TW201326257A - Liquid crystal orientation liquid for light orientation processing technique, and liquid crystal orientation film employing same - Google Patents

Abstract

Provided are a liquid crystal orientation film with which it is possible to alleviate an afterimage resulting from AC driving which occurs with an IPS drive format or an FFS drive format liquid-crystal display element, and a liquid crystal orientation liquid for a light orientation processing technique for said film. A liquid crystal orientation liquid for a light orientation processing technique includes a constituent (A), a constituent (B), and an organic solvent, wherein the degree of inclusion of the constituent (B) is 0.1-15 parts to 100 parts of the constituent (A). Constituent (A): one or more polymers, wherein by illuminating with polarized light, one of the following reactions progresses: photolysis, photodimerization, or photoisomerization, and wherein an anisotropy is applied in either the same direction as the polarized light direction or the perpendicular direction to the polarized light direction. Constituent (B): a polymer having a structure which is represented with formula (1), following: (Chemical Formula 1) (Wherein W1 and W2 are independent bivalent organic groups including an aromatic group with 6-30 carbons, and A is a bivalent organic group including an alkylene group with 2-20 carbons.

Description

Liquid crystal alignment agent for photo-alignment processing method, and liquid crystal alignment film using the same

The present invention relates to a liquid crystal alignment agent for producing a liquid crystal alignment film, and a liquid crystal alignment film obtained by the liquid crystal alignment agent. More specifically, the present invention relates to a photo-alignment treatment method which replaces rubbing treatment, that is, a liquid crystal alignment agent for forming a liquid crystal alignment film by imparting liquid crystal alignment energy by irradiation of polarized ultraviolet rays. And a liquid crystal alignment film obtained from the liquid crystal alignment agent.

In a liquid crystal display element used in a liquid crystal television, a liquid crystal display or the like, generally, a liquid crystal alignment film for controlling an arrangement state of liquid crystals is provided in the element.

Now, according to the most popular method in the industry, the liquid crystal alignment film is a surface of a film formed of a polyaminic acid formed on an electrode substrate and/or a polyimide which is imidized. The cloth of cotton, nylon, polyester, etc. is rubbed in one direction, that is, it is produced by grinding treatment.

In the alignment process of the liquid crystal alignment film, the method of polishing the film surface is simple and can be used in an industrial method excellent in productivity. However, there is an increasing demand for high performance, high definition, and large size of liquid crystal display elements, and the surface of the alignment film which is caused by the polishing process is damaged, dust, mechanical force, or static electricity, or even in the alignment treatment surface. Various problems such as inhomogeneity are becoming more apparent.

In place of the polishing treatment, a photo-alignment method in which liquid crystal alignment energy is imparted by irradiation of polarized radiation is known. Light distribution method In the liquid crystal alignment treatment, those who use a photoisomerization reaction, those who use a photocrosslinking reaction, those who use a photodecomposition reaction, and the like are proposed (see Non-Patent Document 1).

When polyimine is used for a liquid crystal alignment film for photoalignment, it is expected to have higher heat resistance than other ones. Patent Document 1 proposes a polyimine film having an alicyclic structure having a cyclobutane ring or the like in its main chain in the photo-alignment method.

The above-mentioned photo-alignment method has attracted attention with the attitude of the non-polishing alignment treatment method, and has industrially advantageous points for easy manufacturing process production, and is controlled by IPS driving or fringe field switching. The liquid crystal alignment film obtained by the liquid crystal display device of the FFS drive mode can further improve the performance of the contrast or viewing angle characteristics of the liquid crystal display device compared to the liquid crystal alignment film obtained by the polishing process. Upgrade.

In addition, in the liquid crystal alignment film used in the liquid crystal display device of the IPS driving method or the FFS driving method, in addition to the basic characteristics such as excellent liquid crystal alignment property or electrical characteristics, it is also necessary to suppress liquid crystal display in the IPS driving mode or the FFS driving mode. An afterimage caused by the AC drive that occurs in the component. However, in the liquid crystal alignment film obtained by the photo-alignment method, the alignment regulation force and stability of the liquid crystal are not sufficient, and it is difficult to satisfy the above characteristics.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-297313

[Non-patent literature]

[Non-Patent Document 1] "Liquid Crystal Light Alignment Film" Miki-shi, Shimura Functional Materials, November 1997 Vol.17 No.11 13-22

The present invention provides a liquid crystal alignment film for suppressing an afterimage caused by AC driving in a liquid crystal display device of an IPS driving method or an FFS driving method, and a light alignment for obtaining the liquid crystal alignment film. The purpose of the liquid crystal alignment agent for the treatment method.

In order to achieve the above object, the inventors of the present invention have found that it is possible to carry out any reaction of photodecomposition, photodimerization or photoisomerization by irradiation of polarized radiation, and by containing A liquid crystal alignment agent which is formed by a polymer which imparts anisotropy in the same direction as the polarizing direction or a direction perpendicular to the polarizing direction, a polymer having a rigid aromatic group and a soft alkyl group, and an organic solvent. the goal of.

Accordingly, the present invention is intended to be as described below.

A liquid crystal alignment agent comprising the following component (A), component (B) and an organic solvent, and the content of the component (B) is 0.1 to 15 parts by mass based on 100 parts by mass of the component (A). (A) component: any reaction of photodecomposition, photodimerization, or photoisomerization is performed by irradiating the polarized radiation, and the difference may be given in the same direction as the polarization direction or in the direction perpendicular to the polarization direction. One or two or more kinds of polymers; (B): a polymer containing a structure represented by the following formula (1); [Chemical Formula 1]-W ₁ -AW ₂ - (1) (Formula ( In 1), W ₁ and W ₂ are each independently a divalent organic group having an aromatic group having 6 to 30 carbon atoms; and A is a divalent organic group having an alkylene group having 2 to 20 carbon atoms.

2. The liquid crystal alignment agent according to the above-mentioned item 1, wherein the component (A) is subjected to a photodecomposition reaction by irradiating the polarized radiation, and an anisotropy is imparted in the direction perpendicular to the polarizing direction. Or two or more kinds of polymers.

3. The liquid crystal alignment agent according to the above 1 or 2, wherein the component (A) is a polyimine precursor containing a structural unit represented by the following formula (2) and the polyimine precursor At least one polymer selected from the group consisting of imidized polymers.

(In the formula (2), X ₁ is at least one selected from the group consisting of the structures represented by the following formulas (X1-1) to (X1-9), and a Y ₁ -based divalent organic group; R ₁ is a group; A hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

In the formula (X1-1), R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group. Or phenyl, which may be the same or different.

4. The liquid crystal alignment agent according to the above-mentioned item 3, wherein the component (A) is a polyimine containing 60 mol% or more of a structural unit represented by the above formula (2) for 1 mol of the total structural unit. At least one selected from the group consisting of a precursor and a ruthenium imidized polymer of the polyimide precursor.

5. The liquid crystal alignment agent according to the above-mentioned formula (2), wherein X ₁ is at least one selected from the group consisting of the structures represented by the above formula (X1-1).

6. The liquid crystal alignment agent according to any one of the above-mentioned formulas (2), wherein X ₁ is formed by a structure represented by the following formulas (X1-10) to (X1-11). At least one selected from the group.

The liquid crystal alignment agent according to any one of the above-mentioned formulas (2), wherein Y ₁ is selected from the group consisting of the structures represented by the following formulas (4) and (5). At least one.

(In the formula (5), Z ₁ is a single bond, an ester bond, a guanamine bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms.)

8. The liquid crystal alignment agent according to the above-mentioned item (2), wherein Y ₁ is a structure represented by the above formula (4).

The liquid crystal alignment agent according to any one of the above aspects, wherein the component (B) is a polyimine precursor having a structural unit represented by the following formula (3) and the polyimine. At least one polymer selected from the group consisting of a precursor of an imidized polymer.

(In the formula (3), X ₂ is a tetravalent organic group having an aromatic group having 6 to 20 carbon atoms and having a bond to an aromatic group. Y ₂ is represented by the following formula (Y2-1) and ( Y2-2) at least one divalent organic group selected from the group formed; A ₁ and A ₂ are each independently a hydrogen atom, or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent ; R ₂ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) (In the formula (Y2-1), A ₃ is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. In the formula (Y2-2), A ₄ is a single bond, -O-, -S-, -NR ₁₂ -, ester bond, guanamine bond, thioester bond, urea bond, carbonate bond, urethane bond; R ₁₂ hydrogen atom, methyl group, or t-butoxycarbonyl group; A ₅ system Alkyl groups with a carbon number of 2 to 20.)

10. The liquid crystal alignment agent according to the above-mentioned item 9, wherein the component (B) is a polyimine containing 60 mol% or more of a structural unit represented by the above formula (3) for 1 mol of the total structural unit. At least one polymer selected from the group consisting of a precursor and a ruthenium imidized polymer of the polyimide precursor.

11. The liquid crystal alignment agent according to the above formula (3), wherein the X ₂ of the formula (3) is at least selected from the group consisting of the structures represented by the following formulas (X2-1) to (X2-3). 1 species.

12. The liquid crystal alignment agent according to the above-mentioned item 11, wherein X ₂ of the above formula (3) is the above formula (X2-1).

The liquid crystal alignment agent of the above formula (3), wherein Y ₂ of the above formula (3) is a group represented by the following formulas (Y2-3) to (Y2-12) At least one of the selected ones.

(In the formulae (Y2-10) and (Y2-11), R _{13 is} each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may be the same or different.)

A liquid crystal alignment film obtained by baking the liquid crystal alignment agent according to any one of 1 to 13 above.

A liquid crystal alignment film obtained by applying the liquid crystal alignment agent according to any one of the above 1 to 13, which is obtained by firing and then irradiating the polarized radiation.

A liquid crystal alignment film which is coated as described in any one of the above 1 to 13 The liquid crystal alignment agent described in the above article is fired, irradiated with polarized radiation, and heated at 150 ° C to 300 ° C.

A liquid crystal display device comprising the liquid crystal alignment film according to any one of the above 14 to 16.

The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can suppress an afterimage caused by AC driving occurring in a liquid crystal display element of an IPS driving method or an FFS driving method.

In the liquid crystal alignment film of the present invention, although it is not clear how to solve the problem of the present invention, the following considerations are possible.

In general, it is known that by increasing the anisotropy of the liquid crystal alignment film and/or by increasing the interaction between the liquid crystal alignment film and the liquid crystal, it is possible to suppress the occurrence of an alternating current in the liquid crystal display element of the IPS driving method or the FFS driving method. The afterimage caused by the drive. Further, even if the obtained liquid crystal alignment film is sufficiently anisotropically imparted by the photo-alignment method, it is necessary to have a certain ratio or more of a specific portion to be reacted by radiation irradiation, so that it is difficult to increase the interaction with the liquid crystal. Specifically, when the structure in which the interaction with the liquid crystal is increased is introduced into the polymer, the reactivity of the photoreaction site may be lowered or the density of the photoreactive site may be lowered, and sufficient anisotropy may not be obtained.

The inventors of the present invention have found that the component (A) which imparts anisotropy by irradiating the polarized radiation has a liquid crystal similar to that of a soft skeleton having both an aromatic group-containing rigid skeleton and an alkyl group-containing alkyl group. The polymer ((B) component) is preferably a mixed specific for the component (A) The amount of the liquid crystal alignment film and the liquid crystal can be increased by the photo-alignment method while maintaining the anisotropy when the polarized radiation is irradiated.

The liquid crystal and the component (B) having a similar skeleton are expected to have high mobility when heated due to a soft skeleton. There may be several heating steps during the photoalignment process or when the liquid crystal display device is fabricated. The inventors of the present invention considered that the kinetic property of the component (B) is enhanced during the heating step, and the orientation is realigned along the anisotropy imparted by the irradiation of the polarized radiation. By realigning the component (B), even in the liquid crystal alignment film obtained by the photo-alignment method, a liquid crystal alignment film having high anisotropy and high interaction with the liquid crystal can be obtained.

From the above, it is understood that the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can suppress the AC driving due to the liquid crystal display element of the IPS driving method or the FFS driving method while having high liquid crystal alignment properties. The resulting afterimage.

[Formation of the Invention] <(A) component>

The component (A) contained in the liquid crystal alignment agent of the present invention is subjected to any reaction of photodecomposition, photodimerization or photoisomerization by irradiation of polarized radiation, and may be in the same direction as the polarization direction. Or one or two or more kinds of polymers which impart anisotropy in the direction perpendicular to the direction of polarization.

The component (A) of the present invention is a polymerization of a portion which undergoes photoreaction, photodimerization or photoisomerization by irradiation with radiation. The structure is not particularly limited. In the structure of the photodimerization reaction, a polymer having a structure having a cinnamyl group represented by the following formula (A-1) can be mentioned. The structure of the photoisomerization reaction includes a polymer containing an azobenzene skeleton represented by the following formula (A-2). The structure in which the photodegradation reaction is carried out includes a polymer containing an oxime imine skeleton having an alicyclic group represented by the following formula (A-3) and at least one selected from the group of the polymer precursor. 1 polymer.

In the formula (A-1), Q is a divalent aromatic group. In the formula (A-3), X is a tetravalent alicyclic group and a Y-based divalent organic group.

The obtained liquid crystal alignment film has high heat resistance, and in the case of a liquid crystal display element, in order to obtain a liquid crystal display element having high reliability of high voltage holding ratio and having high anisotropy of the obtained liquid crystal alignment film, the following formula is used ( A-3) an anthraquinone-based polymer having an alicyclic group and an oxime imine skeleton having an alicyclic group is more preferable.

In the formula (A-1), Q is a divalent aromatic group. In the formula (A-3), X is a tetravalent alicyclic group and a Y-based divalent organic group.

The polymer containing a quinone imine structure having an alicyclic skeleton and a precursor of the polymer have high sensitivity to photoreaction and high anisotropy of the obtained liquid crystal alignment film, and are described in the present invention (A). In terms of ingredients The polyimine precursor of the structural unit represented by the following formula (2) and the quinone imidized polymer of the polyimine precursor are preferred. From the viewpoint of solubility to an organic solvent, a polyimine precursor containing a structural unit represented by the following formula (2) is particularly preferable.

In the formula (2), R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of easiness of hydrazine imidation by heating, it is particularly preferable that a hydrogen atom or a methyl group is used. X ₁ is at least one selected from the group consisting of the structures represented by the following formulas (X1-1) to (X1-9).

In the formula (X1-1), R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkenyl group. Or phenyl, which may be the same or different. From the viewpoint of liquid crystal alignment, R ₁ , R ₂ , R ₃ , and R ₄ are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and more preferably At least one selected from the group consisting of the following formulas (X1-10) to (X1-11).

Y ₁ is a divalent organic group, and the structure is not particularly limited. Since the obtained liquid crystal alignment film has high anisotropy, it is preferable to use at least one selected from the group consisting of the following formulas (4) and (5).

In the formula (5), Z ₁ is a single bond, an ester bond, a guanamine bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms.

In Z ₁ , the ester bond is represented by -C(O)O- or -OC(O)-. The guanamine bond may represent a structure represented by -C(O)NH-, or -C(O)NR-, -NHC(O)-, or -NRC(O)-. R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, and a dicyclohexyl group. The alkenyl group is a structure in which one or more CH-CH structures present in the above alkyl group are substituted with a C=C structure, and more specifically, a vinyl group, an allyl group, a 1-propenyl group, Isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like. The alkynyl group may be a structure in which one or more CH ₂ -CH ₂ structures present in the alkyl group are substituted with a C≡C structure, and more specifically, an ethynyl group, a 1-propynyl group, and 2 - propynyl and the like. As an aryl group, a phenyl group is mentioned, for example.

The thioester bond may represent a structure represented by -C(O)S- or -SC(O)-.

When Z ₁ is an organic group having 2 to 10 carbon atoms, it can be represented by the structure of the following formula (6).

[Chem. 15]-Z ₄ -R ₉ -Z ₅ -R ₁₀ -Z ₆ - (6)

Z ₄ , Z ₅ and Z ₆ in the formula (6) are each independently a single bond, -O-, -S-, -NR ₁₁ -, an ester bond, a guanamine bond, a thioester bond, a urea bond, a carbonate Bond or urethane bond. R ₁₁ is a hydrogen atom, a methyl group or a t-butoxycarbonyl group.

In Z ₄ , Z ₅ and Z ₆ , the ester bond, the guanamine bond and the thioester bond may have the same structure as the ester bond, the guanamine bond and the thioester bond.

The urea bond may represent a structure represented by -NH-C(O)NH- or -NR-C(O)NR-. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a combination of these having 1 to 10 carbon atoms, and may be the same as the above-mentioned alkyl group, alkenyl group, alkynyl group or aryl group.

In terms of a carbonate bond, a structure represented by -O-C(O)-O- can be represented.

The urethane bond may represent -NH-C(O)-O-, -OC(O)-NH-, -NR-C(O)-O- or -OC(O)-NR- The structure of the display. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a combination of these having 1 to 10 carbon atoms, and may be the same as the above-mentioned alkyl group, alkenyl group, alkynyl group or aryl group.

R ₉ and R ₁₀ in the formula (6) are each independently a single bond or are selected from a group consisting of a C 1-10 alkyl group, an alkenyl group, an alkynyl group, an extended aryl group, and a combination thereof. Construction. When any one of R ₉ and R ₁₀ is a single bond, R ₉ or R _{10 is a group} derived from an alkyl group having 2 to 10 carbon atoms, an alkenyl group, an alkynyl group, an extended aryl group, and a combination thereof. Selected structure.

The alkylene group may have a structure in which one hydrogen atom is removed from the alkyl group. More specifically, it may, for example, be a methylene group, a 1,1-extended ethyl group, a 1,2-extended ethyl group, a 1,2-extended propyl group, a 1,3-propanyl group or a 1,4-extended group. 1, 1, 2-butyl, 1,2-exylpentyl, 1,2-extended hexyl, 2,3-butylene, 2,4-amyl, 1,2-cyclopropyl, 1,2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentyl, 1,2-extended cyclohexyl and the like.

Examples of the alkenyl group include a structure in which one hydrogen atom is removed from the alkenyl group. More specifically, 1,1-extended vinyl group, 1,2-extended vinyl group, 1,2-extended vinylmethylene group, 1-methyl-1,2-extended vinyl group, 1, 2-extended vinyl-1,1-extended ethyl, 1,2-extended vinyl-1,2-extended ethyl, 1,2-extended vinyl-1,2-extended propyl, 1,2- Vinyl-1,3-propanyl, 1,2-vinyl-1,4-1,4-butyl, 1,2-vinyl-1,2-butylene, and the like.

Examples of the alkynyl group include a structure in which one hydrogen atom is removed from the alkynyl group. More specifically, an ethynyl group, an exetylene group, an ethynyl group, a 1-ethylidene group, an ethynyl group, a 2-ethyl group, an ethynyl group-1, 2 - propyl, ethynyl-1,3-propanyl, ethynyl-1,4-tert-butyl, ethynyl-1,2-tert-butyl and the like.

The aspect of the aryl group may be a structure in which one hydrogen atom is removed from the aryl group. More specifically, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene and the like.

In the case of a structure having a high linearity or a rigid structure on Y ₁ , in order to obtain a liquid crystal alignment film having good liquid crystal alignment, Z ₁ is a single bond or a structure of the following formulas (A1-1) to (A1-25). good.

The more the Y ₁ is a rigid structure, the Y ₁ system is particularly preferably a structure represented by the above formula (4) in order to obtain a liquid crystal alignment film having excellent liquid crystal alignment properties.

The ratio of the structural unit represented by the above formula (2) to the polyimine precursor containing the structural unit represented by the above formula (2) and the ruthenium imidized polymer of the polyimine precursor The total structural unit in the material is preferably from 60 mol% to 100 mol%, in terms of 1 mol. The ratio of the structural unit represented by the above formula (2) is preferably 80 mol% to 100 mol%, more preferably 90 mol%, in order to obtain a liquid crystal alignment film having good liquid crystal alignment. ~100% of the mole is better.

In addition to the structural unit represented by the above formula (2), the component (A) of the present invention may be a polyimine precursor having a structural unit represented by the following formula (7) and the polyimine precursor. Iridium imidized polymer.

In the formula (7), R ₁ is synonymous with R ₁ Department of the formula (2) of the. X ₃ is a tetravalent organic group, and the structure is not particularly limited. Specific examples are given by the structures of the following formulae (X-9) to (X-42). From the viewpoint of the availability of the compound, X may be X-17, X-25, X-26, X-27, X-28, X-32 or X-39. Further, from the viewpoint of obtaining a liquid crystal alignment film which rapidly relaxes the residual charge accumulated in the DC voltage, it is preferable to use a tetracarboxylic dianhydride having an aromatic ring structure, and X to X-26, X-27, X-28, X-32, X-35 or X-37 are better.

In the above formula (7), Y ₃ is a divalent organic group, and the structure is not particularly limited. Specific examples of Y ₃ include the following formulas (Y-1) to (Y-74).

In order to improve the solubility of the organic solvent of the component (A), the structural aspects other than the formula (4) and the formula (5) are contained in the presence of Y-8, Y-20, Y-21, Y-22, Y. -28, Y-29, Y-30, Y-72, Y-73 or Y-74 structural units are preferred.

When the ratio of the structural unit represented by the above formula (7) is high in the component (A), the liquid crystal alignment property of the liquid crystal alignment film is lowered, and the ratio of the structural unit represented by the above formula (7) is 1 to the total structural unit. For the ear, it is preferably 0 to 40 mol%, and 0 to 20 mol% is more preferably.

<(B) component>

The component (B) of the present invention is a polymer having a structure represented by the following formula (1).

[化31]-W ₁ -AW ₂ - (1)

In the formula (1), W ₁ and W ₂ are each independently a divalent organic group having an aromatic group having 6 to 30 carbon atoms, which may be the same or different. Examples of the aromatic group contained in W ₁ and W ₂ include benzene, naphthalene, anthracene, biphenyl or triphenyl. A is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. Examples of the alkyl group having 2 to 20 carbon atoms include 1,1-extended ethyl group, 1,2-extended ethyl group, 1,2-extended propyl group, 1,3-propanyl group, and 1,4- Butyl, 1,5-extended pentamyl, 1,6-extended hexyl, 2,3-butylene, 2,4-exopentyl and the like.

In order to obtain a liquid crystal alignment film having high liquid crystal alignment, the component (B) is an imidization polymerization of a polyimine precursor containing a structure represented by the above formula (1) and the polyimide precursor. It is preferred that at least one polymer selected from the group of the objects is formed.

Specifically, at least one selected from the group consisting of a polyimine precursor having a structural unit represented by the following formula (3) and a quinone imidized polymer of the polyimine precursor Better.

In the formula (3), the R _{2 group} is synonymous with R _{1 of the} above formula (2), and preferred examples are also included. A ₁ and A ₂ each independently represent a hydrogen atom or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent, and may be the same as the above-mentioned alkyl group, alkenyl group or alkynyl group. structure.

The alkyl group, the alkenyl group, and the alkynyl group described above may have a substituent of a carbon number of from 1 to 10, and may form a ring structure by a substituent. Further, the formation of a ring structure by a substituent means that a substituent or a substituent is bonded to a part of a parent skeleton to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, and a phosphate group. , amidino, alkyl, alkenyl, alkynyl.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

A phenyl group is mentioned as an aryl group of a substituent. The aryl group may be further substituted with the other substituents described above.

The organooxy group as a substituent may represent a structure represented by O-R. These R may be the same or different, and the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group and the like can be exemplified. R for these may be substituted with the above substituents. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

As the organothio group as a substituent, a structure represented by -S-R can be represented. In the aspect of R, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group or the like can be exemplified. R for these may be substituted with the above substituents. Alkylthio group Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group and the like.

The aspect of the organoalkylene group as a substituent may represent a structure represented by -Si-(R) ₃ . These R may be the same or different, and the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group and the like can be exemplified. R for these may be substituted with the above substituents. Specific examples of the alkyl fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group, a tripentyl decyl group, a trihexyl decyl group, and a pentyl group. Methyl decyl group, hexyl dimethyl decyl group, and the like.

As the thiol group of the substituent, a structure represented by -C(O)-R can be represented. In the aspect of R, the aforementioned alkyl group, alkenyl group, aryl group or the like can be exemplified. R for these may be substituted with the above substituents. Specific examples of the mercapto group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group, and the like.

The ester group as a substituent may represent a structure represented by -C(O)O-R or -OC(O)-R. Examples of the R include, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. R for these may be substituted with the above substituents.

The thioester group as a substituent may represent a structure represented by -C(S)O-R or -OC(S)-R. Examples of the R include, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. R for these may be substituted with the above substituents.

As the phosphate group of the substituent, a structure represented by -OP(O)-(OR) ₂ can be represented. These R may be the same or different, and the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group and the like can be exemplified. R for these may be substituted with the above substituents.

As the amide group of the substituent, it may represent -C(O)NH ₂ , -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ or -NRC(O)R The configuration shown. These R may be the same or different, and the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group and the like can be exemplified. R for these may be substituted with the above substituents.

The aryl group as a substituent may be the same as the above-mentioned aryl group. The aryl group may be further substituted with the other substituents described above.

The alkyl group as a substituent is the same as the above-mentioned alkyl group. The alkyl group may be further substituted with the other substituents described above.

The alkenyl group as a substituent may be the same as the above-mentioned alkenyl group. The alkenyl group may be further substituted with the other substituents described above.

The alkynyl group as a substituent is the same as the alkynyl group mentioned above. The alkynyl group may be further substituted with the other substituents described above.

In general, when a bulky structure is introduced, the reactivity of the amine group or the liquid crystal alignment property is lowered, and the A ₁ and A ₂ groups are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. Preferably, it is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

X ₂ is a tetravalent organic group having an aromatic group having 6 to 20 carbon atoms and having a bond to an aromatic group. Examples of the aromatic group having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, biphenyl, and triphenyl. In order to improve the interaction with the liquid crystal and to enhance the effect of suppressing the afterimage, it is preferable that the X ₂ is a tetravalent organic group formed only of an aromatic group, and more preferably, the following formula (X2-1) )~ (X2-3) shows the structure. Among them, the structure shown by the formula (X2-1) is particularly preferable.

Y ₂ is at least one divalent organic group selected from the group consisting of the following formulas (Y2-1) to (Y2-2).

In the formula (Y2-1), A ₃ is a divalent organic group having an alkylene group having 2 to 20 carbon atoms, and may have a plurality of alkylene groups. Examples of the alkyl group having 2 to 20 carbon atoms include 1,1-extended ethyl group, 1,2-extended ethyl group, 1,2-extended propyl group, 1,3-propanyl group, and 1,4- Butyl, 1,5-extended pentamyl, 1,6-extended hexyl, 2,3-butylene, 2,4-exopentyl and the like. From the viewpoint of liquid crystal alignment, A ₃ is preferably a divalent organic group having an alkylene group having 2 to 10 carbon atoms.

In the formula (Y2-2), A ₄ is a single bond, -O-, -S-, -NR ₁₂ -, an ester bond, a guanamine bond, a thioester bond, a urea bond, a carbonate bond or a urethane. A bond; R ₁₂ is a hydrogen atom, a methyl group or a t-butoxycarbonyl group, and these may represent the same configuration as described above. From the viewpoint of liquid crystal alignment, A ₅ is an alkylene group having 2 to 20 carbon atoms and may have the same structure as the above-mentioned alkylene group. From the viewpoint of liquid crystal alignment, the A ₄ is preferably a single bond, and the A ₅ is preferably a C 2 to 6 alkyl group.

Specific examples of Y ₂ which can improve the interaction with the liquid crystal and improve the liquid crystal alignment property include the structures represented by the following formulas (Y2-3) to (Y2-12). Among them, the structure shown by the following formula (Y2-3) is particularly preferable.

The ratio of the structural unit represented by the above formula (3) to the polyimine precursor containing the structural unit represented by the above formula (3) and the ruthenium imidized polymer of the polyimine precursor The total structural unit in the material is preferably from 60 mol% to 100 mol%, in terms of 1 mol. The ratio of the structural unit represented by the above formula (3) is preferably 80 mol% to 100 mol%, more preferably 90 mol%, in order to obtain a liquid crystal alignment film having good liquid crystal alignment. ~100% of the mole is better.

The component (B) used in the present invention may be a polyimine precursor containing a structural unit represented by the following formula (8) in addition to the structural unit represented by the above formula (3), and the polyazide. An amine imidized polymer of an amine precursor.

In the formula (8), R ₂ , A ₁ and A ₂ are synonymous with R ₂ , A ₁ and A ₂ in the formula (3), and preferred examples are also included. X ₄ is a tetravalent organic group having an alicyclic group, and the structure is not particularly limited as long as it is a tetravalent organic group having an alicyclic group. Specific examples thereof include the above formulas (X1-1) to (X1-9), (X-9) to (X-15), (X-22 to 25), and (X-39). ), (X-40). Y ₄ is a divalent organic group, and its structure is not particularly limited. Specific examples thereof include the above formulas (Y2-3) to (Y2-12), the above formula (4), the above formula (5), and the formula (Y-1) to (Y-74). .

When the ratio of the structural unit represented by the above formula (8) contained in the component (B) is high, the liquid crystal alignment property of the liquid crystal alignment film is lowered, so the ratio of the structural unit represented by the above formula (8) is In terms of 1 mol of the whole structural unit, it is preferably 0 to 40 mol%, more preferably 0 to 20 mol%.

<Method for producing polyimine precursor>

The polyphthalamide which is a polyimide precursor used in the present invention can be synthesized by the methods shown in the following (1) to (3).

(1) When synthesized from polyaminic acid

Polyammonium esters can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine.

Specifically, the polyglycolic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 times. Hours to synthesize.

In terms of the esterifying agent, it is preferably one which can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide II. Acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide -t-butyl phthalic acid, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyl III Nitroene, 4-(4,6-dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholine ruthenium chloride, and the like. The amount of the esterifying agent to be added is preferably 2 to 6 mol equivalents per 1 mol of the repeating unit of the polyamic acid.

The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the polymer. One type may be used or two or more types may be used in combination. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer is unlikely to occur and that a high molecular weight body can be easily obtained.

(2) When synthesized by the reaction of a tetracarboxylic acid diester dichloride with a diamine

Polyammonium esters can be synthesized from tetracarboxylic acid diester dichlorides and diamines.

Specifically, the tetracarboxylic acid diester dichloride and the diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours. Good for 1~4 hours to synthesize.

Among the above-mentioned bases, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used. However, in order to stably carry out the reaction, pyridine is preferred. The amount of the base to be added is preferably from 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and one type or mixture of two can be used. More than one kind. The concentration of the polymer at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer is less likely to occur and that a high molecular weight body is easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent used for the synthesis of the polyphthalate is dehydrated as much as possible, and it is preferable to avoid the intrusion of external air in a nitrogen atmosphere.

(3) When synthesizing poly-proline from tetracarboxylic acid diester and diamine

Polyammonium esters can be synthesized by polycondensation of a tetracarboxylic acid diester with a diamine.

Specifically, the tetracarboxylic acid diester and the diamine are reacted in the presence of a condensing agent, a base, and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C for 30 minutes to 24 hours, preferably. It is synthesized for 3 to 15 hours.

Among the above condensing agents, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride can be used. N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazaphenylmethylmorpholine oxime, O-(benzotriazol-1-yl)-N,N,N ',N'-Tetramethylhydrazine tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylphosphonium hexafluorophosphate, (2,3 - Dihydro-2-thioketo-3-benzoxazolinyl)phosphonic acid diphenyl or the like. The amount of the condensing agent to be added is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.

Among the above bases, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is preferably from 2 to 4 times the molar amount of the diamine component from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

Further, in the above reaction, the addition of Lewis acid as an additive allows the reaction to proceed more efficiently. In terms of Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The amount of Lewis acid added is preferably from 0 to 1.0 times the molar amount of the diamine component.

In the synthesis method of the above three polyglycolates, in order to obtain a high molecular weight polyphthalate, the synthesis method of the above (1) or (2) is particularly preferable.

The polypolyurethane solution obtained as described above can be poured into a poor solvent while being more agitated to precipitate a polymer. The precipitation is carried out several times, washed with a poor solvent, and dried at room temperature or under heating to obtain a purified polyphthalate powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl quercetin, acetone, toluene, and the like.

<Method for producing polylysine>

The polyamic acid used in the present invention as a polyimide precursor can be synthesized by the method shown below.

Specifically, the tetracarboxylic dianhydride and the diamine may be reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 12 hours. Hours to synthesize.

The organic solvent used in the above reaction is N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in terms of solubility of the monomer and the polymer. It is preferable to use one type or a mixture of two or more types. The concentration of the polymer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer is less likely to occur and that a high molecular weight body is easily obtained.

The obtained polyamic acid is prepared as described above by allowing the reaction solution to be injected into a poor solvent while stirring more, thereby recovering the polymer. Further, the precipitate is precipitated several times, washed with a poor solvent, and dried at room temperature or under heating to obtain a purified polyphthalate powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl quercetin, acetone, toluene, and the like.

<Method for producing polyimine]

The polyimine used in the present invention can be produced by ruthenium imidization of a polyamidimide precursor such as polylysine or polylysine. When the polyimine is produced from a polyphthalate, the polypolyurethane solution or the polyphthalate resin powder is dissolved in an organic solvent, and the resulting polymer is obtained. The chemical imidization of a basic catalyst to a proline solution is simple. The chemical ruthenium iodization allows the ruthenium imidization reaction to proceed at a lower temperature, and the molecular weight reduction of the polymer is less likely to occur during the imidization process.

The chemical imidization can be carried out by stirring a polyphthalate to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, a solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is more preferable because it has sufficient alkalinity when the reaction proceeds.

The temperature at which the ruthenium imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be carried out for 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid ester group. The oxime imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time. In the solution after the imidization reaction, the added catalyst or the like remains, and the obtained quinone imidized polymer is recovered by the following means and re-dissolved in an organic solvent to obtain the liquid crystal alignment of the present invention. The agent is better.

When the polyimine is produced from polyamic acid, it is simple to chemically add a catalyst to the solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic dianhydride. The chemical ruthenium iodization allows the ruthenium imidization reaction to proceed at a lower temperature, and the molecular weight reduction of the polymer is less likely to occur during the imidization process.

Chemical ruthenium iodization by polymerization which is intended to imidize The mixture is stirred in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, a solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a suitable basicity when the reaction proceeds. Further, as the acid anhydride, anhydrous acetic acid, anhydrous trimellitic acid, anhydrous pyromellitic acid, or the like may be used. Among them, when anhydrous acetic acid is used, it is preferred because it is easily purified after completion of the reaction.

The temperature at which the ruthenium imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be carried out for 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid group, and the amount of the acid anhydride is 1 to 50 moles of the amic acid group. Ear times, preferably 3 to 30 moles. The oxime imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time.

In the solution after the imidization reaction of the polyperurethane or polylysine, the added catalyst or the like remains, and the obtained ruthenium-imided polymer is recovered by the following means to be organic. It is preferred that the solvent is redissolved as the liquid crystal alignment agent of the present invention.

The solution of the obtained polyimine is carried out as described above, and it can be poured into a poor solvent while stirring more, and the polymer is precipitated. The precipitation is carried out several times, washed with a poor solvent, and dried at room temperature or under heating to obtain a purified polyphthalate powder.

The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl quercetin, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention has a form of a solution in which the component (A) and the component (B) are dissolved in an organic solvent. The molecular weight of the polymer of the component (A) and the component (B) is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 5,000 to 50,000.

The concentration of the polymer containing the component (A) and the component (B) contained in the liquid crystal alignment agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed, but uniform and defect-free. In view of the coating film, it is preferable that it is 1% by mass or more, and it is preferably 10% by mass or less from the viewpoint of storage stability of the solution. In particular, it is preferably 2 to 8 mass%.

The component (A) in the liquid crystal alignment agent of the present invention exhibits high anisotropy when irradiated with polarized radiation, and exhibits good liquid crystal alignment when it is a liquid crystal alignment film, and is usually used for an organic solvent. It is contained in an amount of 1 to 10% by mass, preferably 2 to 8% by mass. In addition, if the content of the component (B) contained in the liquid crystal alignment agent is too large, the anisotropy cannot be obtained even if the radiation of the polarized light is irradiated, and the liquid crystal alignment property is insufficient, and if it is too small, sufficient invention cannot be obtained. The effect. Therefore, the content of the component (B) is preferably 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass per 100 parts by mass of the component (A).

The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can be uniformly dissolved in the component (A) and the component (B). Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2- Pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl azine, dimethyl碸, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, even a solvent in which the polymer component cannot be uniformly dissolved alone can be mixed into the above-mentioned organic solvent insofar as the polymer does not precipitate.

The liquid crystal alignment agent of the present invention may contain a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate, in addition to the organic solvent for dissolving the polymer. As the solvent, generally, a solvent having a lower surface tension than the above organic solvent can be used. To cite specific examples, ethyl acesulfame, butyl acesulfame, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1 -Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol Diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cyproterone acetate, dipropylene glycol, 2-( 2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more kinds.

In addition to the above, the liquid crystal alignment agent of the present invention may be added with the components (A) and (B) insofar as the effects of the present invention are not impaired. For the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, the polymer other than the polymer is a dielectric or conductive material for changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film. A phthalocyanine coupling agent, a crosslinkable compound for the purpose of improving the hardness or density of a film as a liquid crystal alignment film, or even an imidization of a ruthenium phthalate when the film is fired. Amidoxime accelerator and the like.

<Liquid alignment film>

In the liquid crystal alignment film of the present invention, a liquid crystal alignment agent is applied onto a substrate, dried, and fired to obtain a coating film, and the surface of the coating film is irradiated with polarized light to have almost linear radiation.

The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. From the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. Further, in the reflective liquid crystal display device, it is also possible to use a single-sided substrate in an opaque material such as a germanium wafer, and a material such as aluminum or the like can be used as the electrode. Examples of the method of applying the liquid crystal alignment agent of the present invention include a spin coating method, a printing method, and an ink jet method.

The drying and baking steps after applying the liquid crystal alignment agent of the present invention may be selected to any temperature and time. Usually, in order to sufficiently remove the organic solvent contained, it can be dried at 50 ° C to 120 ° C for 1 minute to 10 minutes, and then fired at 150 ° C to 300 ° C for 5 minutes to 120 minutes. Thickness of film after firing It is not particularly limited, and if it is too thin, the reliability of the liquid crystal display element is lowered, so it is 5 to 300 nm, preferably 10 to 200 nm.

The liquid crystal alignment agent of the present invention is particularly useful for use in a photoalignment process.

Specific examples of the photo-alignment treatment method include radiation that is polarized in a certain direction on the surface of the coating film, and may be heat-treated at a temperature of 150 to 250 ° C as appropriate to impart a liquid crystal alignment energy. For the wavelength of the radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among them, ultraviolet rays having a wavelength of from 100 nm to 400 nm are preferred, and those having a wavelength of from 200 nm to 400 nm are particularly preferred. Further, in order to improve the liquid crystal alignment property, the coated substrate can be irradiated with radiation while being heated at 50 to 250 °C. The amount of radiation irradiated to the bit 1 ~ 10,000mJ / cm ² and the preferred, particularly preferred are the range of ² at 100 ~ 5,000mJ / cm.

In order to excite the realignment of the component (B), it is preferred to heat the polarized ultraviolet light and heat it at a temperature of 150 to 250 ° C, and it is more preferable to heat it at a temperature of 200 to 250 ° C.

<Liquid crystal display element>

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above-described method, and after alignment treatment, a liquid crystal cell is produced by a known method to obtain a liquid crystal display element.

The method for producing the liquid crystal cell is not particularly limited. For example, in a general method, a pair of substrates on which a liquid crystal alignment film is formed is disposed inside the liquid crystal alignment film surface, and a spacer of preferably 1 to 30 μm, more preferably 2 to 10 μm is trapped. After setting, the periphery is fixed with a sealant, and the liquid crystal is injected and sealed. The method of encapsulating the liquid crystal is not particularly limited, and a vacuum method in which a liquid crystal cell is prepared in a reduced pressure state and then injected into a liquid crystal, a dropping method in which a liquid crystal is dropped, and the like are exemplified.

[Examples]

The invention is illustrated in more detail below by way of examples, but the invention is not limited thereto. Further, the compounds used in the examples and comparative examples are abbreviated as follows and the measurement methods of the respective properties are as follows.

NMP: N-methyl-2-pyrrolidone

BCS: Butyl cypress

GBL: γ-butyrolactone

AIBN: 2,2'-azobisisobutyronitrile

DA-1: the following formula (DA-1)

DA-2: the following formula (DA-2)

MA1: the following formula (MA-1)

[viscosity]

In the synthesis example, the viscosity of the polyphthalate and the poly-proline solution was E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample volume 1.1 mL, and conical rotor TE-1 (1° 34'). , R24), measured at a temperature of 25 ° C.

[molecular weight]

Further, the molecular weight of the polyglycolate is measured by a GPC (normal temperature colloidal osmosis chromatography) apparatus, and the number average molecular weight is calculated by a value of polyethylene glycol or polyethylene oxide (hereinafter also referred to as It is Mn) and a weight average molecular weight (hereinafter also referred to as Mw).

GPC device: manufactured by Shodex (GPC-101)

Pipe column: made by Shodex (KD803, KD805 series)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (additive lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) 10ml/L

Flow rate: 1.0ml/min

Standard sample for calibration line preparation: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000) manufactured by TOSOH Co., Ltd. and polyethylene glycol manufactured by POLYMER LABORATORY (peak high molecular weight (Mp) ) about 12,000, 4,000, 1,000). In the measurement, in order to avoid peak overlap, it is mixed 900,000, Samples of four types of 100,000, 12,000, and 1,000, and samples of three types of 150,000, 30,000, and 4,000 were mixed, and two samples were separately measured.

[FCS drive liquid crystal cell AC drive burn-in]

A glass substrate in which a driving electrode is formed on a glass substrate, wherein the first layer is an ITO electrode having an electrode thickness of 50 nm, and the second layer is nitrided at a thickness of 500 nm as an insulating film.边缘, the third layer of the electrode of the ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm) which is a pectinate-shaped electrode (Fringe Field Switching, also referred to as FFS) driving electrode . A liquid crystal alignment agent is applied to the substrate by spin coating. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 250 ° C for 60 minutes to form a coating film having a film thickness of 100 nm. The coating film was irradiated with ultraviolet rays of 254 nm through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, on the glass substrate having a columnar spacer having a height of 4 μm in which the electrode was not formed as the counter substrate, a coating film was formed in the same manner, and the alignment treatment was performed.

In the above, the sealant is printed on the substrate in a group of two substrates, and the other substrate is bonded so that the alignment direction of the liquid crystal alignment film surface is 0°, and then the sealant is cured to form an empty cell. . In this empty cell, liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected by a reduced pressure injection method, and after the injection port was sealed, an FFS driving liquid crystal cell was obtained.

After measuring the VT characteristic (voltage-transmittance characteristic) of the FFS-driven liquid crystal cell at a temperature of 58 ° C, a rectangular wave of ±4 V / 120 Hz was applied for 4 hours. After 4 hours, the voltage was cut off and left at a temperature of 58 ° C for 60 minutes. Then, the VT characteristics were measured again, and the voltage difference (ΔV ₅₀ ) when the transmittance before and after the application of the rectangular wave was 50% was calculated.

(Synthesis Example 1)

After adding 2394 g of NMP to a 3000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 196.34 g (1.00 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added. While stirring the slurry of the tetracarboxylic dianhydride, 101.11 g (0.935 mol) of p-phenylenediamine was added, and NMP was further added to make the solid content concentration 8% by mass, and stirred at room temperature for 24 hours to obtain a polydecylamine. A solution of acid (PAA-1). The viscosity of the polyamic acid solution at a temperature of 25 ° C is 115 mPa. s.

(Synthesis Example 2)

Into a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 5.73 g (20.0 mmol) of 1,5-bis(4-aminophenoxy)pentane was placed and N5.4 6 g was added thereto, while blowing The mixture was stirred while stirring with nitrogen. 4.19 g (19.2 mmol) of pyromellitic dianhydride was added while stirring the diamine solution, and NMP was further added to make the solid content concentration 12% by mass, and stirred at room temperature for 24 hours to obtain poly-proline (PAA- 2) The solution. The polyamic acid solution has a viscosity of 520 mPa at a temperature of 25 ° C. s.

(Synthesis Example 3)

Into a 300 ml four-necked flask equipped with a stirring device, 5.42 g (19.2 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid was placed, and 100 g of NMP was added thereto, followed by stirring to dissolve. Next, 4.45 g (43.98 mmol) of triethylamine and 5.17 g (20.0 mmol) of 1,3-bis(4-aminophenoxy)propane were added, and the mixture was stirred and dissolved. Add 4-(4,6-dimethoxy-1,3,5-triazaben-2-yl)-4-methylpropofolinium chloride (15±2% by weight) while stirring the solution 16.60 g of hydrate), 13.74 g of NMP was further added, and it was made to react for 4 hours under water cooling.

In 872 g of 2-propanol, the obtained polyphthalate solution was added while stirring, and the precipitate was collected by filtration, followed by washing 5 times with 290 g of 2-propanol and drying to obtain polyamine. Acid resin powder. The molecular weight of this polyphthalate was Mn=13462 and Mw=28462.

Into a 50 ml Erlenmeyer flask, 1.08 g of the obtained polyphthalate resin powder was placed, and 9.78 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-1).

(Synthesis Example 4)

After adding 309 g of GBL to a 1000 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 67.25 g was added. (30.0 mmol). Next, NMP 487g was added. While stirring the slurry of the tetracarboxylic dianhydride, 31.14 g (28.80 mmol) of p-phenylenediamine was added, and NMP was added to make the solid content concentration 10% by mass, and stirred at room temperature for 24 hours to obtain polylysine. A solution of (PAA-3). The polyamic acid solution has a viscosity of 471 mPa at a temperature of 25 ° C. s.

(Synthesis Example 5)

To a 300 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 6.43 g (59.46 mmol) of p-phenylenediamine and 2.49 g (10.49 mmol) of DA-1 were added, and 195 g of NMP was placed and stirred. Dissolved. While stirring the solution, 15.09 g (67.31 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added to make the solid content concentration 10% by mass. Stir at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-4). The polyamic acid solution has a viscosity of 230 mPa at a temperature of 25 ° C. s.

(Synthesis Example 6)

To a 300 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 11.93 g (39.98 mmol) of DA-2 was added, and 162 g of NMP was placed and stirred to dissolve. While stirring this solution, 8.03 g (36.82 mmol) of pyromellitic dianhydride was added, and NMP was added to make the solid content concentration 10% by mass, and stirred at room temperature for 24 hours to obtain polyglycine (PAA-5). Solution. The viscosity of the polyaminic acid solution at a temperature of 25 ° C is 108 mPa. s.

(Synthesis Example 7)

Into a 300 ml four-necked flask equipped with a stirring device, 5.19 g (18.4 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid was placed, and 107 g of NMP was added thereto, followed by stirring to dissolve. Next, 4.45 g (44.0 mmol) of triethylamine and 6.00 g of 1,6-bis(4-aminophenoxy)hexane were added. (19.97 mmol), stirred to dissolve. While stirring this solution, 16.88 g of diphenyl (2,3-dihydroxy-2-thioketo-3-benzoxazolyl)phosphonate was added, and 15 g of NMP was further added thereto, and the mixture was reacted for 4 hours under water cooling. Into 2-propanol, 614 g of the obtained polyamidate solution was added thereto while stirring, and the deposited precipitate was collected by filtration, and then washed with 307 g of 2-propanol for 5 times and dried to obtain polylysine. Ester resin powder.

The molecular weight of this polyphthalate was Mn = 6286 and Mw = 17648.

Into a 50 ml Erlenmeyer flask, 2.00 g of the obtained polyphthalate resin powder was placed, and 18.04 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-2).

(Synthesis Example 8)

Into a 300 ml four-necked flask equipped with a stirring device, 5.19 g (18.4 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid was placed, and 109 g of NMP was added thereto, followed by stirring to dissolve. Next, 4.45 g (44.0 mmol) of triethylamine and 6.28 g (19.97 mmol) of 1,7-bis(4-aminophenoxy)heptane were added and stirred to dissolve. While stirring this solution, 16.87 g of diphenyl (2,3-dihydroxy-2-thioketo-3-benzoxazolyl)phosphonic acid was added, and 15 g of NMP was further added thereto, and the mixture was reacted for 4 hours under water cooling. 629 g of the obtained polyamidite solution was added to 2-propanol with stirring, and the deposited precipitate was collected by filtration, and then washed with 314 g of 2-propanol 5 times and dried to obtain a polyamidate. Resin powder.

The molecular weight of this polyphthalate was Mn=5004 and Mw=17542.

The obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask. At the end of 2.00 g, 18.02 g of NMP was added, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-3).

(Synthesis Example 9)

Into a 300 ml four-necked flask equipped with a stirring device, 5.19 g (18.4 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid was placed, and 112 g of NMP was added thereto, followed by stirring to dissolve. Next, 4.45 g (44.0 mmol) of triethylamine and 6.56 g (19.97 mmol) of 1,8-bis(4-aminophenoxy)octane were added, and the mixture was stirred and dissolved. While stirring this solution, 16.87 g of diphenyl (2,3-dihydroxy-2-thioketo-3-benzoxazolyl)phosphonic acid was added, and 15 g of NMP was further added thereto, and the mixture was reacted for 4 hours under water cooling. 642 g of the obtained polyamidite solution was added to 2-propanol with stirring, and the precipitate was collected by filtration, and then washed with 321 g of 2-propanol for 5 times and dried to obtain a polyamidate. Resin powder.

The molecular weight of this polyphthalate was Mn=6319 and Mw=17702.

Into a 50 ml Erlenmeyer flask, 2.00 g of the obtained polyphthalate resin powder was placed, and 18.01 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-4).

(Synthesis Example 10)

In a 300 ml four-necked flask equipped with a stirring device, 12.1 g (35.0 mmol) of MA1 was placed, and 111.7 g of NMP was added thereto, dissolved, and then degassed by a diaphragm pump for 6 minutes. Thereafter, 0.287 g (1.80 mmol) of AIBN was added, followed by degassing for 6 minutes. this Thereafter, the mixture was reacted at 60 ° C for 30 hours to obtain a methacrylate polymer solution (MA-1). The polymer had a number average molecular weight of 13,000 and a weight average molecular weight of 51,000.

(Example 1)

To a 20 ml sample tube in which a stirrer was placed, 7.13 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 1 and 0.29 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 2 were added. NMP 4.60 g and BCS 3.02 g were stirred by a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-1).

(Example 2)

To a 20 ml sample tube in which a stirrer was placed, 3.95 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 1 and 0.19 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 2 were added. NMP 3.88 g, BCS 2.00 g, and 0.02 g of 1-butylimidazole were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-2).

(Example 3)

To a 20 ml sample tube in which a stirrer was placed, 3.79 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 1 and 0.39 g of the polyamidonic acid solution (PAA-2) obtained in Synthesis Example 2 were added. NMP 3.89 g, BCS 2.00 g, and 1-butylimidazole 0.02 g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-3).

(Example 4)

To a 20 ml sample tube in which a stirrer was placed, 7.42 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 1 and the polyamine solution (PAE-1) 0.08 obtained in Synthesis Example 3 were added. g, NMP 4.53g and BCS 3.03g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-4).

(Comparative Example 1)

To a 20 ml sample tube in which a stirrer was placed, 4.16 g of a polyaminic acid solution (PAA-1) obtained in Synthesis Example 1, 3.82 g of NMP, and 2.0 g of BCS were added, and stirred by a magnetic stirrer for 30 minutes to obtain a liquid crystal. Orienting agent (B-1).

(Example 5)

After the liquid crystal alignment agent (A-1) obtained in Example 1 was filtered through a 1.0 μm filter, a glass substrate having an FFS driving electrode was formed on a glass substrate (the FFS driving electrode has the first layer) The ITO electrode having a film thickness of 50 nm, the second layer being an insulating film having a thickness of 500 nm, and the third layer being an ITO electrode having a pectinate shape (electrode width: 3 μm, electrode spacing: 6 μm, electrode height) On: 50 nm)), coating was carried out by spin coating. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 230 ° C for 15 minutes to form a coating film having a film thickness of 100 nm. The coating film was irradiated with a 254 nm ultraviolet light of 1500 mJ/cm ² through a polarizing plate, and heated in a hot air circulating oven at 230 ° C for 30 minutes to obtain a substrate with a liquid crystal alignment film. Further, on the glass substrate having a columnar spacer having a height of 4 μm on which the electrode was not formed as the counter substrate, a coating film was formed in the same manner, and an alignment treatment was performed.

In the above, the sealant is printed on the substrate in a group of two substrates, and the other substrate is bonded so that the alignment direction of the liquid crystal alignment film surface is 0°, and then the sealant is cured to form an empty cell. . In this empty cell, liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected by a reduced pressure injection method, and after the injection port was sealed, an FFS driving liquid crystal cell was obtained. In this case, the FFS drives the liquid crystal cell and evaluates the results of the AC drive sintering characteristics, and the ΔV ₅₀ is 1.8 mV.

(Example 6)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-2) obtained in Example 2 was used. In this case, the FFS was driven to drive the liquid crystal cell, and as a result of evaluating the AC drive sintering characteristics, ΔV ₅₀ was 1.3 mV.

(Example 7)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-3) obtained in Example 3 was used. In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC drive sintering characteristic was evaluated, and ΔV ₅₀ was 1.2 mV.

(Example 8)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-4) obtained in Example 4 was used. In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC-driven burning characteristics was evaluated, and ΔV ₅₀ was 1.1 mV.

(Comparative Example 2)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 6 except that the liquid crystal alignment agent (B-1) obtained in Comparative Example 1 was used. In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC drive sintering characteristics was evaluated, and ΔV _{50 was 5.0} mV.

(Example 9)

To the 50 ml sample tube in which the stirrer was placed, 16.29 g of the polyaminic acid solution (PAA-3) obtained in Synthesis Example 4, and the polyaminic acid solution (PAA-2) obtained in Synthesis Example 2 (0.45 g) were added. , NMP 7.38g, BCS 6.05g and N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine as a ruthenium promoter 0.23g , stirring with a magnetic stirrer for 30 minutes A liquid crystal alignment agent (A-5) was obtained.

(Embodiment 10)

To the 50 ml sample tube in which the stirrer was placed, 10.79 g of the polyaminic acid solution (PAA-3) obtained in Synthesis Example 4, and the polyaminic acid solution (PAA-5) obtained in Synthesis Example 6 were added to 0.31 g. , NMP 5.03g, BCS 6.05g and N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine as a ruthenium promoter The electromagnetic stirrer was stirred for 30 minutes to obtain a liquid crystal alignment agent (A-6).

(Example 11)

To a 50 ml sample tube in which a stirrer was placed, 10.90 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 5 and 0.10 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 2 were added. , NMP 5.08g, BCS 4.26g and N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine 0.15g as a ruthenium promoter The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-7).

(Embodiment 12)

To a 20 ml sample tube in which a stirrer was placed, 7.45 g of the polyamidonic acid solution (PAA-4) obtained in Synthesis Example 5, and the polyamidate solution (PAE-2) obtained in Synthesis Example 7 were added to 0.08 g. g, NMP 4.39g, BCS 3.02g and N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine 0.08 as a ruthenium promoter g, stir with a magnetic stirrer for 30 minutes A liquid crystal alignment agent (A-8) was obtained.

(Example 13)

To a 20 ml sample tube in which a stirrer was placed, 7.43 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 5, and the polyamine solution (PAE-3) obtained in Synthesis Example 8 were added. g, NMP 4.38g, BCS 3.11g and N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine 0.08 as a ruthenium promoter g, stirring with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-9).

(Example 14)

To a 20 ml sample tube in which a stirrer was placed, 7.43 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 5, and the polyamidate solution (PAE-4) 0.08 obtained in Synthesis Example 9 were added. g, NMP 4.35g, BCS 3.02g and N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine 0.08 as a ruthenium promoter g, stirring with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-10).

(Example 15)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-5) obtained in Example 9 was used and the ultraviolet light of 254 nm was irradiated at 500 mJ/cm ² . In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC-driven burning characteristics was evaluated, and ΔV ₅₀ was 0.8 mV.

(Embodiment 16)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-6) obtained in Example 10 was used and the ultraviolet light of 254 nm was irradiated at 500 mJ/cm ² . In this case, the FFS was driven to drive the liquid crystal cell, and as a result of evaluating the AC drive sintering characteristics, ΔV ₅₀ was 1.0 mV.

(Example 17)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-7) obtained in Example 11 was used and the ultraviolet light of 254 nm was irradiated at 500 mJ/cm ² . In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC-driven burning characteristics was evaluated, and ΔV ₅₀ was 0.8 mV.

(Embodiment 18)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-8) obtained in Example 12 was used and the ultraviolet light of 254 nm was irradiated at 500 mJ/cm ² . In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC-driven burning characteristics was evaluated, and ΔV ₅₀ was 0.6 mV.

(Embodiment 19)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-9) obtained in Example 13 was used and the ultraviolet light of 254 nm was irradiated at 500 mJ/cm ² . In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC-driven burning characteristics was evaluated, and ΔV ₅₀ was 1.1 mV.

(Embodiment 20)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-10) obtained in Example 14 was used and the ultraviolet light of 254 nm was irradiated at 500 mJ/cm ² . In this case, the FFS was driven to drive the liquid crystal cell, and the result of the AC-driven burning characteristics was evaluated, and ΔV ₅₀ was 1.1 mV.

(Example 21)

To the 50 ml sample tube in which the stirrer was placed, 12.44 g of the polymer solution (M-1) obtained in Synthesis Example 10, and the polyaminic acid solution (A-2) obtained in Synthesis Example 2 were added. 0.32 g, NMP 2.08 g, and BCS 6.19 g were stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (A-11).

(Example 22)

To the 50 ml sample tube in which the stirrer was placed, 12.41 g of the polymer solution (M-1) of the methacrylate obtained in Synthesis Example 10, and the polyaminic acid solution (A-2) obtained in Synthesis Example 2 were added. 0.54 g, NMP 2.09 g, and BCS 6.20 g were stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (A-12).

(Comparative Example 3)

To a 50 ml sample tube in which a stirrer was placed, 12.44 g of a polymer solution (M-1) obtained in Synthesis Example 10 (M-1), NMP 2.05 g, and BCS 6.21 g were stirred at room temperature for 5 hours. Obtaining liquid crystal alignment agent (B-2).

(Example 23)

Using the liquid crystal alignment agent (A-11) obtained in Example 21, the production of the liquid crystal cell was carried out in the procedure shown below. The substrate was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, and a pixel electrode in the form of a pectinate formed by patterning an ITO film was used. The pixel electrode has a denture-like shape in which the electrode elements of the shape in which the central portion is not bent are plurally arranged. The short side direction of each electrode element was 10 μm wide, and the interval between the electrode elements was 20 μm. Since the pixel electrodes forming the respective pixels are formed by arranging the electrode elements of the word shape in which the central portion is not bent, the shape of each pixel is not rectangular, but is curved in the central portion similarly to the electrode elements. The shape of a word like a thick word. Further, each of the pixels is divided into upper and lower sides by a curved portion at the center thereof, and has an upper first region and a lower second region having a curved portion. The first region and the second region of each pixel are compared, and the electrode elements constituting the pixel electrodes are formed in different directions.

In other words, in the first region of the pixel, the electrode element of the pixel electrode is formed at an angle of +15° (clock rotation) in the first region of the pixel, and the second region of the pixel is formed. The electrode element of the pixel electrode is formed at an angle of -15 (clock rotation). In other words, the first region and the second region of each pixel are mutually in the direction of the rotation operation (In Plane Switching, IPS) of the liquid crystal excited by the applied voltage between the pixel electrode and the counter electrode. Reverse side Formed by the formula. The liquid crystal alignment agent (A-11) obtained in Example 21 was spin-coated on the substrate on which the above electrode was prepared. Subsequently, the film was dried on a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 160 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

Next, the coated film surface was irradiated with ultraviolet rays of 313 nm at 500 mJ/cm ² through a polarizing plate, and then heated in a hot air circulating oven at 160 ° C to obtain a substrate with a liquid crystal alignment film. Further, on the glass substrate having a columnar spacer having a height of 4 μm on which the electrode was not formed as the counter substrate, a coating film was formed in the same manner, and an alignment treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Next, the other substrate was bonded so that the alignment direction of the liquid crystal alignment film surface was 0°, and then the sealant was cured to form an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display device.

The IPS mode liquid crystal cell obtained by the above method is disposed between two polarizing plates having a polarization axis disposed vertically, and the backlight is turned on before the voltage is applied, and the arrangement angle of the liquid crystal cell is adjusted. The brightness of the transmitted light becomes minimum. Then, the rotation angle when the liquid crystal cell is rotated from the second region of the pixel to the darkest angle to the darkest angle of the first region is calculated as the initial alignment azimuth. Next, an alternating voltage of 8 V _PP was applied for 168 hours at a frequency of 30 Hz in an oven at 60 °C. Thereafter, the state in which the pixel electrode of the liquid crystal cell and the counter electrode were short-circuited was directly placed at room temperature for 1 hour. After the placement, the alignment azimuth angle was measured in the same manner, and the difference between the alignment azimuth angles before and after the AC drive was calculated as the angle Δ (deg.). The smaller the difference between the alignment directions before and after the AC drive, the better the AC drive burn-in characteristics can be judged. As a result, the difference in the azimuth angles before and after the AC drive was made such that the angle Δ (deg.) was 0.5°.

(Example 24)

An IPS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (A-12) obtained in Example 22 was used. In the same manner as in Example 23, the IPS was used to drive the liquid crystal cell, and as a result of the AC drive sintering characteristics, the difference in the azimuth angle before and after the AC drive was 0.4 deg.

(Comparative Example 4)

An IPS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (B-2) obtained in Comparative Example 3 was used. In the same manner as in Example 23, the IPS was used to drive the liquid crystal cell, and as a result of the AC drive sintering characteristics, the difference in the orientation azimuth angle before and after the AC drive was Δ° (deg.).

[Industrial Availability]

The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can reduce the afterimage caused by the AC driving in the liquid crystal display element of the IPS driving mode or the FFS driving mode, and can quickly alleviate the accumulated residual electric charge by the DC voltage. Therefore, it is particularly suitable for an IPS driving method having excellent afterimage characteristics or a liquid crystal display element of an FFS driving method or a liquid crystal alignment film of a liquid crystal television.

The entire disclosure of Japanese Patent Application No. 2011-171227, the entire disclosure of which is hereby incorporated by reference in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire content

Claims (17)

A liquid crystal alignment agent comprising the following component (A), component (B), and an organic solvent, and the content of the component (B) is 0.1 to 15 parts by mass based on 100 parts by mass of the component (A). A) component: by irradiating the polarized radiation, any reaction of photodecomposition, photodimerization or photoisomerization is performed, and anisotropy can be imparted in the same direction as the polarization direction or in the direction perpendicular to the polarization direction. One or two or more kinds of polymers; (B): a polymer having a structure represented by the following formula (1); [Chemical Formula 1]-W ₁ -AW ₂ - (1) (Formula (1) In the above, W ₁ and W ₂ are each independently a divalent organic group having an aromatic group having 6 to 30 carbon atoms; and A is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. The liquid crystal alignment agent of claim 1, wherein the component (A) is subjected to a photodecomposition reaction by irradiating the polarized radiation, and one or two kinds of anisotropy may be imparted in a direction perpendicular to the polarization direction. The above polymers. The liquid crystal alignment agent of claim 1 or 2, wherein the component (A) is a polyimine precursor containing a structural unit represented by the following formula (2) and a quinone imine of the polyimine precursor At least one polymer selected from the group of polymers; (In the formula (2), X ₁ is at least one selected from the group consisting of the structures represented by the following formulas (X1-1) to (X1-9); Y ₁ is a divalent organic group; and R ₁ is hydrogen. Atom or carbon number 1~4) (In the formula (X1-1), R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group. Or phenyl). The liquid crystal alignment agent of claim 3, wherein the component (A) is a polyimine precursor containing 60 mol% or more of a structural unit represented by the above formula (2) for 1 mol of the total structural unit; At least one selected from the group consisting of the ruthenium imidized polymer of the polyimide precursor. The liquid crystal alignment agent of claim 3 or 4, wherein, in the above formula (2), X ₁ is at least one selected from the group consisting of the structures represented by the above formula (X1-1). The liquid crystal alignment agent of any one of the above-mentioned formula (2), wherein X ₁ is a group formed by the structures represented by the following formulas (X1-10) to (X1-11) At least one selected, The liquid crystal alignment agent of any one of the above-mentioned formula (2), wherein Y ₁ is at least 1 selected from the group consisting of the structures represented by the following formulas (4) and (5). Species (In the formula (5), Z ₁ is a single bond, an ester bond, a guanamine bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms). The liquid crystal alignment agent of claim 7, wherein, in the above formula (2), Y ₁ is a structure represented by the above formula (4). The liquid crystal alignment agent according to any one of claims 1 to 8, wherein the component (B) is a polyimine precursor having a structural unit represented by the following formula (3) and the polyimine precursor And at least one polymer selected from the group consisting of imidized polymers; (In the formula (3), X ₂ is a tetravalent organic group having an aromatic group having 6 to 20 carbon atoms and having a bond to an aromatic group; and Y ₂ is represented by the following formula (Y2-1) to ( Y2-2) at least one divalent organic group selected from the group formed; A ₁ and A ₂ are each independently a hydrogen atom, or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent ; R ₂ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; (In the formula (Y2-1), A ₃ is a divalent organic group having an alkylene group having 2 to 20 carbon atoms; and in the formula (Y2-2), A ₄ is a single bond, -O-, -S-, -NR ₁₂ -, ester bond, guanamine bond, thioester bond, urea bond, carbonate bond, urethane bond; R ₁₂ hydrogen atom, methyl or t-butoxycarbonyl; A ₅ carbon A number of 2 to 20 alkyl groups). The liquid crystal alignment agent of claim 9, wherein the component (B) is a polyimine precursor containing 60 mol% or more of a structural unit represented by the above formula (3) for 1 mol of the total structural unit; At least one polymer selected from the group consisting of the ruthenium imidized polymer of the polyimine precursor. The liquid crystal alignment agent of claim 9 or 10, wherein X ₂ of the above formula (3) is at least one selected from the group consisting of the following formulas (X2-1) to (X2-3); The liquid crystal alignment agent of claim 11, wherein X ₂ of the above formula (3) is the above formula (X2-1). The liquid crystal alignment agent of any one of the above-mentioned formula (3), wherein the Y ₂ of the above formula (3) is selected from the group consisting of the following formulas (Y2-3) to (Y2-12). At least 1 species; (In the formulae (Y2-10) and (Y2-11), R _{13 is} each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may be the same or different). A liquid crystal alignment film obtained by coating and baking the liquid crystal alignment agent according to any one of claims 1 to 13. A liquid crystal alignment film obtained by coating and firing a liquid crystal alignment agent according to any one of claims 1 to 13, and irradiating the polarized radiation. A liquid crystal alignment film which is obtained by coating and baking the liquid crystal alignment agent according to any one of claims 1 to 13, and irradiating the radiation after being polarized, and heating at 150 to 300 ° C. A liquid crystal display element comprising the liquid crystal alignment film according to any one of claims 14 to 16.