TW201132704A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

A liquid crystal alignment agent is provided. The liquid crystal alignment agent contains diamines showed in the formula (I), polyamide acids, or derivatives thereof. The polyamide acids are synthesized by reacting a mixture of the diamines and other diamines with dicarboxylic anhydrides. The liquid crystal alignment agent is used in the formation of a liquid crystal alignment film of a liquid crystal display device having various display driving methods. The liquid crystal display device using the liquid crystal alignment film has high voltage retention rate and long-term light reliability, and restrains residual direct current. In formula (I), A1 is single bond, -O-, -COO-, -CO-, -CONH-, or alkylene groups having 1 to 6 carbons; R is hydrogen or alkyl groups having 1 to 6 carbons, independently.

Description

201132704 6. Description of the Invention: TECHNICAL FIELD The present invention relates to a liquid crystal alignment agent mainly containing polylysine or a derivative thereof. [Prior Art] Liquid crystal display elements are used in various liquid crystal display devices such as a viewfinder of a camera such as a notebook computer or a desktop computer monitor, and a projection type display, and have recently been used for televisions. Further, the liquid crystal display element is also used as a photonic-related element such as an optical print head, an optical Fourier transform element, or a light valve. The mainstream of the prior liquid crystal display elements is to use a nematic liquid crystal display element 'as an example' to have 1) a twisted nematic (TN) type liquid crystal display element that is twisted by 90 degrees, or 2) a distortion that is usually 180 degrees or more. Twisted Nematic (STN) type liquid crystal display element, and as a component for switching the driving voltage, 3) Thin film transistor (TFT) type liquid crystal display element using thin film electric material has been put into practical use. . These liquid crystal display elements have a drawback in that the angle of view of the image can be appropriately recognized. When viewed from an oblique direction, a decrease in luminance or contrast and a luminance inversion of halftones occur. In recent years, the problem of this viewing angle has been achieved by 1) a ΤΝ·ΤΡΓ type liquid crystal display element using an optical compensation film, 2) a vertical alignment using a vertical alignment and an optical compensation film (formation of an Alignment, VA) type liquid crystal display element, 3 ) Multi-region vertical alignment using a technique of vertical alignment and protruding structures (Muld plus (4) AUg_nt 'MVA) type liquid crystal display element, or 4) Lateral electric field 4 Inverting Switching (In-Plane Switching, IPS) Liquid crystal display device, 5) Electrostatically Controlled Birefringence (ECB) type liquid crystal display element, 6) Optically compensated Bend or Optical self-compensated birefringence (〇Pticauy seif_c〇mpensated Birefringence (〇CB)) The liquid crystal display element and the like have been improved, and these display elements have been put into practical use or are being studied for practical use. The development of liquid crystal display element technology has been achieved not only by improving their driving modes or component configurations, but also by improving the constituent components used in the display elements. Among the constituent members used in the display element, in particular, the liquid crystal alignment film is one of the important factors relating to the display quality of the liquid crystal display element, and as the display element is made higher in quality, the role of the liquid crystal alignment film is important year by year. The liquid crystal alignment film is prepared by using a liquid crystal alignment agent. At present, a liquid crystal alignment agent mainly used is a solution obtained by dissolving polyaminic acid or soluble polyimine in an organic solvent. After the solution is applied onto a substrate, the film is formed by heating or the like to form a polyimide film. Various liquid crystal alignment agents using t compounds other than polyaminic acid or soluble polyimine are also being studied in the industry, but heat resistance, chemical properties (sub-liquid crystallinity), coating properties, liquid crystal alignment properties, From the viewpoints of electrical characteristics, optical characteristics, display characteristics, etc., most of them are not put into practical use. The important characteristics required for the liquid crystal to the film for the purpose of improving the display quality of the liquid crystal display element include a voltage holding ratio and a direct current 'DC'. If the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the brightness is lowered, which causes an obstacle to the normal gray 201132704 display. On the other hand, if DC A is left, the voltage is turned off after the electric house is applied, but a so-called "after-image" in which the image is left is still generated. As an attempt to solve these problems, several methods have recently been proposed. (1) A polyglycine composition in which two or more kinds of polyamic acids having different physical properties are used for forming a liquid crystal alignment film is known (Patent Document i and Patent Document 2). (2) A varnish composition using a polymer component using polyamic acid and polyamine and a solvent is known (Patent Document 3). (3) A varnish composition of two or more kinds of polyamic acid and polyamine which have different physical properties and a solvent is known. (Patent Document 4). (4) A varnish composition using a polymer material which is a polyglycine synthesized using an amine component having a specific structure is known (Patent Document 5). However, the problems of voltage holding ratio and residual DC have not been sufficiently solved by some prior art, and many studies are still continuing. Further, 'the amine is used as a raw material for the polyaniline for forming a liquid crystal alignment film, but the diamine uses a paste chain type: an amine, that is, a diamine having no side chain group, and a side chain type diamine having a side chain. Base diamine. Among these diamines, most of the side chain type diamines have a secret angle (Special Offer 6), and there is no room for improvement in the development of the side chain type diamine for improving electrical characteristics such as residual DC. [Prior Art Document] [Patent Document] 6 201132704 [Patent Document No. 1 1 [Patent Document 0 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 11-193347 [Patent Document] International Publication No. 00/061684 No. Manual [Patent Document, International Publication No. 01/000733 Handbook [Patent Japanese Patent Laid-Open No. 2002-162630]; tΜ, 献6 Japanese Patent Laid-Open No. 3-179923 A liquid crystal alignment agent for liquid crystal display elements having improved retention and residual properties. In the inventors of the present invention, the inventors of the present invention have conducted diligent research to solve the above problems, and found that a diamine having a terminal group having a terminal -OH is used as a diamine. When a raw material is used to produce poly-proline, the liquid crystal alignment agent containing the same is effective in solving the above problems, and the present invention has been completed. Namely, the liquid crystal alignment agent of the present invention is represented by the following item [1]. [1] A liquid crystal alignment agent comprising a polyamine obtained by reacting a diamine represented by the formula (I) or a mixture of the monoamine and another diamine with tetracarboxylic acid dianhydride Acid or its derivatives:

Η2ν

R OH (I)

R 7 201132704 Here, 'A1 is a single bond, -COO-, -CO-, -CONH- or an alkylene group R having a carbon number of 1 to 6' is independently hydrogen or an alkyl group having a carbon number of 丨6. The liquid crystal alignment of the present invention is used for forming a liquid crystal alignment material of a liquid crystal display element of each of the driving modes, and is effective for improving the voltage (four) rate and the residual % in a liquid crystal display element of any age. The above described features and advantages of the present invention will become more apparent from the following detailed description of the embodiments. [Embodiment] First, terms used in the present invention will be described. The triamine represented by the formula (1) is sometimes referred to as a diamine (1). The diamine represented by the other formula is sometimes referred to by the same notation. The tetra-acid dianhydride is sometimes abbreviated as a acid field. For example, the four-acid acid two-needle represented by the formula (Η_υ is sometimes referred to as an acid anhydride (Η-1). The term used in the definition of the chemical formula is arbitrary, It means "not only, the choice of freely, but also the number can be chosen by yourself. For example, : Any Α can be replaced by B, cm, this expression can be divided by π 1 A can be B, c, D or E is substituted, and any of a plurality of A is substituted by any one of B, c, D or E, and also represents a, which is substituted by β, a substituted by C, a substituted by C, and two substituted by e. It may be present in a mixture. However, when it is set to any of the::3 substitutions of the base 3, it does not include a plurality of consecutive substituents which are identical and which are not bonded to any of the carbons constituting the ring. Its 8 201132704 I ^ ^ ^ / αΪ. Bonding position is chemically free of problems. When the same mark is used in multiple formulas, in this case, it must be the same base at the same time. The same base can also be used to select different bases: at this time, when using multiple identical β numbers in one formula It may be different from the group in the other formula, or may be different in part. The "alkyl group" which is not particularly limited is used as a general term for a linear alkyl group and a branched alkyl group. [1] The item [2] to [20] of the following [1] is characterized in that: [2] The liquid crystal alignment agent according to [1] is characterized in that: Α! is -COO- Or a sub-alkyl group having a carbon number of 1 to 3, and R is a gas or a carbon group having a carbon number of 1 to 4. [3] The liquid crystal alignment agent according to the item [1] or [2] is characterized in that The other diamine is a diamine selected from the group consisting of the formula (I-1) to the formula (1_3), the formula (2-1), the formula (2_2), the formula (1), the formula (4-1), and the formula (4-2). At least one diamine in the group: 201132704 -----·Γ" CH2-^^α^-ΝΗ2 (1-1) h2n<J^NH2 (12) rCN4CH2^^^NH2 (1-3) Here, 'a' is 0 or 1 in the formula (1-1); the ring α is 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene or ι, 2,4- Any of the hydrogens of the tris--3,5-diyl group; the cyclohexylene group and the phenylene group may be substituted by a mercapto group, a diethylamino group or a divinylamino group; W1 in the formula (1-2) is _CH2- Or -ΝΗ-; b in the formula (1-3) is an integer of 〇~2:

Here, 'X is a single bond or an alkylene group having 1 to 10 carbon atoms; any -CH2- of the alkylene group may be -〇_, _s_, _NH_, -C(CF3)2-, -CO, , -S〇2·,, CEC_, _N=N_, 13 phenylene, M-substituted or fluorene], 4_diyl substituted; any hydrogen of the benzene ring may be fluorine, sulfhydryl, hydrazine Substituted by -CF3 or -OCF3: 201132704 h2n

(2-2) Here, 'Y1 is an alkyl group having 3 to 30 carbon atoms; any _CH2_ of the alkyl group may be substituted by _〇~CH=CH- or 1,4-cyclohexylene; γ2 is hydrogen or Γ1 : R1

(3) (a) In the formula (3), χ2 is a single bond, -〇-, -COO-, -OCO-, -CONH-=an alkylene group of 1 to 6; R1 is a carbon number of 3 to 30 Alkyl group, cholesterol (base represented by hydrazine; production formula (aj, χ3 and χ4 are independently a single bond or an alkylene group having a carbon number of 1 to 4; 2, and ^ C are independently M-phenylene or 1) , 4-cyclohexylene; R 2 and R 3 are fluoro or methyl, £ and g are independently 0, 1 or 2; c, d and e are independently 2 or 1, and their total is 1 to 3; R 4 is carbon a number of 1 to 30 alkyl groups, a K 1 to 3 fluorene alkoxy group, a carbon number of 2 to 30 alkoxyalkyl groups, or a carbon number of 201132704 «/ / ^ γιχ\. 2 to 30, which are burned Any hydrogen in the base, alkoxy group, alkoxy group and a dilute group may be substituted by fluorine: H2N-^〇LX5

X5-0" -NH, (4-1) 5 where 'X5 is independently -Ο- or an alkylene group having 1 to 6 carbon atoms; j is hydrazine or 1; R is an alkyl group having 1 to 30 carbon atoms, An alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 3 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; the ring τ is fluorene, 4-phenylene or 1,4-ya克己基, X is a Zhuo bond or a sub-smelling odor of 1 to 3 carbon atoms. ^ is 〇 or 1; R6 R7

(4-2} 6 where 'X5 is independently -0- or an alkylene group having 1 to 6 carbon atoms; j is hydrazine or 】; R6 is hydrogen, an alkyl group having 1 to 30 carbon atoms, and a carbon number 如~ Alkoxy group, alkoxyalkyl group having a carbon number of 2 to 3 fluorene, or an alkenyl group having 2 to 30 carbon atoms; and R 7 is an alkyl group or a cholesteryl group having a carbon number of 6 12 201132704 to 30. [4] The liquid crystal alignment agent according to Item 3, wherein the other diamine is at least one type of diamine selected from the group consisting of diamines represented by the formula (3). [5] According to the item [3] The liquid crystal alignment agent is characterized in that the other diamines are represented by the formula (3-1) to the formula (3-7), the formula (3-21) to the formula (3-25), the formula (3-34) and the formula ( 3-35) At least one of the diamines represented: 13 201132704

Here, Y4 is an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms; Υ5 is a carbon number. An alkyl group of 1 to 10, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. [6] The liquid crystal alignment agent according to [3], wherein the 201132704 diamine is at least one diamine selected from the group consisting of diamines represented by the formula (4-1). [7] The liquid crystal alignment agent according to [3], wherein the other diamine is at least one of the diamines represented by the formula (4-1-1) to the formula (4-1-8). : 15 2011327(3⁄4

16201132704. Here, Y6 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. [8] The liquid crystal alignment agent according to [3], wherein the other diamine is selected from the group consisting of formula (1-1) to formula (1-3) and formula (2-1) At least one diamine in the group of amines. [9] The liquid crystal alignment agent according to [3], wherein the other diamine is of the formula (1-1-3), the formula (1-1-5), and the formula (1-1-8). ), Formula (1-1-9), Formula (1-1-12)~Formula (^4), Formula (1-2-2), Formula (1-3-1), Formula (1-3- 2), Formula (2-1-1), Formula (2-1-7), Formula (2-1-10), Formula (2-1-13), < (2·Κ27), Formula (2) -1-28), formula (2-1-32) to formula (2-1-35), formula 1 (2] 1-54) to formula (2-1-56) and formula (2-1-66) At least one of the diamines represented by the formula (2-1-68): 17 201132704

(1-1-8) (1-1-9)

(1-1-14) (1-1-13)

18 201132704

(2-1-34)

(2-1-35)

(2-1-54)

.(CH2)6.

(2-1-66) H3q H2N,

(2-1-56) CH3

Nh2 (2-1-67) H3co, a ^PCH^ (2-1-68) U〇] The liquid crystal matching agent according to the item [9] is characterized in that: the other diamine is a formula (1) -1-8), formula (1-1-9), formula (1 small 12), formula (1_2-2), formula (1-3-1), formula (1-3-2), formula (2 -1-32), at least one of the diamines represented by the formula (2-1-33), and the formula (2-1-66) to the formula (2-1-68), or the diamine (these) mixture.

The invention is characterized in that: tetracarboxylic acid 19 201132704^, [the] special item to the liquid crystal alignment according to any one of the above-mentioned items, wherein the four-dimensional dianhydride is a tetracarboxylic acid other than the aromatic acid-acid two-needle. At least one of acid dianhydrides. The liquid crystal alignment of any one of the above-mentioned items, wherein at least one of the aromatic tetradecanoic dianhydrides and the fourth of the aromatic tetraphthalic anhydrides a mixture of at least one of phthalic acid dianhydride. The liquid crystal alignment agent according to the item [π], which is characterized in that: the aromatic sulphuric acid dianhydride is of the formula (private), the formula (Η 5), the formula (Η 8) ～ (H) a compound represented by -1G), formula (Η_15), formula (Η_19), formula (Η 2()), and formula (Η-21), and tetracarboxylic dianhydride other than aromatic tetracarboxylic dianhydride is a formula (S-1), (S-6), (S-9) to (S-11), (S-21), (s_22), (S-30), (S-) 43), a compound represented by the formula (S-44), the formula (S-45), the formula (S_48) and the formula (S-53):

201132704 U I

o 〇

o o o o o

21 201132704

The liquid crystal alignment agent according to the item [14], wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (H-1), an aromatic tetradecanoic acid The tetracarboxylic dianhydride other than the anhydride is a compound represented by the formula (S_D). [16] The liquid crystal alignment agent according to [14], characterized in that: ^ 香族四纽二由式(五)) The tetracarboxylic dianhydride other than the aromatic compound and the tetracarboxylic dianhydride is a compound of the formula (10), which is represented by the formula (4)). [17] The liquid crystal alignment agent according to any one of the above [1], which further comprises a polyfluorene obtained by using the diamine represented by the formula (I) Amine acid or a derivative thereof. [18] A liquid crystal alignment film which is obtained by applying the liquid crystal alignment agent according to any one of [n] to [17] on a substrate to heat the obtained coating film. form. [19] A liquid crystal display element comprising the liquid crystal alignment film according to [18]. [2〇] A monoamine' is characterized in that it is represented by the formula (1-2):

The liquid crystal alignment agent of the present invention is a composition containing at least one polymer selected from the group consisting of polylysine and a derivative thereof and a solvent. Examples of the derivative of poly-proline include a polyimine obtained by subjecting polyphosphamic acid to a dehydration ring-closure reaction, and a partial ruthenium polycondensation obtained by partially performing a dehydration ring-closure reaction of polyglycine. a proline acid, a polyamidomate, a polyphthalic acid-polyamide copolymer obtained by substituting a part of a tetracarboxylic acid dioxon with a dicarboxylic acid, and a polyamidamide-polyamide copolymer A part or all of the polyamidoximine obtained by the dehydration ring-closing reaction. Among these derivatives, quinonemine and a part of the ruthenium polyamine, more preferably polyimine. In the following description other than the example of 201132704, unless otherwise specified, "polylactoic acid" is used as a general term for polyamines and derivatives of such polylysines. In the case of a liquid crystal alignment agent, a diamine (I) or a mixture of a diamine (I) and another diamine is used as a diamine which reacts with an acid anhydride.

In the formula (I), A1 is a single bond, _〇·, <〇〇_, _c〇_, _c〇NH_ or an alkylene group having 1 to 6 carbon atoms, preferably _c〇〇_ or a carbon number of 1~ 3 alkylene, more preferably, -CO hawthorn - or even "R is independently a hydrogen or carbon number 6 alkyl group, ^ hydrogen or a carbon number of 1 to 4, more preferably hydrogen or a third butyl group (The following 5, sometimes referred to simply as t-butyl or t-Bu) 〇 As a preferred example of the monoamine (I), diamine (ι_ι) and diamine are mentioned.

(1-1) (1-2) 24 201132704 As a preferred example of other diamines, _ (1-3), diamine (1), diamine (10), di(1))-diamine and diamine can be listed. (4·2). —amine (1), diamine (4))

(1-1) Here, a is 0 or 1, and the ring is 14-cyclohexylene, 13 cyclohexylene, 1,4-phenylene, pyridinylene or triazole_3,5-diyl Preferred is 1,4-cyclohexylene, iota, 4-phenylene or iota, 2,4-triazole-3,5-diyl. Further, any hydrogen of the cyclohexylene group and the phenylene group may be substituted by a methyl group, a _Cf3 group, a diethyl group or a monoamino group. Preferred examples of the diamine (1_1) are shown below. 25 201132704

(1-1-1) (1-1-2) (1-1-3) (1-1-4)

(1-1-9) (1-1-10) (1-1-11) (1-1-12) jcnc (1-1-13) ^NH2 HzN^· rc (1-1-14) H3C丫h2n human TOC: Among the diamines (1-1-1) to diamines (1-1-15) described in (1-1-15), more preferred are diamines (1-1-3), Amine (1-1-5), diamine (1-1-8), diamine (1-1-9), and diamine (1-1-12) to diamine (1-1-14).

Here, W1 is -CH2- or -NH-. That is, specifically, the diamine (1-2) is a diamine (1-2-1) and a diamine (1-2-2). 26 201132704 j / jyjyil

(1-3) Here, b is an integer of 0 to 2, preferably 0 or 2. That is, preferred examples of the diamine (1-3) are a diamine (1-3-1) and a diamine (1-3-2).

Here, X1 is a single bond or an alkylene group having 1 to 10 carbon atoms, and any -CH2- of the alkylene group may be -0-, -S-, -NH-, -N(CH3)-, - C(CH3)2-, 27 201132704 -C(CF3)2-, -CO-, -S〇r, _CH=CH·, _CEC_, _N=N-, i 3_phenylene, 1,4-phenylene Substituted or pyridazine _14_diyl substituted. Any hydrogen of the benzene ring may be substituted by fluorine, methyl, methoxy, or _CF3 4_〇CF3. Further, it is preferred that X1 is a single bond or any seven of the bases - a carbon number of ι~1〇 which may be substituted by _〇_, 丨, 4-phenylene or π guzin-1,4-diyl One hydrogen of the alkyl 'benzene ring may be substituted by a methyl group. Further, the position of the amino group bonded to the benzene ring is a para or meta position with respect to X1, preferably a para position. Preferred examples of the diamine (2-1) are shown below. 28 201132704

(2-1-4) (2-1-5)

H2N

(2-1-13) .〇x_^.NH2 h2n NH2 h2n

(2-1-14)

H2N

(2-1-20) NH2 h2n

(2-1-21) 29 201132704

NH〇

H2N

(2-1-22) S s (2-1-24) ~Q)~\ nh2 h2n xys^sx\ h2n^^ ^^nh2 (2-1-23) Lamp U (2-1-25) NH,

30 201132704

H2N

(2-1-40) H3C 0 h2n- nh2

(2-1-41)

PhW

H2N

P (2-1-42) b~^ ^~nh2 h2n—^

H2n

H3c H2N—f N. (2-1-47)

, cf3

H2N^ f3c

H2n

Csc^D^c"c^}^nh2 (2-1-52) h2n-c^c

31 201132704

,(CH2)3 (2-1-55)

(2-1-56) H2N H3c, fY XJ ^XH2 (2-1-57) (2-1-58) h2n /CF3 丫l! Aj (2-1-59) "rxjxnjy^ (2-1 -60)

•(CH2)6

P-1-61) .(CH2)4

(2-1-65) 32 201132704 h2n^C^_nCvn_<C)k'nh2

Pn3 h3c r~\ N^ (2-1-66)

H2N

NH 2 F

(2-1-69) h2n

F3c h2n

N N—(\ NH2 (2-1-71) PF3 Λ r\ N—\ ,—NH〇

(2-1-73)

(2-1-76) Among the diamines (2-1-1) to diamines (2-1 to 76), diamines (2-1-1) and diamines (2-1) are more preferable. -7), diamine (2-1-10), diamine (2-1-13), diamine (2-1-27), diamine (2-1-28), diamine (2-1 -32)~Diamine (2-1-35), diamine (2-1-54)~diamine (2-1-56) and diamine (2-1-66)~diamine (2-1 -68). 33

201132704 L h2n

(2-2) Here, Y1 is an alkyl group having 3 to 30 carbon atoms, preferably an alkyl group having 3 to 20 carbon atoms, and more preferably an alkyl group having a prime number of 3 to 10. Further, any -CH2- of these alkyl groups may be substituted by -Ο-, -CH=CH- or 1,4-cyclohexylene. Y2 is hydrogen or Y1. Preferred examples of the diamine (2-2) are shown below.

(2-2-1)

(2-2-3)

34 201132704 In the above formula, Y3 is a burnt group having a charcoal number of 3 to 10, an alkoxy group having a carbon number of 3 to 10, or an alkenyl group having a carbon number of 3 to 10, and Υ4 is an alkyl group having a carbon number of 2 to 10 and a carbon number. 2 to 10 alkoxy groups or alkenyl groups having 2 to 10 carbon atoms. Further, Υ5 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a diluted group having 2 to 10 carbon atoms.

(a) In the formula (), X2 is a single bond, -Ο-, -COO-, -OCO-, -CONH- or an alkylene group having 1 to 6 carbon atoms, and R1 is an alkyl group having 3 to 30 carbon atoms; A cholesteryl group or a group represented by the formula (a). R1 is preferably an alkyl group having 3 to 10 carbon atoms or a group represented by the formula (a). Further, it is preferred that the positions of the two amino groups bonded to the benzene ring are meta-position with respect to X2. In the formula (a), X3 and X4 are independently a single bond or an alkylene group having 1 to 4 carbon atoms. Ring B and Ring C are independently 1,4-phenylene or 1,4-cyclohexylene. R2 and R3 are independently a fluorine or a fluorenyl group, and f and g are independently 〇, 1 or 2 °c, and d and e are independently 0 or 1, and their total is 1 to 3. R4 is a hospital base having a carbon number of 1 to 30, 35 201132704, an alkoxy group having 1 to 30 carbon atoms, an alkoxy group having 2 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, preferably a carbon number of 1 to 30. An alkyl group having 1 fluorene, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 1 carbon atoms. Further, any of the hydrogen groups in the alkyl group, the alkoxy group, the alkoxy group and the base group may be substituted by fluorine. Preferred examples of the diamine (3) are shown below. In the following examples, Y3 is an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkoxyalkyl group having 3 to 10 carbon atoms, or an alkenyl group having 3 to 10 carbon atoms, and γ4 is An alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 1 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Further, Y5 is an alkyl group having a carbon number of 丨1 to 1 Å, an alkoxy group having a carbon number of 10, an alkoxyalkyl group having 2 to 10 carbon atoms, or a phenolic group having 2 to 1 carbon atoms. 36 201132704

Γ5

37 201132704

(3-15) (3-16) (3-14) H2N h2n (3-1 ε, (3-17)

38 201132704 ^ / y uγ/ιι.

Y5

H2N, h2n

Y4 (3-33) h2n (3-34) Η2Ν /=\ ρ H2N . Η2Ν η η2ν η2ν (3-35) (3-36) η} 1, Ν Η (3-37) -Y4 Among the diamines (3-1) to diamines (3-37), more preferably Diamine (3-1) to diamine (3-7), diamine (3-21) to diamine (3-25), diamine (3-34) and diamine (3-35), most preferably Diamine (3-2) to diamine (3-7). 39 201132704 h2n

(4-1) In the formula (4-1), X5 is independently -O- or an alkylene group having 1 to 6 carbon atoms, j is 0 or hR5 is an alkyl group having 1 to 30 carbon atoms, and carbon number is 1 to 30. Alkoxy group, alkoxyalkyl group having 2 to 30 carbon atoms, or alkenyl group having 2 to 30 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number of 2 An alkoxyalkyl group of ～10 or an alkenyl group having 2 to 10 carbon atoms. Ring T is 1,4-phenylene or 1,4-cyclohexylene, and X6 is a single bond or an alkylene group having 1 to 3 carbon atoms, and h is 0 or 1. Further, when j is 1, it is preferred that the positions of the two amino groups bonded to the benzene ring are aligned with respect to X5. Preferred examples of the diamine (4-1) are shown below. In the following examples, Y6 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. 201132704 Y6

(4-1-8) 41 201132704 t y/ki. R6 R7

(4-2) In the formula (4-2), X5 is independently -O- or an alkylene group having 1 to 6 carbon atoms; j is 0 or 1; R6 is hydrogen, an alkyl group having 1 to 30 carbon atoms, carbon The alkoxy group having 1 to 30 carbon atoms, the alkoxyalkyl group having 2 to 30 carbon atoms, or the alkenyl group having 2 to 30 carbon atoms is preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An oxy group, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Further, R7 is an alkyl group or a cholesteryl group having 6 to 30 carbon atoms, preferably an alkyl group having 6 to 10 carbon atoms. Preferred examples of the diamine (4-2) are shown below. In the following examples, Y7 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. . Moreover, Y8 is a competitor with a carbon number of 6 to 10.

Here, the side chain type diamine and the non-side chain type diamine will be described in detail. Diamines can be classified into two types depending on their structures. Namely, a diamine having a side group of a group of 201132704 and a diamine having no side chain group, which is a group branched from the main chain when a skeleton linking two amino groups is regarded as a main chain. Polylysine having a plurality of side chain groups with respect to the main chain of the polymer can be obtained by reacting a diamine having a side chain group with tetrahectoric acid dianhydride. When such a polyglycolic acid having a side bond group with respect to a polymer primary bond is used, the liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer can enlarge the pretilt angle of the liquid crystal display element. That is, the side chain group is a group having an effect of expanding the pretilt angle. The side chain group having such an effect must be a group having 3 or more carbon atoms, and in the present invention, the group having 3 or more carbon atoms is defined as a side chain group. Specific examples thereof include an alkyl group having no carbon atom number or more and a terminal having a carbon number of 3 or more, an alkoxy group having a carbon number of 3 or more, or an alkoxyalkyl group having 3 or more carbon atoms, or an alkyl group having 3 or more carbon atoms. a group of a base, and a group having one or more rings. Further, in the group having one or more rings, 'when the effect of enlarging the pretilt angle is more strongly required', it is preferable that the ring at the end thereof is a wire having a carbon number of 丨 or more, a carbon number i = a methoxy group, & A number 2 or more of an alkoxy group and a carbon number of 2 or more are used as a silk base yarn. A diamine type having such a chain group is cut, and a diamine having such a side chain group is used as a non-side chain amine I = (1) (10) chain type diamine 'and the other di-chain type diamine, diamine (2) 2), 7 (-) and, the amine (2-1) is a side chain type diamine. Μ3), diamine (4)) and diamine (4)) In the TM mode or VA side ==:=1: To: 43 201132704 Large pretilt angle ' Therefore, a side chain type triamine is mainly used. At this time, in order to further control the pretilt angle, it is sufficient to use a non-side chain type diamine in combination. The ratio of the __ diamine to the side chain type diamine can be determined according to the target pretilt angle. Of course, it is also possible to touch only by using a side-chain type diamine by appropriately selecting a side chain group. Since the transverse electric field method has a small angle and requires high liquid crystal alignment, at least one of non-side chain type diamines may be used. In the present invention, at least one of the diamines (1) and the diamine (2_2), diamine (3), and diamine (4) selected from the side chain type diamines are used for the purpose of exhibiting a large pretilt angle. And at least one combination of diamines (4-2). A preferred example of this combination is a combination of a diamine (1) and a diamine (1), a combination of an amine (I) and a diamine (4-1). Moreover, when the purpose of exhibiting a small pretilt angle is used, at least one type of diamine is used in combination with at least one type of non-side chain type diamine. When the root target is pretilted and timed, the side chain type II may be used. The amine is used in combination with a non-side chain type, and is used in the present invention by combining a diamine having a secondary amino group, a tertiary amino group or a nitrogen-containing heterocyclic group in the skeleton of the residue with a diamine (1). The synergistic effect of the OH group of the amine (I) and the nitrogen atom can be utilized to further increase the long-term optical reliability of the diamine (I), that is, the soilability for long-term light irradiation, and the effect is listed below. Preferred examples of the diamine having a secondary amino group, a primary amino group or a nitrogen-containing heterocyclic group in the skeleton of the residue - 44 201132704 y /上 /Xi

(2-1-41)

45 201132704.

H3c ch3h2N^〇_nC}i_C/nh2

H2 (2-1-67)

Cf3 f3c

H2n^v__/^0^~hO~hs, h2 (2-1-75) P-1-76) Among the above examples, diamines (1-1-8) and diamines (1-1) are more preferred. -9), diamine (1_b 12), diamine (1-2-2), diamine (1-3-1), diamine (1-3-2), diamine (2-1- 32), diamine (2-1-33), and diamine (2-1-66) to diamine (2-1-68). The acid anhydride used in the present invention can be classified into an acid anhydride other than an aromatic acid anhydride and an aromatic acid needle. The aromatic acid anhydride refers to two needles obtained by dehydrating a compound having four carboxyl groups directly bonded to an aromatic ring in one molecule. When an aromatic acid anhydride is used, the effect of improving the light resistance of the liquid crystal display element can be obtained, and the effect of reducing residual DC can be obtained. In the liquid crystal alignment agent of the present invention, it is preferable to set the amount of the oxime % to the aromatic acid anhydride in the total amount of the acid anhydride used in the synthesis of the polyamic acid, and it is more preferable to set the stalk to 1 G mol % to 60 stalk. Hey. Preferred examples of the aromatic acid anhydride are shown below. ,

(H-7) Ο

(Η-15) (H-16) 47 201132704

Among these aromatic acid anhydrides, an acid anhydride (H1), an acid anhydride (H-5), an acid anhydride (H-8) to an acid anhydride (H-10), an acid anhydride (H-15), and an acid anhydride (H-17) to an acid anhydride are more preferable ( H-21) 'The most preferred acid anhydride (H-1), acid anhydride (H-5), acid anhydride (H-8) to acid anhydride (H-10), acid anhydride (H-15), and acid anhydride (H-19)~ Anhydride (H-21). Preferred examples of the acid anhydride other than the aromatic acid anhydride are shown below. 48 201132704

(S-5) (S-6) (S-7)

O

0

(S-10) (S-11)

(S-15) (S-16) (S-17) 0 V 〇r^A 0 K- 0 -Λ 0 〇A 0 γ- 〇K- 0 -w 0 Γ °)r^CH2^ 0 〇( S-18) (S-19) (S-20) 49 201132704 ο ο ο Ο Ο

η Ο

Ο Ο C

°^° ο ο (S-25)

Ο

(S-29) η

Ο Ο

(S-36)

(S-37)

50 201132704

(S-47) (S'48)

:K 0·

(S49)

(S-51) (S-52)

Among the acid anhydrides other than the aromatic acid anhydride, an acid anhydride (S1), 51 201132704 '-Γ--anhydride (S-6), an acid gf (S-9), an acid (S-ll), and an acid anhydride (S) are more preferable. -21 ), acid Sf (S-22), acid anhydride (S-30), acid gf (S-43), acid gf (S-44), acid if (S-45), acid if (S-48) As the acid anhydride (S-53), an acid anhydride (S1), an acid anhydride (s-6), an acid anhydride (S-48), and an acid anhydride (S-53) are most preferable. When an acid anhydride other than the aromatic acid anhydride, i.e., an alicyclic acid anhydride or an aliphatic acid anhydride, is used, the effect of improving the heat resistance of the liquid crystal display element and the effect of improving the transparency can be obtained. In the liquid crystal alignment agent of the present invention, it is preferable to set 30 mol/〇1 to mol% of the total amount of the acid anhydride used in the synthesis of the polyamic acid to an acid anhydride other than the aromatic acid anhydride, and it is more preferable to set it as 40 moles % ~ 9 〇 Mo 〇 / 〇. The effect produced by using a diamine having a secondary amino group, a tertiary amino group or a 3 nitrogen heterocyclic group in the skeleton of the residue in combination with the diamine (I) can also be achieved by having the skeleton of the residue An acid anhydride of a secondary amino group, a tertiary amino group or a nitrogen-containing heterocyclic group is obtained by reacting with a diamine. A preferred example of 酉Fuye having a secondary storage group, a tertiary amino group or a nitrogen-containing hetero-m group in the skeleton of the residue is acid liver (S-48). In the present invention, at least one kind of aromatic acid field is used. It is preferable to use at least one type of kSf with an aromatic acid liver to increase the storage stability of the liquid crystal alignment agent. And a, particularly preferably, the acid in the acid anhydride (the combination of h_g and anhydride (S·1)' is also particularly preferably acid liver (H-1) and acid anhydride (s_48).

The group is struggling. J Alternatively, a part of the acid anhydride may be replaced with a two-in-one needle. Thereby, the polymerization reaction (10) of the raw money gorge can be caused, and the progress of the suppression can be suppressed. Therefore, the & 1 of the obtained poly-proline can be easily controlled, for example, the coating can be applied to the coating agent 52 201132704 / yjL·!. The ratio of the dicarboxylic anhydride to the acid anhydride is not particularly limited as long as the effect of the present invention is not impaired. However, as a standard, it is preferably set to 10 mol% or less of the total amount of the acid anhydride. Examples of the dicarboxylic anhydride are maleic anhydride, phthalic acid needle, itaconic acid needle, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride And cyclohexane dicarboxylic anhydride. The molecular weight of the polyproline in the present invention is, in terms of polystyrene-equivalent weight average molecular weight (?^\¥), preferably 1 Torr, 〇〇〇 5 〇〇, 〇〇〇, more preferably 2 〇, 〇〇 〇~200,000. The molecular weight can be determined by measurement by a gel permeation chromatography (GPC) method. The polyproline in the present invention can be confirmed by the following method. Infrared Radiation (IR), Nuclear Magnetic Resonance (NMR) is used to precipitate polylysine using a large amount of poor solvent. The solid components were analyzed. Further, the raw material compound to be used can be confirmed by gas chromatography (Gas Chromatography, GC) or high performance liquid chromatography (High).

Performance Liquid Chromatography (HPLC) or Gas Chromatograph-Mass Spectrometer (GC-MS). Decomposition of polylysine using an aqueous solution of a strong base such as KOH or NaOH, using an organic solvent from its decomposition product. The extracted components were analyzed. The liquid crystal alignment agent of the present invention may further contain other components than the above-mentioned polyamic acid. The other components may be of a type of two or more. Point of view on preventing deterioration of characteristics over time or deterioration caused by the environment 53 201132704

Further, a crosslinking agent which reacts with a crosslinking agent itself to form a network structure, thereby enhancing the film strength of poly-proline, can also be used for the same purpose as described above. Examples of such a crosslinking agent include polyfunctional vinyl ether, maleimide, and alkenyl substituted nadic oxime described in JP-A-H10-310608, JP-A-2004-341030, and the like. Imine compound. When these crosslinking agents are used, the preferred ratio thereof is 〇1〇1〇〇, more preferably 0.01~0.5 by weight based on the total amount of the polymer components. The following is an example of a particularly preferred alkenyl substituted nadic quinone imine compound.

54 201132704

(I na-3) The liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond, from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time. Examples of the compound having a radical polymerizable unsaturated double bond include a (meth) acrylate, a (mercapto) acrylamide derivative (fluorenyl) acrylamide derivative, and a bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radical polymerizable unsaturated double bonds. The liquid crystal alignment agent of the present invention may be further contained from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. Evil compounds. An example of an oxazine compound is indicated.

Here, 'W1 is a phenyl group or an alkyl group having 1 to 2 carbon atoms.

The step contains an epoxy compound. 55 201132704 Λ Oxygen compound can be exemplified by glycidyl ether, glycidyl ester, glycidol makeup 3 epoxy group-containing acrylic resin, glycidyl decylamine, glycidyl isocyanurate, chain aliphatic epoxide And a cyclic aliphatic epoxy compound. The liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include polymers other than polyglycolic acid and low molecular weight compounds, which can be selected and used according to various purposes. For example, by adding polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, organic hydrazine-modified polyurethane or organic hydrazine-modified polyester to the liquid crystal alignment agent of the present invention, it can be expected A liquid crystal display element having high reliability is produced by improving the voltage holding ratio of the liquid crystal display element, reducing the ion density, and improving light resistance and heat resistance. As the low molecular compound, when it is desired to improve the coatability, a surfactant which does not satisfy the purpose can be exemplified, and when it is required to improve the antistatic property, an antistatic agent can be exemplified, and when it is desired to improve the adhesion to the substrate or the resistance In the case of the frictional property, a decane coupling agent or a titanium-based coupling agent may be exemplified, and when the hydrazine imidization is carried out at a low temperature, a brewing imidization catalyst may be exemplified. Specific examples of the decane coupling agent are: vinyl trimethoxy decane, vinyl diethoxy decane, fluorenyl-(2-aminoethyl)_3_aminopropylmethyldimethoxy oxime, Ν-( 2_Aminoethyl)-3-aminopropyldecyltrimethoxy decane, p-aminophenyltrimethoxy decane, p-aminophenyltriethoxy decane, m-gas radix , m-Oxophenyl triethoxy zeoxime, aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, 3-glycidoxypropyl trimethoxy decane, 3-glycidol Oxypropylmethyldi 56 201132704 decyloxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-chloropropyl decyl decyloxydecane, 3-chloro Propyltrimethoxydecane, 3-mercaptopropenyloxypropyltrimethoxyxanthine, 3-mercaptopropyltrimethoxyxanthene, N-(l,3-monomethylbutylene)_3_( Triethoxy phthalocyanine)] • propylamine, and hydrazine, Ν·-bis[3_(dimethoxycarbazide)propyl]ethylenediamine. When the alkane coupling agent is used, it is preferably added in an amount of 0.001 to 〇.〇5 based on the total weight of the polyglycolic acid. Specific examples of the ruthenium imidization catalyst include aliphatic amines such as tridecylamine, triethylamine, tripropylamine, and tributylamine; hydrazine, hydrazine-dimethylaniline, hydrazine, hydrazine _: ethylaniline, methyl Aromatic amines such as aniline and hydroxy-substituted aniline; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy substitution Isoquinoline, imidazole, thiol-substituted hydrazine, hydroxy-substituted stilbene and other cyclic amines. The ruthenium amide catalyst is preferably selected from one or both of ruthenium, fluorenyldiphenylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine and isoquinoline. the above. When the ruthenium amide catalyst is used, it is preferably added in an amount of from 0.01 equivalent to 0.5 equivalent to the carbonyl group of the polyglycolic acid, preferably from 0.05 equivalents to 0.3 equivalents. m The liquid crystal alignment agent of the present invention contains a solvent. The solvent can be selected from the manufacture of poly-proline, or the solvent towel. Solvents • It is one type, and two or more types may be used as a mixed solvent. The solvent is roughly classified into a solvating agent of polylysine and a solvating agent for the purpose of improving coatability. ', 亲's agent is an aprotic polar organic solvent, specific examples thereof are: N-曱57 201132704 yl-2-pyrrolidine _, dinonyl imidazolidinone, n-methyl caprolactam, ν· 曱Propionamide, hydrazine, hydrazine-dimercaptoacetamide, dimethyl sulfoxide, hydrazine, hydrazine-dimercaptoamine, hydrazine, hydrazine-diethylformamide, diethyl acetamide And lactones such as γ_butyrolactone. Other solvents for the purpose of improving coatability and the like can be exemplified by alkyl lactate, 3·methyl_3_methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether, and diethylene glycol. Alcohol monoalkyl ether, ethylene glycol monophenyl ether, triethylene glycol monoalkyl ether, propylene glycol monoterpene ether, propylene glycol monoalkyl ether, dialkyl malonate, dipropylene glycol monoalkyl ether, and An ester compound such as an acetate of these compounds. Among these solvents, particularly preferred are Ν-methyl-2-pyrrolidone, dimethyl hydrazine, ketone, γ-butyrolactone, ethylene glycol monobutyl, diethylene glycol monoethyl ether, propylene glycol monobutyl ether. , propylene glycol monomethyl ether, and dipropylene glycol monoterpene ether. The liquid crystal alignment agent of the present invention is supplied in a form of a solution obtained by dissolving a polymer component containing the above polylysine in a solvent. The preferred concentration of the polymer component at this time is 0.1 wt% (wt%) to 40 wt%. When the liquid crystal alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the contained polymer component with a solvent in advance. In this case, the concentration of the polymer component is preferably 40% by weight or less from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent. The concentration of the polymer component in the liquid crystal alignment agent is sometimes adjusted according to the coating method of the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polymer component is usually set to 58 201132704 y / · / 〆 _ _ soil / 1 · * · 10 wt% or less. In other coating methods, such as dipping or ink jetting, it is possible to reduce the concentration step by step. On the other hand, when the concentration of the polymer component is 〇1 wt% or more, the film thickness of the liquid crystal alignment film obtained is easily optimized. Therefore, in the usual spin coating method, printing method, or the like, the concentration of the polymer component is 〇1 or more, preferably 0.5 wt% / 〇 to 1 〇 wt%. However, depending on the method of applying the liquid crystal alignment agent, it may be used at a lower concentration. Further, when used for producing a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined depending on the means or method for forming the film of the liquid crystal alignment agent. For example, when a film of a liquid crystal alignment agent is formed by using a printing machine, the viscosity of the liquid crystal alignment agent is preferably 5 mp a. s or more from the viewpoint of obtaining a sufficient film thickness. Preferably, it is i〇〇mPa·s or less, more preferably 10 mPa·s to 80 mPa·s. When a liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, the same viewpoint is used. The liquid crystal alignment agent preferably has a degree of penetration of 5 mPa·s to 200 mPa·s, more preferably 10 mPa·s. ~100 mPa. s. The viscosity of the liquid crystal alignment agent is lowered by dilution with a solvent or solidification with stirring. In the present invention, in addition to polyamine (polymer A) obtained by reacting a diamine (1) or a mixture of a diamine and another diamine with an acid anhydride, it is also possible to use no amine (丨). The polylysine obtained (Polymer B). The combined use of the two polylysines is the so-called polymer blending. Specifically, the poly-proline which is obtained without using the diamine (I) is a poly-proline which is obtained by reacting the other diamine with an acid anhydride. Moreover, the effect of using a diamine having a secondary amino group, a tertiary S9 201132704 amino group or a nitrogen-containing heterocyclic group in the skeleton of the residue can also be obtained by: making the diamine, or the diamine and The polyphthalic acid obtained by reacting a mixture of other diamines with an acid anhydride is used as the polymer B, and it is blended with the polymer A. In this case, other diamine mixed with a diamine having a secondary amino group, a tertiary amino group or a nitrogen-containing heterocyclic group in the skeleton of the residue may be selected according to the target pretilt angle. The liquid crystal alignment film of the present invention can be obtained by a step of coating the liquid crystal alignment agent on a substrate, and a step of calcining the coating film thus obtained, optionally, in the calcination step. The obtained film was subjected to a rubbing treatment. The ruthenium is formed in the same manner as the usual liquid crystal alignment film, and the coating film can be formed by applying the liquid crystal alignment agent of the present invention onto the substrate of the liquid helium display element. As a preferable substrate, a substrate made of glass such as an indium tin oxide (Indium Oxuie'ITO) electrode or a color calender sheet can be used. As a method of applying a liquid crystal alignment agent onto a substrate, a spin coating method, a printing method, a dipping method, a dropping method, an ink jet method, or the like is generally known. These methods can also be applied to the present invention. The calcined calcination method can be used for the calcination of the polyacetamide which is required for the dehydration-ring closure reaction. It is generally known to be in the case of a tank or a heat treatment method, and heat treatment on a hot plate. It can also be applied to the present invention. In general, the temperature of about 150 C to 3 GGC is preferably i minutes to 3, and the treatment of the alignment treatment of the liquid crystal alignment film (4) is performed, and if sufficient conditions are obtained in the 201132704 alignment film of the present invention, can. The amount of capillary intrusion is 0.2 mm to 0.8 mm, and the preferred condition for flattening is ±250 mm/sec, and the rotation speed of the roller is 5 rpm to 5 mm/sec. The alignment treatment method of the liquid crystal alignment film is removed. Take the law, =. As a photoalignment method, a transfer method, or the like. The effect of the present invention can be obtained. Secondly, there is a possibility that the secret of the formula (10) can be described as = the inner serge can be used in combination with the rubbing treatment. In the present invention, when a polyamine having a photosensitive group is used in combination with a diamine (1) to produce a poly-proline, and the poly-proline is used to prepare a liquid crystal alignment agent, the above-mentioned The optical alignment method is used to obtain an alignment film. For example, when a polyimide film formed on a substrate by using such a liquid crystal alignment agent is irradiated with linearly polarized ultraviolet light, and then a liquid crystal composition is sealed in a liquid crystal cell produced by laminating two substrates, A liquid crystal display element having a liquid crystal to which a desired alignment state is imparted. Next, 'is an example of a diamine having a photosensitive group. 61 201132704

(2-1-40) (2-1-41)

(2-1-42) h2n

C^C

Nh2 (2-1-43)

NH,

NH2 (2-1-45)

OCHi

,cf3 h2i

H2 (2-1-49)

62 201132704. In a liquid crystal display element having an alignment film produced using a liquid crystal alignment agent containing a polymer having a photosensitive group in a main chain, when a predetermined pretilt angle is to be exhibited, the following method can be appropriately selected: when irradiated A method of irradiating a substrate with linearly polarized light from the viewpoint of ultraviolet light in the case of ultraviolet light, or a method of combining a linear polarized light irradiation from a vertical direction on a beautiful plate and a non-polarized light irradiation from an arbitrary angle on a substrate. The liquid crystal alignment film of the present invention can be preferably obtained by a method further including other steps than the above steps. As such another step, a step of drying the coating film or a step of washing the film before and after the rubbing treatment with a washing liquid may be mentioned. The drying step is the same as the calcination step described above, and a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like are generally known. These methods are equally applicable. The drying step is preferably carried out at a temperature within a range in which the solvent can evaporate, more preferably at a relatively low temperature with respect to the temperature in the calcining step. The liquid crystal alignment film before and after the alignment treatment is cleaned by a cleaning liquid, and examples of the washing method include H spray, steam cleaning, ultrasonic cleaning, and the like. These methods can be used alone or in combination. As the cleaning t 'can be used, pure water' or various alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic cigarettes such as benzene, toluene, and triterpenic benzene, and halogen-based solvents such as dichloropyrene, C:, A, A ketone such as ethyl hydrazine is not limited to these. Of course, these cleaning solutions use a cleaning fluid that is sufficiently purified with less impurities. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention. 63 201132704 *: The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a profilometer or an ellipsometer. The liquid crystal display device of the present invention comprises a pair of substrates, a liquid crystal layer formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment layer for aligning the liquid crystal molecules in a predetermined direction. The liquid crystal alignment film of the present invention can be used as the liquid crystal alignment film. The glass substrate can be used as the substrate, and the electrode can be a liquid crystal composition which is formed on the glass substrate exemplified in the description of the liquid crystal alignment film and which is negative in the electron bank double valley anisotropy. Kelly Kai-kai 57_114532, Japanese Patent Laid-Open 2-4725 ^, Japanese Patent No. 4_224885, No.: Bulletin, Sakamoto Patent Special Kaiping 8·:= This Patent Special Kaiping 10_16_No. Japanese Patent Publication No. 10-168453, a Tai Hun patent, special open patent, special open flat 1〇10436992, Fu I bulletin, 曰本 patent special open patent, special open flat 1〇2^4 利特开平Μ·3 bulletin Japanese Patent Publication No. 10-237000 ^ Bulletin, Japanese Patent Unexamined Patent Application Special Kaiping (4) ^ = 1〇·4 Bulletin, Japanese 10-237035 Bulletin, Japanese Patent Unexamined Patent Special Kaiping (4) tat ^ 平Μ3· Bulletin Japanese Patent Publication No. 64 201132704, Japanese newspaper, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. 10-287875, Japanese Patent Laid-Open Patent, Japanese Patent No. (4), No. 9 Gazette, Japanese Patent Special opening 2__2563〇7 bulletin The liquid crystal composition disclosed in the Japanese Patent Publication No. 2, the Japanese Patent Publication No. 2001-072626, and the Japanese Patent Publication No. 2001-072626, and the like. * "In the case of a liquid crystal display element of a film of a aligning film", it is also possible to use a liquid crystal composition having a positive dielectric anisotropy. == 公报 曰 曰 曰 曰 501 501 501 501 501 501 501 501735 Patent special open 8-157826 ^ newspaper, Japanese patent special Kaiping 8_23 simple number: 9 rhyme 644 bulletin (EP885272A1 ^ 幵 = · moving 346 bulletin (face secret (five) said 5: == (EP722998M manual), 曰本专唬Japanese Patent Application Laid-Open No. Hei 9-255956, Japanese Patent No. JP-A-96, No. 643 (Deleted from the 52nd Documentary Patent Publication No. 10, No. 16 (EP844229A1; Japanese Patent Laid-Open No. Hei No. 1204436, A liquid crystal composition disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A liquid crystal composition having a positive or negative dielectric anisotropy The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film of the present invention on at least one of a pair of substrates so that the liquid crystal alignment film passes inwardly. The spacers face the obtained pair of substrates, and the liquid crystal composition is sealed in a gap formed between the substrates to form a liquid helium layer. When the liquid crystal display element of the present invention is produced, a step of attaching a polarizing film or the like to the substrate may be further included as needed. The liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material can be applied to liquid crystal display elements of various display driving methods by appropriately selecting a polymer ' as a raw material thereof. The liquid crystal display element of the present invention may further have elements other than the constituent elements. In the liquid crystal shell member of the invention, a constituent element which is generally used in a liquid crystal display element such as a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, or a circuit breaker can be mounted. [Examples] μ Hereinafter, the present invention will be described by way of examples. (4) The use of the secret of the secret agent and the two ~ ~ 4 abbreviations - and not. In addition, in the example, the letter L is indicated by the letter L. Therefore, the milliliter is expressed in mL. <Acid anhydride: > Anhydride (H-1)

66 201132704 Anhydride (S-l) ο ο Anhydride (S-6)

Anhydride (S-48)

ο γΛ Ν Ο Μ; 〇 <diamine> Diamine (1-1) 67 201132704

Diamine (1-2)

Diamine (2-1-1)

Diamine (2-1-66)

Diamine (3-7-1) (Y5 = n-pentyl) 68 201132704 —^ W * Λ.

S Solvent> ΝΜΡ · Ν-mercapto-2-n-pyrrolidone BC. Butyl cellosolve (ethylene glycol monobutyl ether) [Synthesis Example 1] According to Japanese Patent Laid-Open Publication No. 20-62371, (Ι·1) Synthesis of (4-(3,5-diamino) phenol) Dinitrobenzyl phenol. 10 g of this compound was mixed with 5% palladium in 50% / (3,5-dimercaptodecylamine 1 mL), then at 403⁄4, 1 g was applied (hydrogen pressure was 680 kPa). After that, the temperature is cooled to the reverse, and the catalyst is removed by hydrazine, and then the solvent is removed under reduced pressure, and the cat is transferred to the target π ^ female β λ, and the yield is 7.5 g '(96%). 69 201132704

Melting point; 230.4 ° C - 233.8 ° C !HNMR; 9.15 (s, 1H), 6.98 (d, 2H, J = 8.35 Hz), 6.72 (d, 2H, J = 8.52 Hz), 5.66 (s, 3H), 4.63 (br s, 4H) [Synthesis Example 2] <Diamine (1-2) (3,5-di-t-butyl-4-phenylphenyl-3,5-diphenylbenzoate) Synthesis> To a 2 L three-necked flask equipped with a thermometer, a mixer, and a dropping funnel, 6.4 g (170 mmol) of a commercially available sodium borohydride was added, and then 500 mL of dehydrated tetrahydrofuran was added. The solution was cooled to 5 ° C or less, and a solution obtained by dissolving commercially available 2,6--second butyl benzene g 50 g (230 mmol) in 500 mL of dehydrotetrahydrofuran was added dropwise thereto. The reaction solution was warmed to room temperature and stirred at room temperature for 8 hours. After stirring, the obtained reaction solution was poured into 3 IV [1 L of hydrochloric acid, and extracted with ethyl acetate EtOAc. The organic layer was washed twice with 1 L of pure water, and dried over anhydrous magnesium sulfate. After removing anhydrous magnesium sulfate by filtration, the solvent was evaporated under reduced pressure to give 2,6-di-t-butyl hydroquinone (yield: 46 y, yield: 91%). Add a commercially available 3,5-dinitrobenzhydrazine gas 47 g (2〇4 mm〇1) to a three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, and then add two gas-fired 300. mL. The solution was cooled to 5. In the following, 2,6 di-tert-butyl hydroquinone 45 g (202 mmol) obtained by the previous method, and triethylamine 42 mL (3〇3 mm〇1) were dissolved in the mixture. A solution of two gas simmer in 200 mL. The temperature of the reaction mixture was raised to room temperature, and the mixture was stirred for 3 hours under a nitrogen atmosphere at room temperature. After Lin, the reaction solution was poured into 1 L of pure water, and extracted with 5 〇〇 mL of a gas. 201132704

^ I ^ IJi-M

The organic layer was washed twice with pure aqueous solution of ammonium sulfate and liquefied L. 1 L. The organic layer was washed with 9 % 1. 3,5-di-third-t-t--4-diphenyl_3,5_2 Indeed &gt; phenylhydrazine vinegar (yield 46 g, yield 55%). Add 3,5-mono-second butyl-4-carbophenyl-3,5-dishoxalylphthalate 45 g obtained by the previous method to a 1 L pressure-bearing dad reaction tube ( 108 mmol), Pd/C powder 4.5 g, then add 150 mL of toluene and 150 mL of ethanol. After reacting for 12 hours at a hydrogen pressure of 8 kgf/cm2 and room temperature, the pd/C powder was removed by filtration, and the solvent was evaporated under reduced pressure to give a crude crystal. The crude crystals were separated and purified by column chromatography (ethylbenzene: ethyl acetate = 1 : 1), and recrystallized from toluene to obtain 3,5-di-tert-butyl-4-hydroxyphenyl- 3,5-Diaminobenzoic acid ester (yield 31 g, yield 81%).

Melting point; 203.1 ° C - 206.5 ° C ^-NMR (ppm); 1.44 (18H, s, -CH3), 3.74 (4H, br*s, -NH2), 5.11 (1H, s, -OH), 6.24 ( 1H, m, arm-H), 6.92 (2H, m, arm.H), 7.26 (2H, m, arm.H).

[Synthesis Example 3] &lt;Synthesis of Poly-Proline 1&gt; Diamine (1-1) 2.55 g, diamine was added to a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet. (2-1-1) 0.591 g and dehydrated NMP 60.0 g 'In a dry nitrogen stream, enter 71 201132704 and stir to dissolve. Then, an acid anhydride (Η·1) i.30 g and an acid anhydride (s-1) 1.75 g were added, and the mixture was reacted at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction is carried out after the reaction temperature is suppressed to about 7 Torr or less. To the obtained solution, BC34.〇g was added to prepare a polyglycine solution (PA1) having a concentration of 6 wt%. The viscosity obtained was: PAi having a viscosity of 26 8 mpa·s. Further, the produced polyaminic acid had a weight average molecular weight of 55, 〇〇〇. Here, the weight average molecular weight of the polymer is determined by diluting the obtained polymer with a dilution ratio of (phosphoric acid/DMF = 0.6/100: weight ratio) to a polymer concentration of about 1 wt%. Then, the chromatographic data processor C-R7A (manufactured by Shimadzu Corporation) was used, and the diluted solution was used as a developing solvent and measured by a GPC method, followed by polystyrene conversion. In addition, the column was made of GF-7HQ (manufactured by Showa Denko KK) and the column temperature was 5 Torr. The measurement was carried out under conditions of a flow rate of 66 mL/min. [Synthesis Example 4 and Synthesis Example 5] &lt;Synthesis 2 of Polyproline and Synthesis of Polyamine 3&gt; In addition to changing the composition of the acid anhydride, the diamine, and the solvent to the ratio shown in Table 1, 1 to prepare a polyaminic acid solution (PA2, PA3). [Synthesis Example 6] &lt;Synthesis of poly-proline acid 4&gt; Diamine (3-7-1) was added to a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen gas introduction port. Two makeup (2-1-1) 2.14 g, and dehydrated NMP 60.0 g were stirred and dissolved under a stream of dry nitrogen. Next, an acid anhydride (H-1) 59.59 g and an acid anhydride (S-1) 72 201132704 2_11 g were added, and the mixture was reacted at room temperature for 30 hours. When the reaction temperature rises during the reaction, the reaction is carried out after the reaction temperature is suppressed to about 70 ° C or lower. To the obtained solution, 34.0 g of BC was added to prepare a polylysine solution (PA4) having a concentration of 6 wt0 / 。. The viscosity of the obtained PA1 was 23.6 mPa·s. Further, the produced polyaminic acid has a weight average molecular weight of about 36,000. This PA4 is used as a polymer solution for blending with PA1 to PA3. [Comparative Synthesis Example 1 and Comparative Synthesis Example 2] In addition to the change of the diamine as shown in Table 1, the preparation of the poly-bristine solution CA1 having a concentration of 6 wt% without using the diamine (I) was prepared according to Synthesis Example 3. Polylysine solution CA2. The weight average molecular weight of the raw material composition and the obtained polyamic acid, including Synthesis Example 3, is summarized in Table 1. &lt;Table 1&gt; Synthesis Example No. PA acid solution name Acid: Anhydride diamine Weight average molecular weight No. Molar fraction No. Molar fraction 3 PA1 (H-1) (S-1) 0.2 0.3 (2- 1-1) (1-1) 0.1 0.4 55,000 4 PA2 (H-1) (S-48) 0.2 0.3 (2-1-1) (Μ) 0.1 0.4 42,000 5 PA3 (H-1) (S-48 0.2 0.3 (2-1-1) (1-2) 0.1 0.4 43,000 6 PA4 (H-1) (S-1) oi 1 0.4 (3-7-1) (2-1-1) 0.1 0.4 36,000 Comparative Synthesis Example 1 CA1 (H-1) (S-1) 0.2 0.3 (2-1-1) 0.5 66,000 Comparative Synthesis Example 2 CA2 (H-1) (S-1) 0.2 0.3 (3-7-1) (2-1-1) 0.1 0.4 395 〇〇〇 (Note) PA acid refers to poly-proline. 73

201132704 A

[Example 1] A polyglycine solution (PA1) having a concentration of 6 wt% prepared in Synthesis Example 3 and a polyglycine solution (PA4) having a concentration of 6 wt% prepared in Synthesis Example 6 were weighed. Mix more than 2/8. The obtained mixture was diluted to 4 wt% with a mixed solvent of NMP/BC = 1/1 (weight ratio) to prepare a liquid crystal alignment agent. Using a liquid crystal alignment agent, a liquid crystal display element was produced as follows. The liquid crystal alignment agent AL1 was coated on a pair of substrates with IT transparent electrodes by spin coating, and dried on a hot plate at 80 ° C for 9 seconds. Next, the substrate was set to be burned for a minute to obtain a substrate on which a liquid crystal alignment film was formed. The surface on which the alignment film is formed is =: side =, and the epoxy resin is placed in the main entrance hole, and the curing agent is allowed to be cured. The liquid crystal cell C is obtained for 30 minutes. Finally at 110 liquid crystal display elements. [Life processing], obtain VA type &lt;liquid crystal composition A &gt; 201132704

5 wt% 7 wt% 8 wt% 8 wt% 14 wt% 14 wt% 10 wt% 10 wt% 12 wt% 12 wt% The obtained liquid crystal display element was passed through the following. Evaluation of pressure retention, residual DC, and pretilt angle. The results are shown in Table 2. &lt;Measurement of Voltage Retention Rate (VHR)&gt; The liquid crystal display element VHR was measured using a liquid crystal evaluation device 6254 manufactured by Toyo Corporation. The measurement conditions were a gate width of 60 pSec, a frequency of 3 Hz, a wave height of ±i v, and a measurement temperature of 60 ° C. 75 201132704

A

^ VJtlK π 朋 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光Evaluation of long-term optical reliability G-channels. The liquid crystal display element with the measured voltage holding ratio is placed on a U(4)5 ed/m2 cold cathode tube type backlight for liquid crystal displays, and the scale is measured again after 2 weeks. rate. The smaller the difference between the retention rate before the money is placed on the backlight and the retention rate determined after 2 weeks, the higher the long-term light reliability. &lt;Measurement of Residual DC by Dielectric Absorption Method&gt; The liquid crystal physical property evaluation device 6254 manufactured by Toyo Konica was used to measure the residual Dc by the dielectric absorption method. The measurement conditions were as follows: applying a direct current of 5 V to the liquid crystal cell for 1 hour, short-circuiting the leap seconds, and observing the potential difference for 3 minutes. The largest residual DC and the smallest residual DC are listed in the table. Further, the measurement temperature was 6 CTC. It can be said that the smaller the value, the better the electrical characteristics. 0 &lt;Measurement of pretilt angle&gt; The pretilt angle is the value of the sample rotation angle which becomes extremely small according to the transmittance after the sample rotation angle-transmittance curve is obtained under orthogonal polarization. And calculate. [Example 2, Example 3, and Comparative Example 1 to Comparative Example 3] Liquid crystal display elements were fabricated in the same manner as in Example 1 except that PA2, PA3, and CA1 were used instead of PA1, respectively, and characteristics were performed in the same manner as in Example 1. evaluation of. In addition, regarding the case of using CA2 instead of PA4 (Comparative Example 3), and the case of using CA1 instead of PA1, CA2 generation 76 201132704 for PA4 (Comparative Example 2), other conditions and real liquid crystal display elements, and examples (4) The party = and the price is made. The results of these are shown in Table 2. Evaluation of Ding Characteristics &lt;Table 2&gt; Example No. Liquid Crystal Alignment Agent_Voltage Retention Rate (%) ?i¥3cTvT~ (°) 1 2 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 PA1+PA4 ~ PA2 + PA4 PA3 + PA4 CA1 + PA4 CA1 + CA2 PA1 + CA2 -------J Maximum and minimum after illumination before irradiation 93.3 93.8 93.6 91.6 91.2 L_9L5_ 90.7 92.2 92.6 80.6 67.1 75.7 0.86 0.71 0.47 0.88 2.45 1.54 0.27 0.22 0.12 0.77 1.28 0.99 90 90 90 90 90 90 . According to these results, it can be seen that the lift can be obtained by using the diamine (1).

The electrical f retention rate and the effect of improving long-term light reliability. In addition, residual DC also passed significant inhibition. Further, according to the comparison between Example 1 and Example 2 and Example 3, it is understood that the effect of improving long-term light reliability is further improved by using a combination of the acid brittle diamine (I) having a tertiary amino group in the residue. [Synthesis Example 7 to Synthesis Example 11 and Comparative Synthesis Example 3 to Comparative Synthesis Example 7] A polyaminic acid solution (PA5 to PA9 and CA3 to CA7) was prepared according to Synthesis Example 3 except that the composition of the acid anhydride, the diamine, and the solvent was changed. ). The results will not be as shown in Table 3. 77 201132704 <Table 3> Synthesis Example No. PA acid solution name anhydride II f Weight average molecular weight No. Molar fraction No. Molar fraction 7 PA5 (H-1) (S-1) 0.25 0.25 (Μ) (2-1-66) (4-1-4-1) 0.20 0.20 0.10 33,000 8 PA6 (H-1) (S-1) 0.25 0.25 (1-2) (2-1-66) (4-1 -4-1 ) 0.20 0.20 0.10 38,000 9 PA7 (H-1) (S-48) 0.25 0.25 (Μ) (2-1-1) (4-1-4-1) 0.20 0.20 0.10 39,000 10 PA8 (H -1) (S-1) 0.25 0.25 (Ι-D (2-1-1) (4-1-4-1) 0.20 0.20 0.10 43,000 11 PA9 (H-1) (S-1) (S-48 0.05 0.40 0.05 (1-1) (2-1-66) (3-7-1) 0.10 0.30 0.10 43,000 Comparative Synthesis Example 3 CA3 (H-1) (S-1) 0.25 0.25 (2-1-1) ) (4-1-4-1 ) 0.40 0.10 62,000 Comparative Synthesis Example 4 CA4 (H-1) (S-1) 0.25 0.25 (2-1-1) (2-1-66) (4-1-4 -1 ) 0.20 0.20 0.10 42,000 Comparative Synthesis Example 5 CA5 (H-1) (S-48) 0.25 0.25 (2-1-1) (4-1-4-1) 0.40 0.10 41,000 Comparative Synthesis Example 6 CA6 (H -1) (S-1) (S-48) 0.05 0.40 0.05 (2-1-1) (2-1-66) (3-7-1) 0.10 0.30 0.10 47,000 Comparative Synthesis Example 7 CA7 (H-1 ) (S-1) (S-6) 0.05 0.40 0.05 (2-1-1) (3-7-1) 0.40 0.10 45,000 (Note) PA acid refers to polyamine [Example 4] 78 201132704: The polyphthalic acid solution PA5 shown in Table 3 was diluted to 4 wt% with a mixed solvent of NMP/BC (weight ratio i/i) to prepare a liquid crystal alignment agent. The liquid crystal alignment agent was applied onto two glass substrates with IT〇 electrodes to form a film having a film thickness of 70 nm. After the film was coated, it was dried at 80 ° C for about 5 minutes, and then dried at 220 ° C. The heat treatment was performed for a minute to form a liquid crystal alignment film. Using a friction treatment device manufactured by Iinuma-gauge Co., Ltd., the frictional amount of the rubbing cloth (hair length of 1.9 min: rayon) was 0.40 mm, the moving speed of the platform was 6 〇mm/sec, and the rotation speed of the roller was A glass substrate on which an alignment film was formed was subjected to a rubbing treatment at 1000 rpm. The other glass substrate was subjected to rubbing treatment in the same manner by changing the rubbing direction by 90° so as to be orthogonal to the rubbing direction of the glass substrate. These substrates were ultrasonically cleaned in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. A gap of 7 μm is spread on another glass substrate. The two substrates were placed facing each other with the surface on which the alignment film was formed and the rubbing direction was orthogonal to each other, and then sealed with an epoxy curing agent to form a 90-folded liquid crystal cell having a gap of 7 pm. To the liquid crystal cell, 1 part by weight of the liquid crystal composition described below was injected, and 5 parts by weight of cholesterol phthalate as an optically active substance was added to form a homogeneous composition, and then the injection port was sealed with a light hardener. . Subsequently, heat treatment was performed for 30 minutes at n 〇 ° c to prepare a TN liquid crystal display element. <Liquid crystal composition B &gt; 79 201132704 C2H5

C3h7

17 wt·% F c5H”

C2HK&gt;c2H4^&gt;^fC5Hi〇C2H4-〇^f 5 wt.°/〇 10 wt·^

With respect to the obtained TN-type liquid crystal display element, the voltage holding ratio, the residual DC using the flicker-free method, and the pretilt angle were evaluated by the following measurement methods. The results are shown in Table 4. &lt;tyt = Measurement of holding ratio (VHR)&gt; Using the liquid crystal physical property evaluation device 6254 manufactured by Tosoh Konica, the VHR of the liquid crystal display element was determined. The measured material is the width of the thumb. 201132704 Yes, the solution is 3 Hz, the wave height is ±1 v, and the measurement temperature is ah. &lt;Evaluation of long-term optical reliability of VHR&gt; The same type of liquid crystal display element as the VA type liquid crystal display element was also subjected to long-term optical reliability in the same manner as in Example 1. &lt;Measurement of residual DC by the flicker-free method&gt;

Using a ^(10) type function generator manufactured by Yokogawa Electric Co., Ltd., a TN type liquid (four) display element mounted on a polarized micromirror manufactured by Nikon X Co., Ltd., which is disposed at a density of 9 degrees, using a jig A rectangular wave of % Hz, 3 V is applied. After overlapping the DC voltage of 3 v for a few minutes in the rectangular wave, the overlap of the DC voltage is terminated, and then the photoelectron multiplication of the Photomes manufactured by the Photo 〇3〇62 oscilloscope manufactured by Agiknt TeChn〇logies Inc. The amount of transmitted light of the g piece. The offset voltage of the function generation H is adjusted such that the variation of the waveform indicating the change in the amount of light displayed by the oscilloscope is minimized, and the offset voltage is recorded as the flicker erase voltage. The largest residual DC and the smallest residual DC are listed in the table. (4) The smaller the value, the better the electrical characteristics. &lt;Measurement of Pretilt Angle&gt; The pretilt angle of the TN liquid crystal display element was measured by a liquid crystal characteristic evaluation apparatus OMS-CA3 type manufactured by a central precision machine. [Example 5 to Example 7 and Comparative Example 4 to Comparative Example 6] Polyacrylic acid solution PA6 to polyaminic acid solution pA8 and polyamine 81 201132704 ^ ^ Λ ^ Acid solution CA3 to polyamic acid solution CA5 A liquid crystal display element was prepared and evaluated in the same manner as in Example 4 for each polyamine acid solution. The results are shown in Table 4. 82 201132704 ^ / -j <Table 4> Example No. 4 5 6 7 PA acid solution name PA5 PA6 PA7 PA8 Voltage keeps light before irradiation (%) Residual D after light irradiation (table large: (V) minimum pretilt angle (.) 97.5 97.8 97.1 97.6 94.9 95.3 94.2 93.7 0.56 0.61 0.48 0.55 0.18 0.11 0.07 0 13 12.4 11.7 12.1 10 1 Comparative Example 4 Comparative Example 5 Comparative Example 6 CA3 CA4 CA5 96.6 97.0 97.5 80.5 86.4 91.7 0.93 1.07 1.21 0.52 0.56 0.32 9.2 8.6 9.5 (&gt; ij Pa acid refers to poly-proline. According to the data in Table 4, 'long-term light reliability by using polyamines obtained by using diamine (I) is improved. Moreover, for residual DC ^ Shows a remarkable effect. The pretilt angle is suitable for the value of the tn plastic liquid crystal display element, and is also suitable for the 〇CB type liquid crystal display element. Further, the voltage holding ratio after the light irradiation of the actual example 6 is compared with the example 7 The ratio of ^ = clearly can be seen in the county 'Example 4 ~ Example 6 shows a better value. Is the skeleton of the ruthenium has a secondary amino group, a tertiary amino group or a diamine or a combination of acid and diamine (1) Long-term light can be [Example 8 and Comparative Example 7 Comparative Example 8] A PA-type liquid crystal display element was produced by using PA9, CA6, and CA7 described in Table 3 in the same manner as in the above, and the results were shown in Table 5. 83 201132704 Table 5 &gt; Pretilt angle (.) pap Γ~^γ CA6 92.2 CA7 ' 90.5

Vo1 1ΡΑ^Ττ^^(〇/ο) I ^cjvj Comparative Example 7 Comparative Example 8 (Note) Capric acid refers to poly-proline. According to the data in Table 5, the condition of the TN-type liquid crystal display device is described. Similarly, when it is a VA type liquid crystal display element and a pA acid solution is used alone, by using the diamine (1), a remarkable effect associated with improving long-term light reliability and suppressing residual DC can be obtained. The liquid crystal alignment agent of the present invention can be used for the formation of a liquid crystal alignment film of liquid display which is various display driving methods. Moreover, the liquid crystal that is not driven is obviously rich, and the residual DC is suppressed. The same is true. [Industrial Applicability] According to the present invention, it is possible to provide a liquid crystal display element which is low in reciprocity and excellent in voltage holding light. Although the present invention has been disclosed above by way of example, the present invention is not intended to limit the spirit and scope of the present invention, and may be modified.

In the case of Si, please attach the scope of the patent to the original one. [Main component symbol description] 84

Claims (1)

201132704 j/jyjun VII. Patent application scope: 1. A liquid crystal alignment agent containing a diamine represented by the formula (I) or a mixture of the diamine and another diamine and a tetracarboxylic dianhydride obtained. Polylysine or its derivatives: Here, A1 is a single bond, -0-, -COO-, -CO-, -CONH- or an alkylene group having 1 to 6 carbon atoms; and R is independently hydrogen or an alkyl group having 1 to 6 carbon atoms. 2. The liquid crystal alignment agent according to claim 1, wherein A1 is -COO- or an alkylene group having 1 to 3 carbon atoms, and R is hydrogen or an alkyl group having 1 to 4 carbon atoms. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the other diamine is selected from the group consisting of formula (1-1) to formula (1-3), formula (2-1), At least one diamine in the group of diamines represented by formula (2-2), formula (3), formula (4-1), and formula (4-2): 85 201132704 ▲ L H2N''O^〇 -NH2 hn^^n4ch2)^〇-nh2 (1-1) (1-2) (1-3) Here, in the formula (1-1), a is 0 or 1; the ring A is 1,4· Any hydrogen of cyclohexylene, 1,3-phenylene, 1,4-phenylene or 1,2,4-trisyl-3,5-diyl; cyclohexylene and phenylene can be Substituted with mercapto, diethylamino or divinylamino; W1 in formula (1-2) is -CH2- or -NH-; b in formula (1-3) is an integer from 0 to 2: Here, X1 is a single bond or an alkylene group having a carbon number of 1 to 1 Å; any -CH2- of the alkylene group may be _〇_, _S_, _NH_, _N(CH3)_, _c(CH3)2 -, -C(CF3)2-, -CO-, -S02-, -CH=CH-, -CeC-, -N=N-, 1,3_phenylene, 1,4-phenylene or anthracene Any of the hydrogens of the benzene ring may be substituted by fluorine, fluorenyl, methoxy, -CF3 or -OCF3: 86 201132704: h2n (2-2) Here, Y1 is an alkyl group having 3 to 30 carbon atoms; any -CH2- of the alkyl group may be substituted by -〇-, -CH=CH- or 1,4-cyclohexylene; Y2 For hydrogen or Y1 : R1 In the formula (3), X2 is a single bond, -〇_, -COO-, -OCO-, -CONH- or a calcined group having a carbon number of 1 to 6; and R1 is a calcined group having a carbon number of 3 to 30, and a cholesteryl group. Or a group represented by the formula (a); in the formula (a), 'X3 and X4 are independently a single bond or an alkylene group having 1 to 4 carbon atoms; and ring B and ring C are independently a 1,4-phenylene group. Or 1,4-cyclohexylene; R2 and R3 are independently fluoro or methyl, f and g are independently 〇, 1 or 2; c, d and e are independently 0 or 1, and their total is 1 to 3; R4 It is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, and these alkyl groups, alkoxy groups, Alkoxyalkyl and alkenyl, 87 201132704 - --IT - Any hydrogen can be replaced by fluorine: H2N (4-1) Here, X5 is independently -Ο- or an alkylene group having 1 to 6 carbon atoms; j is 0 or 1; R5 is an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms. Alkoxyalkyl group having 2 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms; ring T is 1,4-phenylene or 1,4-cyclohexylene; X6 is a single bond or a carbon number 1 to 3 alkylene; h is 0 or 1; R6 R7 (4-2) Here, X5 is independently -0- or an alkylene group having 1 to 6 carbon atoms; j is 0 or 1; R6 is hydrogen, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 1 to 30; An alkoxy group, an alkoxyalkyl group having 2 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R7 is an alkyl group having a carbon number of 6 to 30 or a cholesteryl group. 4. The liquid crystal alignment agent according to claim 3, wherein the 88 201132704 / ^ γ / kL amine is at least 5 selected from the group consisting of diamines represented by formula (3). The liquid crystal alignment agent according to Item 3, wherein the other diamine is represented by the formula (3-1) to the formula (3-7), the formula (3-21) to the formula (3-25), and the formula (3). -34) and at least one of the diamines represented by formula (3_35): Y5 89 201132704 χ L Here, Y4 is an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms; Y5 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. 6. The liquid crystal alignment agent according to claim 3, wherein the other diamine is at least one diamine selected from the group consisting of diamines represented by formula (4-1). 7. The liquid crystal alignment agent according to claim 3, wherein the other diamine is at least one of the diamines represented by the formula (4-1-1) to the formula (4-1-8): 201132704 91 201132704 Here, Y6 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 1 carbon atoms. 8. The liquid crystal alignment agent according to claim 3, wherein the other diamine is a group selected from the group consisting of diamines represented by formula (1_1) to formula (丨_3) and formula (2-1) At least one diamine in the population. 9. The liquid crystal alignment agent according to claim 3, wherein the other diamine is of the formula (1-1-3), the formula (1-1-5), the formula (Μ·8), (1-1-9), Formula (1-1-12)~Formula (1-1-14), Formula (1-2-2), Formula (1-3-1), Formula (1-3- 2), formula (2-1-1), formula (2-1-7), formula (2-1-10), formula (2-1-13), formula (2-1-27), formula ( 2-1-28), formula (2-1-32)~form (2-1-35), formula (2-1-54)~form (2·ΐ_56), and formula (2_1·66)~ 2-1-68) At least one of the diamines represented: 92 201132704 (1-1-8) (1-1-9) 93 201132704 (2,1·32) (2-1-34) N- (2-1-33) (2-1-35) P-1-54) CH2)3 (2-1-55) H3c •(ch2)6. H2N~X3_hCN_0^NH2 h2n N (2-1-56) pH3 (2-1-67) (2) The liquid crystal alignment agent according to claim 9, wherein the other diamine is of the formula (1-1-8), the formula (1-1-9), (1-1-12), formula (US), formula (i-3-l), formula (1-3-2), formula (2-1-32), formula (2-1-33), and At least one of the diamines represented by the formula (2-1-66) to the formula (2-1-68), or a mixture containing the diamines. The liquid crystal alignment agent according to any one of the items of the present invention, wherein the four-dimensional dianhydride is at least one of the group of the four-dimensional dianhydride 94 201132704 -~ r. In the liquid 曰t rt patent, the =: agent according to any one of the items 1 to 10, wherein the dihydrogen liver is at least one of aromatic tetracarboxylic dianhydride. The liquid 曰 aligning agent according to any one of the items 1 to 10, wherein the aromatic tetraphthalic dianhydride of the tetrazine bismuth is the same as the above. a mixture of at least one of four tetrahydro acid dianhydrides other than the aromatic tetracarboxylic acid dianhydride. The liquid crystal alignment agent according to claim 13, wherein the aromatic tetracarboxylic dianhydride is of the formula (Η-1), the formula (Η-5), and the formula (Η-8)~ a compound represented by the formula (Η-10), formula (Η_15), formula (Η_19), formula (Η_2〇), and formula (Η-21), tetradecanoic acid dianhydride other than the aromatic tetracarboxylic dianhydride It is of the formula (S-1), the formula (S-6), the formula (S-9) to the formula (S-11), the formula (S-21), the formula (S-22), and the formula (S-30). Compounds of the formula (S-43), formula (S-44), formula (S-45), formula (S-48) and formula (S-53): 95 201132704 Ο Ο ο ο η Ο Ο ο (Η-10) Ο ο ο .0 η (Η-20) 96 201132704 (S-1) (S-6) (S-9) (S-10) The liquid crystal alignment agent according to claim 14, wherein the sulphate tetrahydro acid is a compound represented by the formula (沁丨), the aromatic The tetracarboxylic dianhydride other than the tetracarboxylic dianhydride is a compound represented by the formula (^). 16. The liquid crystal alignment agent according to claim 14, wherein the aromatic read acid is a tetracarboxylic acid other than the aromatic tetracarboxylic dianhydride represented by the formula (5). The compound represented. The liquid crystal alignment agent of any one of Claims 1 to 16 which further contains the polyfluorene obtained by not using the diamine represented by Formula (I). An acid or a derivative thereof. 18. A liquid crystal alignment film which is obtained by coating a liquid crystal alignment agent according to any one of claims 1 to 17 on a substrate and coating the obtained coating film. A liquid crystal display element having the liquid crystal alignment film according to claim 18 of the patent application. 20. A diamine compound which is a compound represented by the formula (1-2): (1-2) 〇 98 201132704 t ^ ^ Λ.Λ. IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Age dropout: 201132704 37593pitl is the 100105827 Chinese manual without line correction page h2n (2-2) Here, Y1 is an alkyl group having 3 to 30 carbon atoms; any of the alkyl groups may be substituted by -〇-, -CH=CH- or 1,4-cyclohexylene; γ2 For hydrogen or γι : R1 In the formula (3), 'X2 is a single bond, _C00_, _〇c〇_, c〇NH or an alkylene group having 1 to 6 carbon atoms; and R1 is an alkyl group having a carbon number of 3 to 3 Å, a cholesteryl group, or a group represented by the formula (a); wherein 'X3 and X4 are independently a single bond or an alkylene group having 1 to 4 carbon atoms; and ring B and ring C are independently a 1,4-phenylene group or an anthracene. - cyclohexylene; R2 and R3 are independently fluorine or methyl, f and g are independently 0, 142; c, d and e are independently 0 or 1, and the total of c, d and e is 丨~3; R4 is carbon A number of alkyl groups, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 2 to 3 carbon atoms, or 11 201132704 j/Dyjpm is the Chinese version of the specification No. 100105827. : Alkenyl groups of 2 to 30 on March 16, 100, in which any of the alkyl, alkoxy, alkoxyalkyl and alkenyl groups may be substituted by fluorine: Here, X5 is independently -〇- or an alkylene group having 1 to 6 carbon atoms; j is hydrazine or j; R5 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and carbon number 2 a calcined oxyalkyl group of ～30 or an alkenyl group having 2 to 30 carbon atoms; the ring τ is a 丨4_phenylene group or a 1,4-cyclohexylene group; and X6 is a single bond or a carbon atom group of a carbon number W3; h is Here, X5 is independently -0- or an alkylene group having 1 to 6 carbon atoms; j is hydrazine or a work; R is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, carbon a 2 to 3 〇 alkoxyalkyl group, or a carbon number 2 to 30 alkenyl group; rv is a carbon number 6 12 〇〇201132704 37593pitl is the 100105827 Chinese manual no scribe correction page 〇ch3 H3cq \l Date of revision: March 16, 100 H2n NH 2 h2n (2-1-70) (2-1-72) PCF3 nh2 F3cq h2n H2n N 〇cf3 F3cq N Factory (2-1-74) NH '2 (2-1-76) Among the diamines (2-1-1) to diamines (2-1 to 76), diamines (2-1-1) and diamines (2-1) are more preferable. -7), diamine (2-1-10), diamine (2-1-13), diamine (2-1-27), diamine (2-1-28), diamine (2-1 -32)~Diamine (2-1-35), diamine (2-1-54)~diamine (2-1-56) and diamine (2-1-66)~diamine (2-1 -68). 33 201132704 D / jyjpill No Chinese version of the 100105827 no-line correction page Date of revision: March 16th, 1st Here, Y1 is an alkyl group having 3 to 30 carbon atoms, preferably an alkyl group having 3 to 20 carbon atoms, more preferably an alkyl group having 3 to 10 carbon atoms. Further, any -CH2- of these alkyl groups may be substituted by -0, -CH=CH- or 1,4-cyclohexylene. Y2 is 氲 or Y1. 1 Hereinafter, a preferred example of the diamine (2-2) is shown. (2-2-1) (2-2-3) 34 201132704 .5 /DVjpill No. 100105827 Chinese manual without scribe correction page Revision date: March 16, 100 曱 oxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3_Chloropropyl-decyldimethoxy decane, 3-apropylpropyltrimethoxy decane, 3-methylpropenyloxypropyltrimethoxy decane, 3-mercaptopropyltridecyloxy Terpine, N-CU-methylbutene)_3_(triethoxydecylpropylamine, and N,N'-bis[3-(tridecyloxymethyl)propyl]ethylenediamine. When the oxime coupling agent is used, it is preferably added in an amount of from 0.001 to 0.05 by weight based on the total weight of the polyaminic acid. Specific examples of the ruthenium imidization catalyst include aliphatic amines such as tridecylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N_:ethylaniline, and methyl group. Aromatic amines such as aniline and hydroxy-substituted aniline; acridine, methyl-substituted pyridyl, hydroxy-substituted octapeptide, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline a cyclic amine such as a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole, or a hydroxy-substituted imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, and between! One or more of aniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxyacridine and isoquinoline. When stimulating ^1, the amount of the _ added is relative to the poly-acid _ group of § 〜 0.5 0.5, preferably 〇 · 〇 5 equivalents - equivalent. The liquid crystal alignment agent of the present invention contains a solvent. The solvent can be suitably (10) sprayed from the preparation step of the polyaminic acid or the lining. The solvent species can also be used as a mixed solvent of two or more. The solvent is roughly a solvating agent for poly-proline and a straight solution for improving the applicability. J 0 octa-solvent is non-special (4) m. Its frequency: N-A 57 201132704 Revision date: March of the next year On the 16th, the Chinese manual No. 1001〇5827 has no underline correction. Page-2-pyrrolidone, dimethylimidazoline, N_f-caprolactam, n-methylpropionamide, N,N-dimethyl Indoleamine, dimethyl sulfoxide, N,N-dimethyl octaamine, hydrazine, hydrazine-diethylformamide, diethyl acetamide, and γ-butane are intended. Other solvents for the purpose of improving coatability and the like can be exemplified by alkyl hydrazine lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol single-burning test, and one ethylene Alcohol monobutyl group, ethylene glycol monophenyl bond, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoalkyl ether, dialkyl malonate, dipropylene glycol monoalkyl ether, and An ester compound such as an acetate of these compounds. Among these solvents, fluorenyl-indenyl-2-pyrrolidone, dinonyl imidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and propylene glycol are particularly preferable. Methyl ether, and dipropylene glycol monomethyl ether. The liquid crystal alignment agent of the present invention is supplied in a form of a solution obtained by dissolving a polymer component containing the above polylysine in a solvent. The preferred concentration of the polymer component at this time is 〇1 wt% (% by weight) to 40 wt%. When the liquid crystal alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the contained polymer component with a solvent in advance. In this case, the concentration of the polymer component is preferably 40% by weight or less from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to be suitable for easily mixing the solvent in the liquid crystal alignment agent. The concentration of the polymer component in the liquid crystal alignment agent is sometimes adjusted according to the coating method of the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain the film thickness favorably, it is usually 58 201132704. Correction date: March 16, 100 is the 100105827 Chinese manual without a scribe correction page. Diamine (4-1-4-1) (Υ6=n-pentyl) &lt;Solvent&gt; NMP : Ν-methyl-2-pyrrolidone BC : butyl cellosolve (ethylene glycol monobutyl ether) [Synthesis Example 1] &lt;Diamine (1_1) (4, (3,5-diamine) The synthesis of the silk base) is as follows: According to Japanese Patent Laid-Open No. Hei 20-62371, the human dinitron's base is benzene. 10 g of the compound was mixed with 5% of the free-acting, monodecylamine 100 mL, and then it was poured into a sputum (hydrogen pressure of 680 kPa). After the reaction, the temperature was cooled to a chamber, and the catalyst was removed by filtration, and then the solvent was evaporated under reduced pressure to give the object (yield: 7. 5 g, yield: 96%). , 69 201132704 3 oyjpill is the Chinese version of the 100105827 no-line correction page correction period: 100 years of March 16 melting point; 230.4 ° C-233.8 ° C ^ NMR; 9.15 (s, 1H), 6.98 (d, 2H , J-8.35Hz), 6.72 (d, 2H, J= 8.52Hz), 5.66 (s, 3H), 4.63 (br s, 4H) [Synthesis Example 2] <Diamine (1-2) (3,5 Synthesis of -di-tert-butyl-4-ylhydroxyphenyl-3,5-diaminobenzoate)&gt; A commercially available 2 L three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel was added. Side hydrogenated sodium 6.4 g (170 mmol), then 500 mL of dehydrated tetrahydrofuran was added. The solution was cooled to 5. (: In the following, a solution obtained by dissolving 2,6-mono-second butylbenzene (50 g (230 mmol) dissolved in dehydrated tetrahydrocetic bite 500 mL) was added dropwise thereto. Stir at room temperature for 8 hours at room temperature. After stirring, the obtained reaction solution was poured into 1 liter of 3 L hydrochloric acid and extracted with 1 l of ethyl acetate. The organic layer was washed with 1 L of pure water. After 2 times, anhydrous magnesium sulfate was added for drying. After removing anhydrous sulphuric acid and removing the hydrazine, the solvent was removed from the decompression chamber to obtain 2,6_--second butyl-p-benzene test (yield 46 g, yield 91) Add a commercially available 3,5-dinitrophenylhydrazine chloride 47 § (2〇4111111〇1) to a three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, and then add dichloromethane. 300 mL. The solution was cooled to 5×^, and 2,6-di-t-butylhydroquinone 45 g (202 mmol) obtained by the previous method, and triethylamine 42 mL were added dropwise thereto. (3〇3 mm〇1) Dissolve the solution of dichlorohydrazine in 200 mL. The reaction solution is warmed to room temperature and then stirred for 3 hours in a nitrogen rolling environment at room temperature. The reaction solution was poured into pure water i L and extracted with 5 〇〇 mL of dichloromethane. 70 201132704 Revision of the 〇 〇 March 16th is No. 100105827 Chinese manual no scribe correction page VII. Patent application scope A liquid crystal aligning agent containing a polyamine or a derivative thereof obtained by reacting a diamine represented by the formula (I) or a mixture of the diamine and another diamine with a tetracarboxylic dianhydride : Here, A1 is a single bond, -Ο-, -COO-, -CO-, -CONH- or an alkylene group having 1 to 6 carbon atoms; and R is independently an anthracene or an alkyl group having 1 to 6 carbon atoms. 2. The liquid crystal alignment agent according to claim 1, wherein A1 is -COO- or an alkylene group having 1 to 3 carbon atoms, and R is hydrogen or an alkyl group having 1 to 4 carbon atoms. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the other diamine is selected from the group consisting of formula (1-1) to formula 0-3), formula (2-1), At least one diamine in the group of diamines represented by formula (2-2), formula (3), formula (4-1), and formula (4-2): 85 201132704 ό /Dyjpm is 1001〇5827 No. Chinese manual no line correction page H2N—^ ^—CH2-^~~^A^-NH2 H2N^0~0&quot;NH2 H n4^N4CH seven O',2 Revision date: March 16th, 100 (1) -1) 1-3) In the formula (M), a is 0 or 1; ring A is 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene or 1 , 2,4-tris-3,5-diyl; any hydrogen of the cyclohexylene group and the phenylene group may be substituted by a mercapto group, a diethylamino group or a divinylamino group; in the formula (1-2) W1 is -CH2- or -NH-; b in the formula (1-3) is an integer of 0 to 2: Here, 'X1 is a single bond or a calcined group having a carbon number of 1 to 1 Å; any _CH2- of the alkylene group may be -Ο-, -S-, -NH-, -N(CH3)-, -C(CH3)2-, -C(CF3)2-, -CO-, _s〇2_, -CH=CH-, -CeC-, -N=N-, 1,3-phenylene, 1, 4-phenylene or anthracene _i,4_diyl substituted; any hydrogen of the benzene ring may be substituted by fluorine, methyl, decyloxy, _CF3 or _〇匚卩3: 86 201132704 i/iyjpitl No. 100105827 Chinese manual without line correction page Amendment date: March 16, 1 (2-2) Here, Y1 is an alkyl group having a carbon number of 3 to 30; any _〇112_ of the alkyl group may be -0-, -CH=CH- Or 1,4-cyclohexylene substituted; γ2 is hydrogen or γΐ : R1 In the formula (3), 'X2 is a single bond, 〇_, _c〇〇_, _〇c〇-, -CONH- or an alkylene group having 1 to 6 carbon atoms; and Ri is an alkyl group having 3 to 3 carbon atoms. a cholesteryl group or a group represented by the formula (a); wherein, in the formula (a), X and X are independently a single bond or a carbon atom having 1 to 4 carbon atoms; and ring B and ring C are independently a 14-phenylene group; Or 1&gt;4_cyclohexylene; anti-2 and γ are independently fluorine or methyl, f and g are independently 〇, 1 or 2; c, d&amp;e is independently 〇 or 1, c, d and e total R 3 is an alkyl group having a carbon number, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having a carbon number of 2 to 3 Å, or a diluted group having 2 to 30 carbon atoms. , alkoxy, alkoxyalkyl and alkene 87 201132704 ^ /Dy^piii is the Chinese version of the 100105827 no-line correction page. Amendment date: March 16th, 1st, any hydrogen can be fluorine Replaced by: R5 Here, X5 is independently -0- or an alkylene group having 1 to 6 carbon atoms; j is 0 or 1; R5 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and carbon number 2 Alkoxyalkyl group of -30 or an alkenyl group having 2 to 30 carbon atoms; ring T is 1,4-phenylene or 1,4-cyclohexylene; X6 is a single bond or a carbon number of 1 to 3 Alkyl; h is 0 or 1; h2n (4-2) Here, X5 is independently -Ο- or an alkylene group having 1 to 6 carbon atoms; j is 0 or 1; R6 is an anthracene, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 1 to 30; An alkoxy group, an alkoxyalkyl group having 2 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms; and R7 is an alkyl group having a carbon number of 6 to 30 or a cholesteryl group. 4. The liquid crystal alignment agent according to Item 3 of the patent application, wherein 88 201132704 37593pitl is the Chinese specification of No. 100105827. There is no scribe correction page. Date of revision: March 16th, 1st, the other diamine is selected from At least one diamine in the group of diamines represented by the formula (3). 5. The liquid crystal alignment agent according to claim 3, wherein the other diamine is from the formula (3-1) to the formula (3-7), and the formula (3-21) to the formula (3-25) At least one of the diamines represented by the formula (3-34) and the formula (3-35): 〇 89 201132704 j /Dy^pni is the Chinese manual of No. 100105827. There is no scribe correction page. Revision date: March 16, 100. Here, Y4 is an alkyl group having a carbon number of 2 to 10 and an alkoxy group having a carbon number of 2 to 10. An alkoxyalkyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms; Y5 being an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number of 2 to 10; An alkoxyalkyl group or an alkenyl group having 2 to 10 carbon atoms. 6. The liquid crystal alignment agent according to claim 3, wherein the other diamine is at least one diamine selected from the group consisting of diamines represented by formula (4-1). 7. The liquid crystal alignment agent according to claim 3, wherein the other diamine is at least one of diamines represented by formula (4-1-1) to formula (4-1-8). : 90 201132704 For the Chinese manual No. 100105827, there is no scribe correction page. Revision date: March 16th, 1st 91 201132704 J / 丄 is 100105827 Chinese manual without scribe correction page Revision date: March 16, 100, here, Y6 is an alkyl group with a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, carbon An alkoxyalkyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. 8. The liquid crystal alignment agent according to claim 3, wherein the other diamine is selected from the group consisting of diamines represented by formula (1-1) to formula (1-3) and formula (2-1) At least one diamine in the group. 9. The liquid crystal alignment agent according to claim 3, wherein the other diamine is of the formula (1-1-3), the formula (1-1-5), and the formula (1-1-8). , formula (1-1-9), formula (ι_Μ2)~form (M_14), formula (uj), formula (1_31), ^ U3'2)'2-1-1)χ^( 2-1-7 )&gt;^( 2-1-10 )'Λ( 2-1-13 )&gt; $ (2-1-27), (2-1_28), (2 small 32)~ (2 small 35 ), 2^2; 1'54)~ (2-1-56) and (2-1-66) to (2-1-68) at least one of the diamines: 92 201132704 Revision date :1 March 16th is the 100105827 Chinese manual without a line correction page〇❹ H2N—&lt;\ /)—nh9 (1-1-3) Η Η2Ν^/Ν\-ΝΗ; N-N (1-1-8) (1-1-13) (1-1-12) (1-1-9) nh2 h2n (1-1-14) (1-3-1) (1-2-2) (2-1-27) (2-1-28) 93 201132704 ^/ ο^όριτι is the 100105827 Chinese manual without line correction page (2-1-32) Revision date: March 16th, 1st year η2ν CH, (2-1-34) H3d H2 (2-1-33) (2-1-35) (2-1-54) , (CH2)3 (2-1-55) H2N- H3CO h3c h2n CHo (2-1-67) h2n (2-1-68) (2-1-66) The liquid crystal alignment agent of claim 9, wherein the other diamine is of the formula (1-1-8). ), Formula (1_1_9), Formula (ι_ι_ΐ2), Formula (1-2-2), Formula (1-3-1), Formula (1_3-2), Formula (2-1-32), Formula (2- 1-33), and at least one of the diamines represented by the formula (2 small 66) to the formula (2 small 68), or a mixture containing the diamines. 11. For the scope of patent application No. 1 to the liquid crystal alignment agent, the towel of the tetracarboxylic acid is described in the above, and the tetragonal dianhydride of the sulphuric acid is described as 94 201132704 •3 /jyjpul Revision date: 1GG year March 16 is at least one of the Chinese version of the No. l〇_5827 without a scribe correction page. The liquid crystal alignment agent of the first to the first aspect of the invention, wherein the outer tetracarboxylic dianhydride of the above-mentioned y is at least the sulphuric tetracarboxylic acid The anhydride of the tetracarboxylic dianhydride described in the eighth is the aromatic tetracarboxylic acid - a mixture of at least one of tetracarboxylic dianhydrides other than the aromatic tetracarboxylic dianhydride. The liquid crystal alignment agent according to claim 13, wherein the aromatic tetracarboxylic dianhydride is of the formula (Η), the formula (H_5), and the formula (H_8) to (H-10). a compound represented by the formula (H-15), the formula (H-19), the formula (H-20), and the formula (H-21), wherein the tetracarboxylic dianhydride other than the aromatic tetra-retensive dianhydride is From the formula (S-1), the formula (S-6), the formula (S-9) to the formula (S-11), the formula (S-21), the formula (S-22), the formula (S-30), a compound represented by the formula (S-43), the formula (S-44), the formula (S-45), the formula (S-48) and the formula (S-53): 95 201132704 Revision date: March 16th, 1st year J /^yjpui is the 100105827 Chinese manual without line correction page Ο Ο 0 0 0 η Ο Ο 〇 Π 〇 〇 〇 96 201132704 〇 /J^jpnl For the Chinese manual No. 100105827, there is no scribe correction page. (S-11) (S-21) Revision date: March 16, 100 (S-10) Ο 0 (S-43) (S-30) The liquid crystal alignment agent according to Item 14, wherein the aromatic tetra-dianhydride is a compound represented by the formula (5)), and the tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride It is a compound represented by the formula (H). The liquid crystal alignment agent according to claim 14, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula, and the tetracarboxylic dianhydride other than the aromatic tetrazoic acid dianhydride It is a compound represented by the formula (s_48). 97 201132704 The revised period: March 16, 100 is the 100105827 Chinese manual without a scribe line correction. The liquid crystal alignment agent according to any one of the above claims. Further, it further contains polyamic acid or a derivative thereof obtained without using the diamine represented by the formula (1). 18. A liquid crystal alignment film which is applied to a substrate by applying the liquid crystal alignment agent according to any one of claims 1 to 17 and heating the obtained coating film to form 1 ° 19 - a liquid forest member having the liquid crystal alignment 嫉°, 2〇, a diamine compound as described in claim 18, which is a compound represented by the formula (1_2): 98