KR102205666B1 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, compound and polymer - Google Patents

Abstract

(Problem) It is to provide a liquid crystal aligning agent capable of forming a liquid crystal aligning film excellent in reliability with little reduction in voltage retention over a long period of time.
(Solution means) a liquid crystal aligning agent containing a polymer having a structure represented by the following formula (1):
*-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -* (1)
(In formula (1), X ¹ and X ² are a single bond, an oxygen atom, a sulfur atom, a carbonyl group or an ester bond, and both of X ¹ and X ² are not a single bond at the same time, and Y is a cyclic structure. A group obtained by removing two hydrogen atoms from a 5-membered ring or 6-membered ring heteroaromatic compound containing one or two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, provided that: Both of the two bond hands of Y directly emanate from the 5- or 6-membered ring, a plurality of R ¹ is a hydrogen atom or a fluorine atom, m1 and m2 are integers of 0 to 20, and "*" is, Each represents a binding hand).

Description

Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display device, compound, and polymer {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM, LIQUID CRYSTAL DISPLAY DEVICE, COMPOUND AND POLYMER}

The present invention relates to a liquid crystal aligning agent and a liquid crystal display device. Specifically, it is used for a liquid crystal aligning agent capable of forming a liquid crystal alignment film with excellent reliability and less decrease in voltage retention over a long period of time even under severe use conditions, and a liquid crystal display device that does not deteriorate display quality over a long period of time. About.

The liquid crystal display device can be classified into various modes according to the electrode structure and the physical properties of the liquid crystal molecules to be used. For example, a liquid crystal alignment film is formed on the surface of a substrate on which a transparent conductive film is formed to form a substrate for a liquid crystal display element, and the two sheets are arranged opposite to each other, and a layer of nematic liquid crystal having positive dielectric anisotropy in the gap. So-called TN (Twisted Nematic) type (Patent Document 1) in which the long axis of the liquid crystal molecules is continuously twisted 90° from one substrate to the other substrate by forming a cell having a sandwich structure;

STN (Super Twisted Nematic) type (Patent Document 2) capable of realizing a higher duty ratio than a TN type liquid crystal display device;

VA (Vertical Alignment) type (Patent Document 3) in which a layer of nematic liquid crystal having negative dielectric anisotropy is injected into the gap, and the liquid crystal is aligned substantially perpendicular to the substrate;

An IPS (In-Plane Switching) type (Patent Documents 4 and 5) in which the driving direction of the liquid crystal at the time of application of an electric field is only the direction in the substrate surface by arranging the combination electrode in a comb-tooth shape in one substrate surface;

FFS (Fringe Field Switching) type (Patent Document 6) in which the IPS type electrode structure was changed and the aperture ratio of the display element portion was increased to improve brightness;

OCB (Optical Compensated Bend = Optical Compensated Bend) type (Patent Document 7) that has less visual dependence and has excellent high-speed response of video screens

Liquid crystal display elements such as are known.

Resin materials such as polyamic acid, polyimide, polyamide, and polyester are known as the material of the liquid crystal aligning film in these various liquid crystal display elements. In particular, the liquid crystal aligning film made of polyamic acid or polyimide has heat resistance, mechanical strength, and Since it is excellent in affinity with liquid crystals and the like, it is used in many liquid crystal display devices (Patent Document 8).

In such a liquid crystal aligning agent, in recent years, reliability (long-term stability against a harsh environment) has been more demanded than before. The circumstances are as follows.

Compared to conventional notebook PCs, monitor displays, and the like, which have been mainly used for liquid crystal display elements, liquid crystal televisions, which have been widely popular in recent years, have a long replacement cycle and are originally required to have a longer life. Here, in a liquid crystal display element for use in a liquid crystal projector, which has recently been increasing in demand as a home theater, since a light source having a very high irradiation intensity such as a metal halide lamp is used, resistance to light and heat becomes a large problem. In addition, liquid crystal display elements for mobile devices such as cell phones and vehicle-mounted car navigation systems need to increase the brightness of the backlight in order to improve visibility under sunlight containing strong ultraviolet rays. Is concerned about the deterioration of the product. In the case of using these devices as a display of a television game, it is assumed that they are placed under continuous driving for a very long time under the above conditions.

As described above, the liquid crystal display element is exposed to harsh environments that have not been conceivable in the past, such as high intensity light irradiation and long-time driving, along with the increase in versatility, and thus, further longer life is required.

It has been pointed out that the conventionally known liquid crystal alignment film lacks resistance to such harsh environments.

Japanese Laid-Open Patent Publication No. Hei 4-153622 Japanese Published Patent Publication No. 60-107020 Japanese Laid-Open Patent Publication No. Hei 11-258605 Japanese Published Patent Publication No. 56-91277 US Patent Publication No. 5,928,733 Specification Japanese Patent Publication No. 2002-082357 Japanese Laid-Open Patent Publication No. Hei 9-105957 Japanese Published Patent Publication No. 62-165628

The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal aligning agent capable of forming a liquid crystal aligning film with little reduction in voltage retention over a long period of time and excellent reliability.

Another object of the present invention is to provide an excellent liquid crystal display device that does not deteriorate in display quality over a long period of time.

According to the present invention, the above objects and advantages of the present invention are, firstly,

It is achieved by a liquid crystal aligning agent, characterized by containing a polymer having a structure represented by the following formula (1):

*-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -* (1)

(In formula (1), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an ester bond, provided that when both of X ¹ and X ² are single bonds at the same time, No,

Y is obtained by removing two hydrogen atoms from a 5- or 6-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in the ring structure. Group, provided that both of the two bond hands of Y are directly from the 5-membered ring or the 6-membered ring,

A plurality of R ¹ is each independently a hydrogen atom or a fluorine atom,

m1 and m2 are each independently an integer of 0 to 20, and

"*" represents a bond hand, respectively).

The above objects and advantages of the present invention are, secondly,

It is achieved by a liquid crystal display element, characterized by comprising a liquid crystal alignment film formed with the above liquid crystal aligning agent.

Advantageous Effects of Invention According to the present invention, a liquid crystal aligning agent capable of forming a liquid crystal aligning film excellent in reliability with little reduction in voltage retention over a long period of time is provided.

In the liquid crystal display device of the present invention including the liquid crystal aligning film formed by the liquid crystal aligning agent, the display quality does not deteriorate over a long period of time.

Therefore, the technique of the present invention can be suitably applied to applications such as liquid crystal televisions, liquid crystal projectors, mobile phones, portable game machines, and information displays.

1 is a schematic diagram showing an electrode pattern in a liquid crystal cell manufactured in Example 12 and Comparative Examples 4 and 5. FIG.

(Form for carrying out the invention)

The liquid crystal aligning agent of this invention contains a polymer which has a structure represented by said formula (1).

Y in the above formula (1) includes, for example, a group represented by each of the following formulas:

(Wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

Each of X is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms. Group;

n1 and n4 are each independently an integer of 0 to 2;

n2 is 0 or 1;

each n3 is independently an integer of 0 to 3; And

"*" represents a bond hand, respectively).

The alkyl group of R in the above formula is preferably an alkyl group having 1 to 3 carbon atoms, and specifically, it is more preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Examples of the halogen atom of X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group of X include methyl group, ethyl group, n-propyl group, and isopropyl group;

Examples of the fluoroalkyl group include trifluoromethyl group, 2,2,2-trifluoroethyl group, and the like;

Examples of the alkenyl group include a vinyl group and an allyl group;

Examples of the alkoxy group include a methoxy group, an ethoxy group, and an n-propoxy group;

Examples of the fluoroalkoxy group include a trifluoromethoxy group 2,2,2-trifluoroethoxy group and the like, respectively. Each of n1 and n4 is independently preferably 0 or 1, and more preferably 0.

As Y in the formula (1), particularly preferably a pyridinylene group, and among them, a 2,5-pyridinylene group, a 2,6-pyridinylene group, or a 3,5-pyridinylene group is preferable.

R ¹ in the above formula (1) is a hydrogen atom;

As m1 and m2 in the above formula (1), each independently preferably an integer of 0 to 2, respectively.

When X ¹ and X ² in the formula (1) are ester bonds, the bonding direction is arbitrary, but it is preferable that the carbonyl carbon of the ester bond is located inside. As X ¹ and X ² , it is preferable that one of them is an oxygen atom or an ester bond, and the other is a single bond, an oxygen atom, or an ester bond.

As a structure represented by the above formula (1), particularly preferably, it is a structure represented by each of the following formulas, for example:

("*" in the above formula represents a bond hand, respectively).

As long as the polymer contained in the liquid crystal aligning agent of this invention has a structure represented by said formula (1), it can be used suitably without limitation at all other than that. The polymer contained in the liquid crystal aligning agent of the present invention preferably has a structure represented by the formula (1) in the main chain of the polymer.

Here, the main chain of a polymer refers to a portion of a "stem" composed of a chain of the longest atoms in the polymer. To have the structure represented by the above formula (1) in the main chain means that this structure constitutes a part of the main chain. In this case, although the structure represented by the above formula (1) exists in the main chain, it is prohibited to overlap the structure in a part other than the main chain, for example, a side chain (a part branched from the ``stem'' of the polymer). It does not become.

As a polymer having a structure represented by the formula (1) contained in the liquid crystal aligning agent of the present invention, for example, a polyamic acid having a structure represented by the formula (1), an imidized polymer of a polyamic acid, a polyamic acid ester, and poly Organosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like. Among these, it is preferable to use at least one polymer selected from the group consisting of polyamic acid, imidized polymer of polyamic acid, polyamic acid ester, and polyorganosiloxane,

It is more preferable to use one or more polymers selected from the group consisting of polyamic acids and imidized polymers thereof.

The polyamic acid is, for example

A method of reacting a tetracarboxylic acid dianhydride containing a tetracarboxylic acid dianhydride having a structure represented by the above formula (1) and a diamine, or

It can be preferably synthesized by a method of reacting a tetracarboxylic acid dianhydride with a diamine containing a diamine having a structure represented by the above formula (1).

The imidated polymer of the polyamic acid can be obtained by dehydrating and cyclizing the polyamic acid to imidize all or part of the dark acid structure.

Particularly preferably as the polymer contained in the liquid crystal aligning agent of the present invention,

A polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a diamine having a structure represented by the formula (1), and,

It is one or more polymers selected from the group consisting of imidized polymers obtained by dehydrating and cyclizing the polyamic acid.

Hereinafter, a method for synthesizing a polymer particularly preferably contained in the liquid crystal aligning agent of the present invention will be described.

Examples of the tetracarboxylic dianhydride that can be used for the synthesis of the polyamic acid having the structure represented by the above formula (1) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Can be mentioned. Specific examples of these include aliphatic tetracarboxylic acid dianhydrides, such as butane tetracarboxylic acid dianhydrides;

As an 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 anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydro Naphtho[1,2-c]furan-1,3-dione, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-2 anhydride, bicyclo[3.3. 0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-2 anhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecan-3,5,8 , 10-tetraone, etc.;

As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride and the like can be exemplified, and the tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

Among the above, as the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid, it is preferable to contain an alicyclic tetracarboxylic acid dianhydride,

2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, 1,2,3, At least one selected from the group consisting of 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride It is more preferable to contain at least one type selected from these, more preferably 60 mol% or more, particularly preferably 80 mol% or more, based on the total tetracarboxylic dianhydride. It is preferable to use only at least one selected from.

The diamine preferably used in the synthesis of a polyamic acid having a structure represented by the formula (1) above contains a diamine having a structure represented by the formula (1).

The diamine having a structure represented by the above formula (1) is a compound in which an amino group is bonded to the two bonding hands of the structure represented by the above formula (1) either directly or via an appropriate bonding group. As said suitable bonding group, a phenylene group, a naphthylene group, a biphenylene group, etc. are mentioned, for example. The aromatic ring of these groups is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms. It may be substituted. As the bonding group, among the above, a phenylene group which may be substituted is preferable. That is, as a preferable example of the diamine which has a structure represented by said formula (1), the compound represented by the following formula (MDA) is mentioned:

H ₂ N-Ph-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -Ph-NH ₂ … (MDA)

(In formula (MDA), X ¹ , X ² , Y, R ¹ , m1 and m2 each have the same meaning as in the above formula (1),

Two Phs are each independently a phenylene group which may be substituted).

Ph in the formula (MDA) is particularly preferably a 1,4-phenylene group.

As the diamine preferably used for the synthesis of the polyamic acid having the structure represented by the above formula (1), only diamine having the structure represented by the above formula (1) may be used, or other diamines other than this may be used in combination.

Other diamines that can be used here are classified into diamines having a pretilt angle expressing group and diamines not having a pretilt angle expressing group.

As the other diamine having a pretilt each expressing group, it is preferable that it is an aromatic diamine having a pretilt each expressing group, and specific examples thereof include, for example, dodecanoxy-2,4-diaminobenzene, tetradecaneoxy- 2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2, 5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5- Diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesteryloxy-2, 4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis(4-aminobenzoyloxy ) Cholestan, 3,6-bis(4-aminophenoxy) cholestan, 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, N-(2,4-diaminophenyl)-4-(4-heptylcyclohexyl)benzamide, the following formula (A The compound represented by -1), etc. are mentioned:

(In formula (A-1), X ^I and X ^II are, respectively, a single bond, ^* -O-, ^* -COO- or ^* -OOC- (however, the bond hand to which "*" is attached is formula (AI) To the left of);

R ^I is a single bond, a methylene group, or an alkylene group having 2 or 3 carbon atoms;

a is 0 or 1, b is an integer of 0 to 2, provided that a and b are not 0 at the same time;

c is an integer from 1 to 20).

As a divalent group represented by X ^I -R ^I -X ^II -in the formula (A-1), a methylene group, an alkylene group having 2 or 3 carbon atoms, ^* -O-, ^* -COO- or ^* -O- It is preferable that it is CH ₂ CH ₂ -O- (however, the bond hand marked with "*" is bonded with a diaminophenyl group). When c is 3 or more in the group -C _C H _{2C +1} , this group is preferably linear. It is preferable that the two amino groups in the diaminophenyl group are at the 2,4-position or the 3,5-position with respect to the other groups. As a specific example of the compound represented by said formula (A-1), (A-1-1-1), (A-1-1-2), and (A-1-2):

It is preferable that it is a compound represented by each of (in the above formula, "n-" represents that each is linear).

Examples of other diamines that do not have a pretilt expression group include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes and the like which do not have a pretilt expression group.

Among other diamines that do not have each pretilt expression group, examples of aliphatic diamines include 1,1-methaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like;

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, and the like;

As the aromatic diamine, for example, as an aromatic diamine, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) Biphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 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-diaminopyrimidine, 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-amino Phenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)piperazine-4-carboxylic acid, 4-(morphine Polin-4-yl)benzene-1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, α-amino-ω-aminophenylalkylene, 4-(2- Aminoethyl)aniline and a compound represented by the following formula;

As the diaminoorganosiloxane, for example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc. can be mentioned, and the diamine described in Japanese Laid-Open Patent Publication No. 2010-97188 can be used. have.

The diamine used to synthesize the polyamic acid having a structure represented by the above formula (1) preferably contains 1 mol% or more of the diamine having the structure represented by the above formula (1), based on the total diamine, 3 It is more preferable to contain at least 5 mol%, and it is still more preferable to contain at least 5 mol%.

When applying the liquid crystal aligning agent of this invention to a vertical alignment type liquid crystal display element, such as VA type, it is preferable to contain 3 mol% or more of other diamines which have a pretilt angle expressing group with respect to all diamines, It is more preferable to contain 5 to 90 mol%, and it is still more preferable to contain 10 to 80 mol%. On the other hand, when the liquid crystal aligning agent of the present invention is applied to a horizontal alignment type liquid crystal display device such as a TN type, an STN type, an IPS type, or an FFS type, the ratio of other diamines having a pretilt angle expressing group is determined by the total diamine. With respect to, it is preferable to set it as 20 mol% or less, and it is more preferable to set it as 10 mol% or less.

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

The synthesis reaction of the polyamic acid is preferably in an organic solvent, preferably -20 to 150°C, more preferably 0 to 100°C under a temperature condition, preferably 0.5 to 24 hours, more preferably This is done for 2 to 10 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethyl Acetamide, N,N-dimethylformamide, N,N-dimethylimidazolidinone, N,N,2-trimethylpropionamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotria Non-protonic polar solvents such as mid;

and phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol. As for the amount of organic solvent used (a), the total amount (b) of the tetracarboxylic acid dianhydride and the diamine compound is preferably 0.1 to 50% by weight, more preferably 5 to 30% by weight, based on the total amount (a+b) of the reaction solution. It is an amount that makes it %.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be provided as it is for preparation of a liquid crystal aligning agent, may be provided for preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or preparation of a liquid crystal aligning agent after purifying the isolated polyamic acid You may provide it to.

When the polyamic acid is dehydrated and cyclized to form an imide, the reaction solution may be provided as it is for the dehydration cyclization reaction, the polyamic acid contained in the reaction solution may be isolated and then provided for the dehydration cyclization reaction, or the isolated polyamic acid After the mental acid is purified, it may be subjected to a dehydration ring closure reaction.

Isolation and purification of the polyamic acid can be performed by a known method.

The imidized product of a polyamic acid having a structure represented by the above formula (1) can be obtained by imidizing the polyamic acid synthesized as described above by dehydrating and cyclizing. At this time, the whole of the mental acid structure may be dehydrated and cyclized to be completely imidized, or only a part of the mental acid structure may be dehydrated and ring-closed to form a partial imide in which the mental acid structure and the imide structure coexist. The imidation ratio of the imidized product of the polyamic acid is preferably 10% or more, and more preferably 30 to 95%.

The dehydration cyclization of polyamic acid can be performed by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration cyclization catalyst to this solution, and heating if necessary. It can be done by Among these, it is preferable to use the method (ii).

On the other hand, in the above method (ii), as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 moles per 1 mole of the mental acid structural unit. Further, as the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, for example. However, it is not limited to these. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per 1 mole of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring closure reaction include organic solvents exemplified as those used for synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180°C, more preferably 10 to 150°C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

In this way, a reaction solution containing an imidized product of a polyamic acid is obtained. This reaction solution may be provided as it is for preparation of a liquid crystal aligning agent, or may be provided for preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, and after isolating and refining the imidide, the liquid crystal aligning agent It may be provided for the preparation of The removal of the dehydrating agent and the dehydration ring closure catalyst, and the isolation and purification of the imide product can be performed by a known method.

The liquid crystal aligning agent of the present invention contains a polymer having a structure represented by the above formula (1) as an essential component, and is preferably constituted as a solution composition dissolved in a solvent described below, but other components are used as necessary. It may contain additionally. Here, as the other components, for example, other polymers, compounds having at least one epoxy group in the molecule (hereinafter, referred to as "epoxy compound"), functional silane compounds, and the like can be mentioned.

The other polymers described above are polymers that do not have a structure represented by the above formula (1), and can be used to improve solution properties (applicability) and electrical properties of the liquid crystal aligning agent of the present invention.

As other polymers, polyamic acids not having the structure represented by the above formula (1), imidized polymers of the polyamic acids, polyamic acid esters, polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly( Styrene-phenylmareimide) derivatives, poly(meth)acrylates, and the like.

The ratio of the other polymers to be used is preferably 90% by weight or less, with the total of the polymers (means the total of the polymer having the structure represented by the formula (1) and other polymers; the same hereinafter) as 100% by weight. It is more preferable that it is 50 weight% or less, and it is especially preferable that it does not contain another polymer.

The epoxy compound and the functional silane compound may be contained in the liquid crystal aligning agent of the present invention in order to further improve the adhesion between the obtained liquid crystal aligning film and the substrate, respectively.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl 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-di Glycidyl-cyclohexylamine etc. are mentioned as a preferable thing.

The blending ratio of these epoxy compounds is preferably 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total of the polymer.

As the functional silane compound, for example, 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-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trime Toxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 ,6-diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, 9-trimethoxysilyl-3,6-diazanonanoic acid methyl, 9-triethoxysilyl-3,6 -Methyl diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3 -Aminopropyl triethoxysilane, etc. are mentioned.

The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, and more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total of the polymer.

The liquid crystal aligning agent of this invention is comprised by dissolving and containing the polymer which has the structure represented by said Formula (1), and other components optionally blended as needed, preferably in a solvent.

As a solvent that can be used for the liquid crystal aligning agent of the present invention, it is preferable to use an organic solvent, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N -Dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methylmethoxypropionate, ethylethoxypro Cypionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol Ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl Ketone, isoamylpropionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone, or two or more may be mixed and used.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity and volatility, but is preferably Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably heated to form a coating film that becomes a liquid crystal aligning film, but when the solid content concentration is less than 1% by weight, the film thickness of the coating film is insufficient. Therefore, when a good liquid crystal aligning film cannot be obtained, on the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive, so that a good liquid crystal aligning film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases. The characteristics become inferior.

The range of particularly preferable solid content concentration differs depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, in the case of spinner method, the range of 1.5 to 4.5% by weight of solid content concentration is particularly preferable. In the case of the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by weight, and thus the solution viscosity to be in the range of 12 to 50 mPa·s. In the case of the ink jet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by weight, and thus the solution viscosity to be in the range of 3 to 15 mPa·s.

The temperature when preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10 to 45 degreeC, More preferably, it is 20 to 30 degreeC.

A liquid crystal aligning film can be formed using the liquid crystal aligning agent of this invention. That is, the liquid crystal aligning film can be formed by applying the liquid crystal aligning agent of this invention on a board|substrate to form a coating film, and preferably passing through the process of rubbing or irradiating the said coating film.

The liquid crystal aligning agent of this invention can be applied to manufacture of a liquid crystal display element which has suitable liquid crystal cells, such as a TN type, STN type, IPS type, FFS type, VA type, and MVA type, for example. However, it is preferable to apply it to a liquid crystal display element having a liquid crystal cell of a so-called horizontal alignment type, such as a TN type, an STN type, an IPS type, and an FFS type, from the viewpoint of the advantageous effects of the present invention to the maximum.

When the liquid crystal alignment film formed of the liquid crystal alignment film of the present invention is applied to a TN-type or STN-type liquid crystal display element, as the substrate, two substrates on which a patterned transparent conductive film is formed are used as a pair, and the liquid crystal The alignment agent is applied on the surface of each substrate on which the transparent conductive film is formed. On the other hand, when the liquid crystal alignment layer is applied to an IPS type or FFS type liquid crystal display device, as the substrate, a substrate having an electrode patterned in a comb-like shape with a transparent conductive film or a metal film on one side, and a counter substrate having no electrode formed thereon Is used as a pair, and the liquid crystal aligning agent is applied to the formation surface of the comb-shaped electrode and one surface of the counter substrate.

In either of the above cases, examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, and polycarbonate can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ , a NESA (registered trademark) film made of SnO ₂ , or the like can be used. As the metal film, for example, a film made of a metal such as chromium can be used. For patterning of a transparent conductive film and a metal film, for example, after forming a patternless transparent conductive film, a method of forming a pattern by a photo-etching method, a sputtering method, etc., a method of using a mask having a desired pattern when forming a transparent conductive film It can be done by etc.

In order to further improve the adhesion between the substrate and the transparent conductive film or metal film and the coating film at the time of application of the liquid crystal aligning agent for photo-alignment onto the substrate, on the substrate and the transparent conductive film or metal film, in advance, A functional silane compound, titanate compound, or the like may be applied.

The application of the liquid crystal aligning agent for photo-alignment onto the substrate can be preferably performed by an appropriate coating method such as an offset printing method, a spin coating method, a roll coater method, and an inkjet printing method, and then, the coated surface is preheated (free Baking) and post-heating (post-baking) to form a coating film. Pre-baking conditions are preferably 0.1 to 5 minutes at 40 to 120°C. Post-baking conditions are preferably 120 to 300°C, more preferably 150 to 250°C, preferably 5 to 200 minutes, and more preferably 10 to 100 minutes.

Subsequently, by passing through a step of performing a rubbing treatment or a light irradiation treatment on the coating film formed as described above, the liquid crystal alignment ability is imparted to the coating film to obtain a liquid crystal alignment film. Here, when at least one of X ¹ and X ² in the formula (1) is an ester bond, it is preferable to perform light irradiation treatment, and in other cases, it is preferable to perform rubbing treatment.

The rubbing treatment can be performed by rubbing the surface of the coating film formed on the substrate in a predetermined direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton.

As the light to be irradiated in the light irradiation treatment, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. As the irradiated light, it is preferable to use ultraviolet rays containing light having a wavelength of 200 to 400 nm. As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an Hg-Xe lamp, an excimer laser, and the like can be used. Ultraviolet rays in the above preferable wavelength range can be obtained by means of using the light source in combination with, for example, a filter, a diffraction grating, or the like. Although polarized light or non-polarized light may be sufficient as the irradiation light, polarized light is preferable. It is preferable that the irradiation direction is from a direction perpendicular to the substrate surface.

The irradiation amount of light is preferably 100 J/m 2 or more, more preferably 400 to 20,000 J/m 2, and still more preferably 1,000 to 10,000 J/m 2.

Using the liquid crystal aligning agent of this invention, it carries out as mentioned above, and can form a liquid crystal aligning film on a board|substrate. A liquid crystal display device can be manufactured as follows using the substrate having this liquid crystal alignment film.

As described above, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a liquid crystal cell having a structure in which a liquid crystal is sandwiched between the pair of substrates is manufactured. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

As a first method, a pair of substrates are disposed to face each other through a gap (cell gap) so that each liquid crystal alignment film faces each other, and the periphery of the pair of substrates is bonded using a sealing agent, and the surface of the substrate and a suitable sealing agent A method of manufacturing a liquid crystal cell is exemplified by injecting and filling liquid crystal into the cell gap partitioned by and then sealing the injection port.

As a second method, for example, an ultraviolet light-curable sealing agent is applied to a predetermined place on one of the two substrates on which the liquid crystal aligning film is formed, and liquid crystal is further dripped at several predetermined points on the liquid crystal aligning film surface. After that, the other substrate is bonded to face the liquid crystal alignment film, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent, thereby manufacturing a liquid crystal cell ( ODF (One Drop Fill) method) is mentioned.

In the case of any of the above methods, it is preferable to remove the flow orientation at the time of liquid crystal filling by heating to a temperature at which the liquid crystal using the liquid crystal cell takes an isotropic phase and then gradually cooling to room temperature. Then, the liquid crystal display device of the present invention can be obtained by bonding the polarizing plate to the outer surface of the liquid crystal cell in a predetermined direction.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used.

In the case of manufacturing a horizontal alignment type liquid crystal display device, a nematic liquid crystal having positive dielectric anisotropy is preferred. For example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclo A hexane liquid crystal, a pyrimidine liquid crystal, a benzene fluoride liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuban liquid crystal, and the like are used. To these liquid crystals, a cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal or the like may be added and used. On the other hand, in the case of manufacturing a vertical alignment type liquid crystal display element, a nematic type liquid crystal having negative dielectric anisotropy is preferable. For example, a dicyanobenzene type liquid crystal, a pyridazine type liquid crystal, a ciprobase type liquid crystal, a subgroup clock liquid crystal, Biphenyl liquid crystal, phenylcyclohexane liquid crystal, or the like can be used.

Examples of the polarizing plate used on the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called ``H film'' in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched with a cellulose acetate protective film, or a polarizing plate made of the H film itself. have.

(Example)

<Synthesis of diamine having a structure represented by the formula (1)>

Synthesis Example MDA-1

According to the following scheme 1, a compound represented by the formula (MDA-1) (compound (MDA-1)) was synthesized:

(In Scheme 1, Boc is a t-butoxycarbonyl group).

In a reaction vessel, 11.8 g (0.050 mol) of 3,5-dibromopyridine, 609 mg (2.0 mmol) of tri-o-tolylphosphine, and 112 mg (0.5 mmol) of palladium acetate as a catalyst were mixed, followed by nitrogen substitution. Thereafter, 152 mL of N,N-dimethylformamide, 16.7 mL (0.120 mol) of triethylamine, and 17.5 mL (0.120 mol) of tert-butyl acrylate were added, followed by reaction at 120° C. for 3 hours under stirring. After completion of the reaction, air was blown into the reaction mixture to deactivate palladium acetate. After removing the catalyst residue by Celite filtration, the organic layer obtained by adding 500 mL of ethyl acetate to the filtrate was extracted and washed four times with 500 mL of distilled water. Then, the solid obtained by removing the solvent from the organic layer under reduced pressure was recrystallized using 150 mL of ethanol to obtain 13.6 g (0.041 mol, 82% yield) of a yellow compound (mda-1-1).

In a reaction vessel equipped with a cock, 13.6 g (0.041 mol) of the compound (mda-1-1) obtained above and 1.36 g of 5 wt% palladium carbon (50 wt% water content) were mixed to perform carbon substitution, and then tetra 80 mL of hydrofuran and 80 mL of ethanol were added, and a balloon containing hydrogen was attached to the bowl, and the container was placed under a hydrogen atmosphere, and the reaction was carried out under stirring at 50° C. for 5 hours under this atmosphere. After completion of the reaction, palladium carbon was removed from the reaction mixture by Celite filtration, and the solvent was removed from the obtained filtrate under reduced pressure, and 13.1 g (0.038 mol, yield 95%) of a light brown compound (mda-1-2) Got it.

In a reaction vessel, 13.1 g (0.039 mol) of the compound (mda-1-2) obtained above, 80 mL of dichloromethane and 40 mL of trifluoroacetic acid were mixed, and the reaction was carried out under stirring at 20° C. for 3 hours. After the completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 120 mL of ethanol to obtain 7.14 g (0.032 mol, 82% yield) of a pale brown compound (mda-1-3).

Next, in a reaction vessel, 7.14 g (0.032 mol) of the compound (mda-1-3) obtained above, 13.4 g (0.064 mol) of 4-(tert-butoxycarbonylamino)phenol, and 128 mL of dichloromethane were mixed. The container was cooled in an ice bath and the internal temperature was maintained at 5° C., while 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 14.7 g (0.077 mol) and N,N-dimethyl-4-aminopyridine 1.56 g After adding (0.013 mol), it reacted under stirring at 20 degreeC for 2 hours. After completion of the reaction, the organic layer obtained by adding 300 mL of ethyl acetate to the reaction mixture was extracted and washed three times with 300 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 100 mL of ethanol to obtain 15.7 g (0.026 mol, 81% yield) of a pale brown compound (mda-1-4).

Further, in a reaction vessel, 15.7 g (0.026 mol) of the compound (mda-1-4) obtained above, 52 mL of dichloromethane, and 26 mL of trifluoroacetic acid were mixed, and the reaction was carried out under stirring at 20°C for 3 hours. After the reaction was completed, 8.86 g (0.022 mol, yield 84%) of a violet compound (MDA-1) was obtained by recrystallization of the obtained solid from the reaction mixture by removing the solvent under reduced pressure using 100 mL of ethanol.

Synthesis Example MDA-2

According to the following scheme 2, a compound represented by the formula (MDA-2) (compound (MDA-2)) was synthesized:

(In Scheme 2, Boc is a t-butoxycarbonyl group).

In the reaction vessel, 3,5-lutidine 6.43 g (0.060 mol), acetonitrile 60 mL, N-chlorosuccinimide 48.1 g (0.360 mol) and 2,2'-azobis (isobutyronitrile) 2.46 g ( 0.015 mol) was mixed, and reaction was carried out under stirring at 80°C for 8 hours. After completion of the reaction, the solid obtained by removing the solvent under reduced pressure from the reaction mixture was purified by column chromatography (filling material: silica gel, developing solvent: hexane/ethyl acetate = 3/1 (volume ratio)) to obtain a light brown compound. (mda-2-1) was obtained 6.65 g (0.038 mol, yield 63%).

Then, in the reaction vessel, the compound obtained above (mda-2-1) 6.65 g (0.038 mol), 4-(tert-butoxycarbonylamino) phenol 15.9 g (0.076 mol), N,N-dimethylacetamide 190 mL and 12.6 g (0.091 mol) of potassium carbonate were mixed and reacted at 90° C. for 5 hours under stirring. After completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was extracted and washed four times with 300 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 100 mL of ethanol to obtain 16.6 g (0.032 mol, 84% yield) of a pale brown compound (mda-2-2).

Further, 16.6 g (0.032 mol) of the compound (mda-2-2) obtained above were mixed with 64 mL of dichloromethane and 32 mL of trifluoroacetic acid, and reacted at 20° C. for 3 hours under stirring. After completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 100 mL of ethanol to obtain 9.26 g (0.029 mol, yield 90%) of a purple compound (MDA-2).

Synthesis Example MDA-3

According to the following Scheme 3, a compound (compound (MDA-3)) represented by formula (MDA-3) was synthesized.

In a flask equipped with a Dean Stark tube, 17.9 g (0.164 mol) of 4-aminophenol, 80 mL of dimethyl sulfoxide, 8.0 mL of toluene and 9.88 g (0.176 mol) of potassium hydroxide were mixed, stirred at 135° C. for 4 hours, and water After removing by azeotrope, the temperature was lowered to 100° C., 11.8 g (0.080 mol) of 2,6-dichloropyridine was added, and the temperature was again raised to 135° C., followed by reaction under stirring for 4 hours. After completion of the reaction, the reaction mixture was poured into 500 mL of distilled water, and the produced precipitate was recovered. The recovered precipitate was recrystallized using 100 mL of ethanol to obtain 15.9 g (0.054 mol, yield 68%) of a violet compound (MDA-3).

Synthesis Example MDA-4

According to the following scheme 4, a compound represented by the formula (MDA-4) (compound (MDA-4)) was synthesized:

(In Scheme 4, Boc is a t-butoxycarbonyl group).

In the reaction vessel, 20.3 g (0.097 mol) of 4-(tert-butoxycarbonylamino)phenol, 300 mL of tetrahydrofuran, and 27.0 mL (0.194 mol) of triethylamine were mixed. A solution in which 19.4 g (0.088 mmol) of 5-bromonicotinoyl chloride was dissolved in 50 mL of tetrahydrofuran was added dropwise while cooling the container under an ice bath. After completion of the dropwise addition, the temperature was raised to 20° C., and the reaction was carried out under stirring at the same temperature for 4 hours. After completion of the reaction, the organic layer obtained by adding 750 mL of ethyl acetate to the reaction mixture was extracted and washed four times with 750 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 150 mL of ethanol to obtain 29.4 g (0.075 mol, yield 85%) of a pale brown compound (mda-4-1).

Next, in the reaction vessel, 29.4 g (0.075 mol) of the compound (mda-4-1) obtained above, N-[4-(4,4,5,5-N-tetramethyl-1,3,2- Dioxaborolan-2-yl)phenyl]carbamic acid tert-butyl 23.9 g (0.075 mol), sodium carbonate 15.9 g (0.150 mol) and [1,1'-bis(diphenylphosphino)ferrocene]dichloro as catalyst After mixing 2.74 g (3.75 mmol) of palladium and purging with nitrogen, 40 mL of toluene, 40 mL of ethanol and 40 mL of distilled water were further added, followed by reaction at 60°C for 16 hours under stirring. After completion of the reaction, air was blown into the reaction mixture to deactivate the palladium catalyst, and then the catalyst residue was removed by filtration through celite. The organic layer obtained by adding 500 mL of ethyl acetate to the filtrate was extracted and washed 4 times with 500 mL of distilled water. The solid obtained by removing the solvent under reduced pressure from the washed organic layer was recrystallized using 200 mL of ethanol to obtain 22.8 g (0.045 mol, yield 60%) of a pale brown compound (mda-4-2).

In a reaction vessel, 22.8 g (0.045 mol) of the compound (mda-4-2) obtained above, 90 mL of dichloromethane, and 45 mL of trifluoroacetic acid were mixed, and the reaction was carried out at 20° C. for 3 hours under stirring. After the completion of the reaction, the solid obtained by removing the solvent under reduced pressure was recrystallized using 30 mL of ethyl acetate and 120 mL of hexane to obtain 11.0 g (0.036 mol, 80% yield) of a brown compound (MDA-4).

Synthesis Example MDA-5

According to the following scheme 5, a compound represented by the formula (MDA-5) (compound (MDA-5)) was synthesized:

(In Scheme 5, Boc is a t-butoxycarbonyl group).

In the reaction vessel, 42.6 g (0.150 mol) of 5-bromo-2-iodopyridine, N-[4-(4,4,5,5-N-tetramethyl-1,3,2-dioxabo) Rolan-2-yl) phenyl] tert-butyl carbamic acid 47.9 g (0.150 mol), sodium carbonate 47.7 g (0.450 mol), and tetrakis (triphenylphosphine) palladium 8.67 g (7.50 mmol) as a catalyst were mixed with nitrogen After substitution, 500 mL of tetrahydrofuran and 250 mL of distilled water were added, and reaction was carried out for 20 hours under stirring at 60°C. After completion of the reaction, air was blown into the reaction mixture to deactivate the palladium catalyst, and then filtered through Celite to remove the catalyst residue. The organic layer obtained by adding 1,000 mL of ethyl acetate to the filtrate was extracted and washed 4 times with 800 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 300 mL of ethanol to obtain 29.3 g (0.084 mol, yield 56%) of a pale brown compound (mda-5-1).

Next, in a reaction vessel, 29.3 g (0.084 mol) of the compound (mda-5-1) obtained above, 1.02 g (3.4 mmol) of tri-o-tolylphosphine, and 189 mg (0.84 mmol) of palladium acetate as a catalyst were added. After mixing and nitrogen substitution, 255 mL of N,N-dimethylformamide, 14.0 mL (0.100 mol) of triethylamine, and 14.6 mL (0.100 mol) of tert-butyl acrylate were added, followed by reaction at 120°C for 4 hours under stirring. . After completion of the reaction, air was blown into the reaction mixture to deactivate the palladium catalyst, followed by filtration with Celite to remove catalyst residues. The organic layer obtained by adding 700 mL of ethyl acetate to the filtrate was extracted and washed four times with 700 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 250 mL of ethanol to obtain 26.2 g (0.066 mol, 79% yield) of a pale brown compound (mda-5-2).

In a reaction vessel equipped with a cock, 26.2 g (0.066 mol) of the compound (mda-5-2) obtained above and 2.62 g of 5 wt% palladium carbon (50 wt% hydrated product) were mixed, followed by nitrogen substitution. , 132 mL of tetrahydrofuran and 132 mL of ethanol were added. A balloon containing hydrogen was attached to the cock of the reaction vessel, and the inside of the vessel was made into a hydrogen atmosphere, and the reaction was carried out for 5 hours under stirring at 50°C under the atmosphere. After completion of the reaction, palladium carbon was removed from the reaction mixture by Celite filtration, and the solvent was removed from the obtained filtrate under reduced pressure, and 24.3 g (0.061 mol, yield 93%) of a light brown compound (mda-5-3) Got it.

In a reaction vessel, 24.3 g (0.061 mol) of the compound (mda-5-3) obtained above, 120 mL of dichloromethane, and 60 mL of trifluoroacetic acid were mixed, and the reaction was carried out for 3 hours under stirring at 20°C. After completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 150 mL of ethanol to obtain 18.5 g (0.054 mol, yield 89%) of a pale brown compound (mda-5-4).

Subsequently, in a reaction vessel, 18.5 g (0.054 mol) of the compound (mda-5-4) obtained above, 11.3 g (0.054 mol) of 4-(tert-butoxycarbonylamino)phenol, and 108 mL of dichloromethane were mixed, Cooling to 5° C. in an ice bath, 12.4 g (0.065 mol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1.32 g (0.011 mol) of N,N-dimethyl-4-aminopyridine ) Was added. Then, it heated up to 20 degreeC, and reacted for 3 hours under stirring at the same temperature. After completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed three times with 500 mL of distilled water. The solid obtained by removing the solvent from the washed organic layer under reduced pressure was recrystallized using 150 mL of ethanol to obtain 25.6 g (0.048 mol, 89% yield) of a pale brown compound (mda-5-5).

Further, in a reaction vessel, 25.6 g (0.048 mol) of the compound (mda-5-5) obtained above, 96 mL of dichloromethane and 48 mL of trifluoroacetic acid were mixed, and the reaction was carried out for 3 hours under stirring at 20°C. After the reaction was completed, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 150 mL of ethanol to obtain 12.7 g (0.038 mol, yield 80%) of a purple compound (MDA-5).

Synthesis Example MDA-6

According to the following scheme 6, a compound represented by the formula (MDA-6) (compound (MDA-6)) was synthesized:

(In Scheme 6, Boc is a t-butoxycarbonyl group).

Into a 500 mL three-necked flask equipped with a dropping lot and a nitrogen introduction tube, 7.1 g of 4-aminophenol and 350 mL of tetrahydrofuran were placed. While maintaining the internal temperature of the flask at 6°C or less, a solution in which 14.6 g of t-butyl dicarbonate was dissolved in 60 mL of tetrahydrofuran was added dropwise from a dropping funnel, and then the reaction was performed at room temperature for 24 hours. After completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was dissolved in 500 mL of ethyl acetate, followed by liquid separation and washing with 500 mL of distilled water. After drying the organic layer with magnesium sulfate, the solvent was removed under reduced pressure, and 12.6 g of white crystals of Intermediate 1 were obtained.

Into a 300 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 10.14 g of intermediate 1 obtained above, 4.05 g of 2,5-dicarboxylic acid pyridine, and 150 mL of methylene chloride were placed, and the suspension was cooled to 0°C under stirring. While maintaining the same temperature, 12.08 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 2.37 g of N,N-dimethylaminopyridine were added thereto, followed by reaction for 6 hours under stirring. . After that, stirring was continued for an additional 6 hours at room temperature. To the reaction mixture after stirring for 12 hours in total, 300 mL of ethyl acetate, 300 mL of tetrahydrofuran, and 300 mL of distilled water were added, followed by liquid separation and washing, and the organic layer was recovered. After the obtained organic layer was concentrated to about 200 mL, 100 mL of ethanol was added to replace the solvent, and then concentrated again, and the precipitated white solid (intermediate 2) was filtered out. The yield of Intermediate 2 was 10.0 g.

In a 300 mL nas flask equipped with a nitrogen introduction tube, 8.4 g of the intermediate 2 obtained above was suspended in 150 mL of methylene chloride, 30 mL of trifluoroacetic acid was added thereto, and the reaction was carried out for 24 hours under stirring. After completion of the reaction, a saturated aqueous sodium carbonate solution was added to the reaction mixture until the pH became 7 or more, and then 200 mL of ethyl acetate and 200 mL of tetrahydrofuran were added to separate the mixture, and the organic layer was recovered. The organic layer was washed three times with 300 mL of distilled water and then concentrated. During concentration, the liquid turned black. The precipitated solid was filtered out and washed with a mixed solvent consisting of ethanol and pure water (ethanol:water = 4:1 (volume ratio)) to obtain 4.2g of a yellow compound (MDA-6).

<Synthesis of a polymer having a structure represented by the formula (1)>

Synthesis Examples PI-1 to PI-11

As tetracarboxylic acid dianhydride and diamine, each of the kinds described in Table 1 was mixed so that the ratio (molar ratio) indicated in the table was mixed, and N-methyl-2-pyrrolidone (NMP) was added to obtain a monomer concentration of 20 It was set as a weight% solution. This solution was reacted at 40° C. for 4 hours under stirring to obtain a solution containing 20% by weight of polyamic acid. In Synthesis Example PI-7, in addition to tetracarboxylic acid dianhydride and diamine, the monoamine described in Table 1 was further used in the ratio (molar ratio) described in the table.

Subsequently, NMP was added to the polyamic acid solution obtained above to dilute the polyamic acid concentration to 10% by weight, and then, pyridine and acetic anhydride were each obtained in Table 1 It added so that it might become the amount of a base material, and it stirred at 110 degreeC for 4 hours, and performed the dehydration ring closure reaction. The reaction mixture after the completion of the reaction was subjected to solvent substitution by NMP to obtain a solution containing 15% by weight of each of the imidized polymers (PI-1) to (PI-11). About the obtained imidized polymer, the imidation ratio measured by ¹ H-NMR was combined with Table 1, and was shown.

Synthesis Example PA-1

As tetracarboxylic acid dianhydride and diamine, except for using those of the kinds shown in Table 1 so as to be the ratio (molar ratio) described in the table, the operation was carried out in the same manner as in Synthesis Example PI-1, and polyamic acid (PA-1 ) To obtain a solution containing 20% by weight.

In this synthesis example, the obtained polyamic acid solution was provided as it is for preparation of a liquid crystal aligning agent without performing a dehydration ring closure reaction.

<Synthesis of other polymers>

Synthesis Examples rpi-1 to rpi-3

As tetracarboxylic acid dianhydride and diamine, each of the kinds listed in Table 1 is used so that the ratio (molar ratio) shown in the table is used, and

Except that the amounts of pyridine and acetic anhydride were adjusted to be the ratios shown in Table 1, the operation was carried out in the same manner as in Synthesis Example PI-1, and the imidized polymers (rpi-1) to (rpi-3) were each 15 weight. A solution containing% was obtained. About the obtained imidized polymer, the imidation ratio measured by ¹ H-NMR was combined with Table 1, and was shown.

Synthesis Examples rpa-1 to rpa-4

As tetracarboxylic acid dianhydride and diamine, the same operation as in Synthesis Example PI-1 was performed, except that those of the kinds described in Table 1 were used so as to be the ratio (molar ratio) described in the table, respectively, and polyamic acid (rpa A solution containing 20% by weight of each of -1) to (rpa-4) was obtained.

In these synthesis examples, the obtained polyamic acid solution was not subjected to dehydration ring closure reaction, and the obtained polyamic acid solution was provided as it is for preparation of a liquid crystal aligning agent.

The abbreviations in the monomer column of Table 1 are the following meanings, respectively.

<Tetracarboxylic acid dianhydride>

TCA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride

BODA: 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride

CB: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride

MTDA: 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan -1,3-dione

PMDA: pyromellitic dianhydride

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

<Diamine>

[Diamine having a structure represented by the above formula (1)]

MDA-1: Compound synthesized in Synthesis Example MDA-1 (MDA-1)

MDA-2: Compound synthesized in Synthesis Example MDA-2 (MDA-2)

MDA-3: Compound synthesized in Synthesis Example MDA-3 (MDA-3)

MDA-4: Compound synthesized in Synthesis Example MDA-4 (MDA-4)

MDA-5: Compound synthesized in Synthesis Example MDA-5 (MDA-5)

MDA-6: Compound synthesized in Synthesis Example MDA-6 (MDA-6)

[Other diamines]

PDA: p-phenylenediamine

HCDA: 3,5-diaminobenzoic acid cholestanyl

35DAB: 3,5-diaminobenzoic acid

HCODA: cholestanyloxy-2,4-diaminobenzene

LDA: 4-{4-[2-(4'-pentyl-1,1'-bicyclohexyl)ethyl]phenoxy}benzene-1,3-diamine

D-1: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

D-2: 1,3-bis(3-aminopropyl)-tetramethyldisiloxane

D-3: 3,6-bis(4-aminobenzoyloxy)cholestane

D-5: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl

D-6: 4,4'-diaminodiphenylmethane

D-7: 2,2'-dimethyl-4,4'-diaminobiphenyl

D-8: 4,4'-diaminodiphenyl ether

DA-2: compound represented by the following formula (DA-2)

DA-3: compound represented by the following formula (DA-3)

mda-1: compound represented by the following formula (mda-1)

mda-2: compound represented by the following formula (mda-2)

[Monoamine]

D-4: aniline

Synthesis Example rps-1

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were added, Mixed at room temperature. Subsequently, after dropping 100 g of deionized water over 30 minutes from the dropping funnel, the reaction was carried out at 80°C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group. It was obtained as a crude transparent liquid. As a result of performing ¹ H-NMR analysis on this polyorganosiloxane, a peak based on an epoxy group was obtained around the chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and it was confirmed that no side reaction of the epoxy group occurred during the reaction. . The weight average molecular weight Mw of the obtained polyorganosiloxane having an epoxy group was 3,500 and the epoxy equivalent was 180 g/mol.

Next, in a 200 mL three-necked flask, 10.0 g of polyorganosiloxane having an epoxy group obtained above, 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as a carboxylic acid, and UCAT 18X as a catalyst (trade name, 0.10 g of San Apro Co., Ltd.) was put, and reaction was carried out under stirring at 100 degreeC for 48 hours. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed three times with water, dried with magnesium sulfate, and the solvent was distilled off to obtain 9.0 g of polyorganosiloxane (rps-1). The weight average molecular weight Mw of the obtained polyorganosiloxane (rps-1) was 9,900.

Example 1

1. Preparation of liquid crystal aligning agent

NMP and butyl cellosolve (BC) were added to the solution containing the imidized polymer (PI-1) obtained in Synthesis Example PI-1 and stirred sufficiently, and the solvent composition was NMP:BC=60:40 (weight ratio) And a solution having a solid content concentration of 2.5% by weight. A liquid crystal aligning agent was prepared by filtering this solution using a filter of 1 micrometers pore diameter.

2. Evaluation of liquid crystal aligning agent

About the printability of the liquid crystal aligning agent prepared above and the reliability of the liquid crystal display element manufactured using the said liquid crystal aligning agent, it evaluated by the following method.

The evaluation results are shown in Table 2.

Examples 2 to 8, 10 and 11 and Comparative Examples 1 to 3

1. Preparation of liquid crystal aligning agent

As the solution containing the polymer, “1. A liquid crystal aligning agent was prepared in the same manner as "Preparation of a liquid crystal aligning agent".

In addition, in Examples 7 and 8, each of two types of polymers was mixed and used in the proportions shown in Table 2.

2. Evaluation of liquid crystal aligning agent

About each liquid crystal aligning agent prepared above, it carried out similarly to the said Example 1, and evaluated.

The evaluation results are shown in Table 2.

Example 9

1. Preparation of liquid crystal aligning agent

To the solution containing the imidized polymer (PI-9) obtained in Synthesis Example PI-9, the polyorganosiloxane (rps-1) obtained in Synthesis Example rps-1 was added, and further NMP and butyl cello Solve (BC) was added and sufficiently stirred to obtain a solution having a solvent composition of NMP:BC=60:40 (weight ratio) and a solid content concentration of 2.5% by weight. Here, the imidized polymer (PI-9) and the polyorganosiloxane (rps-1) were used in a ratio such that the weight ratio of PI-9:rps-1 was 95:5.

A liquid crystal aligning agent was prepared by filtering this solution using a filter with a pore diameter of 1 µm.

2. Evaluation of liquid crystal aligning agent

About the liquid crystal aligning agent prepared above, it carried out similarly to the said Example 1, and evaluated.

The evaluation results are shown in Table 2.

<Evaluation method of liquid crystal aligning agent (1)>

The liquid crystal aligning agents prepared in Examples 1 to 11 and Comparative Examples 1 to 3 were respectively evaluated by the following methods.

1. Evaluation of printability

About the liquid crystal aligning agent prepared in each Example or the comparative example, the printability (continuous printability) when printing to a board|substrate was continuously performed was evaluated.

First, using a liquid crystal aligning film printer (manufactured by Nippon Shashin Insats Co., Ltd., product name "Angstrom S40L-532"), the amount of the liquid crystal aligning agent added to the anilox roll is adjusted to 20 drops (about 0.2 g) reciprocating conditions Then, each liquid crystal aligning agent was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film. Coating to the substrate was performed 20 times while using a new substrate at 1 minute intervals.

Subsequently, the liquid crystal aligning agent was dispensed (one way) on an anilox roll at 1-minute intervals, and the operation|work (empty operation) of making an anilox roll and a printing plate contact each time was performed 10 times in total. In the meantime, printing to a glass substrate is not performed. This idling operation is an operation performed in order to intentionally perform printing of the liquid crystal aligning agent under severe circumstances.

After 10 times of idling, the main printing was performed using a glass substrate. In this printing, after idling, 5 substrates were added at intervals of 30 seconds, and each substrate after applying the liquid crystal aligning agent was heated (prebaked) at 80° C. for 1 minute to remove the solvent, and then at 200° C. It heated for a minute (post-baking) to form a coating film having a thickness of about 80 nm. Printability was evaluated by observing this coating film with a microscope at a magnification of 20 times.

Evaluation was performed based on the following criteria.

When no polymer precipitation was observed in the coating film from the first printing after idling: A (excellent)

When the precipitation of polymer was observed in the coating film in the first printing after idling, but no polymer precipitation was observed during the 5th printing: B (good)

When polymer precipitation is observed in the coating film even after repeating this printing 5 times: C (defective)

About the liquid crystal aligning agent obtained the A evaluation by the said evaluation, the number of times of idling was changed to 25, and the same evaluation was performed again. As a result, when no polymer precipitation was observed in the coating film from the first printing of the main printing after 25 times of idling, it was evaluated as "AA (particularly superior)".

2. Evaluation of the liquid crystal cell

(1) Preparation of liquid crystal cell

Each liquid crystal aligning agent prepared in the above Examples and Comparative Examples was applied on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by using a liquid crystal alignment film printer (manufactured by Nippon Shashin Insats Co., Ltd.), and After heating (pre-baking) for 1 minute on a hot plate of, the solvent was removed, followed by heating (post-baking) for 30 minutes on a 210°C hot plate to form a coating film having an average film thickness of 80 nm.

With respect to this coating film, a rubbing treatment was performed at a roll rotation speed of 500 rpm, a stage movement speed of 3 cm/sec, and a hair foot press-fitting length of 0.4 mm by a rubbing machine having a roll wound with a rayon cloth to impart liquid crystal alignment ability. . Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100°C clean oven for 10 minutes to obtain a substrate having a liquid crystal aligning film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal aligning film.

Next, after applying an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 μm, leaving a liquid crystal injection hole on the outer edge of the surface having one liquid crystal alignment film among the pair of substrates, the pair of substrates The adhesive was cured by overlapping each other so that the orientation film faces were mated. Next, after filling a nematic liquid crystal (Merck company make, product name "MLC-6221") between a pair of substrates from the liquid crystal injection port, a liquid crystal cell was manufactured by sealing the liquid crystal injection port with an acrylic photocurable adhesive.

(2) Evaluation of reliability

Reliability was evaluated about the liquid crystal cell produced above.

First, a voltage of 5 V was applied to a liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate (VHR1) after 167 milliseconds from the release of application was measured. Next, the liquid crystal cell was allowed to stand in an oven at 80°C under irradiation of an LED lamp for 200 hours, and then allowed to stand in room temperature and naturally cooled to room temperature. After applying a voltage of 5 V to the cooled liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention rate (VHR2) after 167 milliseconds from the release of application was measured.

The rate of change (ΔVHR) of the voltage preservation rate at this time was calculated by the following formula (1), and reliability was evaluated according to the following criteria according to the obtained value of ΔVHR.

ΔVHR[%]={(VHR1-VHR2)/(VHR1)}×100　　　(1)

When ΔVHR was less than 1%: A (excellent)

When ΔVHR was 1% or more and less than 2%: B (good)

△ When VHR was 2% or more: C (defective)

Example 12

1. Preparation of liquid crystal aligning agent

NMP and butyl cellosolve (BC) were added to the solution containing the polyamic acid (PA-1) obtained in Synthesis Example PA-1 and stirred sufficiently, so that the solvent composition was NMP:BC=60:40 (weight ratio), It was set as the solution of 2.5 weight% of solid content concentration.

A liquid crystal aligning agent was prepared by filtering this solution using a filter with a pore diameter of 1 µm.

2. Evaluation of liquid crystal aligning agent

About the printability of the liquid crystal aligning agent prepared above and the reliability of the liquid crystal cell manufactured using the said liquid crystal aligning agent, it evaluated by the following method.

The evaluation results are shown in Table 3.

Comparative Examples 4 and 5

1. Preparation of liquid crystal aligning agent

As the solution containing the polymer, “1. A liquid crystal aligning agent was prepared in the same manner as "Preparation of a liquid crystal aligning agent".

2. Evaluation of liquid crystal aligning agent

About each liquid crystal aligning agent prepared above, it carried out similarly to the said Example 12, and evaluated.

The evaluation results are shown in Table 3.

<Evaluation method of liquid crystal aligning agent (2)>

The liquid crystal aligning agent prepared in Example 12 mentioned above and Comparative Examples 4 and 5 was evaluated by the following method, respectively.

1. Evaluation of printability

For each liquid crystal aligning agent prepared in the above Examples and Comparative Examples, as a result of evaluating the continuous printability to the substrate by the same method as in Examples 1 to 11 and Comparative Examples 1 to 3, the one of Example 12 was The results were better than those of Comparative Examples 4 and 5.

2. Evaluation of the liquid crystal cell

(1) Preparation of liquid crystal cell for evaluation of liquid crystal orientation, voltage retention, and contrast

Each liquid crystal aligning agent prepared in the above Examples and Comparative Examples was coated on each transparent electrode surface of two (a pair) glass substrates with transparent electrodes made of an ITO film using a spinner, and then heated at 80° C. for 1 minute. (Pre-baking) to form a coating film, respectively. On the surface of these coating films, using a Hg-Xe lamp, polarized ultraviolet rays including a 254 nm bright line were irradiated from the normal direction of the substrate at an irradiation amount of 10,000 J/m 2, and then heated in a clean oven at 230° C. for 1 hour (post Baking) to form a liquid crystal alignment film on two (a pair) of substrates, respectively.

Next, to one of the pair of substrates subjected to the light irradiation treatment, a liquid crystal injection hole was left on the outer periphery of the surface on which the liquid crystal alignment film was formed, and an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 μm was applied by screen printing. , A pair of substrates were stacked on top of each other so that the liquid crystal aligning film formation surfaces corresponded to each other and the projection direction of the polarization plane at the time of light irradiation coincided with each other, followed by heating at 150° C. for 1 hour to thermally cure the adhesive.

Next, after filling a nematic liquid crystal (Merck company make, product name "MLC-7028") between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of liquid crystal injection, the liquid crystal cell was produced by heating this to 150°C and then gradually cooling it to room temperature.

(2) Evaluation of liquid crystal orientation

With respect to the liquid crystal cell prepared above, the presence or absence of an abnormal domain when the voltage of AC 5V was turned on/off (applied/released) was observed with a polarization microscope.

The case where no abnormal domain was observed in the display region was evaluated as liquid crystal alignment "A (good)", and the case where even one abnormal domain was observed in the display region was evaluated as liquid crystal alignment "C (defective)".

(3) Evaluation of voltage retention rate

To the liquid crystal cell prepared above, a voltage of 5 V was applied with a span of 60 microseconds and 167 milliseconds, and the voltage retention rate after 167 milliseconds from the release of the application was measured.

As a measuring device for the voltage retention rate, the model name "VHR-1" manufactured by Toyo Technica Co., Ltd. was used.

Evaluation was performed according to the following criteria.

When the voltage retention rate was 98% or more: Voltage retention rate “A (good)”

When the voltage retention rate was less than 98%: Voltage retention rate “C (defective)”

(4) Preparation of liquid crystal cell for evaluation of afterimage characteristics

As a pair of substrates, a liquid crystal cell for evaluation of afterimage characteristics (FFS) is carried out in the same manner as in ``(1) Preparation of a liquid crystal cell for evaluation of liquid crystal alignment, voltage retention, and contrast'', except that a substrate pair having the following configuration is used. Type liquid crystal cell) was prepared, and a polarizing plate was bonded to both outer surfaces of the substrate to obtain a liquid crystal display element.

Here, as the electrode substrate, a glass substrate on which two systems of electrodes (electrodes A 101 and B 102) made of chromium having a comb-shaped pattern shown in Fig. 1 are formed;

As the counter substrate, a glass substrate on which an electrode is not formed was used, respectively. The application of the liquid crystal aligning agent was performed on the electrode formation surface of the electrode substrate and one surface of the counter substrate.

(5) Evaluation of afterimage characteristics (burn-in)

The liquid crystal display device prepared above was placed in an environment of 25° C. and 1 atm, and no voltage was applied to the electrode B, and a combined voltage of an AC voltage of 3.5 V and a DC voltage of 5 V was applied to the electrode A for 2 hours. Immediately after 2 hours, a voltage of AC 4V was applied to both electrodes A and B. Then, the time from the time when the voltage of AC 4V was started to be applied to the positive electrodes until the difference in light transmittance between the positive electrodes became invisible to the naked eye was measured.

Evaluation was performed according to the following criteria.

When the time measured above was less than 100 seconds: Afterimage characteristic "A (good)"

In the case of 100 seconds or more and less than 150 seconds: The afterimage characteristic is set to ``B (possible)''

When it exceeds 150 seconds: Afterimage characteristic ``C (defective)''

(6) Evaluation of reliability

As a result of evaluating the reliability of the liquid crystal display device manufactured above by the same method as in Examples 1 to 11 and Comparative Examples 1 to 3, Example 12 is better than Comparative Examples 4 and 5. The results are shown.

Claims (9)

A liquid crystal aligning agent characterized by containing a polymer having a structure represented by the following formula (1):
*-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -* (1)
(In formula (1), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an ester bond, provided that when both of X ¹ and X ² are single bonds at the same time, No,
Y is obtained by removing two hydrogen atoms from a 5- or 6-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in the ring structure. Group, provided that both of the two bond hands of Y are directly from the 5-membered ring or the 6-membered ring,
A plurality of R ¹ is each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 20,
While m1 = m2 = 0, both of X ¹ and X ² are not carbonyl groups at the same time, and
"*" represents a bond hand, respectively). The method of claim 1,
The liquid crystal aligning agent in which Y in Formula (1) is a pyridinylene group. The method of claim 1,
The polymer,
Tetracarboxylic acid dianhydride,
A liquid crystal aligning agent which is a polymer synthesized through a process of reacting a diamine containing a compound represented by the following formula (MDA):
H ₂ N-Ph-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -Ph-NH ₂ … (MDA)
(In formula (MDA), X ¹ , X ² , Y, R ¹ , m1 and m2 each have the same meaning as in the above formula (1),
Two Phs are each independently a phenylene group which may be substituted). The method of claim 3,
The tetracarboxylic acid dianhydride,
2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, 1,2,3, At least one selected from the group consisting of 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride The liquid crystal aligning agent containing the compound of. A liquid crystal aligning film formed by the liquid crystal aligning agent in any one of Claims 1-4. A liquid crystal display device comprising the liquid crystal alignment film according to claim 5. Compound represented by the following formula (MDA):
H ₂ N-Ph-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -Ph-NH ₂ … (MDA)
(In formula (MDA), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an ester bond, provided that when both of X ¹ and X ² are single bonds at the same time, No,
Y is obtained by removing two hydrogen atoms from a 5- or 6-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in the ring structure. Group, provided that both of the two bond hands of Y are directly from the 5-membered ring or the 6-membered ring,
A plurality of R ¹ is each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 20,
While m1 = m2 = 0, there is no case where both X ¹ and X ² are carbonyl groups at the same time,
Two Phs are each independently a phenylene group which may be substituted). Polymer having a structure represented by the following formula (1):
*-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -* (1)
(In formula (1), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an ester bond, provided that when both of X ¹ and X ² are single bonds at the same time, No,
Y is obtained by removing two hydrogen atoms from a 5- or 6-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in the ring structure. Group, provided that both of the two bond hands of Y are directly from the 5-membered ring or the 6-membered ring,
A plurality of R ¹ is each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 20,
While m1 = m2 = 0, both of X ¹ and X ² are not carbonyl groups at the same time, and
"*" represents a bond hand, respectively). Tetracarboxylic acid dianhydride,
A polymer synthesized through a process of reacting a diamine containing a compound represented by the following formula (MDA):
H ₂ N-Ph-X ¹ -(CR ¹ ₂ ) _m1 -Y-(CR ¹ ₂ ) _m2 -X ² -Ph-NH ₂ … (MDA)
(In formula (MDA), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group, or an ester bond, provided that when both of X ¹ and X ² are single bonds at the same time, No,
Y is obtained by removing two hydrogen atoms from a 5- or 6-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in the ring structure. Group, provided that both of the two bond hands of Y are directly from the 5-membered ring or the 6-membered ring,
A plurality of R ¹ is each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 20,
While m1 = m2 = 0, there is no case where both X ¹ and X ² are carbonyl groups at the same time,
Two Phs are each independently a phenylene group which may be substituted).

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