TW200944553A - Liquid-crystal alignment material and liquid-crystal display element - Google Patents

Abstract

A liquid-crystal alignment material is provided which can diminish the liquid-crystal orientation unevenness which occurs in the ODF mode. Also provided is a liquid-crystal display element reduced in display unevenness attributable to the liquid-crystal orientation unevenness occurring in the ODF mode. The liquid-crystal alignment material comprises a polymer obtained by reacting a tetracarboxylic dianhydride ingredient comprising a tetracarboxylic dianhydride represented by the following formula [1] with a diamine ingredient comprising a diamine compound having a carboxy or hydroxy group in the molecule. (Chemical formula 1) [1] (In the formula [1], Y1 is a C4-15 tetravalent organic group and contains a C4-8 nonaromatic cyclic hydrocarbon group.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid used in the production of a liquid crystal alignment film and a liquid crystal display element using the same. [Prior Art] As a liquid crystal display element, there are two electrode substrates in which an Φ alignment film is formed on an electrode, and a long axis of a positive dielectric nematic liquid crystal is directed from one substrate to the other. A so-called twisted nematic (TN) type liquid crystal display element which is twisted by 90°. The substrate on one side forms a comb-tooth shape of the electrode, and drives a planar conversion (IPS) element of the liquid crystal by causing an electric field to generate a lateral direction of the substrate surface. Further, in addition to these, a vertical liquid crystal display element in which a nematic liquid crystal having a negative dielectric is aligned perpendicularly to the substrate surface has been developed. The liquid β ′ used in the liquid crystal display elements is mainly a polyimine-based liquid crystal alignment film, and various polyimide-based alignment films have been developed (for example, refer to Patent Document 1). The liquid crystal display element must be fabricated between the two sheets of the substrate on which the liquid is formed (cell gap), and the step of filling the liquid crystal. The liquid crystal charging system utilizes the pressure difference between the atmospheric pressure and the vacuum to fill the liquid crystal between the boards. Vacuum injection is a common practice. However, since the liquid crystal injection port is provided only on one side of the substrate, in order to charge the liquid crystal between the substrates of 3 to 5 μm, it is difficult to simplify the manufacturing steps of the liquid crystal display element. In this case, the special alignment agent is formed into a continuous layer of liquid crystal to the opposite polarity, or a crystal alignment film having a structure of an isotropic (VA) type alignment film with respect to the liquid crystal. At present, it is a cell gap time in the case of two films, so it is a problem in the manufacture of liquid crystal TVs or large monitors which have been put into practical use in recent years. Therefore, in order to solve the above problems in the vacuum injection method, a liquid crystal dropping method (ODF method) has been developed. In this method, liquid crystal is dropped on a substrate on which a liquid crystal alignment film is formed, and is bonded to another substrate in a vacuum. Thereafter, the sealing material is UV-cured to fill the liquid crystal. On the other hand, as the high definition of the liquid crystal display element is deepened, it becomes necessary to suppress display unevenness. The liquid crystal dropping method can be solved by optimizing the manufacturing steps such as reducing the amount of dripping of the liquid crystal or increasing the degree of vacuum at the time of bonding to reduce the influence of adsorbed water or impurities. However, as the liquid crystal display element manufacturing line has become larger, the optimization of the manufacturing steps so far has become impossible to suppress display unevenness, and thus it has been desired to reduce the alignment unevenness of the liquid crystal alignment film more than the prior art. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 1-249148. SUMMARY OF THE INVENTION [The object of the invention] The ODF method causes physical stress on the alignment film when the liquid crystal is dropped by dropping the liquid crystal on the direct alignment film. Or, in the entire area of the panel, it is necessary to fill the liquid crystal, so it is necessary to add the drop point of the liquid crystal. Therefore, in the lower portion of the liquid crystal droplets or the portion where the droplets of the liquid crystal are connected to the adjacent droplets, so-called alignment unevenness occurs in which the dropping trace or the lattice is uneven, and when it is used as a liquid crystal display element, uneven alignment occurs. The rise of the display shows uneven problems. It is considered that the alignment is uneven, and the adsorbed water or impurities adhering to the surface of the liquid crystal alignment film formed on the substrate on the surface of the liquid crystal alignment film -6-200944553 are concentrated due to the liquid crystal dropped in the ODF step, so that the liquid crystal drops or the liquid crystal The droplets are connected to each other in a portion where the amount of adsorbed water or impurities is different. The present invention has been made in view of the above. That is, the problem to be solved by the present invention is to provide a liquid crystal alignment agent which can reduce the unevenness of liquid crystal alignment which occurs in the ODF method. Further, the present invention provides a liquid crystal display element which reduces display unevenness caused by uneven alignment of liquid crystals which occurs in the ODF mode. [Means for Solving the Problem] The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, found a liquid crystal alignment agent which achieves the object. The present invention has the following gist based on this related knowledge. (1) A liquid crystal alignment agent containing a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula [1] and a diamine compound having a carboxyl group or a hydroxyl group in the molecule. A polymer obtained by reacting an amine component [Chemical Formula 1]

[1] (In the formula [1], Υι is a tetravalent organic group having a carbon number of 4 to 15 having a non-aromatic cyclic structure of 4 to 8 carbon atoms). (2) The liquid crystal alignment agent according to (1) above, wherein the formula [1], 200944553

The Yl system has a structure selected from the following formula [2] to the formula [1 1]. [Chemical 2]

/ —, 丫3丫5 [2]

[8] Wen Yun melon xxrc [3] [4] [5] [6] [7]

(In the formula [2], γ2 to γ5 are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and each of them may be the same or different in the formula [8], and Υ6 and Υ7 are each independently Is a hydrogen atom or a methyl group, each of which may be the same or different

-8 - 200944553, a diamine compound having a carboxyl group, which is a diamine compound represented by the following formula [12] [Chemical Formula 3] (COOH)n [12] nh2 (In the formula [12], the Xi system An organic hydrazine having an aromatic ring having 6 to 30 carbon atoms, and 11 is an integer of 1 to 4). (9) A liquid crystal alignment agent according to the above (8), wherein the diamine compound of the formula [I] is a diamine compound selected from the following formula [13] to formula [17].

[Chemical 4]

In the formula [13], ml is an integer of 1 to 4; in the formula [14], χ2 is a single bond, _CH2- '-C2H4-'-C(CH3)2-'-CF2-'-C(CF3) 2- ' -〇- ' _C〇-, -NH-, _N(CH3)_, -CONH- ' -NHC〇-, _ch2〇-, -OCH2- ' -COO- ' -OCO- ' -CON(CH3 -^ -N(CH3)CO- > m2 and m3 each represent an integer '0 to 4' and m2 + m3 represents an integer of 1 to 4; in the formula [15], 'ιη4 and m5 are each an integer of 1 to 5 In the formula [16], 9-200944553, X3 is a linear or branched alkyl group having a carbon number of 1 to 5, and m6 is an integer of 1 to 5; in the formula [17], 'X4 is a single bond, -CH2-, -c2h4-, -c(ch3)2-, -cf2-, -c(cf3)2-, -o-, -co-, -nh-, -n(ch3)-, -c〇nh-, - NHCO- ' -CH20-, -OCH2-, -COO-, -OCO-, -0:〇1^((:113)- or -:^((:113)(:〇-,1117 is 1 to 4 (1) The liquid crystal alignment agent according to the above (9), wherein in the formula [13], ml is an integer of 1 to 2. (1 1 ) The liquid crystal alignment as described in the above (9) In the formula [14], @, x2 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -〇-, -CO-, -NH-, -N(CH3)- , -CONH-, -NHCO-, -COO- or -OCO-, m2 and m3 are all integers of 1. (1) The liquid crystal alignment agent according to the above (9), wherein, in the formula [17], X4 is a single bond, -CH2., -0-, -CO-, -NH-, -CONH-, The liquid crystal 0 alignment described in any one of the above (1) to (12), wherein the NHCO-, -CH20-, -OCH2-, -COO- or -OCO-, m7 is an integer of 1 to 2. The liquid crystal according to any one of the above (1) to (1), wherein the liquid crystal has a hydroxyl group or a hydroxyl group. The liquid crystal alignment agent according to any one of the above (1) to (14), wherein the liquid crystal alignment agent is a liquid crystal alignment agent, wherein the solvent is contained in the solvent of the liquid crystal alignment agent. The polymer in the agent is a polyimine obtained by dehydration ring-closure of poly-proline. -10-200944553 (16) A liquid crystal alignment film using the liquid crystal according to any one of (1) above. Obtained by an alignment agent. (17) A liquid crystal display element having the above (liquid crystal alignment film. [Effect of the invention] The liquid crystal alignment agent of the present invention can be used in a relatively simple manner, and the liquid crystal alignment agent of the present invention can be reduced to occur. The liquid crystal display element having a liquid crystal alignment film obtained by a crystal alignment agent is excellent in liquid crystal display elements, and is applicable to a large-screen and high-definition liquid crystal. [Best Mode for Carrying Out the Invention] The present invention relates to Containing a component containing a tetracarboxylic dianhydride represented by the formula π] (hereinafter, also referred to as a specific acid dianhydride), and a specific component having a hydroxyl group or a hydroxyl group in the molecule, which is also referred to as a specific diamine compound. a liquid crystal alignment agent of a polymer into which the diamine component is added, a liquid crystal display element using the liquid crystal alignment film, and a polymer contained in the liquid crystal alignment agent of the present invention, a fixed acid dianhydride and When a liquid crystal having a high polarity of a carboxyl group or a hydroxyl group is obtained by a liquid crystal alignment agent containing such a polymer, a liquid crystal which is adsorbed on the surface of the liquid crystal alignment film and adsorbs water or impurities is dripped, It can be suppressed by adhering to the liquid crystal alignment film table to the method described in the above (15 1 6). Further, the liquid material of the present invention is the reliability of the liquid material of the present invention. The specific structure of the tetracarboxylic dianhydride to form an amine compound (a liquid crystal obtained by a reaction. The raw material uses a special diamine compound. The liquid crystal alignment film, the adsorbed water in the ODF step or the -11 - 200944553 impurity is Concentration, the display unevenness caused by this can be alleviated. Thereby, the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can obtain a high display which does not occur in the liquid crystal alignment unevenness which occurs in the 〇DF method. A liquid crystal display element of the present invention. The polymer used in the present invention is obtained by reacting a tetracarboxylic dianhydride component containing a specific acid dianhydride with a diamine component containing a specific diamine compound to obtain a cyclic water-dehydrating acid. The poor S of the polycondensation of the hydrazine of the hydrazine of the hydrazine of the acid to the amine of the acid to the amine <tetracarboxylic dianhydride component > tetracarboxylic acid used in the present invention The dianhydride component contains a tetracarboxylic dianhydride represented by the formula [1], that is, a specific acid dianhydride, and a tetracarboxylic dianhydride other than the specific acid dianhydride may be used in combination. specific When at least one compound selected from the group consisting of acid dianhydrides is preferred, the effect achieved by the present invention can be made more remarkable. 〇[Specific acid dianhydride] The specific acid dianhydride used in the present invention is The tetracarboxylic dianhydride represented by the formula [1].

'Y, a non-aromatic cyclic structure having a carbon number of 4 to 8-12-200944553 (alicyclic structure) having a carbon number of 4 to 15, preferably 4 to 12, a tetravalent organic group . In the formula [1], specific examples of Υι include the following formulas [2] to [11]. [Chemical 6] Υ 2|4

Υ3 Ϋ5

[2] [3] [4]

In the formula [2], Y2 to Ys are each independently a group selected from a hydrogen atom 'methyl group, a chlorine atom and a benzene ring, and each may be the same or different; in the formula [8], Υ6 and Υ7 are each independently The hydrogen atom or the methyl group may each be the same or different. In the formula [1], a particularly preferable structure is a formula [2], a formula [4], a formula [5], a formula [7] or a formula [8] in terms of polymerization reactivity or ease of synthesis. ]. The specific acid dianhydrides exemplified above may be used alone or in combination of two or more. [Other tetracarboxylic dianhydride] In the present invention, other tetracarboxylic dianhydrides other than the specific acid dianhydride may be used as the tetracarboxylic dianhydride component without impairing the effects of the present invention. Specific examples thereof include, for example, a description of -13-200944553, for example, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Anhydride, naphthalene tetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,5,6-nonanedicarboxylic dianhydride, 3,3',4,4'-linked Pyromellitic dianhydride, 2,3,3,4-diphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4,-diphenyl Ketotetracarboxylic dianhydride, bis(3,4-dimercaptophenyl) maple, bis(3,4-dicarboxyphenyl)methane, 2,2·bis (3,4_di.

Carboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)di Methyl decane, bis(3,4-Q-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis(3,4-dicarboxyphenyl) Pyridine, 3,3,,4,4'-diphenyl maple tetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, and the like. The other acid dianhydrides exemplified above may be used alone or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment property, the voltage holding property, and the charge accumulation when the liquid crystal alignment film is formed. <Diamine compound> The diamine compound used in the present invention contains a diamine compound having a carboxyl group or a hydroxyl group in the molecule, that is, a specific diamine compound, and a diamine compound other than the specific diamine compound may be used. That is, other diamined compounds. When the diamine compound is at least one compound selected from the group consisting of specific diamine compounds, the effect achieved by the present invention can be made more remarkable and preferable. [Specific diamine compound] -14- 200944553 The specific diamine compound of the present invention is a diamine compound having a carboxyl group or a hydroxyl group in the molecule. The specific structure of the diamine compound having a carboxyl group in the molecule is not particularly limited, but is preferably a compound represented by the following formula [1 2 ]. [Chemical 7] ❿ (COOH)

[12] In the formula [12], Χι is an organic group having an aromatic ring having 6 to 30 carbon atoms, and η is an integer of 1 to 4. Desirable X!, represented by the formula [12a], has a carbon number of 6 to 30 and a structure in which 1 to 4 of any hydrogen atom is substituted by a carboxyl group. [化8]

Cl 2 a] In the formula [12a], g is an integer of 0 to 2, and Q represents a single bond, an ether bond, a carbonyl group, a carboxyl group, an amine group, a guanamine bond or an alkylene group having 1 to 11 carbon atoms, etc. Any hydrogen atom may be substituted by a fluorine atom or a methyl group. Preferred compounds include compounds of the following formulas [13] to [17] -15- 200944553 [Chemical 9] NH2 (COOH) m3H2Nx3^COOH) m1 H2NX^X2'Oi_NH2 (fc〇OH) m2 [14 ]

[13]

Η2Ν0^〇^〇^ (^〇〇H)m7

Cl 7] In the formula [13], ml is an integer from 1 to 4; in the formula [14], X2 is a single

Key, -CH2_, -C2H4_, -C(CH3)2_, -CF2_, -C(CF3)2_, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO -, -CH20-,

-OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, m2 and m3 each represent an integer from 0 to 4, and m2 + m3 represents an integer from 1 to 4; In [15], m4 and m5 are each an integer of 1 to 5; in the formula [16], X3 is a linear or branched alkyl group having 1 to 5 carbon atoms, and m6 is an integer of 1 to 5; Where X4 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -〇_, -CO-, _NH-, _N(CH3) _, -CONH_, -NHCO-, -CH20-, -0CH2-, -COO-, -OCO-, -CON(CH3). or -N(CH3)CO-, m7 is an integer from 1 to 4. In the preferred formula [13], m 1 is an integer diamine compound of 1 to 2; in the formula [14], X2 is a single bond, _〇1^2-, -(:2114-, -(: ((:113)2-, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO- or _OCO-' m2 and m3 are all 1 An integer diamine compound; in the formula [17], 'X4 is a single bond, -CH2-, -0-, -CO-, -NH-, -CONH-, -NHCO-, _CH2〇-, _0Ch2-, _C00_ or _0C0·, m7 is an integer diamine compound of i to 2. -16- 200944553 Among the diamine compounds represented by the formula [13] to the formula [17], preferred specific examples include the following formula [ 18] to the diamine compound of the formula [28].

H2N

[19]

ΟΟΗ JH2 [2 0]

Η2νη〇- ch2ch2cooh h2 h2n^^cooh χχ

Ch2ch2cooh ' η2

Ch2ch2cooh [2 6] [Chem. 11]

NH2 H2N

ΪΟΟΗ COOH Φ [27] [28]

In the formula [27], X5 is a single bond, -CH2-, -0-, -CO-, -NH-, CONH-, -NHCO-, -CH2O-, -〇CH2-, -COO- or -OCO In [28], X6 is a single bond, -CH2-, -0-, -CO-, -NH-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO- or -OCO-. The specific structure of the diamine compound having a hydroxyl group in the molecule is not particularly limited, and a preferred compound 'is a compound of the following formula [2 9 ] to formula [3 3 ]. -17- 200944553 [Chem. 12]

In the formula [2 9], m8 is an integer of 1 to 4; in the formula [30], X7 is a single bond, -(^2-, -22114-, -(:((:113)2-, -0) [2-, -&lt;:(€?3)2-, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, -OCH2- , -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, m9 and mlO each represent an integer from 〇4, and m9 + ml0 represents an integer from 1 to 4; Wherein mil and ml2 are each an integer of 1 to 5; in the formula [32], X8 is a linear or branched alkyl group having 1 to 5 carbon atoms, and ml3 is an integer of 1 to 5; in the formula [33], Χ9 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -Ο-, -CO-, -NH-, -N(CH3) -, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, ml4 is an integer from 1 to 4. In the preferred formula [29], m8 is an integer diamine compound of 1 to 2; in the formula [30], 'X7 is a single bond, -(:112-, -(:2114-, -(:((:1) €3) 2-, -〇-, -CO-, -NH-, -N(CH3)·, -CONH-, -NHCO-, -COO- or -OCO-' m9 and mlO are all integers of 1. a diamine compound; in the formula [33], X9 is a single bond, -CH2-, -0-, -C0-, -NH-, -CONH-, -NHCO-, -CH20- And 〇CH2-, -COO- or -OCO-, and ml4 is an integer diamine compound of 1 to -18-200944553 2. Among the diamine compounds represented by the formula [29] to the formula [33], preferably Specific examples of the 'diamine compound of the following formula [34] to formula [44] can be cited.

CH2CH2OH [3 8] CH2CH2OH HzN-Q- -〇-nh2 H2N^p^NH2 HzN^^H2 HzN [34] [35]

〇tp&quot;H2 [化14] [4 1] ch2ch2oh [4 2] h2n

[4 3] [44]

In the formula [43], X,. Is a single bond, -CH2·, -0-, -CO-, -NH-, -CONH-, -NHCO-, -CH20-, -〇CH2-, -COO- or -OCO-; in formula [44] And ^ is a single bond, -CH2-, -0-, -CO-, -NH-, -CONH-, _NHCO-, -CH2O-, -OCH--, -COO-0CO-. The specific diamine compound exemplified above may be used singly or in combination of two or more. [Other diamine compounds] In the present invention, other diamine compounds other than the specific diamine compound may be used as the diamine component without impairing the effects of the present invention. Specific examples thereof are as follows. -19- 200944553 For example, P-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-P-phenylenediamine, m-phenylene Diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-methoxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'- Biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2' -diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4 diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-di Aminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4' - sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-amino Phenyl) decane, dimethyl-bis (3- Aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenyl Amine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4 '·Diaminodiphenyl)amine, N-methyl(3,3′-diaminodiphenyl)amine, N-methyl(3,4′-diaminodiphenyl)amine, N -methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2, 3'-Diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5 -diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diamino-20-200944553 naphthalene, 1,2-bis(4-aminophenyl) Ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1 , 4-bis(4-aminophenyl) , 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-'aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1 , 4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene φ bis(methylene)] Aniline, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[ 1,3-Benzene bis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylene double ( Methyl)]diphenylamine, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3 -Benzene bis[(4-aminophenyl)formamidine], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzene) Formate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylene© double 3-amino benzoate), bis(4-aminophenyl)terephthalic acid, bis(3-aminophenyl) Terephthalic acid, bis(4-aminophenyl)isophthalic acid, bis(3-aminophenyl)isophthalic acid, N,N'-(1,4-phenylene)bis (4- Aminobenzoguanamine), &gt;^,&gt;^'-(1,3-phenylene)bis(4-aminophenylguanamine), hydrazine, Ν'-(1,4-phenylene) bis ( 3-aminophenyl phthalamide), hydrazine, Ν'-(1,3-phenylene) bis(3-aminophenylguanamine), hydrazine, Ν'-bis(4-aminophenyl)-p-phenylene Ammonium formate, hydrazine, Ν'-bis(3-aminophenyl)phthalic acid decylamine, hydrazine, Ν'-bis(4-aminophenyl)isophthalic acid decylamine, hydrazine, hydrazine - bis(3-aminophenyl)isophthalic acid decylamine, 9,10-bis(4-aminophenyl)phosphonium-21 - 200944553, 4,4'-bis(4-aminophenoxyl) Diphenyl hydrazine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amine 4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'- (3-Amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4 - bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1, 5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1 , 7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1 , 8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1, 〇-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-Aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane . Bis(4-Aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5- Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10- Diamino decane, 1,1 1-diaminoundecane, 1,12-diaminododecane, and the like. Further, examples of the diamine side chain include an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a hetero ring, and a macrocyclic substituent which is formed by the above, and the second-22-200944553 amine, specifically In other words, a diamine represented by the following formula [DA1] to formula [DA26] can be mentioned. [化15]

[DAI] [DA2] CDA3] [DA4] [DA5] In the formula [DA1] to the formula [DA5], I is an alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group.

[Chemistry 16]

[DA8] [DA9] From the formula [DA6] to the formula [DA9], 'R2 is not -COO-, -OCO-, -CONH-, -NHCO-, -CH2-, -〇-, -CO- or -NH -R3 represents an alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group. -23- 200944553 [Chem. 17]

[DAI 0] [DAI 1] In the formula [DA10] and the formula [DA11], R4 represents -0-, -OCH2-, _CH2〇-, -C00CH2- or -CH2OCO-, and R5 is a carbon number of 1 or more and 22 γ. An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group. [化!8]

[DA 12] [DA 13] [DAI 4] In the formula [DA12] to the formula [DA14], R6 represents -COO-, -OCO-, c〇NH-, -NHCO-, -COOCH2-, -CH2OCO-, -CH20-, _〇CH2- or -CH2-, and R7 is an alkyl group having 1 or more and 22 or less carbon atoms, an alkyl group having an alkyl group or a fluorine-containing alkoxy group. [like 9]

In the formula [DA15] and the formula [DA16], R8 represents -COO·, -OCO-, c〇NH- '-NHCO- &gt; -COOCH2- ' -CH2OCO- ' -CH2O- ' -24- 200944553 -OCH2- , -CH2-, -Ο-, or -NH-, R9 is oxy, cyano, trifluoromethyl, nitro, azo, indolyl, ethionyl, ethoxylated or hydroxy. 〇 [Chem. 20] 〇

Η2Νχ^ νη7

❿ [Chem. 21]

[化22] -25 200944553

Further, a diamine-based oxime house represented by the following formula [DA27] may also be mentioned. [Chem. 23]

H2N-(CH2)3

Ch3 I Si—(CH 2 ) 3 —NH 2 CHa [DA 2 7] In the formula [DA27], m is an integer of 1 to 10. The other diamine compound exemplified above may be used alone or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment property, the voltage holding property, and the charge accumulated in the liquid crystal alignment film. &lt;Polymer&gt; The polymer used in the present invention is a polymer of at least one of polyamine and polyimine. The polyamic acid is a polylysine obtained by a reaction of a tetracarboxylic dianhydride component containing a specific acid dianhydride with a diamine component containing a specific diamine compound. Then, the polyimine is a polyimine obtained by subjecting the above polyamic acid to dehydration ring closure. The related polylysine and polyimine are suitable as polymers for obtaining a liquid crystal alignment film. In the present invention, the content of the specific diamine compound in the diamine component is increased, and the ODF step of adsorbing water or impurities on the surface of the liquid crystal alignment film is -26-200944553. When the liquid crystal is dropped, the adhesion to the liquid crystal alignment film can be suppressed. The adsorbed water or impurities on the surface are concentrated. Therefore, the content of the specific diamine compound in the diamine component is preferably from 5 mol% to 100 mol%. More preferably, it is from 1% to 5% by mole, more preferably from 10% to 80% by mole, and most preferably from 20% to 80% by volume. Further, the content of the specific acid dianhydride in the tetracarboxylic dianhydride component is preferably from 5 mol% to 100 mol%. More preferably, it is from 1% by mole to 丨〇〇% by mole, and even more preferably from 20% by mole to 1% by mole, most preferably from 50% by mole to 1% by mole. [Method for Producing Polymer] The polyglycine used in the present invention can be a known polymerization method. In general, a method of reacting a tetracarboxylic dianhydride component with a diamine compound in an organic solvent. The reaction of the tetracarboxylic dianhydride with the diamine compound is relatively easy to carry out in the ® organic solvent, and is advantageous from the viewpoint that by-products are not formed. The organic solvent used in this case is not particularly limited as long as it is a polylysine dissolved. Specific examples thereof are as follows. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-D pyrrolidone, N-methylcaprolactam, dimethyl hydrazine , tetramethyl urea, pyridox, dimethyl hydrazine, hexamethylarylene, butyl vinegar, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl fluorenyl Ketone 'methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone 'methyl lysis fiber -27- 200944553

Agent, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol , diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate Monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3 -methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene , propyl ether, dihexyl ether, dioxane, η-hexane, η-pentane, η-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, lactic acid Ethyl ester, acetic acid , Ethyl acetate, butyl acetate, η-, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy propionic acid

Methyl ester, methyl 3-ethoxypropionate ethyl, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate , 3-methoxypropionic acid butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination. Further, even a solvent which does not dissolve the polyamic acid may be used in the above solvent as long as it does not precipitate the produced polyamic acid. Further, since the water in the organic solvent hinders the polymerization reaction, and in order to hydrolyze the produced polylysine, it is preferred that the organic solvent be dehydrated as much as possible. As a method of reacting a tetracarboxylic dianhydride and a diamine compound in an organic solvent, a method of dispersing or dissolving a diamine compound in an organic solvent, and directly adding a tetracarboxylic dianhydride, or a method of dispersing or dissolving in an organic solvent; and conversely adding a diamine compound to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent; and a tetracarboxylic acid dianhydride and a diamine compound are alternately added. The method, etc., can be any of these methods. • When the tetracarboxylic dianhydride or the diamine compound is a compound of a plurality of kinds, it can be reacted in a state of being mixed beforehand, and it can be reacted in an individual order and reacted individually. A high molecular weight body in which a low molecular weight body is subjected to a mixed reaction may also be used. The temperature at which the above polylysine is synthesized may be any temperature selected from -20 ° C to 150 ° C, but preferably in the range of -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration, but since the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction liquid becomes too high and uniform stirring becomes difficult 'tetracarboxylic dianhydride and diamine. The total concentration in the reaction solution of the component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The anti-β should be carried out at a high concentration in the initial stage, and then an organic solvent can be added. In the synthesis reaction of polyamine, the ratio of the number of moles of the diamine component to the number of moles of the tetracarboxylic dianhydride component is preferably from 0.8 to 1.2. The usual polycondensation reaction is similar to the fact that the closer the molar ratio is to 1.0, the greater the molecular weight of the polylysine formed. The polyimine used in the present invention is a polyimine obtained by subjecting the above polyamic acid to dehydration ring closure, and is suitable as a polymer for obtaining a liquid crystal alignment film. In the polyimine used in the present invention, the dehydration ring closure ratio of the valeric acid group is -29-200944553 (the imidization ratio), and does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the purpose or purpose thereof. use. Examples of the method for imidizing polyphosphonium hydrazide include a hydrazine imidization in which a solution of polylysine is directly heated, and a catalyst oxime imidization in which a catalyst is added to a solution of polyamic acid. The temperature at which the polyaminic acid is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 25 (rc, while removing water formed by the hydrazine imidization reaction to It is preferred to carry out the outside of the system. The catalyst of φ poly-proline is imidized, and a basic catalyst and an acid anhydride can be added to the solution of poly-proline, by -2 0 to 250 ° C. Preferably, the stirring is carried out at a temperature of from 180 ° C. The amount of the basic catalyst is 〇. 5 to 30 moles of the valeric acid group is preferably 2 to 20 moles, and the amount of the acid anhydride is guanamine. The acid group is 1 to 50 moles, preferably 3 to 30 moles. As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. may be mentioned. Further, pyridine is preferred because it has a moderate basicity required for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, among which acetic anhydride is used because of the reaction. Purification after completion is preferred and preferred. The imidization rate of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. In the amine, the dehydration ring closure ratio of the proline group (the imidization ratio) must not be 1%, and can be adjusted according to its use or purpose. Especially preferably 50% or more. When the reaction solution of valine or polyimine is recovered, when the polymer component is recovered, the reaction solution may be precipitated by putting it into a weak solvent. The weak solvent used in the precipitation is exemplified by methanol. Acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. The polymer precipitated in a weak solvent can be filtered and recovered. Drying at normal temperature or after heating under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the reprecipitation recovery 2 to 10 times, impurities in the polymer can be reduced. In this case, it is preferred to use a weak solvent of three or more kinds, such as an alcohol, a ketone or a hydrocarbon, to further improve the purification efficiency. The molecular weight of the polyglycolic acid and the polyimine used in the present invention. Consider the strength of the film and apply In the case of the workability at the time of film formation and the uniformity of the coating film, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000. &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention is a coating liquid for producing a liquid crystal alignment film, and the main component thereof is a resin component for forming a resin film and an organic solvent for dissolving the resin component. In the present invention, the resin component described above contains the resin component of the polymer used in the present invention. In this case, the content of the resin component is from 1% by mass to 20% by mass, preferably from 2% by mass to 1%. 0% by mass. In the present invention, the above-mentioned resin components may be all of the polymers used in the present invention, and the polymers of the present invention and other polymers may be used. In this case, the content of the other polymer -31 - 200944553 other than the polymer of the present invention in the resin component is from 0.5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass. The other polymer to be used may, for example, be a polylysine or a polyimine obtained by reacting another acid dianhydride other than the specific acid dianhydride with another diamine compound other than the specific diamine compound. The organic solvent in which the resin component is dissolved is not particularly limited. Specific examples include hydrazine, Ν'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone , N-ethyl 吡 pyrrolidone, N-vinyl pyrrolidone, dimethyl sub-milling, tetramethyl urea, pyridine, dimethyl milling, hexamethyl sulfoxide, r-butyrolactone, 1,3-dimethyl -imidazolidinone, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, Propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents can be used in combination of two or more types. When the polyimine is dissolved in an organic solvent, it can be heated for the purpose of promoting the dissolution of the polyimide. Since the heating temperature is too high, the molecular weight of the polyimide may be lowered, and the temperature 30 is preferably from 10 °C. The concentration of the solution of the specific polyimine is not particularly limited, but the concentration of the specific polyimine in the solution is preferably from 1 ' to 20% by mass, more preferably 3, because it is easily mixed uniformly with the specific amine compound. It is up to 15% by mass, particularly preferably from 3 to 10% by mass. The liquid crystal alignment agent ' of the present invention' may contain components other than the above. As an example, a solvent or a compound which improves film thickness uniformity or surface smoothness when a liquid crystal alignment agent is used as a coating liquid, and a compound which improves adhesion between a liquid crystal alignment film and a substrate -32-200944553 are also contained. Specific examples of the solvent (weak solvent) for improving the uniformity of the film thickness or the surface smoothness include the following. For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve 'butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, and butyl Kikabi alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol 'ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol oxime monobutyl ether, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl Ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetic acid Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Butyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, &amp; diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, η-hexane, Η-pentane, η-octane Diethyl ether, methyl lactate 'ethyl lactate, methyl acetate, ethyl acetate, η-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy propyl Methyl ester, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Ester, butyl 3-methoxypropionate, methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, 1-hexanol, propylene glycol-1-monoethyl ether-2-33 - 200944553 Acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, η-propyl lactate, n-butyl lactate, isoamyl lactate A solvent or the like having a low surface tension such as an ester. Among these, butyl cellosolve, propylene glycol monomethyl ether or ethyl lactate is preferred. These weak solvents may be used in one type or in combination of plural kinds. When the solvent is used as described above, the solvent contained in the liquid crystal alignment agent is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass. ▲ As a compound for improving the uniformity of the film thickness or the surface smoothness, a fluorine-based surfactant, a polyoxyalkylene-based surfactant, a nonionic surfactant, or the like can be given. More specifically, for example, EF-TOP EF301, EF303, EF3 52 (manufactured by Tohkem Product Co., Ltd.), MEGAFAC F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorade FC43 0, FC431 (manufactured by Sumitomo 3M Co., Ltd.) ), Asahiguard AG710, Surflon S-3 82, SC 101, SC102, SC 103, SC104, SC105, SC 1 06 ❹ (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include those having a functional decane or a compound containing an epoxy group. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethyl-34-200944553 oxygen Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethylmethoxydecane, 3 -ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-amine Propyltriethoxydecane, N-triethoxycarbamidopropyltriethylenetriamine, -N-trimethoxycarbamidopropyltriethylenetriamine, 1〇-trimethoxymethyl矽alkyl-1,4,7-triazadecane, 10-triethoxycarbamimidyl-1,4,7-tri-xazadecane, 9-trimethoxyformamidin-3,6 - diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N -benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N - double (oxidation Alkyl-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, :^,:^,:^',]^', -tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetrahydration Glyceryl-4,4'-diaminodiphenylmethane, and the like. When the compound for improving the adhesion to the substrate is used, the amount thereof is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. 20 parts by mass. When the amount is less than -35 - 200944553, 0.1 parts by mass cannot be expected to have an effect of adhesion, and when it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated. In the liquid crystal alignment agent of the present invention, in addition to the above, a dielectric or a conductive material which changes electrical characteristics such as a dielectric constant or conductivity of the liquid crystal alignment film may be added without departing from the effects of the present invention. A substance or a crosslinkable compound which is intended to increase the hardness or density of the film when the liquid crystal alignment film is formed may be added. The concentration of the solid content in the liquid crystal alignment agent of the present invention can be appropriately changed depending on the film thickness of the target liquid crystal alignment film, but a coating film having no defects can be formed, and a suitable film as a liquid crystal alignment film can be obtained. For the reason of the thickness, it is preferably from 1 to 20% by mass, more preferably from 2 to 10% by mass. &lt;Liquid Crystal Alignment Film/Liquid Crystal Display Element&gt; The liquid crystal alignment agent of the present invention can be subjected to honing treatment, alignment treatment by light irradiation or the like, or alignment in the vertical alignment, etc. after application and baking on a substrate. After the treatment, it is used as a liquid crystal alignment film. In this case, the substrate to be used for the purpose of the substrate is not particularly limited, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used. Further, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed, from the viewpoint of simplification of the process. Further, in the reflective liquid crystal display device, an opaque material such as a germanium wafer may be used as the substrate on only one side, and a material such as aluminum or the like may be used as the electrode. The coating liquid method of the liquid crystal alignment agent is not particularly limited, but industrially, the method of -35-200944553 is carried out by screen printing, offset printing, flexographic printing, ink jetting, etc., as a general method. As other coating liquid methods, there are immersion, roll coating, slit coater, spin coating, etc., and these can be used depending on the purpose. After the liquid crystal alignment agent is applied onto the substrate, the solvent can be evaporated by a heating means such as a hot plate at 50 to 300 ° C, preferably 80 to 250 ° C to form a coating film. The thickness of the coating film after firing is too low in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal Φ display element may be lowered, preferably 5 to 300. Nm is more preferably 10 to 100 nm. When the liquid crystal is horizontally aligned or obliquely aligned, the coating film after firing is treated by honing or polarized ultraviolet irradiation or the like. In the liquid crystal display device of the present invention, a liquid crystal display cell is produced by a known method from the liquid crystal alignment agent of the present invention, and a liquid crystal cell is produced by a conventional method. An example of the production of the liquid crystal cell is as follows: one of the substrates on which the liquid crystal alignment film is formed is disposed on the liquid crystal alignment film of the substrate on one side, and the spacer is disposed on the liquid crystal alignment film, so that the liquid crystal alignment film surface is inside. The substrate is sealed by a method of injecting liquid crystals under reduced pressure, or a method of sealing the substrate after dropping the liquid crystal through the liquid crystal alignment film surface of the spacer, and then sealing the substrate. The thickness of the spacer at this time is preferably 1 to 3 〇μηι, more preferably 2 to 10 μηη 〇 $1] ± $ 乍 乍 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Excellent for those who are large screens and high-definition LCD TVs. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but not limited thereto. Hereinafter, the abbreviations and structures of the compounds used in the examples are shown in #° (tetracarboxylic dianhydride)

BODA: bicyclo[3,3,〇]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TDA: 3,4- Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride PMDA: pyromellitic dianhydride [Chemical 24]

(Diamine compound) p-PDA : p-phenylenediamine m-PDA: m - benzene rub diamine PCH7DAB: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy Benzene DBA: 3,5-diaminobenzoic acid-38- 200944553 2,4-DAA: 2,4-diamino-N,N-diallylaniline DADPA: 4,4'-diaminodi Phenylamine

H2N h2

P-PDA

H2

(Organic solvent) NMP : N-methyl-2-pyrrolidone BCS : butyl cellosolve GBL : γ-butyrolactone ❹ &lt;Molecular weight measurement&gt; The molecular weight of the polyimine in the synthesis example is the normal temperature of the Showa Denko company. A gel permeation chromatography (GPC) apparatus (GPC-101) and a pipe column (KD-8 03, KD-8 05) manufactured by Shodex Co., Ltd. were measured as follows.

Column temperature: 50 °C Dissolution: Ν, Ν '-dimethylformamide (as additive, lithium bromide hydrate (LiBr*H2〇) is 30mmol/L, dish acid. Anhydrous crystal (〇-phosphoric acid) ) is 30 mmol / L, tetrahydrofuran (THF) is 10 ml / L) -39 - 200944553 Flow rate: 1.0 ml / minute calibration line made of standard sample · TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight) 900,000, 150,000, 100,000, 30,000), and Polyethylene glycol (molecular weight of about 12,000, 4,000 '1,000) manufactured by Polymer Laboratories. &lt;Measurement of oxime imidization ratio&gt; The ruthenium imidization ratio of polyimine in the synthesis example was measured by the following procedure. 20 mg of polyimine powder was placed in an NMR sample tube (NMR sampling tube standard φ 5 manufactured by Kusano Scientific Co., Ltd.), and dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethyl decane) was mixed. Product) 0.53ml, the force of the mouth ultrasonic to make it completely dissolved. This solution was measured for proton NMR of 500 MHz using an NMR measuring instrument (JNW-ECA500) manufactured by Nippon Electronics DATUM Co., Ltd. The ruthenium imidization ratio is determined by using protons from the unaltered structure before and after imidization as the reference proton, and the maximum integral enthalpy (integrated value of a peak) of the proton is used, and appears at 9.5 to l〇. The proton maximum integral enthalpy of the NH group derived from valine near ppm is obtained by the following formula.醯 imidization rate (%) = ( 1-α · x / y ) X 1 〇〇 is in the above formula, x is the maximum integral of protons from the NH group of proline, y is the maximum integral 基准 of the reference proton, When α is a poly-proline (the imidization ratio is 0%), the ratio of the protons of the reference 200944553 to one of the ruthenium protons of lysine is proportional to the number of protons. &lt;Synthesis Example 1&gt; BOD A (3 · 7 5 g, 15 mmol), DBA (2.3 g, 15 mmol), and PCH7DAB (3_8 g, 1 mmol) were mixed in NMP (16. 5 g) to 5 After reacting at 0 ° C for 5 hours, CBDA ( 1.96 g, 10 mmol) and NMP (13.0 g) were added, and the reaction was carried out at 40 ° C for 12 hours to obtain a polyaminic acid solution having a resin φ content of 29% by mass. A). The polyamic acid had a number average molecular weight of 22,700 and a weight average molecular weight of 45,100. &lt;Synthesis Example 2&gt; TD A (3.Og, 1 Ommol), DBA (2.3 g, 15 mmo 1 ), and PCH7DAB (3.8 g, 10 mmol) were mixed in NMP (28.8 g) at 5 〇 ° After reacting for 5 hours, CBDA (2.9 g, 15 mmol) and NMP (19. 3 g) were added, and the reaction was carried out at 40 ° C for 12 hours to obtain a poly-proline acid β solution. After adding hydrazine to the polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.4 g) and pyridine (1.0 g) as a ruthenium amide catalyst were added at 40 ° C. It reacted for 2 hours. The reaction solution was poured into methanol (250 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyimine had a hydrazide conversion ratio of 59%, a number average molecular weight of 11,700, and a weight average molecular weight of 24,100. -41 - 200944553 &lt;Synthesis Example 3&gt; After the NMP was added to the polyamidic acid solution (20.0 g) obtained in Synthesis Example 2 and diluted to 6 mass%, acetic anhydride (2 _) was added as a ruthenium catalyst. 4 g ) and pyridine (1.0 g) were reacted at 50 ° C for 3 hours. This reaction solution was poured into methanol (250 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (C). The polyimine had an oxime imidization ratio of 82%, a number average molecular weight of 13,600, and a weight average molecular weight of 1,400. &lt;Synthesis Example 4&gt; CBDA (5.0 g, 25 mmol), 2,4-DAA (1.6 g, 8 · 0 mm ο 1 ), DBA (1.2 g, 8.0 mmol), and PCH7DAB (4.0 g, 1) Ommol) was mixed in NMP (47.3 g), and reacted at 23 ° C for 15 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (4.3 g) and pyridine (3.3 g) as a ruthenium amide catalyst were added to make 5 (TC) The reaction solution was poured into methanol (260 ml), and the obtained precipitate was filtered, and the precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyamidimide had a ruthenium iodide ratio of 96%, a number average molecular weight of 19,100, and a weight average molecular weight of 45,500. <Synthesis Example 5 &gt; BODA (24.4 g, 1000 mmol), DBA (13.8 g, 9 1 mmol ) 200944553 , and PCH7DAB ( 14.8g, 39mmol) were mixed in NMP (141.6g), and reacted at 80 ° C for 5 hours, then added CBDA (6.0g, 31mmol) and NMP (94.4g), After the reaction was carried out for 12 hours at 401, a polyaminic acid solution was obtained. After the NMP was added to the polyamic acid solution (50. g) to be diluted to 6 mass%, acetic anhydride as a ruthenium catalyst was added ( 5.6 g ) and pyridine (4 · 3 g ) were reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (600 m 1 ) and filtered. The precipitate obtained was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder (E). The ruthenium imidization ratio of the polyimine was 55%. The average molecular weight was 1,900, and the weight average molecular weight was 62,700. &lt;Synthesis Example 6&gt; BODA (24.4 g, 1000 mmol), DBA (11.9 g, 78 mmol), and PCH7DAB (19. 8 g, 52 mmol) were used in NMP (149. After Og) was mixed and reacted at 80 ° C for 5 hours, CBDA (6.0 g, 31 mmol) and NMP (99.2 g) were added and reacted at 40 ° C for 12 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (80.0 g) to dilute to 6 mass%, acetic anhydride (17.9 g) and pyridine (13.8 g) as a ruthenium amide catalyst were added at 90 ° C. The reaction solution was poured into methanol (1 000 ml), and the obtained precipitate was filtered, and the precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder (F). The polyamidimide has an oxime imidization ratio of 81%, a number average molecular weight of -43 to 200944553 20, and a weight average molecular weight of 68,100. &lt;Synthesis Example 7&gt; BODA (24.4 g, 100 mmol), DBA (1 3 · 8 g, 9 1 mm ο 1 ), and PCH7DAB (14.8 g, 39 mmol) were mixed in NMP (141.6 g) to 80 After V was allowed to react for 5 hours, CBDA (6.0 g, 31 mmol) and NMP (94.4 g) were added, and the mixture was reacted at 40 ° C for 12 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (50.0 g) and diluting it to 6 mass%, acetic anhydride (11.2 g) and pyridine (8.7 g) which are ruthenium amide catalysts were added, and the mixture was made at 90 °C. Reaction for 3.5 hours. This reaction solution was poured into methanol (600 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (G). The polyimine had an oxime imidization ratio of 80%, a number average molecular weight of 1,500, and a weight average molecular weight of 62,200. &lt;Synthesis Example 8&gt; TDA (1 2.0 g, 40 mm ο 1 ), DBA (3.0 g, 20 mmol), and p-PDA (2.2 g, 20 mmol) were mixed in NMP (68.8 g) to 5 0 The reaction was allowed to proceed for 15 hours at ° C to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (50. Og) and diluting it to 6% by mass, acetic anhydride (2 3 · 7 g ) as a ruthenium amide catalyst and pyridine (1 1.0 g ) were added to The reaction was allowed to proceed at 50 ° C for 3 hours. This reaction solution was poured into methanol (8 2 0 m 1 ), and the obtained precipitate was filtered. This precipitate 200944553 was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (Η). The polyamidimide had a ruthenium iodide ratio of 88%, a number average molecular weight of 17,700, and a weight average molecular weight of 65,700. &lt;Synthesis Example 9&gt; TD A (6.0 g, 20 mm ο 1 ), DB A (1.5 g, 10 mm ο 1 ), and DADPA (2.0 g, 10 mmol) were mixed in NMP (38.1 g). The reaction was carried out at 50 φ ° C for 15 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (30.0 g) and diluting it to 6% by mass, acetic anhydride (12.9 g) and pyridine (6.0 g) as a ruthenium amide catalyst were added thereto, and the mixture was added at 50 ° C at 50 ° C. Reaction for 3 hours. The reaction solution was poured into methanol (500 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (1). The polyimine has a ruthenium iodide ratio of 88%, a number average molecular weight of 18,000, and a weight average molecular weight of 72,900. ❹ &lt;Synthesis Example 1 〇&gt; CBD A (3.0 g, 16 mmol), p-PD A (0.9 g, 8 mmο 1 ), and PCH7DAB (3.0 g, 8 mmol) were mixed in NMP (39.4 g) to The mixture was reacted at 2 ° C for 20 hours to obtain a polyaminic acid solution (J) having a resin content of 15% by mass. This polyamic acid had a number average molecular weight of 27,000 and a weight average molecular weight of 63,000. <Synthesis Example 11&gt; -45- 200944553 PMDA (2.6 g, 12 mmol), p-PDA (0.7 g, 6 mmol), and PCH7DAB (2.3 g, 6 mmol) were mixed in NMP (32.0 g) to 2 3 ° C was allowed to react for 20 hours to obtain a polyaminic acid solution (K) having a resin content of 15% by mass. The polyamic acid had a number average molecular weight of 28,300 and a weight average molecular weight of 71,200. &lt;Synthesis Example 1 2 &gt; TD A (3 · 1 g, 1 Ommol ) , m-PD A (1 · 7 g, 16 mmo 1 ), and PCH7DAB (4. 〇g, l〇mm〇l) After mixing in NMP (28.4 g) and reacting at 50 ° C for 5 hours, CBDA (3.0 g, 16 mmol) and NMP (18_9 g) were added, and reacted at 40 ° C for 12 hours to obtain polylysine. Solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.6 g) as a ruthenium amide catalyst and pyridine (1.1 g) were added to 5 (TC). The reaction solution was allowed to react for 3 hours, and the reaction solution was poured into methanol (250 ml), and the obtained precipitate was filtered, and the precipitate was washed with methanol, and dried under reduced pressure to give a polyimine. Powder (L). The polyimine has a hydrazide conversion ratio of 79%, a number average molecular weight of 12,000, and a weight average molecular weight of 27,900. 200944553 [Table i] Synthesis Example Tetracarboxylic dianhydride (mmol) Diamine Compound (mmol) Ruthenium amination rate (%) Specific acid dianhydride Other acid dianhydride Specific diamine Other diamine 1 Polylysine (A) CBDA (10) BODA (15) - DBA (15) PCH7DAB ( 10) - 2 Polyimine powder (B) TDA(IO) CBDA(15) - DBA(15) PCH7DAB(10) 59 3 Polyimine powder (C) TDA(IO) CBDA(15) - DBA( 15) PCH7DAB(10) 82 4 Polyimine powder (D) CBDA(25) - DBA(8) PCH7DAB(10) 2,4-DAA(8) 96 5 Polyimine powder (6) CBDA(31) BODA (IOO) - DBA(91) PCH7DAB(39) 55 6 Polyimine powder (F) CBDA(31) BODA(100O) - DBA(78) PCH7DAB(52) 81 7 Polyimine powder (G) CBDA(31) BODA(100O) - DBA(91) PCH7DAB(39) 80 8 Polyimine powder (H) TDA(40) - DBA(20) p-PDA(20) 88 9 Polyimine powder (I) TDA(20) - DBA(10) DADPA(IO) 88 10 Poly-proline (J) CBDA (16 ) - - p-PDA (8) PCH7DAB(8) - 11 Poly-proline (K) - PMDA(12) - p-PDA (6) PCH7DAB(6) - 12 Polyimide powder (L) TDA(10) CBDA( 16) - - m-PDA(16) PCH7DAB(10) 79 -47- 200944553 The column of 'tetracarboxylic dianhydride' in the table and the "-" in the block of "diamine compound" indicate that This acid dianhydride and a specific diamine were used. &lt;Example 1&gt; In the polyaminic acid solution (A) (10.Og) obtained in Synthesis Example 1, NMP (12.5 g) and BCS (25.5 g) were added. The liquid crystal alignment agent [i] was obtained by stirring at 251: for 2 hours. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. ❹ [Production of liquid crystal cell] The liquid crystal alignment agent [1] obtained above was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then at 220 ° C. The hot air circulating oven was fired for 15 minutes to prepare a liquid crystal alignment film having a film thickness of 100 nm. Two sheets of the substrate having the liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on one of the liquid crystal alignment film surfaces, and then a sealant was printed thereon, and after bonding, the sealant was cured to prepare an empty liquid crystal cell. . In this empty liquid crystal cell, liquid crystal ML C-66 0 8 (manufactured by MERCK. JAPAN Co., Ltd.) was injected by a reduced pressure injection method, and the injection port was closed to obtain a nematic liquid crystal cell. As a result of observing the liquid crystal cell by a polarizing microscope, the liquid crystal was uniformly aligned vertically, and no alignment defect was observed. [Evaluation of Surface Free Energy Polarity Term] In the present invention, the surface of the liquid crystal alignment film is easily adsorbed with adsorbed water or impurities. When the liquid crystal is dropped in the ODF step, the adsorbed water or impurities adhering to the surface of the liquid crystal alignment film are suppressed. The concentrated evaluation method focuses on the surface free energy polarity term of the liquid crystal alignment film. The greater the recovery, the higher the effect. The liquid crystal alignment agent [1] obtained above was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C for 5 minutes, and then subjected to a hot air circulating oven at 220 ° C for 15 minutes. The film was fired to prepare a liquid crystal alignment film having a film thickness of 100 nm. The contact angle of pure water with diiodomethane was measured using a substrate with this liquid crystal alignment film. Using these contact angles, the surface free energy (also called surface tension) is calculated according to the method of DKOWΕΝS et al., as described in the literature [JOURNAL OF APPLIED POLYMER SCIENCE VOL. 13, pp. 1741-1747 (1969)]. Polarity term. (l+COS0)xyL = 2(YSdxYLd)l/2 + 2(YSpxyLp)l/2 Equation [i] • where yL=yLd+yLp ' YS=ySd+YSp θ: contact angle of the liquid on the coating film Γί: surface free energy of liquid YLd: surface free energy dispersion of liquid yLP: surface free energy polarity of liquid ys: surface free energy of coating film ysd: surface free energy dispersion of coating film ySp: surface freedom of coating film Energy polarity term -49- 200944553 Moreover, the surface tension of water at 20 °C (7L = 72.8, r Ld = 21.8 ' r Lp = 5 1 .0 ) ( mPa s ) and the surface tension of diiodomethane (r L = 50.8, γ Ld = 49.5 &gt; r Lp = l .3 ) (mPa-s) Substituting into the formula [i], the following formula [ii] is obtained in the case of pure water, and the formula [iii] is obtained in the case of diiodomethane. ]. Among them, 01 and 02 are each a contact angle of water with diiodomethane (CH2I2). (l+COS0 1)x72.8 = 2(YSdx2 1.8)l/2 + 2(ySpx5 1.O)l/2 Equation [ii] (l+COS02)x5O.8 = 2(YSdx49.5)l/ 2 + 2(ySpx 1.3) 1/2 Formula [iii] Therefore, the contact angles of pure water and diiodomethane are substituted in the formula [ii] and the formula [iii], and the rsP is obtained by the cubic equation. Further, the contact angle was measured by using a contact angle measuring device CA-W (manufactured by Kyowa Interface Chemical Co., Ltd.), and water 3//1, diiodomethane 1#1 was dropped on the coating film, and the contact angle after 5 seconds was measured. And ask for it. The result series is shown in Table 2 below. <Example 2> NMP (24. NMP (12.3 g) and BCS (41.5 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [2]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. -50-200944553 A liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent [2]. As a result, the liquid crystal was uniformly aligned vertically, no alignment defects were observed, and the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. &lt;Example 3&gt; In the polyimine powder (C) (5 · 1 g) obtained in Synthesis Example 3, NMP (24. 3 g) was added and Φ was stirred at 70 ° C for 40 hours. Dissolved. NMP (27.1 g) and BCS (26.3 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [3]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [3], a liquid crystal cell was produced in the same manner as in Example 1. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. © The result series is shown in Table 2 below. <Example 4> NMP (24. NMP (26. g) and BCS (27.5 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [4]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. -51 - 200944553 A liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent [4]. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. &lt;Example 5&gt; NMP (25.0 g) was added to the polyimine powder (E) (5.0 g) obtained in Synthesis Example 5, and the mixture was dissolved by stirring at 70 ° C for 40 hours. NMP (16.5 g) and BCS (37.1 g) were added to the solution, and the mixture was stirred at 25 t for 2 hours to obtain a liquid crystal alignment agent [5]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [5], a liquid crystal cell was produced in the same manner as in Example 1. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. Q &lt;Example 6&gt; NMP (24.5 g) was added to the polyimine powder (F) (5 · 1 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C for 40 hours. . NMP (28.1 g) and BCS (25.1 g) were added to the solution to obtain a liquid crystal alignment agent [6] by stirring at 25 ° C for 2 hours. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. -52- 200944553 A liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent [6]. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. &lt;Example 7&gt; In the polyimine powder (G) (5.0 g) obtained in Synthesis Example 7, Φ was added to NMP (24.1 g), and the mixture was dissolved by stirring at 7 (TC) for 40 hours. NMP (22.0 g) and BCS (31.5 g) were added to the solution, and the liquid crystal alignment agent [7] was obtained by stirring at 25 ° C for 2 hours. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent. The resin component was uniformly dissolved. The liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent [7]. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. 1 The surface free energy polarity term was evaluated in the same manner. Θ The results are shown in Table 2 to be described later. <Example 8> NMP (24.0) was added to the polyimine powder (Η) (5.0 g) obtained in Synthesis Example 8. g), dissolved by stirring at 70 ° C for 40 hours, and NMP (22.0 g) and BCS (41.1 g ) were added to the solution to obtain a liquid crystal by stirring at 25 ° C for 2 hours. The alignment agent [8]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. -53- 20094 4553 [Production of liquid crystal cell] The liquid crystal alignment agent [8] obtained above was spin-coated on a glass substrate with an IT0 electrode, and dried on a hot plate at 80 ° C for 5 minutes, then '220. The hot air circulation type oven was fired for 15 minutes to produce a liquid crystal alignment film having a film thickness of 10 Onm. The coating surface was made of a honing device having a drum diameter of 12 mm, and the number of rotations of the drum was 300 rPm, and the speed of the drum was used. 20 mm/sec and a press-in amount of 0.5 mm were honed to obtain a substrate with a liquid crystal alignment film. In order to evaluate the alignment state of the liquid crystal cells, two substrates having the liquid crystal alignment film were prepared, and one liquid crystal was attached thereto. After dispersing a spacer of 6 μm on the alignment film surface, a sealant is printed thereon, and after bonding, the sealant is cured to prepare an empty liquid crystal cell. In this empty liquid crystal cell, liquid crystal MLC-2003 is injected by a vacuum injection method. (manufactured by MERCK JAPAN Co., Ltd.), the inlet cell was closed to obtain a nematic liquid crystal cell. As a result of observing the liquid crystal cell by a polarizing microscope, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Similarly to evaluate the surface From the energy polarity term, the results are shown in Table 2 to be described later. <Example 9> NMP ( 25. lg ) was added to the polyimine powder (f) (5.1 g) obtained in Synthesis Example 9 by The solution was dissolved by stirring at 7 ° C for 4 hours, and NMP (22.2 g) and BCS (40.9 g ) were added to the solution to obtain a liquid crystal alignment agent by stirring at 25 ° C for 2 hours. ]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. -54- 200944553 A liquid crystal cell was produced in the same manner as in Example 8 using the obtained liquid crystal alignment agent [9]. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. &lt;Comparative Example 1 &gt; NMP (1. 13 g) and BCS (11.5 g) were added to the poly (protonic acid) solution (J) (1 0.3 g) obtained in Synthesis Example 10 by 25 ° C The mixture was stirred for 2 hours to obtain a liquid crystal alignment agent [1 0]. In the liquid crystal alignment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [1 〇], a liquid crystal cell was produced in the same manner as in Example 1. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. 〇 <Comparative Example 2 &gt; NMP (ll.lg) and BCS (13.2 g) were added to the polyaminic acid solution (κ) (10 〇g) obtained in Synthesis Example 1 1 by using 2 5 °C. Stirring was carried out for 2 hours to obtain a liquid crystal alignment agent [1 1 ]. In the liquid crystal alignment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [1 1 ], a liquid crystal cell was produced in the same manner as in Example 1. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. -55-200944553 &lt;Comparative Example 3 &gt; NMP (25·1 g) was added to the polyimine powder (L) (5.1 g) obtained in Synthesis Example 12, and stirred at 70 ° C for 40 hours. And let it dissolve. NMP (17, 2 g) and BCS (46.1 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [12]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. A liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent [1 2]. As a result, the liquid crystal was uniformly aligned vertically, and no alignment defect or the like was observed. Further, the surface free energy polarity term was evaluated in the same manner as in the first embodiment. The result series is shown in Table 2 which will be described later. In addition, in Table 2, the "-" of the ruthenium iodization rate means that the ruthenium imidization ratio is not calculated. -56- 200944553 [Table 2] Liquid crystal alignment agent 醯 imidization ratio (%) Surface free energy polarity term (mN/m) Liquid crystal alignment Example 1 [1] - 4.3 Good Example 2 [2] 59 4.0 Good Example 3 [3] 82 3.5 Good Example 4 [4] 96 5.9 Good Example 5 [5] 55 6.7 Good Example 6 [6] 81 4.5 Good Example 7 [7] 80 6.6 Good Example 8 [8 88 23.0 Good Example 9 [91 88 23.5 Good Comparative Example 1 [10] 2.3 Good Comparative Example 2 [Π] - 2.2 Good Comparative Example 3 Γ121 79 2.5 Good [Industrial Applicability] Liquid Crystal Aligning Agent of the Present Invention A liquid crystal alignment film which can reduce the unevenness of liquid crystal alignment which occurs in the ODF method can be obtained. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained therefrom can be applied to a large-screen, high-definition liquid crystal television or the like in order to suppress display unevenness and excellent reliability. As a result, it is suitable for a liquid crystal display element such as a TN element, an STN element, or a TFT liquid crystal element, which is more suitable for vertical alignment type or horizontal alignment type (IPs). In addition, in the present invention, the specification, the scope of the patent application, and the summary of the Japanese Patent Application No. 2008-A No. -57-

Claims (1)

200944553 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula π] and having a carboxyl group or a hydroxyl group in the molecule. a polymer obtained by reacting a diamine component of a diamine compound, [Chemical Formula 1] [1] ❹ (In the formula [1], Y! is a tetravalent organic group having 4 to 15 carbon atoms in a non-aromatic cyclic structure having 4 to 8 carbon atoms). 2. In the liquid crystal alignment agent of the first aspect of the patent application, in the formula [1], Υι is a base selected by the following formula [2] to the formula ’] ΙΤΣ XX XXrC Ο [4] [5] [6] C7] [8] [9] (In the formula [2], Y2 to 丫5 are each independently selected from a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and each may be the same or different; in the formula [8] ' Υ6 -58- 200944553, Y7 are each independently a hydrogen atom or a methyl group, each of which may be the same or different} 〇3 · As in the liquid crystal alignment agent of claim 2, in the formula [1], Υι is [2] » 4. The liquid crystal alignment agent of claim 2, wherein in the formula [1], Υι is the formula [4]. 5. The liquid crystal alignment agent of claim 2, wherein ] 〇中' Υι is the formula [5]. 6. For the liquid crystal alignment agent of the second paragraph of the patent application, in the formula [1], Υι is the formula [7]. 7. The liquid crystal according to the second item of the patent application In the formula [1], Υι is a formula [8]. The liquid crystal alignment agent of any one of the above claims 1 to 7 wherein the diamine compound having a carboxyl group is the following formula [ 12] The diamine compound represented by ❹ [Chemical 3] (?00Η)η 1 [12] Η#,, Η2 (In the formula [12], Χι is an organic group having an aromatic ring having 6 to 30 carbon atoms. 'η is 1 to 4 9. The liquid crystal alignment agent of claim 8, wherein the diamine compound of the formula [12] is a diamine compound selected from the following formula 3] to the formula [17], -59-200944553 [ 4] (CH2)meCOOH H2N (CH2)m4C00H cH2)m5C〇〇H [15] h2n- ΌΌ^Η2 Η2Ν0^0^0^Η2 L (b〇〇H)m7 [17] [16] In the formula [13], ml is an integer of 1 to 4; in the formula [14], X2 is a single bond, -ch2-, -c2h4-, -c(ch3)2-, -cf2_, -c(cf3)2 -, -o-, -co-, -nh-, -n(ch3)-, -conh-, -nhco-, -ch2o-, -och2-, -COO-, -OCO-, -C0N(CH3) - or -N(CH3)C0-, m2 and m3 each represent an integer of 〇4, and m2 + m3 represents an integer of 1 to 4; in the formula [15], m4 and m5 are each an integer of 1 to 5; In [16], X3 is a linear or branched alkyl group having 1 to 5 carbon atoms, and m6 is an integer of 1 to 5; in the formula [17], X4 is a single bond, -&lt;: 112-, -(: 2114-, -(:((:113)2-, -〇?2-, -C(CF3)2-,-0-, -C0-, -NH-'-N(CH3)-, -C0NH- , -nhco-, -ch2o-, -och2-, -coo-, -oco-, -con(ch3)- or -N(CH3)CO-, m7 is an integer from 1 to 4.) The liquid crystal alignment agent of the ninth aspect, wherein in the formula [13], ml is an integer of 1 to 2. 1 1. The liquid crystal alignment agent of claim 9, wherein in the formula [14], X2 is a single bond. , -CH2-, -C2H4-, -C(CH3)2-, -0- '-CO-, -NH- '-N(CH3)-, -CONH-, -NHCO-, -COO- or -OCO -, m2 and m3 are all integers of 1. -60- 200944553 12.If applying A liquid crystal alignment agent having a range of 9 items, wherein in the formula [1 7], X4 is a single bond, -(:112-, -〇-, -(:0-, -:^11-, -(:0&gt;^ 11-, -NHCO·, -CH20-, -OCH2-, -COO- or -OCO-, m7 is an integer from 1 to 2. * 1 3. As in any of the scope of claims 2 to 2 The liquid crystal alignment agent, wherein the diamine compound having a carboxyl group or a hydroxyl group is from 5 to 100 mol% in the diamine component. 0. The liquid crystal alignment according to any one of claims 1 to 13. The liquid crystal alignment agent of any one of the liquid crystal alignment agents of any one of claims 1 to 4, wherein the liquid crystal alignment agent is polymerized in the liquid crystal alignment agent, wherein 5 to 80% by mass of the solvent contained in the liquid crystal alignment agent is a weak solvent. A polyimine obtained by dehydration ring-closing of a poly-proline. The liquid crystal alignment film is characterized by using the liquid crystal alignment agent according to any one of claims 1 to 15. 〇1 7. A liquid crystal display element characterized by having a liquid crystal alignment film of claim 16 of the patent application. -61 - 200944553 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: none -3- 200944553 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: