bis ( Allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine;), fluorene, Ν'-dodedecyl-bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-taudecyl-bis(allylhydrylbicyclo[2.2.1]hept-5-ene 38 1361324 25623pif -2,3-dicarboxy quinone imine), N,N1-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), .. Ν,Ν1-Cyclohexylene-bis(allylhydrazinobicyclo) Ρ.2:1]g:5-ene-2,3-dicarboxyarsenine), U-bis{34-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindole Imino)propoxy} 6^(l,2-bis{3'-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxy imide)propoxy}ethane ) ' 1.2- double {3' -(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, 1.2-bis{3'-(mercaptopropyl double ring卩.2.1]hept-5-ene-2,3-dicarboxy quinone imine) propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, bis[2'-{3'-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine) propoxy}ethyl]ether, M-double {3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) Propoxy}butane, M-bis{31-(allylhydrazinobicyclop.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}butane, N,N '-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-p-phenylene-bis(allyl) Indenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 39 25623pif N,N'-m-phenylene- (allylbicyclop.2.1)hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxyamine) v.....................................N , N'-{(1-indolyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), hydrazine , Ν1-p-diphenylene (xylylene)-bis(allylbicyclo[2.2.1]hept-5-fine-2,3-di-trans-acid imide), hydrazine, Ν1-p-difluorene Phenyl-bis(allylhydrazinobicyclo[22.1]hept-5-ene-2,3-dicarboxyindolimine), hydrazine, Ν'-m-diphenylene bis-allyl bicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-m-diphenylene bis-allyl (allyl fluorenylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), 2.2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) Phenoxy}phenyl]propane, 2.2-bis[4'-{4'-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy Phenyl]propane, 2.2-bis[4'-{4|-(nonylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy} Phenyl]propane, double {4-( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} methane, double {4-(allyl fluorenylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine) phenyl} decane 1361324 25623pif bis {4-(methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene. Amine)phenyl}曱戈, bis{4-(methylallylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxy...imine] ϋί曱Alkane, ............................. Double {4-(allylbicyclo[2.2.1 G-_5-ene-2,3-dicarboxy quinone imine) phenyl} bond, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯iamine). 笨 }} ether, _ bis {4-(mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} ether, double { 4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)phenyl}, double {4-(allylhydrazinobicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine) stupid base 飒, bis {4-(methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine) sulfone, • I,6·bis (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyanthracene 'amine)_3-light base-hexane, 1, 12-double (曱Allyl bicyclopurine .2.1] hept-5-ene-2,3-dicarboxy quinone imine)-3,6-di-perylene-dodecane, 1,3-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinoid imine)-5-light group·cyclohexene, 1,5-bis{3H allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) propoxy}-3-carbyl-heptane, 41 1361324 25623pif 1.4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine)-2-hydroxy-benzene, 1.4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)-2,5-di Light base-stupid, oxime, Ν1-p-(2-hydroxy) stilbene-bis(allylbicyclo[2.2.1]hept-5-frost-2,3-di-trans-acid imine), Ν,Ν'-p-(2-hydroxy) stilbene phenyl-bis(allylhydrazino ring [2.2.1]hept-5-ene-2,3-dicarboxy quinazoline), hydrazine, hydrazine '-Inter (2-hydroxy) stilbene phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), Ν, Ν'-between (2 -hydroxy) xylylene-bis(nonylallylbicycloindole.2.1) hept-5-fine 2,3-di-trans-acid imine), hydrazine, Ν'-pair (2,3-di Hydroxy) stilbene phenyl-bis(allylbicyclo[2.2,1]g-5-^-2,3-two rebellion Imine), 2,2-bis[1-(44allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2'-light-phenoxy }phenyl]propylamine, • double {4-(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-lightyl-phenyl}indole Calcined, bis{3-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-4- per phenyl-phenyl} bond, double {3-(fluorenyl) Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) _5_light phenyl-phenyl}, 1,1,1-tris{4,-(allyl Indenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)}phenoxymethylpropane, 42 1361324 25623pif N,N\N"-tris(ethylene decylene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinimide)isocyanurate. Moreover, it may also be the following compound containing an asymmetric alkylene group and a phenylene group.

The above alkenyl-substituted nadic acid ruthenium imide compound may be used singly or in combination of two or more kinds. Examples of the preferred alkenyl substituted nadic acid ylidene imine compounds described above are listed below. Ν,Ν'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N'-ethylene-bis(allyl Base bisbicyclo[2.2.1]hept-5-ene-2,3-di 43 1361324 25623pif carboxy quinone imine), hydrazine, Ν'-ethylene-bis(methylallylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν·-trisinyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imino), hydrazine, Ν1-hexamethylene-bis(allylbicycloindole.2.1)hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-hexamethylene fluorenyl - bis (allylmethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, NL dodecamethylene-bis (allyl bicyclo [2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-dodedecyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene_2, 3_Dicarboxy quinone imine ' Ν, Ν '-cyclohexylene-bis (allyl bicyclo [2_2.1] hept-5-ene-2,3-dicarboxy quinone imine), Ν, Ν 1- Cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy acid imide), 'Ν, Ν1-p-phenylene-bis(allyl bicyclol) [2·2.1]hept-5-ene-2,3-dicarboxy quinone imine) Ν,Ν'-p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), hydrazine, Ν'-m-phenylene- Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), hydrazine, Ν'-m-phenylene-bis(allylhydrazinobicyclo[2.2.1 ]hept-5-ene-2,3- 44 1361324 25623pif dicarboxy quinone imine), Fanchong-{(1-indolyl)-2,4-phenylene}-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine), ... Ν, Ν 1-p-diphenylene phenyl-bis(allyl tombened bicyclo [HI]hept-5-ene-2,3- Dicarboxy quinone imine), hydrazine, Ν'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline), hydrazine, Ν'-m-Diphenyl phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-m-diphenylene phenyl- Bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2.2-bis[4'-{4'-(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, 2.2-bis[4'-{41-(allylhydrylbicyclo[2.2.1]heptane- 5-ene-2,3-.dicarboxy quinone imine)phenoxy}phenyl]propane, 2.2- double [4444 mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenoxy} phenyl] propane, 'double {4-(allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimide)phenyl}methane, bis{4-(allylhydrylbicycloindole.2.1)hept-5-ene-2,3-di Carboxylimine)phenyl}decane, bis{4-(mercaptopropylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)phenyl}methane, double { 4-(decylallylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxy 45 1361324 25623pif quinone imine)phenyl}decane, kiln 趟 double {4_(allyl Bicyclo[2]g-hept-5-ene-2,3 two-county quinone imine) aniline)^W-based bicyclic Tao Geng 2: trans-diuretic imine) phenylpropyl bicyclo [2,2· 1] Geng-5 Lu 2,3·2 County Brewing Subunits} Milled Double, {4-(Dilylpropylbicyclo[2.2.1]hept-5u 2,3-dicarboxyarmine) Aniline Propylmethyl double % [2.2.1] Gg _5 · ene 2, 3 _ 叛 酿 酿 酿 ^ ^ } 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 碾 2 2 2 2 Example of 3_二敌基亚亚^ The best _-substituted Nadik surface imine compound 醯Ethylene·bis(10)propyl bicyclo[2.2.1]g _5 pu 2,3·2 County:: base · double (dilute propyl Base double ring [2·2.1] material ^ county:;) ethyl, methyl group double ring [2.2.1] Geng Fu 2,3 · two base brewing @ base double ring [2·2·_ϋ2'3Ί dicarboxy Ν 'Ν /ΝMethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2, 46 1361324 25623pif quinone imine), N,N1-hexamethylene-bis(allylmethyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), Ν,Ν'-docamethylene-bis(allylbicyclo ρ.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), fluorene, fluorene 1-dodecyl fluorenyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine), hydrazine, hydrazine 1-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-cyclohexylene-double ( Allyl fluorenylbicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine), fluorene, fluorene 1-p-phenylene-bis(allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine), hydrazine, Ν'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), 'Ν,Ν' -m-phenylene-bis(allylhydrazinobicyclo[2 .2.1] hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2 .1] G--5-fine-2,3-di-rebelletic imine), hydrazine, Ν'-p-diphenylene phenyl-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine), hydrazine, Ν'-p-diphenyl phenyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene 47 1361324 25623pif -2,3-di Carboxylimine), N,N'-m-diphenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), team: Sub-diphenyl phenyl-bis-propyl hydrazino stack ring 卩 ^ 庚 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2_bis[4'-{4'-(dilylpropyl) Indenylbicyclo[2.2.1]hept-5-lean-2,3-dicarbenylimine)phenoxy}indolyl]propane, 2'bis[4']4'-(methallyl Bicyclo[2.2.1]hept-5-rare-2,3-dimethylarsenazo) stupidoxy} stupyl]propane, double {4-(allylbicyclo[2 21]hept_5_ Alkene 2,3_dicarboxy quinone imine) phenyl}methane, amine ^1 propyl methyl bicyclo [2·2.1] hept-5-ene diacetamide) benzene Double base (}4 Ι 稀 丙基 双 双 双 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Preferably, &lt;chemical 5 (a-2) and compound (a-3)c 48

25623pif

(a-1) (a-2)

(a-3)

The proportion of the t-alkenyl substituted naphthoic acid-absorbing imine compound is in the range of the weight ratio with respect to the polymer component, and more preferably 〇·〇1 to 2'. When the amount of the nalylene-substituted naphthoic acid oxime &amp; imine compound of the present invention is within this range, a liquid crystal alignment agent varnish which can maintain long-term reliability, liquid crystal alignment property, and display quality balance can be obtained. / * The polymer component used in the present invention is at least one polymer selected from polylysine and derivatives thereof. Further, the polyglycolic acid of the present invention is obtained by reacting at least one of the carboxylic dianhydrides of the formulae (1) to (17) shown below with a diamine. 49 1361324 25623pif

50 1^01^24 25623pif

〇(17) In the formula (16) and the formula (17), Ph represents a phenyl group, and Me is a preferred tetracarboxylic dianhydride used in the present invention, and is a formula and a formula of the formula (16). At least one of the compounds shown in (17), or a compound of at least one of the compounds of the formula (i.e. and the compound of the formula (17) and/or one of the compounds of the formula (I5). . A part of the tetracarboxylic dianhydride used in the present invention can be obtained by replacing the - part of the reading acid dianhydride with a Wei: reaction termination, which can suppress the reaction to continue to control the obtained polymer (polylactoic acid) Molecular: The ratio of the acid dianhydride may not detract from the effects of the present invention, and it is preferred to make it a total amount of the total four-salt dianhydride and a g mo in the garden. Or, any diamine may be used in the present invention. However, in the case of the VA type liquid crystal display element, the oblique angle (_lt angle) of the case of ~$, and the inclination of the 0CB type liquid crystal display element of about -20 ° or so Angle, TN type liquid crystal _ ^ Requires 7 &lt; In the case of the display element, it is required to be 3. ~1G. The left and right tilt angles, crystal display 夂 1PS type discharge 51 1361324 25623pif crystal display elements require 0. ~3. a small inclination angle. Therefore, 'the adjustment of the inclination angle must be considered. Among them, the diamine can be divided into two according to its structure. That is, when the osteopone connecting the two amines i (amin〇) is regarded as the main chain, The group that is consumed by the autonomous chain is the diamine of the side chain group, and has no side a diamine of a bond group. By reacting a diamine having a side chain group with a tetracarboxylic dianhydride, a polylysine or a polyimine having a plurality of side chain groups relative to the main chain of the polymer can be obtained. When using the (tetra)amine acid or the polyaniline having a side chain group relative to the polymer main chain, the liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer can increase the liquid crystal display without 7G pieces. The angle of inclination, that is, the side chain group is a group having an effect of increasing the inclination angle, and may be selected from a group having a carbon number of 3 or more, a group having a carbon number of 3 or more, and a number of carbons of 3 or more. a oxy-steryl group, a sterol bone (four) group, and an alkoxy group having a carbon number greater than or equal to 3 carbon atoms or a carbon number of 3 or more in the present invention. A diamine having such a side chain group is referred to as a side chain = a diamine having such a side chain group is referred to as a non-side chain type diamine. Further, by combining a side chain type diamine with a non ===, When the tilt angle required for each of the elements is not required to be angled, at least one of the non-side chain type diamines may be used. Crystal display element, 0CB type liquid crystal Display element side, etc.::; when using a combination of a non-side chain type diamine to a side chain type non-side chain type diamine. Of course, the size of the inclination angle of the heart is determined by the size of the field and the side chain. The base may be used only with the side chain type diamine or 52 1361324 25623pif corresponding to the desired tilt angle. Thus, the liquid crystal alignment agent of the present invention can be applied to any kind of liquid crystal display element. The specificity of the side bond group is as follows. The gram is initially exemplified by alkane, an alkoxyalkyl group, an alkyl carbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, Alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarboxy, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylamino Carbonyl group and the like. Further, the alkyl group, the alkenyl group and the alkynyl group in these groups are all groups having a carbon number of 3 or more. Among them, in the alkoxyalkyl group, the total carbon number is preferably 3 or more. Further, these groups may be linear or branched. Secondly, the terminal ring has an alkyl group having a carbon number of 3 or more, a carbon number of 3 or more oxy groups, or a group having a higher than 3 oxy oxime group as a substituent, and examples thereof include a phenyl group, a phenylalkyl group, and a benzene group. Alkoxy group, phenoxy group: benzoquinone carbonyl group, stupid base group, phenoxy group, phenylamine group, f hexyl hexyloxy group, ring wire having a carbon number of 3 or more, cyclohexyl group Cyclohexyloxy, cyclohexyloxy, ring &amp; phenyl, cyclohexylphenylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl), benzyl, bis (cyclo) a group of a hexyl) phenylalkyl group, a bis(cyclohexyl)oxycarbonyl)oxy group, and a cyclohexyl bis(phenyl)oxyl group. In addition, bis(cyclohexyl) and bis(phenyl) may be used not only for the single-segment but also for the sub-fourth. . ^ can be 2 or more than 2 or more benzene rings or cyclohexane rings via early,,, ..., -C00...OC〇...(7) hop or sub 53 5361324 25623pif alkyl bond with carbon number of 3, and The terminal ring has an alkyl group having a carbon number of 3 or more, a fluorine-substituted alkyl group having a carbon number of 3 or more, an alkoxy group having a carbon number of 3 or more, or an alkoxyalkyl group having a carbon number of 3 or more as a substitution. The set of rings of the base...······ . . - -. - * .... ....... Do.-· , ..... · . .... base. Of course, a group having a steroid skeleton can also be effective as a side chain group. Preferred examples of the non-side chain type diamine are listed below. H2n-a1-nh2 (I)

In the formulae (I) to (W), A] is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; and A3 is independently a single bond, -0 -, -C0_, _CONH_, -NHCO·, _C(CH3)2-, -C(CF3)2-, -0-A, -S-, -SS-, -S〇2_, -SA-S-, Or a linear alkylene group having a carbon number of 17*12; any hydrogen of the cyclohexane ring and the benzene ring may be substituted by fluorine, -CH3, -OH, -C00H, -S03H, Ρ03Η2, benzyl or hydroxybenzyl. 54 1361324 25623pif Examples of the diamine represented by the formula (I) are the compound (I-1) to the compound (I-4). H2n(ch2)2nh2 h2n(ch2)4nh2 H2N(CH2)6NH2 h2n(ch2)12nh2 (1-1) '0-2)· ........(I-3) * ..... ....M)'- The examples of the diamine represented by the formula (Π) are the compound (U-1) and the compound (Π-2).

H2n-&lt;^)^nh2 h2N-0j-nh2 (11-1) (II-2) An example of the diamine represented by the formula (IE) is a compound (ΠΙ-1)~ a compound (ΙΠ-3).

H?N

(in-1) Examples of the diamine represented by the formula (IV) are the compound (IV-1) to the compound (IV-16). Η2Ν_^ΝΗ2 Η2^ΝΗ2 Η2Ν^ (IV-1) H2N—j)—NH2 (IV-3)

H2n-y nh2

H2N~^<~NH2 (IV-5)

(IV-2) OH

H2N v NH2 (IV-6) HO NH2

(IV-4) C〇〇H

H2N ^ NH2 (IV-8) (IV-7) 55 1361324 25623pif

An example of the diamine represented by the formula (V) is a compound (V-1) to a compound (V-34).

(V-1)

(V-2)

(V-3)

(V-12) (V-13) 56 1361324 25623pif

(V-16) (V-17)

Η2Ν^〇κ〇&quot;^^0'ν&lt;0ΚΝΗ2

(V-19) (V-18)

(V-21) (V-20)

H2N0^S-S0^-NH2 H2N{^SVS0&gt;- (V-22) (V-23)

NH 2 h2n-^s-sr〇-NH^ h2n (V-24) (V-25) NH2

(V-26) h, 〇&quot;s^^sO·Call (V-27) 57 1361324 .2'5623pif CH,

H2N—/Τ Λ\ H2N one (V-31) (V-32)

NH 2

HO OH 〇H OH (V-33) (V-34) Examples of the diamine represented by the formula (VI) are the compound (VI-1) to the compound (VI-6).

NH2 H2N^x (VI-1)

(VI-2) (VI-4) (VI-3)

(VI-5) (VI-6) An example of the diamine represented by the formula (W) is a compound (YE-1) to a compound (VE-16) ° 58 1361324 25623pif

(VIM) (VI1-2)

1VII-3)....................(VIW)

More preferably, among the above diamines, the compound (IV-1) to the compound (IV-5), the compound (IV-15), the compound (IV-16), the compound (V-1) to the compound (V-20) ), compound (V-26), compound (V-27), compound (V-31), compound (VI-1), compound (VI-2), compound (VI-6), compound (VE-1) ~ Compound (W-5), particularly preferred examples are compound (IV-1), compound (IV-2), chemistry 59 25623pif j (15), compound (IV-16), compound (v compound (H3) ), and the compound (w —— compound (&quot;ΐ &gt;., - species.;. also. can be hearty ^S (10))., can use these characters alone (VI) in the use of two Or two or more. The ratio of the compound (1)' to the desired amount of electricity and the amount of electricity required depends on the mechanism of the selected diamine: the whole is 'better'. The human D is W 疋 5 mol% ~ 80 Mol%. As described above, at least one diamine is used in the present invention, especially a VA type liquid crystal display element, a (10) type liquid crystal display element, a §τν type liquid crystal display element, etc., which require a large tilt angle. Use class, it preferred to use a side chain type diamines. Preferred examples of side chain type diamines of formula (M) ~ formula (Ying) amine bis FIG.

(VIII) wherein 'R is an early bond, -〇-, -CO-, -COO-, -OCO-, -CONH·, -CH2〇-, -CF20-, or a sub-entertainment with a carbon number of 1 to 6^ Any of -CH2- in the alkylene group may be substituted by -〇-, -CH=CH- or -OC-; R7 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having a carbon number An alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms 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 -C triple C-substitution. JZ4

25623pif

-nrn, 中 ' R , R 9 and R 2 () are independently a single bond, -0-, _C00_, ^ ^ C〇NH-'alkylene having a carbon number of 1 to 4, carbon number i~3

a base or a n-alkyloxy group of % 3; a ring B and a ring C ^ 1,4 phenylene or 1 &gt; 4 - cyclohexylene; r21 and r22 are independently a gas - a base such as m2 Independently 〇, w2; e, f, and g are independent integers of ～3, and the total of e, f, and § is greater than or equal to i; r23 is an alkyl group of carbon ～2 3 to 30, and an alkane having a carbon number of 3 to 3 〇. An oxy group, or a carbon number of 3, an oxygen-based filament, these filaments, an alkoxy group, and an alkoxyalkyl group, any hydrogen may be substituted by fluorine, and any _CH^ may be a difluoromethylene group or a formula (D- 2) The group shown is substituted.

(D-2) 1 to 10, wherein R24, R25, R26 and R27 are independently an integer having a carbon number of a burnt group or a stupid group, and η is from 1 to 100.

Wherein R 8 is independently hydrogen or a fluorenyl group; R 9 is a hydrogen atom (IX) such as 61 1361324 25623 pif alkyl group of 1 to 30, or an alkenyl group having a number of 2 to 3 fluorene; and, independently, a single bond, _ or - CH2y

Wherein 'R8 is independently hydrogen or a fluorenyl group; R9 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; independently a single bond, _c〇_^-CHr; And Ru is independently hydrogen, an alkyl group having a carbon number of 1 to 3 Å, or a stupid group. &amp;

Wherein R13 is an alkyl group having a number of 3 to 30, and any 'CH2' of the alkyl group may be substituted by 〇_, -CH=CH4 C$_; and R14 is independently an alkylene group having a carbon number of 1 to 6. a ring: 1,4-phenylene or 1,4-cyclohexylene 'a is 0 or 1; b is 0, 1 or 2; and, c is independently 〇 or 1

Wherein R15 is an alkyl group having a carbon number of 3 to 30 or a carbon number of 3 to 3 (alkyl); R16 is hydrogen, an alkyl group having a carbon number of 丨~, or a carbon number of 62 1361324

25623pif

A fluorinated alkyl group; R17 is independently -0- or an alkylene group having a carbon number of 1 to 6; and d is independently 0 or 1. The following shows an example of a compound (Μ)

(VIII-11) In the formula (Μ-1) to the formula (Μ_11), R28 is an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, preferably a carbon number of 5 to 30. 25 alkyl or an alkoxy group having a carbon number of 5 to 25. R29 is an alkane having a carbon number of 3 to 30. 63 1361324 25623pif

The alkoxy group having a carbon number of 3 to 30 is preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. R30 ρ30 ρ30

(VIII-16) (VIII-17) In the formula (M-12) to the formula (M-17), R30 is a basic group having a carbon number of 4 to 30, preferably a carbon group having a carbon number of 6 to 25. . R31 is a carbon number of 6~

The base of 30 is preferably a burnt group having a carbon number of 8 to 25.

H2n (VIII-22)

H2N (VIII-23) 64 1361324 25623pif

H2N (VIII-24)

H2N

H2N (VIII-25) (VII Bu 26)

H2N

H2N

(VIII-29) (VIII-30)

H2N h2n (VIII-35) (Vlli-36)

CH3 ch3 Si-O-Si-R32 I I ch3 ch3 65 1361324

In the formula 25623pif (Μ18)~(Μ—37), R32 and R33 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, preferably carbon. The number is 3 to 25 alkyl groups or the alkoxy group having a carbon number of 3 to 25. ...........

Among the above compounds, preferred are the compound (VID-1) to the compound (Μ-11), more preferably the compound (ΥΙΠ-2), the compound (Shen-4), the compound (VHI-5), and the compound (observation) One 6). In the formula (K), it is preferred that 66 1361324 25623pif of two "NH2-(Ph)-R]G-0-" is bonded to the 3 position of the steroid nucleus, and the other is bonded to the 6 position. The bonding position of the two amine groups with respect to R1Q is preferably bonded to the meta or para position. ................. έΤ(ΙΧ) The example of the diamine of the ¥ ¥ 可 可 可 & 勿 勿 勿 勿 勿 勿 勿 勿 IX IX IX IX IX IX IX IX IX IX IX IX IX IX IX IX IX IX IX IX

• In the formula (X), the bonding position of the two "NH2-fR12-)(Ph)-R1()-0-" with respect to the benzene ring is preferably relative to the carbon bonded to the steroid core. Bit or alignment. The bonding sites of the two amine groups with respect to the benzene ring are preferably meta or para to R1Q, respectively. Examples of the diamine represented by the formula (X) are the compound (X-1) to the compound (X-8). 67 1361324 25623pif

68 1361324 25623pif

69 1361324

25623pif In formula (XI), the preferred bonding position of the two amine groups relative to the benzene ring is meta or para position relative to R14. An example of the diamine represented by the formula (XI) is a compound -(Xt-1)^^ compound (XI = 8). ...............

R34 R34

70 1361324

25623pif

In the formula (XI-1) to the formula (XI-8), R34 is a burnt group having a carbon number of 3,730, and Rd is a burnt group having a carbon number of 3 to 20. In the above formula (ΧΠ), the preferred bonding position of the two amine groups with respect to the benzene ring is a meta or para position with respect to R17. A preferred example of the diamine represented by the formula (M) is the compound (XH-1) to the compound (XU-3). 71

25623pif

(XII-3) In the above formula, R36 is an alkyl group having 6 to 20 carbon atoms, and R37 is a nitrogen atom or a number of 1 to 10. The compound (M) to the compound (M) may be used singly or in combination of two or more kinds. The ratio of the compound (view) to the compound (XE) in the total amount of the diamine can be adjusted according to the selected diamine structure and the desired tilt angle, preferably from 1 m〇1% to 1 (8), more preferably 1〇111〇1°/()~1〇〇111〇1%.

Among the compounds (VDI) to (XH), preferred are the following compounds (Μ-2), compounds (view 4), compounds (5-5), and compounds (V1D-6).

Wherein 'R28 and R29 are independently an alkyl group having a carbon number of 3 to 3 Å or an alkoxy group having a carbon number of 72 1361324 25623 pif of 3 to 3 Å. The second one is preferably mixed from the compound (1) to the compound

The didiamine and the self-compound (!) di-compound (邳). ―1), the human, the sub-, and especially the mixed use of the compound (IV)

16), compound (= 2), compound (W-15), compound (IV-2), not selected, ) ~ compound (V - 13) and compound (W cm less - species of 浯Human) and compound (view -6) selected to - 4), chemistry 2 r. Further, the proportion of the two selected from the compound (-2), the compound (amine in the amine: -, ~5) and the compound (5)-6) is preferably 10 read ~ (10) mo. More preferably, 3〇m〇I%~1〇〇in〇i〇/〇. The diamine in the compound may be a compound (1) to a compound and a diamine other than the compound (5) to the compound (5). Such: the other amine may be any diamine, for example, it may be exemplified by a compound other than the compound (welcome). In the present invention, it is preferred that the amine amine has a diamine or has a Wei. (iv) A sulphur-deficient monoamine or a compound (boron) having a side chain structure. The oxirane-based diamine is not particularly limited as shown in the formula (XV). ,hJ^fA4+

Η2 (XV) wherein Μ and R39· are a filament or a phenyl group having a carbon number of 1 to 3, and 73 1361324 25623pif A4 is independently a fluorenylmethyl group, a phenylene group or an alkyl group-substituted sub-phenyl group. ^For! ~6 of whole bran, m is an integer from 1 to 10. Further, the other diamine is not particularly limited, and in the present invention, it is preferred to use, for example, the above formula (r) to formula (δ,). .......... R40

(2·)

The diamine in the present invention can be imparted to a liquid crystal matching film formed by using the liquid crystal alignment agent of the present invention at a preferred tilt angle by appropriately selecting the kind and combination of the diamine. A part of the diamine in the present invention may be replaced with a monoamine. By replacing a part of the two with a monoamine, the polymerization reaction can be terminated, thereby proceeding, so that it is easy to control the obtained polymer (: guanamine: h. The ratio of the early amine to the diamine) is not damaged. And the 74 1361324 25623pif (four) of the present invention, the job is money _ quantity of 1 1υ1ηο] 0 /. The following is the goal. The average of if = = amine acid and its derivatives can have any weight and no special The weight average molecular weight of the p-tyrosine and its derivatives is 5 χΐ η / 疋, and when used as a component of the liquid crystal alignment agent, it is preferably greater than or equal to (4) denier, more preferably equal to or greater than lxlQ4. Has greater than or equal to 5 Μ 03 (four) Ϊ average The molecular weight poly-proline and its derivatives do not evaporate in the liquid crystal alignment, and have better physical properties as a component of the liquid crystal alignment agent. The weight average molecular weight of the polyaminic acid and its derivatives is Determined by gel permeation chromatography (GPC). For example, the polylysine obtained by diluting with dimethylformamide (DMF) and its derivatives are used to achieve a polyglycine concentration. ^ wt% It was measured by gel permeation chromatography (Gpc) method using Chromatopack C-R7A (manufactured by Shimadzu Corporation) using DMF as a developing solvent, and the weight average molecular weight was determined by polystyrene conversion. In order to accurately measure GPC such as polyacrylic acid or polyacrylic acid, a mineral acid such as phosphoric acid, hydrochloric acid, nitric acid or sulfuric acid or a lithium bromide may be dissolved in a dmp solvent. A developing solvent for an inorganic salt such as a vaporized lithium. The polylysine and the derivative thereof in the present invention can be produced by a known method, for example, a raw material inlet, a nitrogen gas inlet, a thermometer, a stirrer, and a condenser (condenser) a reaction vessel containing at least one of the desired amounts of the diamines of formula (I) to formula (welcome), according to situation 75 1361324

Add the required amount of diamine selected from other diamines to 25623pif and add the required amount of monoamine as needed. ..... ¥. Injecting a solvent (for example, as a guanamine-based polar solvent: Νμmethyl-2-pyrrolidone or dimethyl decylamine) and at least a kind of tetracarboxylic dianhydride, and further, as needed Put in slow acid anhydride. At this time, the total addition of four oxo-dianhydrides

It is allowed to react for 1 to 48 hours under stirring at a temperature of 〇t &gt; c to 70 ° C, whereby a solution of poly-proline is obtained. Further, heating is carried out to raise the reaction temperature (e.g., 50 ° C to 8 Torr), whereby a polymolecular acid having a smaller molecular weight can also be obtained. In the present invention, the polylysine is precipitated with a large amount of poor solvent, and the solid component is completely separated from the solvent by filtration, etc., by infrared spectroscopy (IR), nuclear magnetic resonance (nuclear magnetic resonance).

The preferred total number of moles of hydrazine and diamine is approximately equal (the molar ratio is around 09 1.1). The analysis was carried out by NMR), whereby it was identified. Further, after decomposing the solid polyamic acid with an aqueous solution of a strong alkali, the organic solvent is used for extraction, and the gas chromatograph is used to carry out a high performance liquid chromatography (GPC) and high performance liquid chromatography (high performance liquid chromatography). A liquid chromatograph (HPLC) or gas chromatography mass spectrometer (Gas Chromatography-Mass Spectrophotometer 'GC-MS) was used for analysis, whereby the monomers used were identified. The obtained solution of polylysine can be diluted with a solvent to adjust it to a desired viscosity. In the case where the poly-aracine acid of the present invention is a polylactoic acid derivative, that is, a soluble poly 76,324 25623pif-bromoimine, the poly-proline acid solution and acetic anhydride or propionic anhydride (propionic acid) as a dehydrating agent can be used. An anhydride, an acid such as trifluoroacetic anhydride, and a secondary amine such as triethylamine, β-pyridine, or methyl*7, which are dehydration ring-closing catalysts, are combined at a temperature. Obtained by hydrazine imidization at 2 ° ° c ~ i5 ° °c.

A large amount of poor solvent (methanol (methan), ethanol, isopropanol, etc. (alc〇h〇1) solvent, glycol (solvent) can also be used to make polyamine. The acid is precipitated from the poly-proline solution and the precipitated poly-proline is combined with the same dehydrating agent and dehydration ring-closing catalyst in a solvent of toluene and xylene. Obtained by hydrazine imidization at ~150 °C. In the above hydrazine imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is (U 1 to 1 G (mole ratio). The total amount of the two is preferably a good amount; the tetrahydro acid anhydride used; The oleic anhydride of the acid dianhydride contained in the oleoresin by adjusting the chemical dehydration

The second catalyst I, the reaction temperature and the reaction time, the degree of controllization of the imidization of the ship's obtained a part of the polyimine. As described above, in the acid-=', the second: partially used in the tetra dianhydride in the present invention may be replaced by organic two. If the ratio of the organic di(tetra)amine-polyamide is used to obtain (4), the recognition, the concentration of the organic monocarboxylic acid relative to the tetracarboxylic dianhydride will affect the tree shape (4) Fan_, Cong The good thing is to make it a target of less than or equal to 1 secret. Further, polyamidoquinone imine can be produced by phosphating the polyamido acid-polyamido copolymer chemical quinone imine 77 1361324 25623. The adjustment of the two physical properties, the ease of handling, and the simplification of the step 8 may further include the usual liquid crystal alignment. The liquid crystal alignment agent of the present invention has various additives. The liquid crystal alignment agent is coated on the substrate. And:=: According to (including offset printing (. fine ΡΙ; Γ) / Λ Γ printing machine 赖 S), to T right 拄 ~ from r) and I ink printing press (ink jet P under %) Printing machine) Poly-acid in liquid crystal alignment agent ^0· Wt/r30 Wt% 5 1 -0/0^15 ^0!:Γ! Can be used with the viscosity of the liquid daily alignment agent (after) ... It is used to adjust it appropriately. 高 ^ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高Polar organic solvent, * 2) A mixed solvent for changing the solvent of the table: These solvents are exemplified as a non-protonic secondary organic solvent, such as a non-protonic polar organic solvent, which is a good solvent for the non-L) H t poly-brenolic acid or soluble poly-imine. Di lmidazohdmone ' N- ® «. c-tam), N-methyl propionamide &gt; 78 1361324

25623pif N,N-dimethylacetamide, dimethyl sulfoxide, ν, ν·dimethyl decylamine, hydrazine, hydrazine-diethyl hydrazine &amp;amine, monoethylacetamide, γ-butyrolactone, γ-valerolactone. More preferably, these are exemplified by Ν_methyl_2_pyrrolidone, dimethylimidazoline, γ-butyrolactone, γ-valerolactone and the like. 2) A solvent (hereinafter referred to as another solvent) for the purpose of changing the surface tension, improving the coating property, etc., for example, an alkyl lactate, 3_

Ethylene glycol monomethylbutanol, tetralin, isophorone, ethylene glycol monobutyl hydrazine (ethylene g to c〇1 m〇n〇butyi ether) Diethylene glycol single-base oxime such as alkyl ether, diethylene glycol monoethyl ether, diol monofilament-based acetic acid, propylene glycol monobutyl ether, etc. And malonate diacetate (this mail magnate) and other malonic acid dicalcyl base, dipropylene glycol monomethym and other dipropylene glycol single hospital base - these acetic acid g such as the purpose of the compound. Its towel is better exemplified by ethylene glycol single, _, _ &gt; π

(Ethyl alcohol monoethyl, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.. A protic polar solvent and other solvents of the type and ratio, can be tested = brushability, coating, solubility and storage stability The ratio of the aprotic polar solvent to the other solvent phase and the coating property is excellent, and the other solvent-dispersing agent may contain various additives. The polyamine acid and its derivative or low are selected. Molecular Compounds As described above, various additives of the liquid of the present invention may be added according to a polymer compound other than the respective target organisms, 79 1361324 25623pif, for example, a soluble polymer compound may be used as an additive in an organic solvent by adding a soluble polymer. The compound can control the electrical properties and alignment of the Γ _ alignment film. Examples of the polymer compound can be: polyamine oxime (poIyurethane), polyurea (p〇lyurea): Polyepoxide, polyester polyol ((10) polyol), silicin modified polyurethane, anthrone modified polyester, etc. In addition, low knife compound addition For example, 1) it is desirable to use a surfactant that satisfies this purpose when improving the coatability, 2) use an antistatic agent when it is necessary to improve the antistatic property, 3) desire to improve the adhesion to the substrate or improve the friction resistance (nibbing) A decane coupling agent or a titanium coupling agent may be used in the case of a property, and 4) a ruthenium-imiding catalyst may be used for the hydrazine imidation at a low temperature. Examples of the above decane coupling agent include vinyl trimethoxy fluorene, vinyl triethoxy decane, and N-(2-aminoethyl)-3-aminopropyl decyl decyloxydecane. , Ν-(2.Aminoethyl)-3-aminopropylmethyltrimethoxy oxime, p-aminophenyltrimethoxy zeoxime, p-aminophenyltriethoxydecane, between Aminophenyltrimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxyoxydecane, 3-aminomercaptotriethoxydecane, 3-hydroglycidyloxy 3-glyCy d〇Xy propyl trimethoxy silane, 3-glycidoxypropyl decyl decyloxy decane, 2-(3,4-epoxycyclohexyl)ethyl three曱 矽 矽 、, 3 — propyl propyl decyl 曱 曱 石 、, 3- propyl propyl trimethoxy decane, 3- methacryloxypropyl trimethoxy decane, 3 巯 propyl propyl Trimethoxy decane, dimethylbutylene)·3-(triethyloxyalkyl)-I-propylamine, n,Nl bis[3-(tridecyloxydecyl)propyl]ethylene Amines, etc. 1361324 25623pif For the above-mentioned brewing imidization catalyst, it is preferred to add an aliphatic amine such as trimethylamine, triethylamine, dipropylamine or tributylamine; N,N-dimercaptoaniline (N,N-dimethyl) Aniline :), Le-diethyl phenamine, methyl substituted aniline, hydroxy substituted aniline and other aromatic amines; 0 pyridine, methyl substituted bite, substituted by a base Bite, 啥琳(咖n〇Une), ', dimethyl substituted 喧琳, m 1 base substituted if,, different ^^, methyl substituted foreign material, bribe substituted for the material, material 〇midaz〇le), a material substituted with a methyl group, and a catalyst such as a squama ring core replaced by a county. In particular, N,N•dimethylaniline, o-anisidine, m-phenylaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine or isoquinoline can be mentioned. The amount of the decane coupling agent to be added is usually 〇~0.1 with respect to the weight ratio of the polymer component, and preferably 〇1 to 〇3. The amount of the ruthenium-imiding catalyst to be added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents based on the carbonyl group of the poly-proline and its derivative. The amount of the other additives to be added varies depending on the use thereof, and is usually ό0 to 03, preferably 〇〇〇1 to 0.1, based on the weight ratio of the polymer component. The viscosity of the liquid crystal alignment agent of the present invention varies depending on the coating method, the concentration of the polyglycolic acid and its derivative, the kind of the polylysine and its derivative to be used, and the kind and ratio of the solvent. For example, it is preferably 5 mPa · s to 100 mPa *s (more preferably 1 〇 mpa · s to 80 mpa.s) when applied by a printing machine. If it is less than 5 mpa.s, it is difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa·s, there is a case where printing unevenness is increased. Preferably, it is coated with spin coating 8] 1361324 25623pif (spin coat): $·s~200 mPa · s (better, lGmPa.s~1()() mPa.s). The viscosity of the liquid crystal alignment agent is measured by a rotational viscosity measurement method, for example, using a rotating adhesive (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25. 〇. The present invention Another preferred embodiment of the liquid crystal alignment agent is a composition comprising two or more polymers selected from the group consisting of polyamidoxime and its derivatives. In this case, the 'polymer' and the group are a poly-tyranamic acid or a derivative thereof (polymer component oxime) obtained by reacting a dianhydride with a non-side chain type diamine selected from the compound (I) to the compound (νπ). In addition to the compound (I) to the compound In addition to (YH), a diamine other than the compound (j) to the compound (Μ) may be used in combination. The liquid aBag (10) film formed by using the liquid crystal alignment agent containing the polymer component a may be applied to the liquid crystal display element including the liquid crystal alignment film. Good voltage holding ratio. Another group of polymers is a poly-proline or a derivative thereof obtained by reacting a tetracarboxylic dianhydride with a side chain type diamine selected from a compound (νιπ) to a compound (XU). (polymer composition β y in addition to compounds (view In addition to the compound (view), a diamine other than the compound (I) to the compound (welcome) may be used in combination. The liquid crystal alignment film formed by using the liquid crystal alignment agent containing the polymer component B contains the liquid crystal alignment film. The tilt angle of the liquid crystal display element. Another group of polymers is a polylysine or a derivative thereof obtained by reacting a tetracarboxylic dianhydride with a mixture of the above-mentioned non-side chain type diamine and a side chain type diamine (polymerization) Component C). In addition to the compound (〇~ compound (迎), a diamine other than the above compound may be used in combination. 82 1361324 25623pif In the present invention, it is preferred to use a mixture of the polymer component A and the polymer component B, At least two polymers selected from the polymer component C. For example, in the case of mixing the polymer component A and the polymer component b, the mixing ratio of the polymer is A/B = 99/l to 50/50, more A good ratio is A/B = 95/5 to 80/20. This weight ratio is appropriately adjusted according to the obtained tilt angle. 'If the ratio of the polymer component β is increased, the tilt angle can be increased. Polymer composition C 'It is better to replace the polymer The branching is combined with the polymer component a, and the mixing ratio thereof is the same as above. Further, any of the polymer component A, the polymer component B, and the polymer component C is preferably composed of a plurality of polymers. The liquid crystal alignment agent of the invention may further comprise a polyamic acid other than the polymer component A, the polymer component B and the polymer component c. The liquid crystal alignment film of the invention is the above-mentioned polyfluorene in the liquid crystal alignment agent of the invention. The liquid crystal alignment film formed by baking the amine acid in the state of the film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film can be formed by, for example, a substrate for a liquid crystal display element or a fluoride f (u) The liquid crystal alignment agent of the present invention is applied onto a substrate for measurement such as ri(ie) or shixi (silic〇n), and the film of the liquid crystal alignment agent is heated to, for example, 150. (: ~400. (:, preferably 180 ° C ~ 280 C. The film thickness of the liquid crystal alignment film is preferably 1 〇 nm ~ 3 〇〇 nm, better 疋 30 nm ~ 100 nm. In addition It is good to rub the liquid crystal alignment film. The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the liquid crystal alignment agent or the coating method of the liquid crystal alignment agent. The film thickness can be adjusted by a proillometer or an ellipse. Partial instrument (ellips〇mete〇 and other well-known membranes 83 1361324

The 25623pif thick measuring device was used for the measurement. Further, it is possible to carry out a treatment such as hydrolysis, and it is possible to perform analysis. The liquid crystal display element of the present invention comprises a liquid-display element of the present invention, and the liquid crystal display element of the present invention comprises a pair of bases disposed in opposite directions of D, and a liquid-σ of the present invention formed on the opposite surface of each of the counter plates. And 3) a liquid crystal layer held between the pair of substrates. Correct

The fortune - the better for the electrode shouting board is the transparent plate (such as the glass plate). Electrodes are provided on the surface of at least one or both of the substrates on the surface of the substrate. If the above electrode is an electrode formed on the base of the base, there is no special duty. Such an electrode may, for example, be a copper tin oxide (Indium Tin Oxide, IT0) or a metal continuous electrode which may be formed on the entire surface of the substrate or may be formed into a mosquito shape such as a graph. On the substrate on which the electrode is not provided, the liquid crystal alignment film of the invention is formed on the surface of the substrate, on the wire on which the electrode is disposed, on the electrode

The liquid crystal alignment film of the present invention is formed thereon. The formation of the liquid crystal alignment film of the present invention is as described above. * The above-mentioned liquid crystal layer held between the substrates contains a liquid crystal composition. The liquid crystal composition is not particularly limited, and any liquid crystal composition having a positive dielectric anisotropy and a liquid crystal composition having a negative dielectric anisotropy can be used depending on the driving mode. An example of a preferred liquid crystal composition having a positive dielectric anisotropy is disclosed in Japanese Patent No. 3086228, Japanese Patent No. 263m35, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent No. 84 1361324 25623pif, Japanese-Japanese Gazette, Japanese Patent Laid-Open No. 8-231960, and Japanese Patent Publication No. 8-241644 (EP 885272A1), Patent No. 4, Kaiping 9-302346 (EP8〇6466A1), Japan = Bulletin (EP722998, 曰本专利公告, Japan's 真时时时二二报, Japanese Patent Laid-Open No. 9-255956, Japanese Patent No. 9~241643 (Ρ 852 852 Α Α Α Α 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 852 The company has a 1), a Japanese bulletin, and a Japanese patent. - Patent special open Qin _ bulletin, Japan Constant anisotropy: Night = Revealed in Japanese Patent Special Open 俨. Examples of preferred liquid crystal compositions are No. 2~4725, Japanese Sigma, Japanese Patent Special Patent No. 8_4Q95f^f+4-2, No. 9 Communiqué, No. 9 Gazette, and Japanese Taikoo &quot; Newspaper, 曰本专利特开平8 — This patent is open to the public H^8453^开=10一1_76 bulletin, the day 2369 bulletin _,. newspaper, Japanese patent special Kaiping 10 — this patent special 1G~23_=^ 1G—23699G Bulletin, Japanese 236993 Bulletin n, ^^^ Newspaper, Japanese Patent Special Kaiping 1〇—1〇^237〇〇Τ^!/〇^236994 !^^^^^ 23 Battle Bulletin, Japan I Japanese Patent Laid-Open No. 10 — This patent is open to the public notice, the 曰 _ bulletin, and the 曰本 patent special open two ==. : S5 1361324 *5623pif This patent is open to the public. 〇 237 237 237 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 277 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 127 Special report Japan is called Kaiping 11- This patent is special) nm inch open 2〇〇〇-256307 bulletin, 曰072626 〇19965 #u bulletin, Japanese patent special open 2001- on ^w Japanese patent special open 2〇〇1 Bulletin No. 192657 and the like. One or more kinds of optically active compounds may be added to the liquid crystal composition having positive or negative directionality. The liquid crystal display element of the film may have other members. For example, in the crystal element, the first transparent substrate is used to extinguish the 9BB body, the film, the film, the signal electrode, and the substrate of the ^^2 substrate. ), color filter, color film, pixel electrode, etc. The liquid crystal display element, in particular, the MVA type liquid crystal display device 1 has a small domain called a domain formed on the transparent substrate, and may also form a spacer for adjusting a cell gap between the substrates (spacer) ). The liquid crystal display device of the present invention can be produced by any method, and can be produced, for example, by a method of the following steps: 1) coating a liquid on the two transparent substrates: a step of applying a solvent, and "aligning the applied liquid crystal" Step of drying the agent '3> The step of adding the drying liquid crystal alignment agent to the dehydration and ring closure reaction, "the process of geography, and 4) the alignment film obtained by the alignment treatment, 5) 86 1361324

25623pif A step of sealing liquid crystal between substrates after bonding two substrates, or a step of laminating liquid crystal on one of the substrates and bonding the other substrate. ........ The coating method in the process of applying the liquid crystal alignment agent described above is generally known as '. · · · · ·........ - ...---- -.. ... There are a spin $ method, a printing method, a dipping method, a drop method, an inkjet method, and the like. These methods can also be applied to the present invention.

Further, as a method of performing the above-described drying step and the step of heat treatment required for the dehydration reaction, a method of performing heat treatment in an oven or an infrared furnace is generally known, and on a heating plate (h〇tp丨ate) A method of performing heat treatment or the like. These methods can also be applied to the present invention. The drying step is preferably carried out at a relatively low temperature (50: (~~ WO C) in a range in which the solvent can be evaporated. Preferably, the heat treatment is carried out at a temperature of about l5Q〇c to 300 C. The alignment treatment of the liquid crystal alignment film is performed on an lps type liquid crystal display element, a 〇CB type liquid crystal display element, a TN type liquid crystal display element, and an STN type liquid crystal.

The second is often subjected to rubbing treatment. In the VA type liquid crystal display element; the scoring process is often used, but it can also be processed by the rubbing process. It is known that, in the case, the coating on the substrate is followed by the bonding of the other substrate, and the liquid crystal in the night. In the case of the dropwise addition method, the liquid helium is dropped on the substrate at the bonding month, and then bonded to another adhesive which is used in the case of bonding or ultraviolet rays. Display component. In the liquid crystal display panel, the light-scattering film, and the non-element of the present invention, a polarizing plate (polarizing film), a driving circuit, and the like can be sealed. 87 1361324 25623pif [Embodiment] Hereinafter, the present invention will be described based on examples, but the present invention is not

In addition, the unit milliliter of capacity is represented by the symbol mL. [tetracarboxylic dianhydride] Compound (1 ): pyromellitic dianhydride Compound (7) : 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride &lt; 8) : 1,2,3,4-butane tetracarboxylic dianhydride compound (16):

3,3',4,4'-diphenyl ether tetracarboxylic dianhydride: 〇〇1&gt; octa [diamine] ' compound (V-1) : 4,4'-diaminodiphenyl decane compound ( V — 13 ) : 4,4′-diaminodiphenyl ether compound (VH — 2): 1,3—bis(4-aminobenzylphenyl)propane compound (M-2-1): 1, 3-diamino-5-(4-hexadecylbenzyl)benzene compound (M-5-1): ι,3-diamino-5-(4-(4-(4-pentyl) ring Hexyl)cyclohexyl)phenyl)methyl-stupid 88 1361324

25623pif [Alkenyl substituted imidate compound via alkenyl] Compound (a-1):

(a-1) This compound is BANI-Μ available from Maruzen Petrochemical Co., Ltd.

Compound (a_2):

(a-2) This compound is BANI-X available from Maruzen Petrochemical Co., Ltd.

Compound (a-3):

(a-3) This compound is BANI-Η available from Maruzen Petrochemical Co., Ltd. [solvent]

N-mercapto-2-pyrrolidone: NMP butyl cellosolve (ethylene glycol monobutyl): BC γ-butyrolactone: BL &lt; 1. Synthesis of poly-proline 89 1361324 25623pif [Synthesis Example 1] 3.958 g of compound (- and 60.0 g of dehydration) was added to a 100 mL four-necked flask containing a thermometer, a lion machine, a secret force port, and an inlet of m........ NMP is stirred and dissolved under a dry nitrogen stream. 2.042 g of compound (1)' is reacted at room temperature for 3 hours: when the reaction temperature rises during the reaction, the reaction temperature is inhibited at about less than 70 ° C for reaction. To the obtained solution, 34 〇g was added; • A polyglycine solution having a concentration of 6 wt% was obtained. The polyphosphonium amide PA1. PA1 had a weight average molecular weight of 27, 〇〇〇. ° Ma Xiang (Wei / DMF = 〇.6/10 〇: weight ratio) diluted polylysine to make the polyglycine concentration about 丨wt%, and Chromatopack C — R7A (made by Shimadzu Corporation) , the above dilution = as a developing agent 'determined by the GPC method, converted by polystyrene: to obtain the weight average molecular weight of polylysine In addition, the column (c〇lu=) was measured using GF-7HQ (manufactured by Showa Denko Co., Ltd.) at a column temperature of 5 Torr, at a flow rate of 66 mL/min. Examples 2 and 3] As shown in Table 1, in addition to the tetracarboxylic dianhydride and the diamine, a solution of polyII acid PA2 and a solution of polyglycine were respectively obtained according to Synthesis Example 1. [Synthesis Example 4] 0.438 g of compound 1.796 g of compound (W-2), 0.884 g of compound (v-13), and 90 1361324 were added to a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet.

25623 pif 54.0 g of dehydrated NMP' was dissolved by stirring under a stream of dry nitrogen. Next, 0.633 g of the compound (16), 0.563 g of the compound (7), 1.686 g of the compound (1), and 15.0 g of the dehydrated BL' were reacted at room temperature for 3 Torr. When the reaction temperature rises during the reaction, the reaction temperature is suppressed to be less than about 70 ° C to carry out the reaction. 25.0 g of BC was added to the obtained solution to obtain a polyglycine solution having a concentration of 6 wt%. This polyamic acid was recorded as PA4. PA4 has a weight average molecular weight of 44,000. [Synthesis Examples 5 and 6] As shown in Table 1, a solution of polyamic acid PA5 and a solution of poly-aracine pA6 were obtained according to Synthesis Example 4 except that the tetracarboxylic dianhydride and the diamine were changed. &lt;Table 1&gt; . —*---- Synthesis iH_____ -------- 1 Polyproline No. Tetraphthalic Acid Diamine Diamine Weight Average Molecular Weight Compound Number / No. Moer Fraction Compound No. ♦ Ear points: narrow PA1 (1) 0.5 (\l-2-l) _^0.5 27 000 2 PA2 (7) (16) 0.3 — 0.2 (VH-5-D (V-1) 0.5 0 5 24.000 72.000 i 3 PA3 (1) (7)- 0.1 0.4 (VH-2) 0.5 4 PA4 0) (7) (16) 0:35 0.13 0.02 (V-1) (VD-2) CV-13) oi 0.2 __0.2 44,000 5 PA5 (1) (7) (8) 0.1 0.3 0.1 (VD (ΥΠ-2) 0.05 0.45 55,000 6 PA6 ODPA 0'5 (V-]) -^005 36,000 &lt; 2 · Production of liquid crystal display device > [Examples 1] A polyphosphonate solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a concentration of 6 milk% polyamine solution synthesized in Synthesis Example 3 was mixed at a weight of 1 to 1/9 ( PA3). In the obtained mixture, 10 wt% of an alkenyl-substituted nadic acid ruthenium imine compound, ie, BAM-M, was added per unit weight of the polymer. Thereafter, NMP/BC = 1/1 was added. a mixed solvent of (weight ratio)', which is diluted to 4% by weight to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, A liquid crystal display element was produced as follows. [Example 2] # The concentration of 聚 wt% of the poly-tantoic acid solution (PA2) synthesized in Synthesis Example 2 and the concentration of 6 wt% synthesized in Synthesis Example 3 were mixed by weight I to I79. Each of the polylysine solutions (PA3). In the obtained mixture, 10 wt/min of an alkenyl-substituted nadic acid ylidene imine compound, ie, BANI-M, was added per unit of polymer weight. Thereafter, a mixed solvent of NMp/BC = 1/1 (weight ratio) was added, and the whole was diluted to 4 wi% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. Example 3] A polyamine amine solution (paI) having a concentration of ό wt% synthesized in Synthesis Example 1 and a concentration of 6 wt% synthesized in Synthesis Example 3 were mixed at a weight I ratio of 1/9. Amine/dye (PA3). In the obtained mixture, 10 wt% of the diluted nadic ylidene imine compound, compound (a-3), is added per unit of polymer weight. Thereafter, this combination of NMp/BC = 1/1 (weight ratio) was added, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display element was produced using the obtained liquid crystal alignment agent as follows. [Example 4] Poly 92 25623 pif tyrosine acid solution (PAl) having a concentration of 6% by weight synthesized in Synthesis Example} at a reset ratio of 1/9 and a concentration of 6 wt% of polylysine synthesized in Synthesis Example 3 Solution (PA3). To the obtained mixture, 10 wt% of a ruthenium-substituted nadic acid ruthenium imide compound, i.e., a compound (a-2), was added per unit weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the whole was diluted to 4% by weight to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Comparative Example 1] A polyfefecic acid solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a polyglycine solution (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. . A mixed solvent of NMp/BC = 1/1 (weight ratio) was added to the obtained mixture, and the whole was diluted to 4 to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows. [Example 5] In a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, 1% by weight of an alkenyl-substituted Nadi' kelic acid per unit weight of the polymer was added. An imine compound, that is, a compound (a_〖). Thereafter, a mixed solvent of NMP/BC = 1 / i (weight ratio) was added, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as described below. [Example 6] In a polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4, 2% by weight of the compound "-1" was added per unit weight of the polymer. Thereafter, NMP was added. /BC = 1 / 1 (by weight) mixed solvent, 1361324 25623pif The whole was diluted to 4 Wt ° / 〇 to prepare a liquid crystal alignment agent. Using a % crystal alignment agent, a liquid crystal display element was produced as follows. [Example 7] ................. [Available as a concentration of 6 wt% of polyamine synthesized in Synthesis Example 5 in cold:- (PA5), adding 10 _ / 〇 / = liquid U - 1) per unit of polymer weight. Thereafter, adding nmp / bc = i / i (weight ratio) °, t agent, will be diluted overall A liquid crystal alignment agent was prepared at 4 wt%, and a liquid crystal display element was produced as follows using a liquid crystal alignment agent of y = y yue. [Example 8] Synthesized/indentity 6 wt ° / 〇 in Synthesis Example 5. In the polyamic acid solution (PA5), add 2〇wt〇/o of compound (a-1) per unit of polymer weight. Then add 'NMP/BC= 1/1 (weight ratio) mixed solvent 'Dilute the whole to 4 wt%: make liquid crystal alignment agent. Use The liquid crystal alignment agent obtained was produced as follows, and a liquid crystal display element was produced as follows. [Comparative Example 2] A polyglycine solution having a concentration of 6 wt% synthesized in Synthesis Example 4 (NMP/BC = 1 was added to PA4〇). A mixed solvent of 1 (weight ratio) was diluted to 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display element was produced using the obtained liquid crystal alignment agent as follows. [Comparative Example 3] In Synthesis Example 5 A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a synthetic polyglycine solution (PA5) having a concentration of 6 wt%, and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. The liquid crystal alignment agent 'produces a liquid crystal display element as follows. 94 1361324

25623pif [Comparative Example 4] Dimeric, 6-fold concentration of poly-proline solution synthesized in 6-.w-med., adding 20 wt% of compound per unit of polymer weight (a 'Addition of NMP/BC = 1/1 (weight ratio) mixed solvent, positive-diluted to 4 wt%' to prepare a liquid crystal alignment agent. Using the obtained crystal alignment agent, a liquid crystal display element was produced as follows.> &lt; Method for producing liquid crystal display element (Examples 1 to 4, Comparative Example j)

A liquid crystal alignment agent was applied onto a glass substrate of a ruthenium electrode by a spinner to form a film having a film thickness of 7 Å. After coating, heat and dry at 80 ° for about 5 minutes, &amp; 22 〇. 〇 4 minutes to add the second process to form a liquid crystal alignment film. Next, the * broad film was formed on the glass substrate and ultrasonically cleaned in ultrapure water for 5 minutes, and then dried in a crucible for 30 minutes. WC

Dispersing a gap material of 4 μm on one of the glass substrates, 'forming the liquid crystal alignment film surface as the inner side, and arranging the opposite side of the gaP skin in a parallel manner, and sealing with an epoxy hardener, two: An antiparallel unit (antiparalld ceU) with a gap of 4 μηη. In this unit =, the liquid crystal composition shown below was placed, and the injection port was sealed with a light hardener. The film was heat-treated at 110 C for 30 minutes to produce a liquid crystal display element.者 ' 95 1361324 25623pif

〇-c2h5

5wt. % 7wt. % 8wt.-°/〇 ....- 8wt. % 14wt. %

14wt. % K 10wt. % 10wt. % 12wt. % 12wt. % 96 1361324 25623pif

〇一 CH

C3h7 C3H7 C5H11

C3H7 5wt. % 7wt. % 8wt. % 8wt. % 14wt. % 14wt. % 10wt. % 10wt. %

〇-c2h5 C5H11

〇-c2h5 12wt. % 12wt. % &lt;Production and method of liquid crystal display element (Examples 5 to 8 and Comparative Examples 2 to 4) &gt; A liquid crystal alignment agent was applied to two ITO electrodes with a rotator A film having a film thickness of 70 nm was formed on the glass substrate. After coating, the film was dried by heating at 80 ° C for about 5 minutes, and then heat-treated at 230 ° C for 20 minutes to form a liquid crystal alignment film. Next, the surface of the substrate on which the alignment film was formed was subjected to a rubbing treatment by a rubbing device to carry out an alignment treatment. Thereafter, the alignment film was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. 97 1361324 25623pif Disperse 7 μm of gap material on one of the glass substrates, set the surface on which the liquid crystal alignment film is formed to the inside, and arrange the opposite direction in the rubbing direction, and then seal with epoxy hardener to make a gap. 7 μιη anti-flat....... · -......-..........................-. —......... .-..... Row unit. The liquid crystal composition shown below was injected into this unit, and the injection port was sealed with a photohardener. Next, heat treatment was performed for 30 minutes at ll 〇 ° C to prepare a liquid crystal display element. 17wt. %

F

C2H5 c2h4 17wt, % 16wt. %

10wt. %

5wt. % ο

C3H7 C2H4

10wt. %

6 wt. % 6 wt. % 13 wt. % &lt;3. Evaluation of electrical characteristics&gt; 98 1361324 25623pif For Examples 1 to 8, Comparative Examples! In the case of ～4, the voltage holding ratio is measured as follows: 液, liquid 3, 顾 70 70 1) Measurement of voltage retention, monthly sin determination. .... .... ..........*··*· ~ - <Test Examples 1 to 12> '..... ...... Voltage retention using Toyo Tekmiika Co., Ltd. Rate = liquid crystal property rating (gate width) 60ps, frequency 〇 3 Hz, ,, Gu Gu · · 疋 condition is 'gate 觅 is 6 (TC. It can be said that the larger the electrical characteristics of the temperature measurement and the temperature. 3. Good The results are shown in Table 2 2) Measurement of long-term reliability &lt;Test Examples 1 to 5 (Examples 1 to 4 for the liquid crystal display device produced in Example 1)&gt; Rate, and the retention characteristics were evaluated. The test for maintaining the characteristics was determined. The device was placed in an environment of a temperature of 100 〇C, and the liquid crystal was displayed, and the measurement of the voltage holding ratio was measured. It can be taken over time, and the placement time is greater than or equal to: == holding rate = small amount of New Zealand) The better the long-term reliability. : Fruit 2

<Test Examples 6 to 12 (Examples 5 to 8 and Comparative Examples 2 to 4) &gt; 99 1361324 25623pif With respect to the produced liquid crystal display element, the retention characteristics were evaluated with time ratio. The test method for maintaining the characteristics was to measure the liquid crystal display = the object was placed in an environment of a temperature of 6 Torr, and the time-dependent pressure retention was measured. It can be said that the lower the voltage holding ratio (for example, in the case of the description, the placement time is other hours, if the power is reduced by less than 1%), the long-term reliability is better. The results are shown in Table 3. <Table 3 &gt;

In the case of the liquid crystal display element having the liquid crystal alignment agent of the present invention and 2 parts of the liquid helium alignment film, the voltage is maintained and the deterioration of the storage characteristics can be remarkably suppressed. &gt;,, -, although the present invention has been disclosed in the preferred embodiments as above, but it is intended to limit the invention to anyone skilled in the art, and the present invention can be used in the context of the invention. Therefore, the scope of the present invention is regarded as the scale defined by the post-operative community. ... [Simple description of the diagram] None. [Main component symbol description] No 0 100

Claims (1)

1361324 Amendment date: September 29, 2005, 25,623 pifl is the Chinese patent scope of No. 096134192. There is no slash correction. The scope of the patent application: 1. A liquid crystal alignment agent which contains an alkenyl substituted nadic acid ylide. a polymer component selected from the group consisting of a compound, a poly-proline and a derivative of poly-proline, and a solvent component, wherein the polymer component is at least one of a polymer obtained by reacting a tetraacid dianhydride with a diamine. Tetracarboxylic dianhydride And at least one of the compound represented by the formula (16) and the compound represented by the formula (17) or the compound represented by the formula (16) and the compound represented by the formula (17) and the formula (1) to the formula (1) At least one of the compounds shown in 15) The mixture of the components, the ratio of the composition of the scaly (tetra) compound is = Wt% to 3 Gwt%', and the ratio of the nucleoside imine compound is reduced to the polymer component. 101 1361324 25623pifl is the Chinese patent scope of No. 096134192 without a slash correction. Amendment date: September 29, 100 ο η (16) (17) wherein, Ph represents a phenyl group and Me represents a fluorenyl group. 2. The liquid crystal alignment agent according to claim 1, wherein the alkenyl substituted nadic acid ylide compound is a compound represented by the formula (a), and the 102 25623 pifl is the o% mi92 No line J η Amendment date: September 29, 100 (a) where R1 and R2 are independent of the bird ^ Alkenyl group having 3 to 6 carbon number, carbon number: 5 oxygen: alkyl group broken to 1 to 12, n^ L^2, the slit is 5~8 ring filament, aryl or nodal group. When η is 1, R3 is a ring-burning group with a carbon number of 1, a aryl fluorene with a carbon number of 6~12, and the carbon number is 5~8 (L1 is 2Τ6 山 杏 杏 、, benzyl, _L _(0 V(L2〇)r-R4 is an alkylene group with a stone anomaly of 2~6, R4 is a carbon number of 2 ~όAlkyl, q is 0 or 1, and 1&gt; is a sigh of 2 (L3A is an integer of 30), -(L)s-B2_R5 = is the subfamily of the inverse of the stone, s 〇 or ], b2 is a substitutable group which can be strictly substituted, and R5 is • i~4: A) or -B'T-B1 (B2 is a gas-r mountain a soil) rvL A substituted silk group, T is ^h2-, -c(CH3)2_, _C0·, ms〇2 and βΐ is a phenyl group in which hydrogen can be replaced by -〇Η, and when / is 2, R3 is carbon An alkylene group having a number of 2 to 2 fluorene, a carbaryl having a carbon number of 5 to 8, a arylene group having a carbon number of 6 to 2, and an anthracene (Lk2 and L4 independently having a carbon number of 2 to 6) Aspen and r is an integer from 1 to 30), _ (L3 ) s_B2_L5_ (l3 and L5 are independently a sub-alkyl group having a carbon number of 1 to 4, 3 is a ruthenium or a phenyl group which is an arbitrary chlorine which can be substituted by the detection) - B2_T_B2_ (B, an arbitrary hydrogen can be _ 〇h substituted phenylene, and τ is _ch2_, _C(CH3)2_, _c〇·, _〇, &amp; or -S02-), or -B2-〇-B2-C(CH3)2-B2 -〇-B2- (B2 is independently 103 1361324 25623pifl is the Chinese patent scope of No. 096134192. No slash correction. This revision date: September 29, 100, hydrogen can be replaced by -OH phenylene). 3. The liquid crystal alignment agent according to claim 1, wherein the alkenyl substituted nadic acid ylide compound is at least one of the compounds represented by the formula (a-1) to the formula (a-3). , (a-1) 4. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the diamine is selected from the group consisting of non-side chain type diamines represented by formula (I) to formula (ΥΠ). At least one, 104 1361324 25623pifl is the Chinese patent scope of No. 096134192. There is no slash correction. This revision date: September 29, 100 h2n-a1-nh2 Η2Ν Ν^^ νη2 η2ν ~' ν—^νη2 Η2ν νη2 Ηη2 (I) (Π) (III) (IV) (V) (VI) (VII) wherein Α1 is a linear alkylene group having a carbon number of 2 to 12; Α2 is a linear subunit having a carbon number of 1 to 12 Alkyl; A3 is independently a single bond, -Ο-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, -0-A2-0-,- S-, -SS-, -S02-, -S-A2-S-, or a linear alkylene group having a carbon number; any hydrogen of a cyclohexane ring and a benzoquinone may be fluorine, OH, COOH, S03H , P〇3H2, benzyl or hydroxybenzyl substituted. 5. The liquid crystal alignment agent according to any one of claims 1 to 3 wherein the diamine is selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV 15), formula ( Ϊ́ν=ι6), at least one of the group of non-side chain type diamines of the formula (n) to the formula (ν_ΐ3), and the arc 2), 105 1361324 25623pifl is the Chinese Patent Range No. 096134192 This revision date: September 29, 100 (V-1) (V-2) Nh2 (V-3) (V-7) NH, The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the diamine is a non-side chain 106 1361324 selected from the group consisting of formula (I) to formula (W). 25623pifl is the Chinese patent scope of No. 096134192 without a slash correction. 'Revised date: a mixture of at least one of the group of amines of the type one amine and at least one of the side chain type diamines having a side chain group on September 29, 1999. The side chain group is an alkyl group having a carbon number of 3 or more, an alkoxy group having a carbon number of 3 or more, an alkoxyalkyl group having a carbon number of 3 or more, a group having a steroid skeleton, and a terminal having a carbon number greater than a group selected from the group consisting of an alkyl group having a carbon number of 3 or more and an alkoxy group having a carbon number of 3 or more, h2n-a1-nh2 (I) (II) (Hi) (IV) h2n^-^nh2 η2ν·^~/ V_&gt;^NH2 H2n nh2 (V) Η2Ν〇~Α3〇·Α3·^Α3^ (VI) (VII) nh2 wherein A1 is a linear alkylene group having a carbon number of 2 to 12; and A2 is a linear alkylene group having a carbon number of 1 to 12; A3 is independently a single bond, -0-, -CO-, -CONH-, -NHCO-' -C(CH3)2-' -C(CF3)2-' -0-A2-0-' -S-' -SS-'-S02-'-S-A2-S-, or a linear sub-radical group having a carbon number of 1 to 12; any hydrogen of the cyclohexane ring and the benzene ring may be fluorine, -CH3, -OH, -COOH, -S03H, Ρ03Η2, benzyl or hydroxybenzyl substituted. 107 1361324 25623pifl is the Chinese patent scope of No. 096134192. There is no slash correction. The date of this amendment is: September 29, 1 7 7 · The liquid crystal alignment agent according to item 6 of the patent application, wherein the side chain type diamine is selected a diamine in the group of compounds of the formula (VDI) to (M), (wherein R6 is a single bond, -〇-, -CO-, -COO-, -OCO-, -CONH-, -CH20-, -CF20-, or an alkylene group having a carbon number of 1 to 6, this sub- Any -CH2- in the alkyl group may be substituted by -Ο-, -CH=CH- or -C=C-; R7 is a group having a steroid skeleton, an alkyl group having a carbon number of 3 to 30, and having a carbon number of 3 An alkyl group of ～30 or an alkoxy group having a carbon number of 3 to 30 as a substituent of the substituent or a group represented by the formula (D-1), and any _CH2- of the alkyl group may be -Ο-- -CH = CH- or -OC-, Ri9~~(Z)^r20 wherein R18, R19 and R20 are independently a single bond, _〇_, -COO-, -OCO-, -CONH-, a subring having a carbon number of 1 to 4, and the carbon number is 1 to 3 of an oxygen atomic group or a pyridyloxy group having a carbon number of 1 to 3; ring b and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R21 and R22 are independently Fluorine or methyl 'ml and m2 are independently 〇, 1 or 2; e, f and g are independently 0 to 3 integers 'e, f and g total is greater than or equal to 丨; R23 is carbon number 3 to 30 The base of the burnt group, the carbon number of 3 to 30, or the carbon number is 3 108 1361324 25623pifl. The scope of the Chinese patent of No. 096134192 is not underlined. The date of this correction: the burning of oxygen on September 29~30 In the alkyl group, the alkyl group, the alkoxy group and the alkoxy group, any hydrogen may be substituted by fluorine, and any -CH2- may be substituted by a difluoroindenylene group or a group represented by the formula (D-2). , R24 / R26, ——Si—ί-0-Si-H—— (D-2) R25 \ R27/n Wherein R24, R25, R26 and R27 are independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and η is an integer of 1 to 100) η2ν (IX) ΝΗ 2 (wherein R8 is independently hydrogen or a fluorenyl group; R9 is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and, R1G is independently a single bond, -CO- or -ch2 -) (wherein R8 is independently hydrogen or a fluorenyl group; R9 is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R1G is independently a single bond, -CO- or -CH2-; Further, R11 and R12 are independently hydrogen and have a carbon number of 1 to 30. 109 1361324 25623pifl is the 096134192 Chinese patent range without a slash correction. Amendment date: September 29, 1989 (XI) Alkyl, or phenyl) (wherein R13 is an alkyl group having a carbon number of 3 to 30, and any -CH2- of the alkyl group may be substituted by -0-, -CH=CH- or C-C-; R14 is independently -0- or the carbon number is 1 to 6 alkylene; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 or 2; and, c is independently 0 or 1) (XII) (wherein R15 is an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having 3 to 30 carbon atoms; and R16 is hydrogen, an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30 Fluorinated alkyl; R17 is independently -0- or an alkylene group having 1 to 6 carbon atoms; and, d is independently 0 or 1). 8. The liquid crystal alignment agent according to claim 6, wherein the side chain type diamine is selected from the group consisting of a formula (ΥΙΕ-2), a formula (\11-4), a formula (\1-5), and a formula ((1) Μ—6) A diamine in the group of compounds shown in the formula, 110 1361324 25623pifl is the Chinese patent scope of No. 096134192. No slash correction. Amendment date: September 29, 100 H2n (VI11-5) (VIII-6) Fighting -^7« VV,N'^ Wherein R and R29 are independently alkoxy groups having a number of from 3 to 30. The liquid crystal alignment agent of the alkyl group or the carbon side chain type diamine of the sigh is 3 to 30, wherein the compound _ group - (V - 13) and the formula (VD - 2) 2) The formula (Cong%,,, amine, side chain type diamine is selected from the group consisting of diamines (VDI~5) of the group of the composition and the formula (VDI-6) 111 1361324 25623pifl is the Chinese patent scope of No. 096134192 without a slash correction. Amendment date: September 29, 100 (V-1) (V-2) (V-3) (V-12) (V-13) (VII-2) 112 1361324 25623pifl is the Chinese patent scope of No. 096134192 without a slash correction. Amendment date: September 29, 100 (VIII-5) (VIII-6) wherein R28 and R29 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. 10. The liquid crystal alignment agent according to claim 1, wherein the polymer component is at least two selected from the group consisting of a compound represented by the formula (16) and a formula (17). a tetracarboxylic acid of a mixture of at least one of the compounds of the formula (16) and at least one of the compounds of the formula (17) and at least one of the compounds of the formula (1) to the formula (15) a polyglycine or a derivative thereof obtained by reacting at least one selected from the group consisting of a non-side chain type diamine represented by the formula (I) to the formula (W), a compound represented by the formula (16), and a formula a mixture of at least one of the compounds shown in (17) or at least one of the compound of the formula (16) and at least one of the compounds of the formula (17) and at least one of the compounds of the formula (1) to (15) a polyamic acid or a derivative thereof obtained by reacting at least one selected from the group consisting of a side chain type diamine represented by the formula (M) to the formula (M), and a formula (16) At least one of the compound shown and the compound represented by the formula (17) or the compound represented by the formula (16) and the formula (17) At least one of the compounds shown and the compound represented by the formula (1) to the formula (15) 113 1361324 25623pifl is the Chinese patent range of No. 096134192 without a slash correction. This correction date: at least one of the September 29 a tetracarboxylic dianhydride of the mixture and at least one selected from the group consisting of a non-side chain type diamine selected from the group consisting of formula (I) to formula (W) and a side chain selected from the group consisting of formula () to formula (M) Polylysine or a derivative thereof obtained by reacting a mixture of at least one of a group of diamines, 114 1361324 25623pifl is the Chinese patent scope of No. 096134192 without a slash correction. Amendment date: September 29, 100 (17) (16) (wherein Ph represents a stupid base, Me represents a methyl group; and the polymer component is a mixture of at least two polymers) H2n-a1-nh2 h2n N~/ nh2 H2N’~' \-^NH2 Nh2 h2n A3 Nh2 (l) (ID (III) (IV) (V) h2n h2n ^-a3-〇-a3^NH2a3h^a3O~a3 (VI) (VII) NH 2 115 1361324 25623pifl Amendment date: September 29, 100 is the Chinese patent range of No. 096134192 without a slash correction (wherein A1 is a linear alkylene group having a carbon number of 2 to 12; A2 is a linear alkylene group having a carbon number of 1 to 12; A3 is independently a single bond, -0-, -CO-, -CONH-'-NHCO-'-C(CH3)2-'-C(CF3) 2-'-0-A2-0-'-S-'-SS-, -S02-, -S-A2-S-, or a straight-bonded sub-shallow group having a carbon number of 1 to 12; a cyclohexane ring and Any hydrogen of the benzene ring may be substituted by fluorine, -CH3, -OH, -COOH, -S03H, P〇3H2, benzyl or hydroxybenzyl) (VIII) (wherein R6 is a single bond, _〇_, _CO-, -CO〇_, _〇C〇_, -CONH-, -CH20-, -CF20-, or an alkylene group having a carbon number of 1 to 6, Any -CH2. in the alkylene group may be substituted by -〇-, -CH=CH- or -OC-; R7 is a group having a steroid skeleton, a carbon group having a carbon number of 3 to 30, and having a carbon number of 3~ a phenyl group having a calcination group or a carbon number of 3 to 30 or a carbon group as a substituent, or a group represented by the formula (D-1), and any _CH2_ in the alkyl group may be -Ο-, -CH = CH- or -C^C-, Wherein R18, R19 and R20 are independently a single bond, _c〇〇_, -OCO-, -CONH-, a calcined group having a carbon number of 1 to 4, a lactam group having a number of 丨3, or ^^ is a pyridyloxy group of 1 to 3; ring b and ring c are independently 1,4-phenylene or 1,4-cyclohexylene; R21 and R22 are independently fluorine 116 1361324 25623pifl Revision date: 100 On September 29th, the Chinese patent scope of No. 096134192 has no underline correction or 曱 base 'ml and m2 is independently 〇, ι or 2; e, f and g are independent integers of 0~3, e, f and g The total is greater than or equal to 1; the rule 23 is an alkyl group having a carbon number of 3 to 30, an alkoxy group having a carbon number of 3 to 3 Å, or an alkoxyalkyl group having a carbon number of 3 to 30, an alkyl group, an alkoxy group. In the group and the alkoxyalkyl group, any hydrogen may be substituted by fluorine, and any _CH2- may be substituted by a difluoroindenylene group or a group represented by the formula (D-2). Wherein R24, R25, R26 and R27 are independently a decyl group or a phenyl group having a carbon number of 1 to 10, and η is an integer of 1 to 1 )) (wherein R8 is independently hydrogen or a fluorenyl group; R9 is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R10 is independently a single bond, -CO- or - CHr) 117 1361324 25623pifl Amendment date: September 29, 100 is the Chinese patent range No. 096134192. There is no underline correction (wherein R8 is independently hydrogen or sulfhydryl; R9 is hydrogen, alkyl having 1 to 30 carbon atoms, or An alkenyl group having 2 to 30 carbon atoms; R1G is independently a single bond, -CO- or -CH2-; and R11 and R12 are independently hydrogen, a carbon number of 1 to 30, or a phenyl group) (wherein R13 is an alkyl group having a carbon number of 3 to 30, and any -CH2- of the alkyl group may be substituted by -0-, -CH=CH- or OC-; R14 is independently -Ο- or a carbon number of 1 〜6 alkylene; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or l; b is 0, 1 or 2; and, c is independently 0 or 1) (XII) (wherein R15 is an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having 3 to 30 carbon atoms; and R16 is hydrogen, an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30 Fluorinated alkyl; R17 is independently -0- or an alkylene group having 1 to 6 carbon atoms; and, d is independently 0 or 1). 11. The liquid crystal alignment agent according to claim 10, wherein the polymer component is at least two selected from the group consisting of a compound represented by the formula (16) and a formula (17). Amendment date of at least one of the compounds or at least one of the compounds of the formula (17) and at least one of the compounds of the formula (1) to the formula (15): 118 1361324 25623pifl On September 29, 100, the Chinese patent scope of No. 096134192, the tetracarboxylic dianhydride of the present mixture is not underlined and is selected from the group consisting of formula (IV-丨), formula (IV_2), formula (IV-15), and formula (IV). —16), a poly-proline or a derivative thereof obtained by reacting at least one of a group of non-side chain type diamines represented by the formula (Fig. 2), and a formula (v_υ~) (v_13), At least one of the compound represented by the formula (16) and the compound represented by the formula (17) or the compound represented by the formula (16) and the compound represented by the formula (17) and the formula (〇~) a mixture of at least one of the compounds shown in (15), a tetracarboxylic acid dianhydride, and a compound selected from the formula (堋-2), Polyamine or a derivative thereof obtained by reacting at least one of the group of the side chain type diamine represented by the formula (4) and the formula (Week-5), and the formula ( 16) at least one of a compound represented by the formula (Π) or a compound represented by the formula (16) and at least one compound represented by the formula (17) and a formula (丨) to (15) a tetracarboxylic dianhydride of a mixture of at least one of the compounds shown and selected from the group consisting of formula (IV-1), formula (IV-2), formula (IV-15), formula (iv-16), formula (V1) At least one of the group of the formula (V-13) and the non-side chain type diamine represented by the formula (γ[[~2) and a selected from the group consisting of a formula (2), a formula (泗-4), (νπΐ_5) and polyglycine or a derivative thereof obtained by reacting a mixture of at least one of the group of side chain type diamines represented by the formula (week-6), 119 1361324 25623pifl is the Chinese patent range of No. 096134192 Line revision date of this revision: September 29, 1st (V-3) (V-7) NH〇 (V-12) (V-13) ΝΗ (VII-2) 120 1361324 25623pifl is the Chinese patent scope of No. 096134192. There is no slash correction. This revision date: September 29, 100 HoN y^〇^R28 H2N ^0R29 η/ (VIII-2) h2n (VI11- 4) HoN h2n Or29 Xy η / (VIII-5) h2n (VIII-6) wherein R28 and R29 are independently an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. A liquid crystal alignment film obtained by baking a liquid crystal alignment agent according to any one of claims 1 to 11 in a film state. 13. A type of liquid crystal display device comprising: a pair of substrates disposed oppositely; an electrode formed on one or both of opposite surfaces of the pair of substrates; and each of the pair of substrates facing each other A liquid crystal alignment film according to claim 12; and a liquid crystal layer formed between the pair of substrates. 121