KR20150094711A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(식 (1) 중, P¹ 은 단결합 등을 나타내고, Q¹, Q², Q³ 은 각각 독립적으로 2 가의 벤젠 고리 등을 나타내고, p, q, r 은 각각 독립적으로 0 또는 1 의 정수를 나타내고, P² 는, 수소 원자 등을 나타낸다.)
(B) 성분: 상기 테트라카르복실산 성분과, 또한 디아민 성분이 주사슬에 -CR²¹ ₂-기 (여기서, 2 개의 R²¹ 은, 각각 독립적으로 수소 원자 등을 나타낸다) 를 갖는 디아민만으로 이루어지는 중합체A liquid crystal aligning agent comprising at least one polymer selected from a polyimide precursor and a polyimide obtained by polymerizing a tetracarboxylic acid component and a diamine component, the component (A) and the component (B).
(A): the tetracarboxylic acid component includes at least one selected from 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride and the like, A polymer comprising a diamine having a side chain represented by the formula (1)

(Formula (1) of, P ¹ represents such a single ^{bond, Q 1, Q 2, Q} 3 represents a second such valent benzene ring, each independently, p, q, r are each independently an integer ranging from 0 to 1 And P ² represents a hydrogen atom or the like.)
(B): a polymer composed of only the diamine having the tetracarboxylic acid component and the diamine component having -CR ²¹ ₂ - group (wherein two R ²¹ each independently represent a hydrogen atom or the like) in the main chain

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent used in manufacturing a liquid crystal alignment film, a liquid crystal alignment film using the same, and a liquid crystal display element.

BACKGROUND ART A liquid crystal display element is widely used as a display device at present. A liquid crystal alignment film which is a constituent member of a liquid crystal display element is a film for uniformly arranging liquid crystals, but various characteristics as well as alignment uniformity of the liquid crystal are required.

For example, in the manufacturing process of a liquid crystal alignment film, it is common to carry out an alignment process called rubbing in which the surface of the polymer film is rubbed with a cloth. However, when the rubbing resistance of the liquid crystal alignment film is insufficient, the film is scratched to cause scratches or dust, or the film itself peels off, and the display quality of the liquid crystal display element deteriorates. The liquid crystal display element is driven by applying voltage to the liquid crystal. Therefore, when the voltage holding ratio (VHR) of the liquid crystal alignment film is low, a sufficient voltage is not applied to the liquid crystal and the contrast of display is lowered. Further, if a time is taken for electric charges to accumulate in the liquid crystal alignment film due to the voltage for driving the liquid crystal or to escape from the accumulated electric charge, a phenomenon such as afterimage or display burn-in occurs.

Various proposals have been made to satisfy at the same time some of the above-mentioned demand characteristics. For example, as a method for obtaining a liquid crystal alignment film excellent in rubbing resistance and having less after-image or burn-in, proposal as disclosed in Patent Document 1 has been made. Also, as a method for obtaining a liquid crystal alignment film having excellent liquid crystal aligning property, alignment regulating ability, rubbing resistance, high voltage holding ratio, and reduced charge accumulation, the same proposal as Patent Document 2 has been made.

International Publication WO02 / 33481 pamphlet International Publication No. WO 2004/053583 pamphlet

Recently, a liquid crystal display device mounted on such a mobile phone (smart phone) or a tablet-type terminal is required to display a high definition picture such as a picture or display a moving picture, High-quality display performance equal to or higher than that of the conventional display device is required.

Incidentally, the display screen for the mobile phone or the tablet terminal is a display which is often not seen in other applications, such as the fact that the display is frequently turned on and off (or the backlight frequently turns on and off) Feature. From this point of view, demands for charge accumulation and the like have become more stringent than in the past.

Disclosure of the Invention The object of the present invention is to solve the problems of the above-described conventional techniques, and to provide a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal alignment film capable of obtaining a liquid crystal alignment film having a high voltage holding ratio and a very small charge accumulation while maintaining rubbing resistance. And to provide a display device.

Means for Solving the Problems As a result of intensive studies to attain the above object, the present inventors reached the present invention based on the following points.

1. A liquid crystal aligning agent which comprises the following component (A) and the following component (B).

(A): at least one polymer selected from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing the polyimide precursor, wherein the tetracarboxylic acid component 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester and Dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester dichloride, and the diamine component comprises at least one member selected from the group consisting of a side chain represented by the following formula (1) ≪ RTI ID = 0.0 >

[Chemical Formula 1]

(1), P ¹ represents a single bond or a divalent organic group, Q ¹ , Q ² and Q ³ each independently represent a divalent benzene ring or cyclohexane ring, p, q and r each independently And P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton.

Component (B): at least one polymer selected from a polyimide precursor obtained by polymerization reaction of a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing the polyimide precursor, wherein the tetracarboxylic acid component 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester and 1,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester dichloride, and the diamine component comprises at least one member selected from the group consisting of -CR ²¹ ₂ - group (Wherein two R ^{21 s} each independently represent a hydrogen atom or an organic group and two R ^{21 s} may be combined to form a cyclic structure)

2. The liquid crystal aligning agent according to item 1, wherein in the component (B), the diamine component comprises only a diamine represented by the following formula (2).

(2)

(2), each X independently represents an oxygen atom or a single bond, n represents an integer of 1 to 10, and two R ^{22 s} each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, A fluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom, or two R ^{22 s} may be combined to form an alkylene group having 2 to 7 carbon atoms to form a cyclic structure.)

3. The liquid crystal aligning agent according to 1 or 2, wherein in the component (A), the diamine having a side chain represented by the formula (1) is a diamine represented by the following formula (3).

(3)

(Formula (3) of the, P ¹ represents a single bond or a divalent organic ^{group, Q 1, Q 2, Q} 3 are each independently a divalent group represents a benzene ring or cyclohexane ring, p, q, r are each independently And P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton.

4. A liquid crystal alignment film obtained by applying a liquid crystal aligning agent described in any one of 1. to 3. onto a substrate and firing the liquid crystal alignment agent.

5. A liquid crystal display element having the liquid crystal alignment film described in 4.

Since the liquid crystal aligning agent of the present invention contains specific components (A) and (B), it is possible to maintain the rubbing resistance which is a conventionally required property while maintaining the voltage retention ratio and satisfying strict requirements in modern times It is possible to form a liquid crystal alignment film having a very small amount of charge accumulation.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention contains the component (A) and the component (B). The liquid crystal aligning agent is a solution for preparing a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning the liquid crystal in a predetermined direction. Each component contained in the liquid crystal aligning agent of the present invention will be described in detail below.

≪ Component (A) >

The component (A) contained in the liquid crystal aligning agent of the present invention is preferably at least one selected from the group consisting of a polyimide precursor obtained by polymerization reaction of a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing the polyimide precursor Lt; / RTI > Examples of the polyimide precursor include polyamic acid (also referred to as polyamide acid), polyamic acid ester, and the like.

In the component (A), the tetracarboxylic acid component is preferably 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride (hereinafter also referred to as "TDA" , 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester (hereinafter also referred to as "TDA diester") and 3,4-dicarboxy- , 4-tetrahydro-1-naphthalene succinic acid diester dichloride (hereinafter also referred to as "TDA diester dichloride"). Therefore, as described later in detail, the polymer of component (A) is a polymer having a tetravalent structure represented by the following formula (4) derived from TDA, TDA diester or TDA diester dichloride.

[Chemical Formula 4]

The content of the total amount of TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component in the component (A) is, for example, 20 to 100 mol%, but preferably 40 to 100 mol% Mol%.

In the component (A), the diamine component to be polymerized with the tetracarboxylic acid component includes a diamine having a side chain represented by the above formula (1). The main chain of the diamine is a structure connecting two amino groups of a diamine, and the side chain of the diamine is a structure branched from a structure connecting two amino groups of a diamine. Therefore, the polymer of the component (A) contains a diamine having a side chain represented by the formula (1) in the raw material, and therefore the polymer of the component (A) has a benzene ring, -P ¹ bonded to the benzene ring-is a structure having the (Q ³⁾ _r -P ² a side chain, _{^{- (Q 1) p - (}} Q 2) q.

In the TN (Twisted Nematic) mode in which a comparatively low pretilt angle of 3 to 5 degrees is required in the side chain represented by the formula (1), in an OCB (Optically Compensated Bend) mode in which a pretilt of 8 to 20 is required, (-P ¹ - (Q ¹ ) _p - (Q ² ) _q - (Q ³ ) _r -P ² ) having a relatively low tilting ability.

In the formula (1), P ¹ is preferably -O-, -NHCO- or -CONH-, p is 0 to 1, q is 0 to 1, and r is 0 When p and / or q is 1, P ² is preferably a straight chain alkyl having 1 to 12 carbon atoms, and when p = q = r = 0, P ² is a straight chain alkyl group having 10 to 22 carbon atoms or A divalent organic group having a steroid skeleton and an organic group having 12 to 25 carbon atoms is preferable. Examples of specific structures of side chains having a small tilting ability are shown in Table 1, but the present invention is not limited thereto. In the present specification, the organic group is, for example, a hydrocarbon group which may have -O-, -NHCO-, -CONH-, -COO-, N or O.

[Table 1]

From the viewpoint of electrical properties, the diamine having a long-chain alkyl side chain as shown in [1-1] in Table 1 is preferable, and from the viewpoint of liquid crystal alignability and stability of the pretilt, the side chain represented by [1-9] Is preferred.

On the other hand, in the VA (Vertical Alignment) mode and the like, vertical orientation can be obtained by using a side chain having a high tilt manifestation ability. P is 0 to 1, q is 0 to 1, and q is an integer of 1 to 3. The preferable structure of the formula (1) in the VA mode is that in the formula, P ¹ is -O-, -COO- or -CH ₂ O-, , r is preferably 0 to 1, and P ² is preferably 2 to 22. When p = q = r = 0, P ² is preferably a linear alkyl group having a carbon number of 18 to 22, or a divalent organic group having a steroid skeleton and an organic group having 12 to 25 carbon atoms. The specific structures of the side chains having a large tilting ability are shown in Tables 2-1 and 2-2.

[Table 2-1]

[Table 2-2]

These side chains have high tilting performance and are preferably used in the VA mode. In particular, diamines having side chains such as [1-15] and [1-31] are preferred because they exhibit a high tilting ability and show a vertical orientation with a relatively small amount of side chain. Particularly, [1-18] or [ -34] is preferred because of its high tilt-forming ability and its vertical orientation can be obtained with a very small amount of side chains, in view of the printability of the liquid crystal aligning agent.

On the other hand, in the diamine having a side chain represented by the formula (1), P ¹ is preferably -NHCO-, and P ² is preferably an alkyl group having 1 to 16 carbon atoms, preferably 3 to 10 carbon atoms. Q ¹ , Q ² , Q ³ and p, q, and r are appropriately selected. In the case where such a diamine has a benzene ring in its main chain and has -P ¹ - (Q ¹ ) _P - (Q ² ) _q - (Q ³ ) _r -P ² bonded to the benzene ring as a side chain , The position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amino groups is preferably meta or para.

Examples of the diamine having a side chain represented by the above formula (1) include, for example, the following [DA-1] to [DA-26].

[Chemical Formula 5]

(Wherein [DA-1]) to ([DA-5] of the, R ₆ is an alkyl group or a fluorinated alkyl group having a carbon number of 1 to 22)

[Chemical Formula 6]

(In the formulas [DA-6] to [DA-9], S ₅ may be the same or different and each represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, - O-, -CO-, or -NH-, and R ₆ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.

(7)

(In the formula [DA-10] and the formula [DA-11], S ₆ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO- and R ₇ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

[Chemical Formula 8]

(Wherein [DA-12]) to ([DA-14], S ₇ are, -COO-, -OCO-, -CONH-, -NHCO- , -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH ₂ -, or -CH ₂ -, and R ₈ is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms)

[Chemical Formula 9]

(In the formulas [DA-15] and [DA-16], S ₈ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH _{2 O-, -OCH 2 -, -CH 2} -, -O-, or represents -NH-, R ₉ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, An acetoxy group, or a hydroxyl group.

[Chemical formula 10]

(11)

(In the formulas [DA-17] to [DA-20], R ₁₀ is an alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans-isomer.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

The content of the diamine having a side chain represented by the above formula (1) is preferably 5 to 50 mol% based on the total amount of the diamine component, particularly preferably 5 to 30 mol% from the viewpoint of the uniformity of the pretilt and the printing property Do.

Further, (A) in the composition formula (1) with a diamine having a side chain represented by is a diamine, that is, having a benzene ring in the main chain represented by the formula (3), bonded to the benzene ring -P ¹ - (Q ¹ ) _p - (Q ² ) _q - (Q ³ ) _r -P ² as a side chain is preferred from the viewpoint of availability and the like.

In the diamine represented by the formula (3), the position of each substituent on the benzene ring is not particularly limited, but the positional relationship of the two amino groups is preferably meta or para.

The tetracarboxylic acid component as the raw material of the component (A) may contain other tetracarboxylic acid derivatives other than the above TDA, TDA diester and TDA diester dichloride. Examples of other tetracarboxylic acid derivatives in the component (A) include the following tetracarboxylic acid dianhydrides.

Examples of the tetracarboxylic acid dianhydride having an alicyclic or aliphatic structure include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo Butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,2,4,5 Cyclohexane tetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, bicyclo [3.3.0] octane- 2,4,6,8-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, cis -3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, tri Cyclo [4.2.1.0 ^2,5] nonane -3,4,7,8- tetracarboxylic acid -3,4: 7,8-2 anhydride, hexahydro cyclo [6.6.0.1 ^2,7 .0 ^3,6. 1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5: and the like 11,12-2 anhydride.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid Acid anhydride, 2,3,3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3 ', 4 (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, bis A tetracarboxylic acid dianhydride, a tetracarboxylic acid dianhydride, a 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and the like.

The tetracarboxylic acid dianhydride may be used alone or in combination of two or more, depending on the properties of the liquid crystal alignment film to be formed, such as liquid crystal aligning property, voltage holding property, and accumulated charge.

Other tetracarboxylic acid derivatives that may contain a tetracarboxylic acid component as a raw material of the component (A) include a tetracarboxylic acid dialkyl ester and a tetracarboxylic acid dialkyl diester dichloride. Further, when the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamic acid ester which is a polyimide precursor. The tetracarboxylic acid dialkyl ester which can be used is not particularly limited and includes, for example, aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters. Specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl Ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2, Butanetetracarboxylic acid dialkyl ester, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclohexyltetra Dialkyl carboxylate Stearyl, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5] nonane -3,4,7,8- tetracarboxylic acid -3,4: 7,8-di-alkyl ester, cyclo hexa [6.6.0.1 ^2,7 .0 ^3, and the like 11,12- dialkyl esters: ⁶ .1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5.

Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-biphenyltetracarboxylic acid Biphenyltetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3', 4'-biphenyltetracarboxylic acid dialkyl ester, Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfonyl alkyl ester, 1,2,5,6- Naphthalene tetracarboxylic acid dialkyl ester, and 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester.

The tetracarboxylic acid dialkyl diester dichloride as another tetracarboxylic acid derivative which may contain a tetracarboxylic acid component which is a raw material of the component (A) may be a dichloride of the above tetracarboxylic acid diester .

The content of the total amount of other tetracarboxylic acid derivatives other than TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component in the component (A) is preferably 0 to 80 mol% , And more preferably 0 to 40 mol%.

The diamine component as the raw material of the component (A) may contain other diamines other than the diamine having a side chain represented by the above formula (1). Examples of other diamines in the component (A) include the following alicyclic diamines, aromatic diamines, heterocyclic diamines, aliphatic diamines and urea bond-containing diamines.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'- Dimethyldicyclohexylamine, isophoronediamine, and the like.

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, Diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino- 2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene , 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'- Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis Bis (4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) benzene, Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- Bis (4-aminophenyl) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, 4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, , 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrrene, 1,6-diamino Pyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, (4-aminophenyl) ethane, 1,3-bis (4 (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4-aminophenyl) octane, 1,9-bis Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) propane, Heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) Di (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, Di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane- Di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) decane- Bis [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4 (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- ] Heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- - (4-aminophenoxy) phenoxy] decane, and the like.

Examples of the aromatic-aliphatic diamine include diamines represented by the following formula [DAM].

[Chemical Formula 15]

(In the formula [DAM], Ar represents a benzene ring or a naphthalene ring, R ₁ is an alkylene group having 1 to 5 carbon atoms, and R ₂ is a hydrogen atom or a methyl group.

Specific examples of the aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, Amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (4-aminobutyl) aniline, 3- (4-aminobutyl) aniline, 4- Aniline, 4- (5-methylaminobutyl) aniline, 4- (5-aminopentyl) aniline, 4- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- Amine and the like.

Examples of the heterocyclic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, Diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole Sol and the like.

Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6- 2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino- Diamino-5-methylnonane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.

Examples of urea bond-containing diamines include N, N'-bis (4-aminophenethyl) urea and the like.

The diamine component in the component (A) may contain the following diamines.

[Chemical Formula 16]

In the formula [DA-31], m is an integer of 0 to 3, and in the formula [DA-34], n is an integer of 1 to 5. By introducing [DA-27] or [DA-28], the voltage holding ratio (also referred to as VHR) of a liquid crystal display element using a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be further improved. [DA-29] to [DA-34] are preferable because they are more effective in reducing the accumulated charges of such liquid crystal display elements.

Also, as the diamine component in the component (A), a diaminosiloxane represented by the following formula [DA-35] can be exemplified.

[Chemical Formula 17]

(In the formula [DA-35], m is an integer of 1 to 10)

The diamine component in the component (A) may be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when used as a liquid crystal alignment film. The mixed ratio at that time is not limited.

The molecular weight of the polymer (polyimide precursor, polyimide) of the component (A) is preferably in the range of from 1: 1 to 1: 1, Is preferably from 5,000 to 1,000,000, and more preferably from 10,000 to 150,000, by weight.

The polymer of component (A) is preferably polyimide. The component (A) tends to exist on the surface of the liquid crystal alignment film (that is, the side opposite to the substrate) when the liquid crystal alignment film is used, and the polymer present on the surface of the liquid crystal alignment film directly contacts the liquid crystal and directly contributes to the value of VHR, It is better to have a large number of imide groups which do not undergo reversible reaction. The imidization ratio of the polyimide is preferably 60 to 90%.

≪ Component (B) >

The component (B) contained in the liquid crystal aligning agent of the present invention is preferably at least one selected from the group consisting of a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and a polyimide obtained by imidizing the polyimide precursor Lt; / RTI > Examples of the polyimide precursor include polyamic acid (also referred to as polyamide acid), polyamic acid ester, and the like.

In the component (B), the tetracarboxylic acid component may be at least one selected from the group consisting of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 3,4-dicarboxy- , 2,3,4-tetrahydro-1-naphthalenesuccinic acid diester, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester dichloride do. Therefore, as described later in detail, the polymer of component (B) is also a polymer having a tetravalent structure represented by the above formula (4) derived from TDA, TDA diester or TDA diester dichloride.

The content of the total amount of TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component in the component (B) is from 20 to 100 mol%, preferably from 40 to 100 mol% .

Further, in the component (B), the diamine component to be polymerized with the tetracarboxylic acid component is preferably a -CR ²¹ ₂ - group in the main chain (wherein two R ^{21 s} each independently represent a hydrogen atom or an organic group, (Hereinafter also referred to as " diamine having -CR ²¹ ₂ - group in the main chain ") having two R ^{21 s} may be combined to form a cyclic structure. If the diamine has a -CR ²¹ ₂ - group in the main chain, one kind may be used, or two or more kinds may be used in combination. Since the diamine component of the component (B) is only a diamine having a -CR ²¹ ₂ - group in the main chain, the polymer of the component (B) will have -CR ²¹ ₂ - in the main chain The branch structure. The main chain of the diamine is a structure connecting two amino groups of the diamine. Examples of the organic group represented by R ²¹ in the -CR ²¹ ₂ - group include an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, and a fluorine atom. In addition, two R ^{21 s} may be united to form, for example, an alkylene group having 2 to 7 carbon atoms to form a cyclic structure.

Examples of the diamine having -CR ²¹ ₂ - group in the main chain include the following alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, aliphatic diamines, urea bond-containing diamines, and the like.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'- Dimethyldicyclohexylamine, isophoronediamine, and the like.

Examples of the aromatic diamine include 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2-bis [ (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Bis (4-aminophenyl) cyclohexane,?,? '- bis (4-aminophenyl) -1,4-diisopropylbenzene, 2,2- Bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) Bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis Aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8- Di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenoxy) decane, di Di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di Di (4-aminophenyl) decane-1,10-dioate, 1,3-bis [4- ( (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminophenoxy) phenoxy] Bis [4- (4-aminophenoxy) phenoxy] heptane, 1,7-bis [4- Bis [4- (4-aminophenoxy) phenoxy] octane, 1,1-bis [4- -Aminophenoxy) phenoxy] decane, and the like.

Examples of the aromatic-aliphatic diamine include diamines represented by the following formula [DAM].

[Chemical Formula 18]

(In the formula [DAM], Ar represents a benzene ring or a naphthalene ring, R ₁ represents an alkylene group having 1 to 5 carbon atoms, and R ₂ represents a hydrogen atom or a methyl group)

Specific examples of the aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, Amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (4-aminobutyl) aniline, 3- (4-aminobutyl) aniline, 4- Aniline, 4- (5-methylaminobutyl) aniline, 4- (5-aminopentyl) aniline, 4- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- Amine and the like.

Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6- 2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino- Diamino-5-methylnonane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.

Examples of urea bond-containing diamines include N, N'-bis (4-aminophenethyl) urea and the like.

Further, as the diamine having -CR ²¹ ₂ - group in the main chain of the component (B), the diamine represented by the formula (2) is preferable from the viewpoint of availability. Examples of such diamines include, for example, diamines exemplified as aromatic diamines in the description of the component (B).

As described above, a polyimide precursor obtained by polymerizing a tetracarboxylic acid component containing a diamine having -CR ²¹ ₂ - group in its main chain and a TDA, TDA diester or TDA diester dichloride (hereinafter also referred to as "TDA etc.") Or a polyimide is contained in the liquid crystal aligning agent together with the component (A), it is presumed that a liquid crystal alignment film having a very high resistance is obtained. When a voltage is applied to a liquid crystal alignment film having a very high resistance, a current hardly flows in comparison with a liquid crystal alignment agent having a low resistance, and a voltage is hardly accumulated in the liquid crystal alignment film itself. It is presumed that a small liquid crystal alignment film was obtained. In addition, since the accumulated charge itself is very small, it takes a long time for the accumulated charge to escape, so that the conventional problem of burn-in of after-image or display is not caused.

The tetracarboxylic acid component as the raw material of the component (B) may contain other tetracarboxylic acid derivatives other than the TDA, TDA diester and TDA diester dichloride. As other tetracarboxylic acid derivatives in the component (B), other tetracarboxylic acid derivatives in the component (A) may be mentioned.

The content of the total amount of other tetracarboxylic acid derivatives other than TDA, TDA diester and TDA diester dichloride with respect to the total amount of the tetracarboxylic acid component in the component (B) is preferably 0 to 80 mol% , And more preferably 0 to 60 mol%.

The tetracarboxylic acid component in the component (B) may be the same as or different from the tetracarboxylic acid component in the component (A).

The molecular weight of the polymer (polyimide precursor, polyimide) of the component (A) is preferably in the range of from 1: 1 to 1: 1, Is preferably from 5,000 to 1,000,000, and more preferably from 10,000 to 150,000, by weight.

The polymer of component (B) is preferably a polyimide precursor. This is because the component (B) tends to exist on the side of the substrate on which the liquid crystal aligning agent is applied (that is, on the side opposite to the liquid crystal alignment film surface) when the liquid crystal alignment film is used and the polymer of the component (B) The adhesion to the substrate is good and the printing property is excellent.

The ratio of the component (A) to the component (B) contained in the liquid crystal aligning agent of the present invention is not particularly limited. For example, the ratio of the component (A) :( B) = 5 to 50:95 to 50 (A): Component (B) = 5 to 30: 95 to 70 in terms of mass ratio.

As described above, the liquid crystal aligning agent of the present invention is a polymer obtained by reacting a tetracarboxylic acid component including TDA and the like with a diamine component containing a diamine having a side chain represented by the formula (1) And a specific component (B) which is a polymer obtained by reacting a tetracarboxylic acid component including TDA and the like and a diamine component comprising only a diamine having -CR ²¹ ₂ - group in its main chain, Likewise, it is possible to form a liquid crystal alignment film having a very high charge retention and a very small charge accumulation so as to satisfy strict requirements in modern times, while maintaining the rubbing resistance which is conventionally required. Therefore, it is possible to provide a display for a cellular phone or a tablet terminal having a feature that is not seen in other applications such as frequent on / off display (or frequent on / off operation of the backlight) It can also be used preferably for screen applications.

The effect of the present invention as described above can be attained by mixing a specific component (A) which is a polymer obtained by reacting a tetracarboxylic acid component including TDA and the like with a diamine component containing a diamine having a side chain represented by the formula (1) (B) which is a polymer obtained by reacting a tetracarboxylic acid component including a tetracarboxylic acid component including a tetracarboxylic acid component and a diamine component containing only a diamine having a -CR ²¹ ₂ - group in a main chain thereof. For example, when a polymer that does not contain TDA or the like is used as the raw material, the RDC is large, that is, the charge accumulation is large, and further, the rubbing property is also poor, and the effect of the liquid crystal aligning agent of the present invention can not be exhibited. Also, with regard to the component (B), when a polymer not containing TDA or the like as a raw material is used, RDC is large. Even when TDA or the like is used as a raw material, the use of a diamine having -CR ²¹ ₂ - in the main chain as a diamine component of the raw material results in a large RDC.

Further, when a polymer of the component (A) or a polymer of the component (B) is obtained by the polymerization reaction of the tetracarboxylic acid component and the diamine component of each raw material, a known synthesis technique may be used. Generally, the tetracarboxylic acid component and the diamine component are reacted in an organic solvent. The reaction between the tetracarboxylic acid component and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.

The organic solvent used for the reaction of the tetracarboxylic acid component and the diamine component is not particularly limited as far as the resulting polyamic acid can be dissolved. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cellosolve, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, But are not limited to, sorbose, ethylcellosolve, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol , Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene Recol 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, Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, N-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, lactic acid, methylene chloride, propylene carbonate, propylene carbonate, Methyl, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoacetate Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-methoxypropionic acid butyl, diglyme, -Butoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination. Further, a solvent which does not dissolve the polyamic acid may be used in combination with the solvent insofar as the produced polyamic acid is not precipitated.

In addition, water in the organic solvent inhibits the polymerization reaction, and further causes hydrolysis of the resulting polyamic acid. Therefore, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.

When the tetracarboxylic acid component and the diamine component are reacted in an organic solvent, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is added as it is or dispersed or dissolved in an organic solvent , A method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. . When the tetracarboxylic acid component or the diamine component is composed of a plurality of compounds, they may be reacted in a previously mixed state, or they may be subjected to sequential reactions individually, or the low molecular weight compounds reacted individually may be mixed and reacted to form a high molecular weight You can.

The polymerization temperature at that time can be selected from any of -20 DEG C to 150 DEG C, but is preferably in the range of -5 DEG C to 100 DEG C. If the concentration is excessively low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is excessively high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to carry out uniform stirring. Therefore, The total concentration of the acid component and the diamine component in the reaction solution is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyamic acid, the ratio of the total number of moles of the tetracarboxylic acid component to the total number of moles of the diamine component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamic acid.

The polyimide can be obtained by subjecting a polyimide precursor such as polyamic acid or polyamic acid ester to dehydration ring closure. In the polyimide, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, but may be arbitrarily adjusted depending on the purpose and purpose in the range of 0% to 100%.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which a solution of a polyamic acid or a polyamic acid ester is directly heated, and a catalyst imidization in which a catalyst is added to a solution of a polyamic acid or a polyamic acid ester.

The temperature at which the polyamic acid or the polyamic acid ester is thermally imidized in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water generated by the imidization reaction is removed while removing it from the system desirable.

The catalyst imidation of a polyamic acid or a polyamic acid ester can be carried out by adding a basic catalyst and an acid anhydride to a solution of a polyamic acid or a polyamic acid ester and stirring at -20 to 250 ° C, preferably 0 to 180 ° C have. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferred because it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Of these, use of acetic anhydride is preferable since the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

Examples of the method for synthesizing the polyamic acid ester include tetracarboxylic acid diester dichloride obtained by reacting the tetracarboxylic acid diester with a halogenating agent such as thionyl chloride, sulfuryl chloride, oxalyl chloride or phosphorus oxychloride, and diamines Or a method of reacting a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent or a base. Alternatively, it is also possible to polymerize the polyamic acid in advance and esterify the carboxylic acid in the amic acid using a polymer reaction.

Specifically, the tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, For 4 hours.

As the base, pyridine, triethylamine, and 4-dimethylaminopyridine can be used, but pyridine is preferable for the reaction to proceed mildly. The amount of the base to be added is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

When the condensation polymerization is carried out in the presence of a condensing agent, it is possible to use condensation polymerization such as triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N, N ', N'-tetramethyluronium tetrafluoroborate, O (benzotriazol-1-yl) N, N ', N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzoxazolyl) 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholinium chloride n-hydrate and the like can be used.

Further, in the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount relative to the tetracarboxylic acid diester.

The solvent used in the above reaction may be a solvent used when the polyamic acid shown above is polymerized. From the solubility of the monomer and the polymer, N-methyl-2-pyrrolidone and? -Butyrolactone are preferable These may be used alone or in combination of two or more. The concentration at the time of the synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that the precipitation of the polymer hardly occurs and the high molecular weight material is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the introduction of outside air in a nitrogen atmosphere.

When a polyimide precursor such as polyamic acid or polyamic acid ester or a polyimide precursor or polyimide such as polyamic acid or polyamic acid ester produced from a reaction solution of polyimide is recovered, the reaction solution is added to a poor solvent It can be precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by pouring into a poor solvent may be filtered and recovered, and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, by repeating the operation of redissolving the polymer recovered and recovered in the organic solvent and re-precipitating and recovering the polymer solution 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be exemplified, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

The polyimide precursor obtained by such a polymerization reaction of a tetracarboxylic acid component and a diamine component is, for example, a polymer having a repeating unit represented by the following formula [a]. The polyimide in which the polyimide precursor having such a repeating unit is subjected to dehydration ring closure is polyimide.

[Chemical Formula 19]

(In the formula [a], R ₁₁ is a tetravalent organic group derived from a tetracarboxylic acid component (for example, the following formula (c)) of the raw material, and R ₁₂ is a diamine component (b)), A ₁₁ and A ₁₂ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different from each other, and j represents a positive integer.

In the above formula [a], each of R ₁₁ and R ₁₂ may be a single kind and may be a polymer having the same repeating unit, and may be a polymer having repeating units having a structure in which plural kinds of R ₁₁ and R ₁₂ are highly different.

In the formula [a], R ₁₁ is represented by Since the group derived from a raw material of the tetracarboxylic acid component, (A) component and (B) a polyimide precursor, R ₁₁ is the formula (4) of the component Structure. Further, R ₁₂ is because the group derived from the raw material diamine component, (A) the polyimide precursor of the component, R ₁₂ is _{^{-P 1 - (Q 1) p}} - (Q 2) q - (Q 3) r has a side chain represented by the -P ^2, the polyimide precursor of the addition of component (B) is, R ₁₂ is -CR ²¹ ₂ in the main chain-has a.

[Chemical Formula 20]

(In the formulas [b] and [c], R ₁₁ and R ₁₂ are the same as defined in formula [a]

The liquid crystal aligning agent of the present invention further contains an organic solvent in addition to the components (A) and (B). The liquid crystal aligning agent of the present invention is in the form of a solution in which the components (A) and (B) are dissolved in an organic solvent.

The liquid crystal aligning agent of the present invention may be produced as long as the components (A) and (B) have the form of a solution dissolved in an organic solvent. For example, a method of mixing the component (A) and the powder of the component (B) and dissolving them in an organic solvent, a method of mixing a powder of the component (A) and a solution of the component (B) And the powder of component (B), and a method of mixing a solution of component (A) and a solution of component (B). (A) and the component (B) can be obtained even when the positive solvent in which the component (A) dissolves and the two solvents in which the component (B) dissolve are different, B) is more preferable.

Here, the solution of the component (A) and the solution of the component (B) may be the reaction solution obtained itself when the component (A) or the component (B) is synthesized in an organic solvent, May be diluted with water. When the component (A) or the component (B) is obtained as a powder, it may be dissolved in an organic solvent to form a solution.

The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the component (A) and the component (B) are uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- Pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone, gamma -butyrolactone, 1,3-dimethyl-imidazolidinone, 3- Methoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination of two or more. In addition, even a solvent which can not uniformly dissolve the component (A) or the component (B) alone may be mixed with the organic solvent as long as the components (A) and (B) are not precipitated.

The liquid crystal aligning agent of the present invention may contain, as the polymer component, a polymer other than the component (A) and the component (B) insofar as the effect of the present invention is not impaired. These other polymers include, for example, polyamic acid, polyamic acid ester, polyimide or polyamide which do not contain any of TDA, TDA diester and TDA diester dichloride as raw materials.

The content (concentration) of the polymer component contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the liquid crystal alignment film (polyimide film) to be formed, but from the viewpoint of forming a uniform and defect- The content of the polymer component in the solvent is preferably 0.5% by mass or more, more preferably 15% by mass or less, and still more preferably 1% by mass to 10% by mass from the viewpoint of the storage stability of the solution. In this case, it is also possible to prepare a concentrated solution of the polymer component in advance, and to dilute the concentrated solution in the case where the concentrated solution is used as a liquid crystal aligning agent. The concentration of the concentrated solution of such a polymer component is preferably 10 to 30% by mass, more preferably 10 to 15% by mass. The powder of the polymer component may be dissolved in an organic solvent and heated at the time of preparing the solution. The heating temperature is preferably 20 占 폚 to 150 占 폚, and particularly preferably 20 占 폚 to 80 占 폚. When a polymer other than the component (A) and the component (B) is also contained, the content of the polymer other than the component (A) and the component (B) in the polymer component is preferably from 0.5% by mass to 15% , Preferably 1% by mass to 10% by mass.

The liquid crystal aligning agent of the present invention may contain components other than the polymer component. Examples thereof include a solvent or a compound that improves film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness or the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, 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 monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, 1-hexanol, n-pentane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, Propoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, And a solvent having a low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, .

These poor solvents may be used alone or in combination. When such a solvent is used, it is preferably from 5 to 80 mass%, more preferably from 20 to 60 mass%, of the total solvent contained in the liquid crystal aligning agent.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EF Top EF301, EF303 and EF352 (manufactured by Tohchem Products), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink & Chemicals, Inc.), Florad FC430 and FC431 (manufactured by Sumitomo 3M) , Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

Specific examples of the compound improving the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

Further, in addition to the improvement in adhesion between the substrate and the film, the following phenoplast additive may be introduced into the liquid crystal aligning agent in order to further prevent degradation of electric characteristics due to the backlight. Specific phenoplast-based additives are shown below, but are not limited to these structures.

[Chemical Formula 21]

When a compound improving the adhesion with the substrate is used, the amount of the compound used is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal aligning agent . If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the liquid crystal alignability may deteriorate.

The liquid crystal aligning agent of the present invention may contain, in addition to the above-mentioned components, a dielectric substance or a conductive substance, or a liquid crystal alignment film, for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal alignment film, A crosslinkable compound for the purpose of increasing the hardness or density of the film of the film.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film without rubbing treatment, light irradiation or the like, or without orientation treatment in a vertical alignment application, after coating and baking on a substrate. Here, 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. It is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for liquid crystal driving is formed from the viewpoint of process simplification. In a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side, and a material for reflecting light such as aluminum can be used as the electrode in this case.

The method of applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. As other coating methods, there are dip, roll coater, slit coater, spinner and the like, and they may be used depending on the purpose. In the present invention, it is presumed that the liquid crystal aligning agent is separated into the layer of component (A) and the layer of component (B) in the step of applying the liquid crystal aligning agent to the substrate.

The baking after the liquid crystal aligning agent is coated on the substrate can be carried out by heating means such as a hot plate at 50 to 300 ° C, preferably 80 to 250 ° C, and the solvent can be evaporated to form a coated film. The thickness of the coating film formed after firing is disadvantageous from the viewpoint of power consumption of the liquid crystal display element if it is too thick, and the reliability of the liquid crystal display element is deteriorated when it is too thin, so that it is preferably 5 to 300 nm, Is 10 to 100 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like. It is presumed that the liquid crystal alignment film thus obtained is separated into two layers, that is, a layer derived from the component (A) and a layer derived from the component (B).

The liquid crystal display element of the present invention is obtained by obtaining a substrate on which a liquid crystal alignment layer is formed from the liquid crystal aligning agent of the present invention by the above-described technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element. A liquid crystal layer formed between the substrate and the liquid crystal layer and having the liquid crystal alignment layer formed by the liquid crystal aligning agent of the present invention; Display device. The liquid crystal display of the present invention may be a liquid crystal display device of a twisted nematic (TN) type, a vertical alignment (VA) type, an in-plane switching (IPS) Optically Compensated Bend), and the like.

As a manufacturing method of a liquid crystal cell, a pair of substrates having a liquid crystal alignment film formed thereon is prepared, a spacer is scattered on the liquid crystal alignment film of the substrate of one substrate, the liquid crystal alignment film surface is made inward, ), A method in which a liquid crystal is injected under reduced pressure, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed and bonded. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

Examples of the liquid crystal include a positive type liquid crystal having positive dielectric anisotropy and a negative type liquid crystal having negative dielectric anisotropy. More specifically, for example, MLC-2003, MLC-6608, MLC- 6609 can be used.

As described above, the liquid crystal display element manufactured by using the liquid crystal aligning agent of the present invention is excellent in the voltage retention ratio and satisfying the strict requirements in the modern state while maintaining the rubbing resistance which is a conventionally required characteristic. Charge accumulation is so small that it can be advantageously used, for example, in a mobile phone or a tablet terminal.

Example

Hereinafter, the present invention will be described in further detail with reference to examples. However, it goes without saying that the present invention is not limited to these embodiments. The abbreviations used below and measurement methods of the respective characteristics are as follows.

(Tetracarboxylic acid dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

TDA: 3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride

PPHT: N, N'-bis (1,2-cyclohexanedicarboxylic anhydride-4-ylcarbonyl) -1,4-phenylenediamine

(Diamine)

DBA: 3,5-diaminobenzoic acid

p-PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

BAPU: 1,3-bis (4-aminophenethyl) urea

APC16: 1,3-Diamino-4-hexadecyloxybenzene

APC18: 1,3-Diamino-4-octadecyloxybenzene

DADPA: 4,4'-diaminodiphenylamine

DA-5MG: 1,5-bis (4-aminophenoxy) pentane

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

GBL:? -Butyrolactone

(additive)

LS-2450: 3-Aminopropyldiethoxymethylsilane

LS-3150: 3-aminopropyltriethoxysilane

TM-BIP: 2,2'-bis [4-hydroxy-3,5-bis (hydroxymethyl) phenyl] propane

LS-2450 and LS-3150 are trade names of Shin-Etsu Chemical Co., Ltd., respectively.

[Measurement of molecular weight of polymer]

The molecular weight of the polyimide and polyamic acid in the synthesis examples was measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (Hereinafter, also referred to as Mw).

GPC apparatus: manufactured by Shodex Co., Ltd. (GPC-101)

Column: manufactured by Shodex Co., Ltd. (serial of KD803, KD805)

Column temperature: 50 ° C

Eluent: N, N-dimethylformamide (30 m mol / l of lithium bromide-hydrate (LiBr.H ₂ O) as additive, 30 mmol / l of phosphoric acid anhydrous crystal (o-phosphoric acid) (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150000, 100000, 30000) manufactured by Tosoh Corporation and polyethylene glycol (peak top molecular weight (Mp) of about 12,000, 4000 , 1000). In order to avoid overlapping of peaks, two samples of samples mixed with four types of 900000, 100000, 12000 and 1000 and three samples of 150000, 30000 and 4000 were separately measured.

[Measurement of imidization rate]

The imidization rate of the polyimide was measured as follows. 20 mg of the polyimide powder was placed in an NMR sample tube, and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture) was added and completely dissolved. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNM-ECA500) manufactured by Nippon Dental Electronics. A proton originating from a structure which does not change before and after imidization is defined as a reference proton, and a peak integrated value of the proton and a proton peak integrated value derived from an NH group of a polyamic acid appearing in the vicinity of 9.5 to 10.0 ppm By using the following equation.

Imidization ratio (%) = (1 -? X / y) x 100

In the above formula, x is the proton peak integrated value derived from the NH group of the polyamic acid, y is the peak integrated value of the reference proton, and? Is the NH group of the polyamic acid in the case of the polyamic acid (0% imidization ratio) The ratio of the number of reference protons to one proton.

[Production of liquid crystal cell]

The liquid crystal aligning agent was spin-coated on a glass substrate having a transparent electrode formed thereon, dried on a hot plate at 80 DEG C for 60 seconds, and then fired in an IR (infrared) oven at 220 DEG C for 20 minutes under a nitrogen atmosphere, To form a 100 nm coating film. The coated surface was rubbed with a cotton cloth (YA-25C manufactured by Yoshikawa) with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation rate of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.4 mm, A substrate having an alignment film formed thereon was obtained.

Two sheets of the substrates were prepared, spacers of 4 m were spread on the surface of the liquid crystal alignment film, and a sealant (NX-1500T manufactured by Sumitomo Chemical Co., Ltd.) was printed thereon with a seal dispenser, The liquid crystal aligning film faced the liquid crystal alignment film so that the direction of rubbing was straight. Then, the sealant was cured (temporary curing: 80 ° C for 10 minutes, final curing: 150 ° C for 1 hour and 45 minutes). A liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) was injected into this vacant cell by a reduced pressure injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. These operations were carried out using the respective liquid crystal aligning agents obtained in Examples 1 to 8 and Comparative Examples 1 to 5.

[Evaluation of rubbing resistance]

At the step of obtaining the substrate on which the liquid crystal alignment film was formed in [Production of Liquid Crystal Cell], the surface of the liquid crystal alignment film was observed with a confocal laser microscope and naked eye, and evaluation was carried out based on the following criteria. The results are shown in Table 3.

○: No scratches or rubbing scratches are observed even with the naked eye by a laser microscope.

?: No abrasive scratches or rubbing scratches were observed in the naked eye, but scrapes and rubbing scratches were observed with a laser microscope.

X: Rubbing scratches are observed even with naked eyes by a film or by a laser microscope.

[Measurement of VHR (voltage holding ratio)] [

A voltage of 4 V was applied to the twisted nematic liquid crystal cell manufactured by the method described in [Manufacture of Liquid Crystal Cell] described above at a temperature of 60 캜 for 60 μs, and the voltage after 166.7 ms was measured. Was evaluated as a voltage holding ratio, and evaluation was carried out based on the following criteria. VHR-1 voltage maintenance ratio measuring apparatus manufactured by Toyo Technica Co., Ltd. was used for measurement of the voltage holding ratio. The results are shown in Table 3.

⊚: exceeding 85%

?: 80% to 85%

?: Less than 80%

[Measurement of volume resistivity]

Each of the compositions [AL-1] to [AL-10] was filtered with a filter having a size of 0.2 mu m and then applied on a glass substrate having an ITO transparent electrode formed thereon by spin coating. After drying for 1 minute on a hot plate at 80 DEG C, Followed by baking at 220 DEG C for 20 minutes to form a film having a film thickness of 220 nm. Aluminum was vapor-deposited on the surface of the coating film by a vacuum deposition method with a mask at a vacuum degree of 1.0 10 ^-3 Pa at a deposition rate of 1 nm / s to form an upper electrode of 1.0 mmφ, thereby obtaining a sample for measuring the volume resistivity .

A voltage of 10 V was applied between the ITO electrode and the aluminum electrode of this sample, and the current value after 180 seconds from the voltage application was measured. The volume resistivity was calculated from this value, the electrode area and the film thickness.

The resistance value was measured under the condition that the backlight of the LED was provided under the sample substrate and lighted. The device used for the measurement was a nitrogen gas atmosphere using a shield box SM-1 equipped with a positioner equipped with a MEASURE Jig, manufactured by KEITHLEY, Inc., 6517A ELECTROMETER. The results are shown in Table 4.

[Measurement of RDC (residual DC voltage)] [

A direct current voltage was applied from 0 V to 0.1 V at intervals of 0.1 V to a twisted nematic liquid crystal cell manufactured by the method described in the above [Production of Liquid Crystal Cell], and a flicker amplitude level photoelectric conversion And the calibration curve for the flicker amplitude level and the applied voltage was prepared. After the liquid crystal cell was left standing for 5 minutes, the AC voltage was applied to V50 (the voltage at half the luminance) and the DC voltage of 5.0 V was applied for 1 hour, and then the flicker amplitude level immediately after the DC voltage was set to 0 V was measured , And the RDC was estimated by contrast with the previously prepared calibration curve. The method of estimating the RDC is referred to as the flicker reference method. If the RDC is small, it can be said that the charge accumulation is small. The results are shown in Table 3.

?: Less than 0.05

?: 0.05 or more and less than 0.08

?: 0.08 or more and less than 0.20

×: 0.20 or more

[Synthesis Example]

The numerical values in the parentheses described later on the tetracarboxylic acid component, the diamine component and the like represent the molar fraction of the raw material monomer in the synthesis of the polymer.

(Synthesis Example 1)

Preparation of the composition [AL-1: TDA (50) CBDA (50) / DDM (100)] and the polymerization of polyamic acid [PAA-1: TDA (50) CBDA

2.78 g (14.01 mmol) of DDM was measured in a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, and 17.40 g of GBL was added and dissolved. The solution was cooled to about 10 캜 under a nitrogen atmosphere, 2.10 g (6.99 mmol) was added in small portions, and the mixture was returned to room temperature and reacted for 2 hours. Thereafter, 1.26 g (6.42 mmol) of CBDA and 17.40 g of NMP were added, and the mixture was returned to room temperature and reacted for 4 hours to obtain a solution of 15 mass% of polyamic acid [PAA-1]. The polyamic acid [PAA-1] thus obtained had a number average molecular weight of 15,200 and a weight average molecular weight of 47,500.

15.02 g of the resulting 15 mass% polyamic acid [PAA-1] solution was measured, and 16.89 g of GBL and 5.64 g of BCS were added to a 50 ml Erlenmeyer flask equipped with a stirrer. The mixture was stirred at room temperature for 2 hours, A composition [AL-1] having a solid concentration of 6.0 mass%, GBL of 59 mass%, NMP of 20 mass%, and BCS of 15 mass% was obtained.

(Synthesis Example 2)

Preparation of the composition [AL-2: TDA (50) CBDA (50) / DDM (100) + LS-3150

14.12 g of a solution of 15 mass% of polyamic acid [PAA-1] obtained in Synthesis Example 1 was measured and taken in a 50 ml Erlenmeyer flask equipped with a stirrer. 15.56 g of GBL, 5.56 g of BCS and LS- 0.42 g of a solution diluted by mass% was added and stirred at room temperature for 2 hours to obtain a composition [AL-2] having a solid concentration of 6.0% by mass, GBL of 59% by mass, NMP of 20% by mass, and BCS of 15% .

(Synthesis Example 3)

Preparation of composition [AL-3: TDA (50) CBDA (50) / DDM (100) + LS-3150 (1) + TM-BIP

14.12 g of a solution of 15 mass% of polyamic acid [PAA-1] obtained in Synthesis Example 1 was measured and taken in a 50 ml Erlenmeyer flask equipped with a stirrer. 15.35 g of GBL, 5.35 g of BCS, 0.42 g of a solution diluted by mass%, 0.42 g of a solution obtained by diluting TM-BIP with 5% by mass of NMP, was added and stirred at room temperature for 2 hours to obtain a solution having a solid concentration of 6.0% by mass, GBL of 59% by mass, 20% by mass, and BCS of 15% by mass.

(Synthesis Example 4)

(50) CBDA (50) / BAPU (20) DDM (80) of polyamic acid [PAA-2: TDA ) + LS-3150 (1) + TM-BIP (1)

0.71 g (2.38 mmol) of BAPU and 1.90 g (9.58 mmol) of DDM were measured in a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 20.18 g of GBL was added and dissolved, The mixture was cooled to about 10 DEG C under an atmosphere, 1.80 g (6.30 mmol) of TDA was added little by little, and the mixture was allowed to react at room temperature for 2 hours. Thereafter, 1.08 g (5.44 mmol) of CBDA and 20.18 g of NMP were added, and the mixture was returned to room temperature and reacted for 4 hours to obtain a solution of 12 mass% of polyamic acid [PAA-2]. The polyamic acid [PAA-2] thus obtained had a number average molecular weight of 12,700 and a weight average molecular weight of 38,200.

15.01 g of the obtained 12 mass% polyamic acid [PAA-2] solution was taken in a 50 ml Erlenmeyer flask equipped with a stirrer, and 9.78 g of GBL, 4.50 g of BCS and LS-3150 were diluted with NMP to 5 mass% And 0.36 g of TM-BIP diluted with NMP in an amount of 5% by mass, and the mixture was stirred at room temperature for 2 hours to obtain a solution having a solid concentration of 6.0% by mass, GBL of 59% by mass, NMP of 20% by mass, Thereby obtaining a composition [AL-4] having a BCS of 15 mass%.

(Synthesis Example 5)

(TDA (30) CBDA (70) / DDM (100) + LS-3150 (1)) of polyamic acid [PAA-3: TDA (30) CBDA + TM-BIP (1)]

2.97 g (14.98 mmol) of DDM was measured in a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 18.09 g of GBL was added and dissolved, and the solution was cooled to about 10 캜 under a nitrogen atmosphere. In an amount of 1.35 g (4.50 mmol), and the mixture was returned to room temperature and reacted for 2 hours. Thereafter, 2.05 g (10.50 mmol) of CBDA and 18.09 g of NMP were added, and the mixture was returned to room temperature and reacted for 4 hours to obtain a solution of 15 mass% of polyamic acid [PAA-3]. The polyamic acid [PAA-3] thus obtained had a number average molecular weight of 11,000 and a weight average molecular weight of 41,000.

15.00 g of GBM, 5.63 g of BCS and LS-3150 were diluted to 5% by mass with NMP to obtain a solution of 15 mass% of the obtained polyamic acid [PAA-3] in a 50 ml Erlenmeyer flask equipped with a stirrer. 0.45 g of a solution prepared by diluting TM-BIP with 5% by mass of NMP and 0.45 g of a solution obtained by diluting TM-BIP with 5% by mass of NMP were added and stirred at room temperature for 2 hours to obtain a solution having a solid concentration of 6.0% by mass, GBL of 59% A composition [AL-5] having a BCS of 15 mass% was obtained.

(Synthesis Example 6)

(70) CBDA (30) / DDM (100) + LS-3150 (1) were prepared by the polymerization of polyamic acid [PAA-4: TDA (70) CBDA + TM-BIP (1)]

2.97 g (14.98 mmol) of DDM was measured in a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 19.86 g of GBL was added and dissolved, and the solution was cooled to about 10 캜 under a nitrogen atmosphere. (10.48 mmol) was added in small portions, and the mixture was returned to room temperature and reacted for 2 hours. Thereafter, 0.88 g (4.50 mmol) of CBDA and 19.86 g of NMP were added, and the mixture was returned to room temperature and reacted for 4 hours to obtain a solution of 15 mass% of polyamic acid [PAA-4]. The polyamic acid [PAA-4] thus obtained had a number average molecular weight of 14,500 and a weight average molecular weight of 45,100.

15.00 g of GBM, 5.63 g of BCS and LS-3150 were diluted to 5% by mass with NMP to obtain a solution of 15.00 g of the obtained 15 mass% polyamic acid [PAA-4] solution in a 50 ml Erlenmeyer flask equipped with a stirrer. 0.45 g of a solution prepared by diluting TM-BIP with 5% by mass of NMP and 0.45 g of a solution obtained by diluting TM-BIP with 5% by mass of NMP were added and stirred at room temperature for 2 hours to obtain a solution having a solid concentration of 6.0% by mass, GBL of 59% Thereby obtaining a composition [AL-6] having a BCS of 15 mass%.

(Synthesis Example 7)

Polymerization of polyamic acid [PAA-5: TDA (100) / p-PDA (90) APC18 (10)

N-methyl-2-pyrrolidone (NMP) was added to a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer using 9.00 g (0.030 mol) of TDA, 2.92 g (0.027 mol) Was reacted in the presence of 73.40 g at 50 DEG C for 24 hours to obtain a solution of polyamic acid [PAA-5]. The polyamic acid [PAA-5] thus obtained had a number average molecular weight of 15,800 and a weight average molecular weight of 49,200.

(Synthesis Example 8)

Preparation of polyimide [SPI-1: TDA (100) / p-PDA (90) APC18 (10)

20.00 g of the solution of polyamic acid [PAA-5] obtained in Synthesis Example 7, 30.67 g of NMP, 7.16 g of acetic anhydride and 3.32 g of pyridine were added to a 100 ml Erlenmeyer flask equipped with a stirrer, After stirring, the mixture was reacted at 40 DEG C for 3 hours with stirring. After completion of the reaction, polymer (polyimide) was precipitated slowly along with 214 g of methanol, stirred for 30 minutes, and then the solid was recovered by filtration. The resulting solid was sufficiently washed with methanol, and then vacuum-dried at 100 占 폚 to obtain a polyimide powder. The imidization rate of the obtained polyimide [SPI-1] was 85%.

29.00 g of GBL was added to 2.60 g of the obtained polyimide powder and dissolved by stirring at 50 캜 for 24 hours to confirm that it was completely dissolved. Then, 4.00 g of GBL and 6.15 g of a 2% by mass GBL solution of LS-2450 were added The mixture was stirred at 50 캜 for 24 minutes to obtain a polyimide solution [SPI-1a] having a solid content concentration of 6.0% by mass and a GBL of 94% by mass.

(Synthesis Example 9)

Polymerization of polyamic acid [PAA-6: TDA / BAPU (30) p-PDA (60) APC18]

(0.031 mol) of TDA, 2.77 g (0.0093 mol) of BAPU, 2.01 g (0.019 mol) of p-PDA, and 1.17 g of APC18 in a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer (0.0031 mol) was reacted in 86.38 g of NMP at 50 DEG C for 24 hours to obtain a solution of polyamic acid [PAA-6]. The polyamic acid [PAA-6] thus obtained had a number average molecular weight of 10,500 and a weight average molecular weight of 35,900.

(Synthesis Example 10)

Preparation of polyimide [SPI-2: TDA / BAPU (30) p-PDA (60) APC18]

30.00 g of the solution of the polyamic acid [PAA-6] obtained in Synthesis Example 9, 50.50 g of NMP, 10.01 g of acetic anhydride and 4.65 g of pyridine were added to a 100 ml Erlenmeyer flask equipped with a stirrer, After stirring, the mixture was reacted at 40 DEG C for 3 hours with stirring. After completion of the reaction, the polymer was slowly precipitated in 580 g of methanol, stirred for 30 minutes, and then the solid was recovered by filtration. The resulting solid was sufficiently washed with methanol, and then vacuum-dried at 100 占 폚 to obtain a polyimide powder. The imidization rate of the obtained polyimide [SPI-2] was 82%.

30.59 g of GBL was added to 2.66 g of the obtained polyimide powder and dissolved by stirring at 50 DEG C for 24 hours to confirm that it was completely dissolved. 6.55 g of GBL and 6.83 g of a 2 mass% GBL solution of LS-2450 were added The mixture was stirred at 50 캜 for 24 minutes to obtain a polyimide solution [SPI-2a] having a solid content concentration of 6.0% by mass and a GBL of 94% by mass.

(Synthesis Example 11)

Polymerization of polyamic acid [PAA-7: TDA (100) / p-PDA (90) APC16 (10)

7.51 g (0.025 mol) of TDA, 2.43 g (0.023 mol) of p-PDA and 0.87 g (0.0025 mol) of APC16 were added to a 50 mL four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. Was reacted in 61.26 g at 50 DEG C for 24 hours to obtain a solution of polyamic acid [PAA-7]. The polyamic acid [PAA-7] thus obtained had a number average molecular weight of 13,600 and a weight average molecular weight of 50,200.

(Synthesis Example 12)

Preparation of polyimide [SPI-3: TDA (100) / p-PDA (90) APC16 (10)]

20.00 g of the solution of the polyamic acid [PAA-7] obtained in Synthesis Example 11, 30.67 g of NMP, 7.18 g of acetic anhydride and 3.33 g of pyridine were added to a 100 ml Erlenmeyer flask equipped with a stirrer, After stirring, the mixture was reacted at 40 DEG C for 3 hours with stirring. After completion of the reaction, the polymer was slowly precipitated into 214 g of methanol, stirred for 30 minutes, and then the solid was recovered by filtration. The resulting solid was sufficiently washed with methanol, and then vacuum-dried at 100 ° C to obtain a polyimide powder. The imidization rate of the obtained polyimide [SPI-3] was 88%.

To 2.60 g of the obtained polyimide powder, 29.90 g of GBL was added and dissolved by stirring at 50 캜 for 24 hours to confirm that it was completely dissolved. Then, 4.00 g of GBL and 6.15 g of a 2% by mass GBL solution of LS- The mixture was stirred at 50 캜 for 24 minutes to obtain a polyimide solution [SPI-3a] having 6.0% by mass and 94% by mass of GBL.

(Comparative Synthesis Example 1)

Polymerization of polyamic acid [PAA-8: PPHT (90) CBDA (10) / p-PDA (90) APC18

A 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer was reacted with 2.44 g of PPHT, 0.12 g of CBDA, 0.58 g of p-PDA, 0.26 g of APC18 and 19.11 g of NMP for 4 hours to obtain polyamic acid A solution of [PAA-8] was obtained. The polyamic acid [PAA-8] thus obtained had a number average molecular weight of 13,000 and a weight average molecular weight of 45,000.

(Comparative Synthesis Example 2)

Preparation of polyimide [SPI-4: PPHT (90) CBDA (10) / p-PDA (90) APC18

22.49 g of the solution of the polyamic acid [PAA-8] obtained in Comparative Synthesis Example 1, 33.72 g of NMP, 5.96 g of acetic anhydride and 2.77 g of pyridine were added to a 100 ml Erlenmeyer flask equipped with a stirrer, And the mixture was stirred at 70 캜 for 3 hours for reaction. After completion of the reaction, the polymer was slowly precipitated in 250 g of methanol, stirred for 30 minutes, and then the solid was recovered by filtration. The resulting solid was sufficiently washed with methanol, and then vacuum-dried at 100 ° C to obtain a polyimide powder. The imidization ratio of the obtained polyimide [SPI-4] was 88%.

33.00 g of GBL was added to 2.60 g of the obtained polyimide powder and dissolved by stirring at 50 占 폚 for 24 hours to confirm that the polyimide solution was completely dissolved. A polyimide solution SPI having a solid content concentration of 6.0% by mass and a GBL of 94% by mass -4a].

(Comparative Synthesis Example 3)

7: TDA (50) CBDA (50) / DDM (20) p (80)) of the polyamic acid [PAA-9: TDA (50) CBDA -PDA (80) + LS-3150 (1)

1.58 g (8.00 mmol) of DDM and 3.46 g (32.00 mmol) of p-PDA were measured in a 100 mL four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. 41.32 g of GBL was added to dissolve , Cooled to about 10 캜 in a nitrogen atmosphere, 6.00 g (20.00 mmol) of TDA was added little by little, and the mixture was allowed to react at room temperature for 2 hours. Thereafter, 3.52 g (18.00 mmol) of CBDA and 41.32 g of NMP were added, and the mixture was returned to room temperature and reacted for 4 hours to obtain a solution of 15 mass% of polyamic acid [PAA-9]. The polyamic acid [PAA-9] thus obtained had a number average molecular weight of 7,100 and a weight average molecular weight of 15,000.

97.2 g of GBL, 48.6 g of BCS and 0.15 g of LS-3150 were added to a solution of 15 mass% of the polyamic acid PAA-9 thus obtained and stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0 mass% Composition [AL-7] having 20 mass%, 20 mass% NMP and 15 mass% BCS was obtained.

(Comparative Synthesis Example 4)

(ALDA 8: TDA (70) CBDA (30) / DDM (20) p) was prepared by the polymerization of polyamic acid [PAA-10: TDA (70) CBDA -PDA (80) + LS-3150 (1)

1.58 g (8.00 mmol) of DDM and 3.46 g (32.00 mmol) of p-PDA were measured in a 100 mL four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. 43.46 g of GBL was added to dissolve , Cooled to about 10 캜 in a nitrogen atmosphere, 8.40 g (28.00 mmol) of TDA was added little by little, and the reaction was allowed to return to room temperature for 2 hours. Thereafter, 1.88 g (9.60 mmol) of CBDA and 43.46 g of NMP were added and the mixture was returned to room temperature and reacted for 4 hours to obtain a solution of 15 mass% of polyamic acid [PAA-10]. The solution of the obtained polyamic acid [PAA-10] had a number average molecular weight of 7,100 and a weight average molecular weight of 15,000.

97.2 g of GBL, 48.6 g of BCS and 0.15 g of LS-3150 were added to the solution of the resulting polyamic acid [PAA-10], and the mixture was stirred at room temperature for 2 hours to obtain a solid content concentration of 6.0 mass%, a GBL of 59 mass% Of 20 mass% and BCS of 15 mass% was obtained.

(Comparative Synthesis Example 5)

(50) CBDA (50) / DBA (30) DDM (70)] and the polymerization of the polyamic acid [PAA-11: TDA ) + LS-3150 (1) + TM-BIP (1)

2.08 g (10.50 mmol) of DDM and 0.68 g (4.50 mmol) of DBA were measured in a 100 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer, 18.06 g of GBL was added and dissolved, The mixture was cooled to about 10 DEG C under an atmosphere, 2.25 g (7.5 mmol) of TDA was added little by little, and the mixture was allowed to react at room temperature for 2 hours. Thereafter, 1.35 g (6.90 mmol) of CBDA and 18.06 g of NMP were added and the mixture was returned to room temperature and reacted for 4 hours to obtain a solution of 15 mass% of polyamic acid [PAA-11]. The polyamic acid [PAA-11] thus obtained had a number average molecular weight of 9,400 and a weight average molecular weight of 25,900.

15.05 g of the obtained solution of polyamic acid [PAA-11] was measured and taken in a 50 ml Erlenmeyer flask equipped with a stirrer, and 16.02 g of GBL, 5.64 g of BCS and 0.45 g of LS-3150 diluted with NMP to 5% , And 0.45 g of a solution prepared by diluting TM-BIP with NMP in an amount of 5 mass% were added and stirred at room temperature for 2 hours to obtain a polymer solution having a solid concentration of 6.0 mass%, GBL of 59 mass%, NMP of 20 mass%, BCS of 15 mass % Of the composition [AL-9].

(Comparative Synthesis Example 6)

(ALDA 10: TDA (20) CBDA (80) / DADPA (80) DDM (20)) of polyamic acid [PAA-12: TDA (20) CBDA )]

2.39 g (12.00 mmol) of DADPA and 0.59 g (3.00 mmol) of DDM were measured in a 100 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. 55.37 g of NMP was added and dissolved, The mixture was cooled to about 10 占 폚 under ambient atmosphere, and then 0.90 g (3.0 mmol) of TDA and 2.26 g (11.55 mmol) of CBDA were added little by little and the mixture was reacted for 4 hours at room temperature to obtain a solution of polyamic acid [PAA-12] .

61.01 g of the obtained solution of the polyamic acid [PAA-12] was measured, and 24.60 g of BCS and 36.91 g of NMP were added to a 200 ml Erlenmeyer flask equipped with a stirrer and stirred at room temperature for 2 hours to obtain a solid content concentration of 5.0 % By mass, a composition [AL-10] having 75% by mass of NMP and 20% by mass of BCS.

(Comparative Synthesis Example 7)

The polymerization of polyamic acid [PAA-13: TDA (100) / DA-5MG (100)] and the preparation of polyimide [SPI-5: TDA (100)

A solution of polyamic acid [PAA-13] was obtained by reacting 3.72 g of DA-5MG and 3.70 g of TDA in 66.88 g of NMP for 4 hours in a 100 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer.

74.31 g of the obtained solution of the polyamic acid [PAA-13], 72.31 g of NMP, 15.48 g of acetic anhydride and 7.19 g of pyridine were added to a 200 ml Erlenmeyer flask equipped with a stirrer. The mixture was stirred at room temperature for 30 minutes, The mixture was stirred at 40 ° C for 3 hours for reaction. After completion of the reaction, the polymer was slowly precipitated in 500 g of methanol, stirred for 30 minutes, and then the solid was recovered by filtration. The resultant solid was sufficiently washed with methanol, and then vacuum-dried at 100 ° C to obtain a polyimide ([SPI-5]) powder.

80.00 g of GBL and 15.00 g of BCS were added to 5.00 g of the obtained polyimide powder and stirred at 50 占 폚 for 6 hours to obtain a polyimide solution having a solid concentration of 5.0 mass%, NMP of 80 mass% and BCS of 15 mass% SPI-5a].

(Example 1) [AL-1]: [SPI-1a] = 80: 20

Were mixed so that the mass ratio of [AL-1] and [SPI-1a] was 80:20, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Example 2) [AL-2]: [SPI-1a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-2] and [SPI-1a] was 80:20, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Example 3) [AL-3]: [SPI-1a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-3] and [SPI-1a] was 80: 20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Example 4) [AL-3]: [SPI-2a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-3] and [SPI-2a] was 80:20, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Example 5) [AL-5]: [SPI-1a] = 80: 20

Were mixed so that the mass ratio of [AL-5] and [SPI-1a] was 80:20, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Example 6) [AL-6]: [SPI-1a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-6] and [SPI-1a] was 80:20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Example 7) [AL-3]: [SPI-3a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-3] and [SPI-3a] was 80: 20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Example 8) [AL-4]: [SPI-1a] = 80: 20

[AL-4] and [SPI-1a] were mixed in a mass ratio of 80:20, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Comparative Example 1) [AL-9]: [SPI-1a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-9] and [SPI-1a] was 80:20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Comparative Example 2) [AL-3]: [SPI-4a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-3] and [SPI-4a] was 80:20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Comparative Example 3) [AL-7]: [SPI-1a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-7] and [SPI-1a] was 80: 20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Comparative Example 4) [AL-8]: [SPI-1a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-8] and [SPI-1a] was 80:20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

(Comparative Example 5) [AL-10]: [SPI-5a] = 80: 20

The mixture was mixed so that the mass ratio of [AL-10] and [SPI-5a] was 80: 20 and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent.

[Table 3]

[Table 4]

As shown in Table 3, a polymer obtained by reacting a tetracarboxylic acid component containing TDA with a diamine component containing a diamine having a side chain represented by the above formula (1) and a tetracarboxylic acid component containing TDA And a diamine component comprising only a diamine having -CR ²¹ ₂ - in the main chain, were excellent in VHR and rubbing resistance, and also had a very low RDC.

On the other hand, Comparative Example 2, which uses a polymer not containing TDA as a raw material, and Comparative Examples 1, 3, and 4, wherein a diamine component of the raw material as a component (B) also contains a diamine having -CR ²¹ ₂ - And Comparative Example 5 in which the diamine having a side chain represented by the formula (1) was not used as the component (A), RDC was significantly larger than those in Examples 1 to 8. It can be seen from Table 4 that the composition [AL-7] to [AL-10] using a polymer containing diamine not having -CR ²¹ ₂ - in the main chain has a low volume resistivity, To (AL-10) were used as the component (B), it is estimated that the RDC was large.

Claims (5)

A liquid crystal aligning agent characterized by containing the following component (A) and the following component (B).
(A): at least one polymer selected from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing the polyimide precursor, wherein the tetracarboxylic acid component 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester and Dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester dichloride, and the diamine component comprises at least one member selected from the group consisting of a side chain represented by the following formula (1) &Lt; RTI ID = 0.0 &gt;
[Chemical Formula 1]

(1), P ¹ represents a single bond or a divalent organic group, Q ¹ , Q ² and Q ³ each independently represent a divalent benzene ring or cyclohexane ring, p, q and r each independently And P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton.
Component (B): at least one polymer selected from a polyimide precursor obtained by polymerization reaction of a tetracarboxylic acid component and a diamine component and a polyimide obtained by imidizing the polyimide precursor, wherein the tetracarboxylic acid component 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester and 1,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid diester dichloride, and the diamine component comprises at least one member selected from the group consisting of -CR ²¹ ₂ - group (Wherein two R ^{21 s} each independently represent a hydrogen atom or an organic group and two R ^{21 s} may be combined to form a cyclic structure) The method according to claim 1,
Wherein the diamine component in the component (B) is composed only of a diamine represented by the following formula (2).
(2)

(2), each X independently represents an oxygen atom or a single bond, n represents an integer of 1 to 10, and two R ^{22 s} each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, A fluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom, or two R ^{22 s} may be united to form an alkylene group having 2 to 7 carbon atoms to form a cyclic structure.) 3. The method according to claim 1 or 2,
A liquid crystal aligning agent characterized in that, in the component (A), the diamine having a side chain represented by the formula (1) is a diamine represented by the following formula (3).
(3)

(Formula (3) of the, P ¹ represents a single bond or a divalent organic ^{group, Q 1, Q 2, Q} 3 are each independently a divalent group represents a benzene ring or cyclohexane ring, p, q, r are each independently Represents an integer of 0 or 1, and P ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 3 to a substrate and firing the liquid crystal alignment agent. A liquid crystal display element having the liquid crystal alignment film according to claim 4.