TW202144551A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention addresses the problem of providing: a liquid crystal alignment agent which makes it possible to produce a liquid crystal alignment film having excellent film hardness at low cost; and a liquid crystal display element equipped with the liquid crystal alignment film. Further provided is a liquid crystal alignment agent which makes it possible to produce a liquid crystal alignment film and a liquid crystal display element which are superior in various properties other than film hardness. The liquid crystal alignment agent is characterized by comprising a component (A). Component (A): at least one polymer (A) selected from the group consisting of a (polyimide precursor)-polyurea copolymer having a repeating unit represented by formula (m1) and a repeating unit represented by formula (1) and an imidized polymer of the copolymer, in which at least one of the repeating unit represented by formula (m1) and the repeating unit represented by formula (1) is derived from an aromatic diamine (a) having any one of the structures respectively represented by formulae (S1) to (S2), and the polymer (A) can be produced without using an aliphatic diamine. (The meaning of each of the substituents is as defined in the description.).

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

Conventionally, as liquid crystal display elements, various driving methods with different electrode structures and the physical properties of liquid crystal molecules used have been developed. For example, TN (Twisted Nematic) type and STN (Super Twisted Nematic) type are known. , VA (Vertical Alignment, vertical alignment) type, IPS (In-Plane Switching, in-plane switching) type, FFS (Fringe Field Switching, boundary electric field switching) type and other display elements. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As the material of the liquid crystal alignment film, for example, polyamic acid, polyamic acid ester, polyimide, polyamide and the like are known. VA type liquid crystal display element, which is one of the driving methods of liquid crystal display element, is proposed as a technology to accelerate the response speed of liquid crystal, and it is proposed to add a photopolymerizable compound to the liquid crystal composition in advance, and then add a photopolymerizable compound to the liquid crystal composition. A liquid crystal display element of a PSA (Polymer Sustained Alignment, polymer stabilized alignment) method that irradiates ultraviolet rays while applying a voltage (for example, refer to Patent Document 1 and Non-Patent Document 1).

In recent years, large-screen and high-definition LCD TVs have become the mainstream, and the development of small display terminals such as smart phones and tablet PCs has become more and more popular. Based on these backgrounds, in order to improve the performance of the liquid crystal alignment film and make the various characteristics of the liquid crystal display element (such as liquid crystal alignment and voltage holding ratio) more excellent, various liquid crystal alignment agents have been proposed (for example, refer to Patent Document 2). In addition to the above-mentioned properties, it is also necessary that the film hardness is high. If a liquid crystal alignment film with low film hardness is used in the liquid crystal display element, the film will become thinner during the manufacturing process of the liquid crystal display element, and the thinned part will cause poor alignment of the liquid crystal, resulting in bright spots and lower display quality. In addition to the manufacturing steps, in recent years, touch-panel type displays have become popular, and high film hardness is required in order to prevent thinning of the film due to touch-panel operation. As means for solving the above-mentioned problems, in Patent Document 3, a polyimide-based liquid crystal aligning agent obtained by using a specific tetracarboxylic dianhydride having a carbon-carbon triple bond is proposed. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2003-307720 Patent Document 2: WO2014/126102 Patent Document 3: Japanese Patent Laid-Open No. 2019-014837 [Non-patent literature]

Non-Patent Document 1: K. Hanaoka, SID 04 DIGEST, P1200-1202

[The problem to be solved by the invention]

After producing a liquid crystal alignment film using the method described in Patent Document 2, the present inventors found out that the obtained alignment film has low film hardness. Furthermore, it is possible to produce a liquid crystal alignment film by using the method described in Patent Document 3, but since tetracarboxylic dianhydride must be newly synthesized, there is a disadvantage that the cost of a liquid crystal alignment agent using it increases.

The subject of this invention is to provide the liquid crystal aligning agent which can obtain the liquid crystal aligning film excellent in film hardness at low cost, and the liquid crystal display element provided with this liquid crystal aligning film. Furthermore, the subject of this invention is to provide the liquid crystal aligning agent which can obtain the liquid crystal aligning film which is excellent in various characteristics other than film hardness, and a liquid crystal display element. [means to solve the problem]

As a result of earnestly researching in order to achieve the above-mentioned subject, the present inventors found that a liquid crystal aligning agent containing a specific component is effective in achieving the above-mentioned object, and completed the present invention.

(X₁ 表示4價有機基，Y₁ 表示源自芳香族二胺之2價有機基，2個R₁ 分別獨立地表示氫原子或碳數1~5之烷基，2個Z₁ 分別獨立地表示氫原子、可具有取代基之碳數1~10之烷基、可具有取代基之碳數2~10之烯基、可具有取代基之碳數2~10之炔基、第三丁氧羰基或9-茀基甲氧羰基)，

(A₁ 為2價有機基，A₂ 為源自芳香族二胺之2價有機基，C₁ 及C₂ 分別獨立地為氫原子或碳數1~3之烷基)，

(X¹ 及X² 分別獨立地表示單鍵、-(CH₂ )_a -(a為1~15之整數)、-CONH-、-NHCO-、-CO-N(CH₃ )-、-NH-、-O-、 -COO-、-OCO-或-((CH₂ )_a1 -A₁ )_m1 -，其中a1為1~15之整數，A₁ 表示氧原子或-COO-，m₁ 為1~2之整數，G¹ 及G² 分別獨立地表示選自碳數6~12之2價芳香族基及碳數3~8之2價脂環式基之2價環狀基，上述環狀基上之任意氫原子可經取代，m及n分別獨立地為0~3之整數，m+n為1~6，較佳為1~4，R¹ 表示碳數1~20之烷基、碳數1~20之烷氧基或碳數2~20之烷氧基烷基，形成R¹ 之任意氫原子可經氟原子取代，X¹ 、X² 、G¹ 、G² 、a1及A₁ 存在複數時，複數存在之X¹ 、X² 、G¹ 、G² 、a1及A₁ 分別獨立地具有上述定義)，

(X^2a 表示-CONH-、-NHCO-、-O-、-CH₂ O-、-COO-或 -OCO-，R² 表示具有類固醇骨架之構造)。 [發明效果]Therefore, this invention has the following summary based on this knowledge. A liquid crystal aligning agent characterized by containing the following (A) component. (A) Component: selected from a polyimide precursor-polyurea copolymer having a repeating unit represented by the following formula (m1) and a repeating unit represented by the following formula (1), and an imidized polymer thereof At least one polymer (A) of at least one of the group, the repeating unit represented by the above formula (m1) and at least one of the repeating units represented by the above formula (1) are derived from having the following formulas (S1)～( The aromatic diamine (a) of any one of the structures represented by S2), the above-mentioned polymer (A) is obtained without using an aliphatic diamine,

(X ₁ represents a tetravalent organic group, Y ₁ represents a divalent organic group derived from an aromatic diamine, two R ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and two Z ₁ each independently Denotes a hydrogen atom, an optionally substituted alkyl group with 1 to 10 carbon atoms, an optionally substituted alkenyl group with 2 to 10 carbon atoms, an optionally substituted alkynyl group with 2 to 10 carbon atoms, and a tertiary butyl group oxycarbonyl or 9-intenylmethoxycarbonyl),

(A ₁ is a divalent organic group, A ₂ is a divalent organic group derived from an aromatic diamine, C ₁ and C ₂ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),

(X ¹ and X ² each independently represent a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH -, -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -, wherein a1 is an integer from 1 to 15, A ₁ represents an oxygen atom or -COO-, and m ₁ is An integer of 1 to 2, G ¹ and G ² each independently represent a divalent cyclic group selected from a bivalent aromatic group having 6 to 12 carbon atoms and a bivalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the base can be substituted, m and n are each independently an integer of 0 to 3, m+n is 1 to 6, preferably 1 to 4, and R ¹ represents an alkyl group with 1 to 20 carbon atoms , alkoxy with 1~20 carbons or alkoxyalkyl with 2~20 carbons, ^{any hydrogen atom forming R 1} can be substituted by fluorine atom, X ¹ , X ² , G ¹ , G ² , a1 and When A ₁ exists a complex number, X ¹ , X ² , G ¹ , G ² , a1 and A _{1 of the} complex number exist independently have the above definitions),

(X ^2a represents -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO-, and R ² represents a structure having a steroid skeleton). [Inventive effect]

According to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film and a liquid crystal display element with excellent film hardness can be obtained at low cost. Furthermore, according to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film and a liquid crystal display element excellent in various properties other than film hardness can be obtained. The mechanism for obtaining the above-mentioned effects of the present invention is not yet clear, but one reason is considered to be that by using an aromatic diamine as a constituent component of the above-mentioned polymer, the aromatic rings of the obtained polymer can form a stack with each other, and the film has a urea bond in the molecule. Most hydrogen bonds can be formed.

In this specification, "aromatic diamine" means a diamine in which at least one amine group is directly bonded to an aromatic ring, and a part of its structure may contain an aliphatic group. The "aliphatic diamine" refers to a diamine in which two amine groups are directly bonded to an aliphatic group, and a part of the structure may contain an aromatic group. The aliphatic group includes both an acyclic aliphatic group and a cycloaliphatic group (alicyclic group). In this specification, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are exemplified as the halogen atom.

Hereinafter, each component contained in the liquid crystal aligning agent of the present disclosure and other components arbitrarily mixed as required will be described. <Polymer (A)> The liquid crystal aligning agent of the present invention is selected from a polyimide precursor-polyurea copolymer having a repeating unit represented by the above formula (m1) and a repeating unit represented by the above formula (1), and an imide thereof At least one of the above-mentioned repeating units in the polymer (A) is derived from at least one of the above-mentioned repeating units of the group formed by the chemical compounds derived from the aroma having the structure represented by the above-mentioned formulas (S1) to (S2) As for the aliphatic diamine (a), the above-mentioned polymer (A) is obtained without using an aliphatic diamine.

(aromatic diamine (a)) At least one of the repeating unit represented by the formula (m1) and the repeating unit represented by the above formula (1) is derived from an aromatic diamine having any one of the structures represented by the above formulas (S1) to (S2) (a). It is preferable that the said aromatic diamine (a) has the structure represented by the said formula (S1)-(S2) in a side chain.

Specific examples of the structures represented by the above formulae (S1) to (S2) are the structures represented by the following formulae (S1-1) to (S1-7) and (S2-a). Moreover, in formula (S2-a), X represents formula (X1), formula (X2) or -CH ₂ O-, and Col represents formula (Col-1), formula (Col-2) or formula (Col-3) , G represents formula (G1), formula (G2), formula (G3) or formula (G4). ✽ indicates a bond key.

In the above formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. X ^P represents -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH ₂ O _{-, - CH 2 OCO -,} - COO- or -OCO-. A ₁ represents oxygen atom or -COO-✽ (but, the bond with "✽" is bonded to (CH ₂ ) _a2 ), A ₂ represents oxygen atom or ✽-COO- (but, with "✽" The bond of " is bonded to (CH ₂ ) _a2 ), a ₁ and a ₃ are independently an integer of 0 or 1, a ₂ is an integer of 1 to 10, and Cy represents 1,4-cyclohexylene or 1,4-phenylene.

(X為單鍵、-O-、-C(CH₃ )₂ -、-NH-、-CO-、-(CH₂ )_m -、-SO₂ -、-O-(CH₂ )_m -O-、-O-C(CH₃ )₂ -、-CO-(CH₂ )_m -、 -NH-(CH₂ )_m -、-SO₂ -(CH₂ )_m -、-CONH-(CH₂ )_m -、-CONH-(CH₂ )_m -NHCO-或-COO-(CH₂ )_m -OCO-之2價有機基。m為1~8之整數。Y表示上述式(S1)~(S2)之任一構造。上述式(d2)中，2個Y可互為相同亦可不同)。It is preferable that it has at least one benzene ring as said aromatic diamine (a). More preferably, it is an aromatic diamine having 6 to 50 carbon atoms. Specific examples of the aromatic diamine (a) are diamines represented by the following formula (d1) or formula (d2).

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m -O -, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m Divalent organic group of -, -CONH-(CH ₂ ) _m -NHCO- or -COO-(CH ₂ ) _m -OCO-. m is an integer of 1 to 8. Y represents the above formulas (S1) to (S2) Any structure. In the above formula (d2), two Ys may be the same or different from each other).

(X^v1 ~X^v4 、X^p1 ~X^p8 分別獨立地表示-(CH₂ )_a -(a為1~15之整數)、-CONH-、-NHCO-、-CO-N(CH₃ )-、-NH-、-O-、 -CH₂ O-、-CH₂ -OCO-、-COO-或-OCO-，X^v5 ~X^v6 、X^s1 ~X^s4 分別獨立地表示-O-、-CH₂ O-、-COO-或-OCO-。X_a ~X_f 分別獨立地表示單鍵、-O-、-NH-或-O-(CH₂ )_m -O-(m為1~8之整數)，R^v1 ~R^v4 、R^1a ~R^1h 分別獨立地表示-C_n H_2n+1 (n為1~20之整數)、-O-C_n H_2n+1 (n為2~20之整數))。Preferred examples of the diamine represented by the above formula (d1) are the following formulae (d1-1) to (d1-6). Preferred examples of the diamine represented by the above formula (d2) are the following formulae (d2-1) to (d2-6).

(X ^v1 to X ^v4 and X ^p1 to X ^p8 independently represent -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )- , -NH -, - O-, -CH 2 O -, - CH 2 -OCO -, - COO- or ^{-OCO-, X v5 ~ X v6,} X s1 ~ X s4 each independently represent -O -, - CH ₂ O-, -COO- or -OCO-. X _a ~X _f respectively independently represent a single bond, -O-, -NH- or -O-(CH ₂ ) _m -O- (m is 1~8 R ^v1 ~R ^v4 , R ^1a ~R ^1h independently represent -C _n H _2n+1 (n is an integer from 1 to 20), -OC _n H _2n+1 (n is an integer from 2 to 20) integer)).

(式(3b-1)中，A₁ 表示單鍵、-CH₂ -、-C₂ H₄ -、 -C(CH₃ )₂ -、-CF₂ -、-C(CF₃ )₂ -、-O-、-CO-、-NH-、 -N(CH₃ )-、-CONH-、-NHCO-、-CH₂ O-、-OCH₂ -、-COO-、-OCO-、-CO-N(CH₃ )-或-N(CH₃ )-CO-，m1及m2分別獨立地表示0~4之整數，且m1+m2表示1~4之整數。式(3b-2)中，m3及m4分別獨立表示1~5之整數。式(3b-3)中，A² 表示碳數1~5之直鏈或分支烷基，m5表示1~5之整數。式(3b-4)中，A³ 及A⁴ 分別獨立地表示單鍵、-CH₂ -、-C₂ H₄ -、 -C(CH₃ )₂ -、-CF₂ -、-C(CF₃ )₂ -、-O-、-CO-、-NH-、 -N(CH₃ )-、-CONH-、-NHCO-、-CH₂ O-、-OCH₂ -、-COO-、-OCO-、-CO-N(CH₃ )-或-N(CH₃ )-CO-，m6表示1~4之整數)。

(n為1~6之整數)。

(Boc表示第三丁氧羰基)

The repeating unit which the said polymer (A) has may originate in the aromatic diamine (henceforth "other aromatic diamine") other than the aromatic diamine (a). Specific examples of other aromatic diamines include p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, 2,4-diaminobenzoic acid, 2,4-diaminobenzoic acid, Diamines having carboxyl groups such as 5-diaminobenzoic acid, 3,5-diaminobenzoic acid, or diamine compounds represented by the following formulae (3b-1) to (3b-4), 4,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1 ,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4- Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis (4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy base)-3-fluoroaniline, bis(2-(4-aminophenoxy)ethyl)ether, 4-amino-4'-(2-(4-aminophenoxy)ethoxy) Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamine 2,2'-bis(trifluoromethyl)biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diamine naphthalene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , 2,2'-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenethyl)urea and other diamines with urea bonds, methacrylic acid 2-(2,4 Diamines having a photopolymerizable group at the terminal, such as -diaminophenoxy)ethyl ester, 2,4-diamino-N,N-diallylaniline, etc., the following formulae (R1) to (R5 ) and other diamines with radical initiation function, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis(4-aminobenzene) Diamine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyridine having a photosensitizing function that exhibits a sensitizing action by light irradiation , 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, diamines with heterocycles of the following formulae (z-1)~(z-18), etc., Diamines having a diphenylamine skeleton of the above formulas (Dp-1) to (Dp-9), etc., and groups of the following formulas (5-1) to (5-10), etc. "-N(D)- "(D represents a protecting group that is removed by heating and is replaced by a hydrogen atom, preferably 3-butoxycarbonyl) diamines, the following formulas (Ox-1) to (Ox-2), etc. Aromatic diamines having 6 to 30 carbon atoms, such as diamines having an oxazoline structure, are not limited thereto.

(In formula (3b-1), A ₁ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O -, - CO -, - NH-, -N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CO- N(CH ₃ )- or -N(CH ₃ )-CO-, m1 and m2 each independently represent an integer from 0 to 4, and m1+m2 represent an integer from 1 to 4. In formula (3b-2), m3 and m4 independently represent an integer of 1 to 5. In formula (3b-3), A ² represents a straight-chain or branched alkyl group having 1 to 5 carbon atoms, and m5 represents an integer of 1 to 5. In formula (3b-4) , A ³ and A ⁴ independently represent a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O -, - CO -, - NH- , -N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CO-N ( CH ₃ )- or -N(CH ₃ )-CO-, m6 represents an integer from 1 to 4).

(n is an integer from 1 to 6).

(Boc represents the third butoxycarbonyl group)

The above-mentioned 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and diamine having a photopolymerizable group at the terminal are represented by the above formulae (R1) to (R5) The diamines and the diamines represented by the above formulae (z-1) to (z-18) can be used in the production of the polymer (A) from the viewpoint of improving the response speed of the liquid crystal display element using the PSA method or SC-PVA mode. Use 1 type or 2 or more types.

Among the above-mentioned other aromatic diamines, from the viewpoint of appropriately obtaining the effects of the present invention, p-phenylenediamine, 3,5-diaminobenzoic acid, and 4,4'-diaminodiphenyl are preferred. Methane, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2-(2,4-diaminophenoxy methacrylate) group) ethyl ester, 2,4-diamino-N,N-diallylaniline, diamine represented by the above formulae (R1)~(R5), the above formulae (z-1)~(z-18) The diamine represented, the diamine represented by the above formulae (Dp-1) to (Dp-9), and the diamine represented by the above formula (Ox-1) to (Ox-2).

(Repeating unit represented by formula (m1)) In the above formula (m1), Y ₁ represents a divalent organic group derived from an aromatic diamine. Examples of the aromatic diamine include the above-mentioned aromatic diamine (a) and the above-mentioned other aromatic diamines. _{At least one of Y 1 in the} above formula (m1) _{and A 2 in} the above formula (1) represents a divalent organic group derived from an aromatic diamine (a).

(X表示選自由下述式(x-1)~(x-13)之任一者的構造)。

(R¹ ~R⁴ 分別獨立地表示氫原子、鹵素原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基，含氟原子之碳數1~6之1價有機基或苯基。R⁵ 及R⁶ 分別獨立地表示氫原子或甲基。j及k為0或1之整數，A₁ 及2個A₂ 分別獨立地表示單鍵、-O-、-CO-、-COO-、伸苯基、磺醯基或醯胺基。✽1係鍵結於一酸酐基之鍵結鍵，✽2係鍵結於另一酸酐基之鍵結鍵。上述式(x-13)中，2個A₂ 可互為相同亦可不同)。In the above formula (m1), X ₁ represents a tetravalent organic group. X _{1 is} preferably a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof. Examples of the tetravalent organic group include, for example, a tetravalent organic group derived from aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof, or a tetravalent organic group derived from A tetravalent organic group of aromatic tetracarboxylic dianhydride or its derivatives. X _{1 is} preferably a tetravalent organic group derived from tetracarboxylic dianhydride represented by the following formula (3) or a derivative thereof.

(X represents a structure selected from any one of the following formulae (x-1) to (x-13)).

(R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, and a fluorine atom with 1 carbon number A monovalent organic group or phenyl group of ~6. R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group. j and k are integers of 0 or 1, A ₁ and 2 A ₂ independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl or amide group.✽1 is a bond to an acid anhydride group, ✽2 is a bond to another acid anhydride group Bonding. In the above formula (x-13), the two A ₂ may be the same or different from each other).

More preferable specific examples of the above formula (x-1) include the following formulae (X1-1) to (X1-6). In the formula, ✽ represents a bond bond.

Preferred specific examples of the above formulae (x-12) and (x-13) are the following formulae (x-14) to (x-29). In the formula, ✽ represents a bond bond.

As a preferable example of the tetracarboxylic dianhydride represented by the above formula (3) or its derivative, X is the above formulae (x-1) to (x-7), (x-11) to (x-13) The tetracarboxylic dianhydride represented by the formula (3) or a derivative thereof.

In the above formula (m1), two R _1s each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group. In the above formula (m1), two Z ₁ each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms which may have a substituent, an alkenyl group with 2 to 10 carbon atoms which may have a substituent, and a group which may have a substituent The alkynyl group having 2 to 10 carbon atoms, the third butoxycarbonyl group, or the 9-intenylmethoxycarbonyl group preferably represents a hydrogen atom or a methyl group. In the above formula (m1), each of X ₁ , Y ₁ , R ₁ , and Z ₁ is one type, or two or more types may be used.

(Repeating unit represented by formula (1)) In the above formula (1), A ₁ is a divalent organic group. A _{1 is} preferably a divalent organic group derived from diisocyanate. Examples of A ₁ include, for example, a divalent aromatic group having at least one benzene ring having 6 to 30 carbon atoms, a divalent aliphatic group having 4 to 30 carbon atoms, or an alicyclic group. Specific examples of A of Example ₁ is derived from o - xylylene diisocyanate, m - phenylene diisocyanate, of - xylylene diisocyanate, toluene diisocyanates (e.g., 2,4-toluene diisocyanate), 1,4-bis Cyanate-2-methoxybenzene, 2,5-diisocyanatoxylene, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diisocyanatodi Phenylmethane, 4,4'-diisocyanatodiphenyl ether, 4,4'-diisocyanatodiphenyl bismuth, 3,3'-diisocyanatodiphenyl bismuth and 2,2' - Divalent organic groups of aromatic diisocyanates such as benzophenone diisocyanate, acyclic aliphatic groups derived from isophorone diisocyanate, hexamethylene diisocyanate and tetramethylene diisocyanate, etc. Or the divalent organic group of alicyclic diisocyanate. Among them, A ₁ is a divalent organic group derived from 2,4-diisocyanatotoluene, and is preferred from the viewpoints of availability, polymerization reactivity, and voltage retention.

In the above formula (1), A ₂ is a divalent organic group derived from an aromatic diamine. Examples of the aromatic diamine include the above-mentioned aromatic diamine (a) and the above-mentioned other aromatic diamines.

_{At least one of Y 1 in the} above-mentioned formula (m1) _{and A 2 in} the above-mentioned formula (1) represents a divalent organic group derived from the above-mentioned aromatic diamine (a). In the above formula (1), C ₁ and C ₂ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. In the above formula (1), each of A ₁ , A ₂ , C ₁ and C ₂ is one type, or two or more types may be used.

(repeating unit constituting polymer (A)) The polymer (A) of the present invention has a repeating unit represented by the above formula (m1) and a repeating unit represented by the above formula (1). The polymer (A) may have a repeating unit represented by the above formula (m1) and a repeating unit and a terminal group represented by the above formula (1). The polymer (A) may also have the repeating unit represented by the above formula (m1) and any repeating unit other than the repeating unit represented by the above formula (1) (hereinafter also referred to as other repeating units), but preferably the above-mentioned repeating unit. The repeating unit represented by the formula (m1), the repeating unit represented by the above formula (1), and the terminal group are formed.

Here, the term "terminal group" can be said to be a group bonded to the terminal of the repeating unit constituting the above-mentioned polymer (A). Examples of the terminal groups are amine groups, carboxyl groups, acid anhydride groups, isocyanate groups or derivatives thereof. An amine group, a carboxyl group, an acid anhydride group, and an isocyanate group are obtained by a usual condensation reaction, and the above-mentioned derivatives can be obtained by, for example, modifying a terminal group using a terminal modifier as described later.

The above-mentioned polymer (A) can be obtained without using an aliphatic diamine. Therefore, the polymer (A) does not contain a group derived from an aliphatic diamine. That is, the repeating unit represented by the above formula (m1) and the repeating unit represented by the above formula (1) do not contain a group derived from an aliphatic diamine. Likewise, the above-mentioned other repeating units do not contain groups derived from aliphatic diamines.

The content ratio of the repeating unit represented by the formula (m1) is preferably 10 to 90 mol %, more preferably 25 to 75 mol % of the total repeating unit constituting the polymer (A). The content ratio of the repeating unit represented by the formula (1) is preferably 10 to 90 mol %, more preferably 25 to 75 mol % of the total repeating unit constituting the polymer (A). In addition, the above-mentioned Y ₁ is a repeating unit represented by the formula (m1) derived from the divalent organic group of the above-mentioned aromatic diamine (a), and the above-mentioned A ₂ is a divalent organic group derived from the above-mentioned aromatic diamine (a). The total of the repeating units represented by the formula (1) of the group is preferably 10 to 90 mol %, more preferably 10 to 85 mol % of the total repeating units constituting the polymer (A).

<Polymer (B)> From the viewpoint of improving electrical properties, the liquid crystal alignment agent of the present invention further contains at least one polymer selected from the group consisting of polyimide precursors and imidized polymers thereof, and is different from polymer (A) Polymer (B). In particular, by further containing the polymer (B), the liquid crystal alignment can be improved. The polymer (B) is preferably at least one polymer selected from the group consisting of polyimide precursors having repeating units represented by the following formula (m2) and imidized polymers thereof.

(X₂ 表示4價有機基。Y₂ 表示2價有機基。R₂ 、Z₂ 分別與式(m1)之R₁ 、Z₁ 同義，2個R₂ 、Z₂ 可互為相同亦可不同)。

(X ₂ represents a tetravalent organic group. Y ₂ represents a divalent organic group. R ₂ and Z ₂ are synonymous with _{R 1} and Z _{1 in} formula (m1), respectively, and _{two R 2} and Z ₂ may be the same or different from each other. ).

The polymer (B) preferably does not have the repeating unit represented by the above formula (1). As _{the tetravalent organic group of X 2,} the tetravalent organic group derived from aliphatic tetracarboxylic dianhydride, the tetravalent organic group derived from alicyclic tetracarboxylic dianhydride, or the tetravalent organic group derived from aromatic tetracarboxylic dianhydride are exemplified. The tetravalent organic group of the anhydride is exemplified by the tetravalent organic group exemplified by X ₁ of the above formula (m1) as a specific example. From the viewpoint of effectively obtaining the effects of the present invention, the tetravalent organic groups represented by the above formulae (x-1) to (x-13) are preferred (these are collectively referred to as specific tetravalent organic groups).

In the polymer (B), from the viewpoint of effectively obtaining the effects of the present invention, X ₂ is the repeating unit of the above-mentioned specific tetravalent organic group, and preferably comprises more than 5 mol% of all repeating units contained in the polymer (B), more preferably Contains more than 10 mol%. The polymer (B) preferably has wherein X ₂ is a repeating unit of the above formulae (x-1) to (x-11) and X ₂ is a repeating unit of the above formula (x-12) to (x-13).

As a _{specific example of Y 2} , in addition to the divalent organic group derived from the aromatic diamine exemplified in the above-mentioned polymer (A), 1,3-bis(3-aminopropyl)-tetramethyl is exemplified. Divalent organic groups of diamines containing siloxane groups such as disiloxane. From the viewpoint of improving electrical properties, the polymer (B) is preferably a repeating unit containing a divalent organic group (these are collectively referred to as a specific divalent organic group) from which two amine groups are removed from a diamine selected from the following groups. The polymer: Y ₂ has a nitrogen atom-containing structure of diamine and 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminophenol Benzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and the above formula (3b- 1) to the diamine having a carboxyl group such as the diamine compound represented by the formula (3b-4).

In the polymer (B), from the viewpoint of improving electrical properties, Y ₂ is the repeating unit of the above-mentioned specific divalent organic group, including 1 mol % or more of all repeating units contained in the polymer (B), and may also include 5 mol %. ear % or more.

From the viewpoint of improving electrical properties, the content ratio of component (A) and component (B) may be 10/90 to 90/10 in terms of the mass ratio of [(A) component]/[(B) component], or Can be 20/80~90/10, can be 20/80~80/20.

<Production of polymer (A) and polymer (B)> The polyimide precursor-polyurea copolymer of the above-mentioned polymer (A) can be obtained by, for example, combining the component (a) containing a compound containing two isocyanate groups in the molecule and the component containing two primary or secondary amines in the molecule. The (b) component of the compound of a base reacts with the (c) component containing a tetracarboxylic dianhydride or its derivative(s), and is produced. (a) component, (b) component, and (c) component may each be 1 type, or may be 2 or more types.

As the component (a), Examples of the compound represented by, for example, (the same as in the formula A ₁ (. 1) A ₁₎ to _{O = C = NA 1 -N =} C = O.

(式[b]中，C₁ 、C₂ 、A₂ 與式(1)中之C₁ 、C₂ 、A₂ 相同)。 作為以上述式[b]表示之化合物的具體例，舉例為例如上述芳香族二胺(a)、上述其他芳香族二胺。As the component (b), for example, a compound represented by the following formula [b] is exemplified.

(In the formula [b] _{in, C 1, C 2, A} 2 in the formula (1) in the C _1, C _2, the same as A _2). As a specific example of the compound represented by the said formula [b], the said aromatic diamine (a), and the said other aromatic diamine are mentioned, for example.

The component (b) may contain, for example, at least one nitrogen-containing heterocyclic ring selected from the group consisting of a nitrogen-containing heterocyclic ring (excluding the imide imide ring contained in polyimide), a secondary amine group, and a tertiary amine group Atomic structure of aromatic diamines. However, (b) component does not contain aliphatic diamine.

Examples of the above nitrogen-containing heterocycle include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyrazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, Quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, hexamethyleneimine, etc. Among them, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine is preferable.

上述式(n)中，R表示氫原子或碳數1~10之1價烴基。「✽」表示與烴基鍵結之鍵結鍵。The secondary amine group and the tertiary amine group which the diamine having a nitrogen atom-containing structure can have are represented by, for example, the following formula (n).

In the above formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. "✽" represents a bond to a hydrocarbon group.

Examples of the monovalent hydrocarbon group for R in the above formula (n) include alkyl groups such as methyl, ethyl, propyl, etc.; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, methylphenyl, and the like. . R is preferably a hydrogen atom or a methyl group.

Specific examples of the diamine having a nitrogen atom-containing structure include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, and 3,6-diaminocarbamate azoles, N-methyl-3,6-diaminocarbazole, diamines represented by the above formulae (z-1) to (z-18), and the above formulae (Dp-1) to (Dp-9) Represented diamine.

As a tetracarboxylic dianhydride or its derivative(s) contained in (c) component, for example, the tetracarboxylic dianhydride or its derivative(s) represented by said formula (3) is mentioned.

It is preferable that the tetracarboxylic dianhydride represented by Formula (3) or its derivative(s) is 1 mol% or more of the whole component (c). More preferably, it is 5 mol % or more, and particularly preferably 10 mol % or more.

The reaction of (a) component, (b) component, and (c) component is usually performed in an organic solvent. The organic solvent used at this time is not particularly limited as long as it dissolves the produced polyimide precursor-polyurea copolymer. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactamide, dimethylacetamide sulfite, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethyl pentanol, diterpenes, ethyl amyl ketone, methyl alcohol Nonyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Vegetarian acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetic acid Esters, propylene glycol monomethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate , tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone , methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl propionate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propionate ester, butyl 3-methoxypropionate, diglyme or 4-hydroxy-4-methyl-2-pentanone, etc. These may be used alone or in combination. In addition, even if it is a solvent which cannot dissolve a polyimide precursor, if it is a range which does not precipitate the polyimide precursor which is produced|generated, it can be mixed with the said solvent and can be used. In addition, the moisture in the organic solvent will hinder the polymerization reaction and further cause the hydrolysis of the polyimide precursor produced. Therefore, the organic solvent is preferably dehydrated and dried.

As the order of making (a) component, (b) component, and (c) component react, after making (a) component and (b) component react, for example, the method of adding (c) component and reacting is mentioned. By such reaction, since the obtained polyimide precursor having the repeating unit represented by the formula (m1) becomes a random bond between the repeating unit represented by the formula (1) and the repeating unit represented by the formula (m1). Random copolymers are therefore preferred.

On the other hand, there is a step of reacting the (a) component and the (b) component to obtain a urea-based polymer composed of the repeating unit represented by the formula (1), and the step of reacting the (b) component and the (c) component to obtain The step of making the polyimide precursor formed from the repeating unit represented by the formula (m1), followed by the urea-based polymer formed by the repeating unit represented by the formula (1) and the urea polymer formed by the repeating unit represented by the formula (m1) The method of reacting the polyimide precursor formed by the repeating unit represented by the obtained polymer having the repeating unit represented by the formula (1) becomes a block copolymer of polyurea and polyimide precursor. The structure, that is, compared with the above-mentioned random copolymer, is a polymer structure composed of a urea-based polymer with a higher degree of polymerization and a polyimide precursor.

The temperature at which the component (a), the component (b), and the component (c) are reacted can be selected at any temperature from -20 to 150°C, but preferably in the range of -5 to 100°C. In addition, the reaction can be carried out at any concentration. The total concentration of the component (a), the component (b), and the component (c) in the reaction liquid is preferably 1 to 50 mass %, and more preferably 5 to 30 mass %. The initial stage of the reaction may be carried out at a high concentration, and then an organic solvent may be added.

The ratio of the reacted (a) component, (b) component and (c) component, for example in molar ratio, is preferably the total amount of (a) component and (c) component: (b) component = 0.8: 1~1.2:1. The ratio of the component (a) in the total amount of the component (a) and the component (c) is preferably 20 to 60 mol %.

As a polyimide precursor of the said polymer (B), a polyamic acid, a polyamic acid ester, etc. are mentioned, for example. The polyimide precursor of the above-mentioned polymer (B) can be synthesized by, for example, a conventional method described in International Publication WO2013/157586. The diamine component of the polyimide precursor used to manufacture the polymer (B) may also contain a heterocyclic ring selected from nitrogen atoms (excluding the imide ring possessed by the polyimide), a secondary amine group and at least one diamine with a nitrogen atomic structure from the group of tertiary amine groups. Such a nitrogen atom-containing structure is, for example, as described in the description of the above-mentioned polymer (A).

[Terminal modifier] When synthesizing the polymers (A) and (B) of the present invention, an appropriate terminal modifier can also be used together with the above-mentioned tetracarboxylic acid derivative component, diamine component, and diisocyanate component as appropriate to synthesize terminal-modified polymers. polymer.

二碳酸二-第三丁酯、二碳酸二烯丙酯等之二碳酸二酯化合物；丙烯醯氯、甲基丙烯醯氯、菸鹼醯氯等之氯羰基化合物；苯胺、2-胺基酚、3-胺基酚、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、環己基胺、正丁基胺、正戊基胺、正己基胺、正庚基胺、正辛基胺等之單胺化合物；異氰酸乙酯、異氰酸苯酯、異氰酸萘酯等之單異氰酸酯化合物等。As the terminal modifier, for example, acetic anhydride, maleic anhydride, terresic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride can be exemplified. , compounds represented by the following formulae (m-1)~(m-6), 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4 ,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynyl phthalic anhydride and other acid monoanhydrides;

Dicarbonate diester compounds such as di-tert-butyl dicarbonate, diallyl dicarbonate, etc.; chlorocarbonyl compounds such as acryl chloride, methacryloyl chloride, nicotine chloride, etc.; aniline, 2-aminophenol , 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzene Monoamine compounds of formic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.; ethyl isocyanate, phenyl isocyanate, isocyanate Monoisocyanate compounds such as naphthyl esters, etc.

The usage ratio of the terminal modifier is preferably 20 mol parts or less, more preferably 10 mol parts or less, based on 100 mol parts in total of the diamine components used.

In addition, by making the polyimide precursor of polymer (A)-polyurea copolymer or the imide precursor of polymer (B) (hereinafter also collectively referred to as "polyimide precursor") ring-closed (imidization) to obtain polyimide. In addition, in this specification, the imidization rate is the ratio of the imino group in the total amount of the imino group derived from tetracarboxylic dianhydride or its derivative and the carboxyl group (or its derivative).

As a method of imidizing the polyimide precursor, for example, thermal imidization by directly heating the solution of the polyimide precursor or by adding a catalyst to the solution of the polyimide precursor Mordine imidization.

The molecular weights of the polymers (A) and (B) used in the present invention are determined by the GPC (gel permeation chromatography) method when the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of film formation and the film coating properties are considered. The measured weight average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

The blending ratio of the polymer component used in the method for producing the liquid crystal alignment film of the present invention is not particularly limited, but for example, the total amount of the polymer component contained in the liquid crystal alignment agent is 0.1 to 30% by mass, preferably 3 to 10% by mass %. The total content of the polymers (A) and (B) contained in the liquid crystal aligning agent is preferably 1 to 9 mass %, more preferably 1.5 to 9 mass %. Also referred to as the total, the case where 1 or 2 or more of the constituent elements is 0 mass % is also included.

Moreover, in addition to the polymer (A) and the polymer (B), the liquid crystal alignment agent used in the manufacture of the liquid crystal alignment film may be mixed with other polymers. In this case, the content of other polymers is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass, of the total amount of polymer components. Examples of other polymers other than these include acrylic polymers, methacrylic polymers, polystyrene, polyamide, polysiloxane, and the like.

The solvent contained in the liquid crystal aligning agent is not particularly limited if it can dissolve the polymer (A), for example, lactone solvents such as γ-valerolactone, γ-butyrolactone, etc.; γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2 - Pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, etc. lactamide solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamamine, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and other amide solvents; 4-hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone (two isobutyl ketone), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl pyruvate methyl oxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether Ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, diisopropyl Ether, diisoamyl ether; carbonate solvents such as ethylidene carbonate and propylidene carbonate, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 2,6-dimethyl-4-heptane Alcohol (diisobutylcarbitol), etc. These can be used individually or in mixture of 2 or more types.

As a preferred solvent combination, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether can be exemplified , N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-Butyrolactone and 4-hydroxy-4-methyl-2-heptanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4 -Hydroxy-4-methyl-2-heptanone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-heptanone and diisobutyl ketone, N-methyl-2 -pyrrolidone with 4-hydroxy-4-methyl-2-heptanone with dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-heptanone with Propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-heptanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4-methyl -2-heptanone and diisobutyl ketone, gamma-butyrolactone and 4-hydroxy-4-methyl-2-heptanone and propylene glycol diacetate, N-methyl-2-pyrrolidone and gamma -Butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2- Pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl carbitol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl -2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, etc. The type and content of these solvents can be appropriately selected according to the coating apparatus of the liquid crystal alignment agent, coating conditions, coating environment, and the like.

<Liquid crystal alignment agent> The liquid crystal aligning agent of this invention can also add other components other than the above, for example, a crosslinking compound, a functional silane compound, a surfactant, a compound which has a photopolymerizable group etc. as needed.

The crosslinkable compound can be used for the purpose of improving the strength of the liquid crystal alignment film. Examples of the crosslinkable compound include compounds having isocyanate groups or cyclocarbonate groups described in paragraphs [0109] to [0113] of International Publication WO2016/047771, or compounds having an isocyanate group selected from lower alkoxyalkyl groups. The compound of at least one group of the group is also exemplified as a compound having a blocked isocyanate group.

The blocked isocyanate compound can be obtained as a commercial product, for example, CORONATE AP STAB M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (the above are manufactured by TOSOH), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (the above are manufactured by Mitsui Chemicals Co., Ltd.), etc.

As a specific example of a preferable crosslinkable compound, the compound represented by following formula (CL-1)-(CL-11) is illustrated.

An example of the above-mentioned crosslinkable compound is not limited to this. Moreover, the crosslinking compound used for the liquid crystal aligning agent of this invention may be 1 type, and may combine 2 or more types.

The content of other crosslinkable compounds in the liquid crystal aligning agent of the present invention is 0.1 to 150 parts by mass, or 0.1 to 100 parts by mass, or 1 to 50 parts by mass relative to 100 parts by mass of the polymer component.

The functional silane compound can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the base sheet. As a specific example, the silane compound described in the paragraph [0019] of International Publication No. 2014/119682 can be mentioned. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, with respect to 100 parts by mass of the polymer component.

The surfactant can be used for the purpose of improving the film thickness uniformity and surface smoothness of the liquid crystal alignment film. As said compound, a fluorine type surfactant, a silicone type surfactant, a nonionic type surfactant, etc. are mentioned. Specific examples of these are the surfactants described in paragraph [0117] of International Publication WO2016/047771. The usage-amount of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

The compound having a photopolymerizable group can be exemplified by a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule, for example, the following formulas (M-1) to (M-7) represented compound.

Furthermore, in the liquid crystal alignment agent of the present invention, as a compound that promotes charge transfer in the liquid crystal alignment film and promotes the charge separation of the element, the paragraph [0194 ] to [0200] describe the nitrogen atom-containing heterocyclic amine compounds represented by the formulae [M1] to [M156], more preferably 3-picoline and 4-picoline. The amine compound may be directly added to the liquid crystal aligning agent, but it is preferably added as a solution with a concentration of 0.1 to 10 mass %, preferably 1 to 7 mass %. The solvent is not particularly limited as long as it can dissolve the polymer component.

In the liquid crystal aligning agent of the present invention, an imidization accelerator or the like may be added for the purpose of more efficiently performing imidization by heating at the time of firing the coating film.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) can be appropriately selected considering viscosity, volatility, etc., but is preferably 0.5~ 15 mass %, More preferably, it is the range of 1-10 mass %. The range of the particularly preferred solid content concentration varies with the method used to coat the liquid crystal aligning agent on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 mass %. When using the printing method, the solid content concentration is set in the range of 3 to 9 mass %, whereby the optimum solution viscosity is in the range of 12 to 50 mPa･s. In the case of using the ink jet method, the solid content concentration is set in the range of 1 to 5 mass %, whereby the optimum solution viscosity is in the range of 3 to 15 mPa･s.

<Liquid crystal alignment film and liquid crystal display element> The liquid crystal alignment film of the present invention is obtained from the above-mentioned liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used for a horizontal alignment type or a vertical alignment type liquid crystal alignment film, but is suitable for a liquid crystal alignment film of a vertical alignment type liquid crystal display element such as a VA mode or a PSA mode. The liquid crystal display element of this invention is provided with the said liquid crystal alignment film. The liquid crystal display element of the present invention can be manufactured by a method including, for example, the following steps (1) to (3) or steps (1) to (4). (1) The step of coating the liquid crystal alignment agent on the substrate The liquid crystal aligning agent of the present invention is coated on one side of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as roll coating method, spin coating method, printing method, ink jet method and the like. The substrate here is not particularly limited as long as it is a substrate with high transparency, and plastic substrates such as acrylic substrates and polycarbonate substrates may be used in addition to glass substrates and silicon nitride substrates. In addition, if the reflective liquid crystal display element is a substrate with only one side, an opaque material such as a silicon wafer may be used, and a material such as aluminum that reflects light may also be used for the electrode in this case. (2) Step of firing the coating film After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing the applied alignment agent from sagging. The pre-baking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The pre-baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Next, it is preferable to further implement a heating (post-baking) step. The post-baking temperature is preferably 80 to 300°C, more preferably 120 to 250°C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.

The coating film formed in the above step (1) can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to an alignment energy imparting treatment. Examples of the alignment energy imparting treatment include, for example, a rubbing treatment in which the coating film is rubbed in a certain direction with a roller wound with a cloth made of fibers such as nylon, rayon, cotton, etc., and a rubbing treatment in which the coating film is irradiated with polarized or non-polarized radiation. Photo-alignment processing, etc.

In the photo-alignment treatment, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation irradiated to the coating film. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. Furthermore, when the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction, or a combination of these may be performed. When irradiating non-polarized radiation, the irradiating direction is the oblique direction. (3) Step of forming the liquid crystal layer (3-1) Case of VA type liquid crystal display element Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was arranged between the two substrates arranged to face each other. Specific examples are the following two methods. The first method is a method known in the past. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other. Next, the peripheral parts of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected and filled in the intercellular space separated by the substrate surface and the sealant to contact the film surface, and then the injection hole is sealed.

In addition, the second method is a method called an ODF (One Drop Fill) method. On a specific part of one of the two substrates on which the liquid crystal alignment film is formed, a sealant such as UV curable is applied, and then the liquid crystal composition is dropped on specific parts on the surface of the liquid crystal alignment film. Then, the other substrate is attached so that the liquid crystal alignment film faces, and the liquid crystal composition is pressed and spread to the entire surface of the substrate to make contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant. In any of the methods, it is desirable to further heat the liquid crystal composition used to a temperature at which the isotropic phase is obtained, and then gradually cool to room temperature, thereby removing the flow alignment during liquid crystal filling.

(3-2) Case of manufacturing PSA type liquid crystal display element It is the same as the above-mentioned (3-1) except that the liquid crystal composition containing a polymerizable compound is injected or dropped. As a polymerizable compound, the polymerizable compound represented by the said formula (M-1) - (M-7) is mentioned, for example. (3-3) In the case of forming a coating film on a substrate using a liquid crystal aligning agent containing a compound having a polymerizable group In the same manner as in the above (3-1), a method of manufacturing a liquid crystal display element through a step of irradiating ultraviolet rays to be described later can be employed. According to this method, a liquid crystal display element excellent in response speed even with a small amount of light irradiation can be obtained, as in the case of producing a PSA-type liquid crystal display element as described above. The compound having a polymerizable group may be a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule as represented by the above formulas (M-1) to (M-7), The content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the polymer component. In addition, the above-mentioned polymerizable group may be possessed by the polymer used for the liquid crystal aligning agent, and examples of these polymers include, for example, a polymer obtained by using a diamine component including a diamine having the above-mentioned photopolymerizable group at the terminal during the reaction. .

(4) The step of irradiating ultraviolet rays to irradiate the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (3-2) or (3-3). The voltage applied here can be, for example, 5-50V direct current or alternating current. In addition, as the irradiation light, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but preferably ultraviolet rays including light having a wavelength of 300 to 400 nm are used. As a light source of irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be used. The irradiation amount of light is preferably 1,000 to 200,000 J/m ² , more preferably 1,000 to 100,000 J/m ² .

Next, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. As the polarizing plate attached to the outer surface of the liquid crystal cell, for example, a polarizing film called "H film" that absorbs iodine while extending and aligning polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate. Polarizing plate made of H film itself.

The liquid crystal display element of the present invention can be effectively applied to various devices, such as clocks, portable game machines, word processors, notebook computers, car navigation systems, cameras, PDAs, digital cameras, mobile phones, smart phones, various Various display devices such as monitors, LCD TVs, and information displays. [Example]

Examples are given below to illustrate. This description is not to be construed as being limited to them. The abbreviations used below are as follows.

(diisocyanate) A-1: 2,4-toluene diisocyanate

(tetracarboxylic dianhydride) B-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride B-2: Pyromellitic Anhydride

(diamine compound) C-1: 4,4'-Diaminodiphenylmethane C-2: N-(3-methylpyridyl)-3,5-diaminobenzylamide C-3: 1,3-Diamino-4-{4-(4-n-heptylcyclohexyl)phenoxy}benzene C-4: 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane C-5: 2,2-bis{4-(4-aminophenoxy)phenyl}propane Moreover, C-1-C-3 and C-5 are aromatic diamine, and C-4 is aliphatic diamine.

(Organic solvents) NMP: N-methyl-2-pyrrolidone BCS: Butyl Cellosolve

The measurement method performed for this example is shown below. (Measurement of the molecular weight of the polymer) The molecular weight of the polymer was measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight and the weight average molecular weight were calculated in terms of polyethylene glycol and polyethylene oxide. GPC apparatus: GPC-101 manufactured by Showa Denko Co., Ltd. Column: Column manufactured by Shodex Co., Ltd. (KD-803 and KD-805 are connected in series) Column temperature: 50°C Eluent: N,N-dimethylformamide (as an additive , lithium bromide monohydrate (LiBr･H ₂ O) is 30mmol/L, phosphoric acid･anhydrous crystal (o-phosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10ml/L) Flow rate: 1.0ml/min Calibration line Standard sample: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, 30,000) manufactured by TOSOH Corporation and polyethylene glycol (molecular weight; about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories

<Synthesis example 1> C-1 (1.78 g, 9.00 mmol), C-2 (1.31 g, 5.36 mmol), C-3 (1.37 g, 3.59 mmol) and NMP (25 g) were added to a 4-neck flask and stirred to complete the diamine dissolve. Next, A-1 (1.57 g, 9.00 mmol) and NMP (8.9 g) were added to react at 25°C for 1 hour. Subsequently, B-1 (1.73 g, 8.82 mmol) and NMP (9.4 g) were added, and the reaction was continued for 16 hours to obtain a solution having a concentration of 15 mass % of the polyamic acid-polyurea copolymer (A). The polyamic acid-polyurea copolymer (A) had a number average molecular weight of 10,200 and a weight average molecular weight of 34,700.

<Comparative Synthesis Example 1> According to the method described in Synthesis Example 1 of Paragraph [0167] of WO2014/126102, a polyamic acid-polyurea solution containing diamines other than aromatic diamines was synthesized. C-4 (1.53 g, 8.98 mmol), C-2 (1.31 g, 5.36 mmol), C-3 (1.37 g, 3.59 mmol) and NMP (24 g) were added to a 4-neck flask and stirred to complete the diamine dissolve. Next, A-1 (1.57 g, 9.00 mmol) and NMP (8.9 g) were added to react at 40° C. for 15 hours. Subsequently, B-1 (1.66 g, 8.46 mmol) and NMP (9.4 g) were added and reacted for 10 hours to obtain a solution with a concentration of 15 mass % of the polyamic acid-polyurea copolymer (B). The polyamic acid-polyurea copolymer (B) had a number average molecular weight of 9,500 and a weight average molecular weight of 32,800.

<Comparative Synthesis Example 2> C-1 (9.12 g, 46.0 mmol), C-2 (8.36 g, 34.5 mmol), C-5 (14.3 g, 34.8 mmol) and NMP (179 g) were added to a 4-neck flask and stirred to complete the diamine dissolve. Next, B-1 (14.8 g, 75.4 mmol) and NMP (42.7 g) were added and reacted at 25°C for 1.5 hours. Subsequently, B-2 (7.52 g, 34.5 mmol) and NMP (81.8 g) were added, and the reaction was continued for 17 hours to obtain a solution having a polyamic acid (C) concentration of 15% by mass. The number average molecular weight of this polyamic acid (C) was 9,600, and the weight average molecular weight was 23,000.

<Example 1> NMP and BCS were added to the solution of the polyamide-polyurea copolymer (A) obtained in Synthesis Example 1 and stirred to obtain a polymer solid content concentration of 3 mass %, NMP 52 mass %, and BCS 45 mass % The liquid crystal alignment agent (1). Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a homogeneous solution.

<Comparative Examples 1 to 2> The same procedure as in Example 1 was carried out, except that the solution of the polyamic acid-polyurea copolymer (B) and the solution of the polyamic acid (C) were used instead of the solution of the polyamic acid-polyurea copolymer (A). The method respectively modulates the liquid crystal alignment agent (2) and the liquid crystal alignment agent (3).

<Example 2> The liquid crystal aligning agent (1) was mixed in the ratio of 30 mass %, and the liquid crystal aligning agent (3) was mixed in the ratio of 70 mass %, and the liquid crystal aligning agent (4) was obtained. Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a homogeneous solution.

<Comparative Example 3> The liquid crystal alignment agent (5) was prepared in the same manner as in Example 2, except that the liquid crystal alignment agent (2) was used instead of the liquid crystal alignment agent (1).

[Evaluation of pencil hardness] The liquid crystal alignment agents obtained in Examples and Comparative Examples were coated on an ITO substrate of 30 mm×40 mm by spin coating. Then, it was dried on a hot plate at 80° C. for 1 minute and 30 seconds, and fired in a hot air circulation oven at 230° C. for 20 minutes to obtain a substrate with a liquid crystal alignment film with a thickness of 100 nm. This board|substrate was measured by the pencil hardness test method (JIS K5400). The results are shown in Table 1. The larger the pencil hardness value, the higher the film hardness.

[Evaluation of Surface Energy] For the substrate with liquid crystal alignment film obtained by the same method as the evaluation of pencil hardness, the contact angle using water and diiodomethane was measured with an automatic contact angle meter (DMo-701, manufactured by Kyowa Interface Science Co., Ltd.). The surface energy of each liquid crystal alignment film was calculated using the result of the obtained contact angle. The results are shown in Table 2. The lower the surface energy, the higher the liquid crystal alignment.

[Table 1] Liquid crystal alignment agent polymer composition pencil hardness Example 1 (1) Polyamide-Polyurea Copolymer (A) (100) 6H Comparative Example 1 (2) Polyamide-polyurea copolymer (B) (100) 4H Comparative Example 2 (3) Polyamide (C) (100) 3H Example 2 (4) Polyamic acid-polyurea copolymer (A) (30) Polyamic acid (C) (70) 5H Comparative Example 3 (5) Polyamic acid-polyurea copolymer (B) (30) Polyamic acid (C) (70) 3H In the table, the numerical value in the parentheses of the polymer composition represents the blending ratio (parts by mass) of each polymer with respect to 100 parts by mass of the total of the polymer components used for the preparation of the liquid crystal aligning agent.

[Table 2] Liquid crystal alignment agent polymer composition Surface energy (mN/m) Example 1 (1) Polyamide-Polyurea Copolymer (A) (100) 36.6 Comparative Example 1 (2) Polyamide-polyurea copolymer (B) (100) 38.2 Comparative Example 2 (3) Polyamide (C) (100) 52.7 Example 2 (4) Polyamic acid-polyurea copolymer (A) (30) Polyamic acid (C) (70) 41.3 In the table, the numerical value in the parentheses of the polymer composition represents the blending ratio (parts by mass) of each polymer with respect to 100 parts by mass of the total of the polymer components used for the preparation of the liquid crystal aligning agent.

As shown in Table 1 and Table 2, the liquid crystal aligning agents of Examples 1 and 2 including the polyamic acid-polyurea copolymer obtained by using aromatic diamine (a) and not using aliphatic diamine are compared with the comparative examples. Comparing the liquid crystal alignment agents of 1 to 3, a liquid crystal alignment film with excellent film hardness and liquid crystal alignment can be obtained.

Furthermore, the entire contents of the specification, the scope of application, the drawings, and the abstract of Japanese Patent Application No. 2020-060312 filed on March 30, 2020 are incorporated herein by reference as a disclosure of the specification of the present invention.

Claims (16)

A liquid crystal aligning agent, characterized by containing the following (A) component, (A) component: selected from the group consisting of a polyimide having a repeating unit represented by the following formula (m1) and a repeating unit represented by the following formula (1) The polymer (A) of at least one of the group consisting of the precursor-polyurea copolymer and its imidized polymers, the repeating unit represented by the aforementioned formula (m1) and the aforementioned repeating unit represented by the formula (1) At least one of them is derived from an aromatic diamine (a) having any one of the structures represented by the following formulae (S1) to (S2), and the polymer (A) is obtained without using an aliphatic diamine,

(X ₁ represents a tetravalent organic group, Y ₁ represents a divalent organic group derived from an aromatic diamine, two R ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and two Z ₁ each independently Denotes a hydrogen atom, an optionally substituted alkyl group with 1 to 10 carbon atoms, an optionally substituted alkenyl group with 2 to 10 carbon atoms, an optionally substituted alkynyl group with 2 to 10 carbon atoms, and a tertiary butyl group oxycarbonyl or 9-intenylmethoxycarbonyl),

(A ₁ is a divalent organic group, A ₂ is a divalent organic group derived from an aromatic diamine, C ₁ and C ₂ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),

(X ¹ and X ² each independently represent a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -, where a1 is an integer from 1 to 15, A ₁ represents an oxygen atom or -COO-, and m ₁ is 1~ An integer of 2, G ¹ and G ² each independently represent a divalent cyclic group selected from a bivalent aromatic group having 6 to 12 carbon atoms and a bivalent alicyclic group having 3 to 8 carbon atoms, and the aforementioned cyclic group Any hydrogen atom above can be substituted, m and n are independently integers from 0 to 3, m+n is 1 to 6, R ¹ represents an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms group or an alkoxyalkyl group having 2 to 20 carbon atoms, ^{any hydrogen atom forming R 1} can be substituted by a fluorine atom, and when X ¹ , X ² , G ¹ , G ² , a1 and A ₁ exist in plural, the X ¹ , X ² , G ¹ , G ² , a1 and A ₁ each independently have the above definitions),

(X ^2a represents -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO-, and R ² represents a structure having a steroid skeleton). The liquid crystal alignment agent of claim 1, wherein the liquid crystal alignment agent further contains (B) component, (B) Component: at least one polymer selected from the group consisting of a polyimide precursor and an imidized polymer thereof, and is different from the polymer (A). The liquid crystal aligning agent according to claim 1 or 2, wherein the aromatic diamine (a) is a diamine represented by the following formula (d1) or formula (d2),

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m -O -, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m Divalent organic group of -, -CONH-(CH ₂ ) _m -NHCO- or -COO-(CH ₂ ) _m -OCO-, m is an integer from 1 to 8, and Y represents the aforementioned formulas (S1) to (S2) In any structure, in the aforementioned formula (d2), two Ys may be the same or different from each other). The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the aforementioned formulas (S1) to (S2) are selected from the group consisting of the following formulas (S1-1) to (S1-7) and (S2-a) any structure of the structure,

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, and X ^P represents -(CH ₂ ) _a -(a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH _{2 O-, -CH 2} OCO-, -COO- or -OCO-, A ₁ represents an oxygen atom or -COO-✽ (but, the bond with "✽" is bonded to (CH ₂ ) _a2 ), A ₂ represents an oxygen atom or ✽-COO- (but, The bond with "✽" is bonded to (CH ₂ ) _a2 ), a ₁ and a ₃ are independently an integer of 0 or 1, a ₂ is an integer of 1 to 10, and Cy represents 1,4- cyclohexylene or 1,4-phenylene),

(wherein, X represents formula (X1), formula (X2) or -CH ₂ O-, Col represents formula (Col-1), formula (Col-2) or formula (Col-3), and G represents formula (G1) ), formula (G2), formula (G3) or formula (G4)). The liquid crystal aligning agent according to any one of claims 1 to 4, wherein _{at least one of Y 1 of the aforementioned formula (m1) and A 2} of the aforementioned formula (1) represents 2 derived from the aforementioned aromatic diamine (a) Valence organic base. The liquid crystal aligning agent according to any one of claims 1 to 5, wherein in the aforementioned formula (1), A ₁ is a divalent aromatic group having at least one benzene ring with a carbon number of 6 to 30 or a carbon number of 4 to 30. Divalent acyclic aliphatic or alicyclic group. The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the polymer (A) is obtained by using a compound containing two isocyanate groups in the molecule. The liquid crystal aligning agent according to any one of claims 2 to 7, wherein the aforementioned polymer (B) is selected from the group consisting of polyimide precursors having repeating units represented by the following formula (m2) and imidization polymerization thereof at least one polymer of a group of things,

(X ₂ represents a tetravalent organic group, Y ₂ represents a divalent organic group, R ₂ and Z ₂ are synonymous with _{R 1} and Z _{1 in} formula (m1), respectively, and the _{two R 2} and Z ₂ may be the same or different from each other ). The liquid crystal aligning agent according to any one of claims 2 to 8, wherein the aforementioned polymer (B) does not have the repeating unit represented by the aforementioned formula (1). The liquid crystal aligning agent according to any one of claims 1 to 9, wherein at least one of the aforementioned polymers (A) and (B) uses a tetracarboxylic dianhydride or a derivative thereof represented by the following formula (3) obtained from the tetracarboxylic acid component,

(X represents a structure selected from the group formed by the following (x-1)~(x-13)),

(R ¹ to R ⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom having 1 carbon atoms. A monovalent organic group or phenyl group of ~6, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, j and k are integers of 0 or 1, A ₁ and A ₂ each independently represent a single bond, -O -, -CO-, -COO-, phenylene, sulfonyl or amido group, ✽1 is a bond to an acid anhydride group, ✽2 is a bond to another acid anhydride group , in the aforementioned formula (x-13), the two A ₂ may be the same or different from each other). The liquid crystal aligning agent according to any one of claims 1 to 10, wherein the polymer (A) uses a heterocyclic ring selected from the group consisting of nitrogen atoms It is obtained by at least one aromatic diamine having a nitrogen atom-containing structure in the group consisting of an amine group and a tertiary amine group. The liquid crystal aligning agent according to any one of claims 2 to 11, wherein the polymer (B) uses a heterocyclic ring selected from the group consisting of nitrogen atoms (excluding the amide ring of polyimide), a secondary It is obtained from at least one diamine of nitrogen atom-containing structure of the group consisting of amine group and tertiary amine group. The liquid crystal aligning agent according to any one of claims 2 to 12, wherein the content ratio of the aforementioned (A) component and (B) component [(A) component]/[(B) component] The mass ratio is 10/90~ 90/10. A liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of claims 1 to 13. A liquid crystal display element comprising the liquid crystal alignment film of claim 14. A method for manufacturing a liquid crystal display element, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 13 on a pair of substrates having a conductive film to form a coating film, and a layer of intervening liquid crystal molecules makes the coating film opposite to each other. A liquid crystal cell is formed by opposingly arranged in a directional manner, and the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates.