KR102338603B1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

(Project) A composition with good printability is provided.
(Solution) A composition containing at least one polymer (A) selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and a solvent, wherein the solvent is a compound represented by the following formula (b-1A) , The specific solvent (B) which is at least 1 sort(s) chosen from the group which consists of a compound represented by a following formula (b-1B), a compound represented by a following formula (b1), and a following formula (b2) is included. However, in the following formula, X and Y are -COO- or -OCO-, A and C ¹ are a monovalent hydrocarbon group having 1 to 6 carbon atoms, and B is a divalent hydrocarbon group having 1 to 12 carbon atoms. R ¹ , R ² is an alkyl group having 3 to 6 carbon atoms, R ³ is a hydrogen atom or a methyl group, and n4 is 2 or 3. R is a C1-C3 alkyl group, and n is an integer of 0-2. m is an integer of 0-2.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a composition, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element.

Conventionally, the liquid crystal aligning film which a display element has, the surface protective film for display elements or lighting devices, an interlayer insulating film, etc. are produced by apply|coating a polymer composition on a board|substrate. For example, as a liquid crystal display element, various types of driving systems have been developed that differ in electrode structure and physical properties of liquid crystal molecules to be used. TN type, STN type, vertical alignment type (VA type), in-plane switching Various liquid crystal display elements, such as a type|mold (IPS type|mold), an FFS type|mold, and an optical compensation bend type (OCB type), are known. These liquid crystal display elements have a liquid crystal aligning film for orientating a liquid crystal molecule. As a material of a liquid crystal aligning film, since various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable, a polyamic acid and a polyimide are generally used.

Polymer compositions, such as a liquid crystal aligning agent WHEREIN: A polymer component is melt|dissolving in the solvent, A liquid crystal aligning film is formed by apply|coating the said liquid crystal aligning agent to a board|substrate and heating. Here, as a solvent for a liquid crystal aligning agent, for the purpose of dissolving a polymer uniformly, for example, aprotic polar solvents, such as N-methyl- 2-pyrrolidone and (gamma)-butyrolactone, are generally used. do. In addition, as a solvent for a liquid crystal aligning agent, in order to make favorable the applicability|paintability (printability) of the liquid crystal aligning agent at the time of apply|coating a liquid crystal aligning agent to a board|substrate with positive solvents, such as these polyamic acids normally, yes For example, a poor solvent with a relatively low surface tension, such as butyl cellosolve, is used together (for example, refer patent document 1 and patent document 2).

In recent years, a liquid crystal display element is not only used for display terminals, such as a personal computer, like the prior art, but is used for various uses, such as a liquid crystal television, a car navigation system, a mobile phone, a smart phone, and an information display, for example. With such multi-purpose increase, further improvement of display quality, improvement of product yield, etc. are required for liquid crystal display elements, and it is one of the constituent members of a liquid crystal display element along with improvement of a drive method and element structure. The improvement of the liquid crystal aligning agent which is a phosphorus liquid crystal aligning film and the forming material of the said liquid crystal aligning film is advancing. For example, as a liquid crystal aligning agent, it is calculated|required that the applicability|paintability (printability) at the time of apply|coating on a board|substrate is favorable from viewpoints, such as display quality and a yield, and various materials for improving printability are proposed. (For example, refer patent document 3 and patent document 4).

Japanese Laid-Open Patent Publication No. 2010-97188 Japanese Laid-Open Patent Publication No. 2010-156934 Japanese Laid-Open Patent Publication No. 2011-257527 Japanese Laid-Open Patent Publication No. 2011-257736

The request|requirement with respect to performance improvement of a liquid crystal display element and a yield improvement is still increasing, and further improvement is calculated|required also about the printability of a liquid crystal aligning agent.

This invention was made in view of the said subject, and its main object is to provide the liquid crystal aligning film and liquid crystal display element which were produced using the composition and liquid crystal aligning agent with favorable printability, and the said liquid crystal aligning agent.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the subject of the prior art as mentioned above, the present inventors WHEREIN: In the composition containing polyimide or its precursor as a polymer component, the said subject is solved by using a specific solvent as at least a part of solvent component. It has been found that a solution is possible, and the present invention has been completed. Specifically, the following compositions, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element are provided by this invention.

According to the first aspect, the present invention is a composition comprising at least one polymer (A) selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and a solvent, wherein the solvent comprises the following formula (b- A specific solvent (B) which is at least one selected from the group consisting of a compound represented by 1A), a compound represented by the following formula (b-1B), a compound represented by the following formula (b1), and a compound represented by the following formula (b2) It provides a composition comprising. Further, in the second aspect, the present invention provides a liquid crystal aligning agent containing the polymer (A) and a solvent, wherein the solvent contains the specific solvent (B):

(In the formula (b-1A), X and Y are each independently -COO- or -OCO-, A and C ¹ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and B is 1 carbon atom. -12 is a divalent hydrocarbon group);

(in formula (b-1B), R ¹ and R ² are each independently an alkyl group having 3 to 6 carbon atoms, R ³ is each independently a hydrogen atom or a methyl group, and n4 is 2 or 3);

(in formula (b1), R is a C1-C3 alkyl group, n is an integer of 0-2;

In formula (b2), m is an integer of 0-2).

The said composition and liquid crystal aligning agent have favorable applicability|paintability (printability) with respect to a board|substrate by including a specific solvent (B) as a solvent component. Moreover, the composition of this invention can be used suitably also as an insulating film for display elements and lighting devices, and a protective film use other than a liquid crystal aligning film use.

One aspect of the composition of this invention and a liquid crystal aligning agent is that the said solvent contains the compound represented by said Formula (b-1A). Moreover, in another one aspect of the composition of this invention and a liquid crystal aligning agent, the said solvent contains the compound represented by said Formula (b-1B). In these cases, even when stored for a long period of time in a low-temperature environment, it is difficult to produce a precipitate in the composition or in the aligning agent, and storage stability is good. Moreover, the applicability|paintability with respect to the board|substrate of a composition or a liquid crystal aligning agent is also favorable. Moreover, even if it narrows a liquid crystal display element, the liquid crystal display element which shows favorable display quality is obtained.

Another one aspect of the composition of this invention and a liquid crystal aligning agent is that the said solvent contains the compound represented by said Formula (b1) or (b2). In this case, the solubility of the polymer with respect to a solvent is favorable. Moreover, a boiling point is moderately high, and, as for the compound represented by said formula (b1) or (b2), at the time of printing to the board|substrate of a composition or liquid crystal aligning agent by this, it WHEREIN: It can suppress that a solvent volatilizes from a printing machine. . Therefore, it is difficult for a polymer component to precipitate on a printing machine, and as a result, printability (in particular, printability in the case of continuing printing over a long period of time, hereinafter also referred to as "long-term printability") can be made favorable.

Liquid crystal aligning agent of this invention WHEREIN: The said polymer (A) is a part derived from at least 1 sort(s) of diamine chosen from the group which consists of a compound represented by each of following formula (d-1) - formula (d-5) It is preferred to include a polymer having a structure:

(In formula (d-1), X ¹ and X ² are each independently a single bond, -O-, -S-, -OCO- or -COO-, Y ¹ is an oxygen atom or a sulfur atom; , R ¹¹ and R ¹² are each independently an alkanediyl group having 1 to 3 carbon atoms, R ⁸ and R ⁹ are each independently a hydrogen atom or a protecting group;

n1 is 0 or 1, n2 and n3 are integers satisfying n2+n3=2 for n1=0, n2=n3=1 for n1=1;

In formula (d-2), X ³ is a single bond, -O-, or -S-, and m1 is an integer of 0 to 3;

m2 is an integer from 1 to 12 in the case of m1 = 0, and m2 = 2 when m1 is an integer from 1 to 3;

In the formula (d-3), R ³ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group;

In formula (d-4), X ⁴ and X ⁵ each independently represent a single bond, -O-, -COO- or -OCO-, R ⁷ is an alkanediyl group having 1 to 3 carbon atoms, A ⁴ is a single bond or an alkanediyl group having 1 to 3 carbon atoms;

a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, k is 0 or 1; provided that a and b do not simultaneously become 0;

In the formula (d-5), A ⁵ represents a single bond, an alkanediyl group having 1 to 12 carbon atoms or a fluoroalkanediyl group having 1 to 6 carbon atoms, A ⁶ is -O-, -COO-, -OCO-, represents -NHCO-, -CONH- or -CO-, and A ⁷ represents a monovalent organic group having a steroid skeleton).

When at least one part of the polymer component of a liquid crystal aligning agent is a polymer (A) obtained using said specific diamine, the said effect is high and it is suitable.

The liquid crystal aligning agent of this invention WHEREIN: The amine compound (C) which has one primary amino group and a nitrogen-containing aromatic heterocycle in a molecule|numerator, and the said primary amino group is couple|bonded with the chain hydrocarbon group or the alicyclic hydrocarbon group is further may be contained.

The liquid crystal aligning agent which contains the said polymer (A) as at least one part of a polymer component WHEREIN: When the said amine compound (C) is included as an additive, when a liquid crystal aligning agent is stored in a low-temperature environment for a long period of time, the said amine compound The problem that (C) precipitates in an aligning agent may arise. According to this point and the liquid crystal aligning agent of this structure, by setting the said specific solvent (B) as a solvent component, even when it stores in a low-temperature environment for a long period of time, it is hard to produce a precipitate in an aligning agent, and storage stability is favorable . Moreover, the applicability|paintability with respect to the board|substrate of a liquid crystal aligning agent is also favorable.

In a 3rd aspect, this invention provides the liquid crystal aligning film formed by the liquid crystal aligning agent of this invention. Moreover, this invention provides the liquid crystal display element provided with the said liquid crystal aligning film in a 4th aspect. Since the said liquid crystal aligning film is formed using the liquid crystal aligning agent with favorable printability, the yield of a liquid crystal display element can be raised.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic structural diagram of an FFS-type liquid crystal cell.
2 is a schematic plan view of a top electrode used for manufacturing a liquid crystal display element by a photo-alignment method. Fig. 2(a) is a top view of the top electrode, and Fig. 2(b) is a partially enlarged view of the top electrode.
FIG. 3 is a diagram showing four types of driving electrodes.

(Form for implementing the invention)

≪Composition and liquid crystal aligning agent≫

The composition and liquid crystal aligning agent which concern on this invention contain, as a polymer component, at least 1 sort(s) of polymer (A) selected from the group which consists of polyamic acid, a polyimide, and polyamic acid ester, The said polymer (A) is a solvent It is prepared as a liquid composition dispersed or dissolved in The composition which concerns on this invention becomes like this. Preferably it is a liquid crystal aligning agent.

«Polymer (A)»

<Polyamic acid>

The polyamic acid in this invention can be obtained by making tetracarboxylic dianhydride and diamine react.

[Tetracarboxylic acid dianhydride]

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As specific examples thereof,

Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride;

As alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a,4, 5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4 ,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3- Oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3 -furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-2 anhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride, the following formula (t-1)

(In formula (t-1), X ⁷ , X ⁸ , X ⁹ and X ¹⁰ are each independently a single bond or a methylene group, and j is an integer of 1 to 3)

compounds represented by ;

As aromatic tetracarboxylic dianhydride, For example, pyromellitic dianhydride etc.;

In addition to those mentioned respectively, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

Here, as a compound represented by said formula (t-1), bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo [4.3.0] nonane- 2,4,7,9-tetracarboxylic dianhydride, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4.4.0]decane-2,4, 8,10-tetracarboxylic dianhydride, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic dianhydride, etc. are mentioned. Especially, as a compound represented by said formula (t-1), in a liquid crystal aligning film use, from a viewpoint of making high stability of a liquid-crystal orientation, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Dianhydrides are preferred.

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid, among the above, the compound represented by said Formula (t-1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4- At least one compound selected from the group consisting of cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride (hereinafter also referred to as specific tetracarboxylic dianhydride) is preferably used. When using the specific tetracarboxylic dianhydride, the total amount of the specific tetracarboxylic dianhydride used is preferably 10 mol% or more with respect to the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid, It is more preferable that it is 20-100 mol%. Moreover, the polymer which has a partial structure derived from specific tetracarboxylic dianhydride is obtained by superposition|polymerization which contains specific tetracarboxylic dianhydride in a monomer composition.

[diamine]

As diamine used for the synthesis|combination of a polyamic acid, the compound represented by the said Formula (d-1), the compound represented by the said Formula (d-2), the compound represented by the said Formula (d-3), the said Formula (d-4) It is preferable to contain the at least 1 sort(s) of diamine (henceforth a "specific diamine") selected from the group which consists of a compound represented by and the compound represented by said Formula (d-5).

(Compound represented by Formula (d-1))

In the formula (d-1), as the ^{alkanediyl group having 1 to 3 carbon atoms for R 11} and R ¹² , for example, a methylene group, an ethylene group, a propane-1,2-diyl group, and a propane-1,3- A diyl group, a propane-2, 3-diyl group, etc. are mentioned. Among these, a methylene group, an ethylene group, or a propane-1,3-diyl group is preferable.

X ¹ and X ² are a single bond, -O-, -S-, -OCO-, or -COO-. In addition, X ¹ and X ² may be the same or different. Among these, a single bond, -O-, or -S- is preferable.

Y ¹ is an oxygen atom or a sulfur atom. Preferably, it is an oxygen atom.

The protecting group of R ⁸ and R ⁹ is preferably a group that is released by heat, and examples thereof include a carbamate protecting group, an amide protecting group, an imide protecting group, and a sulfonamide protecting group. As ^{the protecting group for R 8} and R ⁹ , among them, a carbamate protecting group is preferable, and specific examples include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, 1, 1-dimethyl-2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2-(trimethylsilyl)ethoxycarbonyl group, etc. are mentioned. Among these, a tert-butoxycarbonyl group is particularly preferable from the viewpoint of high desorption property by heat and of reducing the amount of residual in the film of the deprotected portion.

In the case of n1=0, two primary amino groups which the compound represented by Formula (d-1) has may be couple|bonded with the same benzene ring, and may couple|bond with two different benzene rings one by one. On the other hand, in the case of n1=1, each of the two primary amino groups is couple|bonded with each different benzene ring one by one.

The bonding position of the primary amino group on the benzene ring is not particularly limited. For example, when there is one primary amino group on the benzene ring, the bonding position may be any of the 2-position, 3-position, and 4-position with respect to the other groups, and it is the 3-position or 4-position. It is preferable, and it is more preferable that it is 4-position. Moreover, when there are two primary amino groups on a benzene ring, the bonding position with respect to another group is 2, 4-position, 2, 5-position, etc. are mentioned, for example, Among them, 2, 4- position is desirable.

The hydrogen atom on the benzene ring to which the primary amino group is bonded may be a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom, or a fluorine atom. Examples of the monovalent hydrocarbon group in this case include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms (phenyl group, tolyl group, etc.); and an aralkyl group having 5 to 10 carbon atoms (such as a benzyl group).

In addition, the "hydrocarbon group" in this specification is the meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In addition, the "chain hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain. In addition, the chain structure may be saturated or unsaturated may be sufficient as it. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are also included. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be constituted by only the aromatic ring structure, and a chain structure or the structure of an alicyclic hydrocarbon may be included in a part thereof.

As a preferable specific example of the compound represented by said formula (d-1), As a compound of n1=0, For example, 4,4'- diamino diphenylamine, 2, 4- diamino diphenylamine, etc.;

As the compound in which n1 = 1, for example, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea, 1,3-bis(3-aminobenzyl)urea, 1-(4-aminobenzyl)-3-(4-aminophenethyl)urea, 1,3-bis(2-(4-aminophenoxy)ethyl)urea, 1,3-bis(3-(4- Aminophenoxy)propyl)urea, 1,3-bis(4-aminobenzyl)thiourea, 1,3-bis(2-aminobenzyl)urea, 1,3-bis(2-aminophenethyl)urea, 1 , 3-bis(2-(2-aminobenzoyloxy)ethyl)urea, 1,3-bis(3-(2-aminobenzoyloxy)propyl)urea, etc.;

each can be In addition, as a compound represented by said Formula (d-1), these compounds can be used individually by 1 type or in combination of 2 or more type.

(Compound represented by Formula (d-2))

In the formula (d-2), X ³ represents a single bond, -O- or -S-, preferably a single bond or -O-.

In the case of m1 = 0, m2 is an integer from 1 to 12. In this case, from a viewpoint of making the heat resistance of the polymer obtained favorable, Preferably m2 is 1-10, More preferably, it is 1-8. Moreover, the use of a liquid crystal aligning film WHEREIN: From a viewpoint of making rubbing tolerance favorable while maintaining favorable liquid-crystal orientation, it is preferable that it is m1=0, From a viewpoint of making small the pretilt angle of a liquid crystal molecule, m1 is 1-3 It is preferably an integer of .

Although the bonding position of the primary amino group on the benzene ring is not specifically limited, It is preferable that each primary amino group is 3-position or 4-position with respect to another group, and 4-position is more preferable. The hydrogen atom on the benzene ring to which the primary amino group is bonded may be a monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent group in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom, or a fluorine atom.

Preferred specific examples of the compound represented by the formula (d-2) include, for example, bis(4-aminophenoxy)methane, bis(4-aminophenoxy)ethane, bis(4-aminophenoxy)propane, bis( 4-aminophenoxy)butane, bis(4-aminophenoxy)pentane, bis(4-aminophenoxy)hexane, bis(4-aminophenoxy)heptane, bis(4-aminophenoxy)octane, bis( 4-aminophenoxy)nonane, bis(4-aminophenoxy)decane, bis(4-aminophenyl)methane, bis(4-aminophenyl)ethane, bis(4-aminophenyl)propane, bis(4-amino Phenyl)butane, bis(4-aminophenyl)pentane, bis(4-aminophenyl)hexane, bis(4-aminophenyl)heptane, bis(4-aminophenyl)octane, bis(4-aminophenyl)nonane, bis (4-aminophenyl)decane, 1,3-bis(4-aminophenylsulfanyl)propane, 1,4-bis(4-aminophenylsulfanyl)butane, etc. are mentioned. In addition, as a compound represented by said Formula (d-2), the compound of these illustrations can be used individually by 1 type or in mixture of 2 or more types.

(Compound represented by Formula (d-3))

In the formula (d-3), R ³ is a monovalent hydrocarbon group having 1 to 12 carbon atoms. Specific examples of R ³ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and decyl group;

alkenyl groups such as a vinyl group and an allyl group;

cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group;

Aryl groups, such as a phenyl group and a tolyl group;

Aralkyl groups, such as a benzyl group, etc. are mentioned. It is preferable that it is 1-6, and, as for carbon number of R<^{3>, it is more preferable that it is 1-3.} It is preferable that R<^3> is a chain hydrocarbon group, It is more preferable that it is a chain hydrocarbon group containing a carbon-carbon double bond, It is still more preferable that it is an alkenyl group.

R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. As the art hydrocarbon group, there can be an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 5 to 12 carbon atoms in the chain hydrocarbon group, a 3 to 12 carbon atoms having 1 to 12 carbon atoms, the groups exemplified in the concrete example, the description of the R ³ can R ⁴ is preferably a hydrogen atom or a chain hydrocarbon group having 1 to 12 carbon atoms. Moreover, it is preferable that it is C1-C6, and, as for the hydrocarbon group in ^{R<4>, it is more preferable that it is C1-C3.}

R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and it is preferable that both are hydrogen atoms.

In the diaminophenyl group of the formula (d-3), the bonding position of the two primary amino groups is not particularly limited, but with respect to the group having an N-allyl structure bonded to the benzene ring, the 2,4-position or 2; The 5-position is preferable, and the 2,4-position is more preferable. The hydrogen atom on the benzene ring to which the primary amino group is bonded may be a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom, or a fluorine atom. .

Preferred specific examples of the compound represented by the formula (d-3) include 2,4-diamino-N,N-diallylaniline, 2,5-diamino-N,N-diallylaniline, the following formula The compound etc. which are represented by each of (d-3-1)-(d-3-3) are mentioned. In addition, the compound represented by said formula (d-3) can be used individually by 1 type or in mixture of 2 or more types.

(Compound represented by Formula (d-4))

In formula (d-4), ^{as a divalent group represented by "-X 4} -(R ⁷ -X ⁵ ) _k -", a C1-C3 alkanediyl group, *-O-, *-COO-, or It is preferable that it is *-OC ₂ H ₄ -O- (however, the bond attached to "*" bonds to a diaminophenyl group).

The group "-C _c H _2c+1 " is preferably linear, and specific examples thereof include, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-hep tadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned.

The two primary amino groups in the diaminophenyl group are preferably at the 2,4-position or the 3,5-position with respect to the ^{group “X 4 ”, more preferably the 2,4-position.} The hydrogen atom on the benzene ring to which the primary amino group is bonded may be a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group in which at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom, or a fluorine atom. .

As a preferable specific example of the compound represented by said formula (d-4), the compound etc. which are represented by each of following formula (d-4-1) - formula (d-4-12) are mentioned, for example.

(Compound represented by Formula (d-5))

In the formula (d-5), A ⁵ represents a single bond, an alkanediyl group having 1 to 12 carbon atoms or a fluoroalkanediyl group having 1 to 6 carbon atoms, and A ⁶ is -O-, -COO-, -OCO- , -NHCO-, -CONH-, or -CO- is represented, and A ⁷ represents a monovalent organic group having a steroid skeleton.

^{The alkanediyl group having 1 to 12 carbon atoms in A 5} in the formula (d-5) is preferably an alkanediyl group having 1 to 4 carbon atoms, methylene group, ethylene group, 1,3-propanediyl group, 1 A ,4-butanediyl group is more preferable. The fluoroalkanediyl group having 1 to 6 carbon atoms is preferably a perfluoroalkanediyl group having 1 to 4 carbon atoms, -CF ₂ -, perfluoroethylene group, 1,3-perfluoropropanediyl group, 1,4 -Perfluorobutanediyl group is more preferable.

As A ⁶ , -O- is preferable.

The steroid skeleton for A ⁷ refers to a structure comprising a cyclopentano-perhydrophenanthrene nucleus or a structure in which one or two or more of its carbon-carbon bonds are double bonds. As a monovalent organic group which has such a steroid skeleton, a C17-40 thing is preferable.

As a preferable specific example of the compound represented by said Formula (d-5), in the use of a liquid crystal aligning film, from the point which provides a high pretilt angle to a coating film, 1-cholesteryloxymethyl-2,4-diaminobenzene, 1 -cholesteryloxymethyl-3,5-diaminobenzene, 1- (1-cholesteryloxy-1,1-difluoromethyl) -2,4-diaminobenzene, 1- (1-cholester Lyloxy-1,1-difluoromethyl)-3,5-diaminobenzene, 1-(1-cholestanyloxy-1,1-difluoromethyl)-2,4-diaminobenzene, 1 -(1-cholestanyloxy-1,1-difluoromethyl)-3,5-diaminobenzene, 3-(2,4-diaminophenylmethoxy)-4,4-dimethylcholestane, 3 -(1-(2,4-diaminophenyl)-1,1-difluoromethoxy)-4,4-dimethylcholestane, 3-(3,5-diaminophenylmethoxy)-4,4- Dimethylcholestane, 3-(1-(3,5-diaminophenyl)-1,1-difluoromethoxy)-4,4-dimethylcholestane, 3-((2,4-diaminophenyl)methyl Toxy) cholan-24-acid hexadecyl, 3-(1- (2,4-diaminophenyl) -1,1-difluoromethoxy) cholan-24-acid hexadecyl, 3-((3,5- Diaminophenyl) methoxy) cholan-24-acid hexadecyl, 3-(1- (3,5-diaminophenyl) -1,1-difluoromethoxy) cholan-24-acid hexadecyl, 3-( 2,4-diaminophenylmethoxy)cholan-24-acid stearyl, 3-(1-(2,4-diaminophenyl)-1,1-difluoromethoxy)cholan-24-acid stearyl, 3-(3,5-diaminophenylmethoxy)cholan-24-acid Stearyl, 3-(1-(3,5-diaminophenyl)-1,1-difluoromethoxy)cholan-24-acid Stearyl, 1-cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl, 1-cholestanyloxy-2,4-diaminobenzene and 3,5-diamino It is preferable to use at least one selected from the group consisting of cholestanyl benzoate, and further among these, 1-cholesteryloxy-2,4- At least one selected from the group consisting of diaminobenzene, 3,5-diaminobenzoic acid cholesteryl, 1-cholestanyloxy-2,4-diaminobenzene, and 3,5-diaminobenzoic acid cholestanyl Particular preference is given to using phases.

Synthesis of polyamic acid WHEREIN: As specific diamine, according to the drive mode of the liquid crystal display element to be manufactured, it can select and use it suitably from the said compound. The liquid crystal aligning agent suitable for FFS(Fringe Field Switching) type liquid crystal display elements can be manufactured by using the compound specifically, represented by said Formula (d-1) as said specific diamine. Furthermore, by using at least 1 sort(s) selected from the group which consists of a compound represented by said Formula (d-2), and a compound represented by said Formula (d-3), the liquid crystal suitable for TN (Twisted Nematic) type liquid crystal display elements By using at least 1 sort(s) selected from the group which can manufacture an aligning agent and the group which consists of a group represented by said Formula (d-4), and a compound represented by said Formula (d-5), for liquid crystal display elements of a vertical alignment type A liquid crystal aligning agent suitable for can be prepared.

(Other diamines)

As diamine used for the synthesis|combination of polyamic acid, you may use compounds (other diamines) other than said specific diamine. As said other diamine, aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane etc. are mentioned, for example. Specific examples of these other diamines include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis(aminomethyl)cyclohexane. second;

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) and the like;

As the aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis[4 -(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis (4-aminophenyl) hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)bisaniline, 4,4'-(m-phenylenediisopropylidene)bisaniline, 1, 4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4- Bis-(4-aminophenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1-(4-amino Phenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 4-(4′-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate , 4-(4'-trifluoromethylbenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1 ,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 4-aminobenzylamine, 3-aminobenzylamine, 2,2-bis[4-( 4-aminophenoxy)phenyl]propane;

As diaminoorganosiloxane, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane etc. are mentioned respectively, for example, In addition, the diamine of Unexamined-Japanese-Patent No. 2010-97188 is used. can In addition, these other diamines can be used individually by 1 type or in combination of 2 or more types.

When a polymer (A) contains the polymer (henceforth a "specific polymer") which has a partial structure derived from specific diamine WHEREIN: The content rate of a specific polymer is a composition or a liquid crystal aligning agent from a printable viewpoint. With respect to 100 parts by weight of the total amount of the polymer component contained in It is particularly preferable to

When the specific amine compound (C) detailed below is included as an additive in the liquid crystal aligning agent which concerns on this invention, a polymer (A) is diamine (henceforth "carboxyl group-containing diamine") which has a carboxyl group. It is preferred to include a polymer having a derived partial structure. Such a polymer, for example, in the case of polyamic acid, can be obtained by using a carboxyl group-containing diamine as at least a part of the other diamines used for the synthesis of polyamic acid. It is preferable that the said carboxyl group-containing diamine is an aromatic diamine, and the compound etc. which are specifically, represented by each of following formula (e1-1) and formula (e1-2) are mentioned, for example.

(In formulas (e1-1) and (e1-2), R ²⁰ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and Z ¹ is a single bond, an oxygen atom, or a carbon number an alkanediyl group of 1 to 3;

r2, r5 and r6 are each independently an integer of 1 or 2, r1, r3 and r4 are each independently an integer of 0-2, r7 and r8 are each independently 0 satisfying r7+r8=2 is an integer of -2;

provided that r3+r5+r7≤5 and r4+r6+r8≤5;

wherein, when a plurality of R ²⁰ are present, those R ²⁰ independently have the above definition).

In the formulas (e1-1) and (e1-2), as ^{the alkyl group having 1 to 10 carbon atoms in R 20} , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group , octyl group, nonyl group, decyl group, etc. are mentioned, and these may be linear or branched. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a hexyloxy group.

As a C1-C3 alkanediyl group in Z<^1> , a methylene group, an ethylene group, trimethylene group, etc. are mentioned, for example.

r1, r3 and r4 are preferably 0 or 1, more preferably 0.

Specific examples of the carboxyl group-containing diamine include 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid and the like as a compound represented by the formula (e1-1);

As a compound represented by said Formula (e1-2), For example, 4,4'- diaminobiphenyl-3,3'- dicarboxylic acid, 4,4'- diaminobiphenyl-2,2'- dicarboxylic acid , 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3, 3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3, 3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl ether-3-carboxylic acid and the like;

can be heard

The usage-amount of the specific diamine at the time of synthesize|combining a polyamic acid can be set arbitrarily according to the compound to be used. For example, when using the compound represented by the said Formula (d-1), it is preferable to set it as 10 mol% or more with respect to all the diamines, and, as for the usage-amount, it is more preferable to set it as 30 mol% or more. In addition, when using the compound represented by the above formula (d-2), from the viewpoint of imparting a low oblique alignment angle to the liquid crystal molecules, the amount used is preferably 10 mol% or more with respect to all diamines, It is more preferable to set it as 30 mol% or more, and it is still more preferable to set it as 50 mol% or more.

When using the compound represented by the formula (d-3), the amount used is preferably 5 mol% or more, and 10 mol% or more, based on the total diamine, from the viewpoint of improving the stability of the voltage retention ratio. It is more preferable to

In the case of using at least one selected from the group consisting of the compound represented by the formula (d-4) and the compound represented by the formula (d-5), the amount used (two or more compounds) from the viewpoint of imparting good orientation. It is preferable to set it as 5 mol% or more with respect to all the diamines, and, as for the total amount, when using it, it is more preferable to set it as 10 mol% or more. In addition, as specific diamine, 1 type of the above compounds can be used individually or in combination of 2 or more type.

When using carboxyl group-containing diamine as said other diamine, it is preferable that the usage ratio makes carboxyl group-containing diamine 5 mol% or more with respect to all the diamines, 10-90 mol% is more preferable, 10-90 mol% is more preferable, and 10- 70 mol% is more preferable.

With respect to the liquid crystal aligning agent for TN-type liquid crystal display elements, at the time of the synthesis|combination of polyamic acid, for the purpose of providing an appropriate oblique orientation angle with respect to a liquid crystal molecule, with tetracarboxylic dianhydride and diamine, a following formula You may use the monoamine represented by (m-1).

(In formula (m-1), R ²³ is an alkyl group or alkoxy group having 6 to ^{20 carbon atoms, R 24} is a divalent organic group, and h is 0 or 1).

In the formula (m-1), as ^{the alkyl group having 6 to 20} carbon atoms for R 23 , for example, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, A pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group etc. are mentioned, Linear or branched form may be sufficient as these. As the alkoxy group of 6 to 20 carbon atoms, for example, an alkyl group having a carbon number of 6 to 20 of the example, and the like groups (-OR ²³⁾ bound to the oxygen atom.

Examples of the divalent organic group for R ²⁴ include divalent hydrocarbon groups such as divalent chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups, and between carbon-carbon bonds in hydrocarbon groups, -O-, - and groups having a functional group such as CO-, -COO- and -S-, and heterocyclic-containing groups. Specific examples of the divalent hydrocarbon group include a chain hydrocarbon group, for example, a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, and a furnace. Nandiyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, octadecanediyl group, icoxylene group, vinylene group, propenediyl group, butenediyl group, pentenediyl group, ethynylene group, propynylene group, etc.;

As the alicyclic hydrocarbon group, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclohexenylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclode Silene group, cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclooctadecylene group, cycloicoxylene group, bicyclohexylene group, norbornylene group, adaman a tylene group;

As an aromatic hydrocarbon group, For example, a phenylene group, a biphenylene group, etc.;

each can be Among them, R ²⁴ is preferably a chain hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.

As a preferable specific example of the monoamine represented by said formula (m-1), n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-hexadecylamine, 1,3- aliphatic monoamines such as dimethylbutylamine, 1,5-dimethylhexylamine, and 2-ethylhexylamine;

Aromatics such as p-aminophenylhexane, p-aminophenyloctane, p-aminophenyldodecane, p-aminophenylhexadecane, p-aminophenoxyoctane, p-aminophenoxydodecane, and p-aminophenoxyhexadecane monoamine;

and the like.

The use ratio of the monoamine is a mole for tetracarboxylic dianhydride, b mole for diamine, and monoamine from the viewpoint of suppressing the monoamine liberated in the prepared liquid crystal cell from affecting the display properties. When it is set as c mole, it is preferable to satisfy "2(ab)≥c>0".

In addition, the monoamine represented by the above formula (m-1) may be reacted and polymerized with respect to the reaction product after the reaction of tetracarboxylic dianhydride and diamine, or tetracarboxylic dianhydride, diamine and monoamine The three components may be reacted and polymerized at the same time.

[Molecular weight modifier]

When synthesizing polyamic acid, as described above, together with tetracarboxylic dianhydride and diamine, an appropriate molecular weight modifier may be used to synthesize a terminal-modified polymer. By setting it as such a terminal modification type polymer, the applicability|paintability (printability) of a liquid crystal aligning agent can further be improved, without impairing the effect of this invention.

As a molecular weight modifier, an acid monhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. Specific examples of these are acid monoanhydrides, such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, and n-hexadecylsuccinic anhydride. My back;

Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, and a compound represented by the formula (m-1);

As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, respectively, for example.

It is preferable to set it as 20 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine to be used, and, as for the usage ratio of a molecular weight modifier, it is more preferable to set it as 10 weight part or less.

<Synthesis of polyamic acid>

The ratio of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride groups of tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the diamine, 0.3 The ratio used as -1.2 equivalent is more preferable.

The synthesis reaction of polyamic acid is preferably performed in an organic solvent. -20 degreeC - 150 degreeC are preferable and, as for the reaction temperature at this time, 0-100 degreeC is more preferable. Moreover, 0.1 to 24 hours are preferable and, as for reaction time, 0.5 to 12 hours are more preferable.

Here, examples of the organic solvent include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons.

Specific examples of these organic solvents include, for example, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone as the aprotic polar solvent. Don, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotriamide and the like;

As said phenolic solvent, For example, phenol, m-cresol, xylenol, halogenated phenol, etc.;

As said alcohol, For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.;

As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.;

As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methylmethoxypropionate, ethylethoxypropionate, diethyl oxalate, diethyl malonate, isoamylpropioate nate, isoamyl isobutyrate, etc.;

As the ether, for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, di ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tetrahydrofuran, diisopentyl ether, etc.;

As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;

As the hydrocarbon, for example, hexane, heptane, octane, benzene, toluene, xylene and the like;

each can be In addition, a specific solvent (B) can also be used.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvent A), or at least one selected from organic solvent A, alcohols, ketones, esters, ethers, It is preferable to use a mixture with at least one selected from the group consisting of halogenated hydrocarbons and hydrocarbons (organic solvent B). In the latter case, the proportion of the organic solvent B used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight with respect to the total amount of the organic solvent A and the organic solvent B. is below. The amount of the organic solvent used (a) is preferably such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50 wt% with respect to the total amount (a+b) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. After this reaction solution may be used for preparation of compositions, such as a liquid crystal aligning agent, as it is, after isolating the polyamic acid contained in a reaction solution, you may provide for preparation, such as a liquid crystal aligning agent, or after purifying the isolated polyamic acid, liquid crystal You may provide for preparation of an aligning agent etc. When polyamic acid is subjected to dehydration ring closure to obtain a polyimide, the reaction solution may be directly subjected to dehydration ring closure reaction, or polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring closure reaction, or isolated polyamic acid After purification, it may be subjected to a dehydration ring closure reaction. Isolation and purification of polyamic acid can be performed according to a known method.

<Polyimide>

The polyimide according to the present invention can be obtained by imidizing the polyamic acid synthesized as described above by dehydration and ring closure.

The polyimide may be a complete imidized product in which all of the amic acid structure of the polyamic acid, which is a precursor thereof, is cyclized by dehydration, or a partial imidized product in which only a part of the amic acid structure is dehydrated and cyclized to coexist with the amic acid structure and the imide ring structure. is good too It is preferable that the imidation ratio of the polyimide in this invention is 30 % or more, It is more preferable that it is 40 to 99 %, It is more preferable that it is 50 to 99 %. This imidation ratio represents the ratio of the number of imide ring structures with respect to the sum total of the number of the male acid structures of a polyimide, and the number of imide ring structures in percentage. Here, an isoimide ring may be sufficient as a part of an imide ring.

The dehydration ring closure of the polyamic acid is preferably performed by heating the polyamic acid or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating as necessary. . Among these, it is preferable to rely on the latter method.

In the method of adding a dehydrating agent and a dehydration ring closure catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles with respect to 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst to be used is preferably 0.01 to 10 moles with respect to 1 mole of the dehydrating agent to be used. Examples of the organic solvent used for the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0-180°C, more preferably 10-150°C. Reaction time becomes like this. Preferably it is 1.0 to 120 hours, More preferably, it is 2.0 to 30 hours.

In this way, the reaction solution containing a polyimide is obtained. After this reaction solution may be used for preparation of compositions, such as a liquid crystal aligning agent, as it is, and after removing a dehydrating agent and a dehydration ring closure catalyst from a reaction solution, you may provide for preparation, such as a liquid crystal aligning agent, After isolating a polyimide, a liquid crystal aligning agent After refining|purifying the isolated polyimide, you may use for preparation, such as, and you may use for preparation, such as a liquid crystal aligning agent. These purification operations can be performed according to a known method.

<Polyamic acid ester>

The polyamic acid ester contained in the composition such as the liquid crystal aligning agent of the present invention is synthesized by, for example, [I] reacting the polyamic acid obtained by the above synthesis reaction with a hydroxyl group-containing compound, halide, epoxy group-containing compound, etc. Method, [II] A method of reacting a tetracarboxylic acid diester with diamine, and [III] A method of reacting a tetracarboxylic acid diester dihalide with diamine.

Here, as a hydroxyl-containing compound used by method [I], For example, Alcohol, such as methanol, ethanol, and a propanol;

Phenols, such as a phenol and cresol, etc. are mentioned. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane, and the like, and an epoxy group-containing compound As an example, propylene oxide etc. are mentioned. The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid using the alcohols described above. The tetracarboxylic acid diester dihalide used in method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. As the diamine used in the methods [II] and [III], the specific diamine and other diamines exemplified in the synthesis of the polyamic acid can be used, and it is preferable to include the specific diamine. In addition, the polyamic acid ester may have only a dark acid ester structure, and the partial esterification product in which a dark acid structure and a dark acid ester structure coexist may be sufficient as it.

<Solution Viscosity and Weight Average Molecular Weight>

The polyamic acid, polyimide, and polyamic acid ester obtained as described above preferably have a solution viscosity of 10 to 800 mPa·s, and a solution viscosity of 15 to 500 mPa·s when this is used as a solution having a concentration of 10% by weight. It is more preferable to have In addition, the solution viscosity (mPa·s) of the polymer is a polymer having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) About the solution, it is the value measured at 25 degreeC using the E-type rotational viscometer.

The reduced viscosity is not particularly limited as long as it is a range capable of forming a uniform coating film, but it is preferably 0.05 to 3.0 dl/g, more preferably 0.1 to 2.5 dl/g, and 0.3 to 1.5 dl/g. more preferably.

It is preferable that the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) about the polyamic acid, polyimide, and polyamic acid ester contained in compositions, such as a liquid crystal aligning agent which concerns on this invention, is 500-100,000 And, it is more preferable that it is 1,000-50,000.

≪Solvent≫

The composition and liquid crystal aligning agent which concern on this invention, the compound represented by the compound represented by the said Formula (b-1A), the compound represented by the said Formula (b-1B), the said Formula (b1) as a solvent component, and the said Formula ( The specific solvent (B) which is at least 1 sort(s) chosen from the group which consists of a compound represented by b2) is contained. By containing such a specific solvent (B) in compositions, such as a liquid crystal aligning agent, the applicability|paintability with respect to board|substrates, such as a liquid crystal aligning agent, can be made favorable.

<1> the compound represented by the formula (b-1A)

By containing the compound represented by said Formula (b-1A) in compositions, such as a liquid crystal aligning agent, storage stability, such as the applicability|paintability with respect to board|substrates, such as a liquid crystal aligning agent, and a liquid crystal aligning agent, can be made favorable. Moreover, even when a liquid crystal display element is liquid-softened, favorable display quality can be maintained.

About the compound represented by said formula (b-1A), X and Y are each independently -COO- or -OCO-. A and C ¹ each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. B is a C1-C12 divalent hydrocarbon group, Preferably it is a C1-C6 alkylene group.

As a compound represented by said formula (b-1A), what is shown below is mentioned, for example. Moreover, the compound represented by said formula (b-1A) may be used individually by 1 type, and may be used in combination of 2 or more type.

Here, for example, a liquid crystal aligning agent is stored in cryogenic environment (at -15 degreeC, for example) in order to prevent deterioration of a polyamic acid and a polyimide normally from manufacturing until shipment. By the way, in the liquid crystal aligning agent stored at low temperature for a long period of time, a precipitate may generate|occur|produce in a solution. In addition, the precipitate once deposited is difficult to dissolve again, and there is a fear that problems such as poor printing may occur in the manufacturing process of the liquid crystal display element. Although the cause of generation|occurrence|production of such a precipitate is not certain, it is estimated that the butyl cellosolve generally used as a solvent component of a liquid crystal aligning agent is a factor. Therefore, as a solvent for improving the applicability to a substrate, it is desired to find a new organic solvent that replaces butyl cellosolve.

A liquid crystal display is manufactured by opposingly arrange|positioning a pair of board|substrates in which the liquid crystal aligning film was formed, and arrange|positioning a liquid crystal between the pair of board|substrates which opposedly arrange|positioned. In that case, a pair of board|substrates are joined using sealing compounds, such as an epoxy resin. In touch panel display panels typified by smartphones and tablet PCs, attempts have been made to narrow the frame in order to make the movable area of the touch panel wider and to achieve both size reduction of the liquid crystal panel (element). . With the narrowing of this liquid crystal panel, display nonuniformity may be visually recognized in the sealing compound periphery, and the point of display quality was not fully satisfactory. In order to achieve the high definition of a liquid crystal display, and high lifetime improvement, the liquid crystal display element whose display unevenness in such sealing compound periphery is hard to be visually recognized (bezel unevenness tolerance is high) is calculated|required.

In this regard, the compound represented by the formula (b-1A) is useful as a new organic solvent in place of butyl cellosolve. Specifically, the liquid crystal aligning agent containing the compound represented by the above formula (b-1A) as a solvent component has good storage stability for long-term low-temperature storage and good applicability to a substrate, and also responds to liquid softening. .

<2> the compound represented by the formula (b-1B)

By containing the compound represented by said Formula (b-1B) in compositions, such as a liquid crystal aligning agent, storage stability, such as the applicability|paintability with respect to board|substrates, such as a liquid crystal aligning agent, and a liquid crystal aligning agent, can be made favorable. Moreover, even when a liquid crystal display element is liquid-softened, favorable display quality can be maintained.

With respect to the compound represented by the formula (b-1B), R ¹ to ^{R 2} are each independently an alkyl group having 3 to 6 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms. R ³ is each independently a hydrogen atom or a methyl group. n4 is 2 or 3.

When n4 is 2 ^{, it is preferable that two R<3>} are all a hydrogen atom, or it is preferable that one is a hydrogen atom and the other is a methyl group, and it is especially preferable that both are hydrogen atoms.

When n4 is 3 ^{, it is preferable that all three R<3>} are hydrogen atoms, or it is preferable that two are hydrogen atoms and one is a methyl group, and it is especially preferable that all are hydrogen atoms.

As a compound represented by said formula (b-1B), what is shown below is mentioned, for example. In addition, the compound represented by said formula (b-1B) may be used individually by 1 type, and may be used in combination of 2 or more type.

The compound represented by said formula (b-1B) is useful as a new organic solvent replacing butyl cellosolve similarly to said (b-1A). Specifically, the liquid crystal aligning agent containing the compound represented by the above formula (b-1B) as a solvent component has good storage stability for long-term low-temperature storage and good applicability to a substrate, and also responds to liquid softening. .

<3> the compound represented by the formula (b1) or the formula (b2)

The compound represented by said Formula (b1) or Formula (b2) has favorable solubility with respect to a polyamic acid and a polyimide, and a boiling point is moderately high. Therefore, by using such a compound as at least one part of a solvent, at the time of printing to the board|substrate of compositions, such as a liquid crystal aligning agent, volatilization of the solvent from a printing machine can be suppressed, and a polymer component is hard to precipitate on a printing machine. lose As a result, printability (especially long-term printability) can be made favorable. Moreover, since the boiling point of a solvent is not too high, when preheating (prebaking) is performed after printing, WHEREIN: The amount of solvent remaining in a coating film after preheating can be decreased. Therefore, it is possible to suppress adhesion of dust to the surface of the coating film after preheating, thereby suppressing a decrease in the yield of the product.

(Compound represented by the above formula (b1))

About the compound represented by said formula (b1), it is preferable that R is a C1-C3 alkyl group, and it is a C1-C2 alkyl group. n is an integer of 0-2, and it is preferable that it is 1 or 2.

As a compound represented by said Formula (b1), what is shown below is mentioned, for example. In addition, the compound represented by said formula (b1) can be used individually by 1 type or in combination of 2 or more type.

(Compound represented by the above formula (b2))

About the compound represented by said Formula (b2), m is an integer of 0-2, and it is preferable that it is 1 or 2.

As a compound represented by said formula (b2), what is shown below is mentioned, for example. In addition, the compound represented by said formula (b2) can be used individually by 1 type or in combination of 2 or more type.

Moreover, the specific solvent (B) contained in the composition or liquid crystal aligning agent of this invention is a compound represented by the said Formula (b-1A), the compound represented by the said Formula (b-1B), and said Formula (b1) or Formula One of the compounds represented by (b2) may be sufficient. Moreover, you may include these in combination of 2 or more types.

(Other solvents)

It is preferable that compositions, such as a liquid crystal aligning agent of this invention, contain other solvents other than the said specific solvent (B) further as a solvent component. Examples of the other solvent include a solvent capable of dissolving the polymer (A) (hereinafter also referred to as a “first solvent”), and an organic solvent other than the specific solvent (B) as a poor solvent for the polymer (A). .

The first solvent may be a good solvent for the polymer (A), and preferred specific examples thereof include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-pentyl-2. -Pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, N,N,2-trimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, γ-butyrolactone, γ-buty Lolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, Hexamethylphosphotriamide, m-cresol, etc. are mentioned. In addition, the 1st solvent can use said thing individually by 1 type or in mixture of 2 or more types.

In addition, as the poor solvent of the polymer (A), as an organic solvent other than the specific solvent (B) (hereinafter also referred to as “other poor solvents”), for example, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, Methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cell Rosolv), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl Ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, ethylene carbonate, propylene carbonate, diacetone alcohol, diethylene glycol diethyl ether, diisopentyl ether, propylene glycol diacetate, etc. can The said organic solvent can be used individually by 1 type or in mixture of 2 or more types of said thing. In addition, below, the group which consists of said other poor solvents and a specific solvent (B) is also called "2nd solvent."

It is preferable that the content rate of the specific solvent (B) in a liquid crystal aligning agent is 1-70 weight% with respect to the whole quantity of the solvent contained in a liquid crystal aligning agent. When content of a specific solvent (B) is less than 1 weight%, the effect of improving the applicability|paintability with respect to a board|substrate is hard to be acquired, and when it exceeds 70 weight%, a polymer component will become easy to precipitate. The content rate of a specific solvent (B) becomes like this. More preferably, it is 5-70 weight%, More preferably, it is 10-65 weight%.

Moreover, with respect to the whole quantity of the solvent contained in a liquid crystal aligning agent from a viewpoint that the content rate of a said 1st solvent suppresses precipitation of a polymer (A), Preferably it is 5 weight% or more, More preferably, it is 10 It is weight % or more, More preferably, it is 15 weight% or more. In addition, about the upper limit of the content rate of the said 1st solvent, from a viewpoint of obtaining suitably the effect by addition of the said specific solvent (B) with respect to the whole quantity of the solvent contained in a liquid crystal aligning agent, Preferably it is 99 weight. % or less, more preferably 95 weight% or less, and still more preferably 85 weight% or less.

To [ the content rate of said other poor solvent / the whole quantity of the solvent contained in a liquid crystal aligning agent ], Preferably it is 70 weight% or less, More preferably, it is 60 weight% or less, More preferably, it is 50 weight% or less. and particularly preferably 30% by weight or less.

The ratio of the first solvent to the second solvent is preferably 0.03 times (by weight) or more, the amount of the second solvent used relative to the amount used of the first solvent from the viewpoint of improving the applicability to the substrate, It is more preferable to set it as 0.05 times (weight) or more. Moreover, from a viewpoint of suppressing precipitation of a polymer, it is preferable to set it as 2.5 times (weight) or less, and it is more preferable to set it as 2.0 times (weight) or less.

It is preferable that the liquid crystal aligning agent which concerns on this invention does not contain the butyl cellosolve substantially as a solvent. In addition, with respect to the whole quantity of the solvent in which the content rate of a butyl cellosolve is contained in a liquid crystal aligning agent with "a butyl cellosolve is not included substantially" in this specification, Preferably it is 5 weight% or less. , more preferably 3 wt% or less, still more preferably 0.5 wt% or less.

<< other ingredients >>

Although compositions, such as the liquid crystal aligning agent which concern on this invention, contain the above polymer (A) and a solvent, they may contain other components as needed. Examples of such other components include other polymers other than the above polymer (A), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compounds”), functional silane compounds, and the above amine compounds. (C) etc. are mentioned.

[Other polymers]

The other polymers mentioned above can be used for improving solution properties and electrical properties. Examples of such other polymers include polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, and poly(meth)acrylate. When adding the said other polymer to a liquid crystal aligning agent, 50 weight% or less is preferable with respect to the total amount of the polymer component in a liquid crystal aligning agent, as for the compounding ratio, 0.1 to 40 weight% is more preferable, 0.1 to 30 % by weight is more preferable.

[Compound containing an epoxy group]

An epoxy group containing compound can be used in order to improve the adhesiveness with the board|substrate surface in a liquid crystal aligning film. Here, as the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Dil ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol di Glycidyl ether, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N, N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine etc. are mentioned.

When adding these epoxy group containing compounds to a liquid crystal aligning agent, 40 weight part or less is preferable with respect to a total of 100 weight part of the polymer contained in the liquid crystal aligning agent, and, as for the compounding ratio, 0.1-30 weight part is more preferable.

[Functional Silane Compound]

The said functional silane compound can be used for the purpose of the printability improvement of a liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2 -Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-tri Methoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonanoic acid methyl, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, glycidoxymethyl trimethoxysilane, 2-glycidoxyethyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, etc. are mentioned.

When adding these functional silane compounds to a liquid crystal aligning agent, 2 weight part or less is preferable with respect to a total of 100 weight part of a polymer, and, as for the compounding ratio, 0.02-0.2 weight part is more preferable.

[Amine compound (C)]

The amine compound (C) is a compound having one primary amino group and a nitrogen-containing aromatic heterocycle, and has a structure in which the primary amino group is bonded to a chain hydrocarbon group or an alicyclic hydrocarbon group. The said amine compound (C) is a liquid crystal aligning film use. WHEREIN: It can be used for the purpose of improving the electrical characteristics (for example, voltage retention, relaxation rate of a residual electric charge, etc.) of a liquid crystal display element.

The nitrogen-containing aromatic heterocycle in the amine compound (C) may be an aromatic ring containing one or more nitrogen atoms in the ring skeleton. Accordingly, the ring skeleton may contain only a nitrogen atom as a hetero atom, or may contain a nitrogen atom and a hetero atom other than the nitrogen atom (oxygen atom, sulfur atom, etc.). Specific examples of the nitrogen-containing aromatic heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an indole ring, a benzimidazole ring, and a purine ring. , quinoline ring, isoquinoline ring, naphthyridine ring, quinoxaline ring, phthalazine ring, triazine ring, azepine ring, diazepine ring, acridine ring, phenazine ring, phenanthroline ring, oxazole ring, thiazole ring, carbazole ring, A thiadiazole ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, etc. are mentioned. The nitrogen-containing aromatic heterocycle may be one in which a substituent is introduced into a carbon atom constituting the ring exemplified above. Examples of the substituent include a halogen atom, an alkyl group, and an alkoxy group.

In the amine compound (C), the chain hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms. In addition, linear or branched form may be sufficient as the said chain|strand-shaped hydrocarbon group, and saturated or unsaturated may be sufficient as it. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, still more preferably 3 to 10 carbon atoms.

As said amine compound (C), the compound represented by a following formula (c-1) can be used preferably.

(In formula (c-1), A ¹ is a divalent organic group having a chain hydrocarbon group or an alicyclic hydrocarbon group, A ² is a nitrogen-containing aromatic heterocycle;

However, the primary amino group in a formula is couple|bonded with the chain hydrocarbon group or alicyclic hydrocarbon group which ^{A<1> has).}

In the formula (c-1), as the ^{divalent organic group in A 1} , for example, a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, -OR ²¹ -, -CO-R ²¹ -( However, R ²¹ is a divalent chain hydrocarbon group or an alicyclic hydrocarbon group) and the like. In addition, the said divalent organic group is -O-, -NH-, -CO-O-, -CO-NH-, -CO between carbon-carbon bonds in a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group. -, -S-, -S(O) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -O-, phenylene group, etc. a divalent group having a heterocyclic group such as an aromatic hydrocarbon group or a pyridinylene group;

At least one hydrogen atom in the divalent chain hydrocarbon group or the divalent alicyclic hydrocarbon group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromination atom or an iodine atom, an aromatic hydrocarbon group such as a phenyl group, a hydroxyl group, a halogenated alkyl group, etc. A divalent group consisting of;

etc. is fine. For specific examples of the divalent chain hydrocarbon group and the alicyclic hydrocarbon group in A ¹ , the description ^{of R 24 in the formula (m-1) applies.}

Among the above, A ¹ is preferably a divalent organic group having a chain hydrocarbon group, and more preferably a divalent chain hydrocarbon group. It is preferable that A<^1> is C1-C20, It is more preferable that it is C1-C15, It is more preferable that it is C1-C10. The above description applies to the nitrogen-containing aromatic heterocycle of ^{A 2 .}

Specific examples of the amine compound (C) include compounds represented by each of the following formulas (c-1-1) to (c-1-32). In addition, as an amine compound (C), 1 type of these can be used individually or in combination of 2 or more type.

When adding the said amine compound (C) in a liquid crystal aligning agent, the compounding ratio is 1 weight part or more with respect to a total of 100 weight part of a polymer from a viewpoint of obtaining the effect by addition of an amine compound (C) suitably. It is preferable to set it as, and it is more preferable to set it as 2 weight part or more. Moreover, it is preferable to set it as 20 weight part or less with respect to a total of 100 weight part of a polymer from a viewpoint of not impairing stability of a liquid crystal aligning agent, and it is more preferable to set it as 15 weight part or less.

Moreover, as another additive made to contain in a liquid crystal aligning agent, the compound which has an at least 1 oxetanyl group in a molecule|numerator other than the above, antioxidant, etc. are mentioned. These use ratios can be suitably selected according to the additive to be used in the range which does not impair the effect of this invention.

When the said amine compound (C) is contained as an additive in the liquid crystal aligning agent which concerns on this invention, the point which can improve the electrical property of a liquid crystal display element suitably WHEREIN: At least one part of the said polymer (A) is carboxyl It is preferable to have a group. Moreover, as for the number of the carboxyl groups which the said polymer (A) has, it is preferable to set it as 0.1-3 pieces in average value per repeating unit of the polymer (A), It is more preferable to set it as 0.3-2 pieces, It is to set it as 0.5-1.8 pieces more preferably.

The method of adjusting the number of carboxyl groups which a polymer (A) has is not specifically limited, For example, (i) the method performed by adjusting the imidation rate of a polyimide, (ii) used for the synthesis|combination of a polymer (A) The method performed by adjusting carboxyl group content of diamine, etc. are mentioned. Moreover, you may carry out by using said (i) and (ii) together. From the viewpoint of increasing the degree of freedom of the imidization rate of the polymer (A), it is preferable to use the method (ii) above.

When containing the polymer (A) which has a carboxyl group, and the said amine compound (C) in a liquid crystal aligning agent, the compounding ratio of an amine compound (C) is 0.01-2 mol with respect to 1 mol of the carboxyl groups which a polymer (A) has. It is preferable to set it as 0.05-1 mol, It is more preferable to set it as 0.05-1 mol, It is still more preferable to set it as 0.08-0.8 mol.

The solid content concentration (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) of the liquid crystal aligning agent according to the present invention is appropriately selected in consideration of viscosity, volatility, etc., but preferably 1 -10% by weight. That is, the liquid crystal aligning agent according to the present invention is applied to the surface of the substrate as described later, and is preferably heated to form a coating film that is a liquid crystal aligning film or a liquid crystal aligning film, but at this time, when the solid content concentration is less than 1% by weight The film thickness of a coating film becomes too small, and it is difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and it is hard to obtain a favorable liquid crystal aligning film, and the viscosity of a liquid crystal aligning agent increases and it becomes inferior to an application|coating characteristic.

The range of especially preferable solid content concentration changes with the method used when apply|coating a liquid crystal aligning agent to a board|substrate. For example, in the case of spin coating, a solid content concentration of 1.5 to 4.5 wt% is particularly preferable. In the case of the offset printing method, it is especially preferable to make the solid content concentration into the range of 3 to 9 weight%, and to make the solution viscosity into the range of 12 to 50 mPa·s accordingly. In the case of the inkjet method, it is particularly preferable to set the solid content concentration to be in the range of 1 to 8% by weight, and thereby the solution viscosity to be in the range of 3 to 20 mPa·s. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

«Liquid crystal alignment film and liquid crystal display element»

The liquid crystal aligning film which concerns on this invention is formed with the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal display element which concerns on this invention is equipped with the liquid crystal aligning film formed using the said liquid crystal aligning agent. The drive mode to which a liquid crystal display element is applied is not specifically limited, It can apply to various drive modes, such as a TN type, STN type, IPS type, FFS type, VA type, MVA type. Below, while demonstrating the manufacturing method of the liquid crystal display element which concerns on this invention, the manufacturing method of a liquid crystal aligning film is demonstrated in the description.

The liquid crystal display element which concerns on this invention can be manufactured by the process of the following (1)-(3), for example. In the step (1), the substrate used differs depending on the desired driving mode. Steps (2) and (3) are common to each drive mode.

[Step (1): Formation of a coating film]

First, the liquid crystal aligning agent of this invention is apply|coated on a board|substrate, and a coating film is formed on a board|substrate by heating an application surface then.

(1-1) In the case of manufacturing a TN type, STN type or VA type liquid crystal display element, two substrates on which a patterned transparent conductive film is formed are set as a pair, and on each transparent conductive film formation surface, the present invention The liquid crystal aligning agent according to each is preferably applied by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. Here, as a board|substrate, For example, glass, such as float glass and soda glass;

A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate or poly(alicyclic olefin) can be used. As a transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Corporation in the United States) made of _{tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2} O ₃ -SnO ₂ ), etc. are used. can In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming the transparent conductive film, etc. have. At the time of application|coating of a liquid crystal aligning agent, in order to make the adhesiveness of a board|substrate surface and a transparent conductive film and a coating film more favorable, a functional silane compound, a functional titanium compound, etc. You may perform pre-processing to apply|coat in advance.

After application|coating of a liquid crystal aligning agent, for purposes, such as liquid flow prevention of the apply|coated aligning agent, Preferably, preliminary heating (prebaking) is performed. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25 to 10 minutes, More preferably, it is 0.5 to 5 minutes. After that, the solvent is completely removed, and if necessary, a calcination (post-baking) step is performed for the purpose of thermal imidation of the amic acid structure present in the polymer. This baking (post-baking) temperature becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5 to 200 minutes, More preferably, it is 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 µm, more preferably 0.005 to 0.5 µm.

(1-2) In the case of manufacturing an IPS type or FFS type liquid crystal display element, the electrode formation surface of the substrate on which the electrode formed of a transparent conductive film or metal film patterned in a comb-tooth shape is formed, and the electrode is not formed opposite A coating film is formed by respectively apply|coating the liquid crystal aligning agent which concerns on this invention to one surface of a board|substrate, and heating each application surface then. At this time, the material of the substrate and the transparent conductive film used, the coating method, the heating conditions after application, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film are the same as in (1-1) above. . As the metal film, for example, a film made of a metal such as chromium can be used.

In either case of said (1-1) and (1-2), after apply|coating a liquid crystal aligning agent on a board|substrate, the coating film used as an orientation film is formed by removing an organic solvent. At this time, when the polymer contained in the liquid crystal aligning agent is a polyamic acid or an imidized polymer having an imide ring structure and a amic acid structure, a dehydration ring closure reaction proceeds by further heating after coating film formation, and a more imidized coating film can be done as

[Step (2): Orientation ability imparting treatment]

When manufacturing the liquid crystal display element of TN type, STN type, IPS type, or FFS type, the process which provides liquid-crystal orientation ability to the coating film formed in the said process (1) is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. Examples of the treatment include a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and a photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. On the other hand, when manufacturing a VA type liquid crystal display element, although the coating film formed in the said process (1) can be used as a liquid crystal aligning film as it is, you may perform an orientation ability provision process with respect to the said coating film.

Photo-alignment treatment WHEREIN: As radiation irradiated to a coating film, the ultraviolet-ray and visible light containing the light of a wavelength of 150-800 nm can be used, for example. When the radiation is polarized light, linearly polarized light or partially polarized light may be sufficient. In the case where the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When irradiating a non-polarized radiation, the direction of irradiation is made into an oblique direction.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. Ultraviolet rays in a preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter, a diffraction grating, or the like. The radiation dose is preferably 100 to 50,000 J/m 2 , more preferably 300 to 20,000 J/m 2 . In addition, light irradiation to the coating film may be performed while heating the coating film in order to increase the reactivity. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.

In addition, with respect to the liquid crystal aligning film after the rubbing treatment, by irradiating an ultraviolet ray to a part of the liquid crystal aligning film, a treatment to change the pretilt angle of a part of the liquid crystal aligning film, or after forming a resist film on a part of the liquid crystal aligning film surface, prior rubbing After performing a rubbing process in the direction different from a process, you may perform the process which removes a resist film so that a liquid crystal aligning film may have different liquid-crystal orientation ability for every area|region. In this case, it is possible to improve the visibility characteristics of the liquid crystal display element obtained. The liquid crystal aligning film suitable for the liquid crystal display element of VA type can be used suitably also for the liquid crystal display element of PSA(Polymer Sustained Alignment) type.

[Step (3): Construction of liquid crystal cell]

A liquid crystal cell is manufactured by preparing two board|substrates with a liquid crystal aligning film as mentioned above, and arrange|positioning a liquid crystal between the board|substrates of 2 sheets opposingly arranged. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a method known conventionally. First, two substrates are arranged to face each other through a gap (cell gap) so that each liquid crystal aligning film is opposed to each other, and the peripheral portions of the two substrates are bonded using a sealing agent, and the substrate surface and partitioned by the sealing agent After the liquid crystal is injected and filled in the cell gap, the liquid crystal cell is manufactured by sealing the injection port. Note that the second method is a method called an ODF (One Drop Fill) method. After apply|coating an ultraviolet-ray-curable sealing compound to the predetermined place on one board|substrate among two board|substrates in which the liquid crystal aligning film was formed, for example, and dripping a liquid crystal to predetermined several places on the liquid crystal aligning film surface further, liquid crystal A liquid crystal cell is manufactured by bonding the other board|substrate so that an alignment film may oppose, and at the same time, spreading a liquid crystal on the whole surface of a board|substrate, and then irradiating ultraviolet light to the whole surface of a board|substrate to harden|cure a sealing compound. In any case, it is preferable to remove the flow orientation at the time of liquid crystal filling by heating the liquid crystal cell produced as described above to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooling it to room temperature. do.

As a sealing agent, the epoxy resin etc. containing the aluminum oxide sphere as a hardening|curing agent and a spacer can be used, for example.

Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among these, a nematic liquid crystal is preferable, for example, a Cipher base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, and an ester liquid crystal , terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cuban-based liquid crystal, and the like can be used. Moreover, to these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate;

Chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck Corporation);

A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.

And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate sandwiched between a polarizing film called “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol, or a polarizing plate composed of H film itself is mentioned. . Moreover, when rubbing process is performed with respect to a coating film, two board|substrates are opposingly arrange|positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

The liquid crystal display element according to the present invention can be effectively applied to various devices, for example, a watch, a portable game, a word processor, a notebook personal computer, a car navigation system, a camcorder, a PDA, a digital camera, and a portable device. It can be used for display devices, such as a telephone, a smartphone, various monitors, and a liquid crystal television.

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited to these Examples.

In the following examples, the imidation ratio of the polyimide in the polymer solution and the solution viscosity of the polymer solution were measured by the following methods.

[Imidation rate of polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ^<1> H-NMR spectrum, the imidation rate [%] was calculated|required by following formula (x).

Imidization ratio [%] = (1-A ¹ /A ² x α) x 100 ... (x)

(In formula (x), A ¹ is the peak area derived from protons of the NH group appearing in the vicinity of 10 ppm of the chemical shift, A ² is the peak area derived from other protons, and α is the polymer precursor (polyamic acid) It is the ratio of the number of other protons to one proton of the NH group).

[Solution Viscosity of Polymer Solution]

The solution viscosity (mPa·s) of the polymer solution was measured at 25°C using an E-type rotational viscometer.

(Example 1)

[Example 1A]

1,3-bis(4-aminophenethyl)urea (BAPU) = 0.60 g (2.0 mmol) as diamine and p-phenylenediamine (p-PDA) in a 50 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube ) 　 1.95 g (18.0 mmol) was put, 30 g of N-methyl-2-pyrrolidone (NMP) was added, and it was dissolved by stirring while sending nitrogen. While stirring this diamine solution, 3.70 g (18.9 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is added as tetracarboxylic dianhydride, and the solid content concentration is 12% by weight. NMP was added and stirred at room temperature under nitrogen atmosphere for 4 hours to obtain a solution of polyamic acid (PA-1).

To this polyamic acid solution, NMP and a compound represented by the following formula (ba) as a specific solvent (B) (hereinafter referred to as “compound (ba)”) are added, and the solvent composition is NMP: compound (ba) = 60: The liquid crystal aligning agent (S1A) was prepared so that 40 (weight ratio) and polyamic-acid density|concentration might be set to 6.0 weight%.

[Example 2A]

19.2 g (0.098 mol) of CBDA as tetracarboxylic dianhydride and 24.2 g (0.1 mol) of 1,5-bis(4-aminophenoxy)pentane as diamine were dissolved in 343.5 g of NMP, followed by reaction at room temperature for 10 hours. The polymerization reaction proceeded easily and uniformly to obtain polyamic acid (PA-2). To the NMP solution of this polyamic acid (PA-2), NMP and a compound represented by the following formula (bb) as a specific solvent (B) (hereinafter referred to as “compound (bb)”) are added, and the solvent composition is NMP: The liquid crystal aligning agent (S2A) was prepared so that compound (bb)=50:50 (weight ratio) and polyamic-acid density|concentration might be set to 6.0 weight%.

[Example 3A]

22.42 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 18.73 g (0.094) of 4,4'-diaminodiphenylamine (4,4' DADPA) as diamine mol) was mixed in 345.1 g of NMP and reacted at room temperature for 5 hours. The polymerization reaction proceeded easily and uniformly to obtain polyamic acid (PA-3). To the NMP solution of this polyamic acid (PA-3), NMP and a compound represented by the following formula (bc) as a specific solvent (B) (hereinafter referred to as “compound (bc)”) are added, and the solvent composition is NMP: The liquid crystal aligning agent (S3A) was prepared so that compound (bc)=80:20 (weight ratio) and polyamic-acid density|concentration might be set to 6.0 weight%.

[Example 4A]

As diamine, p-PDA = 6.5 g (0.06 mol) and 4-(4-trans-n-heptylcyclohexyl)phenoxy)-1,3-diaminobenzene (PCH7DAB, represented by the above formula (d-4-3) Compound) 15.22 g (0.04 mol) was dissolved in 165 g of NMP, and 19.41 g (0.099 mol) of CBDA as tetracarboxylic dianhydride was added thereto, and reacted at room temperature for 24 hours to contain polyamic acid (PA-4) a solution was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid (PA-4) was 40,000. To 30 g of this solution, NMP and a compound represented by the following formula (bd) as a specific solvent (B) (hereinafter referred to as “compound (bd)”) were added, and the solvent composition was NMP: compound (bd) = 80: 20 (weight ratio), the liquid crystal aligning agent (S4A) of 4.5 weight% of density|concentrations was prepared.

[Example 5A]

1.46 g (13.5 mmol) of p-PDA as diamine and 0.78 g (1.50 mmol) of 3,5-diaminobenzoic acid cholestanyl were mixed in 20.0 g of NMP, and 2.85 g (14.5 g of CBDA) as tetracarboxylic dianhydride mmol) was added, NMP 24.7g was added, and it was made to react at 25 degreeC for 5 hours, and the solution containing polyamic acid (PA-5) was obtained. Next, to 40.0 g of the obtained polyamic acid solution, NMP and a compound represented by the following formula (be) as a specific solvent (B) (hereinafter referred to as “compound (be)”) are added, and the solvent composition is NMP: compound (be ) =75:25 (weight ratio), the liquid crystal aligning agent (S5A) was prepared so that polyamic-acid density|concentration might be set to 4.0 weight%.

[Example 6A]

CBDA 　2.58 g (13.1 mmol) as tetracarboxylic dianhydride and PCH7DAB 　 5.0 g (13.1 mmol) as diamine were dissolved in 43 g of NMP, and reacted by stirring at 20 ° C. for 4 hours to contain polyamic acid (PA-6) a solution was obtained. Next, to the obtained NMP solution of polyamic acid (PA-6), NMP and a compound represented by the following formula (bf) as a specific solvent (B) (hereinafter referred to as “compound (bf)”) were added, and the solvent composition was The liquid crystal aligning agent (S6A) was prepared so that NMP:compound (bf)=35:65 (weight ratio) and solid content concentration might be set to 3.0 weight%.

[Example 7A]

8.724 g (0.04 mol) of pyromellitic dianhydride (PMDA) as tetracarboxylic dianhydride, 2.877 g (0.0266 mol) of p-PDA as diamine, and 4.567 g (0.012 mol) of PCH7DAB as NMP 91.6 g (0.012 mol) in 91.6 g of NMP at room temperature for 3 hours It was made to react, and the solution containing polyamic acid (PA-7) was prepared. To 25 g of this polyamic acid solution, NMP and a compound represented by the following formula (bg) as a specific solvent (B) (hereinafter referred to as “compound (bg)”) are added, and the solvent composition is NMP: compound (bg) = 60 : 40 (weight ratio) and the liquid crystal aligning agent (S7A) were prepared so that it might become 5.0 weight% of solid content concentration.

[Example 8A]

14.64 g (0.072 mol) of 2,4-diamino-N,N-diallylaniline as diamine, 2.96 g (0.016 mol) of n-dodecylamine as monoamine, and 15.69 g (0.08 mol) of CBDA as tetracarboxylic dianhydride mol) was reacted in 300 g of NMP at room temperature for 4 hours to prepare a solution containing a polyamic acid intermediate (PA-8). To the NMP solution of the polyamic acid intermediate, NMP and a compound represented by the following formula (bh) as a specific solvent (B) (hereinafter referred to as “compound (bh)”) are added, and the solvent composition is NMP: compound (bh) =60:40 (weight ratio) and the liquid crystal aligning agent (S8A) of 6.0 weight% of solid content concentration were prepared.

[Example 9A]

Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-2 anhydride (BODA) 4.50 g (0.018 mol) as tetracarboxylic dianhydride, PCH7DAB 0.68 as diamine After making g (0.0018 mol) and p-PDA 1.75 g (0.0162 mol) react at room temperature in 39.3 g of NMPs, it was made to react at 40 degreeC further for 43 hours. NMP was added to 42 g of this polyamic acid solution to prepare a 1% by weight solution, to which 4.18 g of acetic anhydride and 6.48 g of pyridine were added as an imidization catalyst, and reacted at room temperature for 30 minutes and at 120°C for 2 hours. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a white polyimide powder. When the imidation ratio of the obtained polyimide powder (polyimide (PI-1)) was measured, it was 72 %. Liquid crystal aligning agent (S9A) by adding and dissolving NMP and compound (ba) as a specific solvent (B) to this powder so that a solvent composition may be NMP:compound (ba)=50:50 (weight ratio), and solid content concentration of 4.5 weight% ) was prepared.

[Comparative Examples 1A to 9A]

With respect to the solvent composition of the liquid crystal aligning agent, the polymer was synthesized in the same manner as in Examples 1A to 9A above, except that butyl cellosolve (BC) was used in place of the specific solvent (B) as the second solvent, and liquid crystal The aligning agent was prepared, and liquid crystal aligning agent (R1A) - (R9A) were obtained, respectively. In addition, Comparative Example XA (X is an integer of 1 to 9) is an example corresponding to Example XA. That is, in comparative example XA, while synthesize|combining the polymer similar to Example XA, the liquid crystal aligning agent was prepared similarly to Example XA except having replaced with the specific solvent (B) and having used the butyl cellosolve.

[Example 10A]

Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-2 anhydride (BODA) 4.50 g (0.018 mol) as tetracarboxylic dianhydride, the above formula as diamine After reacting the compound (PBCH5DAB) represented by (d-4-2) 2.34 g (0.0054 mol) and 1.92 g (0.0126 mol) of 3,5-diaminobenzoic acid (35DAB) at room temperature in 26.3 g of NMP, further The reaction was carried out at 40°C for 43 hours. NMP was added to 30 g of this polyamic acid solution to prepare a 6% by weight solution, and as an imidization catalyst, 2.4 g of acetic anhydride and 1.8 g of pyridine were added thereto, and reacted at room temperature for 30 minutes and 110°C for 4 hours. The white precipitate obtained by injecting|throwing-in this solution in a large amount of methanol was separated by filtration, and it dried and obtained white polyimide powder. When the imidation ratio of the obtained polyimide powder (polyimide (PI-2)) was measured, it was 72 %. 0.6 g of this powder was dissolved in a mixed solvent of NMP and 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent and compound (ba) as a specific solvent (B), polyimide concentration 6.0 It was set as the weight % solution. A liquid crystal aligning agent (S10A) by adding 0.4 g (equivalent to 0.03 g as 3-AMP) of a 7.5 weight% NMP solution of 3-aminomethylpyridine (3-AMP) to this solution, and stirring at 50 degreeC for 15 hours got it In addition, the liquid crystal aligning agent was prepared so that a solvent composition might become NMP:D1:compound (b-a)=30:20:50 (weight ratio).

[Example 11A]

The same operation as in Example 10A was performed except that the amount of PBCH5DAB used for the synthesis of polyamic acid was 3.90 g (0.0090 mol) and the amount of 3,5-diaminobenzoic acid was changed to 1.37 g (0.0090 mol), and the poly A solution of amic acid was obtained. Moreover, operation similar to Example 10A was performed using the obtained polyamic acid solution, and the polyimide powder was obtained. When the imidation ratio of the obtained polyimide powder (polyimide (PI-3)) was measured, it was 74 %. 0.6 g of this powder was dissolved in a mixed solvent of NMP and 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent and compound (bb) as a specific solvent (B), polyimide concentration 6.0 It was set as the weight % solution. Liquid crystal aligning agent (S11A) by adding 0.8g (equivalent to 0.06 g as 3-AMP) of the 7.5 weight% NMP solution of 3-aminomethylpyridine (3-AMP) to this solution, and stirring at 50 degreeC for 15 hours got it In addition, the liquid crystal aligning agent was prepared so that a solvent composition might become NMP:D2:compound (b-b)=30:30:40 (weight ratio).

[Example 12A]

A solution containing polyamic acid (PA-1) was prepared in the same manner as in Example 1A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent and compound (bc) as a specific solvent (B), so that the solvent composition was D1: compound (bc) =60:0 (weight ratio) and the liquid crystal aligning agent (S12A) of 6.0 weight% of solid content concentration were obtained.

[Example 13A]

A solution containing polyamic acid (PA-2) was prepared in the same manner as in Example 2A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent and compound (bd) as a specific solvent (B), so that the solvent composition was D2: compound (bd) =50:50 (weight ratio) and the liquid crystal aligning agent (S13A) of polyamic-acid density|concentration 6.0 weight% were obtained.

[Example 14A]

A solution containing polyamic acid (PA-3) was prepared in the same manner as in Example 3A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of NMP and 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent, and compound (be) as a specific solvent (B), so that the solvent composition was NMP:D1 : The liquid crystal aligning agent (S14A) of the compound (be)=40:40:20 (weight ratio) and polyamic acid density|concentration 6.0 weight% was obtained.

[Example 15A]

A solution containing polyamic acid (PA-4) was prepared in the same manner as in Example 4A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder and, as an additive, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (E1), NMP and 3-butoxy-N as a first solvent, Dissolve in a mixed solvent of N-dimethylpropionamide (D2) and compound (bf) as a specific solvent (B), so that the solvent composition is NMP:D2:compound (bf)=40:40:20 (weight ratio), polyamic acid The liquid crystal aligning agent (S15A) of density|concentration 6.0 weight% was obtained. In addition, the quantity of the additive (E1) used was made into 5 weight part with respect to the polyamic acid powder.

[Example 16A]

A solution containing polyamic acid (PA-5) was prepared in the same manner as in Example 5A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent and compound (bg) as a specific solvent (B), so that the solvent composition was D1: compound (bg) =75:25 (weight ratio) and the liquid crystal aligning agent (S16A) of polyamic acid density|concentration 6.0 weight% were obtained.

[Example 17A]

A solution containing polyamic acid (PA-6) was prepared in the same manner as in Example 6A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent and compound (bh) as a specific solvent (B), so that the solvent composition was D2: compound (bh) =35:65 (weight ratio) and the liquid crystal aligning agent (S17A) of polyamic acid density|concentration 6.0 weight% were obtained.

[Example 18A]

A solution containing polyamic acid (PA-7) was prepared in the same manner as in Example 7A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of NMP and γ-butyrolactone (D3) as a first solvent, and compound (ba) as a specific solvent (B), so that the solvent composition was NMP:D3:compound (ba)=30 : 30:40 (weight ratio) and the liquid crystal aligning agent (S18A) of polyamic acid density|concentration 6.0 weight% were obtained.

[Example 19A]

A solution containing a polyamic acid intermediate (PA-8) was prepared in the same manner as in Example 8A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of NMP and 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent, and compound (bb) as a specific solvent (B), so that the solvent composition was NMP:D2 : The liquid crystal aligning agent (S19A) of compound (bb)=30:30:40 (weight ratio) and polyamic-acid density|concentration 6.0 weight% was obtained.

[Example 20A]

A powder of polyimide (PI-1) was obtained in the same manner as in Example 9A. This powder was dissolved in a mixed solvent of 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent and compound (bc) as a specific solvent (B), so that the solvent composition was D1: compound (bc) =50:50 (weight ratio) and the liquid crystal aligning agent (S20A) of 6.0 weight% of solid content concentration were obtained.

<Evaluation of storage stability>

About each liquid crystal aligning agent obtained above, after having filtered with a 1.0 micrometer filter and storing at -30 degreeC for 1 month, it returned to room temperature (25 degreeC) and the presence or absence of the precipitate in a liquid crystal aligning agent was observed. The results are shown in Tables 1 and 2 below. In addition, in Table 1 and Table 2, the case where "(circle)" and a precipitate were observed was shown with "x" in the case where a precipitate was not observed in the liquid crystal aligning agent.

<Evaluation of printability>

About each liquid crystal aligning agent prepared above, after filtration with a 1.0 micrometer filter, after storing at -15 degreeC for 6 months, it returned to room temperature (25 degreeC). Next, the liquid crystal aligning agent was apply|coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film using the liquid crystal aligning film printing machine (made by Nippon Corporation). Then, after heating (prebaking) for 1 minute on an 80 degreeC hotplate and removing a solvent, it heated (postbaking) for 10 minutes on a 200 degreeC hotplate, and formed the coating film with an average film thickness of 0.06 micrometer. The coating film was observed under a microscope at a magnification of 20 times to examine the presence or absence of print unevenness and pinholes. Evaluation was performed as printability poor (x) in the case where printability was good (circle) and at least either of the printing unevenness and pinhole was observed in the case where print nonuniformity and a pinhole were not mostly observed. The results are shown in Tables 1 and 2 below.

In addition, the abbreviation in Table 1 and Table 2 is as follows.

(tetracarboxylic acid dianhydride)

AN-1; 1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride

AN-2; 2,3,5-tricarboxycyclopentylacetic acid dianhydride

AN-3; pyromellitic dianhydride

AN-4; Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-2 anhydride

(diamine)

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

DA-2: 2,4-diamino-N,N-diallylaniline

DA-3: 3,5-diaminobenzoic acid cholestanyl

35DAB: 3,5-diaminobenzoic acid

(monoamine)

MA-1: n-dodecylamine

(1st solvent)

D1: 3-methoxy-N,N-dimethylpropionamide

D2: 3-butoxy-N,N-dimethylpropionamide

D3: γ-butyrolactone

(second solvent)

BC: Butyl Cellosolve

(additive)

3-AMP: 3-aminomethylpyridine (compound represented by the above formula (c-1-16))

E1: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane

<Production and evaluation of optical alignment FFS type liquid crystal display element>

(1) Manufacturing of FFS type liquid crystal display device using photo-alignment method

The FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a comb-shaped top electrode 13 formed in this order are combined electrodes formed in this order on one side of a glass substrate 11a having a glass substrate 11a and , a pair of opposing glass substrates 11b on which no electrodes are formed, on the surface of the glass substrate 11a having a transparent electrode and on one surface of the opposing glass substrate 11b, the liquid crystal aligning agent (S1A) obtained above A coating film was formed using the inkjet coating method. Moreover, with respect to a liquid crystal aligning agent (S1A), before apply|coating on a board|substrate, it prepares so that a viscosity may be 18 cP, making a solvent composition "NMP:compound (ba)=60:40 (weight ratio)", and the viscosity is adjusted liquid crystal An aligning agent was applied on the substrate.

Subsequently, this coating film was prebaked for 1 minute on a hotplate at 80°C, and then heated (post-baked) at 230°C for 15 minutes in an oven in which the inside of the tube was substituted with nitrogen to form a coating film having an average film thickness of 0.1 µm. A schematic plan view of the top electrode 13 used here is shown in FIG. 2 . Fig. 2(a) is a top view of the top electrode 13, and Fig. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in Fig. 2(a). In this embodiment, a substrate having a top electrode having a line width d1 of the electrodes of 4 μm and a distance d2 between the electrodes of 6 μm was used. As the top electrode 13, four drive electrodes of electrode A, electrode B, electrode C, and electrode D were used. Fig. 3 shows the configuration of the driving electrode of this liquid crystal display element. In this case, the bottom electrode 15 acts as a common electrode that acts on all of the drive electrodes of the four lines, and each of the areas of the drive electrodes of the four lines becomes a pixel area.

Next, each surface of these coating films is irradiated with 300 J/m of polarized ultraviolet light including a bright line of 313 nm from the substrate normal direction using an Hg-Xe lamp and a Glan Taylor prism, respectively, a pair of substrates having a liquid crystal alignment film got At this time, the irradiation direction of the polarized ultraviolet light was from the normal direction of the substrate, and the polarization plane direction was set so that the direction of the line segment which projected the polarization plane of the polarized ultraviolet light onto the substrate was the direction of the double arrow in FIG.

Next, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 µm is applied to the outer periphery of the surface having a liquid crystal aligning film of one of the substrates by screen printing, and then the liquid crystal aligning film surfaces of a pair of substrates are opposed , the polarization plane of the polarized ultraviolet ray was pressed on top of each other so that the projected directions on the substrate were parallel, and the adhesive was thermosetted at 150°C for 1 hour. Next, after filling the liquid crystal "MLC-6221" manufactured by Merck into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow orientation at the time of liquid crystal injection, after heating this to 150 degreeC, it cooled gradually to room temperature.

Next, the FFS type liquid crystal display element was manufactured by bonding a polarizing plate to the outer both surfaces of a board|substrate. At this time, one of the polarizing plates is adhered so that its polarization direction is parallel to the projection direction of the polarization plane of the polarized ultraviolet light of the liquid crystal aligning film to the substrate surface, and the other is adhered so that its polarization direction is perpendicular to the polarization direction of the previous polarizing plate. did.

By repeating the above method, a total of five FFS type liquid crystal display elements were manufactured, and one each was provided for evaluation of the following liquid crystal orientation, voltage retention, heat resistance, bezel unevenness tolerance, and afterimage characteristic evaluation. . However, ultraviolet irradiation under voltage application was not performed in either case.

(2) Evaluation of liquid crystal orientation

About the FFS-type liquid crystal display element manufactured above, the presence or absence of the abnormal domain in the change of the contrast when a voltage of 5 V was turned ON/OFF (applied/released) was observed with the microscope at a magnification of 50 times. Evaluation was performed as liquid-crystal orientation "good|favorableness" when an abnormal domain was not observed, and the case where an abnormal domain was observed was made into liquid-crystal orientation "poor". In this liquid crystal display element, it was liquid-crystal orientation "good|favorableness."

(3) Evaluation of voltage retention rate

For the FFS-type liquid crystal display device manufactured above, after applying a voltage of 5V at 23° C. with an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention ratio (VHR) after 167 milliseconds from application release was measured. , the voltage retention rate was 99.4%. In addition, as a measuring apparatus, the Toyo Technica make, VHR-1 was used.

(4) Evaluation of heat resistance

The voltage retention ratio was measured similarly to evaluation of said (3) voltage retention ratio, and the value was made into initial _{stage VHR(VHR BF} ). Then, about the liquid crystal display element after an initial stage VHR measurement, it left still in 100 degreeC oven for 500 hours. Then, after leaving this liquid crystal display element still at room temperature and standing to cool to room temperature, the voltage retention was measured similarly to the above, and the value was made into VHR _AF . In addition, the rate of change (ΔVHR (%)) of the voltage retention rate before and after application of the thermal stress was obtained by the following formula (EX-2).

ΔVHR(%)=((VHR _{BF -VHR AF} )÷VHR _BF )×100… (EX-2)

Heat resistance evaluation was performed when heat resistance was "good" when the change rate ΔVHR was less than 4%, heat resistance "possible" when it was 4% or more and less than 5%, and heat resistance "poor" when it was 5% or more. As a result, (DELTA)VHR was 2.9 %, and the heat resistance of this liquid crystal display element was "favorable."

(5) Non-uniformity resistance around sealing compound (bezel unevenness resistance)

About the FFS-type liquid crystal display element manufactured above, it stored on 25 degreeC and the conditions of 50 %RH for 30 days, and then, it was driven by alternating voltage 5V, and the lighting state was observed. In the evaluation, when the luminance difference (more black or more white) is not visually recognized in the vicinity of the sealing compound, "excellent" is visually recognized, but when the luminance difference disappears within 5 minutes after lighting up, "good", the luminance difference disappears within 20 minutes more than 5 minutes When it became "possible", the case where a luminance difference was visually recognized even if 20 minutes passed was made into "poor". As a result, in this liquid crystal display element, the luminance difference was not visually recognized in the sealing compound periphery, but it was judged as bezel nonuniformity tolerance "excellence".

(6) Evaluation of afterimage characteristics (DC afterimage evaluation)

The photo-alignment FFS type liquid crystal display device prepared above was placed in an environment of 25°C and 1 atm. The bottom electrode was used as a common electrode of all four drive electrodes, and the potential of the bottom electrode was set to 0 V potential (ground potential). A combined voltage consisting of an alternating voltage of 3.5 V and a direct current of 1 V was applied to the electrodes A and C for 2 hours while the electrodes B and D were short-circuited with the common electrode to make 0 V applied. After 2 hours had elapsed, a voltage of 1.5 V AC was immediately applied to all of the electrodes A to D. Then, the luminance between the driving stress applied region (the pixel region of the electrode A and the electrode C) and the driving stress non-applied region (the pixel region of the electrode B and the electrode D) from the time when a voltage of 1.5 V AC is started to be applied to all the driving electrodes The time until the car became visually invisible was measured, and this was made into afterimage erasure|elimination time. In addition, it shows that an afterimage is hard to generate|occur|produce, so that this time is short. The case where the afterimage erasing time was less than 30 seconds was evaluated as "good", the case where it was 30 seconds or more and less than 120 seconds was "possible", and the case where it was 120 seconds or more was evaluated as "bad". The erasing time was 1 second, and the afterimage characteristic was evaluated as "good".

From the above result, while all the liquid crystal aligning agents of the Example using a specific solvent (B) had favorable storage stability at the time of low temperature storage, it was favorable also about the printability after low temperature storage. On the other hand, the liquid crystal aligning agent of a comparative example was poor in storage stability and printability after low temperature storage. From this, it turned out that storage stability can be improved, ensuring the applicability|paintability with respect to a board|substrate by using a specific solvent (B).

(Example 2)

[Example 1B]

1,3-bis(4-aminophenethyl)urea (BAPU) = 0.60 g (2.0 mmol) as diamine and p-phenylenediamine (p-PDA) in a 50 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube ) 　 1.95 g (18.0 mmol) was added, 30 g of N-methyl-2-pyrrolidone (NMP) was added, and stirred while sending nitrogen to dissolve. While stirring this diamine solution, 3.70 g (18.9 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is added as tetracarboxylic dianhydride, and the solid content concentration is 12% by weight. NMP was added and stirred at room temperature under nitrogen atmosphere for 4 hours to obtain a solution of polyamic acid (PA-1).

To this polyamic acid solution, NMP and a compound represented by the following formula (2b-a) as a specific solvent (B) (hereinafter referred to as “compound (2b-a)”) are added, and the solvent composition is NMP: compound (2b) -a)=60:40 (weight ratio), the liquid crystal aligning agent (S1B) was prepared so that polyamic-acid density|concentration might be set to 6.0 weight%.

[Example 2B]

19.2 g (0.098 mol) of CBDA as tetracarboxylic dianhydride and 24.2 g (0.1 mol) of 1,5-bis(4-aminophenoxy)pentane as diamine were dissolved in 343.5 g of NMP, followed by reaction at room temperature for 10 hours. The polymerization reaction proceeded easily and uniformly to obtain polyamic acid (PA-2). NMP and compound (2b-a) as a specific solvent (B) are added to the NMP solution of this polyamic acid (PA-2), and the solvent composition is NMP: compound (2b-a) = 50: 50 (weight ratio), The liquid crystal aligning agent (S2B) was prepared so that polyamic-acid density|concentration might be set to 6.0 weight%.

[Example 3B]

22.42 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 18.73 g (0.094) of 4,4'-diaminodiphenylamine (4,4' DADPA) as diamine mol) was mixed in 345.1 g of NMP and reacted at room temperature for 5 hours. The polymerization reaction proceeded easily and uniformly to obtain polyamic acid (PA-3). NMP and compound (2b-a) as a specific solvent (B) are added to the NMP solution of this polyamic acid (PA-3), and the solvent composition is NMP: compound (2b-a) = 80: 20 (weight ratio), The liquid crystal aligning agent (S3B) was prepared so that polyamic-acid density|concentration might be set to 6.0 weight%.

[Example 4B]

6.5 g (0.06 mol) of p-PDA as a diamine and 4-(4-trans-n-heptylcyclohexyl)phenoxy)-1,3-diaminobenzene (PCH7DAB, represented by the above formula (d-4-3) Compound) 15.22 g (0.04 mol) was dissolved in 165 g of NMP, and 19.41 g (0.099 mol) of CBDA as tetracarboxylic dianhydride was added thereto, and reacted at room temperature for 24 hours to contain polyamic acid (PA-4) a solution was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid (PA-4) was 40,000. To 30 g of this solution, NMP, diethylene glycol diethyl ether (DEDG) and compound (2b-a) as a specific solvent (B) were added, and the solvent composition was NMP: DEDG: compound (2b-a) = 80: 10: 10 (weight ratio) and the liquid crystal aligning agent (S4B) of 4.5 weight% of density|concentrations were prepared.

[Example 5B]

1.46 g (13.5 mmol) of p-PDA as diamine and 0.78 g (1.50 mmol) of 3,5-diaminobenzoic acid cholestanyl (DA-3) were mixed in 20.0 g of NMP, and as tetracarboxylic dianhydride At the same time as CBDA = 2.85 g (14.5 mmol) was added, 24.7 g of NMP was added, and the mixture was reacted at 25° C. for 5 hours to obtain a solution containing polyamic acid (PA-5). Next, to 40.0 g of the obtained polyamic acid solution, NMP and compound (2b-a) as a specific solvent (B) were added, and the solvent composition was NMP: compound (2b-a) = 75: 25 (weight ratio), polyamic acid concentration The liquid crystal aligning agent (S5B) was prepared so that it might be set to 4.0 weight%.

[Example 6B]

CBDA 　2.58 g (13.1 mmol) as tetracarboxylic dianhydride and PCH7DAB 　 5.0 g (13.1 mmol) as diamine were dissolved in 43 g of NMP, and stirred at 20 ° C. for 4 hours to react with polyamic acid (PA-6) a solution was obtained. Next, to the obtained NMP solution of polyamic acid (PA-6), NMP and compound (2b-a) as a specific solvent (B) were added, and the solvent composition was NMP: compound (2b-a) = 35: 65 (weight ratio) ), the liquid crystal aligning agent (S6B) was prepared so that solid content concentration might be set to 3.0 weight%.

[Example 7B]

8.724 g (0.04 mol) of pyromellitic dianhydride (PMDA) as tetracarboxylic dianhydride, 2.877 g (0.0266 mol) of p-PDA as a diamine, and 4.567 g (0.012 mol) of PCH7DAB (0.012 mol) as a diamine in 91.6 g of NMP at room temperature for 3 hours It was made to react, and the solution containing polyamic acid (PA-7) was prepared. To 25 g of this polyamic acid solution, NMP and a compound represented by the following formula (2b-b) as a specific solvent (B) (hereinafter referred to as “compound (2b-b)”) were added, and the solvent composition was NMP: compound ( 2b-b) = 60:40 (weight ratio), the liquid crystal aligning agent (S7B) was prepared so that it might be set to 5.0 weight% of solid content concentration.

[Example 8B]

14.64 g (0.072 mol) of 2,4-diamino-N,N-diallylaniline as a diamine, 2.96 g (0.016 mol) of n-dodecylamine as a monoamine, and 15.69 g (0.08 mol) of CBDA as tetracarboxylic dianhydride mol) was reacted in 300 g of NMP at room temperature for 4 hours to prepare a solution containing a polyamic acid intermediate (PA-8). NMP and compound (2b-a) as a specific solvent (B) were added to the NMP solution of this polyamic acid intermediate, and the solvent composition was NMP: compound (2b-a) = 60: 40 (weight ratio), solid content concentration 6.0 weight % liquid crystal aligning agent (S8B) was prepared.

[Example 9B]

Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-2 anhydride (BODA) 4.50 g (0.018 mol) as tetracarboxylic dianhydride, PCH7DAB 0.68 as diamine After making g (0.0018 mol) and p-PDA 1.75 g (0.0162 mol) react at room temperature in 39.3 g of NMPs, it was made to react at 40 degreeC further for 43 hours. NMP was added to 42 g of this polyamic acid solution to prepare a 1% by weight solution, to which 4.18 g of acetic anhydride and 6.48 g of pyridine were added as imidation catalysts, and reacted at room temperature for 30 minutes and at 120°C for 2 hours. The white precipitate obtained by injecting|throwing-in this solution in a large amount of methanol was separated by filtration, and it dried and obtained white polyimide powder. When the imidation ratio of the obtained polyimide powder (polyimide (PI-1)) was measured, it was 72 %. To this powder, NMP and compound (2b-a) as a specific solvent (B) are added and dissolved, so that the solvent composition is NMP:compound (2b-a)=50:50 (weight ratio), liquid crystal so that the solid content concentration is 4.5% by weight An aligning agent (S9B) was prepared.

[Comparative Examples 1B, 3B to 9B]

With respect to the solvent composition of the liquid crystal aligning agent, the polymer was synthesized in the same manner as in Examples 1B and 3B to 9B, except that butyl cellosolve (BC) was used instead of the specific solvent (B) as the second solvent. Simultaneously, the liquid crystal aligning agent was prepared, and the liquid crystal aligning agent (R1B) and (R3B) - (R9B) were obtained, respectively.

[Comparative Example 2B]

Regarding the solvent composition of the liquid crystal aligning agent, except that ethylene glycol dimethyl ether was used instead of the specific solvent (B) as the second solvent, the polymer was synthesized in the same manner as in Example 2B, and the liquid crystal aligning agent was prepared at the same time , and a liquid crystal aligning agent (R2B) was obtained.

In addition, comparative example XB (X is an integer of 1-9) is an example corresponding to Example XB. That is, in Comparative Example XB, while synthesizing the same polymer as in Example XB, the liquid crystal aligning agent was similar to Example XB except that butyl cellosolve or ethylene glycol dimethyl ether was used instead of the specific solvent (B). was prepared

[Example 10B]

Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-2 anhydride (BODA) 4.50 g (0.018 mol) as tetracarboxylic dianhydride, the above formula as diamine After reacting the compound (PBCH5DAB) represented by (d-4-2) 2.34 g (0.0054 mol) and 1.92 g (0.0126 mol) of 3,5-diaminobenzoic acid (35DAB) at room temperature in 26.3 g of NMP, further The reaction was carried out at 40°C for 43 hours. NMP was added to 30 g of this polyamic acid solution to prepare a 6 wt% solution, and as an imidization catalyst, 2.4 g of acetic anhydride and 1.8 g of pyridine were added thereto, and reacted at room temperature for 30 minutes and 110°C for 4 hours. The white precipitate obtained by injecting|throwing-in this solution in a large amount of methanol was separated by filtration, and it dried and obtained white polyimide powder. When the imidation ratio of the obtained polyimide powder (polyimide (PI-2)) was measured, it was 72 %. 0.6 g of this powder was dissolved in a mixed solvent of NMP and 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent, and compound (2b-a) as a specific solvent (B), polyimide It was set as the solution with a density|concentration 6.0 weight%. A liquid crystal aligning agent (S10B) by adding 0.4 g (equivalent to 0.03 g as 3-AMP) of the 7.5 weight% NMP solution of 3-aminomethylpyridine (3-AMP) to this solution, and stirring at 50 degreeC for 15 hours got it In addition, the liquid crystal aligning agent was prepared so that a solvent composition might become NMP:D1:compound (2b-a)=30:20:50 (weight ratio).

[Example 11B]

The same operation as in Example 10B was performed, except that the amount of PBCH5DAB used for the synthesis of polyamic acid was 3.90 g (0.0090 mol) and the amount of 3,5-diaminobenzoic acid was changed to 1.37 g (0.0090 mol), and the poly A solution of amic acid was obtained. Moreover, operation similar to Example 10B was performed using the obtained polyamic acid solution, and the polyimide powder was obtained. When the imidation ratio of the obtained polyimide powder (polyimide (PI-3)) was measured, it was 74 %. 0.6 g of this powder was dissolved in a mixed solvent of NMP and 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent, and compound (2b-b) as a specific solvent (B), polyimide It was set as the solution with a density|concentration 6.0 weight%. Liquid crystal aligning agent (S11B) by adding 0.8g (equivalent to 0.06 g as 3-AMP) of the 7.5 weight% NMP solution of 3-aminomethylpyridine (3-AMP) to this solution, and stirring at 50 degreeC for 15 hours got it In addition, the liquid crystal aligning agent was prepared so that a solvent composition might become NMP:D2:compound (2b-b)=30:30:40 (weight ratio).

[Example 12B]

A solution containing polyamic acid (PA-1) was prepared in the same manner as in Example 1A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent and compound (2b-b) as a specific solvent (B), so that the solvent composition was D1: compound ( 2b-b)=60:40 (weight ratio) and the liquid crystal aligning agent (S12B) of 6.0 weight% of solid content concentration were obtained.

[Example 13B]

A solution containing polyamic acid (PA-2) was prepared in the same manner as in Example 2B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent and compound (2b-a) as a specific solvent (B), and the solvent composition was D2: compound ( 2b-a) = 50:50 (weight ratio) and the liquid crystal aligning agent (S13B) of 6.0 weight% of polyamic-acid density|concentrations were obtained.

[Example 14B]

A solution containing polyamic acid (PA-3) was prepared in the same manner as in Example 3B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of NMP and 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent, and compound (2b-a) as a specific solvent (B), so that the solvent composition was NMP : The liquid crystal aligning agent (S14B) of D1: compound (2b-a) =40:40:20 (weight ratio) and polyamic acid density|concentration 6.0 weight% was obtained.

[Example 15B]

A solution containing polyamic acid (PA-4) was prepared in the same manner as in Example 4B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder and, as an additive, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (E1), NMP and 3-butoxy-N as a first solvent, Dissolve in a mixed solvent of N-dimethylpropionamide (D2) and compound (2b-a) as a specific solvent (B), so that the solvent composition is NMP:D2:compound (2b-a)=40:40:20 (weight ratio) ), the liquid crystal aligning agent (S15B) of polyamic acid density|concentration 6.0 weight% was obtained. In addition, the quantity of the additive (E1) used was made into 5 weight part with respect to the polyamic acid powder.

[Example 16B]

A solution containing polyamic acid (PA-5) was prepared in the same manner as in Example 5B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent and compound (2b-a) as a specific solvent (B), so that the solvent composition was D1: compound ( 2b-a)=75:25 (weight ratio) and the liquid crystal aligning agent (S16B) of polyamic acid density|concentration 6.0 weight% were obtained.

[Example 17B]

A solution containing polyamic acid (PA-6) was prepared in the same manner as in Example 6B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent and compound (2b-a) as a specific solvent (B), so that the solvent composition was D2: compound ( 2b-a)=35:65 (weight ratio) and the liquid crystal aligning agent (S17B) of polyamic acid density|concentration 6.0 weight% were obtained.

[Example 18B]

A solution containing polyamic acid (PA-7) was prepared in the same manner as in Example 7B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of NMP and γ-butyrolactone (D3) as a first solvent and compound (2b-a) as a specific solvent (B), so that the solvent composition was NMP:D3:compound (2b- a) = 30:30:40 (weight ratio) and the liquid crystal aligning agent (S18B) of polyamic acid density|concentration 6.0 weight% were obtained.

[Example 19B]

A solution containing a polyamic acid intermediate (PA-8) was prepared in the same manner as in Example 8B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder was dissolved in a mixed solvent of NMP and 3-butoxy-N,N-dimethylpropionamide (D2) as a first solvent, and compound (2b-b) as a specific solvent (B), so that the solvent composition was NMP : The liquid crystal aligning agent (S19B) of D2: compound (2b-b) =30:30:40 (weight ratio) and polyamic acid density|concentration 6.0 weight% was obtained.

[Example 20B]

A powder of polyimide (PI-1) was obtained in the same manner as in Example 9B. This powder was dissolved in a mixed solvent of 3-methoxy-N,N-dimethylpropionamide (D1) as a first solvent and compound (2b-a) as a specific solvent (B), so that the solvent composition was D1: compound ( 2b-a) = 50:50 (weight ratio) and the liquid crystal aligning agent (S20B) of 6.0 weight% of solid content concentration were obtained.

<Evaluation of storage stability>

About each liquid crystal aligning agent obtained above, after having filtered with a 1.0 micrometer filter and storing at -30 degreeC for 1 month, it returned to room temperature (25 degreeC) and the presence or absence of the precipitate in a liquid crystal aligning agent was observed. The results are shown in Tables 3 and 4 below. In addition, in Table 3 and Table 4, the case where "(circle)" and a precipitate were observed was shown with "x" in the case where a precipitate was not observed in a liquid crystal aligning agent.

<Evaluation of printability>

About each liquid crystal aligning agent prepared above, after filtration with a 1.0 micrometer filter, after storing at -15 degreeC for 6 months, it returned to room temperature (25 degreeC). Next, the liquid crystal aligning agent was apply|coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film using the liquid crystal aligning film printing machine (made by Nippon Corporation). Then, after heating (prebaking) for 1 minute on an 80 degreeC hotplate and removing a solvent, it heated (postbaking) for 10 minutes on a 200 degreeC hotplate, and formed the coating film with an average film thickness of 0.06 micrometer. The coating film was observed under a microscope at a magnification of 20 times to examine the presence or absence of print unevenness and pinholes. Evaluation was performed by making the case where print nonuniformity and pinhole hardly observed was good printability ((circle)), and the case where at least any of the printing nonuniformity and pinhole was observed was made printability poor (x). The results are shown in Tables 3 and 4 below.

In addition, the abbreviation in Table 3 and Table 4 is as follows.

(tetracarboxylic acid dianhydride)

AN-1; 1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride

AN-2; 2,3,5-tricarboxycyclopentylacetic acid dianhydride

AN-3; pyromellitic dianhydride

AN-4; Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-2 anhydride

(diamine)

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

DA-2: 2,4-diamino-N,N-diallylaniline

DA-3: 3,5-diaminobenzoic acid cholestanyl

35DAB: 3,5-diaminobenzoic acid

(monoamine)

MA-1: n-dodecylamine

(1st solvent)

D1: 3-methoxy-N,N-dimethylpropionamide

D2: 3-butoxy-N,N-dimethylpropionamide

D3: γ-butyrolactone

(second solvent)

D4: ethylene glycol dimethyl ether

DEDG: diethylene glycol diethyl ether

BC: Butyl Cellosolve

(additive)

3-AMP: 3-aminomethylpyridine (compound represented by the above formula (c-1-16))

E1: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane

<Production and evaluation of optical alignment FFS type liquid crystal display element>

(1) Manufacturing of FFS type liquid crystal display device using photo-alignment method

The FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a comb-shaped top electrode 13 formed in this order are combined electrodes formed in this order on one side of a glass substrate 11a having a glass substrate 11a and , The liquid crystal aligning agent (S1B) obtained above in the surface which has a transparent electrode of the glass substrate 11a, and one surface of the opposing glass substrate 11b making a pair of opposing glass substrates 11b in which the electrode is not formed, and was used to form a coating film by an inkjet coating method. In addition, with respect to the liquid crystal aligning agent (S1B), before applying on the substrate, the solvent composition was set to "NMP: (2b-a) = 60: 40 (weight ratio)", it was prepared so that the viscosity was 18 cP, and the viscosity was adjusted The liquid crystal aligning agent was apply|coated on the board|substrate.

Subsequently, this coating film was prebaked for 1 minute on a hotplate at 80°C, and then heated (post-baked) at 230°C for 15 minutes in an oven in which the inside of the tube was substituted with nitrogen to form a coating film having an average film thickness of 1,000 Å. A schematic plan view of the top electrode 13 used here is shown in FIG. 2 . Fig. 2(a) is a top view of the top electrode 13, and Fig. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in Fig. 2(a). In this embodiment, a substrate having a top electrode having a line width d1 of the electrodes of 4 μm and a distance d2 between the electrodes of 6 μm was used. In addition, as the top electrode 13, the drive electrode of 4 systems|system|groups of electrode A, electrode B, electrode C, and electrode D was used. Fig. 3 shows the configuration of the driving electrode of this liquid crystal display element. In this case, the bottom electrode 15 acts as a common electrode that acts on all of the drive electrodes of the four lines, and each of the areas of the drive electrodes of the four lines becomes a pixel area.

Next, each surface of these coating films is irradiated with 300 J/m of polarized ultraviolet light including a bright line of 313 nm from the substrate normal direction using an Hg-Xe lamp and a Glan Taylor prism, respectively, a pair of substrates having a liquid crystal alignment film got At this time, the irradiation direction of the polarized ultraviolet ray is from the normal direction of the substrate, and the polarization plane direction is set so that the direction of the line segment projected on the substrate is the direction of the double arrow in FIG.

Next, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 µm is applied to the outer periphery of the surface having a liquid crystal aligning film of one of the substrates by screen printing, and then the liquid crystal aligning film surfaces of a pair of substrates are opposed to each other, and polarized ultraviolet rays The polarization planes of the substrate were pressed together so that the projected directions were parallel to each other, and the adhesive was thermosetted at 150°C for 1 hour. Next, after filling the liquid crystal "MLC-6221" manufactured by Merck into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow orientation at the time of liquid crystal injection, after heating this to 150 degreeC, it cooled gradually to room temperature.

Next, the FFS type liquid crystal display element was manufactured by bonding a polarizing plate to the outer both surfaces of a board|substrate. At this time, one of the polarizing plates is adhered so that its polarization direction is parallel to the projection direction of the polarization plane of the polarized ultraviolet light of the liquid crystal aligning film to the substrate surface, and the other is adhered so that its polarization direction is perpendicular to the polarization direction of the previous polarizing plate. did.

By repeating the above method, a total of five FFS type liquid crystal display elements were manufactured, and one each was provided for evaluation of the following liquid crystal alignment property, evaluation of voltage retention, evaluation of heat resistance, bezel unevenness tolerance, and evaluation of afterimage characteristics. . However, ultraviolet irradiation under voltage application was not performed in either case.

(2) Evaluation of liquid crystal orientation

About the FFS-type liquid crystal display element manufactured above, the presence or absence of the abnormal domain in the change of the contrast when a voltage of 5 V was turned ON/OFF (applied/released) was observed with the microscope at a magnification of 50 times. Evaluation was performed as liquid-crystal orientation "good|favorableness" in the case where an abnormal domain was not observed, and the case where an abnormal domain was observed was made into liquid-crystal orientation "poor". In this liquid crystal display element, it was liquid-crystal orientation "good|favorableness."

(3) Evaluation of voltage retention rate

For the FFS-type liquid crystal display device manufactured above, after applying a voltage of 5V at 23° C. with an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention ratio (VHR) after 167 milliseconds from application release was measured. , the voltage retention rate was 99.4%. In addition, as a measuring apparatus, the Toyo Technica make, VHR-1 was used.

(4) Evaluation of heat resistance

The voltage retention ratio was measured similarly to evaluation of said (3) voltage retention ratio, and the value was made into initial _{stage VHR(VHR BF} ). Then, about the liquid crystal display element after an initial stage VHR measurement, it left still in 100 degreeC oven for 500 hours. Then, after leaving this liquid crystal display element still at room temperature and standing to cool to room temperature, the voltage retention was measured as mentioned above, and the value was made into VHR _AF . In addition, the rate of change (ΔVHR (%)) of the voltage retention rate before and after application of the thermal stress was obtained by the following formula (EX-2).

ΔVHR(%)=((VHR _{BF -VHR AF} )÷VHR _BF )×100… (EX-2)

Heat resistance evaluation was performed when heat resistance was "good" when the change rate ΔVHR was less than 4%, heat resistance "possible" when it was 4% or more and less than 5%, and heat resistance "poor" when it was 5% or more. As a result, (DELTA)VHR was 2.9 %, and the heat resistance of this liquid crystal display element was "favorable."

(5) Non-uniformity resistance around sealing compound (bezel unevenness resistance)

About the FFS-type liquid crystal display element manufactured above, it stored on 25 degreeC and the conditions of 50 %RH for 30 days, and then, it was driven by alternating voltage 5V, and the lighting state was observed. In the evaluation, when the luminance difference (more black or more white) is not visually recognized in the vicinity of the sealing compound, "excellent" is visually recognized, but when the luminance difference disappears within 5 minutes after lighting up, "good", the luminance difference disappears within 20 minutes more than 5 minutes When it became "possible", the case where a luminance difference was visually recognized even if 20 minutes passed was made into "poor". As a result, in this liquid crystal display element, the luminance difference was not visually recognized in the sealing compound periphery, but it was judged as "excellence".

(6) Evaluation of afterimage characteristics (DC afterimage evaluation)

The photo-alignment liquid crystal display device prepared above was placed in an environment of 25°C and 1 atm. The bottom electrode was used as a common electrode of all four drive electrodes, and the potential of the bottom electrode was set to 0 V potential (ground potential). A combined voltage consisting of an AC voltage of 3.5 V and a DC voltage of 1 V was applied to the electrodes A and C for 2 hours while the electrodes B and D were short-circuited with the common electrode so that 0 V was applied. After 2 hours had elapsed, a voltage of 1.5 V AC was immediately applied to all of the electrodes A to D. Then, the luminance between the driving stress applied region (the pixel region of the electrode A and the electrode C) and the driving stress non-applied region (the pixel region of the electrode B and the electrode D) from the time when a voltage of 1.5 V AC is started to be applied to all the driving electrodes The time until the car could not be visually confirmed was measured, and this was made into afterimage erasure|elimination time. In addition, it shows that an afterimage is hard to generate|occur|produce, so that this time is short. The case where the afterimage erasing time was less than 30 seconds was evaluated as "good", the case where it was 30 seconds or more and less than 120 seconds was "possible", and the case where it was 120 seconds or more was evaluated as "bad". The erasing time was 1 second, and the afterimage characteristic was evaluated as "good".

As shown in Table 3 and Table 4, the liquid crystal aligning agent of the Example using a specific solvent (B) was favorable also about the printability after low temperature storage while the storage stability at the time of storing all at low temperature was favorable. On the other hand, the liquid crystal aligning agent of a comparative example was poor in storage stability and printability after low temperature storage. From this point, it turned out that storage stability can be improved, ensuring the applicability|paintability with respect to a board|substrate by using a specific solvent (B).

(Example 3)

<Synthesis of polyimide>

[Synthesis Example 1: Synthesis of polyimide (PI-1C)]

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic dianhydride, 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine and 3,5- 10.5 g (0.02 mol) of diaminobenzoic acid cholestanyl (HCDA) was dissolved in 166 g of N-methyl-2-pyrrolidone (NMP), reacted at 60°C for 6 hours, and polyamic acid was contained in 20 wt% a solution was obtained. A small amount of the obtained polyamic acid solution was fractionated, and N-methyl-2-pyrrolidone was added to obtain a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity measured was 90 mPa·s.

Next, NMP was added to the obtained polyamic acid solution to make a solution with a polyamic acid concentration of 7 weight%, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the polyimide (PI) having an imidization rate of about 68% by replacing the solvent in the system with new NMP (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed out of the system by this operation; the same hereinafter) A solution containing 26 wt% of -1C) was obtained. A small amount of the obtained polyimide solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 45 mPa·s.

[Synthesis Example 2: Synthesis of polyimide (PI-2C)]

22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, 5.2 g (0.01 mol) of HCDA and 4.0 g (0.02 mol) of 4,4'-diaminodiphenylmethane (DDM) ) was dissolved in 157 g of NMP, and the reaction was performed at 60°C for 6 hours to obtain a solution containing 20% by weight of polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, and NMP was added to obtain a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity measured was 110 mPa·s.

Next, NMP was added to the obtained polyamic acid solution to make a solution with a polyamic acid concentration of 7 weight%, 16.6 g of pyridine and 21.4 g of acetic anhydride were added, and the dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP to obtain a solution containing 26 wt% of polyimide (PI-2C) having an imidation ratio of about 82%. A small amount of the obtained polyimide solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 62 mPa·s.

[Synthesis Example 3: Synthesis of polyimide (PI-3C)]

2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2anhydride (BODA) 24.9g (0.10mol) as tetracarboxylic dianhydride, 8.6g PDA as diamine (0.08 mol) and HCDA 10.4 g (0.02 mol) were melt|dissolved in NMP 176g, reaction was performed at 60 degreeC for 6 hours, and the solution containing 20 weight% of polyamic acids was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 103 mPa·s.

Next, NMP was added to the obtained polyamic acid solution to make a solution with a polyamic acid concentration of 7 weight%, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh NMP to obtain a solution containing 26 wt% of polyimide (PI-3C) having an imidization rate of about 71%. A small amount of the obtained polyimide solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 57 mPa·s.

<Preparation of liquid crystal aligning agent>

[Example 1C]

In a solution containing 100 parts by weight of the synthesized polyimide (PI-1C), as a solvent, NMP, ethylene glycol mono-n-butyl ether (butylcellosolve, BC) and a compound represented by the following formula (b1-1) (hereinafter referred to as) . A liquid crystal aligning agent (S-1) was prepared by filtering this solution using the filter with a hole diameter of 1 micrometer.

[Examples 2C to 18C, Comparative Examples 1C to 4C]

Liquid crystal aligning agents (S-2) to (S-18), (SR-1) to (SR-1) to in the same manner as in Example 1C, except that the polyimide to be used and the solvent composition were changed as described in Table 5 below. (SR-4) was prepared, respectively.

<Evaluation of printability>

Printability was evaluated about each liquid crystal aligning agent prepared above. Evaluation was performed as follows. First, about each of the prepared liquid crystal aligning agents, using a liquid crystal aligning film printing machine (Nippon Shashin Insatsu Co., Ltd. make, Angstrom type "S40L-532"), the dripping amount of the liquid crystal aligning agent to an anilox roll is 20 drops reciprocally (about 0.2 g), it apply|coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film. Application|coating to the board|substrate was performed 20 times, using a new board|substrate at 1-minute intervals.

Then, the liquid crystal aligning agent was dispensed (one way) on the anilox roll at 1-minute intervals, and the operation|work (henceforth, an idle operation) which made an anilox roll and a printing plate contact each time (henceforth, a total of 10 times) was performed (previously, Printing to a glass substrate is not performed). In addition, this idle operation is not performed in the normal manufacturing process of a liquid crystal display element, but is operation performed in order to implement the printing to the board|substrate of a liquid crystal aligning agent on purposely severe condition.

Main printing was performed using the glass substrate after 10 times of idling. In this printing, after idling, 5 substrates are put in at intervals of 30 seconds, each substrate coated with liquid crystal aligning agent is heated (pre-baked) at 80° C. for 1 minute to remove the solvent, and then heated at 200° C. for 10 minutes. (post-baking) was carried out, and the coating film with a film thickness of about 80 nm was formed. Printability was evaluated by observing the pattern edge part (outer peripheral part of a print pattern) of this coating film with the microscope with a magnification of 20 times. Evaluation was good (○) when no precipitates (presumed to be polyimide) were observed from the first printing after idling, and precipitates were observed in the first printing after idling, but during this printing 5 times The case where the precipitate disappeared was regarded as good (Δ), and the case where the precipitate was observed even after repeating this printing 5 times was regarded as defective (x). The evaluation results are shown in Table 5 below. Moreover, in the liquid crystal aligning agent with favorable printability, while injecting|throwing-in a board|substrate continuously, it turns out that a precipitate improves (disappears) by an experiment.

Moreover, the printability of the liquid crystal aligning agent was evaluated by performing operation similar to the above except having changed the frequency|count of an idle run to 15 times, 20 times, and 25 times, respectively. The evaluation results are combined with Table 5 below and shown.

<Evaluation of the dry level of the membrane surface>

The dry level of the film|membrane surface was evaluated about the coating film after prebaking in the said "evaluation of printability". Evaluation was performed by making the case where a sticky feeling did not remain good (circle) on the film|membrane surface when it touched by hand, and the case where the sticky feeling remained was bad (x). The evaluation results are shown in Table 5 below. In addition, here, it evaluated using the board|substrate of this printing implemented after 10 times of idling.

In addition, the symbol of the solvent composition in Table 5 has the following meaning, respectively.

a: N-methyl-2-pyrrolidone (NMP)

b: ethylene glycol mono-n-butyl ether (BC)

d: compound (b1-1)

e: a compound represented by the following formula (b2-1)

f: a compound represented by the following formula (b2-2)

g: N-vinyl-2-pyrrolidone

h: N-cyclohexyl-2-pyrrolidone

i: N-octyl-2-pyrrolidone

About printability, in all, in the liquid crystal aligning agent of an Example, the precipitate was not observed from the main printing 1st time after 10 times of idle rotations. This was also the case after 15 idle runs. In addition, when the number of idle runs was increased to 20 or 25 times, some precipitates were observed in the first printing of the main print, but the precipitates disappeared until the end of the main printing of 5 times. From these, it turned out that the liquid crystal aligning agent of an Example was hard to generate|occur|produce a precipitate during printing, and printability was favorable.

10: liquid crystal display element
11a, 11b: glass substrate
12: liquid crystal alignment film
13: top electrode
14: insulating layer
15: bottom electrode
16: liquid crystal layer

Claims (9)

delete As a liquid crystal aligning agent containing at least 1 sort(s) of polymer (A) chosen from the group which consists of polyamic acid, a polyimide, and polyamic acid ester, and a solvent,
Liquid crystal aligning agent containing the specific solvent (B) whose said solvent is at least 1 sort(s) chosen from the group which consists of a compound represented by a following formula (b1), and a compound represented by a following formula (b2):

(in formula (b1), R is a C1-C3 alkyl group, n is an integer of 0-2;
In formula (b2), m is an integer of 0-2). 3. The method of claim 2,
The said polymer (A) is liquid-crystal orientation containing the polymer which has a partial structure derived from at least 1 sort(s) of diamine chosen from the group which consists of compounds represented by each of following formula (d-1) - formula (d-5) my:

(In formula (d-1), X ¹ and X ² are each independently a single bond, -O-, -S-, -OCO- or -COO-, Y ¹ is an oxygen atom or a sulfur atom; , R ¹¹ and R ¹² are each independently an alkanediyl group having 1 to 3 carbon atoms, R ⁸ and R ⁹ are each independently a hydrogen atom or a protecting group;
n1 is 0 or 1, n2 and n3 are integers satisfying n2+n3=2 for n1=0, n2=n3=1 for n1=1;
In formula (d-2), X ³ is a single bond, -O-, or -S-, and m1 is an integer of 0 to 3;
m2 is an integer from 1 to 12 in the case of m1 = 0, and m2 = 2 when m1 is an integer from 1 to 3;
In the formula (d-3), R ³ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group;
In formula (d-4), X ⁴ and X ⁵ are each independently a single bond, -O-, -COO- or -OCO-, R ⁷ is an alkanediyl group having 1 to 3 carbon atoms, A ⁴ is a single bond or an alkanediyl group having 1 to 3 carbon atoms;
a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, k is 0 or 1; provided that a and b do not simultaneously become 0;
In the formula (d-5), A ⁵ represents a single bond, an alkanediyl group having 1 to 12 carbon atoms or a fluoroalkanediyl group having 1 to 6 carbon atoms, A ⁶ is -O-, -COO-, -OCO-, represents -NHCO-, -CONH- or -CO-, and A ⁷ represents a monovalent organic group having a steroid skeleton). 3. The method of claim 2,
The liquid crystal aligning agent whose content of the said specific solvent (B) is 1-70 weight% of the whole quantity of the said solvent. 3. The method of claim 2,
The polymer (A) is a compound represented by the following formula (t-1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and pyromelli Liquid crystal aligning agent which is a polymer which has a partial structure derived from at least 1 sort(s) of tetracarboxylic dianhydride selected from the group which consists of tric acid dianhydride:

(In formula (t-1), X ⁷ , X ⁸ , X ⁹ and X ¹⁰ are each independently a single bond or a methylene group, and j is an integer of 1 to 3). 3. The method of claim 2,
The liquid crystal aligning agent which further contains the amine compound (C) which has one primary amino group and nitrogen-containing aromatic heterocycle in a molecule|numerator, and the said primary amino group is couple|bonded with the chain hydrocarbon group or the alicyclic hydrocarbon group. 7. The method of claim 6,
The liquid crystal aligning agent whose said amine compound (C) is a compound represented by a following formula (c-1):

(In formula (c-1), A ¹ is a divalent organic group having a chain hydrocarbon group or an alicyclic hydrocarbon group, A ² is a nitrogen-containing aromatic heterocycle;
However, the primary amino group in a formula is couple|bonded with the chain hydrocarbon group or alicyclic hydrocarbon group which ^{A<1> has).} The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 2-7. A liquid crystal display element provided with the liquid crystal aligning film of Claim 8.

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