JP6520716B2 - Liquid crystal aligning agent and liquid crystal display device using the same - Google Patents

Description

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

Liquid crystal display devices are known as lightweight, thin and low power consumption display devices. In recent years, high-definition liquid crystal display devices for mobile phones and tablet-type terminals, which have been rapidly increasing their share, have achieved remarkable development that high display quality is required.
The liquid crystal display element is configured by sandwiching a liquid crystal layer by a pair of transparent substrates provided with electrodes. In a liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that liquid crystals are in a desired alignment state between substrates. That is, the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate holding the liquid crystal in contact with the liquid crystal, and plays the role of aligning the liquid crystal in a certain direction between the substrates. Furthermore, the liquid crystal alignment film can control the pretilt angle of the liquid crystal. A method (see Patent Document 1) and a method (see Patent Document 2) of increasing the pretilt angle mainly by selecting a polyimide structure are known.

Japanese Patent Application Laid-Open No. 09-278724 Japanese Patent Application Laid-Open No. 10-123532

In recent years, liquid crystal display devices have been used for mobile applications such as smartphones and mobile phones. In these applications, in order to secure a display surface as large as possible, a so-called narrowing of the frame is required in which the width of the sealing agent used to bond the substrates of the liquid crystal display element is narrower than in the past. With the narrowing of the frame of the panel, the application position of the sealing agent used when producing the liquid crystal display element is to be applied at the position in contact with the end of the liquid crystal alignment film or on the upper portion of the liquid crystal alignment film. However, since polyimide has no or few polar groups, covalent bonds are not formed on the surface of the sealing agent and the liquid crystal alignment film, resulting in insufficient adhesion between the substrates. In such a case, particularly when used under high temperature and high humidity conditions, water is likely to be mixed in between the sealing agent and the liquid crystal alignment film, and display unevenness may occur in the vicinity of the frame of the liquid crystal display element. It occurs. Therefore, it becomes an issue to improve the adhesion (adhesion) between the polyimide-based liquid crystal alignment film and the sealing agent or the substrate. The improvement of the adhesion of the liquid crystal alignment film to the sealing agent and the substrate as described above needs to be achieved without lowering the liquid crystal alignment and electrical properties of the liquid crystal alignment film, and further, these properties are also required. It is required to improve the
The main object of the present invention is to provide a liquid crystal aligning agent capable of improving the adhesion between a liquid crystal alignment film and a sealing agent or a substrate without deteriorating the liquid crystal alignment property or the electrical properties.

（Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基である。Ｒ_１は、水素原子、又は炭素数１〜５のアルキル基である。Ａ_１及びＡ_２は、それぞれ独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、又は炭素数２〜１０のアルキニル基であり、これらの基は置換基を有していてもよい。）MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in order to solve the said subject. That is, the gist of the present invention is as follows.
1. The liquid crystal aligning agent characterized by containing following (A) component, (B) component, and the organic solvent.
Component (A): at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (1) and an imidized polymer of the polyimide precursor.
Component (B): a compound having a hydroxyalkylamide group.

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

（Ｘ_２は、炭素数１〜２０の脂肪族炭化水素基、又は芳香族炭化水素基を含むｎ価の有機基であり、ｎは２〜６の整数である。Ｒ_２及びＲ_３は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基、炭素数２〜４のアルケニル基、又は炭素数２〜４のアルキニル基であり、これらの基は置換基を有していてもよい。なお、Ｒ_２及びＲ_３のうち少なくとも１つは、置換基としてヒドロキシ基を有する。）2. The liquid crystal aligning agent according to the above 1, wherein the component (B) is a compound having two or more hydroxyalkylamide groups.
3. The liquid crystal aligning agent according to the above 1 or 2, wherein the component (B) is contained in an amount of 0.1 to 20% by mass with respect to the component (A).
4. 3. Liquid crystal aligning agent in any one of said 1-3 whose component (B) is represented by following formula (2).

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

（Ｒ_４〜Ｒ_７は、それぞれ独立して、水素原子、炭化水素基、又はヒドロキシ基で置換された炭化水素基である。）5. At least one of R ₂ and _{R 3,} but the following formula (3), the liquid crystal aligning agent according to any one of the above 1 to 4.

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

6. 5. The liquid crystal aligning agent as described in any one of 1 to 5 above, wherein the atom directly bonded to the carbonyl group in X ₂ is a carbon atom not forming an aromatic ring.
7. X ₂ is an aliphatic hydrocarbon group, the liquid crystal alignment agent according to any of the above 1-6.
8. R ₂ and R _3, a compound represented by the following formula (4), the liquid crystal alignment agent according to any one of the above 1 to 7.

9. 9. Liquid crystal aligning agent in any one of said 1-8 whose component (B) is one of the following compounds.

（Ｒ_８〜Ｒ_１１は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、アルケニル基、又はフェニル基である。）10. X ₁ is at least one structure selected from the group consisting of the following formulas (X-1) ~ (X -14), the liquid crystal alignment agent according to any of the above 1-9.

(R _{8 to} R ₁₁ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyl group, or a phenyl group.)

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

(Ｒ_１２は単結合、又は炭素数１〜３０の２価の有機基であり、Ｒ_１３は水素原子、ハロゲン原子又は炭素数１〜３０の１価の有機基であり、ａは１〜４の整数であり、ａが２以上の場合は、(Ｒ_１２−Ｒ_１３)は、互いに同一でも異なっていてもよい。Ｒ_１４は単結合、−Ｏ−、−Ｓ−、−ＮＲ_１５−、アミド結合、エステル結合、ウレア結合、又は炭素数１〜４０の２価の有機基であり、Ｒ_１５は、水素原子、又はメチル基である。)12. Y ₁ is at least one structure selected from the group consisting of the following formulas (5) and (6), a liquid crystal aligning agent according to any one of the above 1 to 11.

(R ₁₂ is a single bond or a divalent organic group having 1 to 30 carbon atoms, R ₁₃ is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms, a is 1 to 4 of an integer, if a is 2 or more, _(R 12 _{-R 13)} is good _{.R 14} be the same as or different from each other a single bond, -O -, - S -, - NR 15 -, amide bond, an ester bond, a urea bond, or a divalent organic group having a carbon number of 1 to 40, R ₁₅ is a hydrogen atom or a methyl group.)

13. The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent in any one of said 1-12, and baking it.
14. The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent in any one of said 1-12, and irradiating the radiation which polarized the wavelength of 100-400 nm.
15. 14. Liquid crystal aligning film as described in said 13 or 14 whose film thickness after baking is 5-300 nm.
16. The liquid crystal display element which comprises the liquid crystal aligning film in any one of said 13-15.
17. The transverse electric field drive type liquid crystal display element which comprises the liquid crystal aligning film in any one of said 13-15.

By using the liquid crystal alignment agent of the present invention, the adhesion between the sealing agent and the liquid crystal alignment film can be enhanced, and the occurrence of display unevenness near the frame of the liquid crystal display element can be suppressed under high temperature and high humidity conditions. You can get Thereby, the liquid crystal display element which has a liquid crystal aligning film of this invention can solve the display nonuniformity of a frame vicinity by improving the adhesiveness of a sealing agent and a liquid crystal aligning film, and can be a large screen and a high definition liquid crystal display.
Furthermore, by using the liquid crystal aligning agent of the present invention, it is possible to achieve the above-mentioned problems without lowering the liquid crystal alignment property or the electrical properties.

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

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

In Formula (1), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. In the polyimide precursor, two or more types of X ₁ may be mixed. If Specific examples of X _1, include the structures represented by the following formula (X-1) ~ (X -44).

R _{8 to} R ₁₁ in the above formula (X-1) 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, an alkynyl group, or phenyl It is a group. When R _{8 to} R ₁₁ have a bulky structure, a hydrogen atom, a methyl group or an ethyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable because the liquid crystal alignment may be lowered.

上記（Ｘ−１）〜（Ｘ−１４）から選ばれる構造の好ましい割合としては、Ｘ_１全体の２０モル％以上であり、より好ましくは６０モル％以上、さらに好ましくは８０モル％以上である。In formula (1), X ₁ is preferably a structure selected from (X-1) to (X-14) from the viewpoint of the availability of monomers.
Since the reliability of the liquid crystal alignment film obtained can be further enhanced, the structure of X _{1 is} a structure consisting of only aliphatic groups such as (X-1) to (X-7) and (X-10) Is preferable, and the structure represented by (X-1) is more preferable. Furthermore, to show the good liquid crystal alignment property, the structure of _{X 1,} more preferably the following formula (X1-1) or (Xl-2).

The preferred ratio of structure selected from the (X-1) ~ (X -14), and the _{X 1} total 20 mol% or more, more preferably 60 mol% or more, even more preferably at least 80 mol% .

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

Examples of the alkenyl group include those in which one or more CH ₂ —CH ₂ structures present in the above alkyl group are replaced by a CH = CH structure, and more specifically, a vinyl group, an allyl group, 1— Propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like.
Examples of the alkynyl group include those in which one or more CH ₂ -CH ₂ structures present in the above alkyl group are replaced by a C≡C structure, and more specifically, ethynyl group, 1-propynyl group, 2 -Propynyl group etc. are mentioned.

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

As a halogen group which is a substituent, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.
The aryl group which is a substituent includes a phenyl group. This aryl group may be further substituted by the other substituent described above.
As the organooxy group which is a substituent, a structure represented by -O-R can be shown. R may be the same or different and can be exemplified by the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the like described above. The substituent mentioned above may further substitute by these R. Specific examples of the organooxy 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 which is a substituent, a structure represented by -S-R can be shown. As R, the alkyl group mentioned above, an alkenyl group, an alkynyl group, an aryl group etc. can be illustrated. The substituent mentioned above may further substitute by these R. Specific examples of the organothio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group and the like.
As an organosilyl group which is a substituent, a structure represented by -Si- (R) ₃ can be shown. R may be the same or different and can be exemplified by the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the like described above. The substituent mentioned above may further substitute by these R. Specific examples of the organosilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group and the like.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. As R, the above-mentioned alkyl group, alkenyl group, aryl group and the like can be exemplified. The substituent mentioned above may further substitute by these R. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
As a substituted ester group, a structure represented by -C (O) O-R or -OC (O) -R can be shown. As R, the alkyl group mentioned above, an alkenyl group, an alkynyl group, an aryl group etc. can be illustrated. The substituent mentioned above may further substitute by these R.

As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -R can be shown. As R, the alkyl group mentioned above, an alkenyl group, an alkynyl group, an aryl group etc. can be illustrated. The substituent mentioned above may further substitute by these R.
As a phosphate ester group which is a substituent, the structure represented by -OP (O)-(OR) ₂ can be shown. R may be the same or different and can be exemplified by the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the like described above. The substituent mentioned above may further substitute by these R.

As an amide group which is a substituent, -C (O) NH ₂ or -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ , -NRC (O) R The structure represented by can be shown. The R may be the same or different and can be exemplified by the alkyl group, the alkenyl group, the alkynyl group and the aryl group described above. The substituent mentioned above may further substitute by these R.
As an aryl group which is a substituent, the same thing as the aryl group mentioned above can be mentioned. This aryl group may be further substituted by the other substituent described above.
As an alkyl group which is a substituent, the same thing as the alkyl group mentioned above can be mentioned. This alkyl group may be further substituted with any of the other substituents described above.

As an alkenyl group which is a substituent, the same thing as the alkenyl group mentioned above can be mentioned. This alkenyl group may be further substituted with any of the other substituents described above.
As an alkynyl group which is a substituent, the same thing as the alkynyl group mentioned above can be mentioned. This alkynyl group may be further substituted with any of the other substituents described above.
Generally, introducing a bulky structure may lower the reactivity of the amino group and the liquid crystal alignment, and therefore, as A ₁ and A ₂ , a hydrogen atom or a carbon number of 1 which may have a substituent The alkyl group of 5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

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

（式（Ｙ−１０９）中、ｍ、及びｎは、それぞれ１〜１１の整数であり、ｍ＋ｎは２〜１２の整数である。式（Ｙ−１１４）中、ｈは１〜３の整数であり、式（Ｙ−１１１）及び（Ｙ−１１７）中、ｊは０〜３の整数である。）

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

式（５）中、Ｒ_１２は単結合、又は炭素数１〜３０の２価の有機基であり、Ｒ_１３は水素原子、ハロゲン原子又は炭素数１〜３０の１価の有機基である。
ａは１〜４の整数であり、ａが２以上の場合は、（Ｒ_１２−Ｒ_１３）は、互いに同一でも異なっていてもよい。
式（６）中のＲ_１４は、単結合、−Ｏ−、−Ｓ−、−ＮＲ_１５−、アミド結合、エステル結合、ウレア結合、又は炭素数１〜４０の２価の有機基であり、Ｒ_１５は、水素原子、又はメチル基である。The structure of Y ₁ is more preferably at least one structure selected from the group consisting of the following formulas (5) and (6), from the viewpoint of liquid crystal alignment of the liquid crystal alignment film to be obtained and the pretilt angle.

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

As a specific example of Y ₁ represented by the formula (5) and the formula (6), a structure with high linearity can enhance the alignment of the liquid crystal when it is a liquid crystal alignment film. ), (Y-21), (Y-22), (Y-23), (Y-25), (Y-43) to (Y-46), (Y-48), (Y-63), (Y-71) to (Y-75), (Y-98), (Y-99), (Y- 100), (Y-118) and the like are preferable.
The proportion of the structure that can increase the liquid crystal alignment property, is preferably at least 20 mole% of the total Y _1, more preferably 60 mol% or more, still more preferably 80 mol% or more. Usually, it is preferably 90 mol% or less.

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

Ｘ_２は炭素数１〜２０の脂肪族炭化水素基、又は芳香族炭化水素基を含むｎ価の有機基である。ｎは２〜６の整数である。<(B) component>
The component (B) contained in the liquid crystal aligning agent of the present invention is a compound having a hydroxyalkylamide group. Other components are not particularly limited as long as the component (B) has a hydroxyalkylamide group, but a compound represented by the following formula (2) can be mentioned as a preferred example from the viewpoint of availability etc. .

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

R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkenyl group having 2 to 4 carbon atoms which may have a substituent, or It is a C2-C4 alkynyl group which may have a substituent. In addition, at least one of R ₂ and R ₃ represents a hydrocarbon group substituted with a hydroxy group.
Among them, the atom directly bonded to the carbonyl group in X _{2 of} Formula (2) is preferably a carbon atom which does not form an aromatic ring from the viewpoint of liquid crystal alignment. Further, X ₂ in the formula (2) is preferably an aliphatic hydrocarbon group from the viewpoint of liquid crystal alignment and solubility, and more preferably having 1 to 10 carbon atoms.
In Formula (2), n is preferably 2 to 4 from the viewpoint of solubility.

式（３）中、Ｒ_４〜Ｒ_７は、それぞれ独立して、水素原子、炭化水素基、又はヒドロキシ基で置換された炭化水素基である。

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

In formula (3), R _{4 to} R ₇ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.

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

  When the amount of the component (B) is too large, it affects the liquid crystal alignment and the pretilt angle, and when it is too small, the effect of the present invention can not be obtained. Therefore, 0.1-20 mass% is preferable with respect to (A) component, and, as for content of (B) component, 1-10 mass% is more preferable.

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

The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent. It will not specifically limit, if the produced | generated polyimide precursor melt | dissolves as a solvent used in that case. Although the specific example of the solvent used for reaction is given to the following, it is not limited to these examples. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone It can be mentioned.
Further, when the solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D-1] to formula [D-3]. Solvents can be used.

式［Ｄ−１］中、Ｄ^１は炭素数１〜３のアルキル基を示し、式［Ｄ−２］中、Ｄ^２は炭素数１〜３のアルキル基を示し、式［Ｄ−３］中、Ｄ^３は炭素数１〜４のアルキル基を示す。

In Formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in Formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, Formula [D-3] among, ^{D 3} is an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, it may be used by mixing with the above-mentioned solvent in the range which the generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and causes hydrolysis of the produced polyimide precursor, it is preferable to use the solvent which has been dehydrated and dried.
The concentration of the polyamic acid polymer in the reaction system is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight polymer is easily obtained.
The polymer can be precipitated and recovered by injecting the polyamic acid obtained as described above into the following poor solvent while thoroughly agitating the reaction solution. Further, precipitation is carried out several times, and after washing with a poor solvent, the powder of purified polyamic acid can be obtained by normal temperature or heat drying. The poor solvent is not particularly limited, and water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned.

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

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

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

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

(2) In the case of producing by reaction of tetracarboxylic acid diester dichloride with diamine Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and a solvent, -20 to 150 ° C, preferably 0 to 50 C. for 30 minutes to 24 hours, preferably 1 to 4 hours.
As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds mildly. The amount of the base added is preferably 2 to 4 moles, preferably 2.5 to 3 moles, per mole of the tetracarboxylic acid diester dichloride, in terms of easy removal and high molecular weight. Molar is more preferred.

  The solvent used for the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of monomers and polymers, and one or more of these may be used as a mixture. The polymer concentration at the time of production is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer hardly occurs and a polymer can be easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for producing the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent external air from being mixed in a nitrogen atmosphere.

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

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base added is preferably 2 to 4 moles per mole of the diamine component, in terms of easy removal and high molecular weight.
In the above reaction, addition of a Lewis acid as an additive allows the reaction to proceed efficiently. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times mol, more preferably 0 to 0.5 times mol based on the diamine component.
Among the above three methods for producing polyamic acid, a high molecular weight polyamic acid ester can be obtained, and therefore the production method of the above (1) or the above (2) is particularly preferable.
The polymer can be precipitated by injecting the solution of the polyamic acid ester obtained as described above into the following poor solvent while stirring well. Precipitation is carried out several times, and after washing with a poor solvent, normal temperature or heat drying can be carried out to obtain a powder of purified polyamic acid ester. The poor solvent is not particularly limited, and water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned.

<Polyimide>
The polyimide used in the present invention can be produced by imidizing the above-described polyamic acid ester or polyamic acid. When manufacturing a polyimide from a polyamic acid ester, chemical imidization which adds a basic catalyst to the polyamic acid solution obtained by dissolving the said polyamic acid ester solution or polyamic acid ester resin powder in a solvent is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature, and molecular weight reduction of the polymer does not easily occur in the imidization process.
Chemical imidization can be carried out by stirring the polyamic acid ester to be imidized in the presence of a basic catalyst in a solvent. As a solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, triethylamine is preferable because it has sufficient basicity to allow the reaction to proceed.

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

When producing a polyimide from polyamic acid, chemical imidization which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature, and molecular weight reduction of the polymer does not easily occur in the imidization process.
Chemical imidization can be carried out by stirring the polyamic acid to be imidized in a solvent in the presence of a basic catalyst and an acid anhydride. As a solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine. Among them, pyridine is preferable because it has appropriate basicity to allow the reaction to proceed. Further, as the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned, and it is preferable to use acetic anhydride among them because purification after completion of the reaction becomes easy.
The temperature at which the imidization reaction is carried out can be −20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time can be 1 to 100 hours, preferably 1 to 5 hours.
The amount of the basic 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, preferably 3 to 3 moles of the amic acid group. It is 30 molar times. The imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, reaction time and the like.

上記式（Ｂ−１）から（Ｂ−１７）におけるＤは、それぞれ独立して、ｔｅｒｔ−ブトキシカルボニル基又は９−フルオレニルメトキシカルボニル基である。式（Ｂ−１４）〜（Ｂ−１７）に存在する複数のＤは、互いに同一であっても異なってもよい。加熱による脱保護後の塩基性が高くなるほど、ポリアミック酸エステル及びポリアミック酸のイミド化促進効果がさらに高まる。よって、熱イミド化促進効果をより高めるという点から（Ｂ−１４）〜（Ｂ−１７）が好ましく、中でも（Ｂ−１７）が特に好ましい。In the imidation reaction of polyamic acid ester or polyamic acid, an imidation promoter can be used. Specific examples of the imidation promoter are shown below, but the invention is not limited thereto.

D in the said Formula (B-1) to (B-17) is respectively independently a tert- butoxycarbonyl group or 9-fluorenyl methoxy carbonyl group. The plurality of D present in the formulas (B-14) to (B-17) may be the same as or different from one another. The higher the basicity after deprotection by heating, the higher the imidization promoting effect of the polyamic acid ester and the polyamic acid is further enhanced. Therefore, (B-14) to (B-17) are preferable in that the thermal imidization promoting effect is further enhanced, and (B-17) is particularly preferable.

Since the added catalyst or the like remains in the solution after the imidization reaction of the polyamic acid ester or polyamic acid, the obtained imidized polymer is recovered by the means described below, and redissolved in a solvent It is preferable to set it as the liquid crystal aligning agent of this invention.
The solution of the polyimide obtained as mentioned above can precipitate a polymer by inject | pouring into the following poor solvent, stirring it well. Precipitation is carried out several times, and after washing with a poor solvent, normal temperature or heat drying can be carried out to obtain a powder of purified polyamic acid ester.
The poor solvent is not particularly limited, and methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and the like can be mentioned.

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

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

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.
Furthermore, when the solubility to the solvent of the polymer of this invention is high, it is preferable to use the solvent shown by said Formula [D-1]-Formula [D-3].
It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 20-99 mass% of the whole solvent contained in a liquid crystal aligning agent. Among these, 20 to 90% by mass is preferable. More preferably, it is 30-80 mass%.

The liquid crystal aligning agent of the present invention may use a solvent (also referred to as a poor solvent) that improves the coating property and surface smoothness of the liquid crystal alignment film when the liquid crystal aligning agent is applied, as long as the effects of the present invention are not impaired it can. Specific examples of the poor solvent are listed below, but the present invention is not limited to these examples.
For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol , 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethanedi 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methyl pentyl acetate, 2-ethyl butyl acetate, 2-ethyl hexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate Tart, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, milk Methyl, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropion Ethyl acid, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid The isoamyl ester, the solvent shown by said Formula [D-1]-Formula [D-3], etc. can be mentioned.
Among these, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

The poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and more preferably 20 to 70% by mass of the total amount of solvents contained in the liquid crystal aligning agent.
The liquid crystal aligning agent of the present invention is a polymer other than the polymer described in the present invention, the dielectric constant of the liquid crystal alignment film, electric conductivity, etc., as long as the effects of the present invention are not impaired. Crosslinkability for the purpose of improving the hardness and density of the film when it is made into a liquid crystal alignment film, a dielectric or conductive substance for changing the characteristics, a silane coupling agent for improving the adhesion between the liquid crystal alignment film and the substrate A compound, and also an imidization accelerator for the purpose of efficiently advancing imidation by heating of a polyimide precursor when baking a coating film may be added.

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

  As a coating method of the liquid crystal aligning agent of this invention, a spin coat method, the printing method, the inkjet method etc. are mentioned. The drying and baking steps after the application of the liquid crystal aligning agent of the present invention can be performed at any temperature and time. Usually, in order to sufficiently remove the contained solvent, it is dried at 50 to 120 ° C., preferably 60 to 100 ° C., for 1 to 10 minutes, preferably 2 to 5 minutes, and then 150 to 300 ° C., preferably At 200 to 240 ° C. for 5 to 120 minutes, preferably 10 to 30 minutes. The thickness of the coated film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be reduced, so it is 5 to 300 nm, preferably 10 to 200 nm.

As a method of carrying out the alignment process of the obtained liquid crystal aligning film, the rubbing method, the photo alignment treatment method, etc. are mentioned.
The rubbing process can be performed using an existing rubbing apparatus. Cotton, nylon, rayon etc. are mentioned as a material of the rubbing cloth in this case. As the conditions for the rubbing treatment, generally, conditions such as a rotational speed of 300 to 2,000 rpm, a feed rate of 5 to 100 mm / s, and a pressing amount of 0.1 to 1.0 mm are used. Thereafter, ultrasonic cleaning using pure water, alcohol or the like removes the residue generated by rubbing.

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

It will not specifically limit, if it is a solvent which melt | dissolves the decomposition product produced | generated by light irradiation as a solvent used for contact processing. As specific examples, water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like. Two or more of these solvents may be used in combination.
From the viewpoint of versatility and safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is more preferable. Water, 2-propane or a mixed solvent of water and 2-propanol is particularly preferred.

In the present invention, the contact treatment of the film containing the polarized radiation and the solution containing the solvent is carried out in such a manner that the film and the solution are preferably in sufficient contact, such as immersion treatment or spray treatment. Be Among them, a method of immersion treatment in a solution containing a solvent, preferably for 10 seconds to 1 hour, more preferably for 1 to 30 minutes is preferable. The contact treatment may be performed at normal temperature or may be heated, but is preferably performed at 10 to 80 ° C., more preferably 20 to 50 ° C. Also, if necessary, means for enhancing contact with ultrasonic waves can be provided.
After the contact treatment, in order to remove the solvent in the solution used, rinsing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone or the like, drying, or both is performed. You may

Furthermore, the membrane subjected to the contact treatment with a solution containing a solvent may be heated at 150 ° C. or higher for the purpose of drying of the solvent and reorientation of molecular chains in the membrane.
As temperature of heating, 150-300 ° C is preferred. A higher temperature promotes reorientation of molecular chains, but too high a temperature may involve decomposition of molecular chains. Therefore, as heating temperature, 180-250 degreeC is more preferable, and 200-230 degreeC is especially preferable.
If the heating time is too short, the effect of molecular chain reorientation may not be obtained, and if it is too long, the molecular chain may be broken, so 10 seconds to 30 minutes is preferable. 1-10 minutes are more preferable.

<Liquid crystal display element>
The liquid crystal display element of the present invention is characterized by comprising a liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film.
In the liquid crystal display device of the present invention, a substrate with a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the method for producing a liquid crystal alignment film, and then a liquid crystal cell is produced by a known method. It is used as a display element.
As an example of a method of manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure is described as an example. It may be a liquid crystal display element of an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in respective pixel parts constituting an image display.

First, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes can be, for example, ITO electrodes, and are patterned to allow desired image display. Then, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film made of SiO ₂ -TiO ₂ formed by a sol-gel method.
Next, the liquid crystal alignment film of the present invention is formed on each substrate. Next, the other substrate is superimposed on one of the substrates so that the alignment film surfaces face each other, and the periphery is bonded with a sealing material. Usually, spacers are mixed into the sealing material in order to control the substrate gap. In addition, it is preferable that spacers for controlling the substrate gap be dispersed also in the in-plane portion where the sealing material is not provided. In part of the sealing material, an opening capable of being filled with liquid crystal from the outside is provided.

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

  In the sealing agent of the present invention, an inorganic filler may be blended for the purpose of improving adhesion and moisture resistance. The inorganic filler which can be used is not particularly limited, and specifically, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, Asbestos etc. are mentioned. Preferably, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate or silicic acid Aluminum is mentioned. The inorganic fillers may be used as a mixture of two or more.

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

DC-1: 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride DC-2: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride DC-3: 3, 3 ', 4,4'-biphenyltetracarboxylic acid dianhydride DC-4: 1,2,3,4-butanetetracarboxylic acid dianhydride DC-5: bicyclo [3.3.0] octane-2, 4,6,8-Tetracarboxylic acid dianhydride DC-6: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride DC-7: pyromellitic anhydride DC-8: compound DE-1 represented by the following formula (DC-8): compound additive A represented by the following formula (DE-1): compound represented by the following formula (Primid XL 552 (manufactured by Emschemy) )
Additive B: Compound represented by the following formula (Primid SF4510 (manufactured by Emskemy)
Additive C: dipentaerythritol hexaacrylate represented by the following formula (manufactured by Daicel-Cytec)
Additive D: 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane represented by the following formula In the following chemical formulae, Me is a methyl group, Bu is an n-butyl group, Boc Represents a t-butoxy group.

The measuring method of each characteristic is as follows.
[viscosity]
The viscosity of the polyamic acid ester and polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL (milliliter), cone rotor TE-1 (1 ° 34 ', R24) , Measured at a temperature of 25 ° C.
[Molecular weight]
The molecular weight of the polyamic acid ester and the polyamic acid is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and a number average molecular weight (hereinafter, also referred to as Mn) and a weight average molecular weight (hereinafter, as a polyethylene glycol (polyethylene oxide) conversion value). (Also referred to as Mw) was calculated.
GPC apparatus: manufactured by Shodex (GPC-101)
Column: Shodex (KD 803 and KD 805 in series)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additive, 30 mmol / L (liter) of lithium bromide-hydrate (LiBr · H ₂ O), 30 mmol / hour of phosphoric acid / anhydrous crystal (o-phosphoric acid) L, tetrahydrofuran (THF) 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparation of calibration curve: Toso TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, and 30,000) and polymer laboratory company Polyethylene glycol (peak top molecular weight (Mp) is about 12,000, 4,000, and 1,000) was used. In order to avoid overlapping of the peaks, the measurement was made with four mixed samples of 900,000, 100,000, 12,000 and 1,000, and 3 samples of 150,000, 30,000 and 4,000. Two samples of mixed types were run separately.

[Measurement of imidation ratio]
The imidation ratio of the polyimide was measured as follows. 20 mg of polyimide powder is placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) (0 .53 mL) was added and sonicated to dissolve completely. This solution was subjected to proton NMR measurement at 500 MHz with an NMR measurement device (JNW-ECA 500) (manufactured by Nippon Denshi Datum Co., Ltd.).

The imidation ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid appearing around 9.5 to 10.0 ppm It calculated | required by the following formula using integration value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidation ratio is 0%) The ratio of the number of reference protons to.

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

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

Synthesis Example 3
110.47 g (452 mmol) of diamine DA-3 and 18.94 g (79.5 mmol) of DA-2 are weighed into a 2000 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1587 g of NMP is added, and nitrogen is added. The mixture was stirred and dissolved while being fed. While stirring this diamine solution, 111.18 g (496 mmol) of carboxylic acid dianhydride DC-1 is added, NMP is further added so that the solid content concentration becomes 12 mass%, and stirring is carried out at 40 ° C. for 20 hours , A solution of polyamic acid (PAA-3) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 183 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 12356 and Mw = 25544.

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

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

[Preparation of liquid crystal aligning agent]
Example 1
11.00 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 was weighed into a 20 ml sample tube containing a stirrer, 5.00 g of NMP, 4.00 g of BCS, and N as an imidization accelerator. 0.15 g of -α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine and 0.06 g of Additive A are added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent I got A1.
Using this liquid crystal aligning agent A1, a substrate for evaluation of adhesion and a liquid crystal cell were produced in the following procedure.

[Preparation of substrate for evaluation of adhesion, and evaluation]
<Fabrication of substrate>
The liquid crystal aligning agent A1 was applied to a 30 mm × 40 mm ITO substrate by spin coating. Then, it was dried on a hot plate at 80 ° C. for 2 minutes, and then baked for 14 minutes in a hot air circulating oven at 230 ° C. to form a coating having a film thickness of 100 nm. The coated film surface was irradiated with ultraviolet light of 254 nm at 500 mJ / cm ² through a polarizing plate, and then baked for 14 minutes in a hot air circulating oven at 230 ° C. to obtain a substrate with a liquid crystal alignment film.
Two substrates thus obtained were prepared, and a 4 μm bead spacer was coated on the liquid crystal alignment film surface of one of the substrates, and then a sealing agent (manufactured by Kyoritsu Chemical, XN-1500T) was dropped. . Subsequently, the liquid crystal aligning film surface of the other board | substrate was turned inside, and bonding was performed so that the overlap width of a board | substrate might be 1 cm. At that time, the dropping amount of the sealing agent was adjusted so that the diameter of the sealing agent after bonding was 3 mm. The two bonded substrates were fixed by clips and thermally cured at 150 ° C. for 1 hour to produce a substrate for evaluation of adhesion.
<Evaluation of adhesion>
After fixing the end portion of the upper and lower substrate with the table-top precision global universal tester (AGS-X 500N, manufactured by Shimadzu Corporation), the substrate is pushed from above the central portion of the substrate, and the pressure at the time of peeling (N Was measured.

[Preparation of FFS Drive Liquid Crystal Cell, and Evaluation of Liquid Crystal Alignment]
At the beginning, a substrate with an electrode was prepared. The substrate is a glass substrate of 30 mm × 35 mm in size and 0.7 mm in thickness. On the substrate, an IZO electrode having a solid pattern is formed, which constitutes a counter electrode as a first layer. A SiN (silicon nitride) film formed by the CVD method is formed as a second layer on the first counter electrode. The film thickness of the second SiN film is 500 nm and functions as an interlayer insulating film. A comb-like pixel electrode formed by patterning an IZO film as a third layer is disposed on the second-layer SiN film to form two pixels of a first pixel and a second pixel. ing. The size of each pixel is 10 mm in height and about 5 mm in width. At this time, the first opposing electrode and the third pixel electrode are electrically insulated by the action of the second SiN film.

The pixel electrode of the third layer has a comb-like shape configured by arranging a plurality of V-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 3 μm, and the distance between the electrode elements is 6 μm. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent V-shaped electrode elements in the central portion, the shape of each pixel is not rectangular but in the central portion like the electrode elements. It has a shape resembling a bold, bold letter. And each pixel is divided up and down bordering on the central bending part, and has the 1st field of the upper part of a bending part, and the 2nd field of the lower side.
When the first region and the second region of each pixel are compared, the forming directions of the electrode elements of the pixel electrodes constituting them are different. That is, based on the liquid crystal alignment direction of the liquid crystal alignment film described later, the electrode element of the pixel electrode is formed at an angle of + 10 ° in the first region of the pixel, and the electrode of the pixel electrode in the second region of the pixel The elements are formed at an angle of -10 °. That is, in the first area and the second area of each pixel, the directions of rotational movement (in-plane switching) in the plane of the substrate of the liquid crystal induced by voltage application between the pixel electrode and the counter electrode are mutually different. It is configured to be in the opposite direction.

Next, after filtering a liquid crystal aligning agent with a 1.0 micrometer filter, the liquid crystal aligning agent was apply | coated to the prepared said board | substrate with an electrode by spin coat application | coating. Next, after drying on a hot plate at 80 ° C. for 2 minutes, baking was carried out in a hot air circulating oven at 230 ° C. for 14 minutes to form a coating film having a film thickness of 100 nm. The coated film surface was irradiated with ultraviolet light of 254 nm at 500 mJ / cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. In addition, a coating film was similarly formed on a glass substrate having a columnar spacer with a height of 4 μm in which an electrode is not formed as an opposing substrate, and an orientation process was performed.
The above-mentioned two substrates are made into one set, the sealing agent is printed on the substrate, and the other substrate is pasted so that the liquid crystal alignment film face faces each other and the alignment direction is 0 °, and then the sealing agent is cured. Then, an empty cell was produced. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into the empty cell by a pressure reduction injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell.
The alignment state of the liquid crystal cell was observed with a polarizing microscope (ECLIPSE E600 WPOL manufactured by Nikon Corporation), and those having no alignment defect were regarded as “good”, and those having an alignment defect were regarded as “defective”.

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

Example 2
2.20 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 7.33 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were placed in a 20 ml sample tube containing a stirrer. 6.47 g of NMP, 4.00 g of BCS, 0.15 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator, And 0.06g of additive A was added, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent A2.
The adhesion evaluation and the alternating current drive image sticking evaluation were performed by the same method as in Example 1 except that this liquid crystal aligning agent A2 was used.

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

Comparative Example 1
A liquid crystal aligning agent B1 was obtained in the same manner as in Example 1 except that the additive A was not added. The adhesion evaluation and the alternating current drive image sticking evaluation were performed by the same method as in Example 1 except that this liquid crystal aligning agent B1 was used.
Comparative Example 2
A liquid crystal aligning agent B2 was obtained in the same manner as in Example 2 except that the additive A was not added. The adhesion evaluation and the alternating current drive image sticking evaluation were performed by the same method as in Example 2 except that this liquid crystal aligning agent B2 was used.

Comparative Example 3
A liquid crystal aligning agent B3 was obtained in the same manner as in Example 3 except that the additive A was not added. The adhesion evaluation and the alternating current drive image sticking evaluation were performed by the same method as in Example 3 except that this liquid crystal aligning agent B3 was used.

In Table 2, the composition etc. of the component contained in the liquid crystal aligning agent obtained in Examples 1-3 and Comparative Examples 1-3 were shown collectively. In Table 2, (mixing ratio) of the polyimide-based polymer represents the mixing ratio (mass%) of each polymer. The (ratio) of the solvent represents the ratio (% by mass) of each organic solvent to the entire polymer solution. The additive (phr) represents the additive content ratio (% by mass) to the polymer solid content. Moreover, the unit of solid content concentration is mass%.
Table 3 summarizes the preparation conditions of the FFS drive liquid crystal cell in Examples 1 to 3 and Comparative Examples 1 to 3. In Table 3, "-" represents untreated.
In Table 4, each evaluation result in Examples 1-3 and Comparative Examples 1-3, etc. were shown collectively.

Synthesis Example 6
4.58 g (42.4 mmol) of diamine DA-5 and 1.79 g (4.71 mmol) of diamine DA-12 are weighed into a 500 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 84.7 g of NMP Then, 254 g of GBL and 8.40 g (106 mmol) of pyridine as a base were added and dissolved by stirring while feeding nitrogen. Next, 14.4 g (44.2 mmol) of DE-1 was added while stirring this diamine solution, and allowed to react overnight at 15 ° C. After stirring overnight, 1.23 g (13.6 mmol) of acryloyl chloride was added and allowed to react at 15 ° C. for 4 hours. The resulting polyamic acid ester solution is poured into 1477 g of IPA with stirring, and the precipitated white precipitate is collected by filtration, and then the precipitate is washed 5 times with 738 g of IPA and dried to obtain white. 17.3 g of polyamic acid ester resin powder was obtained. The yield was 96.9%. Moreover, the molecular weight of this polyamic acid ester was Mn = 14,288 and Mw = 29,956.
The obtained polyamic acid ester resin powder 3.69g was added to a 100 mL Erlenmeyer flask, 33.2g of GBL was added, and stirred and dissolved at room temperature under a nitrogen atmosphere for 24 hours to obtain a polyamic acid ester solution (PAE-1).

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

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

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

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

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

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

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

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

Synthesis Example 15
In a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 4.21 g (16.8 mmol) of carboxylic acid dianhydride DC, 2.95 g (6.82 mmol) of diamine DA-18 and diamine DA- 6 was weighed out in 2.42 g (15.9 mmol), mixed in 21.4 g of NMP, reacted at 80 ° C. for 5 hours while flowing nitrogen, and then 1.10 g of carboxylic acid dianhydride DC-2 5.61 mmol) and 10.7 g of NMP were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid having a solid content concentration of 25% by mass.
NMP is added to 30.0 g of the obtained polyamic acid solution and diluted so that the solid concentration becomes 6 mass%, 4.40 g of acetic anhydride and 3.30 g of pyridine are added as an imidization catalyst, and the mixture is heated at 80 ° C. It was made to react for 3.5 hours. The reaction solution was poured into 460 ml of methanol and the resulting precipitate was filtered off. Subsequently, the precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (5). The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,600 and the weight average molecular weight was 43,500.
Subsequently, 2.50 g of polyimide powder (5) is weighed, 18.3 g of NMP is added, and it is made to stir and stir at 70 degreeC under nitrogen atmosphere for 24 hours, and solid content concentration makes it 12 mass% polyimide solution (PI-5) I got

Synthesis Example 16
3.77 g (10.00 mmol) of diamine DA-21 was weighed into a 100 mL four-necked flask with a stirrer and a nitrogen inlet tube, and after 50.0 g of NMP was added and all dissolved, it was confirmed that carboxylic acid Anhydrate DC-6 was slowly added as a solid at 9.01 g (30.00 mmol), and reacted at 40 ° C. for 3 hours while flowing nitrogen.
Meanwhile, 9.73 g (90.00 mmol) of diamine DA-5 was weighed into a 300 mL four-necked flask equipped with a mechanical stirrer, and the reaction solution previously prepared with 111.1 g of NMP was added and all dissolved. After confirmation, slowly add 20.27 g (67.50 mmol) of carboxylic acid dianhydride as a solid slowly, wash the flask wall with 10.00 g of NMP, and react at 40 ° C. for 6 hours to obtain a polyamic acid solution. The The number average molecular weight of this polyamic acid was 10,200, and the weight average molecular weight was 23,600.
Next, 40.00 g of the polyamic acid solution obtained above is weighed into a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 74.3 g of NMP is added, and 19.02 g (186.29 mmol) of acetic anhydride After adding 8.84 g (111.71 mmol) of pyridine and stirring at room temperature for 30 minutes, the mixture was allowed to react at 40 ° C. for 2.5 hours. After completion of the reaction, the reaction solution was returned to room temperature and slowly poured into 500 ml of methanol cooled to about 10 ° C. to precipitate a solid, and the precipitate was separated by filtration. Subsequently, the precipitate was washed twice with 200 ml of methanol and vacuum dried at 100 ° C. to obtain a polyimide powder (6).
4.0 g of the polyimide powder (6) obtained by the above operation is weighed into a 100 ml eggplant flask with a branch equipped with a stirrer, and 62.67 g of GBL is added and dissolved by stirring at 50 ° C. under a nitrogen atmosphere The polyimide solution (PI-6) having a solid content concentration of 6.0% by mass was obtained.

Synthesis Example 17
In a 500 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 19.86 g (0.101 mol) of carboxylic acid dianhydride DC. 9.81 g (0.045 mol) of carboxylic acid dianhydride DC-7. , 5.50 g (0.045 mol) of diamine DA-22, 12.20 g (0.060 mol) of diamine DA-24, and 13.16 g (0.045 mol) of diamine DA-19 in 242.1 g of NMP The reaction was carried out at room temperature with flowing nitrogen for 18 hours to obtain a polyamic acid solution with a solid concentration of 20% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 597 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 12224 and Mw = 36140.
Next, 210.0 g of NMP is added to 140.0 g of the polyamic acid solution obtained above and diluted to prepare a polyamic acid solution having a solid concentration of 8.0% by mass, and 21.08 g of acetic anhydride and pyridine 8. 99 g was added and allowed to react at 50 ° C. for 2 hours for chemical imidization. The obtained polyimide solution was cooled to about room temperature and then poured into 1330 g of methanol, and the precipitate was separated by filtration. Subsequently, the precipitate was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (7). The number average molecular weight of this polyimide was 10,920 and the weight average molecular weight was 31,108. Further, the imidation ratio was 85%.
Measure 11.0 g of the polyimide powder (7) obtained by the above operation in a 100 ml eggplant flask with a branch equipped with a stirrer, add 80, 7 g of GBL and stir at 50 ° C. for 20 hours under nitrogen atmosphere to dissolve As a result, a polyimide solution (PI-7) having a solid content concentration of 12.0% by mass was obtained.

Synthesis Example 18
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 18.53 g (0.095 mol) of carboxylic acid dianhydride DCC 8.83 g (0.041 mol) of carboxylic acid dianhydride DC-7 6.29 g (0.054 mol) of diamine DA-23, 8.23 g (0.041 mol) of diamine DA-24, 12.98 g (0.041 mol) of diamine DA-20, in 239.1 g of NMP, The reaction was performed for 22 hours while flowing nitrogen at room temperature to obtain a 20 wt% solution of polyamic acid (PAA-2). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 693 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 20366 and Mw = 54052.
Next, 240.0 g of NMP is added to 160.0 g of the polyamic acid solution obtained above in a 500 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and diluted to obtain a solid content concentration of 8.0 mass% A solution was prepared, 22.26 g of acetic anhydride and 9.49 g of pyridine were added, and the mixture was reacted at 50 ° C. for 2 hours for imidation. The obtained polyimide solution was cooled to about room temperature and then poured into 1511 g of methanol, and the precipitate was separated by filtration. Subsequently, the precipitate was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (8). The number average molecular weight of this polyimide was 13306, and the weight average molecular weight was 35615. Further, the imidation ratio was 85%.
Measure 11.0 g of the polyimide powder (8) obtained by the above operation in a 100 ml eggplant flask with a branch equipped with a stirrer, add 80, 7 g of GBL, and dissolve by stirring at 50 ° C for 20 hours under nitrogen As a result, a polyimide solution (PI-8) having a solid content concentration of 12.0% by mass was obtained.

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

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

Synthesis Example 21
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 5.00 g (17.46 mmol) of diamine DA-10 is weighed, 48.17 g of NMP is added and dissolved, and cooled to 10 ° C. or less in an ice bath 3.50 g (16.06 mmol) of carboxylic acid dianhydride was added little by little, and the mixture was returned to room temperature and allowed to react until the viscosity was stabilized, to obtain a polyamic acid solution (PAA-7) having a solid concentration of 15% by mass. . The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 420 mPa · s, the number average molecular weight was 12,500, and the weight average molecular weight was 33,800.

Synthesis Example 22
1.98 g (10.00 mmol) of diamine DA-7, 8.40 g (40.00 mmol) of diamine DA-8 are weighed into a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 152.10 g of NMP Add and dissolve, cool to about 10 ° C., and slowly add 7.35 g (38.00 mmol) of carboxylic acid dianhydride DC-2 followed by 3.00 g of carboxylic acid dianhydride DC-6 (10. 00 mmol) was added little by little, and allowed to react at room temperature until the viscosity was stabilized, to obtain a polyamic acid solution (PAA-8) having a solid concentration of 12% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 180 mPa · s.

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

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

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

Example 4
4.58 g of the polyimide solution (PI-1) obtained in Synthesis Example 4 and 4.58 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 20, 6.83 g of NMP, 4 BCS .00 g, N-.alpha .- (9-fluorenylmethoxycarbonyl) -N-.tau.-t-butoxycarbonyl-L-histidine, 0.15 g as an imidization accelerator, and 0.06 g of Additive A, added at room temperature The mixture was stirred for 3 hours to obtain a liquid crystal aligning agent A4.

Example 5
3.67 g of the polyimide solution (PI-1) obtained in Synthesis Example 4 and 5.50 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 20 are weighed out, 6.83 g of NMP, and 4 BCS .00 g, N-.alpha .- (9-fluorenylmethoxycarbonyl) -N-.tau.-t-butoxycarbonyl-L-histidine, 0.15 g as an imidization accelerator, and 0.06 g of Additive A, added at room temperature The mixture was stirred for 3 hours to obtain a liquid crystal aligning agent A5.

Example 6
4.59 g of the polyimide solution (PI-2) obtained in Synthesis Example 12, 4.57 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 20, 6.85 g of NMP, and 4 BCS .00 g, N-.alpha .- (9-fluorenylmethoxycarbonyl) -N-.tau.-t-butoxycarbonyl-L-histidine, 0.15 g as an imidization accelerator, and 0.06 g of Additive A, added at room temperature The mixture was stirred for 3 hours to obtain a liquid crystal aligning agent A6.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Evaluation results of adhesion obtained by the same method as in Example 3 using the liquid crystal aligning agents obtained in Examples 4 to 13 and Comparative Examples 4 to 8 and 15 to 18, respectively, and Tables 5-1 and 5-2 collectively show the results of the evaluation of the liquid crystal orientation and the alternating current drive image sticking evaluation.
Similarly, using the liquid crystal aligning agents obtained in the above Examples 14 to 19 and Comparative Examples 9 to 14, respectively, evaluation of adhesion and liquid crystal burning on a liquid crystal cell obtained by the same method as Example 1 The results of the evaluation are summarized in Tables 5-1 and 5-2.

Example 20
8.0 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 21 and 40.0 g of the polyamic acid solution (PAA-8) obtained in Synthesis Example 22 are weighed out, 31.7 g of NMP and BCS 20.0g and 0.30g of Additive A were added, and it stirred at 40 degreeC for 4 hours, and obtained liquid crystal aligning agent A20.

<Measurement of adhesion>
The obtained liquid crystal aligning agent A20 is filtered with a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 5 minutes, and baked at 230 ° C. for 20 minutes Thus, a polyimide film with a film thickness of 100 nm was obtained. A sample substrate for evaluation of adhesion is prepared in the same manner as in Example 1, and after fixing the end portions of the upper and lower substrates with a bench-type precision universal testing machine (manufactured by Shimadzu Corporation, AGS-X 500N), the substrate The pressing was performed from the upper part of the central part, and the pressure (N) at the time of peeling was measured.

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

<Evaluation of liquid crystal alignment>
The evaluation of the alignment state of the liquid crystal cell was performed by the same method as in Example 1 described above.
<AC drive burn-in of liquid crystal cell>
The average value of the angle Δ values of the first and second pixels was calculated as the angle Δ of the liquid crystal cell in the same manner as in Example 1. The alternating current drive image sticking Δ was made less than 0.2 good, and more than it was made bad.

Example 21
8.0 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 23 and 40.0 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 24 were weighed, and 31.7 g of NMP and BCS were weighed. 20.0g and 0.30g of Additive A were added, and it stirred at 40 degreeC for 4 hours, and obtained liquid crystal aligning agent A21.

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

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

  The results of the adhesion evaluation obtained by the same method as in Example 20 using the liquid crystal aligning agents obtained in Examples 20 and 21 and Comparative Examples 20 to 24 respectively, and the liquid crystal alignment of the liquid crystal cell The results of the evaluation and the results of the AC drive burn-in evaluation are summarized in Table 6 below.

Example 22
11.8 g of the polyimide solution (PI-3) obtained in Synthesis Example 13 and 8.3 g of the polyimide solution (PI-4) obtained in Synthesis Example 14 were weighed, and 12.5 g of PB and Additive A The mixture was added with 0.07 g and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent A22.

<Measurement of adhesion>
The obtained liquid crystal aligning agent A22 is filtered with a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and heated at 100 ° C. for 5 minutes on a hot plate at 230 ° C. in a heat circulating clean oven. It heat-processed for 30 minutes and obtained the ITO board | substrate with a polyimide liquid crystal aligning film with a film thickness of 100 nm. A sample substrate for evaluation of adhesion is prepared in the same manner as in Example 1, and after fixing the end portions of the upper and lower substrates with a bench-type precision universal testing machine (manufactured by Shimadzu Corporation, AGS-X 500N), the substrate The pressing was performed from the upper part of the central part, and the pressure (N) at the time of peeling was measured.

<Evaluation of liquid crystal alignment>
The obtained liquid crystal aligning agent A22 was filtered with a 1.0 μm filter, and then a liquid crystal cell was produced. This solution is spin-coated on the ITO surface of a 100 x 100 mm ITO-coated substrate (100 mm long x 100 mm wide, 0.7 mm thick) washed with pure water and IPA, and heated for 5 minutes at 100 ° C on a hot plate. Heat treatment was carried out at 230 ° C. for 30 minutes in a heat circulating clean oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm.
Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined by sandwiching a 6 μm spacer with the liquid crystal alignment film surface inside, and the periphery was adhered with a sealing agent to produce an empty cell. MLC-6608 (manufactured by Merck Japan) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (vertical alignment cell). The obtained liquid crystal cell was heated at 120 ° C. for 1 hour, and the alignment state of the liquid crystal cell was evaluated in the same manner as in Example 1 described above.

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

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

  Evaluation results of adhesion of test substrates obtained by the same method as in Example 22 using the liquid crystal aligning agents obtained in Examples 22 and 23 and Comparative Examples 25 and 26 respectively, and liquid crystal cell Table 7 summarizes the results of the evaluation of the liquid crystal alignment for.

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

<Measurement of adhesion>
The obtained liquid crystal alignment agent A24 is filtered with a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 60 seconds, and IR 220 ° C. Baking was performed for 20 minutes in a nitrogen atmosphere using an oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm. A sample substrate for evaluation of adhesion is prepared in the same manner as in Example 1, and after fixing the end portions of the upper and lower substrates with a bench-type precision universal testing machine (manufactured by Shimadzu Corporation, AGS-X 500N), the substrate The pressing was performed from the upper part of the central part, and the pressure (N) at the time of peeling was measured.

<Evaluation of liquid crystal alignment>
After filtering the obtained liquid crystal aligning agent A24 with a 1.0 μm filter, a liquid crystal cell was produced. This solution is spin-coated on the ITO surface of a 100 x 100 mm ITO-coated substrate (100 mm x 100 mm, thickness 0.7 mm) washed with pure water and IPA, and heated for 60 seconds on a hot plate at a temperature of 80 ° C. After drying, baking was performed for 20 minutes under a nitrogen atmosphere using an IR (infrared) oven at 220 ° C. to form a coating having a film thickness of 100 nm. The coated film surface is rubbed with a rubbing device with a roll diameter of 120 mm using cotton cloth (Yakawa YA-25C) at a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm / sec, and a push amount of 0.4 mm. A film-coated substrate was obtained.
Two ITO substrates with a liquid crystal alignment film obtained are prepared, and the two substrates are combined by sandwiching a 6 μm spacer with the liquid crystal alignment film faces facing each other and the rubbing direction being orthogonal, and bonding the periphery with a sealing agent An empty cell was made. MLC-2003 (manufactured by Merck Japan Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (TN alignment cell). The obtained liquid crystal cell was heated at 120 ° C. for 1 hour, and the alignment state of the liquid crystal cell was evaluated in the same manner as in Example 1 described above.

Example 25
64.2 g of the polyimide solution (PI-7) obtained in Synthesis Example 17 and 27.5 g of the polyimide solution (PI-8) obtained in Synthesis Example 18 are mixed, and further, 23.8 g of GBL and NMP 41 are added to this solution. .8 g, 62.7 g of BCS and 0.66 g of Additive A were added, and the mixture was stirred at 50 ° C for 20 hours to obtain a liquid crystal aligning agent A25.
Example 26
5.0 g of the polyimide solution (PI-9) obtained in Synthesis Example 19 and 20.0 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 25 are weighed, and 0.08 g of Additive A is added, It stirred at room temperature for 24 hours, and obtained liquid crystal aligning agent A26.

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

  The results of the adhesion evaluation obtained by the same method as in Example 24 using the liquid crystal aligning agents obtained in Examples 24 to 26 and Comparative Examples 27 to 29, respectively, and the liquid crystal alignment of the liquid crystal cell The results of the evaluation are summarized in Table 7.

  The liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention satisfies the adhesiveness (adhesiveness) with a sealing agent or a board | substrate, and also the characteristic which compatible liquid crystal alignment property and an electrical property is expressed. In the liquid crystal display element of the IPS and FFS drive systems having such a liquid crystal alignment film of the present invention, display afterimage caused by alternating current drive generated or display burn-in due to residual charge accumulated by DC voltage is suppressed and It has high seal adhesion. Therefore, it can be used in a wide range of liquid crystal display devices that require high display quality.

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

Claims (11)

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

(X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group. R ₁ is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are And each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and these groups each have a substituent Also good.)
Component (B): Any compound represented by the following formula .

The liquid crystal aligning agent of Claim 1 which the said (B) component contains 0.1-20 mass% with respect to the said (A) component. X ₁ is at least one structure selected from the group consisting of the following formulas (X-1) ~ (X -14), the liquid crystal alignment agent according to claim 1 or 2.

(R _{8 to} R ₁₁ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyl group, or a phenyl group.) The liquid crystal aligning agent in any one of Claims 1-3 which is at least 1 type of structure chosen from the group which X < ₁ > becomes from following formula (X1-1) and (X1-2).

The liquid crystal aligning agent according to any one of claims 1 to 4 , wherein Y ₁ is at least one structure selected from the group consisting of the following formulas (5) and (6).

(R ₁₂ is a single bond or a divalent organic group having 1 to 30 carbon atoms, R ₁₃ is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms, a is 1 to 4 of an integer, if a is 2 or more, _(R 12 _{-R 13)} is good _{.R 14} be the same as or different from each other a single bond, -O -, - S -, - NR 15 -, amide bond, an ester bond, a urea bond, or a divalent organic group having a carbon number of 1 to 40, R ₁₅ is a hydrogen atom or a methyl group.) The liquid crystal alignment agent according to any one of claims 1 to 5 applied method of firing to the liquid crystal alignment film. Method of manufacturing a liquid crystal alignment film a liquid crystal alignment agent according to any one of claims 1 to 5 applied is irradiated with a radiation is polarized wavelengths 100 to 400 nm. The film thickness after baking is 5-300 nm , The manufacturing method of the liquid crystal aligning film of Claim 6 or 7. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-5 . The liquid crystal display element which comprises the liquid crystal aligning film of Claim 9 . A transverse electric field drive liquid crystal display device comprising the liquid crystal alignment film according to claim 9 .