KR20220159955A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent capable of obtaining a liquid crystal aligning film having a high voltage retention even after exposure to high temperature and high humidity for a long time, and a quick relaxation of accumulated electric charges and excellent afterimage characteristics, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the same provides Furthermore, the liquid crystal aligning agent which can obtain the liquid crystal aligning film which has high light transmittance, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element using the same are provided.
A first repeating unit (a1) selected from the group consisting of a repeating unit represented by the following formula (1-a) and a repeating unit represented by the following formula (1-i), a repeating unit represented by the following formula (2-a), and The liquid crystal aligning agent containing the polymer component which has a 2nd repeating unit (a2) chosen from the group which consists of a repeating unit represented by following formula (2-i). (The meaning of each substituent is as described in the specification.)

Description

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

This invention relates to the liquid crystal display element which has a liquid crystal aligning agent, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

Conventionally, as a liquid crystal display device, various driving methods having different electrode structures or physical properties of liquid crystal molecules used have been developed. For example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment ) type, IPS type (In Plane Switching), FFS (Fringe Field Switching) type, and other various display elements are known. These liquid crystal display elements have a liquid crystal alignment film for orienting liquid crystal molecules. As a material of a liquid crystal alignment film, polyamic acid, polyamic acid ester, polyimide, polyamide, etc. are known, for example.

In a VA liquid crystal display element, which is one of the driving methods of a liquid crystal display element, a photopolymerizable compound is previously added to a liquid crystal composition, and a vertical alignment film such as polyimide is used, and ultraviolet rays are applied while applying a voltage to a liquid crystal cell. A technology (Polymer Sustained Alignment (PSA) method element) of speeding up the response speed of liquid crystal by irradiation (for example, see Patent Document 1 and Non-Patent Document 1) is known.

On the other hand, in this type of liquid crystal display element, when static electricity is accumulated in the liquid crystal cell or electric charge is accumulated in the liquid crystal cell by application of a positive and negative asymmetric voltage generated by driving, these accumulated electric charges are transferred to the liquid crystal. It affects the display as a disorder of orientation or an afterimage, and remarkably deteriorates the display quality of the liquid crystal device. As a liquid crystal aligning film that solves such a subject, Patent Document 2 proposes a polyimide-based liquid crystal aligning film having a pyrrole structure.

Also, in recent years, large-screen, high-definition liquid crystal televisions have been widely put into practical use, and in liquid crystal display elements in these applications, compared to display applications that mainly display characters and still images, the demand for afterimages is higher. Characteristics capable of withstanding long-term use in harsh and severe use environments are required. Therefore, the liquid crystal aligning film used therein is required to be more reliable than before, and as for the electrical properties of the liquid crystal aligning film, not only the initial properties are good, but also good properties, for example, even after exposure to high temperature and high humidity for a long time. maintenance is required. As a liquid crystal aligning film that solves such a subject, Patent Document 3 proposes a polyimide-based liquid crystal aligning film having a diphenylamine structure.

Japanese Unexamined Patent Publication No. 2003-307720 International Publication No. 2019/013339 International Publication No. 2009/093709

K. Hanaoka, SID 04 DIGEST, P1200-1202

However, in ultra-high-definition liquid crystal display devices such as 4K and 8K, since the share of black matrix (BM), TFT, etc. increases and the aperture ratio of the panel decreases, improvement in the transmittance of the display portion is regarded as important.

In view of the above circumstances, an object of the present invention is a liquid crystal aligning agent capable of obtaining a liquid crystal aligning film having a high voltage retention rate even after exposure to high temperature and high humidity for a long time, and an excellent liquid crystal aligning film having an excellent afterimage characteristic, and also a quick relaxation of accumulated electric charge, and its liquid crystal It is providing the liquid crystal aligning film obtained from an aligning agent, and the liquid crystal display element using the same.

Furthermore, it is providing the liquid crystal aligning agent which can obtain the liquid crystal aligning film which has high light transmittance, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element using the same.

This inventor discovered that the liquid crystal aligning agent containing a specific component is effective in order to achieve the said objective, as a result of earnestly researching in order to achieve the said subject, and came to complete this invention.

This invention is based on this knowledge, and makes the following a summary.

A first repeating unit (a1) selected from the group consisting of a repeating unit represented by the following formula (1-a) and a repeating unit represented by the following formula (1-i);

The liquid crystal aligning agent containing the polymer component which has the 2nd repeating unit (a2) chosen from the group which consists of a repeating unit represented by the following formula (2-a) and a repeating unit represented by the following formula (2-i).

[Formula 1]

[Formula 2]

(X ₁ and X ₂ represent a tetravalent organic group. Y ₁ represents a divalent organic group having any of the structures represented by the following formulas (S1) to (S3). Y ₂ represents a divalent organic group represented by the following formula (2c) Represents an organic group. Two R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent organic group. Two Z ₁ and Z ₂ each independently represent a hydrogen atom or a monovalent organic group.)

[Formula 3]

(X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, - NH-, -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -, where a1 is an integer from 1 to 15, and A ₁ is -O- or -COO-, and m ₁ is an integer of 1 to 2. G ¹ and G ² are each independently a group consisting of a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms; Represents a divalent cyclic group selected from. Arbitrary hydrogen atoms on the cyclic group may be substituted. m and n are each independently an integer of 0 to 3, m + n is 1 to 6, preferably 1 to 4. R ¹ represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group ^of 2 to 20 carbon atoms, and any hydrogen atom forming R ¹ may be substituted with a fluorine atom. , X ² , G ¹ , G ² , a1, m ₁ and A ₁ , when a plurality of X ¹ , X ² , G ¹ , G ² , a1, m ₁ and A ₁ are each independently has the above definition.)

[Formula 4]

(X ³ represents a single bond, -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO-. R ² represents an alkyl group of 1 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ² may be substituted with a fluorine atom.)

[Formula 5]

(X ⁴ represents -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO-. R ³ represents a structure having a steroid skeleton.)

[Formula 6]

(R represents a hydrogen atom or a monovalent organic group. * represents a bond.)

In addition, in this specification, * represents a bonding hand in any case. Boc represents a tert-butoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the carbamate-based protecting group include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, even after exposure under high temperature, high humidity for a long time, a liquid crystal aligning film excellent in afterimage characteristics can be obtained with a high voltage retention and a quick relaxation of the accumulated electric charge.

Furthermore, according to the liquid crystal aligning agent of this invention, the liquid crystal aligning film which has a high light transmittance can be obtained.

Although the mechanism by which the said effect of this invention is acquired is not necessarily clear, what is described below is considered as one cause. That is, since hydrolysis of a polymer does not occur easily under high temperature, high humidity by using the liquid crystal aligning agent containing the said polymer, it is thought that the liquid crystal aligning film with high voltage retention is obtained. In addition, as a result of determining the absorbance in the visible region by using the oxidized body of a polymer, which is one of the factors for lowering the light transmittance, as a model compound, the absorbance of the oxidized body made of the polymer is very small, so a liquid crystal alignment film having a high light transmittance It is thought that this is obtained.

Below, each component contained in the liquid crystal aligning agent of this indication and the other component mix|blended arbitrarily as needed are demonstrated.

<Polymer component>

The liquid crystal aligning agent of the present invention comprises a first repeating unit (a1) selected from the group consisting of a repeating unit represented by the formula (1-a) and a repeating unit represented by the formula (1-i);

A polymer component having a second repeating unit (a2) selected from the group consisting of a repeating unit represented by the formula (2-a) and a repeating unit represented by the formula (2-i) is contained.

As a specific aspect of the polymer component, (i) at least one selected from the group consisting of a polyimide precursor having the first repeating unit (a1) and the second repeating unit (a2) in the same molecule and an imidized polymer thereof; At least one polymer selected from the group consisting of a polymer (P-a1 + a2) (hereinafter also referred to as a copolymer), (ii) a polyimide precursor having the first repeating unit (a1) and an imidized polymer thereof ( A mixture of P-a1) and at least one polymer (P-a2) selected from the group consisting of the polyimide precursor having the second repeating unit (a2) and an imidized polymer thereof (hereinafter, also referred to as a polymer blend) can be heard The above copolymer or the above polymer blend may be used alone or in combination.

Moreover, the said polymer component further contains at least 1 sort(s) of polymer selected from the group which consists of a polyimide precursor and its imidation polymer which have neither a 1st repeating unit (a1) nor a 2nd repeating unit (a2). You can do it.

When the polymer component is the copolymer, the total of the first repeating unit (a1) and the second repeating unit (a2) is preferably 5 to 100 mol% of the total repeating units constituting the copolymer, and 10 - 100 mol% is more preferable.

The content of the repeating unit (a1) is preferably 1 to 90 mol%, more preferably 1 to 85 mol%, based on the total repeating units constituting the copolymer.

When the polymer component is the polymer blend, the content of the repeating unit (a1) is 1 mol% or more and 99 mol% of the total repeating units constituting the polymer (P-a1), from the viewpoint of enhancing the liquid-crystal orientation. The following is preferable, 2 mol% or more and 95 mol% or less are more preferable, and 5 mol% or more and 90 mol% or less are still more preferable.

The content of the repeating unit (a2) is preferably 5 mol% or more and 90 mol% or less of the total repeating units constituting the polymer (P-a2) from the viewpoint of efficiently obtaining the effects of the present invention. , 10 mol% or more and 80 mol% or less are more preferable.

The mass ratio of the content of the polymer (P-a2) to the content of the polymer (P-a1) is preferably from 5/95 to 95/5, more preferably from 10/90 to 90/10. to be.

(first repeating unit (a1))

In the formulas (1-a) and (1-i), Y ₁ represents a divalent organic group having structures represented by formulas (S1) to (S3). Y ₁ is preferably a divalent organic group derived from diamine having a structure represented by the above formulas (S1) to (S3).

As a specific example of the divalent organic group which has the structure represented by the said formula (S1) - (S3), 2 derived from the aromatic diamine (d) which has the structure represented by the said formula (S1) - (S3) in a side chain The organic group of GA is mentioned. The divalent organic group having structures represented by the formulas (S1) to (S3) is preferably a group obtained by removing two amino groups from the aromatic diamine (d).

Examples of the substituent on the cyclic group in G ¹ and G ² of the formula (S1) include a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group of 1 to 10 carbon atoms, and a carbon atom-containing alkyl group of 1 to 10 carbon atoms. A carbon-carbon bond having an alkoxy group of 10, an alkenyl group of 1 to 10 carbon atoms, and any methylene group of the halogen atom-containing alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group is interrupted by an oxygen atom. and substituents selected from the group consisting of heteroatom-containing groups.

As a preferable specific example of the structure represented by the said formula (S1), the structure represented by the following formula (S1-1) - (S1-7) is mentioned. As a preferable specific example of the structure represented by the said formula (S3), the structure represented by (S3-a) is mentioned. In addition, in formula (S3-a), X represents formula (X1), formula (X2), or -CH ₂ O-, and Col represents formula (Col-1), formula (Col-2) or formula (Col-3) is represented, and G represents formula (G1), formula (G2), formula (G3) or formula (G4).

[Formula 7]

In the above formula, R ¹ represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms. X ^p is -(CH ₂ ) _a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO-. A ₁ is an oxygen atom or -COO-* (provided that the bond to which “*” is added binds to (CH ₂ ) _a2 ), and A ₂ is an oxygen atom or *-COO- (provided that “*” represents (CH ₂ ) bonded to _a2 ), a ₁ and a ₃ are each independently an integer of 0 or 1, a ₂ is an integer of 1 to 10, and Cy is 1,4 - A cyclohexylene group or a 1,4-phenylene group is shown.

[Formula 8]

In the formula (S2), X ³ is preferably -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO- from the viewpoint of enhancing the liquid-crystal orientation.

R ² is preferably an alkyl group of 3 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms from the viewpoint of liquid crystal orientation. Arbitrary hydrogen atoms forming R ² may be substituted with fluorine atoms.

It is preferable that the said aromatic diamine (d) has at least 1 benzene ring.

As a specific example of aromatic diamine (d), the diamine represented by the following formula (d1) or formula (d2) is mentioned.

[Formula 9]

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m - O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m represents a divalent organic group of -OCO- m is an integer of 1 to 8. Y is the formula (S1 ) to (S3). In the above formula (d2), two Ys may be the same as or different from each other.)

As a preferable example of the diamine represented by the said formula (d1), the following formula (d1-1) - (d1-7) are mentioned. As a preferable example of the diamine represented by the said formula (d2), the following formula (d2-1) - (d2-6) are mentioned.

[Formula 10]

[Formula 11]

(X ^v1 to X ^v4 and X ^p1 to X ^p8 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO-, X ^v5 to X ^v6 , X ^s1 to X ^s4 are each Independently represents -O-, -CH ₂ O-, -COO- or -OCO- X ^v7 is a single bond, -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH -, -O-, -CH ₂ O-, -COO-, or -OCO- X _a to X _f represent a single bond, -O-, -NH-, or -O-(CH ₂ ) _m - Represents O- (m represents an integer of 1 to 8), R ^v1 to R ^v4 and R ^1a to R ^1h are each independently -C _n H _2n+1 (n represents an integer of 1 to 20), or -OC _n H _2n+1 (n represents an integer of 2 to 20).

In the formulas (1-a) and (1-i), X ₁ represents a tetravalent organic group. X ₁ preferably represents a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof. Examples of the tetravalent organic group include a tetravalent organic group derived from an acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from an alicyclic tetracarboxylic acid dianhydride or a derivative thereof, or an aromatic tetracarboxylic group. A tetravalent organic group derived from an acid dianhydride or a derivative thereof is exemplified, preferably a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof represented by the following formula (3).

[Formula 12]

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

[Formula 13]

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

As more preferable specific examples of the formula (x-1), the following formulas (X1-1) to (X1-6) are exemplified.

[Formula 14]

Preferred specific examples of the above formulas (x-12) and (x-13) include the following formulas (x-14) to (x-29).

[Formula 15]

[Formula 16]

Preferable examples of the tetracarboxylic dianhydride or derivative thereof represented by the formula (3) include formulas in which X is the formulas (x-1) to (x-7), (x-11) to (x-13) Tetracarboxylic dianhydride or its derivative represented by (3) is mentioned.

In the formula (1-a), two R ₁ 's each independently represent a hydrogen atom or a monovalent organic group. As an example of the said monovalent organic group, a hydrogen atom or a C1-C5 alkyl group is mentioned. Two R ₁ 's each independently preferably represent a hydrogen atom or an alkyl group of 1 to 3 carbon atoms.

In the formula (1-a), two Z ₁ 's each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an alkenyl group of 2 to 10 carbon atoms which may have a substituent, an alkynyl group of 2 to 10 carbon atoms which may have a substituent, A tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group is mentioned. As said substituent, a halogen atom, a hydroxyl group, a carboxy group, an amino group, a nitrile group etc. are mentioned, for example. Two Z ₁ 's each independently preferably represent a hydrogen atom or a methyl group.

In the formula (1-a) and the formula (1-i), X ₁ , Y ₁ , R ₁ , and Z ₁ may be one type or two or more types, respectively.

(Second repeating unit (a2))

In the formulas (2-a) and (2-i), Y ₂ represents a divalent organic group represented by the formula (2c) below.

[Formula 17]

(R represents a hydrogen atom or a monovalent organic group.)

As a monovalent organic group of R in the said formula (2c), a C1-C12 alkyl group, an alkoxyalkyl group, a phenyl group etc. are mentioned, for example. A methyl group, an ethyl group, a propyl group etc. are mentioned as a C1-C12 alkyl group.

In the formula (2c), R is preferably a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, an alkoxyalkyl group, or a phenyl group from the viewpoint of obtaining the effect of the present invention preferably.

More preferred specific examples of Y ₂ include 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3,6-diaminocarbazole and 9-phenyl- and groups obtained by removing two amino groups from carbazole selected from the group consisting of 3,6-diaminocarbazole.

X ₂ in the formulas (2-a) and (2-i) is the same as X ₁ in the formulas (1-a) and (1-i).

Examples of R ₂ in the formula (2-a) include the same ones as R ₁ in the formula (1-a).

Z ₂ in the formula (2-a) is the same as Z ₁ in the formula (1-a).

In the formula (2-a) and the formula (2-i), X ₂ , Y ₂ , R ₂ , and Z ₂ may be one type or two or more types, respectively.

(third repeat unit)

The polymer component may further have a third repeating unit (a3) selected from the group consisting of a repeating unit represented by the following formula (3-a) and a repeating unit represented by the following formula (3-i).

[Formula 18]

(X ₃ represents a tetravalent organic group. Y ₃ represents a divalent organic group, other than a divalent organic group having a structure represented by the formulas (S1) to (S3) and a divalent organic group represented by the formula (2c) Represents a divalent organic group of 2 pieces of R ₃ and 2 pieces of Z ₃ have the same meaning as R ₁ and Z ₁ in the formula (1-a), respectively.)

As a specific aspect of the polymer component which further has the said 3rd repeating unit (a3), the aspect of a copolymer and a polymer blend is mentioned.

Examples of the copolymer include a polyimide precursor having the first repeating unit (a1), the second repeating unit (a2), and the third repeating unit (a3) in the same molecule and an imidized polymer thereof. At least 1 type of polymer selected from the group is mentioned.

Examples of the polymer blend include at least one polymer (P -a1+a2) and at least one polymer selected from the group consisting of a polyimide precursor having the first repeating unit (a1) and the third repeating unit (a3) in the same molecule and an imidized polymer thereof (P-a1+a3 ) can be used as a mixture of The polymer (P-a1+a3) does not have to have the second repeating unit (a2). The above copolymer or the above polymer blend may be used alone or in combination.

When the polymer component is the copolymer, the content of the repeating unit (a3) is preferably from 5 to 90 mol%, more preferably from 10 to 80 mol%, based on the total repeating units constituting the copolymer.

In this case, the total of the first repeating unit (a1) and the second repeating unit (a2) is preferably 10 to 95 mol%, and more preferably 20 to 90 mol% of the total repeating units constituting the copolymer. desirable.

When the polymer component is the polymer blend, the mass ratio of the content of the polymer (P-a1 + a3) to the content of the polymer (P-a1 + a2) is preferably from 5/95 to 95/5, more preferably It is 10/90 to 90/10.

Y ₃ preferably represents a divalent organic group derived from diamine. Specific examples of the divalent organic group of Y ₃ include p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, 2,4-diaminobenzoic acid, and 2,5- Diaminobenzoic acid, 3,5-diaminobenzoic acid and diamines having a carboxyl group such as diamine compounds represented by the following formulas (3b-1) to formulas (3b-4), 4,4'-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,2-bis(4-aminophenyl)ethane, 1,3-bis( 4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis( 4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy )-3-fluoroaniline, di(2-(4-aminophenoxy)ethyl)ether, 4-amino-4'-(2-(4-aminophenoxy)ethoxy)biphenyl, 2,2'-Dimethyl-4,4'-diaminobiphenyl,3,3'-dimethyl-4,4'-diaminobiphenyl,4,4'-diamino2,2'-bis(trifluoromethyl)bi Phenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,2'-bis[4-(4-aminophenoxy) Phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 1,3-bis (4-amino A diamine having a urea bond such as phenethyl)urea, a photopolymerizable group such as 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N-diallylaniline, etc. Diamines having a radical initiating function such as the following formulas (R1) to (R5), 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis(4- Diamine having a photosensitizing function that exhibits a sensitizing action by light irradiation such as aminophenyl)fluorene, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diaminopyrimidine, heterocyclic diamines such as the following formulas (z-1) to (z-18), the following formulas (Dp-1) to (Dp-9), etc. A diamine having a diphenylamine skeleton of , a group "-N(D)-" such as the following formulas (5-1) to (5-10) (D represents a protecting group that is desorbed by heating and is substituted with a hydrogen atom, preferably two amino groups from diamines (hereinafter also referred to as other diamines) such as diamines having a tert-butoxycarbonyl group) and diamines having an oxazoline structure such as the following formulas (Ox-1) to (Ox-2) Although the organic group from which was removed can be mentioned, it is not limited to these.

[Formula 19]

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

[Formula 20]

[Formula 21]

[Formula 22]

(In formulas (R3) to (R5), n is an integer of 1 to 6.)

[Formula 23]

[Formula 24]

[Formula 25]

The above 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, diamine having a photopolymerizable group at the terminal, diamine represented by the above formulas (R1) to (R5), the above formula (z-1) Diamines represented by - (z-18) may be used singly or in combination of two or more in producing the polymer component from the viewpoint of accelerating the response speed of a liquid crystal display element using a PSA method or an SC-PVA mode. .

As other diamines, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'- Diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N- Diallylaniline, diamines represented by the formulas (R1) to (R5), diamines represented by the formulas (z-1) to (z-18), and diamines represented by the formulas (Dp-1) to (Dp-9) , diamines represented by the formulas (Ox-1) to (Ox-2) are preferable.

X ₃ in the formulas (3-a) and (3-i) is the same as X ₁ in the formulas (1-a) and (1-i).

Examples of R ₃ in the formula (3-a) include the same ones as R ₁ in the formula (1-a).

Examples of Z ₃ in the formula (3-a) include the same ones as Z ₁ in the formula (1-a).

In the formula (3-a) and the formula (3-i), X ₃ , Y ₃ , R ₃ , and Z ₃ may be one type or two or more types, respectively.

<Method for producing polymer>

As for the polyimide precursor used for this invention, polyamic acid, polyamic acid ester, etc. are mentioned. The polyimide precursor used for this invention is compoundable by the well-known method as described in international publication WO2013/157586, for example.

Specifically, it is synthesized by reacting (condensation polymerization) a diamine component and a tetracarboxylic acid derivative component in a solvent. Examples of the tetracarboxylic acid derivative component include tetracarboxylic acid dianhydride or a derivative thereof (tetracarboxylic acid dihalide, tetracarboxylic acid diester, or tetracarboxylic acid diester dihalide). . When a part of a polymer contains an amic acid structure, the polymer (polyamic acid) which has an amic acid structure is obtained by making a tetracarboxylic dianhydride component and a diamine component react, for example. The solvent is not particularly limited as long as the resulting polymer dissolves therein.

For example, when obtaining a polymer having a repeating unit represented by the formula (1-a) in which R ₁ is a hydrogen atom, as the diamine component, -N(Z ₁ )-Y ₁ -N(Z ₁ )- A diamine having a structure of (the definition of Y ₁ and Z ₁ is the same as that of the formula (1-a) above) is used, and as the tetracarboxylic acid derivative component, a tetracarboxylic acid derivative having a structure of the following formula is used

[Formula 26]

(The definition of X ₁ is the same as in Formula (1-a) above.)

Further, polyimide can be obtained by subjecting the polyimide precursor to ring closure (imidization). In addition, the imidation rate as used herein refers to the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof). In polyimide, the imidation rate does not necessarily need to be 100% and can be arbitrarily adjusted depending on the use or purpose.

The imidation rate of the polyimide contained in the liquid crystal aligning agent of the present invention is 10 to 95%, preferably 20 to 95%, more preferably 30 to 90% from the viewpoint of ensuring solubility.

As a method of imidating the polyimide precursor, thermal imidation in which the solution of the polyimide precursor is heated as it is or catalyst imidation in which a catalyst is added to the solution of the polyimide precursor is exemplified.

The temperature in the case of thermally imidating the polyimide precursor in a solution is 100 to 400°C, preferably 120 to 250°C, and it is preferable to carry out the imidation reaction while removing water generated by the imidation reaction out of the system.

Catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times, the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among these, pyridine is preferable because it has appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalyst imidation is controllable by adjusting the catalyst amount, reaction temperature, and reaction time.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate it, when collect|recovering the produced|generated polyimide precursor or polyimide from the polyimide precursor or the reaction solution of a polyimide. Examples of solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by pouring into the solvent can be recovered by filtration, and then dried by heating or at room temperature under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in a solvent and repeating the operation of re-precipitation and recovery 2 to 10 times. As a solvent at this time, alcohols, ketones, hydrocarbons, etc. are mentioned, for example, Since the efficiency of a refinement|purification will further increase when three or more types of solvents chosen from these are used, it is preferable.

The molecular weight of the polymer used in the present invention is 5,000 to 1,000,000 as a weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, when the strength of the liquid crystal alignment film obtained therefrom, workability at the time of film formation and coating properties are considered is preferred, and more preferably from 10,000 to 150,000.

Although the compounding ratio of the polymer component used in the manufacturing method of the liquid crystal aligning film of this invention is not specifically limited, For example, the total amount of the polymer component contained in a liquid crystal aligning agent is 0.1-30 mass %, Preferably it is 3-10 mass % % to be.

Moreover, content of the said copolymer (polymer (P-a1+a2)) contained in a liquid crystal aligning agent is 1.5-9 mass %, Preferably it is 2.5-9 mass %, for example.

In addition, for example, the total content of the polymer blend (mixture of polymer (P-a1) and polymer (P-a2)) contained in the liquid crystal aligning agent is 1.5 to 9% by mass, preferably 2.5 to 9 mass%. % to be.

Moreover, other polymers other than the said copolymer and the said polymer blend may be mixed in the liquid crystal aligning agent used for manufacture of a liquid crystal aligning film. In that case, content of other polymers is 0.5 mass % - 15 mass % of the total amount of polymer components, Preferably they are 1 mass % - 10 mass %. Examples of other polymers include polyimide precursors other than the aforementioned copolymers and polymer blends, imidized polymers thereof, acrylic polymers, methacrylic polymers, polystyrene, polyamides, or polysiloxanes.

The solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the polymer, and examples thereof include lactone solvents such as γ-valerolactone and γ-butyrolactone; γ-butyrolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone , N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2 - Lactam solvents such as pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. an amide solvent; 4-hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone (diisobutyl ketone), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isobaric acid lactate Wheat, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Butyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, Diisopropyl ether and diisopentyl ether; carbonate solvents such as ethylene carbonate and propylene carbonate; 1-hexanol, cyclohexanol, 1,2-ethanediol, and 2,6-dimethyl-4-heptanol (diisobutylcarbinol); and the like. These can be used individually or in mixture of 2 or more types.

Preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2 -Pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4 -Hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2- Pentanone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl- 2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4- Hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, diisobutyl ketone, N-methyl-2-p Rolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl carbinol, N- Methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether. The type and content of such a solvent are appropriately selected depending on the application device, application conditions, and application environment of the liquid crystal aligning agent.

<liquid crystal aligning agent>

The liquid crystal aligning agent of this invention may add other components other than the above, for example, a crosslinkable compound, a functional silane compound, surfactant, the compound which has a photopolymerizable group, etc. as needed.

A crosslinkable compound can be used for the purpose of enhancing the strength of the liquid crystal aligning film. As such a crosslinking compound, at least one selected from the group consisting of compounds having an isocyanate group or a cyclocarbonate group described in paragraphs [0109] to [0113] of International Publication No. WO2016/047771, or a lower alkoxyalkyl group. In addition to the compound having a group, a compound having a block isocyanate group and the like are exemplified.

The block isocyanate compound is available as a commercial item, for example, Colonate AP Stable M, Colonate 2503, 2515, 2507, 2513, 2555, Milionate MS-50 (above, manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals), etc. can be used preferably.

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

[Formula 27]

The above is an example of a crosslinkable compound, and is not limited thereto. Moreover, 1 type may be sufficient as the crosslinkable compound used for the liquid crystal aligning agent of this invention, and you may combine it 2 or more types.

Content of other crosslinkable compounds in the liquid crystal aligning agent of this invention is 0.1-150 mass parts, or 0.1-100 mass parts, or 1-50 mass parts with respect to 100 mass parts of all polymer components.

A functional silane compound can be used for the purpose of improving the adhesiveness of a liquid crystal aligning film and a base substrate. As a specific example, the silane compound of International Publication No. 2014/119682, Paragraph [0019] is mentioned. The content of the functional silane compound is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, based on 100 parts by mass of all polymer components.

Surfactant can be used for the purpose of improving the uniformity and surface smoothness of the film thickness of a liquid crystal aligning film. As said compound, a fluorochemical surfactant, silicone type surfactant, a nonionic surfactant, etc. are mentioned. Specific examples thereof include the surfactant described in paragraph [0117] of International Publication No. WO2016/047771. The amount of surfactant used is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.

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

[Formula 28]

Further, in the liquid crystal aligning agent of the present invention, as a compound that promotes charge transfer in a liquid crystal aligning film and promotes charge release from an element, paragraphs [0194] to [0200] of International Publication No. WO2011/132751 (published on October 27, 2011) , nitrogen atom-containing heterocyclic amine compounds represented by formulas [M1] to formula [M156], more preferably 3-picolylamine and 4-picolylamine can be added. Although you may add this amine compound directly to a liquid crystal aligning agent, it is a density|concentration of 0.1-10 mass %, It is preferable to add, after setting it as a 1-7 mass % solution preferably. This solvent is not particularly limited as long as it dissolves the polymer.

You may add an imidation promoter etc. to the liquid crystal aligning agent of this invention for the purpose of advancing imidation by heating efficiently, when baking a coating film.

The solid content concentration (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) in the liquid crystal aligning agent is appropriately selected in consideration of viscosity, volatility, etc., but is preferably 0.5 to 15 It is mass %, More preferably, it is the range of 1-10 mass %.

The range of a particularly preferable solid content concentration differs according to the method used when apply|coating a liquid crystal aligning agent to a board|substrate. For example, in the case of spin coating, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. In the case of using the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa·s.

<Liquid crystal alignment film/liquid crystal display element>

The liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent. Although the liquid crystal aligning film of this invention can be used for the liquid crystal aligning film of a horizontal alignment type or a vertical alignment type, it is a liquid crystal aligning film suitable especially for the liquid crystal display element of vertical alignment types, such as a VA system or a PSA mode. The liquid crystal display element of this invention is equipped with the said liquid crystal aligning film. The liquid crystal display element of this invention can be manufactured by the method including the following process (1)-(3) or process (1)-(4), for example. In addition, the liquid crystal alignment film of the present invention is coated on a pair of substrates having a conductive film to form a coating film, and the liquid crystal cell is formed by arranging the coating film to face each other through a layer of liquid crystal molecules, and forming a liquid crystal cell. It can be used suitably for the liquid crystal display element obtained by the manufacturing method of the liquid crystal display element which irradiates the said liquid crystal cell with light in the state which applied the voltage between the conductive films which a board|substrate has. More specifically, it is a PSA type liquid crystal display element described later or a liquid crystal display element for SC-PVA mode.

(1) Process of applying a liquid crystal aligning agent on a substrate

The liquid crystal aligning agent of the present invention is applied to one surface of a substrate on which a patterned transparent conductive film is formed, for example, by a suitable coating method such as a roll coater method, a spin coat method, a printing method, or an inkjet method. Here, the substrate is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to a glass substrate or a silicon nitride substrate. Further, in the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is used for only one substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.

(2) Process of firing the coating film

After application of the liquid crystal aligning agent, for the purpose of preventing liquid drop of the applied alignment agent, etc., preheating (prebaking) is preferably performed first. The prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. And, it is preferable that a further heating (post-bake) process is performed. This post-baking temperature is preferably 80 to 300°C, more preferably 120 to 250°C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 5 to 300 nm, and more preferably 10 to 200 nm.

Although the coating film formed in the said process (1) can be used as a liquid crystal aligning film as it is, you may give an orientation ability provision process with respect to the coating film. Examples of the orientation ability imparting treatment include a rubbing treatment in which a coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and an optical alignment treatment in which polarized or non-polarized radiation is irradiated to the coating film, and the like. can

In the photo-alignment treatment, as the radiation applied to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In addition, when the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or a combination thereof may be performed. When irradiating unpolarized radiation, the direction of irradiation is oblique.

(3) Step of forming a liquid crystal layer

(3-1) In case of VA type liquid crystal display element

As mentioned above, two board|substrates on which the liquid crystal aligning film was formed are prepared, and a liquid crystal is arrange|positioned between the board|substrates of 2 sheets opposingly arranged. Specifically, the following two methods are mentioned. The first method is a conventionally known method. First, the board|substrates of 2 sheets are opposedly arranged through a clearance gap (cell gap) so that each liquid crystal aligning film may oppose. Next, the peripheral portions of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected and filled into the substrate surface and the cell gap partitioned by the sealant to bring them into contact with the film surfaces, and then the injection hole is sealed.

In addition, the second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet light-curable sealing agent is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is dripped at several predetermined points on the liquid crystal alignment film surface. Then, the other board|substrate is bonded together so that the liquid crystal aligning film may oppose, and the liquid crystal composition is pressed and spread|spread on the whole surface of a board|substrate, and it is made to contact a film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing compound. In any case, it is preferable to remove the flow alignment during liquid crystal charging by slowly cooling to room temperature after heating to the temperature at which the used liquid crystal composition assumes an isotropic phase.

(3-2) In the case of manufacturing a PSA type liquid crystal display element

It is the same as the above (3-1) except for injecting or dropping the liquid crystal composition containing the polymerizable compound. As a polymeric compound, the polymeric compound represented by the said formula (M-1) - (M-7) is mentioned, for example.

(3-3) When a coating film is formed on a substrate using a liquid crystal aligning agent containing a compound having a polymerizable group

After carrying out similarly to the said (3-1), you may employ|adopt the method of manufacturing a liquid crystal display element through the process of irradiating an ultraviolet-ray mentioned later. According to this method, a liquid crystal display element excellent in response speed can be obtained with a small light irradiation amount, similarly to the case of manufacturing the PSA type liquid crystal display element. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group represented by the above formulas (M-1) to (M-7) in a molecule, and the content thereof is It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components, More preferably, it is 1-20 mass parts. Moreover, the said polymeric group may have the polymer used for a liquid crystal aligning agent, and as such a polymer, the polymer obtained by using for reaction the diamine component containing the diamine which has the said photopolymerizable group at the terminal, for example is mentioned. can

(4) Step of irradiating ultraviolet rays

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

And a liquid crystal display element can be obtained by bonding a polarizing plate together to the outer surface of a liquid crystal cell. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is stretched and oriented is sandwiched between protective films of cellulose acetate or a polarizing plate made of the H film itself. have.

The liquid crystal display device of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, and smart phones. , It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.

Example

Hereinafter, it will be described in more detail based on examples, but the present invention is not limited at all by these examples.

<Synthesis of the liquid crystal aligning agent>

The abbreviation used by preparation of the following liquid crystal aligning agent is as follows.

(acid dianhydride)

BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

TCA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride

(diamine)

DA-1 to DA-11: Compounds represented by the following formulas (DA-1) to (DA-11), respectively

[Formula 29]

[Formula 30]

[Formula 31]

(additive)

AD-1: Compound represented by the following formula (AD-1)

[Formula 32]

(menstruum)

NMP: N-methyl-2-pyrrolidone, BCS: Butyl cellosolve

<Measurement of molecular weight>

Measurement device: room temperature gel permeation chromatography (GPC) (SSC-7200) manufactured by Senshu Scientific Co., Ltd., column: column manufactured by Shodex (KD-803, KD-805 in series), column temperature: 50 ° C., eluent: N, N- Dimethylformamide (as an additive, 30 mmol/L of lithium bromide monohydrate (LiBr H2O), 30 mmol/L of phosphoric acid/anhydrous crystal (o-phosphoric acid), 10 mL/L of tetrahydrofuran (THF)), Flow rate: 1.0 mL/min, standard samples for calibration curve: TSK standard polyethylene oxide (molecular weights: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (molecular weights: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory.

<Measurement of imidization rate>

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Scientific Co., Ltd.), 1.0 mL of deuterated dimethylsulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve. made it 500 MHz proton NMR was measured for this solution with the NMR measuring machine by the JEOL datum company (JNW-ECA500).

For the chemical imidation rate, a proton derived from a structure that does not change before and after imidation is determined as a standard proton, and the peak integration value of this proton and the proton peak integration derived from the NH group of the amic acid appearing around 9.5 to 10.0 ppm Using the value, it was calculated|required by the following calculation formula. In the formula, x is the peak integrated value of protons derived from the NH group of the amic acid, y is the peak integrated value of standard protons, and α is the amic acid in the case of polyamic acid (imidization ratio is 0%) It is the ratio of the number of reference protons to one proton of the NH group.

Imidization rate (%) = (1-α x/y) x 100

<Synthesis Example 1>

BODA (2.50 g, 10.0 mmol), DA-1 (2.76 g, 14.0 mmol) and DA-8 (2.28 g, 6.0 mmol) were dissolved in NMP (30.2 g), reacted at 60°C for 3 hours, and CBDA (1.92 g, 9.8 mmol) and NMP (7.7 g) were added, and it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution (1) was obtained. The number average molecular weight Mn of this polyamic acid was 10,360, and the weight average molecular weight Mw was 30,350.

<Synthesis Example 2>

BODA (2.50 g, 10.0 mmol), DA-2 (2.96 g, 14.0 mmol) and DA-8 (2.28 g, 6.0 mmol) were dissolved in NMP (31.0 g), reacted at 60°C for 3 hours, and CBDA (1.92 g, 9.8 mmol) and NMP (7.7 g) were added, and it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution (2) was obtained. Mn of this polyamic acid was 12,140 and Mw was 37,600.

<Synthesis Example 3>

BODA (2.50 g, 10.0 mmol), DA-4 (2.79 g, 14.0 mmol) and DA-8 (2.28 g, 6.0 mmol) were dissolved in NMP (30.3 g), reacted at 60°C for 3 hours, and CBDA (1.92 g, 9.8 mmol) and NMP (7.7 g) were added, and it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution (3) was obtained. Mn of this polyamic acid was 12,630 and Mw was 36,540.

<Synthesis Example 4>

BODA (2.50 g, 10.0 mmol), DA-3 (5.90 g, 14.0 mmol) and DA-8 (2.28 g, 6.0 mmol) were mixed in NMP (38.3 g), reacted at 60°C for 3 hours, and CBDA (1.81 g, 9.2 mmol) and NMP (7.8 g) were added, and it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution (4) was obtained. Mn of this polyamic acid was 12,340 and Mw was 46,260.

<Synthesis Example 5>

BODA (2.50 g, 10.0 mmol), DA-1 (1.58 g, 8.0 mmol), DA-6 (1.94 g, 8.0 mmol) and DA-9 (1.58 g, 4.0 mmol) were mixed in NMP (30.4 g) After making it react at 60 degreeC for 3 hours, CBDA (1.94g, 9.9mmol) and NMP (7.7g) were added, it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution (5-a) was obtained. Mn of this polyamic acid was 11,450 and Mw was 37,590. The polyamic acid solution (5) was obtained by adding NMP (6.0g) and BCS (8.0g) to the obtained polyamic acid solution (5-a) (6.0g) and stirring at room temperature for 2 hours.

<Synthesis Example 6>

After adding NMP to the polyamic acid solution (5-a) (20.0 g) obtained in Synthesis Example 5 and diluting to 6.5% by mass, acetic anhydride (4.27 g) and pyridine (1.33 g) were added as an imidation catalyst, , and reacted at 50°C for 3 hours. This reaction solution was poured into methanol (270 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide powder was 37%, Mn was 10,980, and Mw was 34,300. NMP (22.0g) was added to the obtained polyimide powder (3.0g), it was stirred and dissolved at 70 degreeC for 12 hours, and the polyimide solution (1) was obtained.

<Synthesis Example 7>

BODA (2.50 g, 10.0 mmol), DA-2 (1.69 g, 8.0 mmol), DA-6 (1.94 g, 8.0 mmol) and DA-9 (1.58 g, 4.0 mmol) were mixed in NMP (30.8 g) After making it react at 60 degreeC for 3 hours, CBDA (1.94g, 9.9mmol) and NMP (7.8g) were added, it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution (6-a) was obtained. Mn of this polyamic acid was 10,860 and Mw was 36,010. The polyamic acid solution (6) was obtained by adding NMP (6.0g) and BCS (8.0g) to the obtained polyamic acid solution (6-a) (6.0g) and stirring at room temperature for 2 hours.

<Synthesis Example 8>

After adding NMP to the polyamic acid solution (6-a) (20.0 g) obtained in Synthesis Example 7 and diluting to 6.5% by mass, acetic anhydride (4.23 g) and pyridine (1.31 g) were added as an imidation catalyst, , and reacted at 50°C for 3 hours. This reaction solution was poured into methanol (270 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide powder was 53%, Mn was 9,920, and Mw was 32,300. NMP (22.0g) was added to the obtained polyimide powder (3.0g), it was stirred and dissolved at 70 degreeC for 12 hours, and the polyimide solution (2) was obtained.

<Synthesis Example 9>

BODA (2.50 g, 10.0 mmol), DA-4 (1.59 g, 8.0 mmol), DA-6 (1.94 g, 8.0 mmol) and DA-9 (1.58 g, 4.0 mmol) were mixed in NMP (30.4 g) After making it react at 60 degreeC for 3 hours, CBDA (1.92g, 9.8 mmol) and NMP (7.7g) were added, it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution (7-a) was obtained. Mn of this polyamic acid was 11,030 and Mw was 33,050. The polyamic acid solution (7) was obtained by adding NMP (6.0g) and BCS (8.0g) to the obtained polyamic acid solution (7-a) (6.0g) and stirring at room temperature for 2 hours.

<Synthesis Example 10>

After adding NMP to the polyamic acid solution (7-a) (20.0 g) obtained in Synthesis Example 9 and diluting to 6.5% by mass, acetic anhydride (4.27 g) and pyridine (1.32 g) were added as an imidation catalyst, , and reacted at 50°C for 3 hours. This reaction solution was poured into methanol (270 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide powder was 58%, Mn was 10,490, and Mw was 31,280. NMP (22.0g) was added to the obtained polyimide powder (3.0g), it was stirred and dissolved at 70 degreeC for 12 hours, and the polyimide solution (3) was obtained.

<Synthesis Example 11>

BODA (2.50 g, 10.0 mmol), DA-3 (3.37 g, 8.0 mmol), DA-7 (1.42 g, 6.0 mmol) and DA-8 (2.28 g, 6.0 mmol) were mixed in NMP (38.3 g) After making it react at 60 degreeC for 3 hours, CBDA (1.95g, 9.9mmol) and NMP (7.8g) were added, it was made to react at 40 degreeC for 3 hours, and the polyamic-acid solution was obtained. Mn of this polyamic acid was 9,100 and Mw was 24,540. After adding NMP to the obtained polyamic-acid solution (20.0g) and diluting to 6.5 mass %, acetic anhydride (3.54g) and pyridine (1.10g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (230 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation ratio of this polyimide powder was 78%, Mn was 9,040, and Mw was 21,020. NMP (22.0g) was added to the obtained polyimide powder (3.0g), it was stirred and dissolved at 70 degreeC for 12 hours, and the polyimide solution (4) was obtained.

<Synthesis Example 12>

TCA (4.37 g, 19.5 mmol), DA-1 (1.58 g, 8.0 mmol), DA-6 (1.94 g, 8.0 mmol) and DA-9 (1.58 g, 4.0 mmol) were mixed in NMP (37.9 g) , It was made to react at 60 degreeC for 6 hours, and the polyamic acid solution was obtained. Mn of this polyamic acid was 11,860 and Mw was 45,870. After adding NMP to the obtained polyamic-acid solution (20.0g) and diluting to 6.5 mass %, acetic anhydride (8.53g) and pyridine (1.32g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4 hours. This reaction solution was poured into methanol (285 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide powder was 66%, Mn was 10,500, and Mw was 41,300. NMP (22.0g) was added to the obtained polyimide powder (3.0g), it was stirred and dissolved at 70 degreeC for 12 hours, and the polyimide solution (5) was obtained.

<Synthesis Example 13>

TCA (4.46 g, 19.9 mmol), DA-4 (1.59 g, 8.0 mmol), DA-6 (1.45 g, 6.0 mmol) and DA-8 (2.28 g, 6.0 mmol) were mixed in NMP (39.1 g) , It was made to react at 60 degreeC for 6 hours, and the polyamic acid solution was obtained. Mn of this polyamic acid was 11,900 and Mw was 44,800. After adding NMP to the obtained polyamic-acid solution (20.0g) and diluting to 6.5 mass %, acetic anhydride (6.66g) and pyridine (1.29g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 2 hours. This reaction solution was poured into methanol (243 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide powder was 73%, Mn was 10,500, and Mw was 40,300. NMP (22.0g) was added to the obtained polyimide powder (3.0g), it was stirred and dissolved at 70 degreeC for 12 hours, and the polyimide solution (6) was obtained.

<Synthesis Example 14>

TCA (4.42 g, 19.7 mmol), DA-3 (3.37 g, 8.0 mmol), DA-8 (2.28 g, 6.0 mmol) and DA-7 (1.42 g, 6.0 mmol) were mixed in NMP (46.0 g) , It was made to react at 60 degreeC for 6 hours, and the polyamic-acid solution was obtained. Mn of this polyamic acid was 11,750 and Mw was 54,510. After adding NMP to the obtained polyamic-acid solution (20.0g) and diluting to 6.5 mass %, acetic anhydride (5.65g) and pyridine (1.09g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 2 hours. This reaction solution was poured into methanol (239 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide powder was 71%, Mn was 10,700, and Mw was 48,300. NMP (22.0g) was added to the obtained polyimide powder (3.0g), it was stirred and dissolved at 70 degreeC for 12 hours, and the polyimide solution (7) was obtained.

<Synthesis Example 15>

BODA (2.50 g, 10.0 mmol), DA-5 (0.99 g, 5.0 mmol), DA-10 (0.66 g, 2.0 mmol), DA-7 (1.43 g, 6.0 mmol) and DA-9 (2.76 g, 7.0 mmol) in NMP (33.4 g) and reacting at 60°C for 3 hours, then adding CBDA (1.93 g, 9.8 mmol) and NMP (7.7 g), reacting at 40°C for 3 hours, and polyamic acid solution got Mn of this polyamic acid was 11,900 and Mw was 44,800. After adding NMP to the obtained polyamic-acid solution (20.0g) and diluting to 6.5 mass %, acetic anhydride (3.96g) and pyridine (1.23g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (270 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide powder was 59%, Mn was 9,260, and Mw was 23,400. After adding NMP (22.0 g) to the obtained polyimide powder (3.0 g) and dissolving by stirring at 70°C for 12 hours, NMP (5.0 g) and BCS (20.0 g) were added and stirred at room temperature for 2 hours to obtain polyimide. Mead solution (8) was obtained.

<Synthesis Example 16>

TCA (4.45 g, 19.8 mmol), DA-5 (1.39 g, 7.0 mmol), DA-10 (1.65 g, 5.0 mmol), DA-7 (0.94 g, 4.0 mmol) and DA-11 (3.03 g, 4.0 mmol) mmol) in NMP (45.9 g) and reacted at 60°C for 6 hours to obtain a polyamic acid solution. Mn of this polyamic acid was 10,360 and Mw was 27,730. After adding NMP to the obtained polyamic-acid solution (20.0g) and diluting to 6.5 mass %, acetic anhydride (7.10g) and pyridine (1.10g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4 hours. This reaction solution was poured into methanol (240 mL), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder. The imidation rate of this polyimide was 68%, Mn was 10,210, and Mw was 23,320. After adding NMP (22.0 g) to the obtained polyimide powder (3.0 g) and dissolving by stirring at 70°C for 12 hours, NMP (5.0 g) and BCS (20.0 g) were added and stirred at room temperature for 2 hours to obtain polyimide. Mead solution (9) was obtained.

The specifications of each polymer obtained in the synthesis example are as shown in Table 1 below.

<Preparation of liquid crystal aligning agent>

[Example 1]

The liquid crystal aligning agent (A-1) was obtained by adding NMP (6.0g) and BCS (8.0g) to the polyamic-acid solution (1) (6.0g) obtained by the synthesis example 1, and stirring at room temperature for 2 hours.

[Example 2, Comparative Examples 1 and 2]

Liquid crystal aligning agents of Example 2 and Comparative Examples 1 and 2 (A -2), (B-1) and (B-2) were obtained.

[Example 3]

The liquid crystal aligning agent (A-3) was obtained by adding NMP (2.0g) and BCS (8.0g) to the polyimide solution (1) (10.0g) obtained by the synthesis example 6, and stirring at room temperature for 2 hours.

[Examples 4 and 5, Comparative Examples 3 to 6]

Example 4 in the same manner as in Example 3 except that the polyimide solutions (2), (5), (3), (4), (6) and (7) were used instead of the polyimide solution (1), respectively. , 5 and the liquid crystal aligning agent (A-4) of Comparative Examples 3-6, (A-5), (B-3) - (B-6) were obtained.

[Example 6]

The polyamic acid solution (5) (7.0 g) obtained in Synthesis Example 5, the polyimide solution (8) (3.0 g) and AD-1 (0.06 g) obtained in Synthesis Example 15 were mixed, and the liquid crystal aligning agent (C-1 ) was obtained.

[Example 7, Comparative Example 7]

Instead of the polyamic acid solution (5), except for using the polyamic acid solutions (6) and (7), respectively, in the same manner as in Example 6, Example 7, the liquid crystal aligning agent (C-2) of Comparative Example 7, (C -3) was obtained.

[Comparative Example 8]

A liquid crystal aligning agent (C -4) was obtained.

In liquid crystal aligning agents (A-1) to (A-5), (B-1) to (B-6), and (C-1) to (C-4) obtained as described above, abnormalities such as cloudiness and precipitation was not observed, and it was confirmed that it was a homogeneous solution. Evaluation of transmittance, production of a liquid crystal cell, evaluation of voltage retention, residual DC voltage, and evaluation of residual image characteristics were performed using the obtained liquid crystal aligning agent.

[Evaluation of transmittance]

Spin the liquid crystal aligning agents (A-1) to (A-4), (B-1) to (B-3), and (C-1) to (C-4) obtained in Examples and Comparative Examples on a quartz substrate It coated and was made to dry for 90 second on a 70 degreeC hot plate. Then, it baked in 230 degreeC IR (infrared ray) type oven for 20 minutes, the coating film of 100 nm in thickness was formed, and the board|substrate with a liquid crystal aligning film was obtained. With this liquid crystal alignment film forming substrate inside, a refractive liquid (contact liquid manufactured by Shimadzu Devices Co., Ltd.) was interposed for the purpose of preventing interference of light using another quartz substrate. For evaluation of the transmittance, UV-3600 (manufactured by Shimadzu Corporation) was used as a measuring device, and the temperature was 25°C and the scan wavelength was measured at 380 to 800 nm. At that time, as a reference, two uncoated quartz substrates with refracting liquid sandwiched therebetween were used. The evaluation is based on transmittance at a wavelength of 550 nm, and the values are shown in Table 3 below.

[Production of liquid crystal display device for evaluating voltage retention and residual DC characteristics]

Using liquid crystal aligning agents (A-1) to (A-5), (B-1) to (B-6), and (C-1) to (C-4) obtained in Examples and Comparative Examples, Production of the liquid crystal cell was performed in the procedure as shown. After spin-coating a liquid crystal aligning agent to the glass substrate with an ITO electrode, and drying for 90 seconds on a 70°C hot plate, it is baked in a 230°C IR oven for 20 minutes to form a liquid crystal alignment film with a film thickness of 100 nm. did Two liquid crystal aligning film forming substrates are prepared, and a bead spacer having a diameter of 4 μm (Nikki Catalyst Chemicals Co., Ltd., Jinsong Ball, SW-D1) is applied on the liquid crystal aligning film of one sheet, and a thermosetting sealing agent is applied. (XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) was printed. Then, after turning the surface of the other board|substrate on the side where the liquid crystal aligning film was formed inside, and bonding together with the previous board|substrate, the sealing compound was hardened and the empty cell was manufactured. Liquid crystal MLC-3023 (manufactured by Merck & Co., Ltd.) was injected into this empty cell by a vacuum injection method to prepare a liquid crystal cell. Next, 10 J/cm ^<2> of UV which passed through the 325 nm or less cut-off filter was irradiated from the outside of the liquid crystal cell in the state which applied the DC voltage of 15V to this liquid crystal cell. In addition, UV illuminance was measured using ORC UV-MO3A. After that, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32/A-1 ) was irradiated for 30 minutes.

[Production of Liquid Crystal Display Element for Evaluating Afterimage Characteristics]

Using liquid crystal aligning agents (A-1) to (A-5), (B-1) to (B-5), and (C-1) to (C-4) obtained in Examples and Comparative Examples, Production of the liquid crystal cell was performed in the procedure as shown. An ITO electrode substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) on which an ITO electrode pattern having a pixel size of 200 μm × 600 μm and a line / space of 3 μm is formed with a liquid crystal aligning agent, and a height After spin-coating on the ITO surface of an ITO electrode-forming glass substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) on which a 3.2 μm photo spacer is patterned, and drying on a hot plate at 70 ° C. for 90 seconds, , It baked in 230 degreeC IR type oven for 20 minutes, and formed the liquid crystal aligning film with a film thickness of 100 nm. In addition, the ITO electrode substrate on which this ITO electrode pattern is formed is divided into 4 parts in a cross checker (checkered pattern) shape, and each of the 4 areas can be independently driven.

Next, a sealing compound (XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) was printed. Then, after turning the surface of the other board|substrate on the side where the liquid crystal aligning film was formed inside, and bonding together with the previous board|substrate, the sealing material was hardened and the empty cell was manufactured. Liquid crystal MLC-3023 (manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced pressure injection method to create a liquid crystal cell. 10 J/cm ^<2> of UV which passed the 325 nm or less cut-off filter was irradiated from the outer side of this liquid crystal cell in the state which applied the DC voltage of 15V to this liquid crystal cell. In addition, UV illuminance was measured using ORC UV-MO3A. After that, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32/A-1 ) was irradiated for 30 minutes.

[Evaluation of voltage retention]

Voltage retention was measured using a liquid crystal cell for voltage retention evaluation after UV irradiation. A voltage of 1 V was applied for 60 μs in a hot air circulation oven at 60° C., the voltage after 16.67 msec was measured, and how much voltage was maintained was calculated as voltage retention. For the measurement of voltage retention, VHR-1 manufactured by Toyo Technica was used. The values are shown in Table 3 below. The higher the value, the better.

[aging]

The liquid crystal cell after the PSA process was left to stand for 3 to 7 days in a high-temperature, high-humidity oven set to 85°C and 85% humidity, and aged under high-temperature, high-humidity conditions. At this time, voltage retention was measured at the initial stage, after PSA treatment, and after aging. In addition, a decrease in voltage retention due to aging (Δ(after PSA treatment - after aging)) was calculated. Each result is shown in Table 3 below.

[Evaluation of residual DC voltage]

With respect to the liquid crystal cell for voltage retention evaluation produced above, a 30 Hz, 7.8 Vpp square wave superimposed with 2 V DC was applied at 25 ° C. for 100 hours, and the DC voltage was cut off. The voltage remaining in the liquid crystal cell after 1 hour ( Residual DC voltage) was determined by the flicker cancellation method. This value is an index of afterimage generated by DC accumulation, and when this value is 50 mV or less, the afterimage characteristic is excellent, that is, it was rated as "good", and when it is greater than 50 mV, it was rated as "poor". The results are shown in Table 3 below.

[Afterimage characteristics]

Using the liquid crystal cell for evaluation of residual image characteristics produced above, an alternating voltage of 60 Hz and 20 Vp-p was applied to two diagonal areas among the four pixel areas, and driven at a temperature of 25 ° C. for 168 hours. Thereafter, all four pixel areas were driven with an AC voltage of 5 Vp-p, and the luminance difference of the pixels was visually observed. A state in which the luminance difference could hardly be confirmed was regarded as "good", and a state in which the luminance difference could be confirmed was regarded as "poor". An evaluation result is shown in Table 3.

*1) Aging 3 days, *2) Aging 7 days

As shown in Table 3, in Examples 1 to 4, 6 and 7 containing polyamic acid or polyimide obtained by using diamine having a structure represented by formula (S1) and diamine having a structure represented by formula (2c) Liquid crystal aligning agent (A-1) - (A-4), (C-1), liquid crystal aligning film obtained using (C-2) corresponds Comparative Examples 1-3, 7, 8 liquid crystal aligning agent ( B-1) - (B-3), (C-3), high transmittance|permeability was obtained compared with the liquid crystal aligning film obtained using (C-4). In addition, a 1% difference in transmittance is a significant difference in the art.

Moreover, when the liquid crystal aligning agent obtained in the Example is used, it turns out that the liquid crystal aligning film which has high voltage retention also in voltage retention and evaluation of aging is obtained. Moreover, it turns out that the liquid crystal aligning film which shows favorable characteristics is obtained also in evaluation of residual DC voltage and evaluation of residual image characteristics.

In addition, all the content of the JP Patent application 2020-060306, a claim, drawing, and the abstract for which it applied on March 30, 2020 is referred here, and it takes in as an indication of the specification of this invention.

Claims (16)

A first repeating unit (a1) selected from the group consisting of a repeating unit represented by the following formula (1-a) and a repeating unit represented by the following formula (1-i);
The liquid crystal aligning agent containing the polymer component which has the 2nd repeating unit (a2) chosen from the group which consists of a repeating unit represented by the following formula (2-a) and a repeating unit represented by the following formula (2-i).

(X ₁ and X ₂ represent a tetravalent organic group. Y ₁ represents a divalent organic group having any of the structures represented by the following formulas (S1) to (S3). Y ₂ represents a divalent organic group represented by the following formula (2c) Represents an organic group. Two R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent organic group. Two Z ₁ and Z ₂ each independently represent a hydrogen atom or a monovalent organic group.)

(X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, - NH-, -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -, where a1 is an integer from 1 to 15, and A ₁ is -O- or -COO-, and m ₁ is an integer of 1 to 2. G ¹ and G ² are each independently a group consisting of a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms; Represents a divalent cyclic group selected from. Arbitrary hydrogen atoms on the cyclic group may be substituted. m and n are each independently an integer of 0 to 3, and m+n is 1 to 6. R ¹ is carbon atoms represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group ^of 2 to ²⁰ carbon atoms, ^and any hydrogen atom forming R ¹ may be substituted with a fluorine atom. When there are a plurality of G ² , a1, m ₁ and A ₁ , the plurality of X ¹ , X ² , G ¹ , G ² , a1, m ₁ and A ₁ each independently have the above definition.)

(X ³ represents a single bond, -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO-. R ² represents an alkyl group of 1 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ² may be substituted with a fluorine atom.)

(X ⁴ represents -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO-. R ³ represents a structure having a steroid skeleton.)

(R represents a hydrogen atom or a monovalent organic group. * represents a bond.) According to claim 1,
The liquid crystal aligning agent in which the said polymer component contains at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor which has the said repeating unit (a1) and the said repeating unit (a2) in the same molecule, and its imidation polymer. According to claim 1,
The polymer component is at least one polymer (P-a1) selected from the group consisting of a polyimide precursor having the repeating unit (a1) and an imidized polymer thereof, and a polyimide precursor having the repeating unit (a2) And the liquid crystal aligning agent containing the mixture of the at least 1 sort(s) of polymer (P-a2) chosen from the group which consists of the imidation polymer. According to any one of claims 1 to 3,
In the formula (1-a) and the formula (1-i), Y ₁ is a divalent organic group derived from diamine represented by formula (d1) or formula (d2) below.

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m - O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m represents a divalent organic group of -OCO- m is an integer of 1 to 8. Y is the formula (S1 ) to (S3). In the above formula (d2), two Ys may be the same as or different from each other.) According to any one of claims 1 to 4,
The liquid crystal aligning agent which is any of the structures where the structure represented by the said formula (S1) is represented by following formula (S1-1) - (S1-7).

(R ¹ represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms. X ^p is -(CH ₂ ) _a - (a is an integer of 1 to 15 is), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO- A ₁ is an oxygen atom or -COO-* (provided that the bond to which “*” is added binds to (CH ₂ ) _a2 ), and A ₂ is an oxygen atom or *-COO- (provided that, The bond hand appended with “*” represents (CH ₂ ) binds to _a2 ), a ₁ and a ₃ are each independently an integer of 0 or 1, a ₂ is an integer of 1 to 10, and Cy is represents a 1,4-cyclohexylene group or a 1,4-phenylene group.) According to any one of claims 1 to 5,
A liquid crystal aligning agent in which the structure represented by the formula (S3) is a structure represented by the following formula (S3-a).

(X represents formula (X1), formula (X2), or -CH ₂ O-, Col represents formula (Col-1), formula (Col-2) or formula (Col-3), and G represents formula (G1), formula (G2), formula (G3) or formula (G4).) According to any one of claims 1 to 6,
In the formula (2c), R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group, or a phenyl group. According to any one of claims 1 to 7,
In the formulas (2-a) and (2-i), Y ₂ is 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3, A liquid crystal aligning agent which is a group obtained by removing two amino groups from carbazole selected from the group consisting of 6-diaminocarbazole and 9-phenyl-3,6-diaminocarbazole. According to any one of claims 1 to 8,
The liquid crystal aligning agent in which the said polymer component further has the 3rd repeating unit (a3) chosen from the group which consists of a repeating unit represented by the following formula (3-a), and a repeating unit represented by the following formula (3-i).

(X ₃ represents a tetravalent organic group. Y ₃ represents a divalent organic group, other than a divalent organic group having a structure represented by the formulas (S1) to (S3) and a divalent organic group represented by the formula (2c) Represents a divalent organic group of 2 pieces of R ₃ and 2 pieces of Z ₃ have the same meaning as R ₁ and Z ₁ in the formula (1-a), respectively.) According to claim 9,
At least one type of polymer (P-a1+a2 ) and at least one polymer selected from the group consisting of a polyimide precursor having the first repeating unit (a1) and the third repeating unit (a3) in the same molecule and an imidized polymer thereof (P-a1+a3) A liquid crystal aligning agent containing a mixture. According to any one of claims 1 to 10,
At least one selected from the group consisting of a polyimide precursor obtained by using a tetracarboxylic acid component in which the polymer component contains a tetracarboxylic dianhydride represented by the following formula (3) or a derivative thereof, and an imidized polymer thereof The liquid crystal aligning agent comprised from the polymer of.

(X represents a structure selected from the group consisting of (x-1) to (x-13) below.)

(R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and a fluorine-containing carbon atom of 1 to 6 represents a monovalent organic group or a phenyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently , represents a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl group, or amide group *1 is a bond bonded to one acid anhydride group, *2 is a bond bonded to the other acid anhydride group In the above formula (x-13), two A ₂ may be the same or different.) According to any one of claims 1 to 11,
The liquid crystal aligning agent further contains at least one crosslinkable compound selected from the group consisting of a compound having an isocyanate group or a cyclocarbonate group, a compound having a lower alkoxyalkyl group, and a compound having a block isocyanate group. . According to claim 3,
The liquid crystal aligning agent whose mass ratio of content of the said polymer (P-a2) with respect to content of the said polymer (P-a1) is 5/95 - 95/5. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-13. A liquid crystal display element provided with the liquid crystal aligning film of Claim 14. The liquid crystal aligning agent according to any one of claims 1 to 13 is coated on a pair of substrates having a conductive film to form a coating film, and the liquid crystal is disposed so that the coating film faces each other through a layer of liquid crystal molecules. A method of manufacturing a liquid crystal display element in which a cell is formed and the liquid crystal cell is irradiated with light in a state in which a voltage is applied between conductive films of the pair of substrates.