KR102151608B1 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, phase difference film and manufacturing method thereof, polymer and compound - Google Patents

Abstract

(R^A는, 탄화수소기의 탄소-탄소 결합간 및 당해 탄화수소기와 서로 이웃하는 위치 중 적어도 어느 하나에, 산소 원자 또는 황 원자를 갖는 2가의 기이고, X¹ 및 X²는, 각각 독립적으로, 단결합, 산소 원자, 황 원자 또는 2가의 유기기임).(Problem) A liquid crystal aligning agent for forming a liquid crystal aligning film capable of suitably expressing various properties required for a liquid crystal display device is provided.
(Solution) At least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide obtained by reacting a tetracarboxylic acid derivative with a diamine containing a compound represented by the following formula (1) Included in the liquid crystal aligning agent:

(R ^A is a divalent group having an oxygen atom or a sulfur atom in at least one of a carbon-carbon bond of a hydrocarbon group and a position adjacent to each other with the hydrocarbon group, and X ¹ and X ² are each independently, It is a single bond, an oxygen atom, a sulfur atom, or a divalent organic group).

Description

A liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, a retardation film, and a method of manufacturing the same, a polymer, and a compound TECHNICAL FIELD OF THE INVENTION

This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, a retardation film, and its manufacturing method, a polymer, and a compound.

Conventionally, as a liquid crystal display device, various driving methods having different electrode structures, physical properties of liquid crystal molecules used, and manufacturing processes have been developed. For example, TN type, STN type, VA type, in-plane switching type (IPS type ), FFS type, and other various liquid crystal display elements are known. These liquid crystal display elements have a liquid crystal aligning film for aligning liquid crystal molecules. As the material of the liquid crystal aligning film, polyamic acid and polyimide are generally used because various properties such as heat resistance, mechanical strength, and affinity with liquid crystal are good.

In addition, recently, liquid crystal display elements are used not only for display terminals such as personal computers, but also for various purposes such as liquid crystal televisions, car navigation systems, mobile phones, smart phones, and information displays. From such a background, the demand for higher performance of a liquid crystal display element is increasing further, and as a liquid crystal aligning film, it is demanded that various characteristics required for a liquid crystal display element can be improved further. In addition, various kinds of a liquid crystal aligning agent for obtaining such a liquid crystal aligning film, a polymer blended with the liquid crystal aligning agent, and a monomer for obtaining the polymer have been proposed (for example, see Patent Documents 1 and 2).

In Patent Document 1, diamine and tetra having no polar group, such as 1,2-bis(4-(4-aminobenzyl)phenyl)ethane, 1,6-bis(4-(4-aminobenzyl)phenyl)hexane, etc. It is disclosed that a polyimide obtained by reaction with a carboxylic acid dianhydride is used as a polymer component of a liquid crystal aligning agent. In addition, in Patent Document 2, in Examples, reaction of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,5-bis[4-(4-aminophenoxy)phenoxy]pentane It is disclosed that the polyamic acid obtained by is used as a polymer component of a liquid crystal aligning agent.

In addition, various optical materials are used for the liquid crystal display element, and among them, the retardation film has the purpose of solving the coloration of the display, but the purpose of solving the viewing angle dependence such as changing the display color and contrast ratio depending on the visual direction. Is being used. As such a retardation film, it is known to have a liquid crystal alignment film formed on the surface of a substrate such as a TAC film, and a liquid crystal layer formed by curing a polymerizable liquid crystal on the surface of the liquid crystal alignment film. In addition, recently, in the production of a liquid crystal alignment film in a retardation film, a photo-alignment method in which a liquid crystal alignment ability is imparted by irradiating polarized or non-polarized radiation to a radiation-sensitive organic thin film formed on the substrate surface has been used. Various liquid crystal aligning agents for retardation films for producing a liquid crystal aligning film by such a method have been proposed (for example, see Patent Document 3).

As a method of producing a retardation film on an industrial scale, a roll-to-roll method has been proposed (for example, see Patent Document 4). This method is a treatment of unwinding a film from a winding body of a long base film, forming a liquid crystal aligning film on the unwound film, and applying a polymerizable liquid crystal onto the liquid crystal aligning film to cure It is a method in which the processing to perform and the processing of laminating a protective film as necessary is performed in a continuous process, and the film after passing through these processes is recovered as a wound body.

Japanese Patent Publication No. 3658798 International Publication No. 2004/053583 Japanese Laid-Open Patent Publication No. 2012-37868 Japanese Laid-Open Patent Publication No. 2000-86786

However, when the polyimide described in Patent Document 1 is used as a polymer component of a liquid crystal aligning agent, the liquid crystal aligning agent tends to have poor coatability to a substrate. Moreover, when the liquid crystal aligning film of an FFS type liquid crystal display element is produced using this liquid crystal aligning agent, the pretilt angle becomes too high, and a viewing angle characteristic is inferior. In a liquid crystal display device using the liquid crystal aligning agent containing the polyamic acid described in Patent Document 2, the voltage retention characteristics and heat resistance are deteriorated.

In addition, the retardation film can be easily produced on an industrial scale by adopting the roll-to-roll method described above, whereas when the adhesion between the liquid crystal aligning film and the base film is insufficient, the film should be used as a wound body after the process is completed. At this time, the liquid crystal aligning film may peel from the substrate film. In this case, a problem such as a decrease in product yield may occur.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid crystal aligning agent for forming a liquid crystal aligning film capable of appropriately expressing various properties required for a liquid crystal display device. Another object is to provide a liquid crystal aligning agent for forming a liquid crystal aligning film for a retardation film having good liquid crystal alignment and good adhesion to a substrate.

The present inventors, as a result of earnestly examining in order to achieve the problems of the prior art as described above, at least any of polyamic acid, polyamic acid ester, and polyimide obtained by a condensation polymerization reaction of a diamine having a specific structure and a tetracarboxylic acid derivative. By containing one polymer, it was found that the above problems could be solved, and the present invention was completed. Specifically, the following liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, a retardation film, and its manufacturing method, a polymer, and a compound are provided by this invention.

In one aspect, the present invention provides at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester compound, and tetracarboxylic acid diester dihalide, and the following formula There is provided a liquid crystal aligning agent containing at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide obtained by reacting a diamine containing the compound represented by (1):

(In formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom in at least one of a carbon-carbon bond of a C1-C30 hydrocarbon group and a position adjacent to each other with the hydrocarbon group, At least one of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom; X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, or a divalent organic group; provided that X ¹ and X ² Is an oxygen atom, and R ^A is -OR ¹ -O- (R ¹ is an alkanediyl group having 1 to 18 carbon atoms), the tetracarboxylic acid derivative is 1,2,3,4-cyclobutanetetra Except for carboxylic acid dianhydride).

In another aspect, the present invention provides a liquid crystal alignment layer formed by using the liquid crystal aligning agent. In addition, a liquid crystal display device including the liquid crystal alignment layer and a retardation film are provided. Further, in another aspect, the step of forming a coating film by applying the liquid crystal aligning agent on a substrate, the step of irradiating the coating film with light, and coating and curing a polymerizable liquid crystal on the coating film after the light irradiation. It provides a method of manufacturing a retardation film including the process. Further, further, at least selected from the group consisting of the compound represented by the above formula (1) and the diamine containing the compound, tetracarboxylic dianhydride, tetracarboxylic acid diester compound, and tetracarboxylic acid diester dihalide. A polymer obtained by reacting one kind of tetracarboxylic acid derivative is provided.

By using a liquid crystal aligning agent containing a polymer obtained by reaction of a diamine represented by the above formula (1) with a tetracarboxylic acid derivative, a liquid crystal aligning film capable of suitably expressing various properties required for a liquid crystal display device can be formed. . Moreover, according to the liquid crystal aligning agent of this invention, a high-quality liquid crystal display element can be manufactured. Further, the liquid crystal aligning film obtained by using the liquid crystal aligning agent of the present invention has good adhesion to the substrate. Therefore, even when the liquid crystal aligning film and the board|substrate are peeled off even when this was made into a winding object and stored etc., therefore, for example, at the time of manufacture of a retardation film, a fall in product yield can be suppressed.

1 is a schematic configuration diagram of an FFS type liquid crystal display element.
2 is a schematic plan view of a top electrode, FIG. 2(a) is a top view of the top electrode, and FIG. 2(b) is a partially enlarged view of the top electrode.

(Form for carrying out the invention)

The liquid crystal aligning agent of this invention contains at least 1 type of polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and contains other components as needed. Hereinafter, each component contained in the liquid crystal aligning agent of the present invention and other components optionally blended as necessary will be described.

<Polymer (P): polyamic acid>

Polyamic acid (hereinafter, also referred to as polyamic acid (P)) as the polymer (P) in the present invention can be obtained by reacting tetracarboxylic dianhydride and diamine.

[Tetracarboxylic acid dianhydride]

Examples of the tetracarboxylic dianhydride used to synthesize the polyamic acid (P) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these, examples of aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and the like;

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, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-2 anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecan-3 , 5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride, etc.;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc.; In addition to those mentioned respectively, the tetracarboxylic dianhydride described in Japanese Laid-Open Patent Publication No. 2010-97188 can be used. In addition, the tetracarboxylic acid dianhydride may be used alone or in combination of two or more.

Examples of tetracarboxylic dianhydride used for synthesis include 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-oxa Bicyclo[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, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-2 anhydride, 4, 9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride , Ethylenediamine tetraacetic acid dianhydride, and pyromellitic acid dianhydride, preferably at least one selected from the group consisting of. Further, from the viewpoint of transparency and solubility in a solvent, it is preferable to contain an alicyclic tetracarboxylic dianhydride, and from the viewpoint of electrical properties, it is preferable to contain an aromatic tetracarboxylic dianhydride.

[Diamine]

The diamine used to synthesize the polyamic acid (P) includes a compound represented by the formula (1).

R ^A in the formula (1) is a divalent group having an oxygen atom or a sulfur atom in at least one of a carbon-carbon bond of a hydrocarbon group having 1 to 30 carbon atoms and a position adjacent to each other with the hydrocarbon group. . Here, the "hydrocarbon group" in this specification is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a linear or branched hydrocarbon group composed of only a chain structure without containing a cyclic structure in the main chain, and may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group including only the structure of an alicyclic hydrocarbon and not including an aromatic ring structure as a ring structure. However, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are included. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to constitute only an aromatic ring structure, and a chain structure or a structure of an alicyclic hydrocarbon may be included in a part thereof.

Specific examples of the hydrocarbon group having 1 to 30 carbon atoms are chain hydrocarbon groups, such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, and furnace. A nandiyl group, a decanediyl group, a dodecanediyl group, a tetradecanediyl group, a pentadecanediyl group, a hexadecanediyl group, an octadecanediyl group, and the like, and these may be linear or branched. Further, examples of the alicyclic hydrocarbon group include groups excluding two hydrogen atoms from cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, pentylcyclohexane, dimethylcyclohexane, and the like; Examples of the aromatic hydrocarbon group include groups excluding two hydrogen atoms from benzene, toluene, xylene, ethylbenzene, propylbenzene, pentylbenzene, and the like; Each can be mentioned. As the hydrocarbon group for R ^A , it is particularly preferable to have a divalent chain hydrocarbon group, more preferably a divalent chain hydrocarbon group, and particularly preferably an alkanediyl group.

Further, at least one of the hydrogen atoms in the hydrocarbon group in R ^A may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of oxygen atoms and sulfur atoms (total number) of R ^A is not particularly limited, and can be appropriately selected according to the carbon number of R ^A from the viewpoint of low pretiltization and improvement of the solubility of the polymer. It is preferably 1 to 5, more preferably 1 to 3. In addition, when R ^A has a plurality of these hetero atoms (oxygen atom and sulfur atom), it may have only one of an oxygen atom and a sulfur atom, and may have two of them.

The position where the oxygen atom or the sulfur atom is introduced may be between the carbon-carbon bonds of the hydrocarbon group, may be positions adjacent to each other, or both. In addition, "between carbon-carbon bonds of a hydrocarbon group" refers to ^{a case where} the position of the hetero atom X ^a is "-R ¹⁰ -X ^a -R ¹¹ -" (however, R ¹⁰ and R ¹¹ are a hydrocarbon group), ``Position adjacent to a hydrocarbon group'' means that the position of the hetero atom X <sup>a</sup> is ``*-X ^a -R ¹² -'' (however, R ¹² is a hydrocarbon group, and ``*'' is a bond with the benzene ring bonded to R ^A ) Means the case.

X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. Here, as the "divalent organic group" in X ¹ and X ² , for example, a substituted or unsubstituted alkanediyl group, a substituted or unsubstituted alkenediyl group, a carbonyl group, an ester group (-COO-) , An amide group (-CO-NH-), etc. are mentioned as a preferable specific example. The alkanediyl group of X ¹ and X ² preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. In addition, the alkendiyl group is preferably 2 to 10 carbon atoms, more preferably 2 to 5, and still more preferably 2 to 3 carbon atoms. In addition, examples of the substituent introduced into the alkanediyl group and the alkenediyl group include an oxygen atom (-O-), a sulfur atom (-S-), a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) And a hydroxyl group.

As X ¹ and X ² , among others, an oxygen atom, an ester group, an amide group, an alkanediyl group having 1 to 10 carbon atoms, or an alkendiyl group having 2 to 10 carbon atoms is preferable, and an oxygen atom, an egg having 1 to 5 carbon atoms It is more preferable that it is a candiyl group or a C2-C5 alkendiyl group, and it is especially preferable that it is an oxygen atom, a methylene group, an ethylene group, or a vinylene group.

It is preferable that the compound represented by the above formula (1) is a compound represented by the following formula (1-1) among the above:

(In formula (1-1), R ² is a C 1 to C 30 divalent hydrocarbon group, X ³ is an oxygen atom or a sulfur atom, X ⁴ is a single bond, an oxygen atom or a sulfur atom; X ¹ and X ² have the same meaning as in the above formula (1)).

As a specific example of R ² in the formula (1-1), the description of the hydrocarbon group having 1 to 30 carbon atoms in R ^A in the formula (1) can be applied. It is preferable that R ² is a divalent chain hydrocarbon group, and it is more preferable that it is an alkanediyl group. The number of carbon atoms in the alkanediyl group is preferably 1 to 20, more preferably 1 to 11, and even more preferably 1 to 8.

X ³ is an oxygen atom or a sulfur atom, and it is preferable that it is an oxygen atom. In addition, X ⁴ is a single bond, an oxygen atom, or a sulfur atom, and it is preferable that it is a single bond or an oxygen atom.

As a preferable specific example of the compound represented by said formula (1), the compound etc. which are each represented by following formula (DA-1)-formula (DA-15) are mentioned, for example.

From the viewpoint of sufficiently obtaining the effect of the present invention, the ratio of the compound represented by the above formula (1) to be used is preferably in the range of 1 to 100 mol% with respect to the total amount of diamine used in the synthesis of polyamic acid. With respect to the lower limit, it is more preferably 5 mol% or more, still more preferably 15 mol% or more, and particularly preferably 20 mol% or more. The compounds represented by the above formula (1) can be used alone or in combination of two or more.

In addition, in the compound represented by the above formula (1), since the group "R ^A " between the two benzene rings is a hydrocarbon group having an oxygen atom or a sulfur atom, the polymer obtained using this is a polymer It is estimated that the solubility of the liquid crystal aligning agent improves, and the coating property of the liquid crystal aligning agent to the substrate is improved. Moreover, it is estimated that rubbing stretchability improves by improving the rotational property of a molecule|numerator, and it becomes possible to express low pretiltization (view angle improvement) of a liquid crystal aligning film by this. The compounds represented by the above formula (1) are all the same in that a polymer capable of forming a liquid crystal alignment film having good various properties such as liquid crystal alignment, voltage retention properties, and heat resistance can be obtained by a condensation polymerization reaction with tetracarboxylic anhydride and the like. Has an action. Therefore, even those not described in the following examples can be used in the present invention.

[Synthesis of the compound represented by the formula (1)]

The compound represented by the above formula (1) can be synthesized by appropriately combining normal methods of organic chemistry. As an example, a method of synthesizing a dinitro intermediate having a nitro group in place of the primary amino group in the above formula (1), and then aminating the nitro group of the obtained dinitro intermediate using an appropriate reduction system is mentioned. .

The method of synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. As an example, for example, when X ¹ and X ² are oxygen atoms, a dihydro compound represented by HO-Ph-R ^A -Ph-OH (Ph is a phenylene group) is synthesized, and the dihydro compound and the halogenated nitro It can be obtained by reacting benzene. Further, when X ¹ and X ² are methylene groups, it can be obtained by reacting a compound represented by Bz-R ^A -Bz (Bz is a phenyl group) with nitrobenzoic acid chloride, and reducing the carbonyl group of the obtained reaction product with a methylene group. When X ¹ and X ² are ester groups, it can be obtained by reacting the dihydro compound and nitrobenzoic acid chloride.

The reduction reaction of the dinitro intermediate may be preferably carried out in an organic solvent, using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, or nickel. Examples of the organic solvent used herein include ethyl acetate, toluene, tetrahydrofuran, and alcohol. However, the synthesis sequence of the compound represented by the above formula (1) is not limited to the above method.

[Other diamines]

As the diamine used for the synthesis of the polyamic acid (P), the compound represented by the formula (1) may be used alone, but other diamines other than the compound may be used in combination with the compound represented by the formula (1). good.

Here, examples of the other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. As a specific example of these diamine compounds, as aliphatic diamine, for example, m-xylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane My back; Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and the like;

As aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis[4-(4-aminophenoxy Si) 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-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-indene -5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, 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)cholestane, 3,6-bis (4-aminophenoxy) cholestan, 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-heptyl company Diclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-( 4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1,3-diamino-4-octadecyloxybenzene, 3-(3,5-diaminobenzoyloxy)cholestane, 3,6-bis(4-aminobenzoyloxy)cholestane, and the following formula (D-1):

(In formula (D-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^Ⅱ is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and n is 0 or 1; provided that a And b never become 0 at the same time)

Compounds represented by;

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

As a divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the above formula (D-1), an alkanediyl group having 1 to 3 carbon atoms, *-O-, *-COO- Or, it is preferable that it is *-OC ₂ H ₄ -O- (however, the bond hand with "*" bonded with a diaminophenyl group).

As a specific example of the group "-C _c H _{2c +1} ", for example, methyl group, 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-heptadecyl group, n-octade A practical group, an n-nonadecyl group, and an n-eicosyl group. 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 group.

As a specific example of the compound represented by said formula (D-1), the compound etc. which are represented by each of following formula (D-1-1)-(D-1-5) are mentioned, for example.

In addition, the diamine used for the synthesis of the polyamic acid (P) can be used singly or in combination of two or more of the above.

When the liquid crystal aligning agent of the present invention is used in the production of a TN type, STN type, or vertical alignment type liquid crystal display element, a group capable of imparting a pretilt angle expression ability to the coating film as the other diamine (hereinafter referred to as ``pretilt It is preferable to contain the diamine which has (it is also called each imparting group"). Examples of the pretilt angle imparting group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, and a group having a polycyclic structure. And the like.

Specific examples of the diamine having each pretilt imparting group include dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, Tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, Cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid ranostanyl, 3,6- Bis(4-aminobenzoyloxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzoyloxy)cyclo Hexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl ) Phenyl)-4-heptylcyclohexane, diamine represented by the above formula (D-1), and the like. Moreover, the said diamine can be used individually by 1 type or in combination of 2 or more types.

In the case of using a diamine having a pretilt angle imparting group, the usage ratio is preferably 5 mol% or more with respect to all diamines, and 10 mol% or more, from the viewpoint of expressing sufficiently high pretilt angle properties. It is more preferable. In addition, the upper limit of the use ratio is not particularly limited, but from the viewpoint of not impairing the effect of the use of the compound represented by the above formula (1), it is preferably 99 mol% or less with respect to the total diamine, 95 It is more preferable to set it as mol% or less.

[Molecular weight regulator]

When synthesizing the polyamic acid (P), a terminal-modified polymer may be synthesized using an appropriate molecular weight modifier together with the tetracarboxylic dianhydride and diamine as described above. By setting it as such a terminal-modified polymer, the coatability (printability) of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention.

As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As specific examples of these, as an acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back; As a monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-dodecylamine, n-octadecylamine My back; As the monoisocyanate compound, for example, phenyl isocyanate, naphthyl isocyanate, and the like; Each can be mentioned.

The ratio of the molecular weight modifier to be used is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine to be used.

[Synthesis of polyamic acid]

The ratio of the tetracarboxylic acid dianhydride and diamine used in the synthesis reaction of the polyamic acid (P) is 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid dianhydride based on 1 equivalent of the amino group of the diamine. It is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable. In addition, the synthesis reaction of the polyamic acid (P) is preferably performed in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0 to 100°C. Further, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

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 are aprotic polar solvents, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-buty Lolactone, tetramethylurea, hexamethylphosphoriamide, and the like; As a phenolic solvent, For example, phenol, m-cresol, xylenol, halogenated phenol, etc.;

Examples of the alcohol include methanol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, and the like; As ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, diethyl malonate, isoamylpropionate, isoamylisobutyrate, and the like; As an ether, for example, diethyl ether, diisopentyl 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, diethylene glycol dimethyl ether, tetrahydrofuran, etc.; Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, and the like; As the hydrocarbon, for example, hexane, heptane, octane, benzene, toluene, xylene, and the like; Each can be mentioned.

At least one selected from the group consisting of these organic solvents, aprotic polar solvents, and phenolic solvents (organic solvents of the first group), or at least one selected from organic solvents of the first group, and alcohol, It is preferable to use a mixture with at least one selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the ratio of the organic solvents of the second group to be used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the organic solvents of the first group and the organic solvents of the second group. It is below, More preferably, it is 30 weight% or less. In addition, the amount of the organic solvent used (α) is preferably such that the total amount (β) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount of the reaction solution (α+β). Do.

In the manner described above, a reaction solution obtained by dissolving polyamic acid (P) 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 a polyimide, 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 purification, may be subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed by a known method.

<Polymer (P): polyamic acid ester>

The polyamic acid ester (hereinafter also referred to as polyamic acid ester (P)) as the polymer (P) of the present invention is, for example, [I] a polyamic acid (P) obtained by the above synthesis reaction, a hydroxyl group-containing compound, a halogen It can be obtained by a method of synthesizing by reacting a cargo, an epoxy group-containing compound, and the like, [II] a method of reacting a tetracarboxylic acid diester compound and a diamine, and [III] a method of reacting a tetracarboxylic acid diesterdihalide and a diamine. have.

Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol, and propanol; And phenols such as phenol and cresol. Further, examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane, etc., and epoxy group-containing compounds As examples, propylene oxide etc. are mentioned. The tetracarboxylic acid diester compound used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the polyamic acid (P) using the above alcohols. Further, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester compound obtained as described above with a suitable chlorinating agent such as thionyl chloride. The diamine used in the methods [II] and [III] includes the compound represented by the above formula (1). Moreover, you may use the other amine mentioned above as needed. Further, the polyamic acid ester may have only a dark acid ester structure, or may be a partial esterified product in which the dark acid structure and the dark acid ester structure coexist.

<Polymer (P): polyimide>

The polyimide (hereinafter also referred to as ``polyimide (P)'') as the polymer (P) contained in the liquid crystal aligning agent of the present invention is obtained by dehydrating and cyclizing the polyamic acid (P) synthesized as described above to be imidized. I can.

The polyimide (P) may be a complete imide product obtained by dehydrating and cyclizing all of the mental acid structure of the polyamic acid as its precursor, and dehydrating and cyclizing a part of the mental acid structure and the dark acid ester structure, and the dark acid structure and the dark acid ester structure At least any of them may be a partial imide product in which an imide ring structure coexists. Polyimide (P) has an imidation ratio of 30% or more, more preferably 40 to 99%, and even more preferably 50 to 99%, in terms of increasing the voltage retention rate. This imidation ratio is a percentage showing the ratio of the number of imide ring structures to the sum of the number of mental acid structures of the polyimide, the number of dark acid ester structures, and the number of imide ring structures. Here, a part of the imide ring may be an isoimide ring.

The dehydration cyclization of the polyamic acid is preferably carried out by heating the polyamic acid or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration cyclization catalyst to this solution, and heating if necessary. . Among these, the latter method is preferred.

In the method of imidization by adding a dehydrating agent and a dehydration ring closure catalyst to a solution of polyamic acid, as the dehydrating agent, 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 mol with respect to 1 mol of the mental acid structure of the polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, for example. 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. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide (P) is obtained. This reaction solution may be provided as it is to the preparation of the liquid crystal aligning agent, or after removing the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, it may be provided to the preparation of the liquid crystal aligning agent, and after isolating the polyimide, it is provided to the preparation of the liquid crystal aligning agent. Alternatively, after purifying the isolated polyimide, it may be provided for preparation of a liquid crystal aligning agent. These purification operations can be performed by known methods.

<Polymer solution viscosity and weight average molecular weight>

When the polyamic acid, polyamic acid ester, and polyimide as the polymer (P) obtained as described above are made into a solution having a concentration of 10% by weight, it is preferable to have a solution viscosity of 10 to 800 mPa·s, and 15 to 500 mPa· It is more preferred to have a solution viscosity of s. In addition, the solution viscosity (mPa·s) of the polymer is 10 weight of the concentration prepared using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer. It is a value measured at 25°C using an E-type rotational viscometer for% of the polymer solution. In addition, with respect to the polyamic acid, polyamic acid ester, and polyimide contained in the liquid crystal aligning agent of the present invention, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is 500 to 100,000. It is preferable and it is more preferable that it is 1,000-50,000.

It is preferable to use 50 to 100 parts by weight, with respect to the total 100 parts by weight of the polymer component in the liquid crystal aligning agent. If it is less than 50 parts by weight, there is a fear that the effects of the present invention cannot be sufficiently obtained. It is more preferably 60 parts by weight or more, and still more preferably 70 parts by weight or more. Polymer (P) can be used individually by 1 type or in combination of 2 or more types.

<Other ingredients>

The liquid crystal aligning agent of this invention may contain other components as needed. Examples of such other components include polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as ``epoxy group-containing compounds''), functional silane compounds, and metal chelate compounds. , Curing accelerators, surfactants, and the like.

[Other polymers]

Other polymers described above can be used to improve solution properties or electrical properties. Examples of such other polymers include a polyamic acid obtained by reaction of a diamine not containing the compound represented by the above formula (1) with a tetracarboxylic dianhydride, a polyimide obtained by dehydration and ring closure of the polyamic acid. Polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, etc. have.

In addition, when using the liquid crystal aligning agent of this invention for a retardation film, as said other polymer, a polymer which has a photo-alignment structure can be used suitably. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposition-type photo-alignment unit. Specifically, a structure exhibiting photo-alignment by photoisomerization, photodimerization, photolysis, etc. is mentioned. For example, azobenzene, cinnamic acid, chalcone, benzophenone, coumarin and polyimide, and derivatives thereof are contained as a basic skeleton. And the like. Among these, it is preferable to include a polymer having a photo-alignment group, and more preferably a polymer into which a group having a cinnamic acid structure (cinnamic acid or a derivative thereof) is introduced. Among them, polyorganosiloxane having a cinnamic acid structure can be preferably used in view of easy introduction of a photo-alignment group into the polymer.

In addition, a polymer having a photo-alignment group can be synthesized by a conventionally known method. For example, polyorganosiloxanes having a photo-alignment group as other polymers include polyorganosiloxanes having an epoxy group and carboxylic acids having a photo-orientation group, preferably in organic solvents such as ethers, esters, and ketones. It can be synthesized by reacting in the presence of a catalyst such as a grade ammonium salt.

When other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, based on the total 100 parts by weight of the polymer contained in the liquid crystal aligning agent. It is preferable, and it is more preferable to set it as 0.1-30 weight part or less.

[Epoxy group-containing compound]

The epoxy group-containing compound can be used in order to improve adhesiveness and electrical properties with the substrate surface in the liquid crystal aligning film. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglyci Dyl 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 as a preferable thing. In addition, as an example of the epoxy group-containing compound, the epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.

When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio 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 contained in the liquid crystal aligning agent. desirable.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printability of a liquid crystal aligning agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and 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-methyl diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like.

When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less, and 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the total polymer contained in the liquid crystal aligning agent. It is more preferable.

[Metal chelate compound]

The metal chelate compound is a liquid crystal aligning agent (especially, a liquid crystal aligning agent for a retardation film) for the purpose of ensuring the mechanical strength of a film formed by low temperature treatment when the polymer component of the liquid crystal aligning agent has an epoxy structure It is contained in. As the metal chelate compound, it is preferable to use an acetylacetone complex or an acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium. Specifically, for example, diisopropoxyethylacetoacetate aluminum, tris(acetylacetonate)aluminum, tris(ethylacetoacetate)aluminum, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis( Acetylacetonate) titanium, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis(ethylacetoacetate)zirconium, and the like. In the case of adding the metal chelate compound, the ratio of use is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, further preferably based on 100 parts by weight of the total of the constituent components including the epoxy structure. It is 1 to 30 parts by weight.

[Hardening accelerator]

When the polymer component in the liquid crystal aligning agent has an epoxy structure, the curing accelerator is a liquid crystal aligning agent (especially, a liquid crystal aligning agent for a retardation film) in order to ensure the mechanical strength of the formed liquid crystal aligning film and the stability with time. It is contained in Article). As the curing accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group, etc. can be used, and among them, a compound having a phenol group or a silanol group is preferable. Do. As a specific example thereof, as a compound having a phenol group, for example, cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, and the like; As a compound having a silanol group, for example, trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis(hydroxydimethylsilyl)benzene , Triphenylsilanol, tri(p-tolyl)silanol, diphenylsilanediol, and the like, respectively. In the case of adding a curing accelerator, the proportion of use is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and even more preferably with respect to 100 parts by weight of the total of the constituent components including the epoxy structure. It is 1 to 30 parts by weight.

[Surfactants]

The surfactant can be contained in a liquid crystal aligning agent (particularly, a liquid crystal aligning agent for retardation films) for the purpose of improving the coating properties of the liquid crystal aligning agent to the substrate. As such a surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant, etc. are mentioned, for example. The ratio of the surfactant to be used is preferably 10 parts by weight or less, and more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the liquid crystal aligning agent.

Further, as the other components, in addition to the above, compounds having at least one oxetanyl group in the molecule, antioxidants, and the like can be mentioned.

<solvent>

The liquid crystal aligning agent of the present invention is prepared as a liquid composition obtained by dispersing or dissolving the polymer (P) and other components used as necessary in a suitable solvent.

As an organic solvent to be used, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydro Roxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, 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 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, isoamylisobutyrate, diisopentyl Ether, ethylene carbonate, propylene carbonate, and the like. These can be used alone or in combination of two or more.

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 serving as a liquid crystal alignment film or a coating film serving as a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes insufficient and it becomes difficult to obtain a good liquid crystal aligning film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive, making it difficult to obtain a good liquid crystal aligning film, and further, the viscosity of the liquid crystal aligning agent increases and the coating property tends to decrease.

The range of a particularly preferable solid content concentration differs depending on the use of the liquid crystal aligning agent and the method used when applying the liquid crystal aligning agent to a substrate. For example, for a liquid crystal aligning agent for a liquid crystal aligning film, in the case of applying to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) Is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of a 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 10-50 degreeC, More preferably, it is 20-30 degreeC. In addition, about the liquid crystal aligning agent for retardation films, it is preferable that the solid content concentration of the liquid crystal aligning agent is in the range of 0.2 to 10% by weight from the viewpoint of making the coating property of the liquid crystal aligning agent and the film thickness of the formed coating film appropriate. It is more preferable that it is in the range of 3-10 weight%.

<Liquid crystal display element and retardation film>

A liquid crystal aligning film can be manufactured by using the liquid crystal aligning agent of this invention demonstrated above. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention can be applied suitably to the liquid crystal aligning film for liquid crystal display elements, and the liquid crystal aligning film for retardation films. Hereinafter, the liquid crystal display device and the retardation film of the present invention will be described.

[Liquid crystal display device]

The liquid crystal display device of the present invention includes a liquid crystal aligning film formed using the liquid crystal aligning agent. The operation mode of the liquid crystal display device of the present invention is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type It can be applied to various driving methods such as. The liquid crystal display device of the present invention can be manufactured, for example, by the following steps (I-1) to (I-3). In step (I-1), the substrate used is different depending on the desired operation mode. Steps (I-2) and (I-3) are common to each operation mode.

[Step (I-1): Formation of coating film]

First, the liquid crystal aligning agent of the present invention is applied on a substrate, and then the coated surface is heated to form a coating film on the substrate.

(I-1A) For example, in the case of manufacturing a TN-type, STN-type or VA-type liquid crystal display device, first, a pair of two substrates on which a patterned transparent conductive film is formed, and the respective transparent conductive films are formed The liquid crystal aligning agent of the present invention is applied to the surface, preferably by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. 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, polyethersulfone, polycarbonate, and poly(alicyclic olefin) can be used. As a transparent conductive film formed on one side of the substrate, a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG in the United States), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. may be used. I can. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo etching after forming a patternless transparent conductive film; A method of using a mask having a desired pattern when forming a transparent conductive film; It can be done by etc. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. are preliminarily applied to the surface of the substrate surface where the coating film is formed. Pre-application treatment may be carried out.

After applying the liquid crystal aligning agent, pre-heating (prebaking) is preferably performed for the purpose of preventing liquid flow of the applied liquid crystal aligning agent. The prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. After that, the solvent is completely removed, and if necessary, a firing (post-baking) step is performed for the purpose of thermally imidizing the dark acid structure present in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80 to 300°C, more preferably 120 to 250°C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the formed film is preferably 0.001 to 1 µm, more preferably 0.005 to 0.5 µm.

(I-1B) In the case of manufacturing an IPS-type or FFS-type liquid crystal display device, an electrode formation surface of a substrate on which an electrode made of a transparent conductive film or a metal film patterned in a comb shape is formed, and an electrode is not formed. A coating film is formed by applying the liquid crystal aligning agent of the present invention to one surface of the counter substrate, and then heating each coating surface. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after application, the patterning method of the transparent conductive film or metal film, the pretreatment of the substrate, and the preferable film thickness of the formed coating film are the same as those of (I-1A) above. . As the metal film, for example, a film made of a metal such as chromium can be used.

In either case of the above (I-1A) and (I-1B), after applying the liquid crystal aligning agent on the substrate, the organic solvent is removed to form an alignment film or a coating film serving as an alignment film. At this time, in the case where the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and a dark acid structure, the dehydration ring closure reaction is performed by additional heating after the coating film is formed. It advances and may be made into a more imidized coating film.

[Step (I-2): Orientation ability imparting treatment]

In the case of manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display device, as a treatment for imparting liquid crystal alignment ability to the coating film formed in the above step (I-1), the coating film is, for example, nylon, rayon. , Rubbing treatment in a predetermined direction is performed with a roll wound with a cloth made of fibers such as cotton. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film, thereby forming a liquid crystal alignment film. On the other hand, in the case of manufacturing a VA type liquid crystal display element, the coating film formed in the above step (I-1) can be used as it is as a liquid crystal alignment film, but a rubbing treatment may be performed on the coating film. In addition, with respect to the liquid crystal alignment film after rubbing treatment, treatment of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating ultraviolet rays to a part of the liquid crystal alignment film, or after forming a resist film on a part of the surface of the liquid crystal alignment film. After the rubbing treatment is performed in a direction different from the rubbing treatment, a treatment for removing the resist film may be performed, and the liquid crystal alignment film may have a different liquid crystal alignment ability for each region. In this case, it is possible to improve the viewing characteristics of the obtained liquid crystal display element. Moreover, a liquid crystal aligning film suitable for a VA type liquid crystal display element can also be used suitably for a PSA (Polymer sustained alignment) type liquid crystal display element. As the treatment for imparting liquid crystal alignment ability to the coating film, a treatment by a photo-alignment method may be employed instead of the rubbing treatment.

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

As described above, two substrates on which a liquid crystal alignment film is formed are prepared, and a liquid crystal cell is produced by disposing a liquid crystal between the two substrates arranged opposite to each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are opposed to each other through a gap (cell gap) so that the respective liquid crystal alignment layers face each other, and the peripheries of the two substrates are bonded using a sealing material, and partitioned by the surface of the substrate and the sealing material. After the liquid crystal is injected and filled in the cell gap, a liquid crystal cell is manufactured by sealing the injection port. Also, the second method is a method called ODF (One Drop Fill) method. After applying, for example, an ultraviolet light-curable sealing material to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and further dropping the liquid crystal at a predetermined number of locations on the liquid crystal alignment film surface, the liquid crystal A liquid crystal cell is manufactured by bonding the other substrate so that the alignment film is opposed to each other, spreading the liquid crystal onto the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealing material. In any case, the liquid crystal cell prepared as described above is further heated to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooled to room temperature to remove the flow orientation during liquid crystal filling. desirable.

As the sealing material, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used. Moreover, as a liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, Among them, a nematic liquid crystal is preferable. For example, a ciprobase liquid crystal, an azocyclic liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, and an ester Liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cuban liquid crystals, and the like can be used. In addition, in these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonnaate, and cholesteryl carbonate; Chiral agents sold under the brand names "C-15" and "CB-15" (manufactured by Merck); Ferroelectric liquid crystals, such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, may be added and used.

And by bonding a polarizing plate to the outer surface of a liquid crystal cell, the liquid crystal display element of this invention can be obtained. As a polarizing plate bonded to the outer surface of a liquid crystal cell, a polarizing plate made of a polarizing plate made of a cellulose acetate protective film or a polarizing plate made of the H film itself is interposed with a polarizing film called ``H film'' absorbing iodine while stretching and aligning polyvinyl alcohol. I can.

[Phase difference film]

In the case of manufacturing a retardation film using the liquid crystal aligning agent of the present invention, it is possible to form a uniform liquid crystal aligning film while suppressing the occurrence of dust or static electricity during the process, and by using a photomask suitable for irradiation with radiation, the substrate Since a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on the image, it is preferable to use a photo-alignment method. Specifically, the manufacturing method including the following steps (II-1) to (II-3) is mentioned.

[Step (II-1): Formation of coating film by liquid crystal aligning agent]

First, the liquid crystal aligning agent of the present invention is applied on a substrate to form a coating film. The substrate used herein is a transparent substrate made of synthetic resin such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, and polycarbonate. Can be illustrated suitably. Among these, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display device. Further, polymethyl methacrylate can be preferably used as a substrate for a retardation film from the viewpoint of low hygroscopicity of a solvent, good optical properties, and low cost. In addition, for the substrate used for application of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the coating film, a conventionally known pretreatment may be performed on the surface of the substrate surface where the coating film is formed.

In most cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to bond the retardation film by precisely controlling the angle with respect to the polarization axis of the polarizing film in a specific direction in order to exhibit the expected optical properties. Therefore, here, by forming a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle on a substrate such as a TAC film or polymethyl methacrylate, the step of bonding the retardation film on the polarizing film while controlling the angle Can be omitted. In addition, this can contribute to the improvement in productivity of the liquid crystal display device. In order to form a liquid crystal aligning film which has liquid crystal aligning ability in the direction of a predetermined angle, it is preferable to perform by the photo-alignment method using the liquid crystal aligning agent of this invention.

The application of the liquid crystal aligning agent onto the substrate can be performed by an appropriate application method, for example, a roll coater method, a spinner method, a printing method, an inkjet method, a bar coater method, an extrusion die method, a direct gravure coater method, and a chamber. Doctor coater method, offset gravure coater method, 1 roll kiss coater method, reverse kiss coater method using small diameter gravure roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method, A forward rotation roll coater method, a blade coater method, a knife coater method, an impregnation coater method, an MB coater method, an MB reverse coater method, and the like can be employed.

After application, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150°C, more preferably 80 to 140°C. The heating time is preferably 0.1 to 15 minutes, more preferably 1 to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1 to 1,000 nm, more preferably 5 to 500 nm.

[Step (II-2): Light irradiation step]

Next, by irradiating light to the coating film formed on the substrate as described above, the liquid crystal alignment ability is imparted to the coating film. Here, as the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be mentioned. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferred. The irradiated light may be polarized or non-polarized. As polarized light, it is preferable to use light containing linearly polarized light.

When the light to be used is polarized light, irradiation of light may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or a combination of these may be performed. In the case of irradiating non-polarization, it is necessary to perform it from a direction that is slanted with respect to the substrate surface.

Examples of the light source to be used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a mercury-xenon lamp (Hg-Xe lamp), and the like. Polarization can be obtained by means of using these light sources in combination with, for example, a filter, a diffraction grating, or the like.

The irradiation amount of light is preferably 0.1 mJ/cm 2 or more and less than 1,000 mJ/cm 2, more preferably 1 to 500 mJ/cm 2, and still more preferably 2 to 200 mJ/cm 2.

[Step (II-3): Formation of liquid crystal layer]

Next, a polymerizable liquid crystal is applied and cured on the coating film after light irradiation in the above manner. Thereby, a coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used here is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation. As such a polymerizable liquid crystal, a conventionally known one can be used, and specifically, for example, Non-Patent Document 1 ("UV curable liquid crystal and its application", liquid crystal, Vol. 3, No. 1 (1999), pp 34- The nematic liquid crystal described in 42) is mentioned. In addition, cholesteric liquid crystal; Discotic liquid crystal; A twisted nematic alignment liquid crystal to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may be a composition further containing a known polymerization initiator or a suitable solvent.

In order to apply the polymerizable liquid crystal as described above on a coating film formed using a liquid crystal aligning agent, for example, a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, and an inkjet method can be employed.

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to at least one treatment selected from heating and light irradiation to cure the coating film to form a liquid crystal layer. It is preferable to perform these treatments superimposedly from the viewpoint of obtaining a good orientation.

The heating temperature of the coating film should be appropriately selected according to the kind of polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80°C. The heating time is preferably 0.5 to 5 minutes.

As irradiation light, unpolarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation amount of light is preferably 50 to 10,000 mJ/cm 2, and more preferably 100 to 5,000 mJ/cm 2.

The thickness of the formed liquid crystal layer is appropriately set according to desired optical properties. For example, when manufacturing a half-wavelength plate in visible light having a wavelength of 540 nm, a thickness such that the retardation film formed has a retardation of 240 to 300 nm is selected, and if it is a 1/4 wave plate, the retardation is 120 A thickness of -150 nm is selected. The thickness of the liquid crystal layer from which the desired phase difference is obtained differs depending on the optical properties of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck Corporation, the thickness for manufacturing a quarter wave plate is in the range of 0.6 to 1.5 µm.

The retardation film obtained as described above can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display device to which the retardation film manufactured by using the liquid crystal aligning agent of the present invention is applied is not limited in its driving method, and for example, known TN type, STN type, IPS type, FFS type, VA type, etc. It can be applied to various methods. The phase difference film is used by bonding the surface on the substrate side of the phase difference film to the outer surface of the polarizing plate disposed on the viewer side of the liquid crystal display element. Therefore, it is preferable that the substrate of the retardation film is made of a TAC agent or an acrylic substrate, and the substrate of the retardation film is set to function also as a protective film of a polarizing film.

The liquid crystal display device of the present invention can be effectively applied to various devices, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, and a smart device. It can be used for various display devices such as phones, various monitors, liquid crystal televisions, and information displays.

(Example)

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

In the following Examples and Synthesis Examples, the weight average molecular weight Mw of the polymer, the imidation ratio and the epoxy equivalent, and the solution viscosity of the polymer solution were measured by the following methods.

[Polymer weight average molecular weight Mw]

Mw is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

Column: Tosoh Corporation make, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40℃

Pressure: 68kgf/㎠

[Imidation rate of polymer]

A solution containing polyimide was added to pure water, and the obtained precipitate was sufficiently 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. Using, to formula (1) from ¹ H-NMR spectrum obtained already asked for imidization rate:

Imidation rate (%) = {(1-A ¹ )/(A ² ×α)} × 100. (One)

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

[Epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methylethyl ketone method described in JIS C 2105.

[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.

<Synthesis of diamine>

[Example 1-1; Synthesis of Compound (DA-1)]

According to the following Scheme 1, a compound represented by the above formula (DA-1) (hereinafter, represented by a compound (DA-1)) was synthesized.

In a 3L 3-neck flask equipped with a thermometer and a three-way cock, 105.1 g (0.53 mol) of 4-(benzyloxy)phenol, 57.5 g (0.25 mol) of 1,5-dibromopentane, 138.2 g (1.0 mol) of potassium carbonate And 1250 ml of dimethylformamide (DMF) were added and mixed. Subsequently, after the temperature was raised to 60°C and reacted for 6 hours, it was mixed with 2000 ml of ethyl acetate, and then liquid-separated and washed with distilled water. Then, the organic layer was concentrated and a solid was deposited. The obtained solid was recrystallized from ethyl acetate and hexane, collected by filtration, and dried to obtain 99.6 g (0.21 mol) of a compound represented by the formula (DA-1-1) (represented by the compound (DA-1-1)). .

Next, 99.6 g (0.21 mol) of the compound (DA-1-1) obtained above and 10 g of 5% Pd/C were weighed and taken into a 2 L 3-neck flask equipped with a thermometer, a three-way cock, and a dropping lot. The inside was vacuum degassed and replaced with nitrogen. Next, 1000 ml of tetrahydrofuran (THF) was added, and 100 ml of hydrazine monohydrate was gradually added dropwise while cooling so as not to exceed 10°C. Then, it was made to react at room temperature for 6 hours. In addition, the solvent used for the reaction was previously substituted with nitrogen. After the reaction, the inorganic salt was removed by filtration, 1000 ml of ethyl acetate was mixed with the filtrate, and then liquid separation and washing were performed with distilled water. Then, the organic layer was concentrated and a solid was deposited. The obtained solid was recovered and dried to obtain 56.4 g (0.20 mol) of a compound (represented by compound (DA-1-2)) represented by the above formula (DA-1-2).

Next, 56.4 g (0.20 mol) of the compound (DA-1-2) obtained above, 56.5 g (0.40 mol) of 4-fluoronitrobenzene, and potassium carbonate in a 1 L 3-neck flask equipped with a thermometer and a three-way cock. 108.1 g (0.78 mol) and 500 ml of dimethylformamide (DMF) were added and mixed. Subsequently, after the temperature was raised to 60°C and reacted for 6 hours, it was mixed with 1000 ml of ethyl acetate, and then liquid-separated and washed with distilled water. Then, the organic layer was concentrated and a solid was deposited. The obtained solid was recrystallized from ethyl acetate and hexane, collected by filtration, and dried to obtain 74.7 g (0.14 mol) of the compound represented by the formula (DA-1-3) (represented by the dinitro intermediate (DA-1-3)). ) Got it.

Next, 74.7 g (0.14 mol) of the dinitro intermediate (DA-1-3), 7.5 g of 5% Pd/C, 200 mL of ethanol, and 800 mL of tetrahydrofuran were added to a 2 L autoclave under a flow of nitrogen. After that, it was replaced with hydrogen again, and reacted at room temperature in the presence of hydrogen. The reaction was followed by liquid chromatography and filtered after confirming the progress of the reaction. The filtrate and 3000 mL of ethyl acetate were mixed, and liquid separation and purification were performed with distilled water after that. A solid was deposited by removing the solvent from the obtained organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from ethanol to obtain 58.3 g (0.12 mol) of compound (DA-1).

[Example 1-2; Synthesis of Compound (DA-2)]

According to the following Scheme 2, a compound represented by the above formula (DA-2) (hereinafter, represented by a compound (DA-2)) was synthesized.

In a 3L 3-neck flask equipped with a thermometer and a three-way cock, 99.5 g (0.5 mol) of 3-phenylpropyl bromide, 51.8 g (0.55 mol) of phenol, 207.3 g (1.5 mol) of potassium carbonate and 2000 ml of dimethylformamide (DMF) were added. Added and mixed. Subsequently, after the temperature was raised to 60°C and reacted for 6 hours, it was mixed with 2000 ml of ethyl acetate, and then liquid-separated and washed with distilled water. Then, the organic layer was concentrated and a solid was deposited. The obtained solid was recrystallized from ethanol, collected by filtration, and dried to obtain 77.5 g (0.37 mol) of a compound represented by the formula (DA-2-1) (represented by the compound (DA-2-1)).

Next, in a 2L 3-neck flask equipped with a thermometer and a three-necked flask, 243.3 g (1.83 mol) of aluminum chloride and 1000 ml of methylene chloride were mixed, and 162.6 g (0.88 mol) of 4-nitrobenzoic acid chloride were added under ice cooling, Dissolved. Next, 400 mL of a methylene chloride solution containing 77.5 g (0.37 mol) of the compound (DA-2-1) was gradually added dropwise. After completion of the dropwise addition, it was reacted for 6 hours while returning to room temperature. After confirming the completion of the reaction by liquid chromatography, the reaction solution was poured into a mixture of 10N hydrochloric acid and ice, followed by extraction with chloroform. Then, it was washed with an aqueous sodium hydrogen carbonate solution, brine, and distilled water, and the organic layer was dried over magnesium sulfate. Subsequently, the solvent was removed by distillation under reduced pressure, and when crystals sufficiently precipitated, it was filtered. The filtrate was washed sequentially with water, ethanol, and toluene, and dried under reduced pressure to obtain 95.0 g (0.19 mol) of a compound represented by the above formula (DA-2-2) (represented by the compound (DA-2-2)).

Next, 95.0 g of compound (DA-2-2) and 500 mL of dichloromethane were put into a 1 L three-necked flask equipped with a thermometer, a dropping lot, and a three-way cock, and under ice cooling, 120 g of trifluoromethanesulfonic acid was gradually added dropwise. . Then, 120 g of triethylsilane was gradually dripped. After completion of the dropwise addition, it was reacted for 10 hours while returning to room temperature. After confirming the completion of the reaction by liquid chromatography, the reaction solution was neutralized with an aqueous sodium carbonate solution and washed with water. 71.9 g (0.15 mol) of the compound represented by the formula (DA-2-3) (represented by the dinitro intermediate (DA-2-3)) was obtained by concentrating the organic layer, depositing a solid, and recrystallization with a toluene solvent. .

Next, 71.9 g (0.15 mol) of the dinitro intermediate (DA-2-3), 7.2 g of 5% Pd/C, 200 ml of ethanol, and 800 ml of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream. After that, it was replaced with hydrogen again, and reacted at room temperature in the presence of hydrogen. The reaction was followed by HPLC and filtered after confirming the progress of the reaction. The filtrate and 3000 mL of ethyl acetate were mixed, and liquid separation and purification were performed with distilled water after that. A solid was deposited by removing the solvent from the obtained organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from ethanol to obtain 53.3 g (0.13 mol) of compound (DA-2).

[Example 1-3; Synthesis of Compound (DA-3)]

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

In a 3L 3-neck flask equipped with a thermometer and a three-way cock, 180.8 g (0.84 mol) of 4-hydroxy-4'-nitrobiphenyl, 80.8 g (0.4 mol) of 1,3-dibromopropane, 221.1 g of potassium carbonate (1.6 mol) and 2000 ml of dimethylformamide (DMF) were added and mixed. Subsequently, after the temperature was raised to 60°C and reacted for 6 hours, it was mixed with 4000 ml of ethyl acetate, and then liquid-separated and washed with distilled water. Then, the organic layer was concentrated and a solid was deposited. The obtained solid was recrystallized from ethanol, collected by filtration, and dried to obtain 103.5 g (0.22 mol) of a compound represented by the formula (DA-3-1) (represented by the dinitro intermediate (DA-3-1)).

Next, 103.5 g (0.22 mol) of the dinitro intermediate (DA-3-1), 10.3 g of 5% Pd/C, 100 mL of ethanol, and 500 mL of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream. After that, it was replaced with hydrogen again, and reacted at room temperature in the presence of hydrogen. The reaction was followed by HPLC and filtered after confirming the progress of the reaction. The filtrate and 1000 mL of ethyl acetate were mixed, and liquid separation and purification were performed with distilled water after that. A solid was deposited by removing the solvent from the obtained organic layer by distillation under reduced pressure. 151.7 g (0.37 mol) of compound (DA-3) was obtained by recrystallizing the precipitated solid from ethanol.

[Example 1-4; Synthesis of Compound (DA-4)]

According to the following Scheme 4, a compound represented by the above formula (DA-4) (hereinafter, represented by a compound (DA-4)) was synthesized.

To a 1 L 3-neck flask equipped with a thermometer, a three-way cock, and a dropping lot, 43.4 g (0.15 mol) of the compound (DA-1-2) obtained by the same method as in Example 1-1 was added, and 60.7 of triethylamine (TEA). g (0.6 mol) and 300 ml of THF were mixed, and a solution of 69.6 g (0.38 mol) of 4-nitrobenzoic acid chloride in 400 ml of THF was gradually added dropwise under ice cooling. After dripping, after reacting at room temperature for 12 hours, it mixed with 1000 ml of ethyl acetate, and liquid separation and washing were carried out with distilled water after that. Then, the organic layer was concentrated and a solid was deposited. The obtained solid was recrystallized from ethyl acetate and hexane, collected by filtration, and dried to obtain 39.6 g (0.07 mol) of the compound represented by the formula (DA-4-1) (represented by the dinitro intermediate (DA-4-1)). ) Got it.

Then, 39.6 g (0.07 mol) of the dinitro intermediate (DA-4-1), 4 g of 5% Pd/C, 100 ml of ethanol and 250 ml of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream. And hydrogen, and reacted at room temperature in the presence of hydrogen. The reaction was followed by HPLC and filtered after confirming the progress of the reaction. A solid was deposited by removing the solvent from the organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from ethanol to obtain 27.4 g (0.05 mol) of a compound (DA-4).

<Synthesis of polymer>

[Example 2-1; Synthesis of Polymer (PA-1)]

10.7 g of pyromellitic dianhydride as tetracarboxylic dianhydride (93 mol parts with respect to 100 mol parts of the total amount of diamine used in the synthesis), and 12.41 g of compound (DA-1) as diamine (50 mol parts of the same), 4.82 g of 4-aminophenyl-4'-aminobenzoate (40 mol parts copper) and 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)] Dianiline was dissolved in 2.07 g (10 mol parts copper) in a mixed solvent of 85 g of N-methyl-2-pyrrolidone (NMP) and 85 g of γ-butyrolactone (GBL), and reacted at 30° C. for 6 hours. Then, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The recovered precipitate was washed with methanol and then dried at 40°C for 15 hours under reduced pressure to obtain 28.2 g of polyamic acid (hereinafter referred to as polymer (PA-1)). The obtained polymer (PA-1) was prepared so as to be 15% by weight with a solvent composition of NMP:GBL=50:50, and the viscosity of this solution was measured to find it was 550 mPa·s. Further, as a result of allowing this polymer solution to stand at 20° C. for 3 days, there was no case of gelation, and storage stability was good.

[Examples 2-2 to 2-5, Example 2-7, Synthesis Examples 1 and 2]

In Example 2-1, a polymer was obtained in the same manner as in Example 2-1, except that the types and amounts of tetracarboxylic dianhydride and diamine used in the reaction were changed as shown in Table 1 below. In addition, the numerical values in Table 1 represent the ratio (mol%) to the total amount of the tetracarboxylic acid dianhydride used in the reaction for the tetracarboxylic acid dianhydride, and for the diamine, the total amount of diamine used in the reaction. It shows the use ratio (mol%) with respect to. For each of the polymer solutions obtained in Examples, as a result of standing at 20°C for 3 days, none of them gelled, and the storage stability was good.

The abbreviations of tetracarboxylic dianhydride and diamine in Table 1 are as follows.

(Tetracarboxylic acid dianhydride)

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

AN-2; Pyromellitic dianhydride

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

AN-4; Ethylenediamine tetraacetic acid dianhydride

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

(Diamine)

da-1; Compound represented by the following formula (da-1)

da-2; 4-aminophenyl-4'-aminobenzoate

da-3; 4,4'-diaminodiphenylmethane

da-4; 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)]dianiline

da-5; 2,4-diamino-N,N-diallylaniline

da-6; 4,4'-diaminodiphenylamine

da-7; 3,5-diaminobenzoic acid

da-8; Cholestanyl 3,5-diaminobenzoic acid

da-9; 4-(tetradecaneoxy)benzene-1,3-diamine

da-10: compound represented by the above formula (DA-15)

da-11: 1,4-bis-(5-amino-pyridin-2-yl)-piperazine

[Example 2-6; Synthesis of Polymer (PI-1)]

16.58 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride (98 mol parts based on 100 mol parts of the total amount of diamine used in the synthesis), and 25.52 g of compound (DA-2) as diamine (copper) 80 mole parts) and 7.89 g (20 mole parts copper) of cholestanyl 3,5-diaminobenzoate were dissolved in 200 g of NMP, and the reaction was performed at room temperature for 6 hours. Next, 250 g of NMP was added, 11.7 g of pyridine and 15.11 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 80°C for 5 hours. Then, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The recovered precipitate was washed with methanol and then dried at 40° C. for 15 hours under reduced pressure to obtain a polyimide (hereinafter referred to as polymer (PI-1)) having an imidation ratio of about 65%. The obtained polymer (PI-1) was prepared so as to be 15% by weight by NMP. The viscosity of this solution was measured and found to be 890 mPa·s.

[Synthesis Example 3; Synthesis of polyorganosiloxane]

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. After 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, the reaction was carried out at 80°C for 6 hours while mixing 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 becomes neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an oxiranyl group. It was obtained as a viscous transparent liquid. As a result of performing ¹ H-NMR analysis on the polyorganosiloxane having an oxiranyl group, a peak based on the oxiranyl group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no negative reaction occurred. As a result of measuring the epoxy equivalent of the polyorganosiloxane having an oxiranyl group, it was 186 g/equivalent.

Next, in a 100 mL 3-neck flask, 9.3 g of polyorganosiloxane having an oxiranyl group obtained above, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid, and 0.10 g of UCAT 18X (brand name, manufactured by San Apro Co., Ltd.) Was put and reacted at 80° C. for 12 hours under stirring. After the reaction was completed, the reaction mixture was added to methanol to recover the resulting precipitate, dissolved in ethyl acetate to form a solution, and the solution was washed three times with water, and then the solvent was distilled off to form an oxiranyl group and a cinnamic acid structure. 6.3 g of polyorganosiloxane (S-1) was obtained as a white powder. With respect to this polyorganosiloxane (S-1), the weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography was 3,500.

<Preparation and evaluation of liquid crystal aligning agent>

[Example 3-1: FFS type liquid crystal display device]

(1) Preparation of liquid crystal aligning agent

As a polymer, 100 parts by weight of the polymer (PA-1) obtained in Example 2-1, a mixed solvent consisting of γ-butyrolactone (GBL), NMP, and butyl cellosolve (BC) (GBL:NMP:BC=40: 40:20 (weight ratio)), and the solid content concentration was set as the solution of 3.5 weight%. A liquid crystal aligning agent was prepared by filtering this solution with a filter of 0.2 micrometers pore diameter.

(2) Evaluation of applicability

The liquid crystal aligning agent prepared above was applied on a glass substrate using a spinner, pre-baked on a hot plate at 80° C. for 1 minute, and then heated in an oven at 200° C. in which nitrogen was replaced for 1 hour (post-baking). By doing so, a coating film having an average film thickness of 1,000Å was formed. This coating film was observed under a microscope at a magnification of 100 to investigate the non-uniformity of the film thickness and the presence or absence of pinholes. The evaluation was performed as coating property "good" when neither film thickness non-uniformity nor pinhole was observed, and coating property "defective" when at least one of film thickness non-uniformity and pinhole was observed. In this example, neither film thickness non-uniformity nor pinhole was observed, and the coatability was "good".

(3) Evaluation of rubbing tolerance

With respect to the coating film obtained above, a rubbing treatment was performed 7 times with a rubbing machine having a roll wound around a cotton cloth at a roll rotation speed of 1000 rpm, a stage movement speed of 20 cm/sec, and a hair foot press fit length of 0.4 mm. A foreign material (a piece of the coating film) due to rubbing abrasion on the obtained substrate was observed with an optical microscope, and the number of foreign materials in a region of 500 µm x 500 µm was measured. In the evaluation, when the number of foreign substances was 3 or less, rubbing resistance "good", when 4 or more and 7 or less were "possible", and when there were 8 or more, rubbing resistance "poor" was performed. As a result, the rubbing resistance of this coating film was "good".

(4) Fabrication of FFS type liquid crystal display device

The FFS type liquid crystal display element shown in FIG. 1 was produced. First, a glass substrate having a bottom electrode 15 having no pattern, a silicon nitride film as the insulating layer 14, and a combination electrode of two systems formed in this order in which the top electrode 13 patterned in a comb-tooth shape is formed on one side ( 11a) and a counter glass substrate 11b with no electrodes formed as a pair, and on the surface of the glass substrate 11a with a transparent electrode and one surface of the counter glass substrate 11b, respectively, in the above (1) The prepared liquid crystal aligning agent was applied using a spinner to form a coating film. Subsequently, this coating film was prebaked on a hot plate at 80°C for 1 minute, and then heated (postbaked) at 230°C for 15 minutes in an oven in which the inside of the tube was purged with nitrogen to form a coating film having an average film thickness of 1,000Å. A schematic plan view of the top electrode 13 is shown in FIG. 2. In addition, FIG. 2(a) is a top view of the top electrode 13, and FIG. 2(b) is an enlarged view of the part C1 surrounded by a broken line in FIG. 2(a). In this example, the line width d1 of the electrodes was set to 4 µm and the distance d2 between the electrodes was set to 6 µm.

Next, rubbing treatment was performed with cotton on each surface of the coating film formed on a glass substrate, and it was set as the liquid crystal aligning film 12. In Fig. 2(b), the rubbing direction with respect to the coating film formed on the glass substrate 11a is indicated by arrows. These substrates were bonded through spacers having a diameter of 3.5 μm so that the rubbing directions of the substrates 11a and 11b were antiparallel to each other, and liquid crystal MLC-6221 (manufactured by Merck) was injected to form the liquid crystal layer 16. Formed. Further, the liquid crystal display element 10 was produced by bonding polarizing plates (not shown) on both outer surfaces of the substrates 11a and 11b so that the polarization directions of the two polarizing plates are orthogonal to each other.

(5) Evaluation of liquid crystal orientation

For the FFS type liquid crystal display device manufactured above, the presence or absence of abnormal domains in the change in brightness and darkness when the voltage of 5 V was turned ON/OFF (applied/released) was observed with a microscope at 50 times magnification. The evaluation was performed as liquid crystal alignment "good" when an abnormal domain was not observed, and liquid crystal alignment "defective" when an abnormal domain was observed. In this liquid crystal display element, liquid crystal orientation was "good".

(6) Evaluation of voltage retention rate

For the FFS type liquid crystal display device manufactured above, a voltage of 5V was applied at 23°C with an application time of 60 microseconds and a span of 167 milliseconds, and the voltage retention rate (VHR) was measured after 167 milliseconds from the release of application. It was 99.2%. In addition, VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

(7) Evaluation of heat resistance

For the FFS type liquid crystal display device manufactured above, the voltage retention rate was measured in the same manner as in (6) above, and the value was taken as the initial VHR (VHR _BF ). Next, about the liquid crystal display element after initial VHR measurement, it was left still in a 100 degreeC oven for 300 hours. After that, this liquid crystal display element was left still under room temperature and left to cool to room temperature, and then the voltage retention rate (VHR _AF ) was measured in the same manner as above. In addition, the rate of change (ΔVHR (%)) of the voltage retention rate before and after application of heat stress was determined by the following equation (2).

ΔVHR=((VHR _BF -VHR _AF )÷VHR _BF )×100… (2)

Heat resistance was evaluated as heat resistance "good" when the rate of change ΔVHR was less than 4%, "possible" when it was 4% or more and less than 5%, and heat resistance "poor" when it was 5% or more. As a result, ΔVHR of the liquid crystal display element of this example was 1.9%, and the heat resistance was "good".

(8) Pre-tilt angle characteristics

For the liquid crystal display device manufactured above, the angle of the inclination of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using He-Ne laser light, and this value was taken as the pretilt angle θ. The crystal rotation method is non-patent document 1 (TJScheffer et al., J. Appl. Phys. vol. 48, p1783 (1977)) and non-patent document 2 (F. Nakano et al., JPN.J. Appl. Phys. vol. 19, p2013 (1980)).

In the evaluation, when the pretilt angle θ was less than 1.0°, the pretilt angle was evaluated as “good”, and the case was 1.0° or more as the pretilt angle evaluation “defective”, the rate of change in the pretilt angle of this liquid crystal display element was It was 0.3°, and the pretilt angle stability was judged as "good".

(9) Contrast evaluation after driving stress (evaluation of AC afterimage characteristics)

An FFS type liquid crystal cell was produced by performing the same operation as in (4) above except that the polarizing plate was not bonded to both outer surfaces of the substrate. For this FFS type liquid crystal cell, the minimum relative transmittance (%) represented by the following formula (3) was measured using a device in which a polarizer and an analyzer were disposed between the light source and the light detector after driving at an AC voltage of 10 V for 30 hours. did:

Minimum relative transmittance (%) = {(β-B ⁰ )/(B ¹⁰⁰ -B ⁰ )}×100… (3)

(In formula (3), B ⁰ is the transmission amount of light under the cross Nicol from the blank; B ¹⁰⁰ is the transmission amount of light under the parallel Nicole in the blank, and β is a liquid crystal display element between the polarizer and the analyzer under the cross Nicol It is the minimum amount of light transmission by inserting between).

The black level in the dark state is indicated by the minimum relative transmittance of the liquid crystal display device, and in the FFS type liquid crystal display device, the lower the black level in the dark state, the better the contrast. Those with a minimum relative transmittance of less than 0.5% were referred to as "good", those of 0.5% or more and less than 1.0% were referred to as "possible", and those with 1.0% or more were referred to as "defective". As a result, the minimum relative transmittance of this liquid crystal cell was 0.2%, and it was judged as "good".

[Example 3-2 to Example 3-5 and Comparative Examples 1 and 2]

In Example 3-1, a liquid crystal aligning agent was prepared in the same manner as in Example 3-1, except that a polymer of the kind shown in Table 2 was used as a polymer, and an FFS type liquid crystal display device was prepared. Evaluation was made. The evaluation results are shown in Table 2 below.

As shown in Table 2, in Examples 3-1 to 3-5, good results were obtained for both the coatability of the liquid crystal aligning agent and the rubbing resistance of the coating film. Moreover, the orientation of liquid crystal molecules in a liquid crystal display element, voltage retention, heat resistance, pretilt angle characteristic, and AC residual image characteristic were also favorable results. On the other hand, in Comparative Example 1, the coating property of the liquid crystal aligning agent was "poor", and the rubbing resistance of the coating film was inferior to that in the examples. In addition, in the liquid crystal display device of Comparative Example 1, the voltage retention rate, the pretilt angle characteristic, and the AC afterimage specification were inferior to those of the Examples. In Comparative Example 2, a polymer obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and compound (DA-1) was used, but the voltage retention rate was low, and the heat resistance of the liquid crystal cell was "poor". .

[Example 3-6: TN type liquid crystal display device]

(1) Preparation of liquid crystal aligning agent

As a polymer, 100 parts by weight of the polymer (PA-7) obtained in Example 2-5 was dissolved in a mixed solvent of NMP and BC (NMP:BC=50:50 (weight ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering with a filter of 0.2 micrometers pore diameter.

(2) Evaluation of printability

The liquid crystal aligning agent prepared in the above (1) was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal aligning film printer (manufactured by Nippon Shashin Insats Co., Ltd.), and on a hot plate at 80°C. After heating (pre-baking) for 1 minute to remove the solvent, heating (post-baking) for 10 minutes on a 200°C hot plate was carried out to form a coating film having an average film thickness of 600 占. This coating film was observed under a microscope at a magnification of 20 times, and the printing unevenness and the presence or absence of pinholes were investigated. In the evaluation, printability ``good'' when neither of the print nonuniformity nor the pinhole is observed, printability ``possible'' when at least one of the print nonuniformity and the pinhole is slightly observed, and at least one of the print nonuniformity and the pinhole The case where a lot of was seen was made into printability "defective". In this example, both printing unevenness and pinholes were not observed, and the printability was "good".

(3) Preparation of TN type liquid crystal cell

The liquid crystal aligning agent prepared in the above (1) was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal aligning film printer (manufactured by Nippon Shashin Insats Co., Ltd.), and on a hot plate at 80°C. After heating (pre-baking) for 1 minute to remove the solvent, heating (post-baking) for 10 minutes on a 200°C hot plate was carried out to form a coating film having an average film thickness of 600 占. 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 fit length of 0.4 mm by a rubbing machine having a roll wound with a rayon cloth, and a liquid crystal alignment ability was imparted. 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. Moreover, the above operation was repeated to obtain a pair (two) of substrates having a liquid crystal aligning film.

Next, to one of the pair of substrates, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 µm was applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates was applied to the liquid crystal alignment film. The sides were overlapped and pressed, and the adhesive was cured. Subsequently, after filling a nematic liquid crystal (MLC-6221, manufactured by Merck) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocurable adhesive to prepare a TN type liquid crystal cell.

(4) Evaluation of liquid crystal orientation

With respect to the TN-type liquid crystal cell manufactured in the above (3), the presence or absence of an abnormal domain when the voltage of 5 V was turned on and off under cross nicol was observed with a microscope at a magnification of 50 times. Evaluation was performed in the same manner as in Example 3-1 (5). As a result, in this liquid crystal cell, liquid crystal orientation was "good".

(5) Evaluation of pretilt angle stability

For the TN-type liquid crystal cell prepared in (3) above, the angle of the inclination of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using He-Ne laser light, and this value was converted to the initial pretilt angle θ _IN . did. The crystal rotation method is Non-Patent Document 1 (TJScheffer et al., J. Appl. Phys. vol. 48, p1783 (1977)) and Non-Patent Document 2 (F. Nakano et al., JPN.J. Appl. Phys. vol. 19). , p2013 (1980)).

Next, an AC voltage of 5 V was applied for 100 hours to the liquid crystal cell after measuring the initial pretilt angle θ _IN . Then, the pretilt angle was measured again by the method similar to the above, and this value was made into the pretilt angle θ _AF after voltage application. These measured values were substituted into the following equation (4), and the amount of change (Δθ(°)) of the pretilt angle before and after voltage application was obtained.

Δθ=｜θ _AF -θ _IN ｜… (4)

When Δθ was less than 3%, pretilt angle stability was "good", when it was 3% or more and less than 4%, pretilt angle stability was "possible", and if it was 4% or more, pretilt angle stability was evaluated as "poor". As a result, the pretilt angle change rate of this liquid crystal cell was 2.8%, and it was judged as "good" pretilt angle stability.

(6) Evaluation of voltage retention and heat resistance

In the same manner as in Example 3-1 (6), the voltage retention rate (VHR _BF ) was measured, and in the same manner as in Example 3-1 (7), the rate of change of the voltage retention rate before and after heat stress was applied According to this, the heat resistance of the liquid crystal display element was evaluated. As a result, VHR _BF was 98.9%. In addition, ΔVHR was 2.9%, and it was judged as "good" heat resistance.

[Example 3-7: VA type liquid crystal display device]

(1) Preparation of liquid crystal aligning agent

As a polymer, NMP and BC were added to 100 parts by weight of the polymer (PI-1) obtained in Example 2-6 to obtain a solution having a solid content concentration of 6.5% by weight and a solvent mixing ratio of NMP:BC=50:50 (weight ratio). After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering with a filter of 0.2 micrometers pore diameter.

(2) Evaluation of printability

Using the liquid crystal aligning agent prepared in the above (1), as a result of examining the printability in the same manner as in (2) of Example 3-5, both printing non-uniformity and pinholes were not observed, and the printability was "good". .

(3) Preparation of VA type liquid crystal cell

The liquid crystal aligning agent prepared above was applied on the transparent electrode surface of a glass substrate (thickness 1 mm) made of an ITO film using a liquid crystal aligning film printer (manufactured by Nippon Shashin Insats Co., Ltd.), and at 80°C. It heated (prebaked) for 1 minute on a hot plate of, and further heated (post-baked) on a hot plate of 200°C for 60 minutes to form a coating film (liquid crystal oriented film) having an average film thickness of 800 占. This operation was repeated to obtain a pair (two) of glass substrates having a liquid crystal aligning film on the transparent conductive film. Next, with respect to one of the pair of substrates, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment layer, and then the pair of substrates were faced with the liquid crystal alignment layer. Then, it overlapped and pressed, and the adhesive was cured. Next, after filling a nematic liquid crystal (MLC-6608, manufactured by Merck) between a pair of substrates from the liquid crystal injection port, a VA type liquid crystal cell was manufactured by sealing the liquid crystal injection port with an acrylic photocurable adhesive.

(4) Evaluation of liquid crystal orientation, voltage retention, and heat resistance

About the VA-type liquid crystal cell manufactured by said (3), as a result of carrying out evaluation of the liquid crystal aligning property similarly to (5) of Example 3-1, the liquid crystal aligning property of this liquid crystal cell was "good". In addition, the voltage retention rate (VHR _BF ) was measured in the same manner as in Example 3-1 (6), and heat resistance (voltage retention rate before and after heat stress was applied in the same manner as in Example 3-1 (7)). The rate of change) was evaluated. As a result, VHR _BF was 99.2%. In addition, ΔHR was 2.4%, and it was judged as "good" heat resistance.

[Example 3-8: retardation film]

(1) Preparation of liquid crystal aligning agent

100 parts by weight of the polymer (PA-2) obtained in Example 2-2 and 5 parts by weight of the polyorganosiloxane (S-1) obtained in Synthesis Example 3, a mixed solvent consisting of NMP and BC (NMP:BC=50: 50 (weight ratio)), and a solid content concentration of 3.5% by weight was obtained. A liquid crystal aligning agent was prepared by filtering this solution with a filter of 0.2 micrometers pore diameter.

(2) Preparation of retardation film

The liquid crystal aligning agent prepared above was applied to one surface of the TAC film as a substrate using a bar coater, and baked in an oven at 120° C. for 2 minutes to form a coating film having a thickness of 100 nm. Subsequently, 10 mJ/cm 2 of polarized ultraviolet rays including a 313 nm bright line was irradiated vertically from the substrate normal to the surface of the coating film using an Hg-Xe lamp and a Glen Taylor prism. Next, after filtering the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) with a filter having a pore diameter of 0.2 μm, the polymerizable liquid crystal was applied on the coated film after light irradiation by a bar coater to form a coating film of the polymerizable liquid crystal. did. After baking for 1 minute in an oven adjusted to a temperature of 50°C, using a Hg-Xe lamp, 1,000mJ/cm2 of unpolarized ultraviolet rays including a bright line of 365 nm were irradiated from a direction perpendicular to the coating surface, and polymerization A phase difference film was produced by curing the liquid crystal to form a liquid crystal layer.

(3) Evaluation of liquid crystal orientation

With respect to the retardation film produced in the above (2), liquid crystal orientation was evaluated by observing the presence or absence of abnormal domains with the naked eye under Cross Nicole and a polarizing microscope (magnification of 2.5 times). In the evaluation, the liquid crystal orientation is "good" when the orientation is good with the naked eye and no abnormal domain is observed with a polarizing microscope, and the liquid crystal orientation is ``possible when the abnormal domain is not observed with the naked eye but the abnormal domain is observed with a polarizing microscope. ", the case where an abnormal domain was observed with the naked eye and a polarizing microscope was carried out as a liquid crystal orientation "defective". As a result, this retardation film was evaluated as "good" liquid crystal orientation.

(4) adhesion

Using the retardation film produced in the above (2), the adhesion of the coating film formed by the liquid crystal aligning agent to the substrate was evaluated. First, using an equally spaced spacer with a guide, a cut was made from the surface of the liquid crystal layer side of the retardation film with a cutter knife, and 10 x 10 grid patterns were formed in a range of 1 cm x 1 cm. Each cut-out depth was made to reach the intermediate|middle degree of the board|substrate thickness from the liquid crystal layer surface. Subsequently, after the cellophane tape was brought into close contact so as to cover the entire surface of the grid pattern, the cellophane tape was peeled off. The cut-off portion of the grid pattern after peeling was observed with the naked eye under the cross nicol to evaluate the adhesion. In the evaluation, if no peeling was observed at the part along the cut line and at the intersection of the grid pattern, the adhesion was "good", and the number of grid eyes in which peeling was observed in the part was less than 15% with respect to the total number of grid patterns. The case was made as adhesion "possible", and the case where the number of lattice eyes in which peeling was observed in the above part was 15% or more with respect to the total number of the lattice pattern was regarded as adhesion "poor". As a result, this phase difference film was adhesive "good".

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 (12)

Diamine containing at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide, and a compound represented by the following formula (1) A liquid crystal aligning agent containing at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide obtained by reaction:

(In formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom in at least one of a carbon-carbon bond of a C1-C30 hydrocarbon group and a position adjacent to each other with the hydrocarbon group, At least one of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom; X ¹ and X ² are each independently an oxygen atom, an alkanediyl group having 1 to 10 carbon atoms, an alkendiyl group having 2 to 10 carbon atoms, an ester A group or an amide group; provided that X ¹ and X ² are oxygen atoms, and R ^A is -OR ¹ -O- (R ¹ is an alkanediyl group having 1 to 18 carbon atoms), the tetracarboxylic acid Except when the derivative is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride). The method of claim 1,
A liquid crystal aligning agent in which the diamine represented by the formula (1) is a diamine represented by the following formula (1-1):

(In formula (1-1), R ² is a C 1 to C 30 divalent hydrocarbon group, and X ¹ and X ² are each independently an oxygen atom, a C 1 to C 10 alkanediyl group, and a C 2 to C 2 10 alkendiyl group, ester group, or amide group, X ³ is an oxygen atom or a sulfur atom, and X ⁴ is a single bond, an oxygen atom or a sulfur atom; provided that X ¹ , X ² , X ³ and X ⁴ is an oxygen atom, and R ² is an alkanediyl group having 1 to 18 carbon atoms, excluding the case where the tetracarboxylic acid derivative is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride). The method of claim 2,
The liquid crystal aligning agent wherein R ² is an alkanediyl group having 1 to 11 carbon atoms. delete The method of claim 1,
The tetracarboxylic acid derivative is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a,4,5,9b-hexa Hydro-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, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-2 anhydride, 4,9-dioxa Tricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, ethylenediamine 4 A liquid crystal aligning agent containing at least one selected from the group consisting of acetic acid dianhydride and pyromellitic dianhydride. The method of claim 1,
The liquid crystal aligning agent which said polymer (P) has a side chain structure which has a pretilt angle expression ability. A liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-3, 5, and 6. A liquid crystal display element comprising the liquid crystal alignment film according to claim 7. A retardation film comprising the liquid crystal aligning film according to claim 7. A step of forming a coating film by applying the liquid crystal aligning agent according to any one of claims 1 to 3, 5 and 6 on a substrate, and
A step of irradiating light to the coating film, and
Step of curing by applying a polymerizable liquid crystal on the coating film after irradiation with light
Method for producing a retardation film comprising a. Diamine containing at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide, and a compound represented by the following formula (1) Polymer obtained by reaction:

(In formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom in at least one of a carbon-carbon bond of a C1-C30 hydrocarbon group and a position adjacent to each other with the hydrocarbon group, At least one of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom; X ¹ and X ² are each independently an oxygen atom, an alkanediyl group having 1 to 10 carbon atoms, an alkendiyl group having 2 to 10 carbon atoms, an ester A group or an amide group; provided that X ¹ and X ² are oxygen atoms, and R ^A is -OR ¹ -O- (R ¹ is an alkanediyl group having 1 to 18 carbon atoms), the tetracarboxylic acid Except when the derivative is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride). Compound represented by the following formula (1):

(In formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom in at least one of a carbon-carbon bond of a C1-C30 hydrocarbon group and a position adjacent to each other with the hydrocarbon group, At least one of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom; X ¹ and X ² are each independently an oxygen atom, an alkanediyl group having 1 to 10 carbon atoms, an alkendiyl group having 2 to 10 carbon atoms, an ester A group or an amide group, except for the case where X ¹ and X ² are oxygen atoms, and R ^A is -OR ¹ -O- (R ¹ is an alkanediyl group having 1 to 18 carbon atoms).

Images