TW201030055A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Abstract

A liquid crystal aligning agent which is characterized by comprising a copolymer produced by reacting a diamine component with tetracarboxylic dianhydride, wherein the diamine component comprises a diamine compound (A) represented by formula [1], a diamine compound (B) represented by formula [2] and a diamine compound (C) having a carboxyl group in the molecule. [In formula [1], p represents an integer of 0 or 1; X1 represents a phenylene; X2 represents a phenylene or a cyclohexylene; X3 represents a cyclohexylene; and X4 represents an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. In formula [2], Y1 represents -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCO-, -CON(CH3)- or -N(CH3)CO-; Y2 represents a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group; Y3 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH3)-, -N(CH3)CO- or -O(CH2)m- (wherein m represents an integer of 1 to 5); Y4 represents a nitrogenated aromatic heterocyclic ring; and n represents an integer of 1 to 4.]

Description

[Technical Field] The present invention relates to a liquid crystal alignment agent used in the production of a liquid crystal alignment film and a liquid crystal display element using the same. [Prior Art] Nowadays, as a liquid crystal alignment film of a liquid crystal display element, the coating will be used

_ A polyimine-based liquid crystal alignment film in which a solution of a polyimine precursor such as polyacrylamide or a solution of a soluble polyimine is used as a liquid crystal alignment agent of P as a main component and is fired. _ As one of the characteristics of the liquid crystal alignment film, the alignment tilt angle of the liquid crystal molecules on the substrate surface can be kept at any 値, and there is a so-called liquid crystal pretilt angle control. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimine which constitutes the liquid crystal alignment film. In the technique of controlling the pretilt angle by the structure of polyimine, a method in which a diamine having a side chain of Φ is used as a part of a polyimine raw material, a pretilt angle due to the use ratio of the diamine It will become larger, so it is easier to control the pretilt angle of the purpose, which is useful as a means to increase the pretilt angle. As a side chain structure of a diamine which increases the pretilt angle of the liquid crystal, a steroid skeleton (for example, see Patent Document 1), a ring structure such as a phenyl group or a cyclohexyl group (for example, see Patent Document 2) has been proposed. Further, it has also been proposed to have three to four diamines in the side chain of the ring structure (for example, refer to Patent Document 3). On the other hand, in the step of producing a liquid crystal alignment film, when a solution of a polyamic acid solution or a solvent-soluble polyimine solution is applied to a substrate, elastic printing or the like can be generally performed on Industrial-5-201030055, and coating is performed. The solvent of the liquid, in addition to N-methyl-2-pyrrolidone or butyrolactone having excellent solubility of the polymer, can also be mixed with butyl sarbuta for the purpose of forming a uniform and defect-free film. However, since the solvent such as butyl sulphate is inferior in the ability to dissolve polyglycine or polyimine, precipitation occurs when a large amount of the mixture is mixed (for example, refer to Patent Document 4). This problem is more pronounced especially in solutions of solvent soluble polyimine. Further, since the polyimine obtained by using the diamine having a side chain as described above tends to lower the uniformity of coating of the solution, it is necessary to increase the amount of the coating improving solvent such as butyl sarbuta. The acceptable amount of solvent mixture also becomes an important property of polyimine. Further, with the high definition of the liquid crystal display TfC element, the liquid crystal alignment film has a high voltage holding ratio from the viewpoint of suppression of reduction in contrast of the liquid crystal display element or reduction of afterimage development. It is more important that the accumulated charge is less when the DC voltage is applied, and the relaxation of the residual charge accumulated by the DC voltage is faster. In the polyimine-based liquid crystal alignment film, the shorter the time from the afterimage of the DC voltage to the disappearance, except for the poly-proline or the polyamine containing the imine group, the known use contains a specific A liquid crystal alignment treatment agent of a tertiary amine having a structure (for example, 'refer to Patent Document 5), or a liquid crystal alignment treatment agent containing a soluble polyimine using a specific diamine having a pyridine skeleton or the like (for example, ' Reference is made to Patent Document 6) and the like. In addition, as a high voltage holding ratio and a short time from the residual voltage to the disappearance of the DC voltage, in addition to poly-proline or its imidized polymer, it is known that • 6 - 201030055 contains a very small amount of selection. A liquid crystal alignment treatment agent containing a compound having one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (for example, 'see Patent Document 7). In recent years, large-screen and high-definition liquid crystal televisions have been widely put into practical use. In the liquid crystal display elements of such applications, the requirements for afterimages are more stringent than those of displays using text or still pictures as main displays. It is also required to have the characteristics of long-term use that can withstand harsh and harsh environments. Therefore, the liquid crystal alignment film used is more necessary than the past, and the electrical characteristics of the liquid crystal alignment film are required to be good not only in the initial characteristics, but also after a long time exposure at a high temperature. Characteristic. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. [Explanation of the Invention] [Resolution of the Invention] 201030055 An object of the present invention is to provide a liquid crystal alignment treatment agent which is less likely to cause precipitation when a weak solvent is mixed in a coating liquid of a liquid crystal alignment treatment agent, and has a liquid crystal The characteristic that the pretilt angle becomes large, even if the liquid crystal is aligned in the vertical direction at a low use ratio, a voltage retention ratio can be obtained, and the residual accumulated by the DC voltage even after exposure for a long time at a high temperature can be obtained. The charge is moderated by a fast liquid crystal alignment film. Further, an object of the present invention is to provide a liquid crystal display element which is highly resistant to long-term use in an environment of excessively severe use by using the liquid crystal alignment agent.

The inventors of the present invention have conducted detailed investigations to achieve the above object, and have found that a novel liquid crystal alignment treatment agent can be achieved. The present invention is based on this finding and has the following gist. (1) A liquid crystal alignment treatment agent comprising a diamine compound (A) represented by the following formula [1], a diamine compound (B) represented by the following formula [2], and a carboxyl group in the molecule. a diamine component of the amine compound diamine compound (C) and a copolymer obtained by reacting with a tetracarboxylic dianhydride;

(In the formula [1], P is an integer of 〇 or 1, X! is a phenyl group, χ2 is a phenyl or cyclohexyl group, X3 is a cyclohexylene group, and X4 is an alkyl group having a carbon number of 3 to 12, carbon. a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms or a fluoroalkoxy group having 3 to 12 carbon atoms. In the formula [2], 丫1 is -0-, -NH-, -N (CH3)-, -CONH-, -NHCO-, -CH20-, -OCO·, -CON(CH3)-, or

-8- 201030055 -N(CH3)CO-, Υ2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group, and Υ3 is a single bond, -〇-, -ΝΗ -, -N(CH3)-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH3)-, -N(CH3)CO-, or - 〇(CH2)m-(tn An integer of 1 to 5), Y4 is a nitrogen-containing aromatic heterocyclic ring, and η is an integer of 1 to 4. (2) The liquid crystal alignment treatment agent according to the above (1), wherein the diamine compound (Α) is a diamine compound represented by the following formula [1'] (Α·

[Chemical 2]

And χ4 is synonymous with the above formula [1]. (3) The liquid crystal alignment treatment agent according to the above (1), wherein the diamine compound (Α) is a diamine compound represented by the following formula [Γ'] (Α1)

[化3] [Γ] (in the formula [1''] 'x''^l, 4-phenylene or 1,4-cyclohexylene, and ', 2 is an alkyl group having a carbon number of 3 to 12, A fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. (4) The liquid crystal alignment treatment agent according to the above (2), wherein The diamine compound (A') is a diamine compound represented by the following formula [1, a]. -9- 201030055 [化4]

X5,

(In the formula [l'a], X5 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. The cis-trans isomer of the thiol group, the cis-trans isomer is a trans isomer. (5) The liquid crystal alignment treatment agent according to the above (2), wherein the diamine compound (Α') It is a diamine compound represented by the following formula [i'b]. [Chemical 5]

(In the formula [l'b], χ6 is an alkyl group having 3 to 12 carbon atoms, a fluorine-based group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. The cis-trans isomer of the 1,4-cyclohexylene group is a trans isomer. (6) The liquid crystal alignment treatment agent according to the above (3), wherein the diamine compound (Α) is A diamine compound represented by the following formula [r, a]. -10- 201030055 [Chemical 6]

Χ··3

Era] (In the formula [l''a], X''3 is an alkyl group having 3 to 12 carbon atoms, a fluorine-based group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a carbon number of 3 The cis-trans isomers of -12 fluoroalkoxy, ® 丨, 4-cyclohexylene are each a trans isomer). (7) The liquid crystal alignment treatment agent according to the above (3), wherein the diamine compound (A'') is a diamine compound represented by the following formula [], b].

[Chemistry 7]

(In the formula [l''b], 'X''4 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a carbon number of 3 to 12 The fluoroalkoxy group, the cis-trans isomer of 1,4-cyclohexylene is a trans isomer). (8) The liquid crystal alignment treatment agent according to any one of the above (2) to (7), wherein γ^·〇·, ΝΗ_, _c〇NH_, -NHCO-, -CON in the formula [2] (CH3)-, or _CH2〇_. (9) The liquid crystal alignment treatment agent according to any one of the above (2) to (8) wherein the Y2 in the formula [2] is a single bond, and the carbon number is 1 to $ linear -11 - 201030055 or a branch Hospital base, or benzene ring. (10) The liquid crystal alignment treatment agent according to any one of the above (2) to (9) wherein γ3 in the formula [2] is a single bond, -Ο-, -CONH-, -NHCO-, _COO_, -oco-, or -〇((:1^2)„1-(111 is an integer of 1 to 5)° (11) The liquid crystal alignment treatment as described in any one of the above (2) to (1) The Y4 in the formula [2] is a pyrrole ring, an imidazole ring 'pyridinium ring, a pyridyl ring, or a mouth steep ring. The reference (1 2 ) is as described in any one of the above (2) to (1 1 ). In the liquid crystal alignment treatment agent of the above formula (2), the liquid crystal alignment treatment agent according to any one of the above (2) to (7), wherein 2] Υι is - 〇-, -ΝΗ-, -CONH-, -NHCO-, -CON(CH3)-, or -CH20-, Y2 is a linear or branched alkyl group having a carbon number of i~5, Y3 Is a single bond, and Y4 is a pyrrole ring, an imidazole ring, a pyridazole ring, a pyridine ring, or a pyrimidine ring, and η is an integer of 1 to 3.

The liquid crystal alignment treatment agent according to any one of the above aspects (2), wherein Υ^-〇-, -ΝΗ-, -CONH., -NHCO-, - in the formula [2] C〇N(CH3)_, or -CH20-, 丫2 is a benzene ring, 丫3 is, -CONH-, -NHC〇-, -C〇0_, 〇c〇-, or -〇(CH2)m_ ( The claw is an integer of 1 to 5), and Y4 is a Rachel ring, an imidazole ring, a pyrazole ring, a pyridyl ring, or a pyrimidine ring, and η is an integer of 1. (15) The liquid crystal amination content (C) according to any one of the above formula (3), wherein the liquid crystal amination content (C) according to any one of the above formulas (3) is a -12- [3] 201030055 [c8] (c〇〇H)k h2n〆1, nh2 (in the formula [3], Z] is an organic group having an aromatic ring having 6 to 30 carbon atoms, and k is 1 to 4 The liquid crystal alignment treatment agent according to the above (1), wherein the diamine compound of [3] is selected from the following formula [3a], formula [3b], and formula [3]. At least one type of diamine compound of the formula [3<1] and the formula [3e].

[Chemistry 9]

[3e] (in the formula [3a], m丨 is an integer of ι~4. In the formula [孙], 匕

C(CH3)2- '-CF2- '-C(CF3)- '-o-, -CO-, _NH_, N(CH3), -OCH single bond, -ch2., _c2H4_,... CONH-, -NHCO -, -CH20-, 2-, -coo-, _oc〇·, _c〇N(CH3), or _n(cH3)c〇, m2 and each represent an integer from 0 to 4, and m2 + m3 represents 1~ An integer of 4. Formula -13- 201030055 In [3c], m4 and m5 are each an integer of 1 to 5. In the formula [3d], Z3 is a linear or branched alkyl group having 1 to 5 carbon atoms, and 1116 is an integer of 1 to 5. In the formula [3e], Z4 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF〇-, -Ο-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-, m7 is 1 (1) The liquid crystal alignment treatment agent according to the above (1), wherein, in the formula [3a], 1 is an integer of 1 to 2. Φ (1 8 ) The liquid crystal alignment treatment agent according to the above (16), wherein in the formula [3b], 'Z2 is a single bond, _(: 112-, -(:2114-, -€((:113)) 2-, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO-, or -OCO-, m2 and m3 are integers of 1 at the same time. (9) The liquid crystal alignment treatment agent according to the above (1), wherein in the formula [3e], 'Z4 is a single bond, -CH2-, -Ο-, -CO-, -NH-, -CONH-, -NHCO -, -CH2〇-, -〇CH2-, -COO-, or -OCO-, m7 is an integer of 1 to 2. The reference (2〇) is as described in any one of the above (2) to (1 9). The liquid crystal alignment treatment agent 'in the diamine component, the diamine compound (A) is 〇5 to 5 〇mol for 1 mol of the diamine compound (C), and the diamine compound (B) is for the diamine compound. (1) The liquid crystal alignment treatment agent described in any one of the above (2) to (2), wherein the liquid crystal alignment treatment agent is in the liquid crystal alignment treatment agent. (2) The liquid crystal-14-201030055 as described in any one of the above (2) to (2 1), wherein the alignment treatment agent The copolymer in the treatment agent is a polyimine obtained by dehydration ring closure of the polyacid. (23) A liquid crystal alignment film characterized by using the liquid crystal alignment according to any one of the above-mentioned (22). (24) A liquid crystal display device having the liquid crystal alignment film described above. [Effect of the Invention] The liquid crystal alignment treatment agent of the present invention can be obtained as a liquid crystal alignment film by a relatively simple method. In the case where the pretilt angle of the liquid crystal is increased, the liquid crystal can be aligned in the vertical direction at a low use ratio. Further, when the weak solvent is mixed in the coating liquid of the liquid crystal alignment treatment agent, precipitation is unlikely to occur. When applied to a large substrate, a liquid crystal alignment film can also be formed, and a high voltage holding ratio can be obtained, and even after exposure at a high temperature for a long φ exposure, the residual charge accumulated by the DC voltage is relaxed and the alignment film is quickly formed. Therefore, the liquid crystal display element having the crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can be applied to a liquid crystal television having excellent reliability, large and high definition, and the like. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The present invention contains a ruthenium amine containing a diamine compound (A), a diamine compound (and a diamine component of the diamine compound (C) and a tetracarboxylic dianhydride: 2) 23), that is, a liquid crystal alignment treatment agent obtained by using a liquid crystal alignment treatment agent obtained by using a liquid crystal alignment treatment agent of a copolymer obtained by a liquid crystal screen of a uniform time, -15-201030055, and further having the liquid crystal alignment Liquid crystal display element of the film. In this case, the diamine compound (A) is a diamine compound represented by the formula [1], and the diamine compound (B) is a diamine compound represented by the formula [2]. The diamine compound (C) has a carboxyl group in the molecule. Amine compound. The diamine compound (A) used in the present invention is a specific diamine (hereinafter also referred to as a specific diamine (A)) having a substituent having a property of increasing the pretilt angle in the side chain. Therefore, the liquid crystal alignment agent obtained by using the specific diamine (A) can align the liquid crystal in the vertical direction even when the specific diamine (A) is at a lower use ratio. Further, by reducing the use ratio, the solubility of the organic solvent of the polymer is increased, and even when a weak solvent is mixed in the coating liquid of the liquid crystal alignment agent, precipitation is unlikely to occur. The diamine compound (B) (hereinafter also referred to as a specific diamine (B)) used in the present invention has a nitrogen-containing aromatic heterocyclic ring in a side chain. Since the nitrogen-containing aromatic heterocyclic ring functions as a charge jump side by the conjugated structure, the liquid crystal alignment film promotes the movement of charges. Further, the nitrogen-containing aromatic heterocyclic ring is bonded to the carboxyl group of the diamine compound (C) (hereinafter also referred to as a specific diamine (C)) by a salt interaction or a so-called hydrogen bond electrostatic interaction. A charge shift is caused between a carboxyl group and a nitrogen-containing aromatic heterocyclic ring. Therefore, the charge moved to the nitrogen-containing aromatic heterocyclic moiety can be efficiently moved in the intramolecular or intermolecular phase of the copolymer. When the liquid crystal alignment treatment agent of the present invention is used as the liquid crystal alignment film -16-201030055, the liquid crystal alignment angle is increased, and the liquid crystal can be aligned in the vertical direction even at a low usage ratio. Further, when a weak solvent is mixed in the coating liquid of the liquid crystal alignment agent, precipitation does not easily occur. Further, a liquid crystal alignment film having a high voltage holding ratio and a rapid relaxation of the residual electric charge accumulated by the DC voltage even after long-time exposure at a high temperature can be obtained. The compounds used in the present invention are explained below.

<Diamine compound (A) > The diamine compound (A) used in the present invention is a diamine compound represented by the following formula [1]. [化10]

In the formula [1], in the formula [1], P is an integer of 0 or 1, X! is a phenylene group, preferably a 1,4-phenylene group, and X2 is a phenylene group, preferably 1,4. - Stretching phenyl' or a cyclohexyl extended phenyl group, preferably 1,4-cyclohexylene, and X3 is a cyclohexyl extended phenyl group, preferably an I, 4-cyclohexylene group. The phenyl group and the cyclohexylene group may have a substituent. X4 is an alkyl group having 3 to 12 carbon atoms, a gas-base group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. The alkyl group, the fluoroalkyl group, the alkoxy group, and the fluoroalkoxy group may be linear or in a linear form, and may preferably have a linear form or a substituent. The amine compound (A) is preferably a diamine compound (A) having the following formula [1,] or a diamine compound (A,) represented by the following formula [1,]. -17- 201030055 [化11]

[化 12]

Hereinafter, the diamine compound (A') and the diamine compound (A") will be described. <Diamine compound (A') > The diamine compound (A') used in the present invention is a diamine compound represented by the following formula [1']. [Chem. 13]

(In the formula [1'], Χι, x2, x3, and 4 are synonymous with the above formula [1]. The binding position of the amine group in the benzene ring to which the amine group in the formula [1'] is bonded is not limited. . Specific examples include a binding group for a side chain (-CH2O-) '2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3 on the ring. 5 positions. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferable to use 2, 4 position, 2, 5 position, and 3, 5 position. If the ease of synthesis of the diamine compound is further considered, the diamine compound of the formula [1'] in the 2,4 position or the 2,5 position is preferably the following formula [i, a] and formula [1] The diamine compound represented by 'b' is preferred because it has a large effect of increasing the pretilt angle of the liquid crystal at a low use ratio. Particularly, the diamine represented by the formula [l, a] is more preferable because it is excellent in the effect. [Chem. 14]

X5 in the formula [l'a] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. . Among them, X5 is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, particularly preferably an alkyl group having 3 to 7 carbon atoms. Further, the cis-trans isomerism of the 1,4-cyclohexylene group in the formula [1'a] is preferably a trans-isomer. ® [Chem. 15]

X6 in the formula [l'b] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. . Wherein X4 is an alkyl group having a carbon number of 3 to 12 or a fluoroalkyl group having a carbon number of 3 to 12, preferably -19 - 201030055 ', preferably an alkyl group having a carbon number of 3 to 12, particularly preferably a carbon number of 3 to 7. Alkyl. Further, the cis-trans isomerism of the 1,4-cyclohexylene group in the formula [l'b] is preferably a trans isomer. A preferred specific example of the diamine compound represented by the formula [Γ] of the present invention is a diamine compound represented by the following formula [1] to the formula [l'f]. Further, X5 to X8 in the following formula are each independently an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluorine having 3 to 12 carbon atoms. Alkoxy. Further, X5 to X8 are each independently an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, preferably an alkyl group having 3 to 12 carbon atoms, particularly preferably having a carbon number of 3 to 7. Alkyl. Further, the cis-trans isomerism of the 1,4-cyclohexylene group in the following formula is each a trans isomer. -20- 201030055

[Chemistry 16]

The method for producing the diamine compound of the formula [Γ] is not particularly limited, but a preferred method is as follows. [Π化]

-21 - 201030055 The dinitro compound of the above formula [1, g] is synthesized by subjecting a nitro group to an amine group by a general method. The method for reducing the dinitro compound is not particularly limited, and generally, palladium-carbon, platinum oxide, nickel-plated nickel, platinum black, rhodium-alumina, and platinum sulfide carbon are used as a catalyst, and ethyl acetate and toluene are used. A method of reducing by hydrogen, helium, hydrogen chloride or the like in a solvent such as tetrahydrofuran, dioxane or an alcohol. X!, χ2, X3, and X4 in the formula [l'g] are the same as those defined in the formula [1]. The dinitro compound of the formula [l'g] can be obtained by reacting a compound having a hydroxyl group represented by the following formula [l'h] with dinitrochlorobenzene or the like. Further, Χι, Χ2, χ3, and x4 in the formula [ l'h] are the same as those defined in the formula [1]. ΗΟ-Χ广Χ 2-Χ3-Χ4 [1Ή] The method of producing a compound having a hydroxyl group represented by the formula [l'h] can be carried out by the following reaction formula (1) or reaction formula (2) The invention is produced by the method, and the present invention is not limited thereto. When X2 is 1,4_cyclohexylene, the synthetic route of the reaction formula (1) can be mentioned. X, X3, and X4 in the reaction formula (1) are the same as those defined in the formula [1]. ‘R represents a protecting group such as a methyl group or a benzyl group, and R2 represents a group VIgBr, MgCl or Li. As a reagent used in the dehydration reaction. Examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as P-toluenesulfonic acid, and acid anhydrides such as acetic anhydride or trifluoroacetic anhydride. As the reduction reaction, a hydrogenation reaction using palladium (Pd) or platinum (Pt) or the like as a catalyst or contact reduction using a metal such as iron, tin or zinc can be used. The reaction of the deprotection group may be a desorption reaction using a methyl group of boron tribromide (BBr3) or a debenzylation reaction using a hydrogenation such as a Pd catalyst.

[Chem. 19]

[Vh-a] Cl'h-c] dehydration

Restore [fh-d]

[l'h-β] deprotection group

X4 Crh-f] Reaction Formula (1) When X2 is a 1,4-phenylene group, a synthetic route of the reaction formula (2) can be mentioned. X^Xs and X4 in the reaction formula (2) are the same as defined in the formula [1], the heart represents a protecting group such as a methyl group or a benzyl group, and T2 represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group. a 'trifluoromethanesulfonyloxy group, B(OH)2, MgBr, MGCl or Li, etc., T3 represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoromethanesulfonyloxy group, an anthracene (ΟΗ) 2, MgBr, MgCl or Li, and the like. The reaction of the deprotection group may be a desorption reaction using a methyl group of ΒΒγ3 or a debenzylation reaction by hydrogenation using a Pd catalyst or the like. -23- 201030055 [化 20] Τι/〇νχΓΤ2 [1'h-g]

Tl^cTXl

Crh-i] xrX4 deprotection group HO〆

X4 [Vh-j] χΓ

Reaction Formula (2) <Diamine Compound (A'1) > The diamine compound (A,) used in the present invention is a diamine compound represented by the following formula [1". [Chem. 21]

In the formula [1"], "丨" is I, 4-phenylene or 1,4-cyclohexylene. The 1,4-phenylene group and the 1,4-cyclohexylene group may have a substituent as necessary. Χι'2 is a fluorenyl group having 3 to 12 carbon atoms, a fluorine-based group having 3 to 12 carbon atoms, a tertiary oxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. The alkyl group, the fluoroalkyl group, the alkoxy group, and the fluoroalkoxy group may be linear or branched, but may be linear or may have a substituent. The binding position of the amine group in the benzene ring to which the amine group in the formula [Γ'] is bonded is not limited. Specific examples include a binding group for a side chain (-ο-α - 201030055), a 2, 3 position, a 2, 4 position, a 2, 5 position, a 2, 6 position, and a 3, 4 position on the benzene ring. , 3, 5 position. Among them, from the viewpoint of reactivity in synthesizing poly-proline, 'the position of 2, 4, 2, 5, and 3, 5 is preferable. In view of the ease of synthesis of the diamine compound, it is preferred to use a 2, 4 position or a 2, 5 position. In the diamine compound of the formula [I1'], the diamine compound represented by the following formula [l, a] and the formula [l, b] is a 1,4-trans-cyclohexylene group. It is preferable that the effect of increasing the pretilt angle of the liquid crystal at a small rate is large. particular

The effect of the diamine compound represented by the formula [l, 'a] is excellent and more preferable. [化22]

X in the formula [1" a, '3 is an alkyl group having 3 to 12 carbon atoms, a fluorine-based group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or fluorine having a carbon number of 3 to 12 Alkoxy. Wherein X', 3 is an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms; preferably an alkyl group having 3 to 12 carbon atoms, particularly preferably an alkyl group having 3 to 7 carbon atoms. base. And the cis-trans isomerism of the 1,4-cyclohexylene group in the formula [l,, a] is preferably a trans-isomer.

-25- 201030055 Gas base, carbon It is better to use χΊ, preferably carbon, formula [l', b]. The X, 5, X, and * groups of the formula [1 ''c] of the present invention, and the carbon number of 3 to X are preferably X''5 ~ > alkyl groups, and alkyl groups. Further, it is an alkoxy group having a trans isomer number of 3 to 12 or a fluoroalkoxy group having a carbon number of 3 to 12. The alkyl group having 3 to 12 carbon atoms or the fluoroalkyl group having 3 to 12 carbon atoms is preferably an alkyl group having 3 to 12 carbon atoms, particularly preferably an alkyl group having 3 to 7 carbon atoms. And the cis-trans isomerism of the 1,4-extended cyclohexyl group is as shown in the formula [1"f] in the preferred embodiment of the diamine compound represented by the trans-formula [1" Amine compound. Further, in the following formula, t each independently represents an alkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms of fluoroalkane-12, or a fluoroalkoxy group having 3 to 12 carbon atoms. The alkyl group independently having a carbon number of 3 to 12 or the fluorine having a carbon number of 3 to 12 is preferably an alkyl group having 3 to 12 carbon atoms, particularly preferably having a carbon number of 3 to 7 in the following formula: 1,4- The cis-trans isomerism of the cyclohexyl group is extended. -26- 201030055

[Chem. 24]

The method for producing the diamine compound represented by the formula [1 ''] is not particularly limited, and a preferred method is as follows. [Chem. 25]

Crg] x" 2 The dinitro compound of the above formula [r'g] is synthesized and converted into an amine group by a general method. The method for reducing the dinitro compound is not limited to -27-201030055. Generally, palladium-carbon, platinum oxide, nickel-plated nickel, platinum black, ruthenium-alumina, and platinum sulfide carbon are used as catalysts in ethyl acetate. A method of reducing by hydrogen, helium, hydrogen chloride or the like in a solvent such as toluene, tetrahydrofuran, dioxane or an alcohol. X, and X''2 in the formula [l, g] are the same as those defined in the formula [1,]. The dinitro compound of the formula [l''g] can be obtained by reacting a compound having a hydroxyl group represented by the following formula [1 " h] with dinitrochlorobenzene or the like. Further, X"] and Χ·'2 in the formula [r'h] are the same as those defined in the formula [1"].

The method for producing a compound having a hydroxyl group represented by the formula [r'h] can be produced by the following reaction formula (1) or the reaction formula (2), but the present invention is not limited thereto. When Χ"ι is 1,4-cyclohexylene, the synthetic route of the reaction formula (1) can be mentioned. X"2 in the reaction formula (1) is the same as defined in the formula [1''], 1 represents a protecting group such as a methyl group or a benzyl group, and R2 represents a hydrazine such as MgBr, MgCl or Li as a dehydration reaction. Examples of the reagent include organic acids such as hydrochloric acid and sulfuric acid, organic acids such as P-toluenesulfonic acid, and acid anhydrides such as acetic anhydride or trifluoroacetic acid. The reduction reaction may be a hydrogenation reaction using palladium (Pd) or uranium (pt) or the like as a catalyst, or a contact reduction reaction using a metal such as iron, tin or dry. -28-201030055 The reaction of the deprotection group is a decarboxylation reaction using a methyl group of boron tribromide (BBr3) or a debenzylation reaction by hydrogenation using a Pd catalyst or the like. [化27]

In the reaction formula (1), when |1 is a 1,4-phenylene group, the synthesis route of the reaction formula (2) can be mentioned. X"2 in the reaction formula (2) is the same as defined in the formula [1"], h represents a protecting group such as a methyl group or a benzyl group, and T2 represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, Trifluoromethanesulfonyloxy, B(0H)2, MgBr, MgC1 or Li, etc., T3 represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a B(OH) group. 2. MgBr, MgCl or Li, etc. The reaction of the deprotection group is exemplified by a desorption reaction using a methyl group of ruthenium 3 or a debenzylation reaction by hydrogenation using a Pd catalyst or the like. -29 - 201030055 [化 28]

<Diamine compound (B) > The diamine compound (B) used in the present invention is represented by the following formula [2]

[化29]

[2]

In the formula [2], 丫] is -〇-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, -OCO-, -CON(CH3)-, or -N (CH3)CO-, Y2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group 'Υ3 is a single bond, -Ο-, -ΝΗ-, -N(CH3) )-, -CONH·, -NHCO-, -COO-, -OCO-, -CON(CH3)-, -N(CH3)CO-, or -〇(CH2)m- (m is an integer from 1 to 5) ) Y4 is a gas-containing aromatic heterocyclic ring, and η is an integer of 1 to 4. The binding position of the two amine groups (-ΝΗ2) in the formula [2] is not limited. Specifically, a binding group for a side chain (γι), 2, 3 positions on the benzene ring, -30-201030055, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3, 5 positions. Among them, the position of 2, 4 position, 2, 5 position, and 3, 5 is preferable from the viewpoint of reactivity in synthesizing polyamic acid. Further, it is considered that the ease of synthesizing the diamine compound is more preferably 2, 4 positions or 2, 5 positions. In the formula [2], 丫] is -〇-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2〇-, -OCO- '-CON(CH3)-, or - N(CH3)C〇-. Among them, a diamine compound is preferably synthesized by -?, -NH-, -CONH-, -NHCO-, -CON(CH3)-, -CH20-, or -OCO-. Particularly preferred, -Ο- '-NH- ' -CONH- ' -NHCO- ' -CON(CH3>- ' ^ -CH2〇-〇[2], Y2 is a single bond, carbon number 1~20 An aliphatic hydrocarbon group, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched, or may have an unsaturated bond. Preferably, the carbon number is 1 to 10. The aliphatic hydrocarbon group. Specific examples of the non-aromatic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a cyclodecane ring. , cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, ring ten Octacyclo ring, cyclopentadecane ring, ring 20 yard ring, tricyclic 20th ring, tricyclotetracosane ring, bicycloheptane ring, decahydronaphthalene ring, raw spinel ring, adamantane ring, etc. Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a phenalylene ring, and the like. Preferably, Y2' can be exemplified by a single bond, a carbon number ^~^ Or branched alkyl, unsaturated alkyl 1 to 10, cyclopropyl ring 201030055, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, raw spinel ring, diamond An alkane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, preferably a single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a raw spinylene ring, an adamantane ring, a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, more preferably a single bond, a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexane ring, a benzene ring or a naphthalene ring, particularly preferably a single bond, a linear or branched alkyl group having a carbon number of 1 to 5, or a benzene ring. In the formula [2], Y3 is a single bond, -ο-, -NH-, -N ( CH3)-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH3)_, -N(CH3)CO-, or -0(CH2)m-(m is 1~5 Integer), preferably a single bond, -0-, -NH-, -CONH-, -NHCO·, -COO-, -OCO-, or -0((^2)1„-(111 is 1~5 Integer), more preferably a single bond, -0-, -:^11-, -C Ο N Η -, - NHC Ο -, - C Ο 〇- ' - 0 c Ο -, or -0 ( c Η 2) m - ( m is an integer from 1 to 5), particularly preferably a single bond, -〇·, -CONH- -NHCO-, -C00-, -0C0-, or - 0(CH2)m- (m is an integer of 1 to 5). In the formula [2], Y4 is a nitrogen-containing aromatic heterocyclic ring, and is selected from the group consisting of the following A nitrogen-containing aromatic heterocyclic ring having at least one structure of the group of the formula [2a], the formula [2b], and the formula [2c]. [Chemical Formula 30] /N-Α·| [2a] [2b] [2c] (In the formula [2c], Ai is a linear or branched alkyl group having 1 to 5 carbon atoms). Specific examples of the nitrogen-containing aromatic heterocyclic ring include a pyrrole ring, a pyrene-32-201030055 ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, and a pyrazole. Phytol ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triterpene ring, oxazine ring, benzazole Ring, benzimidazole ring, chinoline ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, spirobifluorene ring, 叱η ring and the like. In the formula [2], preferred examples of γ4 include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, and a different form. Quinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolin ring, triazole ring, pyrazine ring, benzimidazole ring, benzo Imidazole ring, chinoline ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, preferably pyrrole ring, imidazole Ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, azole ring, pyridazine ring, pyrazoline ring 'triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzophenone Imidazole ring, benzimidazole ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, 卩it D ring, mute ring, azine ring, triazine ring, tris(s) ring, azoazine ring, benzene The imidazole ring and the benzimidazole ring are particularly preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. Further, Y3 is bonded to a substituent which is not adjacent to the formula [2a], the formula [2b], and the formula [2c] contained in Y4. In the formula [2], η is an integer of from 1 to 4, and from the viewpoint of reactivity with tetracarboxylic dianhydride, it is preferably from 1 to 3. The combination of the preferred Υ!, Υ2, Υ3, Υ4, and η in the formula [2] is Υ! -33- 201030055 is -Ο-, -NH-, -CONH-, -NHCO-, -CON(CH3 )-, -CH2〇-, or - OCO-' Y2 is a linear or branched alkyl group having a carbon number of 1 to 10, an unsaturated mechanical group having a carbon number of 1 to 10, a cyclopropane ring, a cyclobutane ring, and a cyclopentane. An alkane ring, a cyclohexane ring, a cycloheptane ring, a raw spinylene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, or an anthracene ring, γ3 is a single bond, -〇-, - ]^11-, -(:0>^-, -NHCO-, -C〇〇_, -〇c〇_, or _〇(CH2)m_(m is an integer from 1 to 5) 'Y4 is a pyrrole ring , imidazole ring, oxazole ring, thiazole ring, pyrazole ring, oral ratio steep ring, pyrimidine ring, quinoline ring, porphyrin ring, isoquinoline ring, indazole ring, anthracene ring, thiadipine Oxazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline a ring, an anthracene ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, or an acridine ring, and η is 1 to 2. Preferably, it is in the formula [2]. The combination of L, γ2, Υ3, Υ4, and η is, Υι is -〇-, -NH-, -CONH-, -NHCO-, -CH20-, or -OCO-, and Y2 is a straight carbon number of 1 to 10. Chain or branched alkyl, unsaturated 1 to 10 carbon, ring ring, original weak ring, diamond ring, benzene ring, naphthalene ring, anthracene ring, or anthracene ring, Υ 3 is a single bond, - 〇-, -NH-, -CONH-, -NHCO-, -COO-, -OCO-, or - 〇(CH2)m- (m is an integer from 1 to 5), Y4 is a pyrrole ring, an imidazole ring, a pyrene An azole ring 'pyridine ring, pyrimidine ring, pyrazoline ring, oxazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, ring, pyrazine ring, benzimidazole ring, or benzene And the imidazole ring 'η is 1 to 2. More preferably, the combination of Υ, Υ2, Υ3, Υ4, and η in the formula [2] is, Υι is -Ο-, -NH-, -CONH ...-NHCO-, -CON(CH3)-, 201030055 -CH20-, or - OCO-, γ2 is a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexane ring, a benzene ring, or a naphthalene ring, and γ3 is a single bond, - 〇_, -C〇NH-, -NHCO-, _C00_, -OCO-, or - 〇(CH2)m- (m is an integer from 1 to 5), 丫4 is a Raleigh ring, an imidazole ring, a pyrazole ring Pyridine ring, pyrimidine , Pyridazine ring cried, Xiao three ring, a triazole ring, a pyrazine ring, an imidazole ring benzyl, or benzimidazole ring, [eta] is 1 or 2 °

The combination of γι, γ2, Υ3, Υ4, and η in the special formula [2] is ' Yi is -◦·, -NH-, -C〇NH-, -NHCO-, -CON(CH3)_, or -ch2o-, Y2 is a single bond, a linear or branched alkyl group having a carbon number of 1 to 5, a benzene ring, γ3 is a single bond, _ 〇-, -C Ο Ν Η -, - NHC Ο -, - C Ο 〇 -, - 〇c 〇-, or -0(CH2)m- is an integer from 1 to 5)' Υ4 is a slightly ring, a oxime ring, a 嗖 ring, a pyridine ring, or a pyrimidine ring, η is 1 ~3. Preferably, the combination of γι, Υ2, Υ3, Υ4, and η in the formula [2] is as shown in the following Tables 1 to 8.

-35- 201030055 [Table η Υι Υ2 Υ3 Υ4 A-1 -Ο- Linear or branched alkyl single bond pyrrole ring A-2 -Ο - Carbon number 1~5 straight chain or branch Single-bonded imidazole ring A-3 -ο- straight or branched alkyl single bond pyrazole ring A-4 -ο- carbon number 1~5 straight or branched alkyl single bond Ring A-5 -0- straight or branched alkyl single bond pyrimidine ring A-6 -ΝΗ - carbon number 1~5 straight or branched alkyl single bond pyrrole ring A-7 -ΝΗ - a linear or branched alkyl single bond of a carbon number of 1 to 5, an imidazole ring A-8 - fluorene - a linear or branched alkyl group having a carbon number of 1 to 5, a pyrazole ring A-9 - ΝΗ - a carbon number of 1 5 linear or branched alkyl single bond shaky steep ring A-10 - ΝΗ - carbon number 1 to 5 linear or branched alkyl single bond pyrimidine ring A-11 -CONH- carbon number 1 to 5 linear or Branched alkyl single bond pyridine ring A-12 -CONH- linear or branched alkyl single bond imidazole ring A-13 -CONH- straight or branched alkyl single bond having 1 to 5 carbon atoms Pyrazole ring A-14 -CONH- a straight or branched alkyl single bond having a carbon number of 1 to 5 than a steep ring A-15 -CONH- a straight or branched alkyl single bond having 1 to 5 carbon atoms Pyrimidine ring A-16 -NHCO- straight or branched alkyl single bond pyrrole ring A-17 -NHCO- having a carbon number of 1 to 5 straight or branched alkyl single bond imidazole ring A-18 - NHCO- linear or branched alkyl single bond pyrazole ring A-19 -NHCO- having a carbon number of 1 to 5, straight or branched alkyl single bond having 1 to 5 carbon atoms _ pyridine ring A-20 -NHCO- carbon number 1 to 5 linear or branched alkyl single bond pyrimidine ring 2] Υι Y2 γ3 Υ4 Α-21 -ch2o- straight or branched alkyl single bond pyrrole Α-22 -ch2o- carbon having 1 to 5 carbon atoms 1 to 5 linear or branched alkyl single bond imidazole ring Α-23 -ch2o- straight or branched alkyl single bond pyrazole ring Α-24 -ch2o- carbon number 1 to 5 Linear or branched alkyl single bond pyridine ring Α-25 -ch2o- straight or branched alkyl single bond pyrimidine Α-26 -con(ch3)- carbon number 1~5 straight chain or Branched alkyl single bond pyrrole ring Α-27 -CON(CH3)- straight or branched alkyl single bond imidazole ring Α-28 -con(ch3) - carbon number 1~5 linear or Branched alkyl single bond pyrazole ring Α-29 -con(ch3)- linear or branched alkyl single bond having a carbon number of 1 to 5 ring Α-30 -CON(CH3)- carbon number 1 ～5 linear or branched alkyl single bond pyrimidine ring 201030055 [Table 3] Yi Y2 Y3 Y4 A-31 -0- phenylcyclopyrrole ring A-32 -0- phenylcycloimidazole ring A-33 -0- benzene Cyclopyrazole ring A-34 -0- phenylcyclopyrrolidine ring A-35 -0- phenyl ring-C0NH-pyrimidine ring A-36 -0- benzene ring-CONH- pyrrole ring A-37 -0- benzene ring- C0NH- Imidazole ring A-38 -0- phenyl ring-C0NH-pyrazole ring A-39 -0 benzene ring-NHC0- pyridine ring A-40 -0- benzene ring-NHC0- pyridinium ring A-41 -0- Benzene ring-NHCO-pyrrole ring A-42 benzene ring-NHC0- imidazole ring A-43 benzene ring-COO-pyrazole ring A-44 benzene ring-COO- pyridine ring A-45 benzene ring-COO-pyrimidine ring A- 46 -0- phenyl ring-COO-pyrrole ring A-47 benzene ring-0C0- imidazole ring A-48 benzene ring-OCO- pyridinium ring A-49 -0- benzene ring-OCO- pyridyl ring A-50 - O- phenyl ring-OCO-pyrimidine ring A-51 -0- phenyl ring-0-(CH2)m- (m: an integer from 1 to 5) pyrrole ring A-52 -0-benzene ring-0-(CH2) M- (m: an integer of 1 to 5) imidazole ring A-53 -0-benzene ring-0-(CH2)m- (m: an integer of 1 to 5) pyrazole ring A-54-o-benzene ring- 0-(CH2)m- (m: an integer from 1 to 5) Pyridinium ring A-55 -NH-benzene ring-0-pyrrole ring A-56 -NH-benzene ring Azole ring A-57 -NH- phenyl ring-0-pyrazole ring A-58 -NH- phenyl ring-0-pyridine ring A-59 -NH-benzene ring-CONH-pyrimidine ring A-60 -NH-benzene ring -CONH- Pyrrole ring-37- 201030055 Table 4]

Yi Y2 γ3 Y4 A-61 -NH- phenyl ring-CONH- oxime ring A-62 -NH- benzene ring-CONH- pyridinium ring A-63 -NH- benzene ring-NHCO- pyridine _ A-64 -NH - Benzene ring-NHCO-pyrimidine ring A-65 -NH- phenyl ring-NHCO- pyrrole ring A-66 -NH- benzene ring-NHCO- oxime ring A-67 -NH- benzene ring-COO- 哩 ring A -68 -NH-benzene ring-COO-pyridine ring A-69 -NH-benzene ring-COO-pyrimidine ring A-70 -NH-benzene ring-COO-pyrrole ring A-71 -NH-benzene ring-OCO-imidazole Ring A-72 -NH- phenyl ring-OCO-pyridinium ring A-73 -NH-benzene ring-OCO-pyridine ring A-74 -NH- Lai-OCO- circadian ring A-75 -NH- benzene ring- 0-(CH2)m- (m: an integer of 1 to 5) pyrrole ring A-76 -NH-benzene ring-0-(CH2)m- (m: an integer of 1 to 5) imidazole ring A-77-NH - Benzene ring-0-(CH2)m- (m: an integer of 1 to 5) Pyrazole ring A-78 -NH- phenyl ring-0-(CH2)m- (m: an integer of 1 to 5) Steep ring 201030055 [Table 5] Yi Y2 Y3 Y4 A-79 -CONH- Phenylcyclopyrrole ring A-80 -CONH- Benzene ring-0- Imidazole ring A-81 -CONH- Phenylpyrazole ring A-82 -CONH - Benzene ring-0-pyrrole ring A-83 -CONH- phenyl ring-CONH-pyrimidine ring A-84 -CONH- phenyl ring-CONH- pyrrole ring A-85 -CONH- phenyl ring-CONH- Azole ring A-86 -CONH- phenyl ring-CONH- pyridinium ring A-87 -CONH- benzene ring-NHCO- pyridine ring A-88 -CONH- phenyl ring-NHCO-pyrimidine ring A-89 -CONH- benzene ring -NHCO- Pyrrole ring A-90 -CONH- Benzene ring-NHCO- Imidazole ring A-91 -CONH- Benzene ring-COO- Pyrazole ring A-92 -CONH- Benzene ring-COO-pyridyl A-93 -CONH - Benzene ring-COO-pyrimidine ring A-94 -CONH- phenyl ring-COO-pyrrole ring A-95 -CONH- benzene ring-OCO- imidazole ring A-96 -CONH- benzene ring-OCO-pyrazole ring A- 97 -CONH- phenyl ring-OCO- pyridine ring A-98 -CONH- benzene ring-OCO-pyrimidine ring A-99 -CONH- phenyl ring-0-(CH2)m- (m: an integer of 1~5) pyrrole Ring A-100 -CONH- phenyl ring-0-(CH2)m- (m: an integer from 1 to 5) imidazole ring A-101 -CONH- phenyl ring-0-(CH2)m- an integer) pyrazole ring A-102 -CONH- phenyl ring-0-(CH2)m- (m: an integer from 1 to 5) pyridine ring A-103 -NHCO- phenylcyclopyrrole ring A-104 -NHCO- phenylcycloimidazole ring A-105 -NHCO- phenylcyclopyrazole ring A-106 -NHCO- phenylcyclopyridinium π ring A-107 -NHCO- phenyl ring-CONH- pyridine _ A-108 -NHCO- phenyl ring-CONH- pyrrole ring A-109 - NHCO- Ben Bad-CONH- Imidazole Ring A-110 -NHCO- Benzene Ring-CONH- Pyrazole Ring-3 9- 201030055 [Table 6]

Yl Y2 Y3 Y4 A-lll -NHCO- phenyl ring-NHCO- pyridyl ring A-112 -NHCO- benzene ring-NHCO- pyrimidine ring A-113 -NHCO- benzene ring-NHCO- pyrrole ring A-114 -NHCO- Benzene ring-NHCO-imidazole ring A-115 -NHCO- benzene ring-COO-pyrazole ring A-116 -NHCO- Lai-COO- pyridox ring A-117 -NHCO- benzene ring-COO- pyridine _ A-118 -NHCO- Lai-COO- Pyrrole ring A-119 -NHCO- Benzene ring-OCO- Imidazole ring A-120 -NHCO- Benzene ring-OCO- Pyrazole ring A-121 -NHCO- Benzene ring-OCO- Shame steep ring A-122 -NHCO- phenyl ring-OCO-pyrimidine ring A-123 -NHCO- phenyl ring-0-(CH2)m- (m: an integer from 1 to 5) pyrrole ring A-124 -NHCO-benzene ring-0 -(CH2)m- (m: an integer from 1 to 5) oxime ring A-125 -NHCO- phenyl ring-0-(CH2)m- (m: an integer from 1 to 5) pyrazole ring A-126 - NHCO- phenyl ring-0-(CH2)m- (m: an integer from 1 to 5) mouth to steep ring 201030055 [Table 7]

Yi Y2 Y3 Y4 A-127 -ch2o- phenylcyclopyrrole ring A-128 -ch2o- phenyl ring-0- imidazole ring A-129 -ch2o- phenyl ring-0-pyridinium ring A-130. -ch2o- benzene ring -0- pyridine ring A-131 -ch2o-benzene ring-CONH- 啼π-ring ring A-132 -ch2o-benzene ring-CONH- pyrrole ring A-133 -ch2o-benzene ring-CONH-imidazole ring A-134 - Ch2o- phenyl ring-CONH-pyrazole ring A-135 -ch2o- benzene ring-NHCO- shame steep ring A-136 -ch2o- benzene ring-NHCO-pyrimidine ring A-137 -ch2o- benzene ring-NHCO- pyrrole ring A-138 -ch2o- phenyl ring-NHCO- imidazole ring A-139 -ch2o- benzene ring-COO-pyrazole ring A-140 -ch2o- benzene ring-COO- 啦口定环 A-141 -ch2o- benzene ring -COO-pyrimidine ring A-142 -ch2o- phenyl ring-COO- pyrrole ring A-143 -ch2o- phenyl ring-OCO- oxime ring A-144 -ch2o- phenyl ring-OCO-pyrazole ring A-145 - Ch2o- benzene ring-OCO- port ratio D ring A-146 -ch2o- benzene ring-OCO- squirrel ring A-147 -ch2o- benzene ring-0-(CH2)m- (m: l 〜5 integer Pyridine ring A-148 -ch2o-benzene ring-0-(CH2)m- (m: an integer of 1 to 5) imidazole ring A-149 -ch2o-benzene ring-0-(CH2)m- (m: l an integer of ～5) pyrazole ring A-150 -ch2o-benzene ring-0-(CH2)m- (m:l 〜5 Number of ϋ ϋ steep ring A-151 -CON(CH3)- phenyl ring-0-pyrrole ring A-152 -CON(CH3)- phenylcycloimidazole ring A-153 -con(ch3)- phenylcyclopyrazole ring A -154 -CON(CH3)- phenyl ring mouth ring A-155 -CON(CH3)-benzene ring-CONH- 唆周环201030055 Table 8] Υι Y2 Ys Y4 A-156 -CON(CH3)- benzene ring -CONH-pyrrole A-157 -CON(CH3)-benzene ring-CONH-imidazole ring A-158 -CON(CH3)-benzene ring-CONH-pyrazole ring A-159 -CON(CH3)-benzene ring- NHCO-pyridine ring A-160-CON(CH3)-benzene ring-NHCO- pyrimidine ring A-161 -CON(CH3)-benzene ring-NHCO- pyrrole ring A-162 -CON(CH3)-benzene ring-NHCO - Imidazole ring A-163 -CON(CH3)-benzene ring-COO-pyrazole ring A-164 -CON(CH3)-benzene ring-COO-pyridyl ring A-165-CON(CH3)-benzene ring-COO - Pyrimidine ring A-166 -CON(CH3)-benzene ring-COO-pyrrole ring A-167 -CON(CH3)-benzene ring-OCO-imidazole ring A-168 -CON(CH3)-benzene ring-OCO-pyridyl Azole ring A-169 -CON(CH3)-benzene ring-OCO- port ratio steep ring A-170 -CON(CH3)-benzene ring-OCO-pyrimidine ring A-171 -CON(CH3)-benzene ring•0 -(CH2)m- (m: an integer from 1 to 5) Pyrrole ring A-172 -CON(CH3)-benzene ring•0-(CH2)m- (m: an integer of 1 to 5) Azole ring A-173 -CON(CH3)-benzene ring-0-(CH2)m- (m: an integer from 1 to 5) Pyrazole ring A-174 -CON(CH3)-benzene ring-0-(CH2) M- (m: an integer from 1 to 5) pyridine ring

The method for producing the diamine compound of the formula [2] of the present invention is not particularly limited, and a preferred method is as follows. [化31]

O2n The dinitro compound represented by the above formula [2d] is synthesized, and the nitro group is converted into an amine group by a general method. The method for reducing the dinitro compound is not particularly limited, and generally, palladium-carbon, platinum oxide, nickel nickel, platinum black, ruthenium--42-201030055 alumina, platinum sulfide carbon, or the like is used as a catalyst. A method in which a solvent such as an ester, toluene, tetrahydrofuran, dioxane or an alcohol is reduced by hydrogen, helium, hydrogen chloride or the like. The dinitro compounds of the formula [2d] in the formula [2d], Υ, Υ2, Υ3, Υ4, and η have the same meaning as the definition of the formula [2], and the combination of 23 and ¥4, The method of combining the dinitro group with the dinitro moiety, the bonding of the dinitro moiety, the bonding of the indole 2, and the subsequent bonding of the crucible 3 and the crucible 4 are carried out. Hey! Is -0-(ether bond), -ΝΗ-(amine bond), -N(CH3)-(methylated amine bond), -CONH-(melamine bond), -NHCO- (trans-guanamine bond) , -CH20- (methyl ether bond), -OCO- (trans ester bond), -CON(CH3)- (N-methylated guanamine bond), or -N(CH3)CO- (N - A binding group such as a methylated trans-amine bond, which is generally formed by an organic synthesis method. For example, when Y i is an ether or a methyl ether bond, a corresponding halogen derivative containing a dinitro group and a hydroxy derivative containing γ 2 , γ 3 and ¥ 4 are reacted in the presence of a base. A method, or a method comprising reacting a hydroxy derivative of a dinitro group with a halogen-substituted derivative containing hydrazine 2, hydrazine 3 and hydrazine 4 in the presence of a base. The case of the amine bond may be a method in which a corresponding halogen derivative containing a dinitro group and an amine-substituted derivative containing γ2, γ3 and γ4 are reacted in the presence of a base. The ester bond may be a method in which a corresponding dinitro acid chloride-containing acid and a hydroxy-substituted derivative containing ruthenium 2, γ3 and ruthenium 4 are reacted in the presence of a base. -43- 201030055 In the case of the trans acetal bond, a corresponding one of a nitro group-containing derivative and an acid chlorided object containing γ2, γ3 and Υ4 may be reacted in the presence of the test. The case of the guanamine bond may be a method in which a corresponding dinitro acid chloride is contained and an amine substituent containing ruthenium 2, iridium 3 and ruthenium 4 is reacted in the presence of ruthenium. The case of the trans-amine bond may be a method in which an amine group-containing substituent containing a dinitro group and an acid chloride-containing object containing γ2, γ3 and Υ4 are reacted in the presence of a base. Specific examples of the dinitro group-containing halogen derivative and the dinitro group-containing derivative include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, and 2,4-dinitro group. Fluorobenzene, 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5 -dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4 -dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol , 2,4-dinitrophenylacetic acid, and the like. The halogen derivative containing a dinitro group and the derivative containing a dinitro group may be used singly or in combination in consideration of the viewpoint of the availability of the raw material and the reaction. <Diamine compound (C) > The diamine compound (C) used in the present invention is a diamine compound having a carboxyl group in the molecule. The specific structure is not particularly limited, but a compound of the formula [-44 - [3] 201030055 3] is preferred. (C00H)k η2ν, νη2 In the formula [3], Ζ! is an organic group having an aromatic ring having 6 to 30 carbon atoms, and is an integer of 1 to 4.

When the compound of the formula [3] is specifically represented, a diamine compound of the following formula [3a], formula [3b], formula [3c], formula [3d] and formula [3e] can be given. [化33]

(CH2)m4COOH Η2Ντ>Γ〇~ΝΗ2 (CH2)m5COOH

(CH2)m6COOH

3 [3d]

[3c] H2N-ΟΟΌ, (COOHJm? [3e] In the formula [3a], 1111 is an integer of 1 to 4. In the formula [3b], Z2 is a single bond, -(:112-, -(:2114-, -(:((:113)2-, -CF2-, -C(CF3)-, -0-, -C0-, -NH-, -N(CH3)-, -C0NH-, -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 is -45- 201030055 is an integer of 1 to 4. In the formula [3c], m4 and m5 are each an integer of 1 to 5. In the formula [3d], Z3 is a linear or branched alkyl group having 1 to 5 carbon atoms, and nu is 1 to 5. An integer of 5. In the formula [3e], Z4 is a single bond, -(:112-, -(:2114-, -(:((:113)2-, -CF2-, -C(CF3)-, - Ο-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2〇-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, Or -N(CH3)CO-, m7 is an integer of 1 to 4. m In the above formula [3a], formula [3b], formula [3c], formula [3d], and the diamine compound of the formula [3e], Preferably, in the formula [3, m丨 is an integer of 1 to 2, and in the formula [3b], Z2 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -Ο- , -CO-, -NH-, -N(CH3)-, -CONH-, - NHCO-, -COO-, or -OCO-, m2 and m3 are both an integer integer structure, and in the formula [3e], Z4 is a single bond, -CH2-, -〇-, -CO-, -NH-, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO-, or -OCO-, m7 is a structure of an integer of 1 to 2. Specific examples of the diamine compound (C) include a compound of the formula [3f] to the formula [3n], and the formula [3p]. -46- 201030055

[34]

[化35]

In the formula [3η], :^ is a single bond, -CH2-, -Ο-, -CO-,

-NH -47- 201030055, -CONH-, -NHCO-, _CH20-, o In the formula [3p], B2 is a single bond, '-CONH- ' -NHCO- ' -CH2〇- ' -OCH2-, -COO -, or -OCO- -CH2-, -0-, -CO- '-NH--OCH2-, -COO-, or -OCO-<other diamine compound> In the present invention, without impairing the present invention Under the limitation of the effect, the diamine compound (A), the diamine compound (B), and the diamine compound (C) may be used as a diamine component as a diamine component. The specific examples include the following fluorene-phenylenediamine '2,3,5,6-tetramethyl-ρ-phenylenediamine, 2,5-dimethyl-anthracene-phenylenediamine , m_phenylene diamine, 2,4-dimethyl-m-phenyleneamine, 2,5-diamine toluene, 2,6-diamine toluene, 2,5•diamine phenol, 2, 4. Diamine phenol, 3,5-diamine phenol, 3,5-diaminobenzyl alcohol, 2, [diaminobenzyl alcohol, 4,6-monoamine resorcinol, 4,4' _Diamine biphenyl, 3,3,-dimethyl-4,4-aminobiphenyl, 3,3, dimethoxy-4,4,diamine biphenyl, 3,3, _-Hydroxy-4,4-aminobiphenyl, 3,3,-difluoro-4,4,biphenyl, 3,3,-trifluoromethyl-4,4,-diaminobiphenyl, 3 , 4, _ diaminobiphenyl, 3,3,-diamine biphenyl, 2,2'-diamine biphenyl, 2,3,-diamine biphenyl, 4,4,-diamine Dimethyl methane, 3,3,-diamine diphenylmethane, 3,4,-diamine diphenylmethane, 2,2'-diamine diphenylmethane, 2,3'.diamine diphenyl Methane, 4,4,-diamine diphenyl ether, 3,3,-diamine diphenyl ether, 3,4,-diamine diphenyl ether, 2,2'-diamine diphenyl ether , 2,3,-diamine diphenyl ether, 4,4, sulfonyl di-48 - 20 1030055 aniline '3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane 3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decyl-double (3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-amine, 4,4 '-diamine diphenylamine, 3,3 '-diamine diphenylamine, 3... Diphenylamine, 2,2'-diaminediphenylamine, 2,3'-diaminediphenylamino (4,4'-diaminediphenyl)amine, N-methyl ( 3,3'-diamine diphenyl, N-methyl(3,4'-diaminediphenyl)amine, N-methyl(2,2'-diyl)amine, N-methyl (2, 3'-Diaminediphenyl)amine, 4,4'-diamine, 3,3'-diamine benzophenone, 3,4'-diamine benzophenone, 1,4-, 2 , 2'-diamine benzophenone, 2,3'-diamine benzophenone, 1,5-di-1,6-diamine naphthalene, 1,7-diamine naphthalene, 1,8-diamine Naphthalene, 2,5-diamine naphthylamine naphthalene, 2,7-diamine naphthalene, 2,8-diamine naphthalene, 1,2-bis(4-aminophenylbenzene, 1,2-bis(3-amine) Phenyl) ethane, 1,3-bis(4-aminophenylbenzene, 1,3-bis(3-aminophenyl)propane, I,4-bis(4-aminophenylbenzene, 1,4 - bis(3-aminophenyl)butane, double 3,5-Diethyl-phenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(phenoxy)benzene, 1,4-bis(4-amine Phenyl)benzene, 1,3-bis(4-yl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-amino)benzene, 4,4 '-[ 1,4-phenylene bis(methyl))diphenylamine [1,3-phenylene bis(methyl)]diphenylamine, 3,4'-[ 1,4-double Methyl)]diphenylamine, 3,4'-[1,3-phenylenebis(extended)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)methyl]3, 3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4-extended [(4-aminophenyl)methanone], 1,4-phenylene bis[(3) -amine, bis(, dimethylthiodiphenyl t,-diamine, N-methyl)amine amine diphenyldiphenyldiamine naphthylamine naphthalene, 2,6-diyl)ethyl)propyl)- 4_Amino 4-aminoaminophenylphenoxy, 4,4,-phenylphenylmethyl) phenylamine, phenylbisphenylphenyl-49-201030055) ketone], 1,3-phenylene Bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], I,4-phenylphenylbis(4-amine) Benzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-stretch Phenyl bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4- Aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, anthracene, Ν'·( 1,4-phenylene) bis(4-aminobenzoic acid) Indoleamine, 1;^-(1,3-phenylene)bis(4-aminobenzamide), hydrazine, Ν'-(1,4-phenylene)bis(3-aminobenzene) Methotrexate, hydrazine, Ν'- (1,3-phenylene) bis(3-aminobenzamide), hydrazine, Ν'-bis(4-aminophenyl)-p-benzoquinone Amine, hydrazine, Ν'-bis(3-aminophenyl)terephthalamide, hydrazine, Ν'-bis(4-aminophenyl)m-xylyleneamine, hydrazine, Ν'-double (3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2'-double (4-Aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexa Fluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methyl Phenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, I,4·bis(4-aminophenoxy) Butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminobenzene Oxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-amino Phenoxy)heptane, 1,7-(3-amine-50-201030055-phenoxy)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, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,1 b (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-diaminepropane, 1,4-diaminebutane, 1,5-diamine Pentane, 1,6-diaminehexane, 1,7-diamine heptane, 1,8-diamine octane, 1,9-diamine decane, 1,1 decane-diamine decane, 1 , 1 1-diamine undecane, 1,12-diamine dodecane, and the like. Further, in addition to the diamine compound (A), the diamine compound (B), and the diamine compound (C), a side chain may have an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and the like. The diamine compound of the large cyclic substituent formed. Specifically, a diamine represented by the following formula [DA 1 ] to formula [DA26] can be given. Φ [化36]

[DA3]

In the formula [DA1] to the formula [DA5], it is a 201030055 alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group having 1 or more and 22 or less carbon atoms. [化37]

[DA6] [DA7]

[DA8] [DA9] In the formula [DA6]~[DA9], R2 represents -COO-, -CONH-, -NHCO-'-CH2-, -0-, -CO-, or -NH- represents carbon An alkyl group having 1 or more and 22 or less or a -OCO- having a carbon number of 1 or more and 22 or less, and a fluoroalkyl group of R3;

In the formula [DA10] and the formula [DA11], R4 represents -Ο-, -52--och2-201030055, -CH20-, -COOCH2-, or -CH2OCO., and R5 is an alkyl group having 1 or more and 22 or less carbon atoms. An alkoxy group having 1 or more and 22 or less carbon atoms, a fluorine-containing alkyl group having 1 or more and 22 or less carbon atoms, or a fluorine-containing alkoxy group having 1 or more and 22 or less carbon atoms. [化39]

In the formula [DA12]~[DA14], R6 represents -(3)0-, ·0^^-, -CONH-, -NHCO-, -COOCH2-, _CH2〇C〇-, _CH2〇-, -OCH2-, or -CH2-, r7 is a hospital group having a carbon number of 1 or more and 22 or less, an alkoxy group having 1 or more and 22 or less carbon atoms, a fluorine-containing alkyl group having 1 or more and 22 or less carbon atoms, or a fluorine-containing alkane having 1 or more and 22 or less carbon atoms. Oxygen. [40]

In the formula [DA15] and the formula [DA16], the 'R8 expression system-C〇〇_, -〇C〇-53- 201030055, -CONH-, -NHCO-, -COOCH2-, -CH2OCO-, -CH20-, - OCH2-, -CH2-, -0-, or -NH., R9 is fluoro, cyano, trifluoromethyl, nitro, azo, methyl, ethyl, ethoxy, or Hydroxyl group

Ch3 ch3

-54- 201030055

[Chem. 42] NH,

-55- 201030055 [Chem. 43]

[化44] H2N—(CH^3)

Ch3 Si-·Ο· I ch3

[DA27]

In the formula [DA27], m is an integer of 1 to 10. Other diamine compounds may be used in combination with one type or two or more types in combination with characteristics such as liquid crystal alignment property, voltage holding property, and accumulated electric charge when used as a liquid crystal alignment film. <tetracarboxylic dianhydride> The tetracarboxylic dianhydride used in the present invention is not particularly limited. Specific examples of the carboxylic acid to obtain a tetracarboxylic dianhydride include the following. Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, -56-201030055 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4- Biphenyltetracarboxylic acid, bis(3.4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3.4-dicarboxyphenyl)anthracene, bis(3) , 4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-dual (3, 4-Dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5-pyridine Tetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid Acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiinthylenetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1, 2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane Alkanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutane IV Carboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5 -Tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3,3,0]octane-2,4,6,8 -tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,7,9-tetracarboxylic acid Bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic acid, tricyclo[6·3·0·0<2,6>]undecane-3,5,9, 11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-di-oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- 1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2.5-di-sided oxytetrahydrofuran)-3-methyl -3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]dodec-4,5,9,10-tetracarboxylic acid, 3,5 , 6-tricarboxyfarbornyl-2: 3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like. -57- 201030055 The tetracarboxylic dianhydride can be used in combination with one type or two or more types in combination with liquid crystal alignment properties, voltage retention characteristics, and accumulated charges when used as a liquid crystal alignment film. <Copolymer> The copolymer of the present invention contains a diamine compound (A), a diamine compound (B), a diamine component of the diamine compound (C), and a tetracarboxylic dianhydride. Polylysine, and polyimine obtained by subjecting the polyamic acid to dehydration ring closure. Any of the polyamic acid and the polyimine can be used as a copolymer for obtaining a liquid crystal alignment film. In the liquid crystal alignment film obtained by using the copolymer of the present invention, the more the content ratio of the diamine compound (A) in the above diamine component, the larger the pretilt angle of the liquid crystal. Therefore, the content of the diamine compound (A) in the diamine component is preferably 0.01 to 99 moles per 1 mole of the diamine compound (C). It is preferably 〇"~75 m, more preferably 0.5~50 m. In the liquid crystal alignment film obtained by using the copolymer of the present invention, the higher the content ratio of the diamine compound (B) in the diamine component, the higher the voltage holding ratio, and even after exposure for a long time at a high temperature. The relaxation of the residual charge accumulated by the DC voltage becomes faster. Therefore, the content of the diamine compound (B) in the diamine component is preferably 0.01 to 99 moles per 1 mole of the diamine compound (C). It is preferably 0.1 to 50 m, more preferably 0.5 to 2 m, and most preferably 0.5 to 10 m. When the polyamine of the present invention is to be obtained by the reaction of a diamine component with a tetracarboxylic dianhydride, a known synthetic method can be used. It is generally a method of reacting tetracarboxylic dianhydride -58 to 201030055 with a diamine in an organic solvent. The reaction is relatively easy to carry out in an organic solvent, and is preferred. The polyamino acid produced by dissolving the diamine and the tetracarboxylic dianhydride may be used, and the following examples are mentioned. >1,>1-dimethylformamide, >1, :^ dimethyl 2 _pyrrolidone, N-methyl caprolactam, dimethyl pyridine, dimethyl hydrazine, hexa Kia Mill, γ-butoxymethylpentanol, dipentene, ethyl amyl ketone, ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone siroli, methyl race Lucas acetate, ethyl ceramide, ethyl carbitol, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol - Tert-butyl | φ ether, diethylene glycol, diethylene glycol monoacetate, dipropylene glycol monoacetate monomethyl ether, dipropylene diethylene glycol monoethyl ether, dipropylene glycol monoacetic acid Ester monoethyl propyl ether, dipropylene glycol monoacetate monopropyl ether, hydroxy acetate, tripropylene glycol methyl ether, 3-methyl-3-propyl ether, ethyl isobutyl ether, diisobutylene, Valerate, butyl ether, diisobutyl ketone, methylcyclohexyl ether, dioxane, η-hexane, η-pentane, η-octyl ketone, ethylene carbonate, propylene carbonate, lactic acid The carboxylic acid dianhydride and the diamine do not produce by-products. Solvent, only not particularly limited. The amine, hydrazine-methyl-2-hydrazine, tetramethyl urea, ester, isopropyl alcohol, methyl decyl ketone, methyl, methyl stilbene, ethylene sulphate, Butyl monoacetate, ethylene glycol, propylene glycol monoacetate, dipropylene glycol monomethyl diethylene glycol dimethyl ether alcohol monomethyl ether, dipropyl ether, dipropylene glycol mono 3-methyl-3 -methoxybutoxybutanol, diisoacetate, butyl butene, propyl ether, dihexane, diethyl ether, cyclomethyl ester, ethyl lactate, -59- 201030055 Ester, ethyl acetate, η-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, digans Methyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination. Further, even if it is a solvent which does not dissolve the poly-proline, it may be used in the above solvent insofar as the produced polyamine does not precipitate. Further, since the water in the organic solvent hinders the polymerization reaction and becomes a cause of the polylysine produced by the hydrolysis, it is preferred that the organic solvent is dried by dehydration. When the diamine component and the tetracarboxylic dianhydride are reacted in an organic solvent, the solution of the diamine component in an organic solvent is stirred or dissolved, and the tetracarboxylic dianhydride or the organic solvent is directly dispersed or dissolved. In the method, a method in which a diamine component is added to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method in which a tetracarboxylic dianhydride and a diamine component are alternately added, and the like can be mentioned, and these methods can be used. Further, when the tetracarboxylic dianhydride or the diamine component is formed of a plurality of compounds, the reaction may be carried out in a state of being mixed beforehand or separately, and the low molecular weight bodies of the respective reactions may be further mixed. The reaction is carried out as a high molecular weight body. The polymerization temperature at this time may be arbitrarily selected from the temperature of -20 to 150 ° C, but preferably in the range of -5 to 10 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is too high to be uniformly stirred, so the diamine component and the tetracarboxylic acid are -60-201030055 The total amount of the dianhydride is preferably from 1 to 50% by mass, more preferably from 5 to 3% by mass, based on the total amount of the reaction solution (1% by mass). The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added. In the polymerization reaction of polyamic acid, the total molar ratio of the tetracarboxylic dianhydride to the molar ratio of the diamine component is preferably from 0.8 to 1.2. Similarly to the general polycondensation reaction, the closer the molar ratio is, the larger the molecular weight of the produced polyamine. The polyimine of the present invention is a polyimine obtained by subjecting the polyamic acid to dehydration ring closure, and can be used as a copolymer for obtaining a liquid crystal alignment film. In the polyimine of the present invention, the dehydration ring closure ratio (imidization ratio) of the proline group is not necessarily required to be 100%, and may be arbitrarily adjusted in accordance with the use or purpose. Examples of the method for imidizing polylysine include thermal imidization in which a solution of polylysine is directly heated, and addition of a catalyst to a solution of polyamic acid to imidize the catalyst. . The temperature at which the polyaminic acid is thermally imidized in the solution is from 1 to 400 ° C, preferably from 120 to 250 ° C, and the water formed by the imidization reaction is removed to the outside of the system. The method is better. The catalyst of poly-proline is imidized into a mixture of polyphthalic acid, and a basic catalyst and an acid anhydride are added at -20 to 250 ° C, preferably 0 to 180 ° C for stirring. The amount of the alkaline catalyst is 醯 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 3 to 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferably moderately alkaline in carrying out the reaction. -61 - 201030055 The acid anhydride may, for example, be acetic anhydride, trimellitic anhydride or pyromellitic anhydride. In the case where acetic anhydride is used, purification after completion of the reaction is easily carried out, which is preferred. The imidization ratio of the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. When the produced polyamine or polyimine is recovered from the reaction solution of polyglycolic acid or polyimine, the reaction solution may be placed in a weak solvent to precipitate. Examples of the weak solvent used for the precipitation include methanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated in a weak solvent is filtered and recovered, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the precipitate-recovered copolymer is redissolved in an organic solvent, and the operation of re-precipitation recovery is repeated 2 to 10 times to reduce impurities in the copolymer. Examples of the weak solvent in this case include alcohols, ketones, and hydrocarbons. When three or more kinds of weak solvents selected from the group are used, the purification efficiency can be further improved, which is preferable. The molecular weight of the polyamic acid and the polyimine contained in the liquid crystal alignment agent of the present invention is GPC (GPC) in consideration of the strength of the obtained coating film, the workability at the time of formation of the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the Permeation Chromatography method is preferably 5,000 to 1,000,000, preferably 10, 〇〇〇1 to 150,000. <Liquid Crystal Alignment Treatment Agent> The liquid crystal alignment treatment agent of the present invention is a coating agent for forming a liquid crystal alignment film, and the liquid to the solvent is dissolved in a solution. Choose a tree. The film containing the film is formed into a tree of resin, which is divided into a resin, and is formed into a tree. In this case, the content of the resin component is preferably 1 to 20% by mass, preferably 3 to 15% by mass, particularly preferably 3 to 10% by mass, based on the entire liquid crystal alignment agent (100% by mass). . In the present invention, the resin component may be either a copolymer of the present invention or a copolymer other than the copolymer of the present invention. In this case, the content of the other copolymer in the resin component is from 0.5 to 15% by mass, preferably from 1 to 1% by mass. The other copolymer is, for example, a diamine component which is reacted with a tetracarboxylic dianhydride, and is obtained by using a diamine compound (A), a diamine compound (B), or a diamine other than the diamine compound (C). Polylysine or polyimine. The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve the organic solvent of the resin component. The liquid crystal alignment agent of the present invention may contain components other than the above. In this example, there is a solvent or a compound which can improve the film thickness uniformity or surface smoothness when the liquid crystal alignment agent is applied, and a compound which can improve the adhesion between the liquid crystal alignment film and the substrate. Specific examples of the solvent for improving the uniformity of the film thickness or the surface smoothness include the following. For example, isopropyl alcohol, methoxymethylpentanol, methyl 赛苏苏, ethyl 赛赛苏, butyl 赛路苏, methyl sarbuta acetate, ethyl 赛-63- 201030055 Lucas acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, B 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, diiso Propyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, hexane, η- Pentane, η-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate η-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvate Ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-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, propylene glycol-1·monoethyl ether- 2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate A solvent having a low surface tension such as an ester. These solvents can be used after using one type or a mixture of plural types. When the solvent is used, the solvent contained in the liquid crystal alignment agent is preferably 5 to -64 - 201030055 80% by mass, preferably 20 to 60% by mass. Examples of the compound for improving the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tohkem Products), Mekkaf F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (Sumitomo 3M) System), AsahiGuard AG710, Shafulong S-3 82, SC101, β SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0 _ 0 1 to 1 part by mass, per part by mass of the resin component contained in the liquid crystal alignment agent. Specific examples of the compound which is used to improve the adhesion between the liquid crystal alignment film and the substrate include the following functional decane-containing compound 'epoxy group-containing compound and the like. • For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxylate, 2-aminopropyltrimethoxysilylene, 2-aminopropyltriethoxylate Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3- Aminopropyltriethoxydecane, N-triethoxycarbamidopropyltriethylamine, N-trimethoxymethylidenepropyltriethylamine, oxime-trimethoxy Methyl decyl-1,4,7-triazadecane, 10-triethoxymethane alkyl-u,? - -65- 201030055 Triazanonane, 9-trimethoxycarboxamido-3,6-diazaindolyl acetate, 9-triethoxycarbamimidin-3,6-diaza Mercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-amine Propyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylidene)-3-aminopropyltrimethoxydecane, N-bis(oxygen) Ethyl ethyl 3-aminopropyl triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Glycidyl 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, ]^少川',1^',-tetraglycidyl-111-xylenediamine, 1,3-double ( >},>1-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl-4, 4'-Diamine diphenylmethane or the like. When the compound to be adhered to the substrate is used in an amount of 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin component contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated. In addition to the above, the liquid crystal alignment agent of the present invention may be added with a dielectric or a conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film, without impairing the effects of the present invention. Further, a crosslinkable compound for the purpose of improving film hardness or density when used as a liquid crystal alignment film can be further added. -66-201030055 <Liquid Crystal Alignment Film/Liquid Crystal Display Element> The liquid crystal alignment treatment agent of the present invention is applied to a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, or vertical alignment. It can be used as a liquid crystal alignment film without performing alignment treatment. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like 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, because the process can be simplified. Further, the reflective liquid crystal display element may be a single-sided substrate, and an opaque substance such as a wafer may be used. In this case, a material that reflects light such as aluminum may be used as the electrode. The coating method of the liquid crystal alignment agent is not particularly limited, but is generally a method of screen printing, lithography, elastic printing, ink jet printing or the like which is used industrially. As another coating method, immersion, roll coating, slit coating, a rotator, or the like may be used, and they may be used in combination with the purpose.烧 After the liquid crystal alignment agent is applied onto the substrate, the solvent is 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. When the thickness of the coating film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element. When the thickness is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm. Good for 10~100nm. When the liquid crystal is horizontally aligned or obliquely aligned, the coating film after firing is treated by rubbing or polarized ultraviolet rays. In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention by the above-described method, and then a liquid crystal cell is produced by a known method, from 67 to 201030055, to form a liquid crystal display element. An example of the production of the liquid crystal cell is a pair of substrates on which a liquid crystal alignment film is to be formed, a spacer is spread on the liquid crystal alignment film of the single substrate, and the other substrate is bonded to the inside of the liquid crystal alignment film surface to form a liquid crystal. A method of sealing by pressure-reducing injection or a method of laminating a liquid crystal on a liquid crystal alignment film surface of a spacer, sealing the substrate, and sealing it. The spacer thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμηη. As described above, the liquid crystal display device produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be used in a large-screen, high-definition liquid crystal television or the like. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail with reference to examples, but the invention is not limited thereto. "Synthesis of Polyamide or Polyimine" The abbreviations of the compounds used in the examples are shown below. <tetracarboxylic dianhydride> CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid Acid dianhydride 201030055 [化45]

<Diamine compound (A')> m-PBCH5DABz : 1,3-diamine-5- {4-[trans-4-(trans-4, η η-pentylcyclohexyl)cyclohexyl] Phenoxymethyl}benzene m-PBCH7DABz : 1,3-diamine-5- { 4-[trans-4-(trans-4-n-heptylcyclohexyl)cyclohexyl]phenoxymethyl }Benzene p-PBCH5DABz : 1,4-diamine-5- { 4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene m-BPCH5DABz : 1,3 -diamine-5 - { 4 -[ 4 -(trans-4 - η-pentylcyclohexyl)phenyl]phenoxymethyl}benzene

-69 - 201030055 [Chem. 46]

NH <diamine compound (A")> trans-4-n-penta PBCH5DAB : 1,3 -diamine-4 - { 4 -[trans-4 -(cyclohexyl)cyclohexyl]phenoxy Benzene-70-201030055 PBCH7DAB : 1,3 -diamine-4 - { 4 -[trans-4 -(trans-4 - η-heptylcyclohexyl)cyclohexyl]phenoxy}benzene BPCH5DAB : 1,3 -diamine-4 - { 4 -[ 4 -(trans - 4 - η-pentylcyclohexyl)phenyl]phenoxy}benzene [47]

<Diamine compound (Β) > G diamine (Β1)~diamine (Β12) -71 - 201030055 [Chem. 48]

[化49]

201030055 DBA : 3,5-diamine benzoic acid [Chem. 50]

Nh2 <other diamines> φ p-PDA : P-phenylenediamine m-PBCH5DABEs : 3,5-diamine-{ 4-[trans-4-(trans-4-n-pentyl) Cyclohexyl)cyclohexyl]phenyl}benzoate PBP5DABZ: 1,3 -diamine-4-[(4-n-pentylphenyl)phenoxymethyl]benzene PCH7DAB : 1,3-diamine 4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene PBP5DAB : 1,3-diamine-4-[(4-n-pentylphenyl)phenoxy] Indolediamine (S 1 ) -73- 201030055 [化51]

<Organic solvent> NMP: N-methyl-2-pyrrolidone BCS: butyl sirolimus <Measurement of molecular weight of poly phthalic acid, polyimine;> The molecular weight of the polyimine in the synthesis example is The room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko Co., Ltd. was used to measure the column (KD-803, KD-805) manufactured by Shodex Co., Ltd. as follows.

Column temperature: 50 ° C Dissolution: N, N'-dimethylformamide (lithium bromide as an additive, water and substance (LiBr · H20) is 30 mmol / L, phosphoric acid • anhydrous crystals (〇201030055 phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) l〇ml/L) Flow rate: 1.0 ml/min Standard proof of calibration curve: TSK standard polyethylene oxide manufactured by Tosoh Company (molecular weight about 900,000 '1 50,000, 1 〇〇, 〇〇〇, 30,000), and polyethylene glycol (molecular weight of about 1 2,000, 4,000, 1,000) manufactured by POLYMER LAB ORATORY. <Measurement of imidization ratio> The imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR sampling tube (NMR Sampling tube standard Φ 5 manufactured by Kusano Scientific Co., Ltd.), and a mixture of hydrogenated dimethyl hydrazine (DMSO-d6, 0.05% TMS (tetramethyl decane) was added. ) 0.5 3ml, completely dissolved by ultrasound. This solution was measured for proton NMR at 500 MHz using a NMR measuring instrument (JNW-ECA500) manufactured by JEOL DATUM. Since the imidization rate has been _ protons from the structure that has not changed before and after imidization as the benchmark proton

W, using the proton peak of the proton, and the proton peak of the NH group from the valeric acid present from 9.5 to 10. Oppm, the enthalpy is calculated by the following formula. Imidization rate (%) = (1-α· x/y)xl00 In the above formula, X is the proton peak product of the NH group of the proline, and y is the peak product from the reference proton, a The ratio of the number of reference protons to one NH proton of valeric acid when the polyamine acid (imine-75-201030055 conversion rate is 0%). <Example 1> BODA (3, 50 g, 14.0 mmol), m-PBCH5DABz (1.87 g, 4.20 mmol), diamine (Bl) (2.03 g, 8.39 mmol), and DBA (2.34 g, 15.4 mmol) After mixing in NMP (20.8 g), the reaction was carried out at 80 ° C for 5 hours, and then CBDA (2.74 g, 14.0 mmol) and NMP (16. 4 g) were introduced, and the reaction was carried out at 40 ° C for 6 hours to obtain polyfluorene. Amino acid solution. After adding NMP to the polyamic acid solution (20.1 g) to dilute the content of the polyproline to 6 mass%, acetic anhydride (2.50 g) and pyridine (1.92 g) were added as an imidization catalyst. The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (3 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol to dryness under reduced pressure at 100 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 54%, a number average molecular weight of 18,500, and a weight average molecular weight of 47,100. NMP (19.5 g) and B C S (27 g 5 g) were added to the polyimine powder (3. g) to obtain a liquid crystal alignment treatment agent [1]. 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. &lt;Production of Liquid Crystal Cell&gt; The liquid crystal alignment treatment agent [1] obtained above was spin-coated on an ITO surface of a substrate having an electrode of 3 cm x 4 cm ITO attached 201030055, and was carried out at 80 ° C for 5 minutes at 2 1 0 ° The film was fired in a hot air circulating oven of C for 1 hour to prepare a polyimide film having a film thickness of 100 nm. The substrate with the liquid crystal alignment film was rubbed on a friction device having a roll diameter of 1 20 mm and a crepe cloth at a speed of 3 rpm, a light speed of 20 mm/sec, and a press-in amount of 0.3 mm. A substrate with a liquid crystal alignment film is obtained. Two sheets of the substrate having the liquid crystal alignment film were prepared, and a 6 μm bead spacer was spread on the surface of the liquid crystal alignment φ film, and then a sealing agent was applied thereto. The liquid crystal alignment film surface of the other substrate was set to the inner side, and the rubbing direction was reversed to form a hollow cell which hardened the sealing agent. In the empty cell, a transparent liquid crystal was injected by a vacuum injection method to obtain an anti-parallel alignment transparent liquid crystal cell. <Evaluation of the pretilt angle> The pretilt angle of the liquid crystal cell produced above was used, and a pretilt angle measuring device (ELSICON) was used. Model: PAS-301) was measured at room temperature. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as described above were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. &lt;Evaluation of voltage holding ratio&gt; The liquid crystal cell after the pretilt angle measurement was at 80. (At the temperature, a voltage of 4V of 60μηι -77-201030055 was applied, and the voltage after 16.67 ms and after 1 667 ms was measured, and the degree of voltage retention was calculated as the voltage holding ratio. The results are shown in Table 12. &lt;Residual charge Mitigation evaluation> The liquid crystal cell after the voltage holding rate measurement was applied with a DC voltage of 10 V for 30 minutes, and after short-circuiting for 1 second, the electricity generated in the liquid crystal cell was measured for 1 800 seconds. The residual charge was measured after the second and after 1 000 sec. The measurement was carried out using a 6254 liquid crystal physical property evaluation device manufactured by Toyo Technica Co., Ltd. The results are shown in Table 12. <Evaluation after high temperature placement> Liquid crystal after residual charge measurement The cells were placed in a high temperature bath set at 100 ° C for 7 days, and the voltage holding ratio and residual charge were measured. The results are shown in Table 12 and Table 13 which will be described later. <Example 2> BODA (3.51 g, 14.0 mmol), m-PBCH5DABz (3.76 g, 8.42 mmol), diamine (Bl) (1.36 g, 5.61 mmol), and DBA (2.13 g, 14.0 mmol) were mixed in NMP (22_0g). After 5 hours of reaction at 80 ° C, CBDA ( 2.75 g, 14.0 mmol) was added. And the NMP ( 17.6g ) ' is reacted at 40 ° C for 6 hours to obtain a poly-proline solution. NMP is added to the poly-proline solution (20.Og), and the content of the poly-proline is diluted. After 6 mass%, acetic anhydride (-78-201030055 4.32 g) and pyridine (3.35 g) were added as an imidization catalyst, and the reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (300 ml). The obtained precipitate was separated by filtration, and the precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder. The imidization ratio of the polyimine was 80. %, the number average molecular weight was 1,800, and the weight average molecular weight was 48,900. NMP (22.0 g) and BCS (25.0 g) were added to the polyimine powder (3.00 g) to obtain a liquid crystal alignment treatment agent [2]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [2], liquid crystal cells were produced in the same manner as in Example 1, and pretilt angle was observed. Evaluation. The results are shown in Table 11. And, without friction treatment, will be The liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, using the liquid crystal cell produced in the same manner as in Example 1, the voltage holding ratio was evaluated and the residual charge was evaluated. And evaluation after high temperature placement. The results are shown in Table 12 and Table 13. &lt;Example 3&gt; BODA (3.50 g, 14.0 mmol), m-PBCH5DABz ( 3.75 g, 8.39 mmol), diamine (B2) (2.87 g, 11.2 mmol) and DBA ( 1.28 g, 8.39 mmol) After mixing in NMP (23.5 g) and reacting at 80 ° C for 5 hours, CBDA ( 2.78 g, 14.2 mmol) and NMP ( 18.8 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polyamine. 79- 201030055 Acid solution. After adding NMP to the polyamic acid solution (25.1 g) and diluting to a content of polyglycine of 6% by mass, acetic anhydride (3.13 g) as an imidization catalyst and pyridine (2.42 g) were added. ), the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (3 50 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at a reduced pressure of 10 (TC) to give a polyimine powder. The imidization ratio of the polyimine was 56%, the number average molecular weight was 17,400, and the weight average molecular weight was 46,600. NMP (21.2 g) and BCS (25.8 g) were added to the polyimine powder (3.00 g) to obtain a liquid crystal alignment treatment agent [3]. No turbidity or precipitation was observed in the liquid crystal alignment treatment agent. An abnormality was observed, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [3], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11 below. The liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. The liquid crystal cell produced in the same manner as in Example 1 was used for voltage measurement. Evaluation of retention rate, evaluation of relaxation of residual charge, and evaluation after high temperature placement. The results are shown in Table 12 and Table 13. &lt;Example 4&gt; BODA (3.4 8 g, 13.9 mmol), m-PBCH5D ABz (3.7 3 g, 8.35 mmol ), Diamine (B3) (0.7 5 g, 2.78 mmol), 201030055 and DBA (2.54 g, 16.7 mmol) were mixed in NMP (22.0 g) at 80 ° (: after 5 hours of reaction, add 06〇8 ( 2.738, 13.9 111111〇1 ) and NMP ( 17.7g), a polyamine acid solution was obtained after 4 hours of reaction at 4 (TC). The polyaminic acid solution had a number average molecular weight of 24,100 and a weight average molecular weight of 57,200. NMP (1 g. 2 g) and BCS (25.0 g) were added to the obtained polyamidic acid solution (15.1 g) to obtain a liquid crystal alignment treatment agent [4]. No turbidity or precipitation was observed in the liquid crystal alignment treatment agent. The resin component was uniformly dissolved, and the liquid crystal cell was produced in the same manner as in Example 1 using the obtained liquid crystal alignment treatment agent [4], and the pretilt angle was evaluated. The results are shown in Table 11. The liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. The liquid crystal cell produced in the same manner as in Example 1 was used for voltage retention. Assessment, mitigation of residual charge And evaluation after high temperature standing. The results are shown in Table 1 2 and Table 13. [Example 5&gt; BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (1.87 g, 4.20 mmol), diamine (B4) (1.81 g, 8.39 mmol), and DBA (2.34 g, 15.4 mmol) were mixed in NMP (20.4 g), and after 5 hours of reaction at 8 ° C, CBDA (2.74 g, 14.0 mmol) and NMP were added. (i6.3g), a 6-hour reaction at 4 ° C gave a polyamine-81 - 201030055 acid solution. After the NMP was added to the polyamic acid solution (25.1 g), and the content of the polyproline was 6 mass%, acetic anhydride (5.39 g) as an imidization catalyst and pyridine (4.18 g) were added. The reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (330 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 81%, a number average molecular weight of 17,500, and a weight average molecular weight of 47,500. NMP (22.7 g) and BCS (25.8 g) were added to the polyimine powder (3.10 g) to obtain a liquid crystal alignment treatment 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 treatment agent [5], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cells produced in the same manner as in Example 1 were used to evaluate the voltage holding ratio, the evaluation of the residual charge relaxation, and the evaluation after the high temperature standing. The results are shown in Table 12 and Table 13. &lt;Example 6&gt; BODA (3.50 g, 14.0 mmol), m-PBCH5D ABz ( 1.87 g, 4.20 mmol), diamine (B5) (0.60 g, 2.80 mmol), 201030055 and DBA (3.19 g, 21.0 mmol) After mixing in NMP (19.8 g) and reacting at 80 ° C for 5 hours, CBDA (2.74 g, I4.〇mmol) and NMP (15.6 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a poly Alanine solution. After adding NMP to the polyamic acid solution (20.lg), the content of the diluted poly-araminic acid was 6% by mass, and acetic anhydride (2.5 1 g) as an imidization catalyst was added, and the D ratio was steep. (1.93 g), the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (270 ml), and the obtained precipitate was separated. The precipitate was washed with methanol, and dried under reduced pressure to obtain a polyimine powder. The imidization ratio of the polyimine was 55%, and the number average molecular weight was 18,800. The average molecular weight is 48,300. In the polyimine powder (3.00 g), NMP (22.1 g) and BCS (25.0 g) are added to obtain a liquid crystal alignment treatment agent [6]. When an abnormal phenomenon such as turbidity or precipitation was observed, it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [6], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. The liquid crystal cell produced in the same manner as in Example 1 was used. Evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation after high temperature standing. The results are shown in Table 12 and Table 13. -83- 201030055 &lt;Example 7&gt; BODA (3.50 g, 14.0 mmol) m-PBCH5DABz ( 2.50g, 5.60 mmol , diamine (B6) (120g, 5.60 mmol), and DBA (2.55g, 16.8 mmol) were mixed in NMP (20.7 g), and after reacting at 80 ° C for 5 hours, CBDA ( 2.74 g, 14.0 mmol) and NMP (16.6 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (20.0 g) and diluted to the content of polyglycine. After 6% by mass, acetic anhydride (2.50 g) and pyridine (1·95 g) as an imidization catalyst were added, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (28). In 0 ml), the obtained precipitate was separated by filtration, and the precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The imidization ratio of the polyimine was 5 6 %, the number average molecular weight was 17,800, and the weight average molecular weight was 48,100. NMP (26.1 g) and BCS (24.1 g) were added to the polyimine powder (3.21 g) to obtain a liquid crystal alignment treatment agent [7]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The obtained liquid crystal alignment treatment agent was used. [7] A liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cell produced in the same manner as in Example 1 was polarized without rubbing treatment. Observation by a microscope confirmed that the liquid crystals were uniformly aligned vertically. Further, using the liquid crystal cell produced in the same manner as in Example 1, the evaluation of the holding ratio of the voltage -84 - 201030055, the evaluation of the relaxation of the residual charge, and the evaluation after the high temperature standing were performed. The results are shown in Table 12 and Table 13. &lt;Example 8&gt; BODA (3.5 1 g, 14.0 mmol), m-PBCH5D ABz (2.5 1 g, 5.61 mmol), diamine (B7) (1.28 g, 5.60 mmol), and DBA (2.56 g, 16.8 mmol) was mixed in NMP (20.9 g), and after reacting at 80 ° C for 5 hours, CBDA ( 2.75 g, 14.0 mmol) and NMP (16.7 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a poly Proline solution. After adding NMP to the polyamic acid solution (25.2 g) and diluting to a content of polyglycolic acid of 6 mass%, acetic anhydride ( 5.398) and pyridine (4.182) as an imidization catalyst were added to 90. °(: The reaction was carried out for 3.5 hours. The reaction solution was poured into methanol (330 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 10 ° C to obtain a poly a quinone imine powder having an imidization ratio of 80% and a number average molecular weight of 17,200' weight average molecular weight of 47,100. The polyimine powder (3.00 g) is added with NMP (19. 5 g), and BCS (2 7 · 5 g ) 'The liquid crystal alignment treatment agent [8] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The obtained liquid crystal alignment treatment agent was used. [8] The liquid crystal cell was produced in the same manner as in Example 1. The pretilt angle was evaluated. The results are shown in Table 且, and the liquid crystal cell-85 produced in the same manner as in Example 1 was used. - 201030055 Observed by polarized light microscope' The liquid crystal cells were uniformly aligned vertically. The evaluation of the voltage holding ratio, the evaluation of the residual charge, and the evaluation after the high-temperature standing were carried out using the liquid crystal cell produced in the same manner as in Example 1. The results are shown in Table 12 and Table 13. &lt;Example 9&gt; BODA (3.51 g, 14.0 mmol), m-PBCH5DABz ( 3.76 g, 8.42 mmol), diamine (B8) (0.64 g, 2.81 mmol), and DBA (2_56 g, 16_8 mmol) After mixing in NMP (22.1 g) and reacting at 80 ° C for 5 hours, CBDA ( 2.75 g, 14.0 mmol) and NMP ( 17.6 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polydecylamine. The acid solution has a number average molecular weight of 2 〇, 9 00 and a weight average molecular weight of 50,900. NMP (1 O.Og) and BCS are added to the obtained polyglycine solution (20.0 g). 3 6 · 5 g ), the liquid crystal alignment treatment agent [9] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The obtained liquid crystal alignment treatment agent [9] In the same manner as in Example 1, liquid crystal cells were produced and the pretilt angle was evaluated. The liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically as in Example 1 except that the rubbing treatment was carried out. The produced liquid crystal cells were subjected to voltage-86-201030055 'evacuation of residual charge and evaluation after high temperature placement. The results are shown in Tables 12 and 13. &lt;Example 1〇&gt; BODA (3.5 lg, 14.0 mmol), m-PBCH5DABz ( 3.76 g, 8.42 mmol), diamine (B9) (1.44 g, 5.61 mmol), and DBA (2.13 g, 14_) 〇mm〇i) was mixed in NMP (22.6 g). After reacting at 80 ° C for 5 hours, cBDA (2.75 g, 14.0 mmol) and NMP ( 18.1 g) were added, and after 4 hours of reaction at 4 (rc) The polyaminic acid solution was obtained. After the NMP was added to the polyamic acid solution (25.0 g), and the content of the polyproline was 6 mass%, acetic anhydride (5.39 g) as an imidization catalyst was added. And pyridine (4.18 g), the reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (330 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol at 100 ° C. The polyimine powder was obtained by drying under reduced pressure. The imidization ratio of the polyimine was 79%, the number average molecular weight was 18,100, and the weight average molecular weight was 48,900. The polyimine powder (3.01 g) was added. NMP (19.5 g) and BCS (27.5 g) obtained a liquid crystal alignment treatment agent [1]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent. It was confirmed that 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 treatment agent [10], and the pretilt angle was evaluated. The results are shown in Table 11. The liquid crystal-87-201030055 produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cell produced in the same manner as in Example 1 was used for voltage. Evaluation of retention rate, evaluation of relaxation of residual charge, and evaluation after high temperature placement. The results are shown in Table 12 and Table 13. &lt;Example 11&gt; BODA (3_48 g, 13.9 mmol), m-PBCH5DABz ( 2.49 g, 5.56) Methyl) (diamine (BIO) (0.90 g, 2.78 mmol), and DBA (2.96 g, 19.5 mmol) were mixed in NMP (20.8 g). After reacting at 80 ° C for 5 hours, CBDA (2.73 g) was added. , 13.9 mmol) and NMP (16. 7 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a number average molecular weight of 23,500 and a weight average molecular weight of 5 5,800. Poly-proline solution (20.0g) added to NM P ( 13.3g ) and BCS (33.4g) were obtained as a treatment agent [11]. 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 treatment agent [1 1], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. Further, using the liquid crystal cell produced in the same manner as in Example 1, the evaluation of the holding ratio of the voltage -88 - 201030055, the evaluation of the relaxation of the residual charge, and the evaluation after the high temperature standing were performed. The results are shown in Table 12 and Table 13. &lt;Example 12&gt; BODA (3.5 Og, 14.0 mmol), m-PBCH5D ABz ( 3.75 g, 8.39 mmol) -amine (Bll) ( 1.80 g, 5.60 mmol), and DBA (2.13 g, 14.0 mmol) The mixture was mixed in NMP (23 g), and after reacting at 80 ° C for 5 hours, CBDA ( 2.74 g, 14.0 mmol) and NMP (I8.5 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain polyfluorene. Amino acid solution. After adding NMP to the polyamic acid solution (20. lg) to dilute the content of the polyproline to 6 mass%, acetic anhydride (4.30 g) as an imidization catalyst and pyridine (3.3) were added. 5 g), the reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (300 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyimine has an imidization ratio of 80%, a number average molecular weight of 18,500, and a weight average molecular weight of 48,900. NMP (19.5 g) and BCS (27.5 g) were added to the polyimine powder (3.04 g) to obtain a liquid crystal alignment treatment agent [1 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. Using the obtained liquid crystal alignment treatment agent [1 2], liquid crystal cells were produced in the same manner as in Example i to evaluate the pretilt angle. The results are as shown! Shown. Further, the liquid crystal -89 - 201030055 produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was vertically aligned in a uniform sentence. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after high-temperature placement were performed. The results are shown in Table 12 and Table 13. &lt;Example 1 3 &gt; BODA ( 3.50 g, 14.0 mmol), m-PBCH5DABz ( 3.75 g, 8.39 mmol), diamine (B12) ( 2.58 g, 8.39 mmol), and DBA (1.70 g, 11.2 mmol) The mixture was mixed in NMP (23.7 g). After reacting at 80 ° C for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (19.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polyfluorene. Amino acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting to a content of polyglycine of 6 mass%, acetic anhydride (4.30 g) as an imidization catalyst, and pyridine (3.3) were added. 5 g ), 3 · 5 hours reaction at 90 ° C. The reaction solution was poured into methanol (2 80 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 81%, a number average molecular weight of 17,800, and a weight average molecular weight of 47,500. NMP (20.8 g) and BCS (29. 3 g) were added to the polyimine powder (3.21 g) to obtain a liquid crystal alignment treatment agent [13]. 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. • 90 - 201030055 Using the obtained liquid crystal alignment treatment agent [13], liquid crystal cells were produced in the same manner as in the examples, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. Further, the liquid crystal cells produced in the same manner as in Example 1 were used to evaluate the voltage holding ratio, the evaluation of the residual charge relaxation, and the evaluation after the high temperature standing. The results are shown in Table 12 and Table 13. &lt;Example 14&gt; BODA (3.51 g, 14.0 mmol), m-PBCH7DABz (4 g, 8.42 mmol), diamine (Bl) ( 1.36 g, 5.6 1 mmol), and DBA (2.13 g, 14.0 mmol) was mixed in NMP (22.8 g), and after reacting for 5 hours at 80 t, CBDA (2.75 g, 14.0 mmol) and NMP (1. 3 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polydecylamine. Acid solution. After adding NMP to the polyamic acid solution (20.2 g) and diluting to a content of polyglycine of 6% by mass, acetic anhydride (4-30 g) and pyridine (3.33 g) as an imidization catalyst were added. The reaction was carried out at 9 (TC) for 3.5 hours. The reaction solution was poured into methanol (270 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyfluorene. The imine powder has an imidization ratio of 80%, a number average molecular weight of 17,900, and a weight average molecular weight of 47,300. The polyamidimide powder (3.00 g) is added to NMP (19_5 g). And -91 - 201030055 BCS (27.5g), the liquid crystal alignment agent [14] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The alignment treatment agent [14] produced liquid crystal cells in the same manner as in Example 1, and evaluated the pretilt angle. The results are shown in Table 11. Further, the liquid crystal produced in the same manner as in Example 1 was used without the rubbing treatment. Observed by a polarizing microscope, confirmed The crystal cells were uniformly aligned vertically. The evaluation of the voltage holding ratio, the evaluation of the residual charge, and the evaluation after the high-temperature standing were carried out using the liquid crystal cell produced in the same manner as in Example 1. The results are shown in Table 12 and Table 13. &lt;Example 15&gt; BODA (3.50 g, 14.0 mol), m-BPC Η 5 DAB z (3.98 g, 8.39 mmol), diamine (Bl) (2.03 g, 8.39 mmol), and DBA (1.70 g) , 1 1.2 mmol) was mixed in NMP (23.2 g), and after 5 hours of reaction at 8 ° C, CBDA ( 2.74 g, 14.0 mmol) and NMP ( 18.5 g) were added, and the reaction was carried out at 40 ° C for 6 hours. Then, a polyaminic acid solution was obtained. NMP was added to the polyamic acid solution (20.0 g), and the content of the poly-proline was 6 mass%, and acetic anhydride was added as an imidization catalyst ( 4.29 g). And pyridine (3.35 g), the reaction was carried out for 4 hours at 80 ° C. The reaction solution was poured into methanol (290 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol at 1 〇. 〇t was dried under reduced pressure -92-201030055 to obtain a polyimide pigment. The imidization ratio of the polyimine was 54%, number average The molecular weight was 17,8, and the weight average molecular weight was 48,100. To the polyimine powder (3.50 g), NMP (22.8 g) and BCS (32.0 g) were added to obtain a liquid crystal alignment treatment agent [15]. 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 treatment agent [15], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. Further, the liquid crystal cells produced in the same manner as in Example 1 were used to evaluate the voltage holding ratio, the evaluation of the residual charge relaxation, and the evaluation after the high temperature standing. The results are shown in Table 12 and Table 13.

&lt;Example 16&gt; BODA (3.48 g, 13.9 mmol), p-PBCH5DABz (3.73 g, 8.35 mmol), diamine (Bl) (2.02 g, 8.35 mmol), and DBA (1.69 g, 11.1 mmol) were The mixture was mixed in NMP (22.7 g), and after reacting at 80 ° C for 5 hours, CBDA (2.73 g, 13.9 mmol) and NMP (18_lg) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (20.5 g) was added to NMP' diluted to a content of polyglycolic acid of 6 mass%, acetic anhydride (-93 - 201030055 4.358) as an imidization catalyst, and pyridine were added. 3.358), 3.5 hours reaction at 90 °. The reaction solution was poured into methanol (2 mL), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder. The polyimine had an imidization ratio of 79%, a number average molecular weight of 16,900, and a weight average molecular weight of 46,800. NMP (22.7 g) and BCS (25.8 g) were added to the polyimine powder (3.30 g) to obtain a liquid crystal alignment treatment agent [16]. 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 treatment agent [16], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. Further, the liquid crystal cells produced in the same manner as in Example 1 were used to evaluate the voltage holding ratio, the evaluation of the residual charge relaxation, and the evaluation after the high temperature standing. The results are shown in Table 12 and Table 13. <Comparative Example 1 &gt; BODA (3.51 g, 14.0 mmol), PCH7DAB ( 1.60 g, 4.21 mmol), diamine (Bl) (2.04 g, 8.42 mmol), and DBA (2.3 5 g, 15.4 mmol) in NMP (20.3 g) was mixed, and after reacting at 8 ° C for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (16.3 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polylysine solution. 201030055 liquid. After adding NMP to the polyamic acid solution (20.3 g) and diluting to a content of polyglycine of 6% by mass, acetic anhydride (2.50 g) as an imidization catalyst and pyridine (1.94 g) were added. The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (280 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 1 Torr to give a polyimine powder. The polyamidimide had an imidization ratio of 54% and a number average molecular weight of 17,000. The weight average molecular weight was 46,700. To the polyimine powder (3.30 g), NMP (24.2 g) and B C S (27 g 5 g) were added to obtain a liquid crystal alignment treatment agent [丨7]. 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 treatment agent [17], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. Further, the liquid crystal cells produced in the same manner as in Example 1 were used to evaluate the voltage holding ratio, the evaluation of the residual charge relaxation, and the evaluation after the high temperature standing. The results are shown in Table 1 2 and Table 13. &lt;Comparative Example 2 &gt; BODA (3.50 g, 14.0 mmol), PCH7DAB (5.31 g,

14.0 mmol), diamine (Bl) ( 1.36 g, 5.60 mmol), and DBA-95-201030055 (1_28 g, 8.39 mmol) were mixed in NMP (23.4 g), and reacted at 80 ° C for 5 hours, then added CBDA (2, 74 g, 14.0 mmol) and NMP (18. 8 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (20.0 g), and the content of the polyamid acid was diluted to 6 mass%, and then acetic anhydride (2.48 g) and pyridine (1.94 g) were added as an imidization catalyst. The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (300 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyimine had an imidization ratio of 55%, an average number average molecular weight of 16,600, and a weight average molecular weight of 46,100. NMP (23.5 g) and BCS (26.7 g) were added to the polyimine powder (3.21 g) to obtain a liquid crystal alignment treatment agent [18]. 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 treatment agent [18], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. Further, the liquid crystal cells produced in the same manner as in Example 1 were used to evaluate the voltage holding ratio, the evaluation of the residual charge relaxation, and the evaluation after the high temperature standing. The results are shown in Table 12 and Table 13. 201030055 &lt;Comparative Example 3 &gt; BODA (3.50 g, 14.0 mmol), m-PBCH5DABEs (3.87 g, 8.39 mmol), diamine (B1) ( 1.36 g, 5.60 mmol), and DBA (2.13 g, 14.0 mmol) After mixing in NMP (22.6 g) and reacting at 80 ° C for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (1 8.1 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polyfluorene. Amino acid solution. After adding NMP' to the polyamic acid solution (20.0 g) to dilute to a content of polyglycolic acid of 6 mass%, acetic anhydride (2.51 g) and pyridine (1.95 g) were added as an imidization catalyst. The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (280 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 54%, an average number average molecular weight of 17,400, and a weight average molecular weight of 47,900. After adding NMP (27.1 g) and BCS (20.0 g) to the polyimine powder (3.01 g), precipitation of the resin component was caused, and a liquid crystal alignment treatment agent could not be obtained. Therefore, it is impossible to produce a liquid crystal cell. &lt;Comparative Example 4 &gt; BODA (3.49 g, 14.0 mmol), PBP5DAB (3.54 g, 8.37 mmol), diamine (Bl) (1.35 g, 5.58 mmol), and DBA (2.12 g, 14_0 mmol) in NMP The mixture was mixed in (22.0 g), and after reacting at 80 ° C for 5 hours, CBDA (2.74 g, 14.0 mmol) and -97-201030055 NMP (1. 6 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polyfluorene. Amino acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting to a content of polyglycolic acid of 6 mass%, acetic anhydride (2.50 g) and pyridine (1.93 g) were added as an imidization catalyst. The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (290 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 55 %, an average number average molecular weight of 16,400, and a weight average molecular weight of 46,900. After adding NMP (28.8 g) and BCS (21.3 g) to the polyimine powder (3.20 g), precipitation of a resin component was caused, and a liquid crystal alignment treatment agent could not be obtained. Therefore, it is impossible to produce a liquid crystal cell. &lt;Comparative Example 5 &gt; BODA (3.48 g, 13.9 mmol), PBCH5DAB (3.61 g, 8.35 mmol), diamine (Bl) (1.35 g, 5.56 mmol), and V·PDA (1.50 g, 13.9 mmol) The mixture was mixed in NMP (21.0 g), and after reacting at 8 ° C for 5 hours, CBDA (2.73 g, 13.9 mmol) and N MP (1 6 · 8 g) were added, and the mixture was reacted at 40 ° C for 6 hours. After the reaction, a polyaminic acid solution was obtained. After adding NMP to the polyamic acid solution (20. Og) and diluting to a content of polyglycine of 6% by mass, acetic anhydride (2.48 g) and pyridine (1.94 g) were added as an imidization catalyst. ), the reaction was carried out at 80 ° C for 4 hours. The -98-201030055 reaction solution was poured into methanol (280 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 55%, an average number average molecular weight of 17,800, and a weight average molecular weight of 48,100. NMP (22-1 g) and BCS (25.0 g) were added to the polyimine powder (3.20 g) to obtain a liquid crystal alignment treatment agent [19]. 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 treatment agent [19], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned with the ground. Further, the liquid crystal cells produced in the same manner as in Example 1 were used to evaluate the voltage holding ratio, the evaluation of the residual charge relaxation, and the evaluation after the high temperature standing. The results are shown in Table 12 and Table 13. &lt;Comparative Example 6&gt; BODA (3.50 g, 14.0 mmol), PBCH5DAB (3.63 g, 8.39 mmol), diamine (SI) (1.35 g, 5.60 mmol), and DBA (2.l3g, 14.0 mmol) were The mixture was mixed in NMP (22.2 g), and after reacting for 5 hours at 80 t, CBDA (2.74 g, 14.0 mmo 1 ) and NMP ( 17.7 g) were added, and the reaction was carried out at 4 ° C for 6 hours to obtain polylysine. Solution. -99 - 201030055 The NMP was added to the polyaminic acid solution (20.1 g) so that the content of the poly-proline was 6 mass%, and after dilution, 'acetic anhydride as an imidization catalyst was added (2 · 50 g ), and pyridox (1 · 9 5 g ) '4 hours reaction at 80 °C. The reaction solution was poured into methanol (2 90 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to give a polyimine powder. The imidization ratio of the polyimine was 54%', the number average molecular weight was 18,100, and the weight average molecular weight was 47,800. NMP (2 2.7 g) and BCS (25.8 g) were added to the polyimine powder (3.11 g) to obtain a liquid crystal alignment treatment agent [20]. 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 treatment agent [20], liquid crystal cells were produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. Further, the liquid crystal cells produced in the same manner as in Example 1 were observed by a polarizing microscope, and it was confirmed that the liquid crystals were uniformly aligned vertically. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after high-temperature placement were performed. The results are shown in Table 12 and Table 13. &lt;Example 21&gt; BODA (3_51 g, 14.0 mm〇l) ' p B CH 5 D AB (1 _ 8 2 g, 4.21 mmol), -amine (Bl) (2.04 g, 8.42 mmol), and DBA ( 2.35g, 15.4 mmol) was mixed in NMP (20.7 g), after -5 - 201030055 8 (TC was reacted for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (1 6.6 g) were added at 40 ° After a reaction for 6 hours, a polyaminic acid solution was obtained. After the NMP' was added to the polyamic acid solution (2 〇.〇g), the content of the polyamid acid was diluted to 6% by mass. To the catalyst, acetic anhydride (2.51 g) and pyridine (1.93 g) were added, and the reaction was carried out for 4 hours at 80 ° C. The reaction solution was poured into methanol (280 ml), and the resulting precipitate was separated by filtration. The product was washed with methanol to obtain a polyimine powder after drying under reduced pressure at i ° ° C. The polyamidimide had an imidization ratio of 5 5 %, a number average molecular weight of 19,100, and a weight average molecular weight of 48. 00. Into the polyimine powder (3.01 g), NMP (19.5 g) and BCS (27.5 g) were added to obtain a liquid crystal alignment treatment agent [21]. No turbidity was observed in the liquid crystal alignment treatment agent. Analysis When the abnormality occurred, it was confirmed that the resin component was uniformly dissolved. &lt;Production of liquid crystal cell&gt; The liquid crystal alignment treatment agent [21] obtained above was spin-coated on the ITO surface of a substrate on which an electrode of 3 Cmx4Cm ITO was attached, and 80 °C was carried out for 5 minutes. The film was fired in a hot air circulating oven at TC for 1 hour to prepare a polyimide film having a thickness of 100 nm. The substrate having the liquid crystal alignment film was 120 mm in diameter. The rubbing device of the cloth was subjected to rubbing treatment under the conditions of a number of revolutions of 3 OO rpm, a roll speed of 20 mm/sec, and a press-in amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film. -101 - 201030055 Preparation of 2 sheets of the liquid crystal The substrate of the alignment film is spread on the surface of the liquid crystal alignment film by 6/m, and then printed on the upper surface by a sealing agent. The liquid crystal alignment film surface of the other substrate is used as the inner side, and is laminated. After the rubbing direction is in the opposite direction, a hollow cell for hardening the sealing agent is prepared, and the transparent liquid crystal is injected into the empty cell by a vacuum injection method to obtain an anti-parallel aligned transparent liquid crystal cell. <Evaluation of pretilt angle> The liquid crystal produced above The pretilt angle was measured at room temperature using a pretilt angle measuring apparatus (Model: PAS-301, manufactured by ELSICON Co., Ltd.), and the results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as described above except for the rubbing treatment was used. The results of observation by a polarizing microscope confirmed that the liquid crystals were uniformly aligned vertically. &lt;Evaluation of voltage holding ratio&gt; The liquid crystal cell after the pretilt angle measurement was applied with a voltage of 4 V of 60 μm at a temperature of 8 ° C, and the voltage after 16.67 ms and after 1667 ms was measured as the voltage retention. Calculated by rate. The results are shown in Table 16. &lt;Evaluation of relaxation of residual charge&gt; After the voltage holding ratio was measured, the liquid crystal cell was applied with a DC voltage of 10 V for 30 minutes, and after being short-circuited for 1 second, the electricity generated in the liquid crystal cell was located at 1 800. The measurement was performed in seconds. The residual charge after 50 seconds and 1 000 seconds was measured again -102- 201030055. Further, it was measured to use a 6254 type liquid crystal property evaluation device manufactured by Dongyang Technica Co., Ltd. The results are shown in Table 17. &lt;Evaluation after high temperature placement&gt; The liquid crystal cell after the measurement of the residual charge was subjected to measurement for 1 day in a high temperature bath set to 1 Torr, and the voltage holding ratio and residual charge were measured. The results are shown in Table 16 and Table. &lt;Example 22&gt; BODA (3.49 g, 14.0 mmol), PBCH5DAB (3.62 g, 8.37 mmol), diamine (Bl) (1.35 g, 5.58 mmol), and DBA (2.12 g, 14.0) Methyl) was mixed in NMP (22_lg), and after reacting at 80 C for 5 hours, CBDA (2_74 g, 14.0 mmol) and NMP (17. 7 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. φ was added to the polyacrylic acid solution (25.lg), and diluted to a content of the polyamidic acid of 6 mass%, and then acetic anhydride (5.4 〇g) as an imidization catalyst, and pyridine ( 4. 18g), the reaction was carried out for 3.5 hours at 90 ° C. The reaction solution was poured into methanol (300 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol at 1 Torr. (: Polyimine powder was obtained after drying under reduced pressure. The imidization ratio of the polyimine was 81%, and the number average molecular weight was 1,900. The weight average molecular weight was 49,500. The liquid phase alignment treatment agent [22] was obtained by adding NMP (22.0 g) and BCS (25 g) to the polyimine powder (3.01 g). - 201030055 No abnormality such as turbidity or precipitation was observed in the treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [22], the liquid crystal cell was produced in the same manner as in Example 2, and the pretilt angle was observed. The results are shown in Table 15. The liquid crystal cells produced in the same manner as in Example 21 were observed by a polarizing microscope except that the rubbing treatment was carried out, and it was confirmed that the liquid crystals were uniformly aligned vertically. Example 2 1 The liquid crystal cell produced in the same manner was subjected to evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after high temperature standing. The results are shown in Table 16 and Table 17. &lt;Example 23&gt; BODA (3.55) g, 14.2 mmol), PBCH5DAB ( 3.68 g,

8.51 mmol), diamine (B2) (2.91 g, 11.4 mmol), and DBA (1.30 g, 8.51 mmol) were mixed in NMP (23.6 g), and after 5 hours of reaction at 8 ° C, CBDA was added ( 2.78 g, 14·2 mmol) and NMP (18.9 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP' was added to the polyamic acid solution (20. g) to be diluted to a content of polyglycolic acid of 6 mass%, acetic anhydride (2.51 g) and pyridine (1.93) were added as an imidization catalyst. g) 'A reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (280 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol to dryness under reduced pressure at 100% to obtain a polyimine powder. The imidization ratio of the polyimine was 55 % 'number - 104 &gt; 201030055 The average molecular weight was 1,800 and the weight average molecular weight was 47,200. NMP (22.7 g) and BCS (25.8 g) were added to the polyimine powder (3.11 g) to obtain a liquid crystal alignment treatment agent [23]. 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 treatment agent [23], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cell produced in the same manner as in Example 21 was used, and the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 24&gt; BODA (3_51 g, 14.0 mmol), PBCH5DAB (3.64 g,

8.42 mmol), diamine (B3) (0.76 g, 2.81 mmol), and DBA (2.56 g, 16·8 mmol) were mixed in NMP (22.0 g). After 5 hours at 80 ° C, CBDA was added. (2.75 g, 14.0 mmol) and NMP (1.76 g)' were reacted at 40 ° C for 6 hours to give a polyaminic acid solution. The polyaminic acid solution had a number average molecular weight of 22,600 and a weight average molecular weight of 54,600. NMP (10.1 g) and BCS (25.0 g) were added to the obtained polyamic acid solution (1. g) to obtain a liquid crystal alignment treatment agent [24]. No abnormality such as turbidity or precipitation was observed in the liquid-to-treatment agent in the liquid-105-201030055, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [24], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was vertically aligned in a uniform manner. Further, using the liquid crystal cell produced in the same manner as in Example 21, the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 25&gt; BODA (3.48 g, 13.9 mmol), PBCH5DAB (1.81 g,

4.17 mmol), diamine (B4) (1·80 g, 8.3 mmol), and DBA (2.33 g, 15.3 mmol) were mixed in NMP (20.2 g) for 5 hours at 8 °C After the reaction, CBD A (2.73 g, 1 3.9 mmol) and NMP (16 lg) were added, and after 4 hours of TC reaction, a polyaminic acid solution was obtained. In the polyamic acid solution (20.0 g) After adding NMP and diluting to a content of polyglycolic acid of 6% by mass, acetic anhydride (4.31 g) and pyridine (3.34 g) were added as an imidization catalyst, and the reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (260 ml), and the obtained precipitate was separated by filtration, and the precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder. The imidization ratio is 80%, the number -106-201030055 average molecular weight is 17,100, and the weight average molecular weight is 46,000. The polyimine powder (3.0 〇g) plus ANMP (22.1 g), and BCS (25.3) g) A liquid crystal alignment treatment agent [25] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [25], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. The same as in Example 21 except that the rubbing treatment was not performed. The liquid crystal cell produced was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cell produced in the same manner as in Example 21 was used to evaluate the voltage holding ratio, the evaluation of the residual charge, and the high temperature. Evaluation after standing. The results are shown in Table 16 and Table 17. &lt;Example 26&gt; BODA (3.50 g, 14.0 mmol), PBCH5DAB (1.82 g,

4.20 mmol), diamine (B5) (0.60 g, 2.80 mmol), and DBA (3.19 g, 2 1.0 mmol) were mixed in NMP (19.7 g), and after 5 hours at 8 ° C, CBDA was added. (2.74 g, 14.0 mmol) and NMP ( 15.7 g) were reacted at 4 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (25.0 g) and diluting to a content of polyglycine of 6% by mass, acetic anhydride (3.13 g) as an imidization catalyst and pyridine (2.42 g) were added. The reaction was carried out at 80 ° C for 4 hours. The -107-201030055 reaction solution was poured into methanol (3 40 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 53%, an average number average molecular weight of 19,400, and a weight average molecular weight of 49,300. NMP (29.3 g) and BCS (33.3 g) were added to the polyimine powder (4.01 g) to obtain a liquid crystal alignment treatment agent [26]. 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 treatment agent [26], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cell produced in the same manner as in Example 21 was used, and the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 2 7 &gt; BODA (3.52 g, 14.1 mmol), PBCH5DAB (2.43 g,

5.63 mmol), diamine (B6) (1.21 g, 5.63 mmol), and DBA (2'57 g, 1 6_9 mmol) were mixed in NMP (20.7 g), and reacted at 80 ° C for 5 hours. CBDA (2.76 g, 14.1 mmol) and NMP (16.6 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. -108- 201030055 After adding NMP to the polyamic acid solution (20.0 g) and diluting to a content of polyglycolic acid of 6 mass%, acetic anhydride (2.51 g) and pyridine were added as an imidization catalyst. (1.93 g), the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (280 ml), and the obtained precipitate was separated. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyamidimide has an imidization ratio of 55 %, an average number average molecular weight of 1,800, and a weight average molecular weight of 48,300. NMP (32.7 g) and BCS (30. lg) were added to the polyimine powder (4.00 g) to obtain a liquid crystal alignment treatment agent [27]. 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 treatment agent [27], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was vertically aligned in a uniform sentence. Further, using the liquid crystal cell produced in the same manner as in Example 21, the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 28&gt; BODA (3.50 g, 14.0 mmol), PBCH5DAB (2.42 g,

5.60 mmol), diamine (B7) (1.28 g, 5.60 mmol), and DBA (2.55 g, 16.8 mmol) were mixed in NMP (20.8 g) for 5 hours at -109-201030055 80 °C After the reaction, CB DA (2.74 g, 14.0 mmol) and NMP (16. 6 g) were added, and the mixture was reacted at 4 Torr for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (20. Og) and diluting to a content of polyamine acid of 6 mass%, acetic anhydride (4.318) and pyridine (3.348) were added as an imidization catalyst. The reaction was carried out at 90° (the reaction was carried out for 3.5 hours). The reaction solution was poured into methanol (260 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a poly The imine imide powder has an imidization ratio of 81%, a number average molecular weight of 16,300, and a weight average molecular weight of 46,300. The polyamidimide powder (3.51 g) is added with NMP (22.8 g). And BCS (3 2. lg), a liquid crystal alignment treatment agent was obtained. [28] No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The alignment treatment agent [28] was prepared in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. The same procedure as in Example 21 was carried out except that the rubbing treatment was not performed. The liquid crystal cell was observed by a polarizing microscope, and it was confirmed that the liquid crystal was present. The liquid crystal cell produced in the same manner as in Example 2 was evaluated by the evaluation of the voltage holding ratio, the evaluation of the residual charge, and the evaluation after the high temperature standing. The results are shown in Table 16 and Table 17. &lt;Example 29&gt; -110- 201030055 BODA (3.51 g, 14.0 mmol), PBCH 5 DAB ( 3.64 g,

8.42 mmol), diamine (B8) (0.64 g, 2.81 mmol), and DBA (2.56 g, 16.8 mmol) were mixed in NMP (20.8 g), and after 80 hours: 5 hours reaction, CBDA (2_75 g, 14.0 mmol) and NMP (16. 6 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. The polyamic acid solution had a number average molecular weight of 21,500 and a weight average molecular weight of 52,300. NMP (10.0 g) and BCS (36.7 g) were added to the obtained polyamic acid solution (20.1 g) to obtain a liquid crystal alignment treatment agent [29]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [29], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, using the liquid crystal cell produced in the same manner as in Example 21, the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 30&gt; BODA (3.50 g, 14.0 mmol), P B C Η 5 D A B (3.6 3 g,

8.39 mmol), diamine (B9) (1.44 g, 5.60 mmol), and DBA (2.13 g, 14.0 mmol) were mixed in NMP (22.3 g) and reacted at -111 - 201030055 8 °C for 5 hours. Then, cBDA (2_74 g, 14.0 mmol) and NMP (1.79 g) were added to carry out a reaction at 40 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting to a content of polyglycolic acid of 6 mass%, acetic anhydride (4·3 1 g) and pyridine were added as an imidization catalyst. 3 · 3 5 g ), the reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (300 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 78%, a number average molecular weight of 17,900, and a weight average molecular weight of 49,100. To the polyimine powder (3.20 g), NMP (20.8 g) and BCS (29. 3 g) were added to obtain a liquid crystal alignment treatment agent [30]. 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 treatment agent [30], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cell produced in the same manner as in Example 21 was used, and the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 31&gt; -112- 201030055 BODA (3.48 g, 13.9 mmol), PBCH 5 DAB (2.4 1 g. 5.56 mmol), diamine (BIO) (0.90 g, 2.78 mmol), and DBA ( 2.96 g) , 19.5 mmol) was mixed in NMP (20.7 g), and after reacting at 80 ° C for 5 hours, CBDA (2.73 g, 13.9 mm 〇l) and NMP (16. 6 g) were added, and the reaction was carried out at 40 ° C for 6 hours. After that, a polyaminic acid solution was obtained. The polyaminic acid solution had a number average molecular weight of 20,100 and an average weight molecular weight of 50,100. To the obtained polyaminic acid solution (10.5 g), hydrazine P (10. 1 g) and BCS (25.0 g) were added to obtain a liquid crystal alignment treatment agent [31]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [31], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, using the liquid crystal cell produced in the same manner as in Example 21, the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 32&gt; BODA (3.49 g, 14.0 mmol), PBCH5DAB (3.62 g, 8.37 mmol), diamine (Bll) (1.79 g, 5.58 mmol), and DBA (2.12 g, 14.0 mmol) in NMP ( Mixing in 22.9 g), -113-201030055 After 5 hours of reaction at 80 ° C, CBDA (2.74 g, 14.0 mmol) and NMP ( 18.3 g) were added to react at 4 Torr for 6 hours to obtain polydecylamine. Acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting to a content of polyglycolic acid of 6 mass%, acetic anhydride (4.318) and pyridine (3.358) were added as an imidization catalyst. The 90 art was subjected to a 3.5 hour reaction. The reaction solution was poured into methanol (290 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder. The polyamidimide had an imidization ratio of 81%, a number average molecular weight of 1,800, and a weight average molecular weight of 48,400. To the polyimine powder (3.31 g), NMP (21.5 g) and BCS (30.3 g) were added to obtain a liquid crystal alignment treatment agent [η]. 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 treatment agent [3 2], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cell produced in the same manner as in Example 2 was used, and the evaluation of the voltage holding ratio, the evaluation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 33&gt; -114- 201030055 BODA (3.50 g, 14.0 mmol), PBCH 5 D AB (3.63 g, 8.39 mmol), diamine (B12) ( 2.58 g, 8.39 mmol), and DBA (1.70) g, 11·2 mmol) was mixed in NMP (23.5 g), and after reacting at 80 ° C for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP ( 18.8 g ) were added at 4 ° C. After the hour reaction, a polyaminic acid solution was obtained. After adding NMP to the polyamic acid solution (20.2 g) and diluting to a content of polyglycolic acid of 6 mass%, acetic anhydride (4 · 3 2 g ) as an imidization catalyst, and pyridine ( 3.3 4 g ), 3 · 5 hours reaction at 90 ° C. The reaction solution was poured into methanol (280 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to give a polyimine powder. The polyamidimide had an imidization ratio of 80%, a number average molecular weight of 17,100, and a weight average molecular weight of 47,100. To the polyimine powder (3.50 g), NMP (22.8 g) and BCS (32.lg) were added to obtain a liquid crystal alignment treatment agent [33]. 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 treatment agent [3 3], liquid crystal cells were produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was vertically aligned in a uniform manner. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after high-temperature placement were carried out -115-201030055. The results are shown in Table 16 and Table 17. &lt;Example 34&gt; BODA (3.48 g, 13.9 mmol), p BC Η 7 D AB (3.8 4 g, 8.35 mmol), diamine (Bl) (1.35 g, 5.56 mmol), and DBA ( 2.12 g, 13.9 mmol) was mixed in NMP (22.4 g), and after reacting at 80 ° C for 5 hours, CBDA (2_73 g, 13.9 mmol) and NMP (18 Og) were added, and the reaction was carried out at 40 ° C. After the hour reaction, a polyaminic acid solution was obtained. After adding NMP to the polyamic acid solution (20. Og) and diluting to a content of polyamine acid of 6 mass%, acetic anhydride (4.318) and pyridine (3.348) were added as an imidization catalyst. The reaction was carried out at 90° (the reaction was carried out for 3.5 hours. The reaction solution was poured into methanol (270 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a poly Yttrium imide powder. The imidization ratio of the polyimine is 81%, the number average molecular weight is 1,800, and the weight average molecular weight is 48,900. NMP (20.2 g) is added to the polyimine powder (3.11 g). And the BCS (28.4 g), the liquid crystal alignment treatment agent [3 4] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The obtained liquid crystal alignment treatment agent was used. [3 4] A liquid crystal cell was produced in the same manner as in Example 2, and the pretilt angle was evaluated. The results are shown in Table 15. The liquid crystal cell produced in the same manner as in Example 21 except that the rubbing treatment was not performed. Observed by a polarizing microscope, it was confirmed that the liquid crystal was in a uniform sentence. Further, the liquid crystal cell produced in the same manner as in Example 21 was used for the evaluation of the voltage holding ratio, the evaluation of the residual charge, and the evaluation after the high-temperature standing. The results are shown in Table 16 and Table 17. &lt;Example 35&gt; BODA (3.51 g, 14.0 mol), PBCH7DAB (3.88 g, 8.42 mmol), diamine (Bl) (2.04 g, 8.42 mmol), and DBA (1.71 g, 11.2 mmol) The mixture was mixed in NMP (23.1 g), and after reacting at 8 ° C for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (18. 4 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain polylysine. After adding NMP to the polyamic acid solution (20.2 g) and diluting to a content of polyglycine of 6% by mass, acetic anhydride (4-52 g) as an imidization catalyst and pyridine (3.61 g) were added. The reaction was carried out at 9 (TC) for 5 hours. The reaction solution was poured into methanol (30 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and then at 100 ° C. After drying under reduced pressure, a polyimine powder is obtained. The imidization ratio of the polyimine is 92%, and the number average molecular weight is 17,100. The amount average molecular weight was 46,900. NMP (22.8 g) and BCS (32.1 g) were added to the polyimine powder (3 - 51 g) to obtain a liquid crystal alignment treatment agent [35]. No turbidity was observed in the liquid crystal alignment treatment agent. Or an abnormal phenomenon such as precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [35], the liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. Further, the liquid crystal cell produced in the same manner as in Example 21 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal was uniformly aligned vertically. Further, the liquid crystal cell produced in the same manner as in Example 21 was used, and the evaluation of the voltage holding ratio, the evaluation of the relaxation of the residual charge, and the evaluation after the high-temperature standing were performed. The results are shown in Table 16 and Table 17. &lt;Example 36&gt; BODA (3.50 g, 14.0 mmol), BPCH5DAB (3.59 g, 8.39 mmol), diamine (Bl) (2.03 g, 8.39 mmol), and DBA (1.70 g, 11.2 mmol) in NMP ( The mixture was mixed in 22.5 g), and after reacting at 8 ° C for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (18 Og) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. . After adding NMP to the polyamic acid solution (20.0 g) and diluting to a content of polyglycine of 6 mass%, acetic anhydride (4.33 L) and pyridine (3.348) were added as an imidization catalyst. The reaction was carried out at 90° (the reaction was carried out for 3.5 hours). The reaction solution was poured into methanol (270 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a poly The imine imide powder has an imidization ratio of 81%, a number average molecular weight of 1,800, and a weight average molecular weight of 48,900. The polyamidimide powder (3.11 g) is added with NMP (22_7 g), And BCS (25.8g), the liquid crystal alignment agent [36] was obtained. In the liquid crystal distribution 201030055, no abnormal phenomenon such as turbidity or precipitation was observed in the treatment agent, and it was confirmed that the resin component was uniformly dissolved. [6 6] A liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. The liquid crystal cell produced in the same manner as in Example 21 except that the rubbing treatment was not performed. Observed by a polarizing microscope, confirmed The liquid crystal cells were uniformly aligned vertically. The evaluation of the voltage holding ratio, the evaluation of the residual charge, and the evaluation after the high-temperature standing were carried out using the liquid crystal cell produced in the same manner as in Example 21. The results are shown in Table 16 and Table 17. &lt;Printability Test&gt; Printing was carried out using the liquid crystal alignment treatment agents obtained in Examples 1 to 16, 21 to 36, and Comparative Examples 1, 2, 5, and 6. The printing machine was a simple printing machine manufactured by Sakamoto Photo Printing Co., Ltd. ( S 1 5 type). Printing on the washed chromium evaporation substrate, printing area 8cmx8cm, printing pressure 0.2mm, 5 pieces of substrate discarded, printing to false drying time of 90 seconds, false drying temperature 70 ° C, 5 In the minute, the pinhole was confirmed by visual observation under the sodium lamp. The number of pinholes in Table 11 and Table 15 is shown as a printability. -119- 201030055 [Table 9] Liquid crystal alignment treatment agent acid dianhydride component diamine component Diamined (A) diamined (B) diamine compound (C) Example 1 [1] CBDA (14.0 mmoO BODA (14.0 mrr) oO m-PBCH5DABz (4.20 mm οί} B1 (8.39 mmol) DBA (15.4mmo0 Example 2 [2] CBDA (14.0mmoi) BODA (14.0mmoD fn-PBCH5DABz (8.42 mmoO B1 (5.61 mmoO DBA (HOmnnol) Example 3 [3] CBDA (14.0 mmol) BODA (14_2 mmol) m-PBCH5DABz (8.39 mmol) B2 (112 mmol) DBA (8.39 mmol) Example 4 [4] CBDA ( 13.9 mmol) BODA (13.9 mmol) m-PBCH5DABz (8.35 mm 〇0 B3 C2.78mmoO DBA (16.7mm〇0 Example 5 [5] CBDA (14.0mm〇0 BODA (14-Ommol) m-PBCH5DABz (450mmd) B4 (8.39 mmol) DBA (15.4 mmol) Example 6 [6] CBDA (14.0 mmol) BODA (14.0mmoD m-P8CH5DABz (4-20 mmol) B5 (2.80 mmol) DBA (21.0 mmol) Example 7 [7] CBDA (14.0 nvno〇BODA (14-Ommol) m-PBCH5DABz (5.60 mmol) B6 (5,60 mmot) DBA (16_8mmot) Example 8 [8] CBDA (t4.0mmoO BODA (14.0mmoD m-PBCH5DABz (5.61 mmol) B7 (5.60 mmot) DBA (16.8 mm 〇 0 Example 9 193 CBDA (14.0 mmol) BODA (14-0mmot) m-PBCH5DABz ¢ 8.42 mmol) B8 (2.81 mmol) DBA (16.8 mmol) Example [10] CBDA (14.0mmoO BODA (14.0mmot) m-PBCH5DABz (8.42mm of) B9 (5.6ImmoO DBA (T4.〇mmol) Example) [11] CBDA (13-9 mmol) BODA (13.9mnx)0 m-PBCH5DABz ¢ 5.56 mm ot) B10 (2.78mmo0 DBA (19.5 mmot) Example 12 [12] CBDA (14.0mmoO BOD A (14.0 mmol) m-PBCH5DABz (8.39 mmol) B11 (5.60 mmol) DBA (14.0 mmoO Example 13 [13] CBDA (14.0mmo〇BODA (14.0mnfK&gt;D m-P8CH5DABz (8.39mm ot) B12 Cfi.39 Mmot) DBA (11 &gt; 2 mmol) Example Μ [14] CBDA (14.0mmo〇BODA (14.0mm〇D m-PBCH7DABz (8.42 mmol) 61 (5.61 mmoi) DBA (14.0mmot) Example 15 [15] CBDA (14.0mmoi) BODA (14-Ommol) m-8PCH5DABz (8.39mm ot) B1 (8.39 mmoO DBA (112mmot) Example 16 [16] CBDA C I3.9mmo〇BODA (13.9mmot) p-PBCH5DAB2 (8.35mmo0 B1 (8.35 mmol) DBA (n.lmmol)

-120- 201030055 [Table 〇] Liquid Crystal Alignment Treatment Agent Acid dianhydride Diamine Component Diamined (A) Diamined Diamine) Diamine Compound (Ο Comparative Example 1 [17] CBDA (14.0 mmol) BODA (14.0 mmol) PCH7DAB (4^1 mmol) B1 (8.42 nimo 〇 DBA (l5.4 mmol) Comparative Example 2 [18] GBOA (14.0 mmol) BODA C 14.0 mm 〇l) PCH7D/B (14.0 mmol) B1 (5.60 mmol) DBA (8.39 mmol) Comparative Example 3 CBDA (14.0 mmol) BODA (14.0 mmol) m-PBCH5DABEs (8.39 mmol) 81 (5j60 mmol) DBA (14.0mmo() Comparative Example 4 CBDA (14.0 mmol) BODA (U.Ommol) PBP5DAB (8.37mm ol) B1 (5.58 mmol) DBA (14.0 mmol) Comparative Example 5 [19] CBDA (13.9 mmol) BODA (l3.9 mm 〇0 PBCH5DAB (8.35 mmol) B1 (5.56 mmol) p-PDA (t3. 9mmol) Comparative Example 6 [20] CBDA (14.0 mmol) BODA (14.0 mmol) PBCH5DAB (8.39 mmol) S1 (5.60 mmol) DBA (14.0 mmol)

-121 201030055 [Table η] Liquid crystal alignment treatment agent imidization ratio (%) BCS introduction ratio 11 (Si%) Pretilt angle C) Printability (number of pinholes) Example 1 [1] 54 59 54.6 &lt;5 Implementation Example 2 [2] 80 53 87.5 &lt;5 Example 3 [3] 56 55 87.6 &lt;5 Example 4 [4] *2 53 87.5 &lt;5 Example 5 [5] 81 53 54.8 &lt;5 Example 6 [6] 55 53 54.6 &lt;5 Example 7 [7] 56 48 86.5 &lt;5 Example 8 C8] 80 59 86.3 &lt;5 Example Θ [9] *2 59 88.4 &lt;5 Example 1 [10] 79 59 87.5 &lt;5 Example η [Π] *2 53 86.2 &lt;5 Example 12 [12] 80 59 87.1 &lt;5 Example 13 [13] 81 59 86.5 &lt;5 Example Η [ Μ] 80 59 86.8 &lt;5 Example 15 [15] 54 59 87.4 &lt;5 Example 16 [16] 79 53 86.5 &lt;5 Comparative Example 1 [17] 54 53 15.2 &lt;5 Comparative Example 2 [18] 55 53 86.9 &lt;30 Comparative Example 3 - 54 43 *3 &gt; 50 Comparative Example 4 - 55 43 *3 &gt; 50 Comparative Example 5 [19] 55 53 82.5 &lt;5 Comparative Example S [20] 54 53 85.0 &lt;;5 -122 - 1 1 : The ratio of BCS used by the entire solvent in the liquid crystal alignment agent. * 2: Glycine. * 3 : It cannot be evaluated because of the precipitation of the resin component. 201030055 [Table 12] Liquid crystal alignment treatment agent voltage retention rate (%> 16.67 ms 1667 ms 16.67 ms 1667 ms after high temperature placement in liquid crystal cell fabrication Example 1 [1] 98.2 67.7 98.0 67.1 Example 2 [2] 98.7 68.7 98.4 68.8 Implementation Example 3 [3] 97.8 67.7 98.0 67.0 Example 4 [4] 97.4 65.3 96.7 65.1 Example 5 [5] 98.6 68.7 98.4 68.4 Example 6 [6] 98.1 67.6 98.5 66.9 Example 7 [7] 98.4 67.7 98.4 67.3 Implementation Example β [8] 98.8 68.7 98.4 68.7 Example 9 [9] 97.7 67.6 97.1 67.4 Example 10 [1〇] 98.7 68.5 98.1 68.1 Example &quot;[&quot;] 97.6 67.5 97.Ϊ 67.2 Example 12 [12] 98.6 68.7 98.4 68.3 Example 13 [13] 98.7 68.6 98.3 68.2 Example Η [Η] 98.6 68.6 98.3 68.4 Example 15 [15] 98.4 68.7 98.4 68.2 Example 16 (10) 98.6 68.6 98.5 68.6 Comparative Example 1 [17] 96.6 64.5 96.2 63.2 Comparative Example 2 [1S] 98.0 67.1 98.0 67.0 Comparative Example 3 - *\ *1 *1 *1 Comparative Example 4 - *1 *1 *ί Comparative Example 5 [19] 97.8 66.8 97.5 66.8 Comparative Example 6 [20] 97.7 66.6 97.4 66.5

* 1 : It cannot be evaluated because of the precipitation of the resin component.

-123- 201030055 [Table 13] Releasing the residual charge of the liquid crystal alignment agent (V) After the liquid crystal cell was fabricated, 50 seconds later, 1000 seconds later, 50 seconds later, and 1000 seconds later, Example 1 [1] 2.46 029 2.55 035 Implementation Example 2 [2] 3.74 0.70 3.80 102 Example 3 [3] 2.98 0.60 3.28 0.65 Example 4 [4] 0.79 0.12 0.90 0.14 Example 5 [5] 2.84 0.55 2.96 0.61 Example 6 [6] 2.54 0.30 2.61 0.38 Implementation Example 7 [73 2.65 058 2.84 0.49 Example 8 [8] 3.53 0.63 2.44 03Ϊ Example 9 [9] 0.75 0.1 1 0.84 0.13 Example 叩 (10) 3.72 0.67 3.80 050 Example 11 [&quot;] 0.73 0.10 0.85 0.11 Example 12 [12] 3.81 0.69 3.80 088 Example 13 [13] 3.65 0.63 3.81 084 Example Η [14] 3.61 0.61 3.78 030 Example 15 [15] 3.90 0.75 4.00 104 Reward 16 [16] 3.61 0.62 3.92 090 Example 1 [Π] 2.56 0.32 2.64 0.41 Comparative Example 2 [18] 3.03 0.74 3.34 077 Comparative Example 3 *1 *1 *1 Comparative Example 4 *1 *1 *1 *1 Comparative Example 5 [19] 4.02 0-98 4.59 138 Comparative Example β [20] 4.12 1.03 4.61 2J04 * 1 : Due to the precipitation of the resin component, it cannot be evaluated. 124 201030055 [Table 14]

Liquid crystal alignment treatment agent Acid dianhydride component Diamine component Diamine compound (A) Diamine compound (B) Diamine compound (Ο Example 21 [2J] GBDA (14.0m mot) BOD/K (14.0iryn〇0 PBCH5DAB ( 4J21 mmol} B1 (8.42 m moi) DBA (15.4 mmo0 Example 22 [22] CBDA (I4.0 mm〇l) BODA (PBCH5DAB (8.37 mmol) B1 (5.58 m moO DBA (t4.0 mmol) Example 2 3 [ 231 CBDA (i4.2mmoi) BODA (ί 42mmoi) PBCH5DAB (8.51 mmol) B2 (11.4mm〇l) DBA (8.51 mmol) Example 24 [24] CBDA (H.Ommcrf) BODA (i4J0mm〇0 PBCH5DAB (8.42mmol) B3 (2.81 rpm 〇 l) DBA (16.8 mfTK) l) Example 25 [25 Ϊ CBDA (13.9 m mo}) BODA (13, 9 mm 〇 0 PBCH 50 AB B4 (8.35 mmol) DBA (15.3 mmol) Example 26 [26 CBDA (14.0mm〇l) BODA (14.0mmot) PBCH5DAB (4_2〇mmol) B5 (2.80m mol) DBA (21.Ommol) Example 27 [27] CBDA (14.1 mmol) BODA (14.1mmo〇PBCH5DAB (5.63 Methyl) B6 (5.63m mol) DBA U6.9mfT&gt; ot) Example 2B [28] CBDA (14.0mmoi) BODA (14.0mrnoi) PBCH50AB [5.60 mmol) 87 (5.6〇mmof) DBA (165mnx&gt;t) Example 2 9 [29] CBDA (14.0mmol) BODA (I4.0mmot) PBCH5DAB ¢8.42 m Mol) ΒΘ (2.81mm〇i) DBA (16.8mmo() Example 30 [30] CBDA (i4.0mm〇i) BODA 〇4.0mmoi) PBCH5DA8 (8.39 mmol) 89 (5.6〇mfn〇l) DBA (I4 , 0mm〇|) Example 31 [31 ] CBDA (l3.9mmoi) BODA (l35mfr»ot) PBCH5DAB (5.56 mmol) B10 (2.78m mol) DBA (I9.5mmo〇 Example 32 [32] CBDA (14.0mmoi BODA {14.0mmo〇PBCH5DAB (8.37 mmol) Bil (5.58m mol) DBA (14.0mrr> 〇0 Example 33 [33] CBDA (14.0m mol) BODA (14.0ίτϊτπ〇0 PBCH5DAB (8.39 mmol) B12 (8.39 m mol) DBA (112 mmol) Example 34 [34] CBDA (13.9 m mol) BODA (13.9 mm 〇l) PBCH7DAB (835 mmol) ΒΪ (5.56 mmol) DBA (13.9 mmol) Example 35 [35] CBDA (14.0mmoi) BODA PBCH7DAB (8.42 mmol) B1 (8.42 m moi) DBA () 12 mmol) Example 36 [36} CBDA (14.0 m mol) BODA (Ϊ 4.0mmoO BPCH5DAB (8.39 mmol) B1 ¢8.39m mol) DBA C11.2mmot -125- 201030055 [Table 15] Liquid crystal alignment treatment agent imidization ratio (%) bcs introduction ratio η (%) Pre-network c*) Printability (number of pinholes) Example 2! [2«] 55 59 53.4 &lt;5 Example 22 Γ22] 81 53 873 &lt;5 Example 23 [231 55 53 87.5 &lt; 5 Example 24 "24] *2 53 87^ &lt;5 Example 25 [25] 80 53 54.5 &lt;5 Example 26 L26J 53 53 54 J2 &lt;5 Example 27 [27] 55 48 86:2 &lt; 5 Example 28 [28] 8! 59 86.1 &lt;5 Example 29 1291 *2 59 88.3 &lt;5 Example 30 (30) 78 5d S7.4 &lt;5 Example 31 [313 * 2 53 85.9 &lt; 5 Example 32 [321 81 S9 87.0 &lt; 5 Example 33 CJ3| 80 59 86.3 &lt;5 Example Μ [34] 81 59 86.5 &lt;5 Example 35 [35] 92 59 86 J &lt; 5 Example 36 [36] 81 53 86.3 &lt;5 * 1 : The ratio of use of BCS in the liquid crystal alignment agent. * 2 ··Glycanic acid》126-201030055 【91«】i£w- I s ^.s S9 •s CK9 •89 •5 9§ 3 ε o5 s 0s U9 •S9 ·£ 游蟹s 0 ^0S0 Xia Indium—9.91 iA99l iss

986 26 9-6 inch 96 Ϊ86 Γ布 6 26 0-6 Gs 26 «86 S.S6 S6 0.86 $86 IB S9 S9 i •s • Bu 9 -91° • ε 6S · £ · £ • s Ms ts 8· 2 8卜9 i Ling•s® 8·8β •86 1°Bu 6 i 9.Bu 6 S6 56 ii 086 896 i

Isitsej ιέ § ca s log [si § [s] [s] s § M § 9i layer m_s H_s mis 0^1« ^1« s 丽 w ΰ 1Λ 9ms SIW production series 5_* 识§ 13 丽 w -127 - 201030055 s Class noisy if stupid §1 ia &lt;Λ^:α&gt;&lt;ΛΛρ&lt;3&gt;〇—〇〇〇〇〇〇〇〇〇〇〇〇—〇—Qc〇rrCviU&gt;cpc〇ir&gt;ocou&gt;»—*-*ιηοοοσσ&gt;〇&lt;οα6^οο oooqcqcacop ο 〇4^iciQ&lt;r&gt;c4c*i^4C&gt; ci C&gt; ci ci ci d 孽113⁄4 (&gt;)«! Chowder Mwssi paper stupid i 〇_竹竹&lt;〇,-〇寸〇〇&gt;-卜l〇U&gt;VP^ 〇r-&lt;o — if&gt;c〇&lt;o&lt;o — &lt;〇— no to o &lt;〇 Ooooooobooboodoo ts 0*0«·&gt;0 CMCMCMOO &lt;Ο〇«Τ5&lt;Λί?0ί^ K-foot®aa&lt; 灌^ «·« ·-t » » * » r 1 c , » Ι·ΠΆ JV · 1 * t^_&lt; t^ti—* «__( I _· I_I . · .· U^l Immi U^T Urn* «·*·&gt;&gt; si 堤丽丽K isigK iK οε I grip κ βζ_« 5_κ 9is SZ_M I series H iyi 揖K tCSIri [Industrial Applicability] Using a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention The liquid crystal display device is excellent in reliability, and is suitable for use in a large-screen, high-definition liquid crystal television, and is industrially useful. Moreover, Japanese Patent Application No. 2008-245037 filed on September 24, 2008, And the entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2008-24 5 03 8 filed on Sep. 24, 2008, the entire contents of

Claims (1)

.201030055 VII. Patent application garden: 1. A liquid crystal alignment treatment agent characterized by containing a copolymer which contains a diamine compound (A) represented by the following formula [1], the following a diamine compound (B) represented by the formula [2], a diamine component of a diamine compound (C) having a diamine compound having a carboxyl group in the molecule, and a reaction with a tetracarboxylic dianhydride; [Chemical Formula 1] P [ 1] [2] (In the formula [1], p is an integer of 0 or 1, X! is a phenyl group, x2 is a phenyl or cyclohexyl group, x3 is a cyclohexyl group, and X4 is a carbon number of 3 to 12. An alkyl group, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms; in the formula [2], 丫1 is -〇-, - NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, -OCO-, -CON(CH3)-, or φ-N(CH3)CO-, Υ2 is a single bond, carbon number 1 to 20 aliphatic hydrocarbon group, non-aromatic cyclic hydrocarbon group, or aromatic hydrocarbon group, γ3 is a single bond, -Ο-, -ΝΗ-, -N(CH3)-, -CONH-, -NHCO-, -COO -, -OCO-, -CON(CH3)-, -N(CH3)CO-' or - 〇(CH2)m- (m is an integer from 1 to 5), Y4 is a nitrogen-containing aromatic heterocycle, and η is 1 to 4 Number). 2. The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the diamine compound (Α) is a diamine compound represented by the following formula [1'] (a, -129- 201030055 [Chemical 2] NH, Η2Ν - 11^5^0, χ, Χ 2'χ3/Χ4 [Γ] (In the formula [1'], Xi, χ2, χ3, and χ4 are the same as the above formula [3] Liquid crystal alignment processing according to item 1 of the patent application scope The diamine compound (A) is a diamine 1] synonymous with the following formula [1 ''], wherein the former compound (Α&quot; [Chemical 3] [Γ] (In the formula [厂], 乂''1 is a 1,4-phenylene group or a 1,4-cycloalkylene group having a carbon number of 3 to 12, a fluoroalkyl group having a carbon number of 3 to 12, A carbon number oxy group or a fluoroalkoxy group having a carbon number of 3 to 12). 4. The liquid crystal alignment treatment of the amine compound (A') as in the second paragraph of the patent application is a diamine compound represented by the following formula [丨| a], and the oxime &quot; 2 is an alkane of 3 to 12 ϋ, two of them (In the formula [l'a], 'X5 is an alkyl group having 3 to 12 carbon atoms, an alkyl group having 3 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkane having a carbon number of 3 to 12 and a fluoroalkane of 12 to 12; Base, I, 4· -130- 201030055 The cis-trans isomerism of the cyclohexyl group is each a trans isomer). 5. The liquid crystal alignment treatment agent of claim 2, wherein the diamine compound (A') is a diamine compound represented by the following formula [1 'b]; (In the formula [l'b], X6 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. The cis-trans isomer of the group, I, 4·cyclohexylene is a trans isomer). 6. The liquid crystal alignment treatment agent of claim 3, wherein the diamine compound (A&quot;) is a diamine compound represented by the following formula [1 &quot;a]; (In the formula [l&quot;a], X&quot;3 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluorine having 3 to 12 carbon atoms. The alkoxy group, the cis-trans isomer of 1,4-cyclohexylene is each trans isomer). 7. The liquid crystal alignment treatment agent of claim 3, wherein the diamine compound (A&quot;) is a diamine compound represented by the following formula [1''b]; • 131 - 201030055 [Chem. 7] The alkyl group, the alkoxy group having a carbon number of 3 to 12, or the cis-trans isomer of the gas oxy-' 1,4 -cyclohexylene having a carbon number of 3 to 12 is a trans isomer). 8. The liquid crystal alignment treatment agent according to any one of claims 2 to 7, wherein Υι in the formula [2] is -0-, -NH-, -CONH·, -NHCO-, -CON (CH3)-, or -CH20-. 9. The liquid crystal alignment treatment agent according to any one of claims 2 to 8, wherein Υ2 in the formula [2] is a single bond, a linear or branched alkyl group having a carbon number of 1 to 5, or benzene ring. The liquid crystal alignment treatment agent of any one of the second to the ninth aspect of the invention, wherein the Υ3 in the formula [2] is a single bond, -〇_, -CONH-, -NHCO-, _c〇 0_, _0C0_' or -CKCHaU· ( „! is an integer of i 〜5. 11. The liquid crystal alignment treatment agent according to any one of claims 2 to 10, wherein Y4 in the formula [2] is pyrrole a ring, an imidazole ring, a pyridinium ring, an acridine ring, or a pyrimidine ring. 1 2. A liquid crystal alignment treatment agent according to any one of claims 2 to 1 wherein n in the formula [2] An integer of 1 to 3. The liquid crystal of the item is -132.201030055 -CONH-, a treatment agent, wherein γ^_〇_, _NH-NHCO-, -CON(CH3)-, or - CH20-' γ2 is a linear or branched base of carbon number 5 'Υ3 is a single bond' Υ4 is a salicious ring, a oxime ring, an anthracene ring, a pyridine ring, or a pyrimidine ring, and η is 1 to 3 In the liquid crystal alignment treatment agent of any one of the second to seventh aspects of the invention, wherein the ¥1 in the formula [2] is _〇_, -Nh_, _c〇NH_, -NHCO- , _CON(CH3)_, or, γ2 is a benzene ring, which is 〇_ , -CONH-, _NHC0·, _C〇〇_, _〇c〇_, or 〇(CH2)m (m is an integer from 1 to 5), and Y4 is a pyrrole ring, an imidazole ring, a pyridinium ring, a pyridine ring, Or a pyrimidine ring, η is an integer of 1. I. The liquid crystal alignment treatment agent of any one of Items 2 to 14 wherein the diamine compound (C) is a diamine compound represented by the following formula [3]; 〇H)k [3] h2n/Zi, nh2 (In the formula [3], Z1 is an organic group having an aromatic ring having a carbon number of 6 to 3 Å, and k is an integer of 1 to 4) ^1. The liquid crystal alignment treatment agent of the fifth aspect of the invention, wherein the diamine compound of the formula [3] is a group selected from the group consisting of the following formula [3a], formula [3b], formula, formula [3d] and formula [3e] At least one diamine compound; -133- 201030055 [Chemical 9] (CH^nuCOOH (CH2)m6COC 6cooh h2 Η2Ν-〇-?-〇·ΝΗ2 (CH2)m5COOH [3c] [3d] (CO〇H)m7 [3e] (in the formula [3a], (1) is an integer of ～4; In [3b], Z2 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)-, -0-, -CO-, -NH-, - N(CH3)·, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO-, -OCO-, -CON(CH3)... or -N(CH3)CO-, m2 and 1η3 An integer of 〇~4, and m2 + m3 represents an integer of 1 to 4; in the formula [3c], 'm4&amp;m5 are each an integer of 1 to 5; in the formula [3(1), z3 is a carbon number of 1 to 5; Linear or branched alkyl, „!6 is an integer from 1 to 5; in the formula [3e], Z4 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C (CF3)-, -Ο- ' _c〇-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -〇CH2-, -COO-, -OCO-, - CON(CH3)-, or -N(CH3)C〇-,... is an integer of !~') e 1 7 . The liquid crystal alignment treatment agent of claim 6 of the patent application, wherein '1 in the formula [3a] ^ is an integer of 1 to 2. 1 8 · As claimed in the patent scope! 6 liquid crystal alignment treatment agent, wherein -134-.201030055 [3b] in 'Z2 is a single Key, _(^2-, -(:2114-'-〇:((:113)2-, -〇-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO -, -COO-, or -OCO-, m2 and m3 are integers of 1. 19. The liquid crystal alignment treatment agent of claim 16, wherein in the formula [3e], 'Z4 is a single bond, _cH2-, -Ο-, -CO., -NH-, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO-, or -OCO-, ΙΠ7 is an integer from 1 to 2. 2 〇. The liquid crystal alignment treatment agent according to any one of the items 2 to 9 wherein the diamine compound (Α) is 〇, 5 to 1 mol of the diamine compound (C). 5〇摩尔, the diamine compound (β) is 〇.5 〜1 〇 mol for 1 mol of the diamine compound (C). 21. As in any of claims 2 to 20 The liquid crystal alignment treatment agent, wherein the liquid crystal alignment treatment agent contains a solvent of 5 to 70% by mass in the liquid crystal alignment treatment agent. 22. The liquid crystal alignment treatment agent of any one of the second to the twenty-first aspect of the invention, wherein the liquid crystal alignment The copolymer in the treating agent is a polyimine obtained by subjecting polylysine to dehydration ring closure. A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of claims 2 to 22. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 23 of the patent application. -135- 201030055 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201030055 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (Chemical 1) (Chemical 1) 4)n [2]