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

Abstract

The invention provides a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display module. The liquid crystal alignment agent comprises a polymer component (A) and a solvent (B). The polymer component (A) comprises a first polymer (A1), the first polymer (A1) is selected from at least one polymer in a group consisting of a polyimide precursor and an imidized polymer of the polyimide precursor, and the polyimide precursor of the first polymer (A1) comprises a structure shown as a formula (I) and a structure shown as a formula (II). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to an alignment agent, an alignment film, and a display component, and particularly to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display component. Background Art

[0002] Known liquid crystal display components are widely used as display parts for personal computers, smart phones, portable phones, or television receivers. A liquid crystal display component may include a liquid crystal layer sandwiched between a component substrate and a color filter substrate, pixel electrodes and common electrodes for applying an electric field to the liquid crystal layer, an alignment film for controlling the alignment of liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) for switching electronic signals supplied to the pixel electrodes. Regarding the driving method of liquid crystal molecules, longitudinal electric field methods such as the twisted nematic (TN) method and the vertical alignment (VA) method, and transverse electric field methods such as the in-plane switching (IPS) method and the fringe field switching (FFS) method are known.

[0003] Currently, the most widely used liquid crystal alignment film in the industry is obtained by rubbing the surface of a film formed on an electrode substrate and composed of polyamic acid and / or polyimide obtained by imidization thereof with a cloth such as cotton, nylon, or polyester in one direction. The rubbing treatment is a simple and highly productive industrial method. However, with the high performance, high fineness, and large size of liquid crystal display components, the alignment film surface forms scratches due to dust, mechanical force, and static electricity generated by the rubbing treatment, resulting in various problems such as non-uniformity in the alignment treatment surface. As an alignment treatment method alternative to the rubbing treatment, a photo-alignment method of imparting liquid crystal alignment ability by irradiating polarized radiation is known. Regarding the photo-alignment method, Japanese Patent Application Laid-Open No. 9-297313 has disclosed those using a photo-isomerization reaction, a photo-crosslinking reaction, or a photo-decomposition reaction.

[0004] However, with the popularization of fast charging technologies for various electronic products such as smart phones and tablet computers today, the charging voltage and current are both increased by more than twice compared to the past, and thus the temperature of the electronic products rises rapidly during charging. Also, due to the high frequency of use of current electronic products, the electronic products experience a high-frequency cycle of rapid temperature rise and fall. Such a high-frequency temperature rise and fall will inevitably affect the display quality of the electronic products.

[0005] It is known through experiments that such high and low temperature shocks will affect the alignment structure stability of a known liquid crystal alignment film prepared by the photo-alignment method, and further cause variations in the contrast of a liquid crystal display component made using this liquid crystal alignment film, which is linked to a decrease in display quality.

[0006] Therefore, how to improve the contrast of the liquid crystal alignment film after experiencing multiple high and low temperature extreme environments (i.e., the high and low temperature shock contrast) is indeed a problem that those skilled in the art urgently want to solve at present. Summary of the Invention

[0007] The present invention provides a liquid crystal aligning agent, a liquid crystal alignment film formed by the liquid crystal aligning agent, and a liquid crystal display component including the liquid crystal alignment film, wherein the liquid crystal display component has good high and low temperature shock contrast (i.e., the liquid crystal display component has high high and low temperature shock contrast).

[0008] The present invention provides a liquid crystal aligning agent, comprising: a polymer component (A), including a first polymer (A1), and the first polymer (A1) is selected from at least one polymer in the group consisting of a polyimide precursor and an imidized polymer of the polyimide precursor; and a solvent (B), wherein the polyimide precursor of the first polymer (A1) includes the structure shown by the following formula (I) and the structure shown by the following formula (II).

[0009]

[0010] In formula (I),

[0011] X 1 represents at least one selected from the group consisting of the structures shown by the following formulas (I-1) to (I-7);

[0012] X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

[0013] A 1 and A 2 each independently represents a substituted or unsubstituted divalent aromatic ring group;

[0014] Y 11 represents -O-, -S-, -COO- or -OCO-;

[0015] Z 1 represents the structure shown by the following formula (Z1-1);

[0016]

[0017] In formula (I-1), X 11 , X 12 , X 13 , and X14 Each independently represents 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, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group, and * represents the bonding position;

[0018] In formulae (I-2) to (I-6), * represents the bonding position;

[0019] In formula (I-7), X 15 and X 16 Each independently represents a hydrogen atom or a methyl group, and * represents the bonding position.

[0020]

[0021] In formula (Z1-1),

[0022] R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms;

[0023] m is an integer from 0 to 4. When m is an integer from 2 to 4, R 1 each independently has the above definition,

[0024] n is an integer from 1 to 3. When n is 2 or 3, R 1 and m each independently have the above definition,

[0025] * represents the bonding position.

[0026]

[0027] In formula (II),

[0028] X 1 represents at least one selected from the group consisting of the structures represented by the aforementioned formulae (I-1) to (I-7);

[0029] X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

[0030] A 3 and A 4 each independently represents a substituted or unsubstituted divalent aromatic ring group;

[0031] Y 21 and Y 22 each independently represents a single bond, an oxygen atom, a sulfur atom, or R 2 represents a group that detaches upon heating, and at least one of Y 21 and Y 22 is and Y21 is different from Y 22 ;

[0032] Z 2 represents a divalent organic group having at least one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure and having 1 to 15 carbon atoms.

[0033] In one embodiment of the present invention, the above-mentioned X 1 represents a structure represented by formula (I-1).

[0034] In one embodiment of the present invention, the above-mentioned X 1 represents a structure represented by formula (I-1-1),

[0035]

[0036] where * represents the bonding position.

[0037] In one embodiment of the present invention, the above-mentioned Z 1 represents a structure represented by the following formula (Z1-1-1),

[0038]

[0039] In formula (Z1-1-1),

[0040] R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms;

[0041] m is an integer from 0 to 4. When m is an integer from 2 to 4, R 1 each independently has the above definition,

[0042] n is an integer from 1 to 3. When n is 2 or 3, R 1 and m each independently have the above definition,

[0043] * represents the bonding position.

[0044] In one embodiment of the present invention, A in the above-mentioned formula (I) 1 and A 2 each independently represent a substituted or unsubstituted 1,4-phenylene group.

[0045] In one embodiment of the present invention, the polyimide precursor of the above-mentioned first polymer (A1) further contains a structure represented by the following formula (III),

[0046]

[0047] In formula (III),

[0048] X 1represents at least one selected from the group consisting of the structures represented by the aforementioned formulas (I-1) to (I-7);

[0049] X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

[0050] Z 31 and Z 31 ' each independently represents a linear hydrocarbon group having 1 to 10 carbon atoms or a single bond;

[0051] Z 32 and Z 32 ' each independently represents -O-, -S-, -CO- or -COO-;

[0052] Z 33 and Z 33 ' each independently represents a linear hydrocarbon group having 1 to 10 carbon atoms or a single bond;

[0053] Z 31 、Z 31 '、Z 33 and Z 33 ' cannot all be single bonds;

[0054] Ring Z represents an aromatic hydrocarbon ring, diphenyl ether or a nitrogen-containing heterocycle;

[0055] B 1 and B 2 each independently represents one selected from the divalent organic groups represented by the following formulas (III-1) to (III-16), and B 1 and B 2 do not have the same structure,

[0056]

[0057]

[0058]

[0059] In formulas (III-1) to (III-16), * represents the bonding position,

[0060] In formula (III-2), B 3 represents an alkylene group having 1 to 5 carbon atoms or -O-;

[0061] In formula (III-14), B 4 represents a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group.

[0062] The present invention provides a liquid crystal alignment film for a photo-alignment method, formed using the above liquid crystal aligning agent.

[0063] The present invention provides a liquid crystal alignment film formed by using the above liquid crystal aligning agent.

[0064] The present invention provides a liquid crystal display component, comprising: the above liquid crystal alignment film.

[0065] Based on the above, the present invention provides a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display component, which enable the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent to have good high and low temperature impact contrast by defining the first polymer (A1) in the polymer component (A) to include the structure represented by formula (I) and the structure represented by formula (II).

[0066] To make the above features and advantages of the present invention more obvious and understandable, specific embodiments are hereinafter given and described in detail as follows. Detailed Embodiments

[0067] <Liquid Crystal Aligning Agent>

[0068] This embodiment provides a liquid crystal aligning agent, comprising a polymer component (A) and a solvent (B).

[0069] Polymer Component (A)

[0070] The polymer component (A) of this embodiment includes a first polymer (A1). Further, the polymer component (A) of this embodiment may optionally include a second polymer (A2). In addition, the polymer component (A) of this embodiment may optionally further include other polymers (A3).

[0071] First Polymer (A1)

[0072] The first polymer (A1) of this embodiment is selected from at least one polymer in the group consisting of a polyimide precursor and an imidized polymer of the polyimide precursor, wherein the polyimide precursor includes polyamic acid, polyamic acid ester, or a combination thereof.

[0073] The polyimide precursor of the first polymer (A1) of this embodiment includes the structure represented by the following formula (I) and the structure represented by the following formula (II).

[0074] The structure represented by the following formula (I) is as follows:

[0075]

[0076] In formula (I),

[0077] X 1 represents at least one selected from the group consisting of the structures represented by the following formulas (I-1) to (I-7);

[0078] X 2Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

[0079] A 1 and A 2 Each independently represents a substituted or unsubstituted divalent aromatic ring group;

[0080] Y 11 represents -O-, -S-, -COO- or -OCO-;

[0081] Z 1 represents a structure represented by the following formula (Z1-1);

[0082]

[0083] In formula (I-1), X 11 , X 12 , X 13 , and X 14 Each independently represents 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, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group, and * represents the bonding position;

[0084] In formulas (I-2) to (I-6), * represents the bonding position;

[0085] In formula (I-7), X 15 and X 16 Each independently represents a hydrogen atom or a methyl group, and * represents the bonding position.

[0086] In one embodiment, the above-mentioned X 1 represents a structure represented by the following formulas (I-1-1) to (I-1-6):

[0087]

[0088] wherein * represents the bonding position.

[0089] In formula (I), X 1 is preferably a structure represented by formula (I-1), more preferably a structure represented by formula (I-1-1) or formula (I-1-6), and still more preferably a structure represented by formula (I-1-1). When X 1 represents a structure represented by formula (I-1), the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent has better high and low temperature impact contrast (i.e., higher high and low temperature impact contrast). Also, when X 1 represents a structure represented by formula (I-1-1), the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent has even better high and low temperature impact contrast (i.e., even higher high and low temperature impact contrast).

[0090] In one embodiment, A in the above formula (I) 1 and A 2 Each independently represents a substituted or unsubstituted 1,4-phenylene group. 1 and A 2 When each independently represents a substituted or unsubstituted 1,4-phenylene group, a liquid crystal display device comprising a liquid crystal alignment film formed by the liquid crystal alignment agent has better high and low temperature impact contrast.

[0091] The structure shown by formula (Z1-1) is as follows:

[0092]

[0093] In formula (Z1-1),

[0094] R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms;

[0095] m is an integer from 0 to 4. When m is an integer from 2 to 4, R 1 each independently having the above definitions,

[0096] n is an integer from 1 to 3. When n is 2 or 3, R 1 and m each independently have the above definitions,

[0097] *Indicates the bond position.

[0098] In one embodiment, the above Z 1 It represents the structure represented by the following formula (Z1-1-1).

[0099]

[0100] In formula (Z1-1-1),

[0101] R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms;

[0102] m is an integer from 0 to 4. When m is an integer from 2 to 4, R 1 each independently having the above definitions,

[0103] n is an integer from 1 to 3. When n is 2 or 3, R 1 and m each independently have the above definitions,

[0104] *Indicates the bond position.

[0105] When Z 1When it represents the structure shown by the following formula (Z1-1-1), a liquid crystal display component including a liquid crystal alignment film formed by a liquid crystal aligning agent has better high and low temperature impact contrast.

[0106] The structure shown by the following formula (II) is as follows:

[0107]

[0108] In formula (II),

[0109] X 1 represents at least one selected from the group consisting of the structures shown by the aforementioned formulas (I-1) to (I-7);

[0110] X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

[0111] A 3 and A 4 each independently represents a substituted or unsubstituted divalent aromatic ring group;

[0112] Y 21 and Y 22 each independently represents a single bond, an oxygen atom, a sulfur atom or R 2 represents a group that dissociates upon heating, and at least one of Y 21 and Y 22 is and Y 21 is different from Y 22 ;

[0113] Z 2 represents a divalent organic group having at least one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure and having 1 to 15 carbon atoms.

[0114] When X in the structure shown by formula (I) 1 and / or X in the structure shown by formula (II) 1 is not at least one selected from the group consisting of the structures shown by formulas (I-1) to (I-7), the high and low temperature impact contrast of the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent is poor (that is, the high and low temperature impact contrast is too low), resulting in poor display quality of the liquid crystal display component.

[0115] When the group between two N-H in the structure shown by formula (I) is not -A 1 -Y 11 -Z 1 -Y 11 -A 2- When it is, the contrast of the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent is poor under high and low temperature impact.

[0116] When the group between two N-H in the structure represented by formula (II) is not -A 3 -Y 21 -Z 2 -Y 22 -A 4 - When it is, the contrast of the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent is poor under high and low temperature impact.

[0117] In one embodiment, the structure represented by formula (I) is the structure represented by the following formula (I-a).

[0118]

[0119] Formula (I-a),

[0120] Y 11 The definition of is the same as Y in formula (I) 11 Same, R 1 、m, and the definition of n are the same as R in formula (Z1-1) 1 、m, and n, which will not be elaborated here,

[0121] R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms;

[0122] r each independently represents an integer from 0 to 5, preferably represents 0;

[0123] When r represents an integer from 2 to 5, R2 each independently has the above definition.

[0124] n is an integer from 1 to 3. When n is 2 or 3, R1 and m each independently have the above definition.

[0125] When the structure represented by formula (I) is the structure represented by formula (I-a), the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent has better contrast under high and low temperature impact.

[0126] In one embodiment, the polyimide precursor of the first polymer (A1) further includes the structure represented by the following formula (III).

[0127]

[0128] In formula (III),

[0129] X 1 Represents at least one selected from the group consisting of the structures represented by the foregoing formulas (I-1) to (I-7);

[0130] X 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

[0131] Z 31 and Z 31 ' each independently represents a linear hydrocarbon group having 1 to 10 carbon atoms or a single bond;

[0132] Z 32 and Z 32 ' each independently represents -O-, -S-, -CO- or -COO-;

[0133] Z 33 and Z 33 ' each independently represents a linear hydrocarbon group having 1 to 10 carbon atoms or a single bond;

[0134] Z 31 、Z 31 '、Z 33 and Z 33 ' cannot all be single bonds;

[0135] Ring Z represents an aromatic hydrocarbon ring, diphenyl ether or a nitrogen-containing heterocycle;

[0136] B 1 and B 2 each independently represents one selected from the divalent organic groups represented by the following formulas (III-1) to (III-16), and B 1 and B 2 do not have the same structure,

[0137]

[0138]

[0139]

[0140] In formulas (III-1) to (III-16), * represents the bonding position. In formula (III-2), B 3 represents an alkylene group having 1 to 5 carbon atoms or -O-; in formula (III-14), B 4 represents a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group.

[0141] When the polyimide precursor of the first polymer (A1) further contains the structure represented by formula (III), the liquid crystal display component including the liquid crystal alignment film formed from the liquid crystal aligning agent has better high and low temperature impact contrast.

[0142] The first polymer (A1) of this embodiment may be selected from at least one polymer in the group consisting of polyimide precursors obtained by reacting a tetracarboxylic dianhydride component (a1) and a diamine component (b1), and imidized polymers of the polyimide precursors. For example, the first polymer (A1) is a polyimide precursor having a structure of an imide precursor such as polyamic acid and polyamic acid ester, or the first polymer (A1) is an imidized polymer (i.e., polyimide) formed from the above polyimide precursor, or the first polymer (A1) contains the above polyimide precursor and the above imidized polymer.

[0143] It should be noted that the structure shown in the above formula (I) is formed by reacting the following alicyclic tetracarboxylic dianhydride (a1-1) with the following diamine compound (b1-1); the structure shown in the above formula (II) is formed by reacting the following alicyclic tetracarboxylic dianhydride (a1-1) with the following diamine compound (b1-2); and the structure shown in the above formula (III) is formed by reacting the following alicyclic tetracarboxylic dianhydride (a1-1) with the following diamine compound (b1-3).

[0144] In addition, the polyimide precursor of the first polymer (A1) may further include, but is not limited to, other structural units other than those of formula (I), formula (II), and formula (III) formed by any one of the tetracarboxylic dianhydrides in the following tetracarboxylic dianhydride component (a1) and any one of the diamines in the following diamine component (b1), which will not be elaborated here.

[0145] Tetracarboxylic dianhydride component (a1)

[0146] In addition to using tetracarboxylic dianhydride compounds, the tetracarboxylic dianhydride component (a1) that reacts with the diamine component (b1) in this embodiment may also use tetracarboxylic dihalides, tetraalkyl esters of tetracarboxylic acids, or tetraalkyl ester dihalides of tetracarboxylic acids and other tetracarboxylic dianhydride derivatives. The tetracarboxylic dianhydride component (a1) may be used alone with one tetracarboxylic dianhydride compound or its derivative, or may be used in combination with a variety of mixtures.

[0147] The tetracarboxylic dianhydride component (a1) may include an alicyclic tetracarboxylic dianhydride (a1-1). The tetracarboxylic dianhydride component (a1) may selectively further include other tetracarboxylic dianhydrides (a1-2).

[0148] Alicyclic tetracarboxylic dianhydride (a1-1)

[0149] The tetracarboxylic dianhydride component (a1) used to react to obtain the first polymer (A1) may include an alicyclic tetracarboxylic dianhydride (a1-1) represented by the following formula (A11) or a derivative thereof. The alicyclic tetracarboxylic dianhydride (a1-1) represented by the formula (A11) or a derivative thereof may be composed of a single tetracarboxylic dianhydride or a derivative thereof, or may be composed of a plurality of tetracarboxylic dianhydrides or derivatives thereof. In this embodiment, the alicyclic tetracarboxylic dianhydride (a1-1) represented by the formula (A11) may be, for example, an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Alternatively, it does not have to be composed only of an alicyclic structure, and a part thereof may also have a chain hydrocarbon structure or an aromatic ring structure. The aromatic tetracarboxylic dianhydride may be, for example, an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. However, it does not have to be composed only of an aromatic ring structure, and a part thereof may also have a chain hydrocarbon structure or an alicyclic structure. The acyclic aliphatic tetracarboxylic dianhydride may be, for example, an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not have to be composed only of a chain hydrocarbon structure, and a part thereof may also have an alicyclic structure or an aromatic ring structure.

[0150]

[0151] In formula (A11), X 1 may be selected from at least one of the structures represented by the following formulas (I-1) to (I-7), and * represents the bonding position.

[0152]

[0153] In formula (I-1), X 11 , X 12 , X 13 , and X 14 each 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, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group, and * represents the bonding position. In one embodiment, X 11 and X 13 each independently represent an alkyl group having 1 to 3 carbon atoms, and X 12 and X 14 each independently represent a hydrogen atom. In another embodiment, X 11 , X 12 , X 13 , and X 14 each independently represent a hydrogen atom.

[0154] In formulas (I-2) to (I-6), * represents the bonding position.

[0155] In formula (I-7), X 15 and X 16 each independently represent a hydrogen atom or a methyl group, and * represents the bonding position.

[0156] In some embodiments, X 1 may represent a structure represented by the following formulas (I-1-1) to (I-1-6).

[0157]

[0158] In formula (A11), X 1 preferably represents a structure represented by formula (I-1), more preferably a structure represented by formula (I-1-1) or formula (I-1-6), and still more preferably a structure represented by formula (I-1-1). When X 1 represents a structure represented by formula (I-1), the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent has better contrast under high and low temperature impact. Also, when X 1 represents a structure represented by formula (I-1-1), the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent has even better contrast under high and low temperature impact.

[0159] When X 1 represents the group represented by formula (I-1-1), the alicyclic tetracarboxylic dianhydride (a1-1) is the tetracarboxylic dianhydride represented by formula (I-1-1a).

[0160]

[0161] When X 1 represents the group represented by formula (I-1-6), the alicyclic tetracarboxylic dianhydride (a1-1) is the tetracarboxylic dianhydride represented by formula (I-1-6a).

[0162]

[0163] Based on the total usage amount of the tetracarboxylic dianhydride component (a1) being 100 moles, the usage amount of the alicyclic tetracarboxylic dianhydride (a1-1) represented by formula (A11) is 30 moles to 100 moles, preferably 40 moles to 100 moles, and more preferably 50 moles to 100 moles.

[0164] When the tetracarboxylic dianhydride component (a1) contains the alicyclic tetracarboxylic dianhydride (a1-1) represented by formula (A11), the liquid crystal display device including the liquid crystal alignment film formed from the liquid crystal aligning agent has good contrast under high and low temperature impact, and the display quality of the liquid crystal display device is excellent.

[0165] When the tetracarboxylic dianhydride component (a1) does not contain the alicyclic tetracarboxylic dianhydride (a1-1) represented by the formula (A11), the high and low temperature shock contrast of the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent is poor, resulting in poor display quality of the liquid crystal display component.

[0166] Other tetracarboxylic dianhydrides (a1-2)

[0167] The other tetracarboxylic dianhydrides (a1-2) may include the tetracarboxylic dianhydride compounds and their derivatives represented by the following formula (A12).

[0168]

[0169] In the formula (A12), X 1 ' may represent the structures represented by the following formula (A12-1) to formula (A12-32), where * represents the bonding position.

[0170]

[0171] In the formula (A12-1), a1 represents an integer of 1 to 12.

[0172]

[0173] In the formula (A12-5), X 11 ' represents a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amide group, and a1 represents an integer of 0 or 1.

[0174]

[0175] In the formula (A12-6), X 11 ' and X 12 ' each independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amide group, and multiple X 12 ' may be the same as or different from each other, and a1 represents an integer of 0 or 1.

[0176]

[0177]

[0178] In the formula (A12-11), a1 represents an integer of 2 to 6.

[0179]

[0180] In the formula (A12-13), a1 represents an integer of 1 or 2.

[0181]

[0182] In formula (A12-14), X 13 ' each independently represents 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, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group, and multiple X 13 ' may be the same as or different from each other. From the viewpoint of liquid crystal alignment, X 13 ' preferably represents a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably represents a hydrogen atom or a methyl group.

[0183]

[0184]

[0185]

[0186] In one embodiment, the structure represented by formula (A12-5) and the structure represented by formula (A12-6) may include, but are not limited to, the structures represented by the following formulas (A12-5-1) to (A12-5-9) and formulas (A12-6-1) to (A12-6-7).

[0187] The structure represented by formula (A12-5) is preferably the structure represented by formula (A12-5-1) or formula (A12-5-6).

[0188]

[0189]

[0190]

[0191] The aforementioned other tetracarboxylic dianhydrides (a1-2) can be used alone or in combination of multiple kinds.

[0192] Based on the total usage amount of the tetracarboxylic dianhydride component (a1) being 100 moles, the usage amount of the other tetracarboxylic dianhydrides (a1-2) is from 0 mole to 70 moles, preferably from 0 mole to 60 moles, and more preferably from 0 mole to 50 moles.

[0193] Based on the total number of moles of the diamine component (b1) described later being 100 moles, the usage amount range of the tetracarboxylic dianhydride component (a1) can be from 20 moles to 200 moles, preferably from 30 moles to 120 moles.

[0194] Diamine component (b1)

[0195] The diamine component (b1) may include a diamine compound (b1-1) and a diamine compound (b1-2). In addition to the diamine compound (b1-1) and the diamine compound (b1-2), the diamine component (b1) may further include a diamine compound (b1-3). Furthermore, the diamine component (b1) may optionally further include a diamine compound (b1-4), other diamine compounds (b1-5), or a combination thereof.

[0196] Diamine compound (b1-1)

[0197] The diamine compound (b1-1) in this example is the diamine compound represented by the following formula (IV).

[0198] H2N-A 1 -Y 11 -Z 1 -Y 11 -A 2 -NH2 Formula (IV)

[0199] In formula (IV),

[0200] A 1 and A 2 each independently represents a substituted or unsubstituted divalent aromatic ring group;

[0201] Y 11 represents -O-, -S-, -COO- or -OCO-;

[0202] Z 1 represents the structure represented by the following formula (Z1-1).

[0203]

[0204] In formula (Z1-1),

[0205] R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms;

[0206] m is an integer from 0 to 4. When m is an integer from 2 to 4, R 1 each independently has the above definition,

[0207] n is an integer from 1 to 3. When n is 2 or 3, R 1 and m each independently have the above definition,

[0208] * represents the bonding position.

[0209] That is to say, the diamine compound (b1-1) in this example is the diamine compound represented by the following formula (IV’).

[0210]

[0211] In formula (IV’), A 1 , A 2 , and Y 11 are defined the same as A 1 , A 2 , and Y 11 in formula (IV), and the definitions of R 1 , m, and n are the same as R 1 , m, and n in formula (Z1-1), and will not be elaborated here.

[0212] In formula (IV) and formula (IV’), A 1 and A 2 each independently represent a substituted or unsubstituted divalent aromatic ring group, where the aforementioned divalent aromatic ring group is a group formed by removing 2 hydrogen atoms from the ring portion of an aromatic ring, and may have substituents on the ring portion. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, biphenyl ring, etc.; nitrogen-containing heterocycles such as pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, etc. Examples of the substituents that the aromatic ring may have include alkyl groups having 1 to 6 carbon atoms, etc. When A 1 and A 2 are the same, the diamine compound (b1-1) can be synthesized simply, and a liquid crystal display component including a liquid crystal alignment film formed by a liquid crystal aligning agent has better high and low temperature impact contrast. Regarding A 1 and A 2 , in terms of obtaining a liquid crystal component with more excellent high and low temperature impact contrast characteristics, among these, a group formed by removing 2 hydrogen atoms from the ring portion of a benzene ring, biphenyl ring, pyridine ring or pyrimidine ring that may have substituents is preferred.

[0213] In one embodiment, in the above formula (IV) and formula (IV’), A 1 and A 2 each independently represent a substituted or unsubstituted 1,4-phenylene. When A 1 and A 2 each independently represent a substituted or unsubstituted 1,4-phenylene, a liquid crystal display component including a liquid crystal alignment film formed by a liquid crystal aligning agent has better high and low temperature impact contrast.

[0214] In formula (Z1-1) in formula (IV) and formula (IV’), R 1represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. When m is an integer from 2 to 4, R 1 may each be the same or different.

[0215] In the formula (IV), R 1 The alkyl group having 1 to 6 carbon atoms may be linear or branched. Specifically, examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, and the like.

[0216] In the formula (IV), R 1 The alkoxy group having 1 to 6 carbon atoms may be exemplified by those formed by bonding the groups exemplified for the alkyl group having 1 to 6 carbon atoms above to an oxygen atom. Specifically, examples include methoxy, ethoxy, and the like.

[0217] In the formula (IV), R 1 The fluoroalkyl group having 1 to 6 carbon atoms may be exemplified by those obtained by substituting at least one hydrogen atom of the groups exemplified for the alkyl group having 1 to 6 carbon atoms above with a fluorine atom.

[0218] When the diamine component (b1) contains the diamine compound (b1-1) represented by the formula (IV), the liquid crystal display element having the liquid crystal alignment film formed therefrom has good high and low temperature shock contrast and the display quality of the liquid crystal display device. Conversely, when the diamine component (b1) does not contain the diamine compound (b1-1) represented by the formula (IV), the liquid crystal display element having the liquid crystal alignment film formed therefrom has a problem of too low high and low temperature shock contrast, resulting in poor display quality.

[0219] In one embodiment, when the diamine compound (b1-1) represented by the formula (IV) has a structure selected from the following formula (IV-1), the liquid crystal display device having the liquid crystal alignment film formed from the liquid crystal aligning agent has better high and low temperature shock contrast.

[0220]

[0221] In the formula (IV-1), A 1 , A 2 , and Y 11 are defined the same as A 1 , A 2 , and Y 11 in the formula (IV), and the definitions of R 1 , m, and n are the same as those of R 1 , m, and n in the formula (Z1-1), and will not be described herein again.

[0222] In the above formula (IV-1), m is an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0.

[0223] In the above formula (IV-1), n is an integer from 1 to 3, preferably 1.

[0224] More preferably, the diamine compound (b1-1) represented by formula (IV) is a structure selected from the following formula (IV-2). At this time, in the liquid crystal display component having the liquid crystal alignment film formed, the interaction with the benzene ring possessed by the liquid crystal molecules is likely to occur, and better high and low temperature impact contrast can be obtained.

[0225]

[0226] In formula (IV-2), Y 11 has the same definition as Y in formula (IV) 11 , and the definitions of R 1 , m, and n are the same as those of R 1 , m, and n in formula (Z1-1), and will not be elaborated here.

[0227] In formula (IV-2), each R 2 independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms;

[0228] Each r independently represents an integer from 0 to 5, preferably 0;

[0229] When r represents an integer from 2 to 5, each R2 independently has the above definition.

[0230] n is an integer from 1 to 3. When n is 2 or 3, each of R1 and m independently has the above definition.

[0231] The phenyl group connected to the amino group in the above formula (IV-2) is preferably a substituted or unsubstituted 1,4-phenylene group. The liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent has better high and low temperature impact contrast.

[0232] Specific examples of the diamine compound (b1-1) include compounds represented by the following formula (IV-3) to formula (IV-11), preferably compounds represented by formula (IV-3), compounds represented by formula (IV-4), compounds represented by formula (IV-10), and compounds represented by formula (IV-11).

[0233]

[0234] The diamine compound (b1-1) represented by the above formula (IV) or formula (IV') can be produced by common methods in organic chemistry. The following are the production methods of the diamine compound (b1-1) described by way of example, but the present embodiment is not limited thereto.

[0235] Specifically, when Y 11 is O or S, n is 1, and A 1 , A 2 are the same nitrobenzene derivatives, as shown in the following reaction formula (1) or reaction formula (2), a commercially available nitrobenzene derivative substituted with a leaving group (X) can be reacted with a dihydroxycyclohexane derivative or a dithiocyclohexane derivative to obtain an intermediate product "dinitro compound". The leaving group (X) is preferably selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyl group (-OTs), and a methanesulfonyl group (-OMs). Only the reaction formula (1) for the reaction of a nitrobenzene derivative with a dihydroxycyclohexane derivative and the reaction formula (2) for the reaction of a nitrobenzene derivative with a dithiocyclohexane derivative are listed below, but the present embodiment is not limited thereto. Among them, the nitrobenzene derivative can be replaced with other nitroaromatic derivatives as reaction raw materials according to the difference of A 1 , A 2 , such as nitro-biphenyl derivatives, nitro-pyridine derivatives, etc.

[0236]

[0237] In reaction formula (1) and reaction formula (2), X is a leaving group; the definitions of R 1 , m are the same as the definitions of R 1 , m in formula (Z1-1) of the above formula (IV) and formula (IV'); the definitions of R 2 , r are the same as the definitions of R 2 , r in the above formula (IV-2), and will not be described herein again.

[0238] The progress of Reaction Formula (1) and Reaction Formula (2) is not particularly limited and can be carried out in the presence of a base. As long as the target product can be synthesized, the base used is not particularly limited, and examples include inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium hydride; and organic bases such as pyridine, dimethylaminopyridine, trimethylamine, triethylamine, tributylamine. Depending on the situation, when a palladium catalyst or a copper catalyst or a copper catalyst is used in combination, the yield can be increased. Specific examples of the palladium catalyst include, but are not limited to, Bis(dibenzylideneacetone)palladium, Tris(dibenzylideneacetone)dipalladium, [1,1’-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), etc. The above reaction solvent can be selected from polar aprotic solvents such as acetonitrile, dimethylformamide (DMF), acetone, dimethylacetamide (DMAc). From the viewpoint of easy synthesis, the base is preferably potassium carbonate.

[0239] The reaction temperature of Reaction Formula (1) or Reaction Formula (2) can be appropriately set according to the reaction mode, preferably -20 to 250 °C, more preferably 0 to 200 °C.

[0240] Next, as shown in the following Reaction Formula (3), the nitro group in the product of Reaction Formula (1) (i.e., the intermediate "dinitro compound") is converted to an amino group by a reduction method to obtain the final product "diamine compound". The following is only an example, but this embodiment is not limited thereto.

[0241]

[0242] Similarly, as shown in the following Reaction Formula (4), the nitro group in the product of Reaction Formula (2) (i.e., the intermediate "dinitro compound") can also be converted to an amino group by a reduction method to obtain the final product "diamine compound". The following is only an example, but this embodiment is not limited thereto.

[0243]

[0244] The reduction method of the dinitro compound is not particularly limited. Examples thereof include a method of using palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide, PtS / C catalysts (Platinumsulfided on carbon), etc. as a catalyst, and performing reduction with hydrogen, hydrazine, and hydrogen chloride in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, and alcohols. A autoclave may also be used as needed to perform the reduction reaction under pressure. On the other hand, when the substituent structure substituting the hydrogen atom of the substituted benzene ring or saturated hydrocarbon group contains an unsaturated bond, when palladium-carbon or platinum-carbon is used, the unsaturated bond may be reduced to a saturated bond. Therefore, reduction conditions using a transition metal such as reduced iron, tin, and tin chloride as a catalyst are preferred.

[0245] The reaction temperature of Reaction Formula (3) and Reaction Formula (4) can be appropriately set according to the reaction mode, and is preferably -20 to 200 °C, more preferably 0 to 150 °C.

[0246] When n is 2 or 3, the compounds represented by the following Formula (1-1) or Formula (2-1) can be used to replace the dihydroxycyclohexane derivative and the dithiocyclohexane derivative, respectively, to obtain the compound represented by the above Formula (IV) (wherein, Y 11 is O or S, and n is 2 or 3).

[0247]

[0248] In Formula (1-1) and Formula (2-1), k is 0 or 1; R 1 , m are defined in the same manner as R 1 , m in Formula (Z1-1) and Formula (IV') of the above Formula (IV).

[0249] On the other hand, when Y 11 is *-COO- or *-OCO- (where the bonding position of "*" is connected to the amino aromatic group), and a diamine compound can be appropriately synthesized by a known method. For example, when Y 11 is a diamine compound of *-COO-, it can be obtained by performing an esterification reaction of a dihydroxycyclohexane derivative (such as 1,4-cyclohexanediol) and a nitroaromatic group formyl chloride derivative (such as nitrobenzoyl chloride), and then reducing the nitro group. For example, when Y 11 is a diamine compound of *-OCO-, it can be obtained by performing an esterification reaction of a cyclohexanedicarbonyl chloride derivative and a nitroaromatic group phenol derivative (such as nitrophenol), and then reducing the nitro group.

[0250] On the other hand, when A 1 , A 2When Y is a different substituted divalent aromatic ring group, the diamine compound can be appropriately synthesized by known methods. Taking the case of a compound where Y is O or S and n is 1 as an example, by using a commercially available hydroxy nitroaromatic derivative and first reacting it with a cyclohexane derivative having two leaving groups (X), a nitro compound having one leaving group (X) is obtained after the reaction. The nitro compound having one leaving group is then reacted with another hydroxy nitroaromatic derivative to obtain a dinitro compound, and then the nitro group is reduced to obtain a diamine compound. 11 Taking the case of a compound where Y is O or S and n is 1 as an example, by using a commercially available hydroxy nitroaromatic derivative and first reacting it with a cyclohexane derivative having two leaving groups (X), a nitro compound having one leaving group (X) is obtained after the reaction. The nitro compound having one leaving group is then reacted with another hydroxy nitroaromatic derivative to obtain a dinitro compound, and then the nitro group is reduced to obtain a diamine compound.

[0251] Based on the total usage amount of the diamine component (b1) being 100 moles, the usage amount of the diamine compound (b1-1) can be 3 moles to 30 moles, preferably 5 moles to 25 moles, and more preferably 7 moles to 20 moles.

[0252] Diamine compound (b1-2)

[0253] The diamine compound (b1-2) in this example is the diamine compound represented by the following formula (V).

[0254] H2N-A 3 -Y 21 -Z 2 -Y 22 -A 4 -NH2 Formula (V)

[0255] In formula (V),

[0256] A 3 and A 4 each independently represent a substituted or unsubstituted divalent aromatic ring group;

[0257] Y 21 and Y 22 each independently represent a single bond, an oxygen atom, a sulfur atom or R 2 represents a group that detaches upon heating, and at least one of Y 21 and Y 22 is and Y 21 is different from Y 22 ;

[0258] Z 2 represents a divalent organic group having at least one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure and having 1 to 15 carbon atoms.

[0259] In formula (V), A 3 and A 4Each independently represents a substituted or unsubstituted divalent aromatic ring group, wherein the substituted divalent aromatic ring group is a group formed by substituting two hydrogen atoms with substituents on the ring portion of the aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, biphenyl ring, etc.; nitrogen-containing heterocycles such as pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, etc. Examples of the substituents that the aromatic ring may have include alkyl groups having 1 to 6 carbon atoms, etc. In A 3 and A 4 are the same, the diamine compound (b1-2) can be synthesized simply, and the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent has better high and low temperature impact contrast. Regarding A 3 and A 4 , in terms of obtaining a liquid crystal component with more excellent high and low temperature impact contrast characteristics, among these, A 3 and A 4 can be a group formed by removing two hydrogen atoms from the ring portion of a benzene ring, biphenyl ring, pyridine ring or pyrimidine ring.

[0260] In formula (V), when Y 21 and Y 22 one of them represents and R 2 represents a group that detaches upon heating; the protecting group represented by R 2 is preferably, for example, a carbamate protecting group, an amide protecting group, an imide protecting group or a sulfonamide protecting group. The protecting group represented by R 2 can have the structure shown in the following formula (V-1), and since the aforementioned protecting group is a high heat leaving group, the residual amount of the deprotected portion in the liquid crystal alignment film can be effectively reduced.

[0261]

[0262] In formula (V-1), Y 1 represents a single bond or a divalent hydrocarbon group having 1 to 4 carbon atoms.

[0263] In formula (V), Z 2A divalent organic group having a chain hydrocarbon structure with 1 to 15 carbon atoms or an alicyclic hydrocarbon structure with 3 to 15 carbon atoms. Among them, the "chain hydrocarbon structure" refers to a straight-chain hydrocarbon structure and a branched-chain hydrocarbon structure that do not contain a cyclic structure but only contain a chain structure. The chain hydrocarbon structure can be saturated or unsaturated. The "alicyclic hydrocarbon structure" refers to a hydrocarbon structure that only contains an alicyclic hydrocarbon structure as the ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon structure is not limited to only containing the structure of an alicyclic hydrocarbon, and a part of it can also contain a chain structure.

[0264] In one embodiment, in formula (V), when A 3 and A 4 represent a divalent group formed by removing two hydrogen atoms from the ring portion of a benzene ring, a pyridine ring or a pyrimidine ring, the ring portion may have substituents, and A 3 and A 4 are the same; and when Z 2 represents and n represents an integer from 1 to 5, the liquid crystal display device with a liquid crystal alignment film formed by using this liquid crystal aligning agent has better high and low temperature impact contrast.

[0265] From the perspective of better high and low temperature impact contrast, relative to the nitrogen atom in formula (A21), the bonding positions of the benzene ring, pyridine ring or pyrimidine ring represented by A1 and A2 in formula (A21) are preferably para positions.

[0266] The diamine compound (b1-2) represented by formula (V) is preferably the diamine compound represented by formula (V-2).

[0267]

[0268] In formula (V-2), Q 1 and Q 2 each independently represent -CH- or a nitrogen atom; Y 21 and Y 22 are defined the same as Y 21 and Y 22 in formula (V), and will not be repeated here; m 1 represents an integer from 1 to 5.

[0269] In one embodiment, the diamine compound (b1-2) of this embodiment may include, but is not limited to, the compounds represented by the following formula (V-3) to formula (V-13), preferably the compound represented by formula (V-3) and the compound represented by formula (V-6). Specific compounds of the diamine compound (b1-2) can be synthesized by common methods suitable for combinatorial organic chemistry. The diamine compound (b1-2) can be used alone or in combination of multiple kinds. In the following formula (V-3) to formula (V-13), Boc represents tert-butyloxycarbonyl.

[0270]

[0271]

[0272] When the diamine component (b1) does not include the diamine compound (b1-2) represented by formula (V), the high and low temperature impact contrast of the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent is poor, resulting in poor display quality of the liquid crystal display component.

[0273] Based on the total usage amount of the diamine component (b1) being 100 moles, the usage amount of the diamine compound (b1-2) can be 3 moles to 30 moles, preferably 5 moles to 25 moles, and more preferably 7 moles to 20 moles.

[0274] Diamine compound (b1-3)

[0275] The diamine compound (b1-3) may include the diamine compound represented by the following formula (B13).

[0276]

[0277] In formula (B13), Z 31 、Z 32 、Z 33 、Z 31 ', Z 32 ', Z 33 ', B 1 、B 2 and the definition of ring Z are the same as Z 31 、Z 32 、Z 33 、Z 31 '、Z 32 '、Z 33 '、B 1 、B 2 in formula (III), and will not be described herein again.

[0278] In some embodiments, the diamine compound (b1-3) represented by formula (B13) is selected from at least one of the structures represented by formula (B13-1) and formula (B13-2).

[0279]

[0280] For formula (B13-1) and formula (B13-2), Z 31 、Z 31 is defined in the same manner as Z 31 、Z 31 in formula (III), and will not be described herein again.

[0281] The diamine compound (b1-3) may include, but is not limited to, compounds represented by the following formula (B13-3) to formula (B13-5), and is preferably a compound represented by formula (B13-3), a compound represented by formula (B13-3), or a combination thereof.

[0282]

[0283] The compound represented by the aforementioned formula (B13-4) can be prepared by the following method.

[0284] Step 1: Dissolve 13.9 grams (0.1 mole) of reactant A (4-nitrophenol; )) and 26.4 grams (0.1 mole) of reactant B (1,4-bis(bromomethyl)benzene; )) in 0.3 L of acetonitrile (ACN), then add 27.6 grams (0.2 mole) of potassium carbonate to form a mixture. Then, stir the mixture at 77 °C for 4 hours, filter after the reaction, and collect the dried filtrate. Next, stir and mix with 1 L of methanol at 50 °C for 1 hour, filter and dry to collect the white solid to obtain the first intermediate

[0285] Step 2: Dissolve 32.2 grams (0.1 mole) of the first intermediate and 21.5 grams (0.1 mole) of reactant C (4-nitro-4'-hydroxy biphenyl; )) in 1 L of ACN, then add 27.6 grams (0.2 mole) of potassium carbonate to form a mixture. Stir the mixture at 79 °C for 3 hours, filter after the reaction. Next, at 50 °C, wash the reaction product with a mixed solution composed of 500 grams of water and 150 grams of methanol for 1 hour. Then, cool, filter, and dry under vacuum to obtain the second intermediate

[0286] Process 3: Dissolve 45.6 grams (0.1 mole) of the second intermediate product in 2.5 L of a mixed solution containing THF and ethanol, and then add 4 grams (10 wt%) of palladium-carbon. Then, heat the mixture to 40 °C, and then slowly titrate 20.0 grams (0.4 mole) of hydrazinium hydroxide. After the titration is completed, heat it to 60 °C. After stirring for 3.5 hours, filter and collect the filtrate, and perform vacuum filtration and vacuum drying to obtain the compound shown in formula (B13-4).

[0287] The compound shown in the aforementioned formula (B13-3) can adopt the same preparation method and reactant molar ratio as the compound shown in formula (B13-4). The difference between the two is that the reactant B used in the compound shown in formula (B13-3) is 1,4-bis(2-bromoethyl)benzene; )), so a different first intermediate product is obtained and a second intermediate product

[0288] The compound shown in the aforementioned formula (B13-5) can adopt the same preparation method and reactant molar ratio as the compound shown in formula (B13-4). The difference between the two is that the reactant C used in the compound shown in formula (B13-5) is 4-(4-nitrophenoxy)phenol so a different second intermediate product is obtained

[0289] The aforementioned diamine compound (b1-3) can be used alone or in combination of multiple kinds.

[0290] When the diamine component (b1) further contains the diamine compound (b1-3), the liquid crystal display component including the liquid crystal alignment film formed by the liquid crystal aligning agent has better high and low temperature impact contrast.

[0291] Based on the total usage amount of the diamine component (b1) being 100 moles, the usage amount of the diamine compound (b1-3) can be 0 mole to 94 moles, preferably 10 moles to 89 moles, and more preferably 20 moles to 86 moles.

[0292] Diamine compound (b1-4)

[0293] The diamine compound (b1-4) may contain at least one of the diamine compounds represented by the following formula (B14-1) and formula (B14-2). The diamine compound preferably contains the diamine compound represented by the following formula (B14-1).

[0294]

[0295] In formula (B14-1), Y 31 represents a divalent organic group represented by the following formula (B14-3). A plurality of Y 32 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In formula (B14-2), a plurality of Y 33 each independently represents a divalent organic group represented by the following formula (B14-3').

[0296]

[0297] In formula (B14-3), each Ar independently represents a divalent benzene ring, biphenyl structure, or naphthalene ring, and the hydrogen atoms of the benzene ring, biphenyl structure, or naphthalene ring may be substituted or unsubstituted by a monovalent substituent group; Y 31 ' represents -(CH2) n -, n represents an integer from 2 to 18, and at least one -CH2- in -(CH2) n - may be substituted or unsubstituted by -O-, -C(=O)-, or -O-C(=O)-; p1 represents an integer of 0 or 1; * represents the bonding position.

[0298] In formula (B14-3'), each Ar' independently represents a divalent benzene ring or biphenyl structure, and the hydrogen atoms of the benzene ring or biphenyl structure may be substituted or unsubstituted by a monovalent substituent group; Y 33 ' represents -(CH2) n -, n represents an integer from 2 to 18, and at least one -CH2- in -(CH2) n - may be substituted or unsubstituted by -O-, -C(=O)-, or -O-C(=O)-; p2 represents an integer of 0 or 1; * represents the bonding position.

[0299] The monovalent substituent group of the aforementioned benzene ring, biphenyl structure, or naphthalene ring may be, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, a cyano group, or a nitro group, etc.

[0300] From the perspective of improving the liquid crystal alignment, the divalent organic group represented by formula (B14-3) preferably contains at least one of the groups represented by formula (B14-3-1) to formula (B14-3-16), where * represents the bonding position.

[0301]

[0302] In formula (B14-3-1), m is from 0 to 1, and n is from 1 to 6.

[0303]

[0304] In formula (B14-3-2), n is from 1 to 6.

[0305]

[0306] In formula (B14-3-3), n is from 2 to 6.

[0307]

[0308] In formula (B14-3-4), n is from 1 to 6.

[0309]

[0310] In formula (B14-3-5), n is from 1 to 6.

[0311]

[0312] In formula (B14-3-6), n is from 2 to 6.

[0313]

[0314] In formula (B14-3-7), n is from 1 to 6.

[0315]

[0316] In formula (B14-3-8), n is from 1 to 6.

[0317]

[0318] In formula (B14-3-9), n is from 2 to 6.

[0319]

[0320] In formula (B14-3-10), m is from 1 to 3, and n is from 1 to 4.

[0321]

[0322] In formula (B14-3-11), n is from 1 to 6.

[0323]

[0324] In formula (B14-3-12), n is from 1 to 6.

[0325]

[0326] In formula (B14-3-13), m is from 0 to 1, and n is from 1 to 6.

[0327]

[0328] In formula (B14-3-14), m is from 1 to 3, and n is from 1 to 4.

[0329]

[0330] From the viewpoint of improving the liquid crystal alignment, the divalent organic group represented by formula (B14-3') preferably contains at least one of the groups represented by formulas (B14-3-7) to (B14-3-16).

[0331] In one embodiment, the diamine compound represented by formula (B14-1) is preferably Y 31 represents the group represented by formula (B14-3-7), the group represented by formula (B14-3-11), or the group represented by formula (B14-3-15), more preferably Y 31 represents the group represented by formula (B14-3-7) or the group represented by formula (B14-3-11), particularly preferably Y 31 represents the group represented by formula (B14-3-7).

[0332] Specifically, when Y 31 represents the group represented by formula (B14-3-7), the diamine compound is, for example, the diamine compound represented by formula (B14-3-7a).

[0333]

[0334] Specifically, when Y 31 represents the group represented by formula (B14-3-11), the diamine compound is, for example, the diamine compound represented by formula (B14-3-11a).

[0335]

[0336] When Y 31 represents the group represented by formula (B14-3-15), the diamine compound is, for example, the diamine compound represented by formula (B14-3-15a).

[0337]

[0338] When the diamine compound (b1-4) contains a plurality of diamine compounds represented by the formula (B14-1), it is preferably Y in the formula (B14-1). 31 represents at least one of the diamine compounds of the formula (B14-3-1) to the formula (B14-3-14) and Y in the formula (B14-1). 31 represents a combination formed by at least one of the diamine compounds of the formula (B14-3-15) to the formula (B14-3-16).

[0339] In one embodiment, the diamine compound represented by the aforementioned formula (B14-2) may include, but is not limited to, the diamine compounds represented by the following formula (B14-2-1) to the formula (B14-2-5).

[0340]

[0341] In the formula (B14-2-1), m is from 1 to 6, and n is from 1 to 6.

[0342]

[0343] In the formula (B1�-2-2), m is from 1 to 6, and n is from 1 to 6.

[0344]

[0345] In the formula (B14-2-3), m is from 2 to 6, and n is from 2 to 6.

[0346]

[0347] The aforementioned diamine compound (b1-4) can be used alone or in combination of multiple kinds.

[0348] Based on the total usage amount of the diamine component (b1) being 100 moles, the usage amount of the diamine compound (b1-4) can be from 0 mole to 94 moles, preferably from 10 moles to 89 moles, and more preferably from 15 moles to 86 moles.

[0349] Other diamine compounds (b1-5)

[0350] The diamine component (b1) may also optionally further contain other diamine compounds (b1-5). For example, the other diamine compounds (b1-5) may include but are not limited to: diamine compounds having a photo-alignment group such as 4,4'-diaminoazobenzene or diamine compounds represented by the following formulas (B15-1) to (B15-3); 2,4-diaminophenol, 2,5-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol or 4,6-diaminoresorcinol; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, or diamine compounds having a carboxyl group such as diamine compounds represented by the following formulas (B15-4) to (B15-7); 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ketone, 1,4-bis(4-aminobenzyl)benzene, 4,4'-diaminodiphenyl ether, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indene-5-amine or 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; diamine compounds having a urea bond such as diamine compounds represented by the following formulas (B15-8) to (B15-10); diamine compounds having an amide bond represented by the following formulas (B15-11) to (B15-13); diamine compounds having a photopolymerizable group at the end such as 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline; diamines having a siloxane bond, such as 3-bis(3-aminopropyl)-tetramethyldisiloxane; diamine compounds represented by the following formulas (B15-14) to (B15-15) etc. diamine compounds having an oxazoline structure; or combinations thereof. The other diamine compounds (b1-5) are preferably diamine compounds represented by formula (B15-8).

[0351]

[0352]

[0353] In formula (B15-4), Y 51 represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-; m1 and m2 each independently represent an integer from 0 to 4, and (m1 + m2) represents an integer from 1 to 4.

[0354]

[0355] In formula (B15-5), m3 and m4 each independently represent an integer from 1 to 5.

[0356]

[0357] In formula (B15-6), Y 52 represents a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; m5 represents an integer from 1 to 5.

[0358]

[0359] In formula (B15-7), Y 53 and Y 54 each independently represent a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)--, or -N(CH3)CO-; m6 represents an integer from 1 to 4.

[0360]

[0361] In formula (B15-8), n1 represents an integer from 0 to 6, and n2 represents an integer from 1 to 6.

[0362]

[0363] In formula (B15-9), n1 represents an integer from 1 to 6, and n2 represents an integer from 1 to 6.

[0364]

[0365] In formula (B15-10), n represents an integer from 1 to 6.

[0366]

[0367] In formula (B15-12), n represents an integer from 1 to 6.

[0368]

[0369] In formula (B15-13), n1 represents an integer from 1 to 6, and n2 represents an integer from 1 to 6.

[0370]

[0371] The aforementioned other diamine compounds (b1-5) can be used alone or in combination of multiple kinds.

[0372] Based on the total usage amount of the diamine component (b1) being 100 moles, the usage amount of other diamine compounds (b1-5) can be from 0 moles to 94 moles, preferably from 10 moles to 89 moles, and more preferably from 15 moles to 86 moles.

[0373] Second polymer (A2)

[0374] In some embodiments, the polymer component (A) further comprises a second polymer (A2).

[0375] The second polymer (A2) is selected from at least one of the group consisting of polyimide precursors formed by reacting a reaction composition comprising a tetracarboxylic dianhydride component (a2) and a diamine component (b2), and imidized polymers formed from the above polyimide precursors, and the second polymer (A2) does not contain the structures represented by formula (I), the structure represented by formula (II), and the structure represented by formula (III) in the first polymer (A1). For example, the second polymer (A2) is a polyimide precursor having a polyamic acid and a polyamic acid ester imide precursor structure, or the second polymer (A2) is an imidized polymer (i.e., polyimide) formed from a polyimide precursor, or the second polymer (A2) comprises the above polyimide precursor and the above imidized polymer, etc. The second polymer (A2) can be used alone or in combination of multiple types.

[0376] In some other embodiments, the weight ratio of the first polymer (A1) to the second polymer (A2) (i.e., the mass ratio of the first polymer (A1) / the second polymer (A2)) is from 10 / 90 to 90 / 10, preferably from 20 / 80 to 90 / 10, and more preferably from 20 / 80 to 80 / 20.

[0377] Tetracarboxylic dianhydride component (a2)

[0378] The tetracarboxylic dianhydride component (a2) is, for example but not limited to, an acyclic aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, or derivatives of these compounds. The acyclic aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are, for example, the tetracarboxylic dianhydride compounds in the first polymer (A1). Preferably, the tetracarboxylic dianhydride component (a2) comprises an alicyclic tetracarboxylic dianhydride represented by formula (A11) or a derivative thereof, or a tetracarboxylic dianhydride compound represented by the above formula (A12) where X1' represents a structure represented by formula (A12-1) to formula (A12-6) or a derivative thereof. The above tetracarboxylic dianhydride component (a2) can be used alone or in combination of multiple types.

[0379] Preferably, the above tetracarboxylic dianhydride component (a2) comprises a tetracarboxylic dianhydride compound (a2-1) represented by formula (A12) and having a structure represented by formula (A12-a) for X1'.

[0380]

[0381] In formula (A12-a), Z11 represents a single bond, and * represents the bonding position.

[0382] The tetracarboxylic dianhydride compound (a2-1) can be used alone or in combination of multiple kinds.

[0383] More preferably, the above tetracarboxylic dianhydride component (a2) comprises a tetracarboxylic dianhydride compound represented by formula (A12-a-1), a tetracarboxylic dianhydride compound represented by formula (A12-a-2), or a combination thereof.

[0384]

[0385]

[0386] In one embodiment, based on the total amount of the tetracarboxylic dianhydride component (a2) being 100 moles, the usage amount of the tetracarboxylic dianhydride compound (a2-1) is 30 moles to 100 moles, preferably 40 moles to 100 moles, and more preferably 50 moles to 100 moles.

[0387] Based on the total number of moles of the following diamine component (b2) being 100 moles, the usage amount range of the tetracarboxylic dianhydride component (a2) can be 20 moles to 200 moles, preferably 30 moles to 120 moles.

[0388] Diamine component (b2)

[0389] The diamine component (b2) is, for example, diamine compounds (b1-4) and (b1-5) in the diamine component (b1) of the first polymer (A1) other than diamine compounds (b1-1), (b1-2), and (b1-3), or a diamine compound (b2-1) having a nitrogen atom-containing structure. The above diamine component (b2) can be used alone or in combination of multiple kinds.

[0390] Diamine compound (b2-1)

[0391] The nitrogen atom-containing structure in the diamine compound (b2-1) having a nitrogen atom-containing structure is selected from at least one of the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group.

[0392] The nitrogen-containing heterocycles of the diamine compound (b2-1) having a nitrogen atom-containing structure are, for example, but not limited to, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrimidine, indole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, quinazoline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine or hexamethyleneimine, etc. Preferably, the above nitrogen-containing heterocycle is pyridine, pyrimidine, pyridazine, piperidine, piperazine, quinoline, carbazole or acridine.

[0393] The nitrogen atom-containing structure in the diamine compound (b2-1) having a nitrogen atom-containing structure is the secondary amino group and the tertiary amino group shown in formula (B21).

[0394]

[0395] In formula (B21), Z represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group; * represents the bonding position.

[0396] The above alkyl group having 1 to 10 carbon atoms is, for example, but not limited to, methyl, ethyl or propyl. The above cycloalkyl group is, for example, but not limited to, cyclohexyl. The above aryl group is, for example, but not limited to, phenyl or tolyl. Preferably, Z is hydrogen or methyl.

[0397] The diamine compound (b2-1) having a nitrogen atom-containing structure is, for example, but not limited to, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, the diamine compounds shown in formula (B21-1) to formula (B21-8), or the diamine compounds shown in formula (B21-9) to formula (B21-26). The diamine compound (b2-1) having a nitrogen atom-containing structure is preferably the diamine compound shown in formula (B21-1).

[0398]

[0399]

[0400] In formula (B21-5), n represents 1 to 4.

[0401]

[0402] In formula (B21-6), n represents 1 to 4.

[0403]

[0404]

[0405]

[0406] The diamine compound (b2-1) having a nitrogen atom-containing structure can be used alone or in combination of multiple kinds.

[0407] In one embodiment, the diamine compound (b2-1) having a nitrogen atom-containing structure is preferably the diamine compound represented by formula (B21-1), and is used in combination with the diamine compound represented by the aforementioned formula (B14-3-15a).

[0408] In one embodiment, based on the total amount of the above diamine component (b2) being 100 moles, the usage amount of the diamine compound (b2-1) having a nitrogen atom-containing structure is 15 moles to 100 moles, preferably 20 moles to 90 moles, and more preferably 25 moles to 80 moles.

[0409] Preparation methods of the first polymer (A1) and the second polymer (A2)

[0410] The preparation of the first polymer (A1) can be carried out by subjecting the aforementioned diamine component (a1) and tetracarboxylic dianhydride component (b1) to a (polycondensation) reaction in a solvent. The preparation of the second polymer (A2) can be carried out by subjecting the aforementioned diamine component (a2) and tetracarboxylic dianhydride component (b2) to a (polycondensation) reaction in a solvent. When a part of the first polymer (A1) or the second polymer (A2) has an amic acid structure, for example, by reacting the tetracarboxylic dianhydride component with the diamine component, a polymer having an amic acid structure (i.e., polyamic acid) is obtained. The aforementioned solvent is not particularly limited, and it only needs to be able to dissolve the formed polymer. For example, specific examples of the solvent can include but are not limited to N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or 1,3-dimethyl-2-imidazolidinone. A specific example of the solvent is preferably N-methyl-2-pyrrolidone. In one embodiment, when the solvent solubility of the polymer is relatively high, the solvent can include methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by the following formulas (AS-1) to (AS-3).

[0411]

[0412] In formula (AS-1), Z 1 represents an alkyl group having 1 to 3 carbon atoms.

[0413]

[0414] In formula (AS-2), Z 2 represents an alkyl group having 1 to 3 carbon atoms.

[0415]

[0416] In formula (AS-3), Z 3 represents an alkyl group having 1 to 4 carbon atoms.

[0417] The aforementioned solvent(s) can be used alone or in combination of multiple solvents. Secondly, even a solvent that cannot dissolve the polymer can still be used in combination with the above-mentioned solvent(s) within the range where the resulting polymer does not precipitate. When the diamine component and the tetracarboxylic dianhydride component react in a solvent, the reaction can be carried out at any concentration, but is preferably 1 wt% to 50 wt%, and more preferably 5 wt% to 30 wt%. The reaction can also be initially carried out at a high concentration and then additional solvent can be added. When carrying out the reaction, the molar ratio of the total molar amount of the diamine component to the total molar amount of the tetracarboxylic dianhydride component is preferably 0.8 to 1.2. Similar to general polycondensation reactions, the closer this molar ratio is to 1.0, the larger the molecular weights of the first polymer (A1) and the second polymer (A2) formed.

[0418] The polymer having an amic acid ester structure can be obtained, for example, by known methods such as the following: (1) a method of further reacting the polyamic acid obtained by the above method with an esterifying agent, (2) a method of reacting a tetracarboxylic acid diester compound with a diamine compound, or (3) a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound.

[0419] The imidized product of the first polymer (A1) or the second polymer (A2) contained in the liquid crystal aligning agent of this example can be obtained, for example, by subjecting the previously obtained polymer to a cyclodehydration reaction. In the above imidized product, the cyclodehydration rate (also referred to as the imidization rate) of the functional group of the amic acid group or its derivative does not necessarily have to be 100%, and the imidization rate can be arbitrarily adjusted according to the use and / or purpose.

[0420] For the method of obtaining the imidized product, it can be, for example, thermal imidization by directly heating the polymer solution obtained from the above reaction, or catalytic imidization by adding a catalyst to the polymer solution. When performing thermal imidization in a solution, the temperature is preferably 100 °C to 400 °C, and more preferably 120 °C to 250 °C. When performing thermal imidization, it is preferable to simultaneously remove the water generated by the imidization reaction from the system.

[0421] The aforementioned catalytic imidization can be carried out, for example, by adding a basic catalyst and an acid anhydride to the polymer solution obtained from the reaction, preferably with stirring at -20°C to 250°C, and more preferably at 0°C to 180°C. The addition amount of the basic catalyst is preferably 0.5 to 30 times the molar equivalent of the amic acid group, and more preferably 2 to 20 times; the addition amount of the acid anhydride is preferably 1 to 50 times the molar equivalent of the amic acid group, and more preferably 3 to 30 times. Specific examples of the basic catalyst may include, but are not limited to, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is more desirable because it has a moderate basicity to promote the reaction. Specific examples of the acid anhydride may include, but are not limited to, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, etc. Among them, if acetic anhydride is used, purification after the reaction is easier, so it is more desirable. The imidization rate of the catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and / or reaction time.

[0422] When recovering the formed imide compound from the reaction solution of the above imidization, the reaction solution can be poured into a solvent to precipitate it. The solvents used for precipitation may include, but are not limited to, methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, etc. After filtering and recovering the polymer precipitated in the solvent, it can be dried at normal pressure or reduced pressure, at room temperature or by heating. Alternatively, the precipitated polymer is redissolved in a solvent and reprecipitated for recovery, and this operation is repeated 2 to 10 times to reduce impurities in the polymer. The solvents used may be, for example, alcohols or ketone hydrocarbons. If three or more solvents selected therefrom are used, the purification efficiency can be further improved, so it is more desirable.

[0423] Solution viscosity and molecular weight of the polymer

[0424] When prepared into a solution with a concentration of 10 wt% to 15 wt%, the solution viscosity of the first polymer (A1) or the second polymer (A2) of this example is not particularly limited. From the perspective of easier operation, its solution viscosity can be, for example, 10 mPa·s to 1000 mPa·s. The solution viscosity (mPa·s) of the polymer is the value measured at 25°C using an E-type rotational viscometer for a polymer solution prepared with a good solvent (such as γ-butyrolactone or N-methyl-2-pyrrolidone, etc.) of the above polymer at a concentration of 10 wt% to 15 wt%.

[0425] The weight-average molecular weight (M w ) of the first polymer (A1) or the second polymer (A2) of this example measured by gel permeation chromatography (GPC) in terms of polystyrene conversion is preferably 1,000 to 500,000, and more preferably 2,000 to 500,000. Secondly, Mw The ratio represented by the number-average molecular weight (M n ) converted to polystyrene measured by GPC, i.e., the molecular weight distribution (M w / M n ), is preferably 15 or less, and more preferably 10 or less. When the molecular weight of the polymer is within the aforementioned molecular weight range, good alignment and stability of the liquid crystal display component can be ensured.

[0426] End-capping agent

[0427] When synthesizing the first polymer (A1) or the second polymer (A2) of this example, the aforementioned tetracarboxylic dianhydride component and diamine component can be used, and an appropriate end-capping agent is used to synthesize a terminally-sealed polymer. The terminally-sealed polymer has the effects of improving the film hardness of the liquid crystal alignment film obtained by coating and improving the adhesion characteristics of the sealant and the liquid crystal alignment film. The terminals of the first polymer (A1) or the second polymer (A2) of this example may, for example, contain amino groups, carboxyl groups, acid anhydride groups, or derivatives thereof. Amino groups, carboxyl groups, acid anhydride groups, or derivatives thereof can be obtained through general condensation reactions or by sealing the terminals using the end-capping agents described later. Similarly, the aforementioned derivatives can be obtained, for example, using the following end-capping agents.

[0428] For example, the end-capping agent may include, but is not limited to, acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-((3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, or 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl dicarbonate or diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, or nicotinoyl chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, or n-octylamine; monoisocyanate compounds such as ethyl isocyanate, phenyl isocyanate, or naphthyl isocyanate, etc.

[0429] The end-capping agent can be used alone or in combination of multiple types.

[0430] Based on 100 mole parts of the total amount of the diamine component used, the amount of the end-capping agent used is preferably 0.01 to 20 mole parts, and more preferably 0.01 to 10 mole parts.

[0431] Other polymer (A3)

[0432] The polymer component (A) of this embodiment may optionally further contain other polymers (A3). The types of other polymers (A3) may include, for example, but are not limited to, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene or its derivatives, poly(styrene-phenylmaleimide) derivatives, or poly(meth)acrylates, etc.

[0433] Solvent (B)

[0434] From the perspective of forming a uniform thin film, the liquid crystal aligning agent takes the form of a coating solution to fabricate a liquid crystal alignment film. The liquid crystal aligning agent of this embodiment is preferably a coating solution containing the above polymer component (A) and solvent (B). Among them, based on the set film thickness to be formed, the concentration of the polymer component (A) in the liquid crystal aligning agent can be appropriately changed. From the perspective of forming a uniform and defect-free coating film, the concentration of the polymer component (A) in the liquid crystal aligning agent is preferably 1 wt% or more. From the perspective of the storage stability of the solution, the concentration of the polymer component (A) in the liquid crystal aligning agent is preferably 10 wt% or less. The ideal concentration of the polymer component (A) can be 2 wt% to 8 wt%. The content of the polymer component (A) in the liquid crystal aligning agent can be appropriately changed by the coating method of the liquid crystal aligning agent and / or the film thickness of the desired liquid crystal alignment film. It is preferably 2 wt% to 10 wt%, and more preferably 3 wt% to 7 wt%.

[0435] The solvent (B) in the liquid crystal aligning agent is, for example, an organic solvent, and there is no particular limitation on the solvent (B) contained in the liquid crystal aligning agent, as long as it can uniformly dissolve the aforementioned polymer. Specific examples thereof may include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 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 or N-cyclohexyl-2-pyrrolidone, etc., and the aforementioned organic solvents are also called good solvents. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or γ-butyrolactone are preferred. Based on the total usage amount of the solvent in the liquid crystal aligning agent being 100 wt%, the usage amount of the good solvent can be 20 wt% to 99 wt%, preferably 20 wt% to 90 wt%, and more preferably 30 wt% to 80 wt%.

[0436] Secondly, the organic solvent in the liquid crystal aligning agent is preferably a mixed solvent of the aforementioned solvent and a solvent (also called a poor solvent) that can improve the coatability during coating of the liquid crystal aligning agent and the surface smoothness of the coating film. Specific examples of the poor solvent to be used in combination may include, but are not limited to, the solvents described later. Based on the total usage amount of the solvent in the liquid crystal aligning agent being 100 wt%, the usage amount of the poor solvent is preferably 1 wt% to 80 wt%, more preferably 10 wt% to 80 wt%, and particularly preferably 20 wt% to 70 wt%. The type and usage amount of the poor solvent can be appropriately selected according to the coating device, coating conditions, and / or coating environment of the liquid crystal aligning agent, etc.

[0437] For example, the lean solvent can be, for example: diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether (butyl cellosolve, ethylene glycol n-butyl ether), ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, or diisobutyl ketone (2,6-dimethyl-4-heptanone), etc.

[0438] Among them, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone are preferred.

[0439] The solvent combination of the good solvent and the poor solvent is preferably, for example but not limited to, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone and propylene glycol diacetate; N,N-dimethyl lactamide and diisobutyl ketone; N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate; N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether; N,N-dimethyl lactamide and ethylene glycol monobutyl ether; N,N-dimethyl lactamide and propylene glycol diacetate; N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether; N,N-dimethyl lactamide and diethylene glycol diethyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether; N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl ketone; N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl methanol; N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether; N-methyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol dimethyl ether; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and propylene glycol diacetate; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and diisobutyl ketone; N-ethyl-2-pyrrolidone, γ-butyrolactone and diisobutyl ketone; or N-ethyl-2-pyrrolidone, N,N-dimethyl lactamide and diisobutyl ketone, etc.

[0440] Specific examples of the solvent (B) are preferably N-methyl-2-pyrrolidone (NMP), ethylene glycol n-butyl ether, N,N-dimethylacetamide, or a combination thereof.

[0441] The aforementioned solvent (B) can be used alone or in combination of multiple solvents.

[0442] Based on 100 parts by weight of the polymer component (A), the solvent (B) is 800 to 4000 parts by weight, preferably 900 to 3500 parts by weight, and more preferably 1000 to 3000 parts by weight.

[0443] Additive (C)

[0444] The liquid crystal aligning agent of this example may also selectively add components other than the polymer component (A) and the organic solvent (hereinafter referred to as additive (C)). These additives (C) may include, for example, but are not limited to: an adhesion promoter (C-1) for improving the adhesion between the liquid crystal alignment film and the substrate or between the liquid crystal alignment film and the sealant, a crosslinkable compound (hereinafter referred to as crosslinkable compound (C-2)) for improving the strength of the liquid crystal alignment film, a compound (C-3) for promoting imidization, a dielectric or conductive substance for adjusting the dielectric constant or resistance of the liquid crystal alignment film, etc.

[0445] Adhesion promoter (C-1)

[0446] The aforementioned adhesion promoter (C-1) can be, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, or 3-isocyanatopropyltriethoxysilane, etc., silane coupling agents.

[0447] The aforementioned adhesion promoter (C-1) can be used alone or in combination of two or more.

[0448] Based on 100 parts by weight of the total amount of the polymer component (A) in the liquid crystal aligning agent, the amount of the adhesion promoter (C-1) used is preferably from 0.1 part by weight to 30 parts by weight, and more preferably from 0.1 part by weight to 20 parts by weight.

[0449] Crosslinking compound (C-2)

[0450] Regarding the aforementioned crosslinking compound, from the viewpoint of exhibiting good resistance to AC afterimage and effectively improving the film strength, it can be a compound having an oxiranyl group, a glycidyl group, at least one group selected from the group consisting of the group represented by the following formula (c2-a) and the group represented by the following formula (c2-b), or a compound selected from the compounds represented by the following formula (c2-c).

[0451]

[0452] In formula (c2-a), G 1 and G 2 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or -CH2-OH.

[0453]

[0454] In formula (c2-b), G 3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms; G 4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms.

[0455]

[0456] In formula (c2-c), G 5 represents a (g1 + g2)-valent organic group containing an aromatic ring. G 6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, g1 represents an integer of 1 to 6, and g2 represents an integer of 0 to 4.

[0457] In formula (c2-c), the (g1 + g2)-valent organic group represented by G 5 may include a (g1 + g2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, a (g1 + g2)-valent organic group formed by directly or indirectly bonding a (g1 + g2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms through a linking group, or a (g1 + g2)-valent group having an aromatic heterocycle. The aromatic hydrocarbon may be, for example, benzene or naphthalene. The aromatic heterocycle may include the exemplified aromatic heterocycles having the specific nitrogen atom-containing structures described above. The linking group may include an alkylene group having 1 to 10 carbon atoms or a group obtained by removing one hydrogen atom from the alkylene group, or a divalent or trivalent cyclohexane. Among them, any hydrogen atom of the alkylene group may also be substituted with an organic group such as a fluorine atom or a trifluoromethyl group. In formula (c2-c), the alkyl group having 1 to 5 carbon atoms represented by G 6 may include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or n-pentyl.

[0458] Compound having an oxiranyl group

[0459] Specific examples of the compound having an oxiranyl group may include N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, and compounds containing a nitrogen atom represented by the following formulas (c2-1) to (c2-3).

[0460]

[0461]

[0462] Compound having an epichlorohydrin group

[0463] Specific examples of the compound having a glycidyl group include the compounds represented by the following formula (c2-4) to formula (c2-13).

[0464]

[0465]

[0466]

[0467] In formula (c2-12), R represents a group represented by formula (c2-12-1), where * represents the bonding position.

[0468]

[0469] Compound having a group represented by formula (c2-a)

[0470] Specific examples of the compound having a group represented by formula (c2-a) include the compounds represented by the following formula (c2-a-1) to formula (c2-a-12).

[0471]

[0472]

[0473]

[0474] Compound having a group represented by formula (c2-b)

[0475] Specific examples of the compound having a group represented by formula (c2-b) include the compounds represented by the following formula (c2-b-1) to formula (c2-b-4).

[0476]

[0477]

[0478] Compound having a group represented by formula (c2-c)

[0479] Specific examples of the compound having a group represented by formula (c2-c) include the compounds represented by the following formula (c2-c-1) to formula (c2-c-10).

[0480]

[0481]

[0482]

[0483] The aforementioned crosslinkable compound (C-2) can be used alone or in combination of two or more.

[0484] In the liquid crystal aligning agent of this embodiment, based on the total usage amount of the polymer in the liquid crystal aligning agent being 100 parts by weight, the usage amount of the crosslinkable compound (C-2) is preferably 0.5 parts by weight to 20 parts by weight. Among them, from the viewpoints of the progress of the crosslinking reaction and showing good resistance to AC afterimages, the usage amount of the crosslinkable compound (C-2) is more preferably 1 part by weight to 15 parts by weight.

[0485] Compound (C-3) for promoting imidization

[0486] The aforementioned compound (C-3) for promoting imidization is preferably a compound having a basic site (for example: primary amino group, aliphatic heterocycle (such as pyrrolidine skeleton), aromatic heterocycle (such as imidazole ring or indole ring), or guanidine group, etc.) (except for the above-mentioned crosslinkable compound (C-2) and adhesion promoter (C-1)), or a compound that generates the basic site when heated. More preferably, the compound (C-3) for promoting imidization is a compound that generates the basic site when heated, and specific examples thereof can be, for example, an amino acid in which part or all of the basic site of the amino acid is protected. Specific examples of the above-mentioned amino acids can include glycine, alanine, cysteine, methionine, asparagine, glutamic acid, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine, or ornithine. For the purpose of the compound (C-3) for promoting imidization, more preferred specific examples can include N-α-(9-fluorenylmethoxycarbonyl)-N-τ-(tert-butoxycarbonyl)-L-histidine.

[0487] The aforementioned compound (C-3) for promoting imidization can be used alone or in combination of multiple kinds.

[0488] <Method for manufacturing a liquid crystal alignment film and a liquid crystal display device>

[0489] This embodiment provides a liquid crystal alignment film formed using the liquid crystal aligning agent as described above.

[0490] Furthermore, this embodiment also provides a liquid crystal alignment film for photo-alignment method formed using the above-mentioned liquid crystal aligning agent.

[0491] This embodiment provides a liquid crystal display device including the liquid crystal alignment film as described above.

[0492] The liquid crystal alignment film of this embodiment is obtained from the aforementioned liquid crystal aligning agent. The liquid crystal alignment film of this embodiment can be used as a horizontally aligned or vertically aligned (VA type) liquid crystal alignment film, and it is a liquid crystal alignment film suitable for horizontally aligned liquid crystal display components such as the IPS mode or the FFS mode. The liquid crystal display component of this embodiment includes the aforementioned liquid crystal alignment film. The liquid crystal display component of this embodiment can be manufactured, for example, by the following processes (1) to (4) or the method of processes (1) to (2) and process (4).

[0493] Process (1): Coating the liquid crystal aligning agent on a substrate

[0494] Using an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method, coat the liquid crystal aligning agent of this embodiment on one surface of a substrate provided with a patterned transparent conductive film. Among them, the substrate is not particularly limited, and it only needs to be a highly transparent substrate. A glass substrate or a silicon nitride substrate can also be used in combination with a plastic substrate such as an acrylic substrate or a polycarbonate substrate. Secondly, in a reflective liquid crystal display component, if it is only a single-sided substrate, an opaque material such as a silicon wafer can also be used, and the electrode used can also be a light-reflecting material such as aluminum. Furthermore, when manufacturing an IPS type or FFS type liquid crystal component, a comb tooth type uses an electrode substrate composed of a patterned transparent conductive film or a metal film that has been provided and a counter substrate without an electrode.

[0495] Examples of the method of coating the liquid crystal aligning agent on the substrate and forming a film include screen printing, lithography, flexography, inkjet method, or spraying method. Among them, the film-forming method is preferably coating by the inkjet method.

[0496] Process (2): Heating the coated liquid crystal aligning agent

[0497] Step (2) is a step of heating the liquid crystal alignment agent coated on the substrate to form a film. After the liquid crystal alignment agent is coated on the substrate, heating means such as a hot plate, a thermal cycle oven, or an infrared (IR) oven can be used to evaporate the solvent or perform thermal imidization of polyamic acid or polyamic acid ester. The drying and heating steps performed after coating the liquid crystal alignment agent of this embodiment can be carried out at any temperature and time, and the drying or heating steps can be performed multiple times. The drying temperature can be, for example, from 40°C to 180°C. From the perspective of shortening the treatment, it can be carried out at 40°C to 150°C. The drying time is not particularly limited and can be, for example, from 1 minute to 10 minutes or from 1 minute to 5 minutes. When performing thermal imidization of polyamic acid or polyamic acid ester, after the aforementioned drying step, a heating step can be further carried out at a temperature of, for example, 150°C to 300°C or 150°C to 250°C. The heating time is not particularly limited and can be, for example, from 5 minutes to 40 minutes or from 5 minutes to 30 minutes. If the film formed after heating is too thin, the reliability of the liquid crystal display device will be reduced. Therefore, the thickness of the film is preferably from 5 nm to 300 nm, and more preferably from 10 nm to 200 nm.

[0498] Step (3): Perform an alignment treatment on the film obtained in step (2)

[0499] Step (3) is to perform an alignment treatment on the film obtained in step (2) as appropriate. In other words, in a horizontally aligned liquid crystal display device such as an IPS mode or an FFS mode, an alignment treatment is performed on the above-mentioned coated film to impart alignment ability. On the other hand, in a vertically aligned liquid crystal display device such as a VA mode or a Polymer Stabilized Alignment (PSA) mode, the formed coated film can be directly used as a liquid crystal alignment film, but an alignment treatment can also be performed on these coated films to impart alignment ability. The alignment treatment of the liquid crystal alignment film can include a rubbing treatment method or a photo-alignment treatment method (also called "photo-alignment method"), and the photo-alignment treatment method is preferably used. The photo-alignment treatment method can include irradiating the surface of the above-mentioned film with radiation that has been deflected in a certain direction and, as appropriate, preferably heating at a temperature of 150°C to 250°C to impart liquid crystal alignment (also called liquid crystal alignment ability). The radiation can use ultraviolet light or visible light with a wavelength of 100 nm to 800 nm. Among them, the radiation is preferably ultraviolet light with a wavelength of 100 nm to 400 nm, and more preferably ultraviolet light with a wavelength of 200 nm to 400 nm.

[0500] The irradiation amount of the aforementioned radiation can be 1 mJ / cm 2 to 10,000 mJ / cm 2 and is preferably 100 mJ / cm 2 to 5,000 mJ / cm 2 and more preferably 100 mJ / cm2 to 1500 mJ / cm 2 , and particularly preferably 100 mJ / cm 2 to 1000 mJ / cm 2 . When using a general liquid crystal alignment agent, the light irradiation amount for the alignment treatment is 100 mJ / cm 2 to 5000 mJ / cm 2 . When irradiating radiation, in order to improve the liquid crystal alignment property, the substrate of the aforementioned film-like material can be heated at 50°C to 250°C while irradiating. The liquid crystal alignment film produced in this way can make the liquid crystal molecules align stably in a certain direction. Secondly, the liquid crystal alignment film irradiated with polarized radiation in the aforementioned method can be subjected to contact treatment with a solvent, or the liquid crystal alignment film irradiated with radiation can be subjected to heat treatment.

[0501] The solvent used for the aforementioned contact treatment is not particularly limited as long as it can dissolve the decomposition products generated from the film-like material after radiation irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, or cyclohexyl acetate, etc. Among them, from the viewpoints of versatility and safety, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate are preferred, and water, 1-methoxy-2-propanol or ethyl lactate are more preferred. The solvent can be used alone or in combination of multiple kinds.

[0502] The temperature for heat treatment of the aforementioned radiation-irradiated coating film is preferably 50°C to 300°C, and more preferably 120°C to 250°C. The time for heat treatment is preferably 1 minute to 30 minutes.

[0503] Step (4): Fabricating a liquid crystal cell

[0504] Prepare two of the aforementioned formed liquid crystal alignment film substrates, and dispose liquid crystal between the two substrates facing each other. For example, the following two methods can be cited. The first method is to first dispose the two substrates facing each other with a spacer (cell gap) interposed therebetween with the liquid crystal alignment films facing each other. Then, bond the peripheral portions of the two substrates with a sealant, and then inject and fill the liquid crystal composition into the cell gap separated by the substrate surfaces and the sealant, and seal the injection hole after it contacts the film surface.

[0505] The second method, called the ODF (One Drop Fill) method. A sealant such as an ultraviolet curable one is coated at a predetermined position on one of the two substrates on which the liquid crystal alignment film has been formed, and a liquid crystal composition is dropped at a plurality of predetermined positions on the surface of the liquid crystal alignment film. Then, the other substrate is attached so as to face the liquid crystal alignment film, and the liquid crystal composition is pressed onto the entire surface of the substrate to bring it into contact with the film surface. Next, ultraviolet light is irradiated onto the entire surface of the substrate to cure the sealant. When performing any of the foregoing methods, it is preferable to further heat the liquid crystal composition used to the temperature at which it becomes an isotropic phase and then slowly cool it to room temperature to remove the flow alignment during liquid crystal filling. Next, when performing a rubbing treatment on the coating film, the two substrates are arranged facing each other with the rubbing directions of the respective coating films forming a predetermined angle, for example, in an orthogonal or anti-parallel manner. The sealant may be, for example, an epoxy resin containing a hardening agent and alumina balls as a spacer. As for the liquid crystal used above, that is, the liquid crystal compound or the liquid crystal composition, it is not particularly limited here. Examples of the liquid crystal composition include nematic liquid crystals and smectic liquid crystals, and nematic liquid crystals are preferred.

[0506] If necessary, a polarizing plate may be attached to the outer surface of the liquid crystal cell to obtain a liquid crystal display component. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing film called an “H film” that extends and aligns polyvinyl alcohol and simultaneously absorbs iodine. It may be a polarizing plate sandwiched by a cellulose acetate protective film, or a polarizing plate composed of the H film itself.

[0507] The present invention will be further described with the following experimental examples, but it should be understood that these experimental examples are only for illustrative purposes and should not be construed as a limitation on the implementation of the present invention.

[0508] Synthesis example of diamine compound (b1-1)

[0509] Synthesis example b1-1-1

[0510] Synthesis example b1-1-1 is a synthesis example of the diamine compound represented by formula (IV-2-1), and the reaction process is as shown in Reaction Process 1 below.

[0511] <Reaction Process 1>

[0512]

[0513] Step 1-1

[0514] Dissolve 11.6 g (0.1 mol) of 1,4 - cyclohexanediol (CAS No.: 556 - 48 - 9, molecular weight 116.16) and 35.3 g (0.25 mol) of 1 - fluoro - 4 - nitrobenzene (CAS No.: 350 - 46 - 9, molecular weight 141.10) in 0.2 L of DMAc, and then add 56.1 g (0.4 mol) of potassium carbonate (molecular weight 140.22) to form a mixture. Stir the mixture at 180 °C for 3 hours, and then filter after the reaction.

[0515] Next, wash the reaction product with a mixed solution composed of 200 g of methanol at 50 °C for 1 hour, then cool and filter, and dry under vacuum to obtain Intermediate 1 (a dinitro compound, molecular weight 358.4).

[0516] Process 1 - 2

[0517] Dissolve 35.8 g (0.1 mol) of Intermediate 1 in a mixed solution composed of 1 L of a mixture of tetrahydrofuran (THF) and ethanol (volume ratio 2.5:1). Then add 7 g (10% by weight) of palladium - carbon. Heat the mixture to 40 °C, and then slowly titrate it into 20.0 g (0.4 mol) of hydrazinium hydroxide. After the titration is completed, heat the mixture to 60 °C and stir for 3.5 hours. Then filter and collect the filtrate, and perform vacuum filtration and vacuum drying to obtain the product (a diamine compound shown in Formula (IV - 2 - 1)).

[0518] Synthesis Example b1 - 1 - 2

[0519] Synthesis Example b1 - 1 - 2 is a synthesis example for synthesizing the diamine compound shown in Formula (IV - 2 - 2), and the reaction process is as follows in Reaction Process 2.

[0520] <Reaction Process 2>

[0521]

[0522] In Reaction Process 2, the processes and the molar amounts of the reactants in Process 2 - 1 and Process 2 - 2 are substantially the same as those in Process 1 - 1 and Process 1 - 2, except that 11.6 g (0.1 mol) of 1,4 - cyclohexanediol (CAS No.: 556 - 48 - 9, molecular weight 116.16) in Process 1 - 1 is replaced with 13.0 g (0.1 mol) of 2 - methyl - 1,4 - cyclohexanediol (CAS No.: 60793 - 35 - 3, molecular weight 130.19) with the same molar amount.

[0523] Synthesis Example b1 - 1 - 3

[0524] Synthesis Example b1-1-3 is a synthesis example of a diamine compound represented by formula (IV-2-8), and the reaction process is as follows in Reaction Process 3.

[0525] <Reaction Process 3>

[0526]

[0527] In Reaction Process 3, the processes and the molar amounts of the reactants in Step 3-1 and Step 3-2 are substantially the same as those in Step 1-1 and Step 1-2, except that 35.3 g (0.25 mol) of 1-fluoro-4-nitrobenzene (CAS No.: 350-46-9, molecular weight 141.10) in Step 1-1 is replaced with 35.3 g (0.25 mol) of 1-fluoro-3-nitrobenzene (CAS No.: 402-67-5, molecular weight 141.10) having the same molar amount.

[0528] Synthesis Example of the First Polymer (A1) (Polyamic Acid)

[0529] Synthesis Example A1-1

[0530] A nitrogen inlet, a stirrer, a condenser and a thermometer were installed on a 500-ml four-necked conical flask, and nitrogen was introduced. Then, 0.003 mol (20 mol%) of diamine compound (b1-a), 0.00225 mol (15 mol%) of diamine compound (b1-h), 0.0075 mol (50 mol%) of diamine compound (b1-k), 0.00225 mol (15 mol%) of diamine compound (b1-m) as diamine components and 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were added, and the mixture was stirred at room temperature until dissolved. Then, 0.015 mol (100 mol%) of a1-a as a tetracarboxylic dianhydride component and 20 g of NMP were added, and the reaction was carried out at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, and the washing and filtration with methanol were repeated three times. After that, the polymer was placed in a vacuum oven and dried at a temperature of 60 °C to obtain the first polymer (A1-1). Here, the first polymer (A1-1) is a polyimide precursor (i.e., polyamic acid (PAA)), and the tetracarboxylic dianhydride component and diamine component for synthesizing the first polymer (A1-1) are shown in Table 1.

[0531] Synthesis Examples A1-2 to A1-7

[0532] The first polymers (A1-2) to (A1-7) of Synthesis Examples A1-2 to A1-7 were prepared in the same procedure as Synthesis Example A1-1, except that the types and amounts of the diamine component and the tetracarboxylic dianhydride component in Synthesis Example A1-1 were changed (as shown in Table 1). In Table 1, the amounts of each component are expressed in "mol%", and the actual number of moles used was calculated by setting 0.015 moles to 100 mol%. For the detailed ratio of the amounts used, refer to Synthesis Example A1-1. The compounds corresponding to the abbreviations in Table 1 are shown in Table 2.

[0533] Synthesis Examples of the First Polymer (A1) (Polyimide)

[0534] Synthesis Example A1-1-PI

[0535] A nitrogen inlet, a stirrer, a condenser, and a thermometer were installed on a 500-ml four-necked conical flask, and nitrogen was introduced. Then, 0.003 moles (20 mol%) of diamine compound (b1-a) as the diamine component, 0.00225 moles (15 mol%) of diamine compound (b1-h), 0.0075 moles (50 mol%) of diamine compound (b1-k), 0.00225 moles (15 mol%) of diamine compound (b1-m), and 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were added, and the mixture was stirred at room temperature until dissolved. Subsequently, 0.015 moles (100 mol%) of a1-a as the tetracarboxylic dianhydride component and 20 g of NMP were added. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride, and 19.75 g of pyridine were added, and the temperature was raised to 60 °C, and stirring was continued for 2 hours to carry out the imidization reaction. After the imidization reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, and the washing and filtering with methanol were repeated three times. Thereafter, the polymer was placed in a vacuum oven and dried at a temperature of 60 °C to obtain the first polymer (A1-1-PI). Here, the first polymer (A1-1-PI) is polyimide, and the tetracarboxylic dianhydride component and the diamine component for synthesizing the first polymer (A1-1-PI) are as shown in Table 1.

[0536] Synthesis Example A1-2-PI

[0537] The first polymer (A1-2-PI) of Synthesis Example A1-2-PI was prepared in the same procedure as Synthesis Example A1-1-PI, except that the types and amounts of the diamine component and the tetracarboxylic dianhydride component in Synthesis Example A1-1-PI were changed (as shown in Table 1).

[0538] Comparative Synthesis Examples A'-1 to A'-6 of Polymer (A') (Polyimide)

[0539] The polymers (A'-1) to (A'-6) of Comparative Synthesis Examples A'-1 to A'-6 were prepared in the same manner as in Synthesis Example A1-1, except that the types and amounts used of the diamine component and the tetracarboxylic dianhydride component in Synthesis Example A1-1 were changed (as shown in Table 1). In Table 2, the amounts of each component are expressed in "mol%", and the actual number of moles used was calculated by setting 0.015 moles as 100 mol%. For the detailed ratio of the amounts used, refer to Synthesis Example A1-1. The compounds corresponding to the abbreviations in Table 2 are shown in Table 3. In Tables 2 and 3, the diamine compounds b1-d(Z), b1-e(Z), b1-f(Z), b1-g(Z), b1-j(Z) are the diamine compounds used in Comparative Synthesis Examples A'-1 to A'-5, respectively.

[0540] [Table 1]

[0541]

[0542] [Table 2]

[0543]

[0544] [Table 3]

[0545]

[0546]

[0547]

[0548] Synthesis Examples of the Second Polymer (A2)

[0549] Synthesis Examples A2-1 to A2-3

[0550] The second polymers (A2-1) to (A2-3) of Synthesis Examples A2-1 to A2-3 were prepared in the same manner as in Synthesis Example A1-1, except that the types and amounts used of the diamine component and the tetracarboxylic dianhydride component in Synthesis Example A1-1 were changed (as shown in Table 4). In Table 4, the amounts of each component are expressed in "mol%", and the actual number of moles used was calculated by setting 0.015 moles as 100 mol%. The compounds corresponding to the abbreviations in Table 4 are shown in Table 5.

[0551] Synthesis Examples of the Second Polymer (A2) (Polyimide)

[0552] Synthesis Examples A2-1-PI to A2-3-PI

[0553] The second polymers (A2-1-PI) to (A2-3-PI) of Synthesis Examples A2-1-PI to A2-3-PI were prepared in the same process as Synthesis Example A1-1-PI, and the difference was that the types and amounts of diamine components and tetracarboxylic dianhydride components in Synthesis Example A1-1-PI were changed (as shown in Table 4).

[0554] [Table 4]

[0555]

[0556] [Table 5]

[0557]

[0558] Examples and Comparative Examples of Liquid Crystal Alignment Agent

[0559] Examples 1 to 10 and Comparative Examples 1 to 6 of the liquid crystal alignment agent are described below:

[0560] Example 1

[0561] a. Liquid crystal alignment agent

[0562] Weigh 50 parts by weight of the first polymer (A1-1), 50 parts by weight of the second polymer (A2-1), and 2000 parts by weight of N-methyl-2-pyrrolidone (abbreviated as B-1), and stir and mix them at room temperature to form the liquid crystal alignment agent of Example 1.

[0563] b. Liquid crystal display component

[0564] Spin coat the previously prepared liquid crystal alignment agent on a glass substrate, and a pixel electrode is formed on the glass substrate. The pixel electrode is an IPS driving electrode having a pair of ITO electrodes (electrode width is 10 μm, electrode spacing is 10 μm, and electrode height is 50 nm). This pair of ITO electrodes each have a comb-shaped shape, and the comb-shaped parts of each other are arranged in a separated and meshed manner. Then, dry the glass substrate coated with the liquid crystal alignment agent on a hot plate at 80 °C for 3 minutes, and then bake it in a hot air circulation oven at 250 °C for 30 minutes to form a coating film with a film thickness of 100 nm.

[0565] After irradiating the coating film surface with ultraviolet light having a wavelength of 254 nm through a polarizing plate, bake it in a hot air circulation oven at 250 °C for 30 minutes to obtain a substrate with a liquid crystal alignment film. In this way, the first unit can be formed.

[0566] Similarly, form a coating film on the counter substrate with the previously prepared liquid crystal alignment agent and perform an alignment treatment. The counter substrate is a glass substrate without an electrode formed but having a columnar spacer with a height of 4 μm. In this way, the second unit can be formed.

[0567] The first unit and the second unit are regarded as a group. A sealant is printed on one of them, and the other is bonded to it with a spacer (cell gap) therebetween such that it faces the liquid crystal alignment film and the alignment direction is 0°. After that, the sealant is cured to obtain an empty cell. The liquid crystal MLC-2041 (manufactured by Merck) is injected into this empty cell by a reduced-pressure injection method, and the injection hole is sealed, thereby obtaining the liquid crystal display component of Example 1.

[0568] The liquid crystal display component of Example 1 was evaluated by the following evaluation methods, and the results are shown in Table 6.

[0569] Examples 2 to 10 and Comparative Examples 1 to 6

[0570] The liquid crystal alignment agents and liquid crystal display components of Examples 2 to 10 and Comparative Examples 1 to 6 were prepared by the same procedures as in Example 1, except that the types and amounts of the components were changed as shown in Table 6. The liquid crystal display components prepared in Examples 2 to 10 and Comparative Examples 1 to 6 were evaluated by the following evaluation methods, and the results are shown in Table 6. The compounds corresponding to the abbreviations in Table 6 are shown in Table 7.

[0571]

[0572] [Table 7]

[0573] Abbreviation Component A1-1 First Polymer (A1-1) A1-2 First Polymer (A1-2) A1-3 First Polymer (A1-3) A1-4 First Polymer (A1-4) A1-5 First Polymer (A1-5) A1-6 First Polymer (A1-6) A1-7 First Polymer (A1-7) A1-1-PI First Polymer (A1-1-PI) A1-2-PI First Polymer (A1-2-PI) A'-1 Polymer (A'-1) A'-2 Polymer (A'-2) A'-3 Polymer (A'-3) A'-4 Polymer (A'-4) A'-5 Polymer (A'-5) A'-6 Polymer (A'-6) A2-1 Second Polymer (A2-1) A2-2 Second Polymer (A2-2) A2-3 Second Polymer (A2-3) A2-1-PI Second Polymer (A2-1-PI) A2-2-PI Second Polymer (A2-2-PI) A2-3-PI Second Polymer (A2-3-PI) B-1 N-methyl-2-pyrrolidone (NMP) B-2 ethylene glycol n-butyl ether B-3 N,N-dimethylacetamide

[0574] [Evaluation Methods]

[0575] High and low temperature impact contrast

[0576] The manufactured liquid crystal display component was placed in an environment of 60°C and 90% humidity for 1 hour, and then in an environment of -20°C for 1 hour in an experimental cycle. The experimental cycle was continuously carried out 24 times to obtain.

[0577] Next, a device in which a polarizer and an analyzer are arranged between a light source and a light quantity detector was used. Under crossed nicols conditions, the light transmittance T0 of the blank was measured; under parallel nicols conditions, the light transmittance T of the blank was measured 100 ; the liquid crystal display component after high and low temperature impact was arranged between the aforementioned polarizer and analyzer, and under crossed nicols conditions, the light transmittance B of the liquid crystal display component was measured.

[0578] Calculate the relative transmittance in the dark state under high and low temperature shock (%) represented by the following mathematical formula (1) based on the above conditions. When the relative transmittance in the dark state under high and low temperature shock is low, it indicates a high high and low temperature shock contrast ratio. That is, when there is a high high and low temperature shock contrast ratio, it indicates a preferable display quality. Among them, the high and low temperature shock contrast ratio is evaluated based on the following criteria.

[0579] Relative transmittance in the dark state under high and low temperature shock (%) = (B - T0) / (T 100 - T0) × 100 (%) --------- Mathematical formula (1)

[0580] ※: Relative transmittance in the dark state under high and low temperature shock (%) ≤ 0.5%.

[0581] ◎: 0.5% < Relative transmittance in the dark state under high and low temperature shock (%) ≤ 0.7%.

[0582] ○: 0.7% < Relative transmittance in the dark state under high and low temperature shock (%) ≤ 1%.

[0583] ╳: Relative transmittance in the dark state under high and low temperature shock (%) > 1%.

[0584] [Evaluation result]

[0585] As can be seen from Table 3, compared with the first polymer (A1) in the polymer component (A) not containing the structure represented by formula (I) or the structure represented by formula (II) (Comparative Examples 1 to 6), the liquid crystal display component with a liquid crystal alignment film formed by a liquid crystal aligning agent in which the first polymer (A1) in the polymer component (A) is defined to contain the structure represented by formula (I) and the structure represented by formula (II) (Experimental Examples 1 to 10) has a good high and low temperature shock contrast ratio.

[0586] When A in formula (I) of the first polymer (A1) 1 and A 2 each independently represent a substituted or unsubstituted 1,4-phenylene group (Experimental Examples 1 to 5, Experimental Examples 8 to 10), the liquid crystal display component with a liquid crystal alignment film formed by a liquid crystal aligning agent has a better high and low temperature shock contrast ratio (that is, a higher high and low temperature shock contrast ratio).

[0587] In summary, the present embodiment provides a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display component, which make the liquid crystal display component with a liquid crystal alignment film formed by a liquid crystal aligning agent have a good high and low temperature shock contrast ratio by defining the first polymer (A1) in the polymer component (A) to contain the structure represented by formula (I) and the structure represented by formula (II).

Claims

1. A liquid crystal aligning agent, comprising: A polymer component (A), including a first polymer (A1), and the first polymer (A1) is selected from at least one polymer in the group consisting of a polyimide precursor and an imidized polymer of the polyimide precursor; and A solvent (B), Wherein the polyimide precursor of the first polymer (A1) includes a structure represented by the following formula (I) and a structure represented by the following formula (II), In formula (I), X 1 represents at least one selected from the group consisting of the structures represented by the following formulas (I-1) to (I-7); X 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; A 1 and A 2 each independently represents a substituted or unsubstituted divalent aromatic ring group; Y 11 represents -O-, -S-, -COO- or -OCO-; Z 1 represents a structure represented by the following formula (Z1-1); In formula (I-1), X 11 , X 12 , X 13 , and X 14 each independently represents 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, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group, and * represents a bonding position; In formulas (I-2) to (I-6), * represents a bonding position; In formula (I-7), X 15 and X 16 each independently represents a hydrogen atom or a methyl group, and * represents the bonding position. In formula (Z1-1), R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; m is an integer from 0 to 4, and when m is an integer from 2 to 4, R 1 each independently has the above definition n is an integer from 1 to 3, and when n is 2 or 3, R 1 and m each independently have the above definitions, * represents a bonding position, In formula (II), X 1 represents at least one selected from the group consisting of the structures represented by the formulas (I-1) to (I-7); X 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; A 3 and A 4 each independently represents a substituted or unsubstituted divalent aromatic ring group; Y 21 and Y 22 each independently represents a single bond, an oxygen atom, a sulfur atom or R 2 represents a group that dissociates upon heating, and Y 21 and Y 22 at least one of which is and Y 21 is different from Y 22 ; Z 2 represents a divalent organic group having at least one of a chain hydrocarbon structure and an alicyclic hydrocarbon structure and having 1 to 15 carbon atoms.

2. The liquid crystal aligning agent according to claim 1, characterized in that, X 1 represents the structure shown by formula (I-1).

3. The liquid crystal aligning agent according to claim 1, characterized in that, X 1 represents the structure represented by the following formula (I-1-1): Wherein * represents a bonding position.

4. The liquid crystal aligning agent according to claim 1, characterized in that, Z 1 represents the structure shown by the following formula (Z1-1-1): In formula (Z1-1-1), R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms; m is an integer from 0 to 4. When m is an integer from 2 to 4, R 1 each independently has the above definition. n is an integer from 1 to 3. When n is 2 or 3, R 1 and m each independently have the above definition. * represents a bonding position.

5. The liquid crystal aligning agent according to claim 1, characterized in that, A in formula (I) 1 and A 2 each independently represents a substituted or unsubstituted 1,4-phenylene group.

6. The liquid crystal aligning agent according to claim 1, characterized in that, The polyimide precursor of the first polymer (A1) further includes a structure represented by the following formula (III), In formula (III), X 1 represents at least one selected from the group consisting of the structures represented by the foregoing formulas (I-1) to (I-7); X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Z 31 and Z 31 each independently represents a linear hydrocarbon group having 1 to 10 carbon atoms or a single bond; Z 32 and Z 32 each independently represents -O-, -S-, -CO- or -COO-; Z 33 and Z 33 each independently represents a linear hydrocarbon group having 1 to 10 carbon atoms or a single bond; Z 31 、Z 31 ', Z 33 and Z 33 ' cannot all be single bonds; Ring Z represents an aromatic hydrocarbon ring, diphenyl ether or a nitrogen-containing heterocyclic ring; B 1 and B 2 each independently represents one selected from divalent organic groups represented by the following formula (III-1) to formula (III-16), and B 1 and B 2 do not have the same structure In formulas (III-1) to (III-16), * represents a bonding position, In formula (III-2), B 3 represents an alkylene group having 1 to 5 carbon atoms or -O-; In formula (III-14), B 4 represents a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group.

7. A liquid crystal alignment film for photo-alignment method, formed by using the liquid crystal aligning agent according to any one of claims 1 to 6.

8. A liquid crystal alignment film, formed by using the liquid crystal aligning agent according to any one of claims 1 to 6.

9. A liquid crystal display component, comprising: The liquid crystal alignment film according to claim 7 or 8.

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