WO2015072554A1

WO2015072554A1 - Liquid crystal aligning agent, and liquid crystal display element using same

Info

Publication number: WO2015072554A1
Application number: PCT/JP2014/080237
Authority: WO
Inventors: 淳彦萬代; 勇歩野口
Original assignee: 日産化学工業株式会社
Priority date: 2013-11-15
Filing date: 2014-11-14
Publication date: 2015-05-21
Also published as: CN105723276B; TW201531527A; KR102391044B1; JPWO2015072554A1; JP6520716B2; KR20160081922A; CN105723276A; TWI637029B

Abstract

Provided is a liquid crystal aligning agent that can increase adhesiveness between a sealing agent and a liquid crystal alignment film, and can suppress display anomalies that may occur under high temperature and high humidity conditions in liquid crystal display elements near the frame. The liquid crystal alignment agent contains a component (A), a component (B), and an organic solvent. Component (A): at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by formula (1), and an imidized polymer of said polyimide precursor. Component (B): a compound having a hydroxyalkylamide group. (X₁ independently represents a tetravalent organic group; Y₁ represents a divalent organic group; R₁ represents a hydrogen atom or a C1-5 alkyl group; and A₁ and A₂ independently represent a hydrogen atom, a C1-10 alkyl group, a C2-10 alkenyl group, or a C2-10 alkynyl group, and said groups may have a substituent.)

Description

Liquid crystal aligning agent and liquid crystal display element using the same

The present invention relates to a liquid crystal alignment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

A liquid crystal display element is known as a lightweight, thin, and low power consumption display device. In recent years, high-definition liquid crystal display elements for mobile phones and tablet terminals, which have rapidly expanded their market share, have made remarkable developments that require high display quality.
A liquid crystal display element is configured by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates. That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on a surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. Furthermore, the pretilt angle of the liquid crystal can be controlled by the liquid crystal alignment film. A method of increasing the pretilt angle by mainly selecting a polyimide structure (see Patent Document 1) and a method of decreasing the pretilt angle (see Patent Document 2) are known.

Japanese Unexamined Patent Publication No. 09-278724 Japanese Unexamined Patent Publication No. 10-123532

In recent years, liquid crystal display elements have been used for mobile applications such as smartphones and mobile phones. In these applications, in order to secure as large a display surface as possible, a so-called narrow frame is required in which the width of the sealant used for bonding the substrates of the liquid crystal display elements is narrower than in the past. Along with the narrowing of the frame of the panel, the application position of the sealant used for manufacturing the liquid crystal display element is applied to the position in contact with the end of the liquid crystal alignment film or the upper part of the liquid crystal alignment film. However, since polyimide has no or few polar groups, there is a problem that a covalent bond is not formed between the sealing agent and the liquid crystal alignment film surface, resulting in insufficient adhesion between the substrates. In such a case, particularly when used under high-temperature and high-humidity conditions, water tends to be mixed from between the sealant and the liquid crystal alignment film, and display unevenness occurs near the frame of the liquid crystal display element. Arise. Therefore, it becomes a problem to improve the adhesion (adhesiveness) between the polyimide-based liquid crystal alignment film and the sealant or the substrate. Improvements in the adhesive properties of the liquid crystal alignment film as described above and the substrate must be achieved without degrading the liquid crystal alignment properties and electrical properties of the liquid crystal alignment film. It is required to improve.
The main object of the present invention is to provide a liquid crystal aligning agent that can improve the adhesion between the liquid crystal aligning film and the sealing agent or the substrate without deteriorating the liquid crystal aligning property and electrical characteristics.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the gist of the present invention is as follows.
1. The liquid crystal aligning agent characterized by containing the following (A) component, (B) component, and an organic solvent.
(A) Component: At least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (1) and an imidized polymer of the polyimide precursor.
(B) Component: A compound having a hydroxyalkylamide group.

(X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group. R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are Each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and these groups have a substituent. May be good.)

2. (B) The liquid crystal aligning agent of said 1 whose component is a compound which has two or more hydroxyalkylamide groups.
3. 3. The liquid crystal aligning agent according to 1 or 2, wherein the component (B) is contained in an amount of 0.1 to 20% by mass with respect to the component (A).
4). (B) The liquid crystal aligning agent in any one of said 1-3 whose component is represented by following formula (2).

(X ₂ is an n-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and n is an integer of 2 to 6. R ₂ and R ₃ are Each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and these groups may have a substituent. (At least one of R ₂ and R ₃ has a hydroxy group as a substituent.)

5. 5. The liquid crystal aligning agent according to any one of 1 to 4 above, wherein at least one of R ₂ and R ₃ is the following formula (3).

(R ₄ to R ₇ are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.)

6). 6. The liquid crystal aligning agent according to any one of 1 to 5 above, wherein the atom directly bonded to the carbonyl group in X ₂ is a carbon atom that does not form an aromatic ring.
7). 7. The liquid crystal aligning agent according to any one of 1 to 6 above, wherein X ₂ is an aliphatic hydrocarbon group.
8). 8. The liquid crystal aligning agent according to any one of 1 to 7 above, wherein R ₂ and R ₃ are compounds represented by the following formula (4).

9. 9. The liquid crystal aligning agent according to any one of 1 to 8 above, wherein the component (B) is any one of the following compounds.

10. 10. The liquid crystal aligning agent according to any one of 1 to 9 above, wherein X ₁ is at least one structure selected from the group consisting of the following formulas (X-1) to (X-14).

(R ₈ to R ₁₁ are each independently 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 alkenyl group, or a phenyl group.)

11. 11. The liquid crystal aligning agent according to any one of 1 to 10 above, wherein X ₁ is at least one structure selected from the group consisting of the following formulas (X1-1) and (X1-2).

12 12. The liquid crystal aligning agent according to any one of 1 to 11 above, wherein Y ₁ is at least one structure selected from the group consisting of the following formulas (5) and (6).

(R ₁₂ is a single bond or a divalent organic group having 1 to 30 carbon atoms, R ₁₃ is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms, and a is 1 to 4 In the case where a is 2 or more, (R ₁₂ -R ₁₃ ) may be the same as or different from each other, and R ₁₄ is a single bond, —O—, —S—, —NR ₁₅ —, An amide bond, an ester bond, a urea bond, or a divalent organic group having 1 to 40 carbon atoms, and R ₁₅ is a hydrogen atom or a methyl group.)

13. 13. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of 1 to 12 above and baking it.
14 A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of the above 1 to 12 and irradiating polarized radiation having a wavelength of 100 to 400 nm.
15. 15. The liquid crystal alignment film as described in 13 or 14 above, wherein the film thickness after firing is from 5 to 300 nm.
16. 16. A liquid crystal display device comprising the liquid crystal alignment film according to any one of 13 to 15 above.
17. 16. A lateral electric field drive type liquid crystal display device comprising the liquid crystal alignment film as described in any one of 13 to 15 above.

By using the liquid crystal aligning agent of the present invention, the adhesion between the sealing agent and the liquid crystal aligning film is improved, and the occurrence of display unevenness near the frame of the liquid crystal display element can be suppressed under high temperature and high humidity conditions. Can be obtained. Thereby, the liquid crystal display element having the liquid crystal alignment film of the present invention can solve the display unevenness in the vicinity of the frame by increasing the adhesiveness between the sealant and the liquid crystal alignment film, and can be a large-screen and high-definition liquid crystal display.
Furthermore, by using the liquid crystal aligning agent of the present invention, it is possible to achieve the above-mentioned problems without deteriorating the liquid crystal alignment properties and electrical characteristics.

<(A) component>
The component (A) contained in the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (1) and an imidized polymer of the polyimide precursor. The polymer.

In the formula (1), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group.
R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
A ₁ and A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and these groups are substituted It may have a group.
Specific examples of the alkyl group for R ₁ include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group. Etc. From the viewpoint of ease of imidization by heating, R ₁ is preferably a hydrogen atom or a methyl group.

In the formula (1), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. Two or more kinds of X ₁ may be mixed in the polyimide precursor. Specific examples of X ₁ include the structures of the following formulas (X-1) to (X-44).

R ₈ to R ₁₁ in the formula (X-1) are each independently 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, or phenyl. It is a group. When R ₈ to R ₁₁ have a bulky structure, the liquid crystal orientation may be lowered, so a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable.

In the formula (1), X ₁ is preferably a structure selected from (X-1) to (X-14) from the viewpoint of availability of monomers.
Since the reliability of the obtained liquid crystal alignment film can be further improved, the structure of X _{1 is} a structure consisting only of an aliphatic group such as (X-1) to (X-7) and (X-10). And the structure represented by (X-1) is more preferable. Further, in order to show good liquid crystal alignment, the structure of X ₁ is more preferably the following formula (X1-1) or (X1-2).

A preferred ratio of the structure selected from the above (X-1) to (X-14) is 20 mol% or more, more preferably 60 mol% or more, further preferably 80 mol% or more of the entire X _1. .

In the formula (1), A ₁ and A ₂ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 2 to Or an alkynyl group having 2 to 10 carbon atoms which may have a substituent.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group.

Examples of the alkenyl group include those in which one or more CH ₂ —CH ₂ structures present in the above alkyl group are replaced with a CH═CH structure, and more specifically, vinyl groups, allyl groups, 1- Examples include propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like.
Alkynyl groups include those in which one or more CH ₂ —CH ₂ structures present in the alkyl group are replaced with C≡C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -Propynyl group and the like.

The above alkyl group, alkenyl group, and alkynyl group may have a substituent, and may further form a ring structure by the substituent. Note that forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.
Examples of substituents include halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls. Group, alkenyl group, alkynyl group and the like.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
A phenyl group is mentioned as an aryl group which is a substituent. This aryl group may be further substituted with the other substituent described above.
The organooxy group as a substituent can have a structure represented by —O—R. R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above. Specific examples of the organooxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.

The organothio group as a substituent can have a structure represented by —S—R. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These Rs may be further substituted with the substituent described above. Specific examples of the organothio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
The organosilyl group as a substituent can have a structure represented by —Si— (R) ₃ . R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above. Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.

The acyl group as a substituent can have a structure represented by —C (O) —R. Examples of R include the alkyl groups, alkenyl groups, and aryl groups described above. These Rs may be further substituted with the substituent described above. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
As the ester group which is a substituent, a structure represented by —C (O) O—R or —OC (O) —R can be shown. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These Rs may be further substituted with the substituent described above.

The thioester group which is a substituent can have a structure represented by —C (S) O—R or —OC (S) —R. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These Rs may be further substituted with the substituent described above.
The phosphate group which is a substituent can have a structure represented by —OP (O) — (OR) ₂ . R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.

Examples of the substituent amide group include —C (O) NH ₂ , —C (O) NHR, —NHC (O) R, —C (O) N (R) ₂ , —NRC (O) R. The structure represented by can be shown. The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.
Examples of the alkyl group as a substituent include the same alkyl groups as described above. This alkyl group may be further substituted with the other substituent described above.

Examples of the alkenyl group as a substituent include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.
Examples of the alkynyl group that is a substituent include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.
In general, when a bulky structure is introduced, there is a possibility that the reactivity of the amino group and the liquid crystal orientation may be lowered. Therefore, as A ₁ and A ₂ , a hydrogen atom or a carbon atom that may have a substituent is 1 An alkyl group of 1 to 5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

In Formula (1), Y ₁ is a divalent organic group derived from diamine, and its structure is not particularly limited. Specific examples of the structure of Y ₁ include the following (Y-1) to (Y-118).

(In the formula (Y-109), m and n are each an integer of 1 to 11, and m + n is an integer of 2 to 12. In the formula (Y-114), h is an integer of 1 to 3. And in formulas (Y-111) and (Y-117), j is an integer from 0 to 3.)

The structure of Y ₁ is more preferably at least one structure selected from the group consisting of the following formulas (5) and (6) from the viewpoint of liquid crystal alignment properties and pretilt angle of the obtained liquid crystal alignment film.

In the formula (5), R ₁₂ is a single bond or a divalent organic group having 1 to 30 carbon atoms, and R ₁₃ is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms.
a is an integer of 1 to 4, and when a is 2 or more, (R ₁₂ -R ₁₃ ) may be the same as or different from each other.
R ₁₄ in Formula (6) is a single bond, —O—, —S—, —NR ₁₅ —, an amide bond, an ester bond, a urea bond, or a divalent organic group having 1 to 40 carbon atoms, R ₁₅ is a hydrogen atom or a methyl group.

As a specific example of Y ₁ represented by the formulas (5) and (6), a highly linear structure can enhance the alignment of the liquid crystal when the liquid crystal alignment film is used. ), (Y-21), (Y-22), (Y-23), (Y-25), (Y-43) to (Y-46), (Y-48), (Y-63), (Y-71) to (Y-75), (Y-98), (Y-99), (Y-100), (Y-118) and the like are preferable.
The proportion of the above structure that can enhance the liquid crystal orientation is preferably 20 mol% or more of Y ₁ as a whole, more preferably 60 mol% or more, and further preferably 80 mol% or more. Usually, it is preferably 90 mol% or less.

When it is desired to increase the pretilt angle of the liquid crystal when the liquid crystal alignment film is used, Y ₁ may have a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination of these in the side chain. preferable. Examples of such Y ₁ include (Y-76) to (Y-97).
The proportion of the above structure for increasing the pretilt angle is preferably 1 to 30 mol%, more preferably 1 to 20 mol% of the entire Y ₁ .
The polyimide precursor used in the present invention is obtained by a reaction between a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyamic acid and polyamic acid ester.

<(B) component>
The component (B) contained in the liquid crystal aligning agent of the present invention is a compound having a hydroxyalkylamide group. As long as the component (B) has a hydroxyalkylamide group, other structures are not particularly limited, but from the viewpoint of availability, a preferred example includes a compound represented by the following formula (2). .

X ₂ is an n-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group. n is an integer of 2 to 6.

R ₂ and R ₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted alkenyl group having 2 to 4 carbon atoms, or An alkynyl group having 2 to 4 carbon atoms which may have a substituent. Further, at least one of R ₂ and R ₃ represents a hydrocarbon group substituted with a hydroxy group.
Among them, wherein in X ₂ (2), directly attached to atoms in a carbonyl group, it is preferable from the viewpoint of the liquid crystal orientation is a carbon atom, which do not form an aromatic ring. X ₂ in the formula (2) is preferably an aliphatic hydrocarbon group and more preferably 1 to 10 carbon atoms from the viewpoint of liquid crystal alignment and solubility.
In the formula (2), n is preferably 2 to 4 from the viewpoint of solubility.

In formula (2), at least one of R ₂ and R ₃ is preferably a structure represented by the following formula (3) from the viewpoint of reactivity, and a structure represented by the following formula (4) More preferably.

In the formula (3), R ₄ to R ₇ are each independently a hydrocarbon group substituted with a hydrogen atom, a hydrocarbon group, or a hydroxy group.

Specific preferred examples of the component (B) include the following compounds.

When the component (B) is too much, the liquid crystal orientation and the pretilt angle are affected, and when it is too little, the effect of the present invention cannot be obtained. Therefore, the content of the component (B) is preferably 0.1 to 20% by mass and more preferably 1 to 10% by mass with respect to the component (A).

<Polyimide precursor-production of polyamic acid>
The polyamic acid which is a polyimide precursor used in the present invention can be produced by the following method.
Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of a solvent at −20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.

The reaction of the diamine component and the tetracarboxylic acid component is usually performed in a solvent. The solvent used at that time is not particularly limited as long as the produced polyimide precursor is soluble. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, or 1,3-dimethyl-imidazolidinone Can be mentioned.
When the solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3]. Can be used.

In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and the formula [D-3] In the formula, D ³ represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyimide precursor, it is preferable to use a dehydrated and dried solvent.
The concentration of the polyamic acid polymer in the reaction system is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
The polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the following poor solvent while thoroughly stirring the reaction solution. In addition, by performing precipitation several times, washing with a poor solvent, and then drying at normal temperature or heat, a purified polyamic acid powder can be obtained. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

<Polyimide precursor-production of polyamic acid ester>
The polyamic acid ester which is a polyimide precursor used in the present invention can be produced by the following production method (1), (2) or (3).
(1) When manufacturing from polyamic acid A polyamic acid ester can be manufactured by esterifying the polyamic acid manufactured as mentioned above. Specifically, it is produced by reacting a polyamic acid and an esterifying agent in the presence of a solvent at −20 to 150 ° C., preferably 0 to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours. can do.

The esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents, more preferably 2 to 2.5 molar equivalents, per 1 mol of the polyamic acid repeating unit.

Examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, or 1,3-dimethyl-imidazo Lysinone is mentioned. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the above formulas [D-1] to [D-3] The indicated solvents can be used.

These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyimide precursor, it is preferable to use a dehydrated and dried solvent.
The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone in view of polymer solubility. These may be used alone or in combination of two or more. Good. The concentration at the time of production is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.

(2) Production by reaction of tetracarboxylic acid diester dichloride and diamine Specifically, tetracarboxylic acid diester dichloride and diamine are −20 to 150 ° C., preferably 0 to 50 ° C. in the presence of a base and a solvent. It can be produced by reacting at 30 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours.
As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The amount of the base added is preferably 2 to 4 times mol, preferably 2.5 to 3 times the amount of tetracarboxylic acid diester dichloride, from the viewpoint of easy removal and high molecular weight. Mole is more preferred.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination. The polymer concentration at the time of production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the production of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

(3) When producing from tetracarboxylic acid diester and diamine Specifically, tetracarboxylic acid diester and diamine are 0 to 150 ° C., preferably 0 to 100 ° C. in the presence of a condensing agent, a base, and an organic solvent. In the above, it can be produced by reacting for 30 minutes to 24 hours, preferably 3 to 15 hours.
Condensation agents include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinyl Methylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like can be used. The addition amount of the condensing agent is preferably 2 to 3 times by mole, more preferably 2 to 2.5 times by mole with respect to the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base added is preferably 2 to 4 times the mol of the diamine component from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
In the above reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times mol, more preferably 0 to 0.5 times mol based on the diamine component.
Among the methods for producing the three polyamic acid esters, since the high molecular weight polyamic acid ester is obtained, the production method (1) or (2) is particularly preferable.
The polyamic acid ester solution obtained as described above can be polymerized by being poured into the following poor solvent while being well stirred. Precipitation is performed several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyamic acid ester powder. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

<Polyimide>
The polyimide used in the present invention can be produced by imidizing the aforementioned polyamic acid ester or polyamic acid. When a polyimide is produced from a polyamic acid ester, chemical imidization in which a basic catalyst is added to a polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in a solvent is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.
Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in the presence of a basic catalyst in a solvent. As a solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.

The temperature for carrying out the imidization reaction is −20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time is 1 to 100 hours, preferably 1 to 5 hours.
The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid ester group.
The imidation rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, reaction time and the like.
Since the added catalyst or the like remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, and redissolved with a solvent, and the liquid crystal aligning agent of the present invention. It is preferable that

When manufacturing a polyimide from a polyamic acid, the chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.
Chemical imidation can be performed by stirring the polyamic acid to be imidized in a solvent in the presence of a basic catalyst and an acid anhydride. As a solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
The temperature for carrying out the imidization reaction is −20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time is 1 to 100 hours, preferably 1 to 5 hours.
The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times of the amic acid group, preferably 3 to 30 mole times. The imidation rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, reaction time and the like.

In the imidation reaction of polyamic acid ester or polyamic acid, an imidization accelerator can be used. Although the specific example of an imidation accelerator is shown below, it is not limited to these.

D in the above formulas (B-1) to (B-17) is each independently a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. A plurality of D present in the formulas (B-14) to (B-17) may be the same as or different from each other. The higher the basicity after deprotection by heating, the higher the effect of promoting imidization of the polyamic acid ester and polyamic acid. Therefore, (B-14) to (B-17) are preferred from the viewpoint of further enhancing the thermal imidization promoting effect, and (B-17) is particularly preferred.

In the solution after the imidation reaction of the polyamic acid ester or polyamic acid, the added catalyst and the like remain, so the obtained imidized polymer is recovered by the means described below and redissolved in a solvent. The liquid crystal aligning agent of the present invention is preferable.
The polyimide solution obtained as described above can be polymerized by pouring into the following poor solvent while stirring well. Precipitation is performed several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyamic acid ester powder.
The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

<Liquid crystal aligning agent>
The liquid crystal aligning agent used in the present invention is at least one polymer selected from the group consisting of the polyimide precursor as the component (A) and an imidized polymer of the polyimide precursor (hereinafter referred to as a heavy polymer having a specific structure). And a compound having a hydroxyalkylamide group as the component (B) are in the form of a solution dissolved in a solvent.
The molecular weight of the specific structure polymer is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

The concentration of the polymer in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed, but from the point of forming a uniform and defect-free coating film, 1 The content is preferably at least 10% by mass, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution. Particularly preferred is 3 to 6.5% by mass.
The solvent (also referred to as a good solvent) contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the specific structure polymer is uniformly dissolved.
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone is preferably used.
Furthermore, when the solubility of the polymer of the present invention in a solvent is high, it is preferable to use a solvent represented by the above formula [D-1] to formula [D-3].
The good solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99% by mass of the whole solvent contained in the liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.

As long as the effects of the present invention are not impaired, the liquid crystal aligning agent of the present invention uses a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied. it can. Although the specific example of a poor solvent is given to the following, it is not limited to these examples.
For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate Tar, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, milk Methyl, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropion Ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, lactate n-propyl ester, lactate n-butyl ester, lactic acid Examples thereof include isoamyl esters and solvents represented by the above formulas [D-1] to [D-3].
Of these, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

The poor solvent is preferably 1 to 80% by mass of the total solvent contained in the liquid crystal aligning agent, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass.
In the liquid crystal aligning agent of the present invention, in addition to the above, as long as the effects of the present invention are not impaired, a polymer other than the polymer described in the present invention, the electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film Dielectric or conductive material for changing characteristics, silane coupling agent for improving adhesion between liquid crystal alignment film and substrate, crosslinkability for increasing hardness and density of liquid crystal alignment film When firing the compound, and further, the coating film, an imidization accelerator for the purpose of efficiently proceeding imidization by heating of the polyimide precursor may be added.

<Liquid crystal alignment film>
<Method for producing liquid crystal alignment film>
The liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent to a substrate, drying and baking. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as a glass substrate, a silicon nitride substrate, an acrylic substrate, or a polycarbonate substrate can be used. Further, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplification of the process. In the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light, such as aluminum, can be used.

Examples of the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention. Usually, in order to sufficiently remove the contained solvent, it is dried at 50 to 120 ° C., preferably 60 to 100 ° C. for 1 to 10 minutes, preferably 2 to 5 minutes, and then 150 to 300 ° C., preferably Is baked at 200 to 240 ° C. for 5 to 120 minutes, preferably 10 to 30 minutes. The thickness of the coating film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is 5 to 300 nm, preferably 10 to 200 nm.

Examples of a method for aligning the obtained liquid crystal alignment film include a rubbing method and a photo-alignment processing method.
The rubbing process can be performed using an existing rubbing apparatus. Examples of the material of the rubbing cloth at this time include cotton, nylon, and rayon. As the conditions for rubbing treatment, generally, conditions of a rotational speed of 300 to 2000 rpm, a feed speed of 5 to 100 mm / s, and a pushing amount of 0.1 to 1.0 mm are used. Thereafter, the residue generated by rubbing is removed by ultrasonic cleaning using pure water or alcohol.

As a specific example of the photo-alignment treatment method, the surface of the coating film is irradiated with radiation deflected in a certain direction, and in some cases, a heat treatment is performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. Is mentioned. As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal orientation, radiation may be irradiated while heating the coated substrate at 50 to 250 ° C. Dose of the radiation is preferably 1 ~ 10,000mJ / cm ^2, particularly preferably 100 ~ 5,000mJ / cm ^2. The liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.
A higher extinction ratio of polarized ultraviolet light is preferable because higher anisotropy can be imparted. Specifically, the extinction ratio of linearly polarized ultraviolet light is preferably 10: 1 or more, and more preferably 20: 1 or more.
In the above, the film irradiated with polarized radiation may then be contact-treated with a solvent containing at least one selected from the group consisting of water and organic solvents.

The solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves a decomposition product generated by light irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- Examples include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like. Two or more of these solvents may be used in combination.
In view of versatility and safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is more preferable. Water, 2-propanol, or a mixed solvent of water and 2-propanol is particularly preferable.

In the present invention, the contact treatment of the film irradiated with polarized radiation and the solution containing the solvent is performed by a method such that the film and the liquid are preferably in sufficient contact with each other, such as immersion treatment or spraying treatment. It is. Among them, a method of immersing in a solution containing a solvent, preferably for 10 seconds to 1 hour, more preferably for 1 to 30 minutes is preferable. The contact treatment may be performed at normal temperature or preferably at 10 to 80 ° C., more preferably at 20 to 50 ° C. Moreover, a means for enhancing contact such as ultrasonic waves can be applied as necessary.
After the contact treatment, in order to remove the solvent in the used solution, rinsing (rinsing) with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, or drying is performed, or both. It's okay.

Furthermore, the film subjected to the contact treatment with the solution containing the solvent may be heated at 150 ° C. or higher for the purpose of drying the solvent and reorienting the molecular chains in the film.
The heating temperature is preferably 150 to 300 ° C. A higher temperature promotes reorientation of molecular chains. However, if the temperature is too high, molecular chains may be decomposed. Therefore, the heating temperature is more preferably 180 to 250 ° C., and particularly preferably 200 to 230 ° C.
If the heating time is too short, there is a possibility that the effect of molecular chain reorientation may not be obtained. If it is too long, the molecular chain may be decomposed. 1 to 10 minutes is more preferable.

<Liquid crystal display element>
The liquid crystal display element of this invention comprises the liquid crystal aligning film obtained by the manufacturing method of the said liquid crystal aligning film.
In the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method for producing a liquid crystal alignment film, a liquid crystal cell is produced by a known method, and a liquid crystal cell is used. This is a display element.
As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Note that an active matrix liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.

First, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes may be ITO electrodes, for example, and are patterned so as to display a desired image. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film made of SiO ₂ —TiO ₂ formed by a sol-gel method.
Next, the liquid crystal alignment film of the present invention is formed on each substrate. Next, the other substrate is superposed on one substrate so that the alignment film surfaces face each other, and the periphery is bonded with a sealant. In order to control the substrate gap, a spacer is usually mixed in the sealing material. In addition, it is preferable that spacers for controlling the substrate gap are also sprayed on the in-plane portion where no sealing material is provided. A part of the sealing material is provided with an opening that can be filled with liquid crystal from the outside.

Next, a liquid crystal material is injected into a space surrounded by two substrates and the sealing material through an opening provided in the sealing material. Thereafter, the opening is sealed with an adhesive. For the injection, a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used. Next, a polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer. By passing through the above process, the liquid crystal display element of this invention is obtained.
In the present invention, as the sealing agent, for example, a resin having a reactive group such as an epoxy group, an acryloyl group, a (meth) acryloyl group, a hydroxyl group, an allyl group, or an acetyl group, which is cured by ultraviolet irradiation or heating is used. . In particular, it is preferable to use a cured resin system having reactive groups of both an epoxy group and a (meth) acryloyl group.

In the sealing agent of the present invention, an inorganic filler may be blended for the purpose of improving adhesiveness and moisture resistance. The inorganic filler that can be used is not particularly limited. Specifically, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid. Barium, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, Examples include asbestos. Preferably, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, or silicic acid Aluminum is mentioned. Two or more of the above inorganic fillers may be mixed and used.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not construed as being limited to these examples. The abbreviations of the compounds used are shown below.
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve IPA: 2-propanol NEP: N-ethyl-2-pyrrolidone PB: propylene glycol monobutyl ether DA-2: represented by the following formula (DA-2) Compound DA-3: Compound DA-4 represented by the following formula (DA-3): Compound DA-5 represented by the following formula (DA-4): p-phenylenediamine DA-6: 3, 5 -Diaminobenzoic acid DA-7: 4,4'-diaminodiphenylmethane DA-8: 4,4'-diaminodiphenylamine DA-9: 1,3-bis (4-aminophenoxy) propane DA-10: 1,5- Bis (4-aminophenoxy) pentane DA-11: Compound DA-12 represented by the following formula (DA-11): In the following formula (DA-12) Compound DA-13 represented: 4,4′-ethylenedianiline DA-14: Compound DA-15 represented by the following formula (DA-14): Compound DA- represented by the following formula (DA-15) 16: Compound DA-17 represented by the following formula (DA-16): Compound DA-18 represented by the following formula (DA-17): Compound DA-19 represented by the following formula (DA-18): Compound DA-20 represented by the following formula (DA-19): Compound DA-21 represented by the following formula (DA-20): Compound DA-22: 4- represented by the following formula (DA-21) Aminobenzylamine DA-23: 3-aminobenzylamine DA-24: N, N-diallyl-2,4-diaminoaniline

DC-1: 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride DC-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride DC-3: 3 3 ′, 4,4′-biphenyltetracarboxylic dianhydride DC-4: 1,2,3,4-butanetetracarboxylic dianhydride DC-5: bicyclo [3.3.0] octane-2, 4,6,8-tetracarboxylic dianhydride DC-6: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride DC-7: pyromellitic anhydride DC-8: Compound represented by the following formula (DC-8) DE-1: Compound additive represented by the following formula (DE-1) A: Compound represented by the following formula (Primid XL552 (manufactured by Emschemie) )
Additive B: Compound represented by the following formula (Primid SF4510 (manufactured by Ms Chemie)
Additive C: Dipentaerythritol hexaacrylate represented by the following formula (manufactured by Daicel-Cytec)
Additive D: 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane represented by the following formula: In the following chemical formula, Me is a methyl group, Bu is an n-butyl group, Boc Represents a t-butoxy group.

The measuring method of each characteristic is as follows.
[viscosity]
The viscosity of the polyamic acid ester and the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.). The temperature was measured at 25 ° C.
[Molecular weight]
The molecular weights of the polyamic acid ester and the polyamic acid were measured by a GPC (room temperature gel permeation chromatography) device, and converted into a polyethylene glycol (polyethylene oxide) conversion value as a number average molecular weight (hereinafter, also referred to as Mn) and a weight average molecular weight (hereinafter, Mw) was calculated.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation and Polymer Laboratories Polyethylene glycol manufactured (peak top molecular weight (Mp) of about 12,000, 4,000, and 1,000) was used. In order to avoid overlapping of peaks, the measurement was performed by mixing four types of 900,000, 100,000, 12,000, and 1,000, and 3 of 150,000, 30,000, and 4,000. Two samples of mixed types were run separately.

[Measurement of imidization rate]
The imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) (0 .53 mL) was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).

The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Synthesis Example 1>
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.92 g (27.0 mmol) of diamine DA-5 and 0.71 g (3.0 mmol) of diamine DA-2 were weighed, and 81.76 g of NMP was measured. In addition, the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 6.46 g (28.8 mmol) of carboxylic dianhydride DC-1 was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 4 hours. As a result, a polyamic acid solution (PAA-1) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 230 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 11,131 and Mw = 30,009.

<Synthesis Example 2>
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.27 g (21.0 mmol) of diamine DA-5 and 2.69 g (9.0 mmol) of diamine DA-4 were weighed, and 61.87 g of NMP. In addition, the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 5.59 g (28.5 mmol) of carboxylic dianhydride DC-2 was added, NMP was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at room temperature for 4 hours. Thus, a solution of polyamic acid solution (PAA-2) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 410 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 9,042 and Mw = 19,958.

<Synthesis Example 3>
In a 2000 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 110.47 g (452 mmol) of diamine DA-3 and 18.94 g (79.5 mmol) of DA-2 were weighed, 1587 g of NMP was added, and nitrogen was added. The mixture was stirred and dissolved while feeding. While stirring this diamine solution, 111.18 g (496 mmol) of carboxylic dianhydride DC-1 was added, NMP was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at 40 ° C. for 20 hours. A solution of polyamic acid (PAA-3) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 183 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 1356 and Mw = 25544.

<Synthesis Example 4>
In a 3000 mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, 950 g of the obtained polyamic acid solution (PAA-3) was weighed, 678 g of NMP was added, and the mixture was stirred for 30 minutes. 77.11 g of acetic anhydride and 19.92 g of pyridine were added to the obtained polyamic acid solution, and heated at 60 ° C. for 3 hours to perform chemical imidization. The obtained reaction solution was poured into 6600 mL of methanol while stirring, and the deposited precipitate was collected by filtration. Subsequently, the precipitate was washed 3 times with 6600 mL of methanol and twice with 2000 mL of methanol. Subsequently, the obtained resin powder was dried at 60 ° C. for 12 hours to obtain a polyimide resin powder.
The imidation ratio of this polyimide resin powder was 75%, and the molecular weight was Mn = 8156 and Mw = 17408.
In a 200 mL Erlenmeyer flask containing a stir bar, 20.69 g of the obtained polyimide resin powder was weighed, 151.71 g of NMP was added, and the mixture was stirred and dissolved at 40 ° C. for 24 hours. A solution (PI-1) was obtained.

<Synthesis Example 5>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, weigh 4.20 g (17.19 mmol) of diamine DA-3 and 7.70 g (25.81 mmol) of diamine DA-4, and add 158 g of NMP. The mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 12.02 g (40.85 mmol) of carboxylic dianhydride DC-3 was added, NMP was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at room temperature for 24 hours. Thus, a solution of polyamic acid (PAA-4) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 390 mPa · s.
The amount of each component used in the synthesis examples and the obtained polyimide polymer are summarized in Table 1.

[Preparation of liquid crystal aligning agent]
Example 1
In a 20 ml sample tube containing a stir bar, 11.00 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 was weighed, 5.00 g of NMP, 4.00 g of BCS, and N as an imidization accelerator. -Α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine (0.15 g) and additive A (0.06 g) were added, and the mixture was stirred at room temperature for 3 hours. A1 was obtained.
Using this liquid crystal aligning agent A1, a substrate for evaluating adhesion and a liquid crystal cell were prepared in the following procedure.

[Production and evaluation of adhesion evaluation substrate]
<Production of substrate>
Liquid crystal aligning agent A1 was apply | coated by spin coat application | coating to the 30 mm x 40 mm ITO board | substrate. Then, it was dried on an 80 ° C. hot plate for 2 minutes, and then baked in a hot air circulation oven at 230 ° C. for 14 minutes to form a coating film having a thickness of 100 nm. The surface of the coating film was irradiated with 254 nm ultraviolet rays through a polarizing plate at 500 mJ / cm ² and then baked in a hot air circulation oven at 230 ° C. for 14 minutes to obtain a substrate with a liquid crystal alignment film.
Two substrates thus obtained were prepared, a 4 μm bead spacer was applied on the liquid crystal alignment film surface of one substrate, and then a sealing agent (XN-1500T, manufactured by Kyoritsu Chemical Co., Ltd.) was dropped. . Next, bonding was performed so that the liquid crystal alignment film surface of the other substrate was inside, and the overlapping width of the substrates was 1 cm. At that time, the amount of the sealing agent dropped was adjusted so that the diameter of the sealing agent after bonding was 3 mm. The two substrates bonded together were fixed with a clip and then thermally cured at 150 ° C. for 1 hour to produce a substrate for adhesion evaluation.
<Evaluation of adhesion>
The substrate is fixed with a desktop precision universal testing machine (Shimadzu Corp., AGS-X 500N), and the edges of the upper and lower substrates are fixed. ) Was measured.

[Production of FFS Drive Liquid Crystal Cell and Evaluation of Liquid Crystal Orientation]
First, a substrate with electrodes was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the substrate, an IZO electrode having a solid pattern constituting a counter electrode as a first layer is formed. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by the CVD method is formed as the second layer. The second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film. On the second SiN film, a comb-like pixel electrode formed by patterning an IZO film as the third layer is arranged to form two pixels, a first pixel and a second pixel. ing. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.

The pixel electrode of the third layer has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 3 μm, and the distance between the electrode elements is 6 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji. Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.
When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the liquid crystal alignment direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed at an angle of + 10 ° in the first region of the pixel, and the electrode of the pixel electrode is formed in the second region of the pixel. The elements are formed at an angle of -10 °. That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.

Next, after filtering a liquid crystal aligning agent with a 1.0 micrometer filter, the liquid crystal aligning agent was apply | coated to the prepared said board | substrate with an electrode by spin coat application | coating. Subsequently, after drying for 2 minutes on an 80 degreeC hotplate, it baked for 14 minutes in 230 degreeC hot-air circulation type oven, and formed the coating film with a film thickness of 100 nm. The coated surface was irradiated with 500 mJ / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. In addition, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
Set the two substrates as a set, print the sealant on the substrate, and bond the other substrate so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is cured. An empty cell was produced. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell.
The alignment state of the liquid crystal cell was observed with a polarizing microscope (Nikon Corporation, ECLIPSE E600WPOL).

[AC drive seizure evaluation of liquid crystal cells]
Using the liquid crystal cell produced above, an AC voltage of ± 10 V was applied for 120 hours at a frequency of 30 Hz in a constant temperature environment of 60 ° C. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for one day.
After leaving, the liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal, and the backlight is turned on with no voltage applied so that the brightness of the transmitted light is minimized. The arrangement angle of the liquid crystal cell was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became darkest to the angle at which the first region became darkest was calculated as an angle Δ. Similarly, for the second pixel, the second area was compared with the first area, and a similar angle Δ was calculated. Then, the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. AC drive image sticking Δ was less than 0.1 and good, and more than that.

<Example 2>
In a 20 ml sample tube containing a stir bar, 2.20 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 7.33 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were weighed. 6.47 g of NMP, 4.00 g of BCS, 0.15 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator, And 0.06g of additive A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A2.
Except for using this liquid crystal aligning agent A2, adhesion evaluation and AC drive image sticking evaluation were performed in the same manner as in Example 1.

<Example 3>
In a 20 ml sample tube containing a stir bar, 4.58 g of the polyimide solution (PI-1) obtained in Synthesis Example 4 and 4.58 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5 were weighed. 6.83 g of NMP, 4.00 g of BCS, 0.15 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator, and 0.06g of additive A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A3.
Using this liquid crystal aligning agent A3, ultraviolet rays of 254 nm were irradiated at 200 mJ / cm ² , soaked in ethyl lactate for 3 minutes, and then soaked in pure water for 1 minute. Thereafter, adhesion evaluation and AC drive image sticking evaluation were performed in the same manner as in Example 1 except that baking was performed in a hot air circulation oven at 230 ° C. for 14 minutes to obtain a substrate with a liquid crystal alignment film.

<Comparative Example 1>
A liquid crystal aligning agent B1 was obtained in the same manner as in Example 1 except that the additive A was not added. Except for using this liquid crystal aligning agent B1, adhesion evaluation and AC drive image sticking evaluation were performed in the same manner as in Example 1.
<Comparative example 2>
A liquid crystal aligning agent B2 was obtained in the same manner as in Example 2 except that the additive A was not added. Adhesion evaluation and AC drive image sticking evaluation were performed by the same method as in Example 2 except that this liquid crystal aligning agent B2 was used.

<Comparative Example 3>
A liquid crystal aligning agent B3 was obtained in the same manner as in Example 3 except that the additive A was not added. Except for using this liquid crystal aligning agent B3, adhesion evaluation and AC drive image sticking evaluation were performed in the same manner as in Example 3.

Table 2 summarizes the composition of the components contained in the liquid crystal aligning agents obtained in Examples 1 to 3 and Comparative Examples 1 to 3. In Table 2, the (mixing ratio) of the polyimide polymer represents the mixing ratio (% by mass) of each polymer. The (ratio) of the solvent represents the ratio (mass%) of each organic solvent to the whole polymer solution. (Phr) of the additive represents the additive content ratio (% by mass) relative to the solid content of the polymer. Moreover, the unit of solid content concentration is the mass%.
Table 3 summarizes the manufacturing conditions of the FFS drive liquid crystal cells in Examples 1 to 3 and Comparative Examples 1 to 3. In Table 3, “-” represents unprocessed.
Table 4 summarizes the evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3.

<Synthesis Example 6>
In a 500 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 4.58 g (42.4 mmol) of diamine DA-5 and 1.79 g (4.71 mmol) of diamine DA-12 were weighed, and 84.7 g of NMP was measured. , 254 g of GBL and 8.40 g (106 mmol) of pyridine as a base were added and dissolved by stirring while feeding nitrogen. Next, 14.1 g (44.2 mmol) of DE-1 was added while stirring the diamine solution, and the mixture was reacted at 15 ° C. overnight. After stirring overnight, 1.23 g (13.6 mmol) of acryloyl chloride was added and reacted at 15 ° C. for 4 hours. The obtained polyamic acid ester solution was added to 1477 g of IPA with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, the precipitate was washed 5 times with 738 g of IPA and dried to obtain a white precipitate. 17.3 g of polyamic acid ester resin powder was obtained. The yield was 96.9%. Moreover, the molecular weight of this polyamic acid ester was Mn = 14,288 and Mw = 29,956.
3.69 g of the obtained polyamic acid ester resin powder was placed in a 100 mL Erlenmeyer flask, 33.2 g of GBL was added, and the mixture was stirred and dissolved at room temperature for 24 hours under a nitrogen atmosphere to obtain a polyamic acid ester solution (PAE-1).

<Synthesis Example 7>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.50 g (23.1 mmol) of diamine DA-5 and 0.59 g (1.22 mmol) of diamine DA-14 were weighed, and 42.8 g of NMP was measured. 129 g of GBL and 4.34 g (54.9 mmol) of pyridine as a base were added and dissolved by stirring while feeding nitrogen. Next, while stirring the diamine solution, 7.44 g (22.9 mmol) of DE-1 was added and reacted at 15 ° C. overnight. After stirring overnight, 0.63 g (7.01 mmol) of acryloyl chloride was added and reacted at 15 ° C. for 4 hours. The obtained polyamic acid ester solution was added to 574 g of IPA with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, the precipitate was washed 5 times with 382 g of IPA and dried to obtain a white precipitate. Thus, 8.82 g of polyamic acid ester resin powder was obtained. The yield was 97.8%. Moreover, the molecular weight of this polyamic acid ester was Mn = 16,617 and Mw = 37,387.
0.80 g of the obtained polyamic acid ester resin powder was placed in a 20 mL Erlenmeyer flask, 7.20 g of GBL was added, and the mixture was stirred and dissolved at room temperature in a nitrogen atmosphere for 24 hours to obtain a polyamic acid ester solution (PAE-2).

<Synthesis Example 8>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.23 g (11.3 mmol) of diamine DA-5 and 0.80 g (3.77 mmol) of diamine DA-13 are weighed, and 27.0 g of NMP is measured. , 91.2 g of GBL and 2.69 g (34.0 mmol) of pyridine as a base were added and dissolved by stirring while feeding nitrogen. Next, while stirring this diamine solution, 4.61 g (14.2 mmol) of DE-1 was added and reacted at 15 ° C. overnight. After stirring overnight, 0.39 g (4.34 mmol) of acryloyl chloride was added and reacted at 15 ° C. for 4 hours. The obtained polyamic acid ester solution was added to 384 g of IPA with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, the precipitate was washed 5 times with 256 g of IPA and dried to obtain a white precipitate. 5.11 g of polyamic acid ester resin powder was obtained. The yield was 89.6%. Moreover, the molecular weight of this polyamic acid ester was Mn = 14,806 and Mw = 32,719.
0.80 g of the obtained polyamic acid ester resin powder was placed in a 20 mL Erlenmeyer flask, 7.20 g of GBL was added, and the mixture was stirred and dissolved at room temperature under a nitrogen atmosphere for 24 hours to obtain a polyamic acid ester solution (PAE-3).

<Synthesis Example 9>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.80 g (25.9 mmol) of diamine DA-5, 1.45 g (6.47 mmol) of diamine DA-2, 111 g of NMP, and 6.18 g (78.1 mmol) of pyridine was added as a base, and dissolved by stirring while feeding nitrogen. Next, 9.89 g (30.4 mmol) of DE-1 was added while stirring the diamine solution, and the mixture was reacted at 15 ° C. overnight. After stirring overnight, 0.38 g (4.21 mmol) of acryloyl chloride was added and reacted at 15 ° C. for 4 hours. The obtained polyamic acid ester solution was poured into 1230 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, the precipitate was washed 5 times with 1230 g of IPA and dried to obtain a white precipitate. 10.2 g of polyamic acid ester resin powder was obtained. The yield was 83.0%. Moreover, the molecular weight of this polyamic acid ester was Mn = 20,786 and Mw = 40,973.
0.80 g of the obtained polyamic acid ester resin powder was placed in a 20 mL Erlenmeyer flask, 7.19 g of GBL was added, and the mixture was stirred and dissolved at room temperature in a nitrogen atmosphere for 24 hours to obtain a polyamic acid ester solution (PAE-4).

<Synthesis Example 10>
In a 1000 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 14.4 g (58.8 mmol) of diamine DA-3, 2.48 g (6.53 mmol) of diamine DA-12, 622 g of NMP, and 11.6 g (147 mmol) of pyridine was added as a base, and dissolved by stirring while feeding nitrogen. Next, 20.0 g (61.4 mmol) of DE-1 was added while stirring the diamine solution, and the mixture was reacted at 15 ° C. overnight. After stirring overnight, 1.70 g (18.8 mmol) of acryloyl chloride was added and reacted at 15 ° C. for 4 hours. The obtained polyamic acid ester solution was poured into 2691 g of IPA with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, the precipitate was washed with 1345 g of IPA five times and dried to obtain a white precipitate. 31.4 g of polyamic acid ester resin powder was obtained. The yield was 95.9%. Moreover, the molecular weight of this polyamic acid ester was Mn = 13,012, Mw = 25,594.
3.70 g of the resulting polyamic acid ester resin powder was placed in a 100 mL Erlenmeyer flask, 33.3 g of NMP was added, and the mixture was stirred and dissolved at room temperature in a nitrogen atmosphere for 24 hours to obtain a polyamic acid ester solution (PAE-5).

<Synthesis Example 11>
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 0.91 g (5.98 mmol) of diamine DA-6 and 4.78 g (23.9 mmol) of diamine DA-8 were weighed and 13.3 g of NMP was measured. And 6.66 g of GBL were added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 4.76 g (24.0 mmol) of carboxylic dianhydride DC-4 was added, 9.99 g of GBL was added, and the mixture was stirred at room temperature for 2 hours. Next, after 20.0 g of GBL was added and stirred, 1.31 g (6.00 mmol) of carboxylic dianhydride DC-7 was added, 4.80 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. An acid solution (PAA-5) was obtained. The viscosity of the obtained polyamic acid solution at 25 ° C. was 4,147 mPa · s. The molecular weight of the polyamic acid was Mn = 24,333 and Mw = 60,010.

<Synthesis Example 12>
In a 1000 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 48.86 g (200 mmol) of diamine DA-3 and 18.47 g (50.0 mmol) of diamine DA-11 were weighed, 770 g of NMP was added, and nitrogen was added. The solution was stirred and dissolved while feeding. While stirring this diamine solution, 51.11 g (228 mmol) of carboxylic dianhydride DC-1 was added, NMP was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at 40 ° C. for 20 hours to be polyamic. An acid solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 193 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 9890 and Mw = 22458.
1200 g of the polyamic acid solution obtained in a 3000 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube was weighed, 400 g of NMP was added, and the mixture was stirred for 30 minutes while flowing nitrogen. To the obtained polyamic acid solution, 93.10 g of acetic anhydride and 24.05 g of pyridine were added and heated at 55 ° C. for 2 and a half hours to perform chemical imidization. The obtained reaction solution was poured into 6600 mL of methanol while stirring, and the deposited precipitate was collected by filtration. Subsequently, the precipitate was washed 3 times with 6600 mL of methanol and twice with 2000 mL of methanol. The obtained resin powder was dried at 60 ° C. for 12 hours to obtain a polyimide resin powder (2).
The imidation ratio of this polyimide resin powder was 70%, and the molecular weights were Mn = 6737 and Mw = 14181.
206.9 g of polyimide resin powder (2) obtained in a 200 mL Erlenmeyer flask containing a stir bar was weighed, 151.71 g of NMP was added, and the mixture was stirred and dissolved at 40 ° C. for 24 hours in a nitrogen atmosphere. A 12 mass% polyimide solution (PI-2) was obtained.

<Synthesis Example 13>
In a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 0.89 g (3.56 mmol) of carboxylic dianhydride DC-5, (2.50 g, 6.33 mmol) of diamine DA-16, diamine DA 1.53 g (6.32 mmol) of -15 and 0.59 g (5.46 mmol) of diamine DA-5 were weighed out, mixed in 16.6 g of NEP, and reacted at 80 ° C. for 5 hours while flowing nitrogen. . Thereafter, 2.80 g (14.3 mmol) of carboxylic acid dianhydride DC-2 and 8.31 g of NEP were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid having a solid content concentration of 25 mass%.
After adding NMP to 30.0 g of the obtained polyamic acid solution and diluting so that the solid content concentration becomes 6% by mass, 4.40 g of acetic anhydride and 3.30 g of pyridine are added as an imidization catalyst, and 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into 460 ml of methanol, and the resulting precipitate was separated by filtration. Subsequently, the precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (3). The imidation ratio of this polyimide was 75%, the number average molecular weight was 16,800, and the weight average molecular weight was 44,300.
Next, 0.50 g of polyimide powder (3) was weighed, 11.3 g of NEP was added, and the mixture was stirred and dissolved at 70 ° C. for 24 hours in a nitrogen atmosphere. To this solution, PB (7.52 g) was added and stirred at 40 ° C. for 4 hours to obtain a polyimide solution (PI-3).

<Synthesis Example 14>
In a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 2.55 g (10.2 mmol) of carboxylic dianhydride DC-5, 1.27 g (3.09 mmol) of diamine DA-17 and diamine DA- 2.67 g (17.5 mmol) was weighed out, mixed in 17.0 g NEP, and reacted at 80 ° C. for 5 hours while flowing nitrogen. Thereafter, 2.00 g (10.2 mmol) of carboxylic acid dianhydride DC-2 and 8.50 g of NEP were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid having a solid content concentration of 25 mass%.
After adding NMP to 30.0 g of the obtained polyamic acid solution and diluting so that the solid content concentration becomes 6% by mass, 4.40 g of acetic anhydride and 3.30 g of pyridine are added as an imidization catalyst, and 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into 460 ml of methanol, and the resulting precipitate was separated by filtration. Subsequently, the precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (4). The imidation ratio of this polyimide was 76%, the number average molecular weight was 18,500, and the weight average molecular weight was 46,500.
Next, 0.80 g of polyimide powder (4) was weighed, 7.52 g of NEP was added, and the mixture was stirred at 70 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyimide solution (PI-4).

<Synthesis Example 15>
In a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 4.21 g (16.8 mmol) of carboxylic dianhydride DC-5, 2.95 g (6.82 mmol) of diamine DA-18, and diamine DA- 6 was weighed out, mixed in 21.4 g of NMP, reacted at 80 ° C. with flowing nitrogen for 5 hours, and then 1.10 g of carboxylic dianhydride DC-2 ( (5.61 mmol) and 10.7 g of NMP were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid having a solid content concentration of 25 mass%.
After adding NMP to 30.0 g of the obtained polyamic acid solution and diluting so that the solid content concentration becomes 6% by mass, 4.40 g of acetic anhydride and 3.30 g of pyridine are added as an imidization catalyst, and 80 ° C. The reaction was performed for 3.5 hours. This reaction solution was put into 460 ml of methanol, and the resulting precipitate was separated by filtration. Subsequently, the precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (5). The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,600, and the weight average molecular weight was 43,500.
Next, 2.50 g of polyimide powder (5) was weighed, 18.3 g of NMP was added, and the mixture was stirred and dissolved at 70 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyimide solution (PI-5) having a solid content concentration of 12% by mass. Got.

<Synthesis Example 16>
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 3.77 g (10.00 mmol) of diamine DA-21 was weighed and 50.0 g of NMP was added. Anhydrous DC-6 was slowly added as a solid in 9.01 g (30.00 mmol), and reacted at 40 ° C. for 3 hours while flowing nitrogen.
On the other hand, to a 300 mL four-necked flask equipped with a mechanical stirrer, 9.73 g (90.00 mmol) of diamine DA-5 was weighed, and 111.1 g of NMP was added to the previously prepared reaction solution. After confirmation, carboxylic dianhydride DC-6 was slowly added in the form of 20.27 g (67.50 mmol) solid, the flask wall was washed with 10.00 g of NMP and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. It was. The polyamic acid had a number average molecular weight of 10,200 and a weight average molecular weight of 23,600.
Next, 40.00 g of the polyamic acid solution obtained above was weighed into a 200 mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, 74.3 g of NMP was added, and 19.02 g (186.29 mmol) of acetic anhydride was added. Then, 8.84 g (111.71 mmol) of pyridine was added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 40 ° C. for 2.5 hours. After completion of the reaction, the reaction solution was returned to room temperature, slowly poured into 500 ml of methanol cooled to about 10 ° C. to precipitate a solid, and the precipitate was separated by filtration. Subsequently, the precipitate was repulped with 200 ml of methanol twice and vacuum dried at 100 ° C. to obtain a polyimide powder (6).
By weighing 4.0 g of the polyimide powder (6) obtained by the above operation into a 100 ml branch eggplant flask equipped with a stir bar, adding 62.67 g of GBL, and stirring and dissolving at 50 ° C. in a nitrogen atmosphere. A polyimide solution (PI-6) having a solid content concentration of 6.0% by mass was obtained.

<Synthesis Example 17>
In a 500 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 19.86 g (0.101 mol) of carboxylic dianhydride DC-2 and 9.81 g (0.045 mol) of carboxylic dianhydride DC-7 Diamine DA-22, 5.50 g (0.045 mol), diamine DA-24, 12.20 g (0.060 mol), and diamine DA-19, 13.16 g (0.045 mol), were weighed in 242.1 g of NMP. The mixture was reacted for 18 hours while flowing nitrogen at room temperature to obtain a polyamic acid solution having a solid concentration of 20% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 597 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 14224 and Mw = 36140.
Next, 210.0 g of NMP was added to 140.0 g of the polyamic acid solution obtained above and diluted to prepare a polyamic acid solution having a solid concentration of 8.0% by mass, and 21.08 g of acetic anhydride and 8. 99 g was added and reacted at 50 ° C. for 2 hours for chemical imidization. The obtained polyimide solution was cooled to about room temperature and then poured into 1330 g of methanol, and the precipitate was separated by filtration. Then, after wash | cleaning a deposit twice with methanol, it dried under reduced pressure at 100 degreeC and obtained the polyimide powder (7). The number average molecular weight of this polyimide was 10920, and the weight average molecular weight was 31108. Moreover, the imidation ratio was 85%.
In a 100 ml branched eggplant flask equipped with a stir bar, 11.0 g of the polyimide powder (7) obtained by the above operation is weighed, 80,7 g of GBL is added, and stirred and dissolved at 50 ° C. for 20 hours in a nitrogen atmosphere. As a result, a polyimide solution (PI-7) having a solid content concentration of 12.0% by mass was obtained.

<Synthesis Example 18>
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 18.53 g (0.095 mol) of carboxylic dianhydride DC-2 and 8.83 g (0.041 mol) of carboxylic dianhydride DC-7 Diamine DA-23, 6.60 g (0.054 mol), diamine DA-24, 8.23 g (0.041 mol), and diamine DA-20, 12.98 g (0.041 mol), were weighed out in 239.1 g of NMP. The mixture was reacted for 22 hours while flowing nitrogen at room temperature to obtain a solution of polyamic acid (PAA-2) having a concentration of 20 wt%. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 693 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 20366 and Mw = 54052.
Next, in a 500 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 240.0 g of NMP was added to 160.0 g of the polyamic acid solution obtained above and diluted to obtain a polyamic acid having a solid content concentration of 8.0% by mass. A solution was prepared, 22.26 g of acetic anhydride and 9.49 g of pyridine were added, and the mixture was reacted at 50 ° C. for 2 hours to imidize. The obtained polyimide solution was cooled to about room temperature and then poured into 1511 g of methanol, and the precipitate was separated by filtration. Then, after wash | cleaning a deposit twice with methanol, it dried under reduced pressure at 100 degreeC and obtained the polyimide powder (8). The number average molecular weight of this polyimide was 13306, and the weight average molecular weight was 35615. Further, the imidization ratio was 85%.
In a 100 ml branched eggplant flask equipped with a stir bar, 11.0 g of the polyimide powder (8) obtained by the above operation is weighed, 80,7 g of GBL is added, and stirred and dissolved at 50 ° C. for 20 hours in a nitrogen atmosphere. As a result, a polyimide solution (PI-8) having a solid concentration of 12.0% by mass was obtained.

<Synthesis Example 19>
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 3.77 g (10.00 mmol) of diamine DA-21 was weighed and 50.0 g of NMP was added. Anhydrous DC-8 was slowly added in the form of 6.73 g (30.00 mmol) of solid and reacted at 40 ° C. for 3 hours under a nitrogen atmosphere.
On the other hand, to a 300 mL four-necked flask equipped with a mechanical stirrer, 9.73 g (90.00 mmol) of diamine DA-5 was weighed, and 111.1 g of NMP was added to the previously prepared reaction solution. After confirmation, 15.13 g (67.50 mmol) of carboxylic acid dianhydride DC-8 was slowly added as a solid, the flask wall was washed with 10.00 g of NMP, reacted at 40 ° C. for 6 hours in a nitrogen atmosphere, and polyamic acid. A solution was obtained. The polyamic acid had a number average molecular weight of 9,000 and a weight average molecular weight of 21,600.
Next, 38.00 g of the polyamic acid solution obtained above was weighed into a 200 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 70.3 g of NMP was added, and 19.02 g (186.29 mmol) of acetic anhydride was added. Then, 8.84 g (111.71 mmol) of pyridine was added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 40 ° C. for 2.5 hours. After completion of the reaction, the reaction solution was returned to room temperature, slowly poured into 500 ml of methanol cooled to about 10 ° C. to precipitate a solid, and the precipitate was separated by filtration. Subsequently, the precipitate was repulped with 200 ml of methanol twice and vacuum dried at 100 ° C. to obtain a polyimide powder (9).
By weighing 4.0 g of the polyimide powder (9) obtained by the above operation into a 100 ml branch eggplant flask equipped with a stir bar, adding 62.67 g of GBL, and stirring and dissolving at 50 ° C. in a nitrogen atmosphere. A polyimide solution (PI-9) having a solid content concentration of 6.0% by mass was obtained.

<Synthesis Example 20>
In a 2000 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 63.76 g (320 mmol) of DA-8 and 12.17 g (79.99 mmol) of DA-6 were added, 1094 g of NMP was added, and nitrogen was fed. Stir to dissolve. While stirring the diamine solution, 112.59 g (383 mmol) of DC-3 was added, NMP was further added so that the solid content concentration was 12% by mass, and the mixture was stirred at room temperature for 24 hours, and polyamic acid (PAA- A solution of 6) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 384 mPa · s.

<Synthesis Example 21>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 5.00 g (17.46 mmol) of diamine DA-10 is weighed, 48.17 g of NMP is added and dissolved, cooled to 10 ° C. or lower in an ice bath, 3.50 g (16.06 mmol) of carboxylic dianhydride DC-7 was added little by little, and the mixture was returned to room temperature and allowed to react until the viscosity was stabilized to obtain a polyamic acid solution (PAA-7) having a solid concentration of 15% by mass. . The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 420 mPa · s, the number average molecular weight was 12,500, and the weight average molecular weight was 33800.

<Synthesis Example 22>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, 1.98 g (10.00 mmol) of diamine DA-7 and 8.40 g (40.00 mmol) of diamine DA-8 were weighed, and 152.10 g of NMP. Add and dissolve, cool to about 10 ° C., add 7.35 g (38.00 mmol) of carboxylic dianhydride DC-2 little by little, followed by 3.00 g (10. 00 mmol) was added little by little, and the reaction was allowed to return to room temperature until the viscosity was stabilized, thereby obtaining a polyamic acid solution (PAA-8) having a solid concentration of 12% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 180 mPa · s.

<Synthesis Example 23>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 4.51 g (17.46 mmol) of diamine DA-9 is measured, 45.39 g of NMP is added and dissolved, and cooled to 10 ° C. or lower in an ice bath. 3.50 g (16.06 mmol) of carboxylic acid dianhydride DC-7 was added little by little, and the reaction was allowed to return to room temperature until the viscosity was stabilized to obtain a polyamic acid solution (PAA-9) having a solid content concentration of 15% by mass. It was. This polyamic acid solution had a viscosity of 390 mPa · s at a temperature of 25 ° C., a number average molecular weight of 11,200 and a weight average molecular weight of 31,800.

<Synthesis Example 24>
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 1.98 g (10.00 mmol) of diamine DA-7 and 8.40 g (40.00 mmol) of diamine DA-8 are weighed, and 144.25 g of NMP is obtained. Add and dissolve, cool to about 10 ° C., add 9.29 g (47.50 mmol) of carboxylic acid dianhydride DC-2 little by little, return to room temperature, and react until the viscosity stabilizes. A polyamic acid solution (PAA-10) having a concentration of 12% by mass was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 250 mPa · s.

<Synthesis Example 25>
In a 500 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 29.73 g (150.00 mmol) of diamine DA-7 was weighed, 169.8 g of NMP and 169.8 g of GBL were added, and all were dissolved. Thereafter, 13.83 g (70.50 mmol) of carboxylic acid dianhydride DC-2 was slowly added as a solid at about 10 ° C. under a nitrogen atmosphere and stirred for 30 minutes, and then carboxylic acid dianhydride DC-7 was added. 16.36 g (50.00 mmol) of solid was added as it was, returned to room temperature and reacted for 6 hours to obtain a polyamic acid solution with a solid content concentration of 15 mass%. The number average molecular weight was 9,400, and the weight average molecular weight was 11,500.
To a 1 L Erlenmeyer flask equipped with a stirrer, 350 g of the polyamic acid solution obtained by the above operation was weighed, 393.75 g of GBL and 131.25 g of BCS were added, and the mixture was stirred for 3 hours. A 0% by mass polyamic acid solution (PAA-11) was obtained.

<Example 4>
4.58 g of the polyimide solution (PI-1) obtained in Synthesis Example 4 and 4.58 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 20 were weighed, 6.83 g of NMP, and 4 BCS. 0.005 g, 0.15 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator, and 0.06 g of additive A were added at room temperature. For 3 hours to obtain a liquid crystal aligning agent A4.

<Example 5>
3.67 g of the polyimide solution (PI-1) obtained in Synthesis Example 4 and 5.50 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 20 were weighed out, 6.83 g of NMP and 4 BCS. 0.005 g, 0.15 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator, and 0.06 g of additive A were added at room temperature. For 3 hours to obtain a liquid crystal aligning agent A5.

<Example 6>
4.59 g of the polyimide solution (PI-2) obtained in Synthesis Example 12 and 4.57 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 20 were weighed out, 6.85 g of NMP, and 4 BCS. 0.005 g, 0.15 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator, and 0.06 g of additive A were added at room temperature. Was stirred for 3 hours to obtain a liquid crystal aligning agent A6.

<Example 7>
9.17 g of the polyimide solution (PI-1) obtained in Synthesis Example 4 was weighed, 6.83 g of NMP, 4.00 g of BCS, and N-α- (9-fluorenylmethoxycarbonyl as an imidization accelerator. ) -N-τ-t-butoxycarbonyl-L-histidine (0.15 g) and additive A (0.06 g) were added, followed by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent A7.

<Example 8>
8.85 g of the polyimide solution (PI-1) obtained in Synthesis Example 12 was weighed, 7.15 g of NMP, 4.00 g of BCS, and N-α- (9-fluorenylmethoxycarbonyl as an imidization accelerator. ) -N-τ-t-butoxycarbonyl-L-histidine (0.15 g) and additive A (0.06 g) were added, followed by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent A7.
<Example 9>
A liquid crystal alignment liquid crystal aligning agent A9 was obtained in the same manner as in Example 4 except that the additive B was added instead of the additive A.
<Example 10>
A liquid crystal alignment liquid crystal aligning agent A10 was obtained by the same method as in Example 5 except that the additive B was added instead of the additive A.

<Example 11>
A liquid crystal alignment liquid crystal aligning agent A11 was obtained in the same manner as in Example 6 except that the additive B was added instead of the additive A.
<Example 12>
Liquid crystal aligning liquid crystal aligning agent A12 was obtained by the same method as Example 7 except having added additive B instead of additive A.
<Example 13>
A liquid crystal alignment liquid crystal aligning agent A13 was obtained in the same manner as in Example 8 except that the additive B was added instead of the additive A.

<Example 14>
4.40 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 6 and 5.50 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 11 were weighed, 0.52 g of NMP, GBL 5.58 g, 4.01 g BCS, 0.15 g N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator, and additives 0.06g of A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A14.

<Example 15>
4.41 g of the polyamic acid ester solution (PAE-2) obtained in Synthesis Example 7 and 5.49 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 11 were weighed, 0.50 g of NMP, GBL 5.60 g, BCS 4.00 g, N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine 0.15 g as an imidization accelerator, and additives 0.06g of A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A15.

<Example 16>
4.42 g of the polyamic acid ester solution (PAE-3) obtained in Synthesis Example 8 and 5.49 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 11 were weighed, 0.50 g of NMP, GBL 5.60 g, BCS 4.00 g, N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine 0.15 g as an imidization accelerator, and additives 0.06g of A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A16.

<Example 17>
4.42 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 9 and 5.50 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 11 were weighed, 0.50 g of NMP, GBL 5.60 g, BCS 4.00 g, N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine 0.15 g as an imidization accelerator, and additives 0.06g of A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A17.

<Example 18>
4.42 g of the polyamic acid ester solution (PAE-5) obtained in Synthesis Example 10 and 5.49 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 11 were weighed, 0.50 g of NMP, GBL 5.60 g, BCS 4.00 g, N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine 0.15 g as an imidization accelerator, and additives 0.06g of A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A16.

<Example 19>
11.0 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 6 was weighed, 4.99 g of GBL, 4.02 g of BCS, and N-α- (9-fluorene as an imidization accelerator. Nylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine (0.15 g) and additive A (0.06 g) were added, and the mixture was stirred at room temperature for 3 hours to obtain liquid crystal aligning agent A19.

<Comparative example 4>
A liquid crystal alignment liquid crystal aligning agent B4 was obtained in the same manner as in Example 4 except that the additive A was not added.
<Comparative Example 5>
A liquid crystal alignment liquid crystal aligning agent B5 was obtained in the same manner as in Example 5 except that the additive A was not added.
<Comparative Example 6>
A liquid crystal alignment liquid crystal aligning agent B6 was obtained in the same manner as in Example 6 except that the additive A was not added.

<Comparative Example 7>
A liquid crystal alignment liquid crystal aligning agent B7 was obtained in the same manner as in Example 7 except that the additive A was not added.
<Comparative Example 8>
A liquid crystal alignment liquid crystal aligning agent B8 was obtained in the same manner as in Example 8 except that the additive A was not added.
<Comparative Example 9>
A liquid crystal alignment liquid crystal aligning agent B9 was obtained in the same manner as in Example 9 except that the additive A was not added.

<Comparative Example 10>
A liquid crystal alignment liquid crystal aligning agent B10 was obtained in the same manner as in Example 10 except that the additive A was not added.
<Comparative Example 11>
A liquid crystal alignment liquid crystal aligning agent B11 was obtained in the same manner as in Example 11 except that the additive A was not added.
<Comparative Example 12>
A liquid crystal alignment liquid crystal aligning agent B12 was obtained in the same manner as in Example 12 except that the additive A was not added.

<Comparative Example 13>
A liquid crystal alignment liquid crystal aligning agent B13 was obtained in the same manner as in Example 13 except that the additive A was not added.
<Comparative example 14>
A liquid crystal alignment liquid crystal aligning agent B14 was obtained in the same manner as in Example 14 except that the additive A was not added.
<Comparative Example 15>
A liquid crystal alignment liquid crystal aligning agent B15 was obtained in the same manner as in Example 5 except that the additive C was added instead of the additive A.

<Comparative Example 16>
A liquid crystal alignment liquid crystal aligning agent B16 was obtained in the same manner as in Example 6 except that the additive C was added instead of the additive A.
<Comparative Example 17>
A liquid crystal alignment liquid crystal aligning agent B17 was obtained in the same manner as in Example 5 except that the additive D was added instead of the additive A.
<Comparative Example 18>
A liquid crystal alignment liquid crystal aligning agent B18 was obtained in the same manner as in Example 6 except that the additive D was added instead of the additive A.

Using the liquid crystal aligning agents obtained in Examples 4 to 13 and Comparative Examples 4 to 8 and 15 to 18 respectively, the results of the adhesion evaluation obtained by the same method as in Example 3, and the liquid crystal cell The results of the evaluation of liquid crystal alignment and the AC drive burn-in evaluation are summarized in Tables 5-1 and 5-2.
Similarly, using the liquid crystal aligning agents obtained in Examples 14 to 19 and Comparative Examples 9 to 14, respectively, the adhesion evaluation and AC drive image sticking of the liquid crystal cell obtained by the same method as in Example 1 The results of the evaluation are summarized in Table 5-1 and Table 5-2.

<Example 20>
8.0 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 21 and 40.0 g of the polyamic acid solution (PAA-8) obtained in Synthesis Example 22 were weighed, and 31.7 g of NMP and BCS were measured. 20.0 g and 0.30 g of additive A were added, and the mixture was stirred at 40 ° C. for 4 hours to obtain liquid crystal aligning agent A20.

<Measurement of adhesion>
The obtained liquid crystal aligning agent A20 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C. for 5 minutes, and then baked at 230 ° C. for 20 minutes. Thus, a polyimide film having a thickness of 100 nm was obtained. A sample substrate for adhesion evaluation was prepared in the same procedure as in Example 1, and the edge portions of the upper and lower substrates were fixed with a tabletop precision universal testing machine (manufactured by Shimadzu Corp., AGS-X 500N). The pressure (N) at the time of peeling was measured by pushing from the upper part of the central part.

<Production of liquid crystal display element>
A substrate similar to that used in Example 1 was prepared, then dried on a hot plate at 50 ° C. for 5 minutes, and then baked at 230 ° C. for 20 minutes to form a 60 nm-thick coating film on each substrate. A membrane was obtained. The polyimide film is rubbed with a rayon cloth in a predetermined rubbing direction (roll diameter 120 mm, rotation speed 500 rpm, moving speed 30 mm / sec, pushing amount 0.3 mm), and then irradiated with ultrasonic waves in pure water for 1 minute. And dried at 80 ° C. for 10 minutes.
Then, using the two types of substrates with the liquid crystal alignment film, the rubbing directions are combined so that they are antiparallel, the periphery is sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 3.8 μm is formed. Produced. A liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain an anti-parallel alignment liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and allowed to stand overnight before being used for each evaluation.

<Evaluation of liquid crystal alignment>
The alignment state of the liquid crystal cell was evaluated by the same method as in Example 1 described above.
<Liquid crystal cell AC drive burn>
The average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell in the same manner as in Example 1. AC drive image sticking Δ was less than 0.2 and good, and more than that.

<Example 21>
8.0 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 23 and 40.0 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 24 were weighed, and 31.7 g of NMP and BCS were measured. 20.0 g and 0.30 g of additive A were added, and the mixture was stirred at 40 ° C. for 4 hours to obtain liquid crystal aligning agent A21.

<Comparative Example 19>
A liquid crystal alignment liquid crystal aligning agent B19 was obtained in the same manner as in Example 20 except that the additive A was not added.
<Comparative Example 20>
A liquid crystal alignment liquid crystal aligning agent B20 was obtained in the same manner as in Example 21 except that the additive A was not added.
<Comparative Example 21>
A liquid crystal alignment liquid crystal aligning agent B21 was obtained in the same manner as in Example 20 except that the additive C was added instead of the additive A.

<Comparative Example 22>
A liquid crystal alignment liquid crystal aligning agent B22 was obtained in the same manner as in Example 21 except that the additive C was added instead of the additive A.
<Comparative Example 23>
A liquid crystal alignment liquid crystal aligning agent B23 was obtained in the same manner as in Example 20 except that the additive D was added instead of the additive A.
<Comparative Example 24>
A liquid crystal alignment liquid crystal aligning agent B24 was obtained in the same manner as in Example 21 except that the additive D was added instead of the additive A.

Using the liquid crystal aligning agents obtained in Examples 20 and 21 and Comparative Examples 20 to 24, respectively, the results of the adhesion evaluation obtained by the same method as in Example 20 and the liquid crystal orientation of the liquid crystal cell Table 6 summarizes the results of the evaluation and the results of the AC drive burn-in evaluation.

<Example 22>
11.8 g of the polyimide solution (PI-3) obtained in Synthesis Example 13 and 8.3 g of the polyimide solution (PI-4) obtained in Synthesis Example 14 were weighed, and 12.5 g of PB and Additive A were added. 0.07g was added and it stirred at 40 degreeC for 4 hours, and obtained liquid crystal aligning agent A22.

<Measurement of adhesion>
The obtained liquid crystal aligning agent A22 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and heated at 100 ° C. for 5 minutes on a hot plate and at 230 ° C. in a heat circulation clean oven. Heat treatment was performed for 30 minutes to obtain an ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm. A sample substrate for adhesion evaluation was prepared in the same procedure as in Example 1, and the edge portions of the upper and lower substrates were fixed with a tabletop precision universal testing machine (manufactured by Shimadzu Corp., AGS-X 500N). The pressure (N) at the time of peeling was measured by pushing from the upper part of the central part.

<Evaluation of liquid crystal alignment>
The obtained liquid crystal aligning agent A22 was filtered through a 1.0 μm filter, and then a liquid crystal cell was prepared. This solution was spin-coated on the ITO surface of a substrate with 100 × 100 mm ITO electrodes (length 100 mm × width 100 mm, thickness 0.7 mm) washed with pure water and IPA, and then on a hot plate at 100 ° C. for 5 minutes. Then, heat treatment was performed at 230 ° C. for 30 minutes in a heat circulation clean oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm.
Two ITO substrates with the obtained liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to prepare an empty cell. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (vertical alignment cell). The obtained liquid crystal cell was heated at 120 ° C. for 1 hour, and the alignment state of the liquid crystal cell was evaluated by the same method as in Example 1 described above.

<Example 23>
20.8 g of the polyimide solution (PI-5) obtained in Synthesis Example 15 was weighed, 1.3 g of NMP, 19.6 g of BCS and 0.13 g of additive A were added, and the mixture was stirred at room temperature for 3 hours. A liquid crystal aligning agent A23 was obtained.

<Comparative Example 25>
A liquid crystal alignment liquid crystal aligning agent B25 was obtained in the same manner as in Example 22 except that the additive A was not added.
<Comparative Example 26>
A liquid crystal alignment liquid crystal aligning agent B26 was obtained in the same manner as in Example 23 except that the additive A was not added.

Using the liquid crystal aligning agents obtained in Examples 22 and 23 and Comparative Examples 25 and 26, respectively, the results of evaluation of adhesion of the test substrate obtained by the same method as in Example 22, and the liquid crystal cell Table 7 summarizes the results of the evaluation of the liquid crystal orientation of the film.

<Example 24>
5.0 g of the polyimide solution (PI-6) obtained in Synthesis Example 16 and 20.0 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 25 were weighed, 0.08 g of Additive A was added, It stirred at room temperature for 24 hours and obtained liquid crystal aligning agent A24.

<Measurement of adhesion>
The obtained liquid crystal aligning agent A24 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C. for 60 seconds, and then IR (infrared ray at 220 ° C. ) Using an oven, baking was performed in a nitrogen atmosphere for 20 minutes to obtain an ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm. A sample substrate for adhesion evaluation was prepared in the same procedure as in Example 1, and the edge portions of the upper and lower substrates were fixed with a tabletop precision universal testing machine (manufactured by Shimadzu Corp., AGS-X 500N). The pressure (N) at the time of peeling was measured by pushing from the upper part of the central part.

<Evaluation of liquid crystal alignment>
The obtained liquid crystal aligning agent A24 was filtered through a 1.0 μm filter, and then a liquid crystal cell was produced. This solution was spin-coated on the ITO surface of a 100 × 100 mm ITO electrode substrate (length 100 mm × width 100 mm, thickness 0.7 mm) washed with pure water and IPA, and heated on a hot plate at a temperature of 80 ° C. for 60 seconds. After drying, baking was performed in a nitrogen atmosphere using an IR (infrared) oven at 220 ° C. for 20 minutes to form a coating film having a thickness of 100 nm. This coating surface was rubbed with a cotton cloth (YA-25C, manufactured by Yoshikawa) using a rubbing machine with a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.4 mm, and liquid crystal alignment A substrate with a film was obtained.
Prepare two ITO substrates with the obtained liquid crystal alignment film, combine the two substrates with a 6 μm spacer so that the liquid crystal alignment film faces each other and the rubbing direction is perpendicular, and bond the periphery with a sealant An empty cell was produced. MLC-2003 (Merck Japan Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (TN-oriented cell). The obtained liquid crystal cell was heated at 120 ° C. for 1 hour, and the alignment state of the liquid crystal cell was evaluated by the same method as in Example 1 described above.

<Example 25>
64.2 g of the polyimide solution (PI-7) obtained in Synthesis Example 17 and 27.5 g of the polyimide solution (PI-8) obtained in Synthesis Example 18 were mixed, and further 23.8 g of GBL and NMP41 were added to this solution. 0.8 g, BCS 62.7 g and Additive A 0.66 g were added and stirred at 50 ° C. for 20 hours to obtain Liquid Crystal Alignment Agent A25.
<Example 26>
5.0 g of the polyimide solution (PI-9) obtained in Synthesis Example 19 and 20.0 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 25 were weighed, 0.08 g of Additive A was added, It stirred at room temperature for 24 hours and obtained liquid crystal aligning agent A26.

<Comparative Example 27>
A liquid crystal alignment liquid crystal aligning agent B27 was obtained in the same manner as in Example 24 except that the additive A was not added.
<Comparative example 28>
A liquid crystal alignment liquid crystal aligning agent B28 was obtained in the same manner as in Example 25 except that the additive A was not added.
<Comparative Example 29>
A liquid crystal alignment liquid crystal aligning agent B29 was obtained in the same manner as in Example 26 except that the additive A was not added.

Using the liquid crystal aligning agents obtained in Examples 24 to 26 and Comparative Examples 27 to 29, respectively, the results of the adhesion evaluation obtained by the same method as in Example 24, and the liquid crystal orientation of the liquid crystal cell Table 7 summarizes the results of the evaluation.

The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention satisfies the adhesiveness (adhesiveness) with the sealant and the substrate, and also exhibits characteristics that are compatible with liquid crystal alignment and electrical characteristics. In an IPS and FFS drive type liquid crystal display device comprising such a liquid crystal alignment film of the present invention, afterimages caused by the generated AC drive and display burn-in due to residual charges accumulated by a DC voltage are suppressed, and High seal adhesion. Therefore, it can be used in a wide range of liquid crystal display elements that require high display quality.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-237319 filed on November 15, 2013 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

The liquid crystal aligning agent characterized by containing the following (A) component, (B) component, and an organic solvent.
(A) Component: At least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (1) and an imidized polymer of the polyimide precursor.
(B) Component: A compound having a hydroxyalkylamide group.

(X 1 is a tetravalent organic group, Y 1 is a divalent organic group. R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A 1 and A 2 are Each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and these groups have a substituent. May be good.)
The liquid crystal aligning agent of Claim 1 whose (B) component is a compound which has two or more hydroxyalkylamide groups.
3. The liquid crystal aligning agent according to claim 1, wherein the component (B) is contained in an amount of 0.1 to 20% by mass relative to the component (A).
The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the component (B) is represented by the following formula (2).

(X 2 is an n-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and n is an integer of 2 to 6. R 2 and R 3 are Each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and these groups may have a substituent. (At least one of R 2 and R 3 has a hydroxy group as a substituent.)
The liquid crystal aligning agent according to any one of claims 1 to 4, wherein at least one of R 2 and R 3 is represented by the following formula (3).

(R 4 to R 7 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.)
6. The liquid crystal aligning agent according to claim 1, wherein the atom directly bonded to the carbonyl group in X 2 is a carbon atom that does not form an aromatic ring.
The liquid crystal aligning agent according to any one of claims 1 to 6, wherein X 2 is an aliphatic hydrocarbon group.
The liquid crystal aligning agent according to any one of claims 1 to 7, wherein R 2 and R 3 are compounds represented by the following formula (4).
The liquid crystal aligning agent according to any one of claims 1 to 8, wherein the component (B) is any one of the following compounds.
X 1 is at least one structure selected from the group consisting of the following formulas (X-1) ~ (X -14), the liquid crystal alignment agent according to any one of claims 1-9.

(R 8 to R 11 are each independently 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 alkenyl group, or a phenyl group.)
X 1 is at least one structure selected from the group consisting of the following formulas (X1-1) and (Xl-2), the liquid crystal alignment agent according to any one of claims 1 to 10.
The liquid crystal aligning agent according to any one of claims 1 to 11, wherein Y 1 has at least one structure selected from the group consisting of the following formulas (5) and (6).

(R 12 is a single bond or a divalent organic group having 1 to 30 carbon atoms, R 13 is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms, and a is 1 to 4 In the case where a is 2 or more, (R 12 -R 13 ) may be the same as or different from each other, and R 14 is a single bond, —O—, —S—, —NR 15 —, An amide bond, an ester bond, a urea bond, or a divalent organic group having 1 to 40 carbon atoms, and R 15 is a hydrogen atom or a methyl group.)
A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of claims 1 to 12.
A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 12 and irradiating polarized radiation having a wavelength of 100 to 400 nm.
The liquid crystal alignment film according to claim 13 or 14, wherein the film thickness after firing is 5 to 300 nm.
A liquid crystal display device comprising the liquid crystal alignment film according to any one of claims 13 to 15.
A lateral electric field drive type liquid crystal display element comprising the liquid crystal alignment film according to any one of claims 13 to 15.