KR102275484B1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

(A) The liquid crystal aligning agent containing a component and (B) component. (A) Component: At least 1 type selected from the group which consists of a polyimide precursor which has at least 1 type of structure chosen from the group which consists of formula [1A] and [1B], and the polyimide which imidated this polyimide precursor. of polymers. [1A] [1B] (X ^A and X ^C each independently represents a protecting group substituted with a hydrogen atom by heat. X ^B represents a single bond or an organic group having 1 to 40 carbon atoms, in that case, an ester group (-COO The atom to which - group) bonds is a carbon atom.) (B) Component: The tetracarboxylic acid component containing tetracarboxylic dianhydride of Formula (B-1), and the diamine of Formula (B-2) The polyamic acid obtained from the diamine component to contain. (B-1) (B-2) (Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring. B ₁ and B ₂ are each Independently, it is a hydrogen atom, a C1-C10 alkyl group which may have a substituent, etc.).

Description

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

This invention relates to a liquid crystal aligning agent, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element provided with this liquid crystal aligning film.

As for the liquid crystal display element used for a liquid crystal television, a liquid crystal display, etc., the liquid crystal aligning film for controlling the arrangement|positioning (it is also called orientation) state of a liquid crystal is normally formed in the element.

Currently, the liquid crystal aligning film, which is industrially most prevalent, is a polyimide precursor formed on an electrode substrate, for example, polyamic acid (also referred to as polyamic acid), polyamic acid ester, polyimide imidized with these, etc. It is produced by performing the so-called rubbing treatment method in which the surface of the resin film formed is rubbed in one direction with a cloth such as cotton, nylon, or polyester.

In the process of controlling the orientation state of a liquid crystal aligning film (it is also mentioned a liquid-crystal orientation treatment method) WHEREIN: The method of rubbing the surface of a resin film is simple, excellent in productivity, and is an industrially useful method. However, the demand for higher performance, higher precision, and larger size of the liquid crystal display device is higher and higher, and scratches and dust on the surface of the liquid crystal aligning film that occur along with the rubbing treatment, the influence by mechanical force or static electricity, and further, the alignment treatment Various problems, such as non-uniformity within the plane, are being revealed.

As a method of replacing the rubbing treatment method, a photo-alignment treatment for controlling the alignment state of a liquid crystal by irradiating polarized ultraviolet light is known. As for the liquid-crystal orientation treatment method using photo-alignment treatment, the thing which used photoisomerization reaction, the thing which used photocrosslinking reaction, the thing which used photolysis reaction, etc. are proposed mechanically (refer nonpatent literature 1).

Moreover, in patent document 1, using the resin film which consists of polyimide-type resin which has alicyclic structures, such as a cyclobutane ring, in a principal chain for a photo-alignment process is proposed. In particular, when polyimide-type resin is used for the liquid crystal aligning film of a photo-alignment method, the usefulness is anticipated at the point which has high heat resistance compared with that of other resin.

The photo-alignment treatment as described above has an advantage that it can be industrially produced by a simple manufacturing process as a rubbing-less liquid-crystal alignment treatment. Furthermore, in the liquid crystal display element of the IPS (In-Plane Switching) drive method or the FFS (Fringe Field Switching) drive method, when the liquid crystal aligning film obtained by the said photo-alignment process is used, compared with the liquid crystal aligning film obtained by the rubbing treatment method It is possible to improve the performance of a liquid crystal display element, for example, the improvement of the contrast and viewing angle characteristic of a liquid crystal display element can be expected. Therefore, the photo-alignment processing method attracts attention especially as a future liquid-crystal orientation processing method.

On the other hand, as a liquid crystal aligning film used in liquid crystal display elements of the IPS drive system or the FFS drive system, in addition to the basic characteristics such as excellent liquid crystal orientation and electrical properties, the liquid crystal does not return to the initial alignment state by long-time alternating current driving. Characteristics such as suppression of an afterimage (hereinafter referred to as an afterimage caused by AC drive) generated by not doing so, and quick relaxation of the residual charge accumulated by a DC voltage are required.

In a polyimide-type liquid crystal aligning film, in order to meet the above request|requirement, various proposals have been made|formed. For example, as a liquid crystal aligning film with a short time until afterimages generated by direct voltage disappear, a liquid crystal aligning agent containing a tertiary amine of a specific structure in addition to polyamic acid or imide group-containing polyamic acid is used. The thing using the liquid crystal aligning agent containing the soluble polyimide which used as a raw material the specific thing which has thing and a pyridine skeleton etc. as a raw material, etc. are proposed (for example, refer patent document 2 and 3).

Moreover, as a liquid crystal aligning film with high voltage retention and short time until afterimages generated by DC voltage disappear, in addition to polyamic acid, its imidized polymer, etc., a compound containing one carboxylic acid group in a molecule, a molecule It is proposed that the liquid crystal aligning agent containing a very small amount of the compound chosen from the compound which contains one carboxylic anhydride group in a molecule|numerator, and the compound which contains one tertiary amino group in a molecule|numerator (for example, patent document 4) Reference).

Moreover, as a liquid crystal aligning film which is excellent in liquid-crystal orientation, voltage retention is high, there are few residual images, is excellent in reliability, and shows a high pretilt angle, Tetracarboxyl which has tetracarboxylic dianhydride and cyclobutane of a specific structure What used the liquid crystal aligning agent containing the polyamic acid obtained from acid dianhydride and a specific thing, and this imidation polymer is known (for example, refer patent document 5).

Moreover, in the liquid crystal display element of a transverse electric field drive system, as a method of suppressing the afterimage by the alternating current drive which generate|occur|produces, the liquid-crystal orientation is favorable and the method of using the specific liquid crystal aligning film with large interaction with liquid crystal molecules is has been proposed (see Patent Document 6).

In addition, in the liquid crystal cell of the IPS drive method or the FFS drive method, static electricity is easily accumulated in the liquid crystal cell, and electric charges are accumulated in the liquid crystal cell even by the application of an asymmetric voltage generated by the drive, and these accumulated charges are transferred to the liquid crystal cell. Disorder of orientation, an afterimage, or exposure influences a display, and reduces the display quality of a liquid crystal element remarkably. When energized again in such a state, in the initial stage, control of the liquid crystal molecules is not performed well, and flicker (flicker) or the like is generated. In particular, in the IPS driving method or the FFS driving method, since the distance between the pixel electrode and the common electrode is closer than that of the conventional electric field method, a strong electric field acts on the alignment film or the liquid crystal layer, and there is a problem that such a problem is easy to become noticeable. .

As a method for solving the accumulation of charges due to asymmetry of the AC drive described above, a first alignment film formed on the electrode, a polymer composed of pyromellitic dianhydride and diamine formed on the surface thereof, and a resistance higher than that of the first alignment film In a liquid crystal display device having a liquid crystal aligning film composed of a low second alignment film, it has been reported that charge accumulation due to asymmetry of AC drive can be suppressed and that the accumulated charge can be relieved quickly (for example, See Patent Document 7).

Japanese Patent Laid-Open No. 9-297313 Japanese Patent Laid-Open No. 9-316200 Japanese Patent Laid-Open No. 10-104633 Japanese Laid-Open Patent Publication No. 8-76128 Japanese Patent Laid-Open No. 9-138414 Japanese Laid-Open Patent Publication No. 11-38415 Japanese Patent Laid-Open No. 2013-167782

“Liquid Crystal Photoalignment Film” Kidowaki, Ichimura Functional Materials, November 1997, Vol. 17 No. 11 pages 13-22

MEANS TO SOLVE THE PROBLEM The present inventors suppress charge accumulation|storage by the asymmetry of alternating current drive which generate|occur|produces in the liquid crystal display element of an IPS drive method or FFS drive method, quick relaxation of the residual charge accumulated by a DC voltage, Furthermore, the residual image by alternating current drive. As a method of obtaining a liquid crystal aligning film that suppresses It paid attention to the liquid crystal aligning agent which blended the component (II) compatible with relaxation|moderation. However, in particular, such a liquid crystal aligning agent did not necessarily solve the said subject in the photo-alignment processing method.

That is, in the liquid crystal aligning film obtained from the liquid crystal aligning agent containing the said two components, by the presence of component (II), suppression of charge accumulation by the asymmetry of alternating current drive and rapid relaxation of the residual electric charge accumulated by a DC voltage are Although compatible, it leads to inhibition of the orientation regulating force of a liquid crystal, the stability of liquid crystal orientation is insufficient, the afterimage by alternating current drive generate|occur|produced, and it was not necessarily able to satisfy|fill all these characteristics.

The present invention is a component that is excellent in liquid crystal alignment property and liquid crystal alignment control force and has high stability of liquid crystal alignment, and a component compatible with suppression of charge accumulation due to asymmetry of AC drive and rapid relaxation of residual charge accumulated by DC voltage In the liquid crystal aligning agent blended with, it aims to provide a liquid crystal aligning film which suppresses charge accumulation by asymmetry of alternating current driving, quick relief of residual electric charge accumulated by direct current voltage, and also suppresses an afterimage by alternating current driving do it with

Moreover, it exists in providing the liquid crystal aligning agent which can provide the liquid crystal display element which has said liquid crystal aligning film, and said liquid crystal aligning film.

As a result of earnestly researching, this inventor discovered that the liquid crystal aligning agent which has a polymer containing a specific structure is very effective in order to achieve said objective, and came to complete this invention.

That is, this invention has the following summary.

1. Following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.

(A) component: at least 1 selected from the group which consists of a polyimide precursor which has at least 1 sort(s) of structure chosen from the group which consists of following formula [1A] and [1B], and the polyimide which imidated this polyimide precursor species of polymers.

[Formula 1]

(X ^A and X ^C each independently represent a protecting group substituted with a hydrogen atom by heat. X ^B represents a single bond or an organic group having 1 to 40 carbon atoms, in which case the ester group (-COO- group) is bonded. Atoms are carbon atoms.)

(B) component: It is obtained by the polycondensation reaction of the tetracarboxylic-acid component containing tetracarboxylic dianhydride of following formula (B-1), and the diamine component containing the diamine of following formula (B-2) The at least 1 sort(s) of polymer chosen from the group which consists of polyimide which imidated a polyamic acid and its polyimide precursor.

[Formula 2]

(Wherein, Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring. B ₁ and B ₂ are each independently a hydrogen atom and a carbon number They are a 1-10 alkyl group, a C1-C10 alkenyl group, or a C1-C10 alkynyl group, and these groups may have a substituent.)

2. Liquid crystal aligning agent of said 1 whose at least 1 sort(s) of structure chosen from the group which consists of said formula [1A] and [1B] is a structure of a following formula [1a], a formula [1b], or a formula [1c] .

[Formula 3]

(In formula [1a], X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms when m is 1. X ^b represents a protecting group substituted with a hydrogen atom by heat. m is an integer of 1 or 2 However, when m is 2, there ^{is no substituent for X a} . In formula [1b], X ^c represents a protecting group substituted with a hydrogen atom by heat. In formula [1c], X ^d is a single bond or represents an organic group having 1 to 20 carbon atoms, X ^e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^f represents a protecting group substituted with a hydrogen atom by heat, and n represents an integer of 1 to 4)

3. The diamine component and tetracarboxylic-acid component containing the diamine which said (A) component has at least 1 sort(s) of structure chosen from the structure shown by the said formula [1a], a formula [1b], and a formula [1c] The liquid crystal aligning agent as described in said 2 which is at least 1 sort(s) of polymer chosen from the polyimide precursor obtained by polycondensing, and the polyimide which imidated this polyimide precursor.

4. Liquid crystal aligning agent of said 3 whose said diamine is diamine represented by following formula [1-1].

[Formula 4]

(wherein, X ^D represents an organic group having 5 to 50 carbon atoms and having at least one structure selected from the group consisting of formula [1a], formula [1b] and formula [1c], A ¹ and A ² are , each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent.

5. Liquid crystal aligning agent as described in said 4 whose said diamine is at least 1 sort(s) of diamine chosen from the group which consists of a following formula [1a-1] - a formula [1c-1].

[Formula 5]

(In formula [1a-1], X ¹ is a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )-, -CON(R ² )-, -N(R ³ )CO represents at least one organic group selected from -, -CH ₂ O-, -COO- and -OCO-, with the proviso that R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ² represents a single bond or an alkylene group having 1 to 10 carbon atoms X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms when m is 1. X ^b is heat substituted with a hydrogen atom m represents an integer of 1 or 2. In that case, when m is 2, there ^{is no substituent for X a} . p represents an integer of 1 to 4, q represents an integer of 1 to 4 indicates.

In formula [1b-1], X ³ and X ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )-, -CON(R ² )-, - At least 1 type selected from N(R ³ )CO-, -CH ₂ O-, -COO-, and -OCO- is represented. However, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ⁴ and X ⁶ each independently represent a single bond or an alkylene group ^{having 1 to 10 carbon atoms, X 5} represents a single bond or an alkylene group having 1 to 10 carbon atoms, and X ^c is a protecting group substituted with a hydrogen atom by heat. and r represents the integer of 1-4.

In the formula [1c-1], X ⁸ is a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )-, -CON(R ² )-, -N(R ³ )CO- , -CH ₂ O-, -COO-, and -OCO- represent at least 1 sort(s). However, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ⁹ represents a single bond or an alkylene group having 1 to 10 carbon atoms, X ^d represents a single bond or an organic group ^{having 1 to 20 carbon atoms, X e} represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^f represents a heat represents a protecting group substituted with a hydrogen atom, n represents an integer of 1 to 4, s represents an integer of 1 to 4, t represents an integer of 1 to 4, formula [1a-1] to formula [1c- In 1], A ¹ to A ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent. .)

6. Liquid crystal aligning agent of said 5 whose said diamine is at least 1 sort(s) of diamine chosen from the group which consists of a following formula [1d-1] - a formula [1d-5].

[Formula 6]

(Formula [1d-1] ~ formula [1d-5] of, R ¹ ~ R ⁷ is at least one kind selected from the group consisting of each independently represent the formula [a-1] ~ formula [a-6] below A ¹ to A ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent do.)

[Formula 7]

(In formula [a-2], R<^1> represents a C1-C5 alkyl group.)

7. The polyimide which imidated the polyimide precursor obtained by the polymer of the said (A) component polycondensing the diamine component containing the diamine shown by following formula [3-1], and a tetracarboxylic-acid component, and this polyimide precursor The liquid crystal aligning agent in any one of said 1-6 which is at least 1 sort(s) chosen from the group which consists of.

[Formula 8]

(In formula [3-1], X ^E represents at least one structure selected from the group consisting of the following formulas [3a-1] to [3a-10], and A ¹ and A ² are each independently , a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent.

[Formula 9]

(In formula [3a-9], n represents the integer of 1-5.)

8. Liquid crystal aligning agent in any one of said 1-7 whose said tetracarboxylic-acid component is tetracarboxylic dianhydride shown by following formula [4].

[Formula 10]

(Z represents at least one structure selected from the group consisting of the following formulas [4a] to [4q].)

[Formula 11]

[Formula 12]

(In formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and in the formula [4g], Z ⁵ and Z ⁶ are each independently , represents a hydrogen atom or a methyl group.)

9. The said tetracarboxylic-acid component, Z in said formula [4] is said formula [4a], a formula [4e] - a formula [4g], a formula [4l], a formula [4m], or a formula [4p] The liquid crystal aligning agent of said 8 which is an at least 1 sort(s) of tetracarboxylic-acid compound chosen from the group which consists of.

10. The polymer of the said (A) component WHEREIN: 5-30 mol of the diamines shown by the said formula [1a-1], a formula [1b-1], and a formula [1c-1] in 100 mol% of all the diamine components %, the liquid crystal aligning agent in any one of said 5-9.

11. Said (B) component WHEREIN: Among said 1-10 whose tetracarboxylic dianhydride represented by said Formula (B-1) is 10-100 mol% with respect to 1 mol of all the tetracarboxylic-acid components The liquid crystal aligning agent in any one of Claims.

12. Said (B) component WHEREIN: The liquid crystal aligning agent in any one of said 1-11 whose diamine of said formula (B-2) is 10-100 mol% with respect to 1 mol of all the diamine components.

_{13. The above 1} to, wherein Y 1 in the formula (B-2) is at least one selected from the group consisting of a divalent organic group having a nitrogen atom represented by the following formulas (YD-1) to (YD-5). The liquid crystal aligning agent in any one of 12.

[Formula 13]

(In formula (YD-1), E ₁ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and Q ₁ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. In 2), W ₁ is a hydrocarbon group having 1 to 10 carbon atoms, E ₂ is a monovalent organic group having 3 to 15 carbon atoms having a nitrogen atom-containing heterocyclic ring, or a disubstituted amino group substituted with an aliphatic group having 1 to 6 carbon atoms In the formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, W ₃ is an alkylene group having 2 to 5 carbon atoms or a biphenylene group, Q ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzene ring, a is an integer from 0 to 1. In formula (YD-4), E ₃ is a heterocyclic ring containing 3 to 15 carbon atoms. In (YD-5), E ₄ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and W ₅ is an alkylene group having 2 to 5 carbon atoms.)

_{14. E 1} , E ₂ , E ₃ , and E ₄ having 3 to 15 carbon atoms in the formulas (YD-1), (YD-2), (YD-4), and (YD-5) The nitrogen atom-containing heterocyclic ring of pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, and isoquinoline The liquid crystal aligning agent in any one of said 1-13 which is at least 1 sort(s) chosen from a group.

_{15. The above 1 to, wherein Y 1 in} the formula (B-2) is at least one selected from the group consisting of a divalent organic group having a nitrogen atom represented by the following formulas (YD-6) to (YD-21). The liquid crystal aligning agent in any one of 14.

[Formula 14]

[Formula 15]

(In formula (YD-17), h is an integer of 1-3, and in formula (YD-14) and formula (YD-21), j is an integer of 0-3.)

16. In the above 15, Y _{1 in} the formula (B-2) is at least one selected from the group consisting of a divalent organic group having a nitrogen atom represented by the formulas (YD-14) and (YD-18). The liquid crystal aligning agent described.

17. Liquid crystal aligning agent in any one of said 1-16 whose polymer of said (B) component is 40-250 mass parts with respect to 100 mass parts of polymers of said (A) component.

18. Any one of 1 to 17 above, containing at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone The liquid crystal aligning agent as described in.

19. At least one selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether The liquid crystal aligning agent in any one of said 1-18 containing the solvent of a kind.

20. A crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group, and polymerizable The liquid crystal aligning agent in any one of said 1-19 containing at least 1 sort(s) chosen from the group which consists of a crosslinkable compound which has an unsaturated bond.

21. The liquid crystal aligning film obtained by apply|coating the liquid crystal aligning agent in any one of said 1-20, and baking.

22. The liquid crystal aligning film obtained by the inkjet method using the liquid crystal aligning agent in any one of said 1-20.

23. The liquid crystal aligning film obtained by irradiating the radiation which polarized to the said liquid crystal aligning film of 21 or 22.

24. Liquid crystal display element which has liquid crystal aligning film in any one of said 21-23.

The liquid crystal aligning agent containing two types of the polyimide precursor which has a specific structure of this invention, or the at least 1 sort(s) of polymer chosen from polyimide, suppression of charge accumulation by the asymmetry of alternating current drive, and the residual accumulated by a direct voltage. The liquid crystal aligning film which suppresses rapid relaxation of an electric charge, and also the residual image by alternating current drive by extension can be formed. In particular, it is useful as a liquid crystal aligning film for photo-alignment processing methods obtained by irradiating the polarized radiation.

Moreover, the liquid crystal display element which has the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention becomes a thing excellent in reliability, and can use it suitably for a large screen, high-definition liquid crystal television, a small and medium-sized car navigation system, a smart phone, etc.

<Specific structure (1A) and specific structure (1B)>

Component (A) of the present invention (hereinafter also referred to as specific polymer (A)) is composed of the following formula [1A] (also referred to as specific structure (1A)) and [1B] (also referred to as specific structure (1B)) It is an at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor which has at least 1 sort(s) of structure chosen from the group, and the polyimide which imidated this polyimide precursor.

[Formula 16]

In formula [1A], X ^A represents the group substituted by the hydrogen atom by heat. This group is called a protecting group in that it bonds to a nitrogen atom, is released by heat, is replaced with a hydrogen atom, and forms an amino group. The temperature at which such a protecting group is removed by heat and is substituted with a hydrogen atom is a calcination temperature at the time of producing a liquid crystal aligning film, Preferably it is 150-300 degreeC, More preferably, it is 200-270. Such a protecting group is not particularly limited as long as it is removed by heat and replaced with a hydrogen atom, and specifically, at least one selected from the group consisting of the following formulas [a-1] to [a-6], among others, a formula A protecting group having a structure represented by [a-1] or [a-6] is preferable.

[Formula 17]

(In formula [a-2], R<^1> represents a C1-C5 alkyl group).

As for formula [1A], the structure shown by a following formula [1a] and a formula [1b] is preferable.

[Formula 18]

In formula [1a], X ^a represents a hydrogen atom or a C1-C20 organic group. Especially, a hydrogen atom or a C1-C10 organic group is preferable. ^{X b} in formula [1a] ^{and X c} in formula [1b] are groups substituted with a hydrogen atom by heat, and are a protecting group of a carboxy group. X ^b and X ^c are the ^{same as those of X A described} above, and are also the same in preferred examples.

In the formulas [1a], m is an integer of 1 or 2, when m is 2, it is not ^a substituent of X. As for m, 1 is preferable.

As a specific example which has a structure of a formula [1a] and/or [1b], the structure of a following formula [XA-1] - a formula [XA-12] is mentioned.

[Formula 19]

(In formula [XA-1] - formula [XA-6], A ¹ - A ⁶ are each independently at least 1 sort(s) chosen from the group which consists of said formula [a-1] - a formula [a-6] In formula [XA-1], n1 represents an integer of 0 to 10, and in formulas [XA-2] to formula [XA-6], n2 to n6 represents an integer of 1 to 10).

[Formula 20]

(In formula [XA-7] - formula [XA-12], A ⁷ - A ¹⁸ are each independently at least 1 sort(s) chosen from the group which consists of said formula [a-1] - a formula [a-6] In formula [XA-7], n7 represents an integer of 0 to 10, and in formulas [XA-8] to formula [XA-12], n8 to n12 represents an integer of 1 to 10).

In formula [1B], X ^B represents a single bond or a C1-C40 organic group. Specific examples of the organic group having 1 to 40 carbon atoms include an ether bond (-O-), an amide bond (-CONH- or NHCO-), an ester bond (-COO- or OCO-), and a thioether bond (-S-) or an alkylene group, an arylene group, or a combination thereof which may contain a thioester bond (-S(=O) _{2 -).} In that case, the atom to which the ester group (-COO-) in Formula [1B] couple|bonds is a carbon atom.

In formula [1B], X ^C is a group substituted with a hydrogen atom by heat, and is a protecting group of a carboxy group. X ^b and X ^c are the ^{same as those of X A described} above, and are also the same in preferred examples.

As said formula [1B], the structure shown by a following formula [1c] is preferable.

[Formula 21]

In formula [1c], X ^d represents a single bond or an organic group having 1 to 20 carbon atoms, and in that case, when X ^d is a single bond, there is no ^{substituent X e .} Especially, a single bond or a C1-C10 organic group is preferable. X ^e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms when ^{X d is not a single bond.} Especially, a hydrogen atom or a C1-C10 organic group is preferable. X ^f is a group substituted with a hydrogen atom by heat, and is a protecting group of a carboxy group. X ^f is the same as above-mentioned X ^A, and it is the same also about a preferable example. n represents the integer of 1-4. Especially, 1 or 2 is preferable.

As a specific example of the structure of a formula [1c], the structure of following formula [XC-1] - [XC-12] is mentioned.

[Formula 22]

(in formula [XC-1] - formula [XC-6], B ¹ - B ⁶ are each independently at least 1 type selected from the group which consists of said formula [a-1] - formula [a-6] In formula [XC-1], n1 represents an integer of 0 to 10, and in formulas [XC-2] to formula [XC-6], n2 to n6 represent an integer of 1 to 10).

[Formula 23]

(In formula [XC-7] - formula [XC-12], B ⁷ - B ¹⁸ are each independently at least 1 sort(s) chosen from the group which consists of said formula [a-1] - a formula [a-6] In formula [XC-7], n7 represents an integer of 0 to 10, and in formulas [XC-8] to formula [XC-12], n8 to n12 represents an integer of 1 to 10).

<Specific Polymer (A)>

The specific polymer (A) of this invention is at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor and the polyimide which imidated this polyimide precursor (it is also generically called a polyimide-type polymer). Especially, it is preferable that the polyimide-type polymer of this invention is the polyimide which imidated the polyimide precursor obtained by making a diamine component and a tetracarboxylic-acid component react, or this polyimide precursor.

A polyimide precursor is a structure shown by a following formula [A].

[Formula 24]

(In formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group, and A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ³ and A ⁴ is each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent. n is a positive integer indicate.)

As said diamine component, the diamine which has two primary or secondary amino groups in a molecule|numerator is mentioned.

As said tetracarboxylic-acid component, tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic-acid dihalide, tetracarboxylic-acid dialkyl ester, or tetracarboxylic-acid dialkyl ester dihalide is mentioned.

Formula [A] a of A ¹ and A ² are, in order to obtain a polyamic acid hydrogen atoms, Having two primary or amino groups of the second class in a molecule, a tetracarboxylic acid compound or tetracarboxylic acid dianhydride It can be obtained by reacting.

^{In order to obtain the polyamic-acid alkylester whose A<1>} and A< ² > in a formula [A] is a C1-C5 alkyl group, the said diamine, tetracarboxylic-acid dihalide, tetracarboxylic-acid dialkyl ester, or tetracarboxylic-acid dialkyl It can be obtained by reacting an ester dihalide. In addition, it may be a polyamic acid obtained by the above methods, introduction of an alkyl group of A ¹ and A ² having 1 to 5 carbon atoms represented by the formula [A].

The specific polymer (A) of this invention is a polymer which has at least 1 sort(s) chosen from the group which consists of a specific structure (1A) and a specific structure (1B).

Although there is no restriction|limiting in particular in the method of introduce|transducing the specific structure (1A) or specific structure (1B) of this invention into a specific polymer (A), The diamine which has a specific structure (1A) or a specific structure (1B) is used as a diamine component It is preferable to do It is especially preferable to use the diamine which has a structure shown by the said formula [1a], a formula [1b], or a formula [1c].

It is preferable to use the diamine (it is also mentioned specific diamine (1)) specifically, shown by following formula [1-1].

[Formula 25]

Formula [1-1] of, A ¹ and A ² are, each independently, an alkynyl group of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms of these substituent groups are the may have

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, and a cyclohexyl 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 substituted with a CH=CH structure. Specifically, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group , a 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 substituted with a C≡C structure. Specifically, an ethynyl group, 1-propynyl group, 2-propynyl group, etc. are mentioned.

As long as said alkyl group, an alkenyl group, and an alkynyl group are C1-C10 as a whole, they may have a substituent, Furthermore, they may form ring structure with a substituent. In addition, the formation of a ring structure by a substituent means that substituents or a substituent and a part of a parent|skeleton couple|bond 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 phosphoric acid ester group, an amide group, an alkyl group, An alkenyl group, an alkynyl group, etc. are mentioned.

A fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned as a halogen group which is a substituent.

A phenyl group is mentioned as an aryl group which is a substituent. The other substituents mentioned above may further substitute by this aryl group.

As an organooxy group which is a substituent, the structure represented by -O-R can be shown. As R, the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. can be illustrated. The above-mentioned substituent may further substitute by these R. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

As an organothio group which is a substituent, the structure represented by -S-R can be shown. As R, the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. can be illustrated. The above-mentioned substituent may further substitute by these R. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.

As an organosilyl group which is a substituent, the _{structure represented by -Si-(R) 3} can be shown. Three R on Si may be the same or different, and can illustrate the alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The above-mentioned substituent may further substitute by these R. Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group. .

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, etc. can be illustrated. The above-mentioned substituent may further substitute by these R. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

As an ester group which is a substituent, the structure represented by -C(O)O-R or -OC(O)-R can be shown. As R, the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. can be illustrated. The above-mentioned substituent 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 above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. can be illustrated. The above-mentioned substituent 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. Two R may be the same or different, and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The above-mentioned substituent may further substitute by these R.

As an amide group which is a substituent, a structure represented by -C(O)NH ₂ , -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , or -NRC(O)R is can indicate These R may be the same or different, and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The above-mentioned substituent may further substitute by these R.

As an aryl group which is a substituent, the thing similar to the above-mentioned aryl group is mentioned. The other substituent mentioned above may further substitute by this aryl group.

As an alkyl group which is a substituent, the thing similar to the above-mentioned alkyl group is mentioned. The other substituent mentioned above may further substitute by this alkyl group.

As an alkenyl group which is a substituent, the thing similar to the above-mentioned alkenyl group is mentioned. The other substituent mentioned above may further substitute by this alkenyl group.

As an alkynyl group which is a substituent, the thing similar to the above-mentioned alkynyl group is mentioned. The other substituent mentioned above may further substitute by this alkynyl group.

In general, when a bulk structure is introduced, since there is a possibility that the reactivity of the amino group or the liquid crystal orientation may be reduced, as A ¹ and A ² , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable, A hydrogen atom, a methyl group or an ethyl group is particularly preferred.

In formula [1-1], X ^D represents a C5-C50 organic group which has at least 1 sort(s) chosen from the group which consists of the structure shown by the said formula [1a], a formula [1b], and a formula [1c].

More specifically, the diamine shown by a following formula [1a-1] - a formula [1c-1] is preferable.

[Formula 26]

In formula [1a-1], X ¹ is a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )-, -CON(R ² )-, -N(R ³ )CO- , -CH ₂ O-, -COO-, and OCO- represent at least 1 sort(s). However, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, a single bond, -O-, -CONH-, -NHCO-, -COO-, or OCO- is preferable.

In formula [1a-1], X<^2> represents a single bond or a C1-C10 alkylene group. Especially, a single bond or a C1-C5 alkylene group is preferable.

In formula [1a-1], X ^a represents a hydrogen atom or a C1-C20 organic group, More preferably, it is a hydrogen atom or a C1-C10 organic group. The organic group having 1 to 10 carbon atoms is preferably -(CH ₂ ) _n -COO-tBu (n = an integer of 1 to 5, tBu represents a tert-butyl group). X ^{b is the same as X A} in the formula [1A], and is the same for a preferred example.

In the formula [1a-1], m is an integer of 1 or 2, when m is 2, it is not ^a substituent of X. p represents the integer of 1-4. Especially, from the point of the availability of a raw material and the easiness of synthesis, 1-3 are preferable, More preferably, it is 1-2. q represents the integer of 1-4. Especially, from the point of the availability of a raw material and the easiness of synthesis, 1-3 are preferable, More preferably, it is 1-2.

In a formula [1b-1], X ³ and X ^{7 are the same as X 1} in the said formula [1a-1], and it is also the same about a preferable example. X ⁴ , X ^{5 ,} and X ^{6 are the same as X 2} in the formula [1a-1], and also the same for preferred examples. X ^{c is the same as X A} in the formula [1A], and is the same for a preferred example. r represents the integer of 1-4. Especially, the point of the availability of a raw material and the easiness of a synthesis|combination to 1-3 are preferable. More preferably, it is 1-2.

In formula [1c-1], X<^{8> is the same definition as X<1} > in the said formula [1a-1], and it is the same also about a preferable example. X ^{9 is the same as X 2} in the formula [1a-1], and is the same for a preferred example. X ^d represents a single bond or an organic group having 1 to 20 carbon atoms. Especially, a single bond or a C1-C10 organic group is preferable. More preferably, it is a single bond or a carbon atom (>CH-). X ^e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. When X ^d is a single bond, there is no ^{substituent X e .} Among them, a hydrogen atom or -NH-COO-tBu (tBu represents a tert-butyl group) is preferable. X ^{f is the same as X b} in the said Formula [1a], and it is the same also about a preferable example.

n, s, and t represent the integers of 1-4. Especially, from the point of the availability of a raw material and the easiness of synthesis, respectively, 1-3 are preferable, and 1-2 are more preferable.

In the formula [1a-1] ~ formula ^{[1c-1], A 1} ~ A 6 are, including preferred examples, the same definition as A ¹ and A ² of the formula [1-1].

Moreover, as a specific diamine, the diamine of a following formula [1d-1] - a formula [1d-9] is mentioned.

[Formula 27]

In formulas [1d-1] to [1d-5], R ¹ to R ⁷ are each independently at least one selected from the group consisting of the above formulas [a-1] to [a-6]. A ¹ - A ¹⁰ are the same definitions ^{as A 1} and A ² of a formula [1-1] including a preferable example.

[Formula 28]

In the formula [1d-6] ~ formula ^{[1d-9], R 8} ~ R 14 is at least one member, each independently, selected from the group consisting of the formula [a-1] ~ formula [a-6]. ~ A ¹¹ A ¹⁸ are, including preferred examples, the same definition as A ¹ and A ² of the formula [1-1].

As specific diamine (1) of this invention, it is preferable to use at least 1 sort(s) chosen from the group which consists of the diamine shown by the said formula [1d-1] - a formula [1d-5].

It is preferable that the specific diamine (1) in a specific polymer (A) is 5-40 mol% in 100 mol% of all the diamine components. Especially, 5-30 mol% is preferable. More preferably, it is 5-20 mol%.

Specific diamine (1) is one type or according to characteristics such as the solubility to the solvent of the specific polymer (A), the applicability of the liquid crystal aligning agent, and the liquid crystal orientation in the case of a liquid crystal aligning film, voltage retention, and accumulated charge. You may mix and use 2 or more types.

As a diamine component at the time of manufacturing a specific polymer (A), it is preferable to use the other diamine (it is also mentioned specific 2nd diamine) shown by following formula [3-1] with specific diamine (1).

[Formula 29]

In formula [3-1], X ^E is at least 1 selected from the structure shown by a following formula [3a-1] - a formula [3a-9].

[Formula 30]

(In formula [3a-9], n represents the integer of 1-5.)

In formula [3-1], A<^1> and A<^2> respectively independently represent a hydrogen atom or a C1-C5 alkyl group.

As specific 2nd diamine, the diamine of a formula [3a-1] - a formula [3a-4], a formula [3a-6], a formula [3a-8], or a formula [3a-9] is preferable. A more preferable thing is a formula [3a-1] - a formula [3a-3], a formula [3a-8], or a formula [3a-9]. Especially preferable is a formula [3a-1], a formula [3a-2], or a formula [3a-9].

As for the specific 2nd diamine in a specific polymer (A), 50-95 mol% is preferable in 100 mol% of all the diamine components, More preferably, it is 60-95 mol%, Especially preferably, it is 80-95 mol%. is mol%.

Specific 2nd diamine is one type or two according to characteristics, such as the solubility to the solvent of a specific polymer (A), applicability|paintability of a liquid crystal aligning agent, the liquid-crystal orientation in the case of setting it as a liquid crystal aligning film, voltage retention, accumulated electric charge, etc. It is also possible to use a mixture of more than one type.

As a diamine component of a specific polymer (A) and a specific polymer (B), unless the effect of this invention is impaired, with specific diamine (1), specific diamine (2), and specific 2nd diamine, other diamine (also referred to as other diamines) may be used.

As other diamines, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'- Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-dia Minodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl) Silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodi Phenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine; N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4- Diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1, 8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis (4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3, 5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl) ) Benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4'- [1 ,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)] Dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1 ,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1 ,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-amino Phenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis( 4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide) , N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl) Terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4, 4'-bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy) ) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane , 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3- Bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy) Pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis( 4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1 ,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy) ) Decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- ( 3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, 11-diaminoundecane, 1,12-diaminododecane, or diamine whose amino group is a secondary amino group is mentioned. Another diamine can be used even if it mixes 1 type or 2 or more types.

As a tetracarboxylic-acid component for manufacturing a specific polymer (A), the tetracarboxylic dianhydride shown by following formula [4] is preferable. In that case, not only the specific tetracarboxylic dianhydride shown by Formula [4], but the tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester which are the tetracarboxylic acid derivatives. A dihalide may also be used (tetracarboxylic dianhydride and its derivatives are collectively referred to as a specific tetracarboxylic acid component).

[Formula 31]

(In formula [4], Z represents at least 1 sort(s) chosen from the group which consists of a following formula [4a] - a formula [4q].)

[Formula 32]

[Formula 33]

Formula [4a] of, Z ¹ ~ Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a chlorine atom or a benzene ring.

In the formula [4g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.

^{Z 1} in formula [4] is from the point of the ease of synthesis or polymerization reactivity at the time of manufacturing a polymer, a formula [4a], a formula [4c] - [4g], a formula [4k] - a formula [4m] Or it is a formula [4p], More preferably, it is a formula [4a], a formula [4e] - a formula [4g], a formula [4l], a formula [4m], or a formula [4p]. A formula [4a], a formula [4e], a formula [4f], a formula [4l], a formula [4m], or a formula [4p] are especially preferable.

More specifically, a following formula [4a-1] or a formula [4a-2] is preferable.

[Formula 34]

50-100 mol% is preferable in 100 mol% of all the tetracarboxylic-acid components, and, as for the specific tetracarboxylic-acid component in specific polymers (A) and (B), 70-100 mol% is more preferable, Especially preferably, it is 80-100 mol%.

A specific tetracarboxylic-acid component is 1 according to characteristics, such as the solubility to the solvent of a specific polymer (A), the applicability|paintability of a liquid crystal aligning agent, the orientation of the liquid crystal in the case of setting it as a liquid crystal aligning film, voltage retention, and accumulated electric charge You can also use it by mixing two or more types.

Unless the effect of this invention is impaired for the polyimide-type polymer of a specific polymer (A), other tetracarboxylic-acid components other than a specific tetracarboxylic-acid component can also be used.

As another tetracarboxylic-acid component, the following tetracarboxylic-acid compound, tetracarboxylic dianhydride, tetracarboxylic-acid dihalide, tetracarboxylic-acid dialkyl ester, or tetracarboxylic-acid dialkyl ester dihalide is mentioned.

Other tetracarboxylic acid components are, specifically, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether; 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4 -dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl Silane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3' ,4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid and the like. Another tetracarboxylic-acid component can also be used 1 type or in mixture of 2 or more types.

<Specific Polymer (B)>

The liquid crystal aligning agent of this invention is polycondensation of the diamine component containing the tetracarboxylic-acid component containing tetracarboxylic dianhydride represented by a following formula (B-1), and the diamine represented by a following formula (B-2) The at least 1 sort(s) of polymer and organic solvent chosen from the group which consists of a polyamic acid obtained by reaction and the imidation polymer of this polyamic acid are contained.

[Formula 35]

When there are too few ratios of tetracarboxylic dianhydride represented by Formula (B-1), the effect of this invention will not be acquired. Therefore, as for the ratio of tetracarboxylic dianhydride represented by Formula (B-1), 10-100 mol% is preferable with respect to 1 mol of all tetracarboxylic dianhydride, More preferably, 30-100 mol %, more preferably 50 to 100 mol%.

The polyamic acid contained in a liquid crystal aligning agent may use tetracarboxylic dianhydride represented by a following formula (B-3) other than tetracarboxylic dianhydride represented by said Formula (B-1).

[Formula 36]

In formula (B-3), X is a tetravalent organic group, and the structure is not specifically limited. If a specific example is given, a following formula (X-1) - a formula (X-42) will be mentioned.

[Formula 37]

[Formula 38]

[Formula 39]

In the formula (X-1), R ₃ to R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, more preferably a hydrogen atom or a methyl group.

At least 1 sort(s) chosen from the group which consists of a structure represented by a following formula (B-4) as tetracarboxylic dianhydride from a viewpoint of the availability of a compound is preferable.

[Formula 40]

(In formula [B-4], X ₁ is at least one selected from the group consisting of structures represented by formulas (X-1) to (X-14).)

Since the reliability of the liquid crystal aligning film obtained can be raised further, as X<_1> , the structure (even if it contains an oxygen atom) which consists only of an aliphatic group like said Formula (X-1) - a formula (X-7) and a formula (X-11) ) is preferable, and the structure of the formula (X-1) is more preferable. Moreover, since favorable liquid-crystal orientation is shown, as _{a structure of X<1>} , a following formula (X1-1) or a formula (X1-2) is further more preferable.

[Formula 41]

Since the effect of this invention may be impaired when the ratio of tetracarboxylic dianhydride represented by Formula (B-3) increases, it is unpreferable. Therefore, as for the ratio of tetracarboxylic dianhydride represented by Formula (B-3), 0-90 mol% is preferable with respect to 1 mol of all tetracarboxylic dianhydride, More preferably, 0-70 mol% , more preferably 0 to 50 mol%.

In the formula (B-2), Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, and B ₁ and B ₂ are each independently , a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or a C1-C10 alkynyl group, these groups may have a substituent.

For groups of these, as defined in A ¹ and A ² in the above formula [1-1], and the same applies to preferred examples.

In general, when a bulk structure is introduced, since there is a possibility of reducing the reactivity of the amino group and the liquid crystal orientation, as B ₁ and B ₂ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable. , a hydrogen atom, a methyl group or an ethyl group is particularly preferred.

_{As Y<1>} in Formula (B-2), if it has at least 1 sort(s) of structure chosen from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, it will not specifically limit as an organic group. As a specific example, the divalent organic group which has at least 1 sort(s) of structure selected from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring represented by a following formula (YD-1) - a formula (YD-5) is mentioned.

[Formula 42]

In the formula (YD-1), E ₁ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and Q ₁ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

In the formula (YD-2), W ₁ is a hydrocarbon group having 1 to 10, E ₂ is a monovalent organic group having a carbon number of 3-15 having a heterocyclic ring containing a nitrogen atom, or with an aliphatic group having 1 to 6 carbon atoms It is a substituted disubstituted amino group.

In the formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, W ₃ is an alkylene group having 2 to 5 carbon atoms or a biphenylene group, Q ₂ is a hydrogen atom, a C1-C5 alkyl group, or a benzene ring, and a is the integer of 0-1.

In formula (YD-4), E ₃ is a C3-C15 nitrogen atom containing heterocyclic ring.

In the formula (YD-5), E ₄ is a heterocyclic ring containing the nitrogen atom of a carbon number of 3 ~ 15, W ₅ is an alkylene group having a carbon number of 2-5.

Containing a nitrogen atom having 3 to 15 carbon atoms _{in E 1} , E ₂ , E ₃ , and E ₄ in formulas (YD-1), (YD-2), (YD-4), and (YD-5) As a heterocyclic ring, if it is a well-known structure, it will not specifically limit. Among these, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, isoquinoline, etc. are mentioned, Piperazine , piperidine, indole, benzimidazole, imidazole, carbazole, or pyridine is more preferable.

_{Moreover, as a specific example of Y<1>} in Formula (B-2), the divalent organic group which has a nitrogen atom represented by a following formula (YD-6) - a formula (YD-21) is mentioned. Since the charge accumulation by alternating current drive can be suppressed, a formula (YD-14) - a formula (YD-21) are more preferable, and a formula (YD-14) or a formula (YD-18) is especially preferable.

[Formula 43]

[Formula 44]

[Formula 45]

In formula (YD-17), h is an integer of 1-3, and j is an integer of 0-3 in formula (YD-14) and formula (YD-21).

It is preferable that the ratio of the diamine represented by Formula (B-2) in the polyamic acid of this invention and the imidation polymer of this polyamic acid is 10-100 mol% with respect to 1 mol of all diamines, More preferably is 30 to 100 mol%, more preferably 50 to 100 mol%.

The polyamic acid contained in the liquid crystal aligning agent of this invention may use the diamine represented by a following formula (B-5) other than the diamine represented by the said Formula (B-2).

_{Y 2} in the following formula (B-5) is a divalent organic group, the structure is not particularly limited, and two or more types may be mixed. If a specific example is shown, the divalent organic group of the structure shown by a following formula (Y-1) - a formula (Y-76) will be mentioned. _{B 1} and B ₂ in the following formula (B-5) have the same definitions _{as B 1} and B _{2 in the} formula (B-2) including preferred examples.

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

Among these, in order to obtain a good liquid crystal alignment property, preferably a diamine, high linearity, and a Y ₂ formula (Y-7), formula (Y-21) ~ formula (Y-23), formula (Y-25) ~ Formula (Y-27), Formula (Y-43) - Formula (Y-46), Formula (Y-48), Formula (Y-63), Formula (Y-71), or Formula (Y-73) - Diamine which has a divalent organic group represented by Formula (Y-76) is preferable.

Since the effect of this invention may be impaired when the ratio of the diamine represented by Formula (B-5) increases, it is unpreferable. Therefore, as for the ratio of the diamine represented by a formula (B-5), 0-90 mol% is preferable with respect to 1 mol of all diamines, More preferably, 0-70 mol%, More preferably, it is 0-50 mol%. to be.

<The manufacturing method of a specific polymer (A) and a specific polymer (B)>

In this invention, the method of manufacturing a specific polymer (A) and a specific polymer (B) is not specifically limited. Usually, it is obtained by making a diamine component and a tetracarboxylic-acid component react. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and derivatives of tetracarboxylic acid is reacted with a diamine component composed of one or more diamines, The method of obtaining polyamic acid is mentioned. Specifically, polyamic acid is obtained by polycondensing tetracarboxylic dianhydride and primary or secondary diamine to obtain polyamic acid, tetracarboxylic acid and primary or secondary diamine are subjected to dehydration polycondensation reaction to produce polyamic acid The method of obtaining a polyamic acid by polycondensing a tetracarboxylic-acid dihalide and primary or secondary diamine is used.

In order to obtain a polyamic acid alkylester, a method of polycondensing tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a primary or secondary diamine, a tetracarboxylic acid dihalide obtained by dialkyl esterification of a carboxylic acid group, A method of polycondensing primary or secondary diamine, or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain a polyimide, the method of ring-closing said polyamic acid or polyamic-acid alkylester, and setting it as a polyimide is used.

Reaction of a diamine component and a tetracarboxylic-acid component is normally performed 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 below, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a following formula [D-1] - a formula [D -3] can be used.

[Formula 55]

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents a C1-C4 alkyl group).

These solvents may be used independently or may be used in mixture. Moreover, even if it is a solvent in which a polyimide precursor is not dissolved, you may use it in the range in which the produced|generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since the water|moisture content in a solvent inhibits a polymerization reaction and becomes a cause of hydrolyzing the produced|generated polyimide precursor by extension, it is preferable to use the solvent which carried out dehydration and drying.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, a solution obtained by dispersing or dissolving the diamine component in the solvent is stirred and the tetracarboxylic acid component is added as it is or by dispersing or dissolving it in the solvent. A method of adding a diamine component to a solution in which a carboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. are mentioned, Any of these methods may be used . Moreover, when making a diamine component or a tetracarboxylic-acid component use two or more types, respectively, and making it react, you may make it react in the state mixed beforehand, you may make it react individually sequentially, In addition, the low molecular-weight body made to react individually is mixed and reacted, and a polymer can be done with

Although the polymerization temperature in that case can select arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC.

In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. The reaction initial stage can be performed at high concentration, and a solvent can be added after that.

In the polymerization reaction of a polyimide precursor, it is preferable that ratio of the total number of moles of a diamine component and the total number of moles of a tetracarboxylic-acid component is 0.8-1.2. As in a typical polycondensation reaction, the closer this molar ratio to 1.0, the greater the molecular weight of the polyimide precursor produced.

The polyimide is a polyimide obtained by ring-closing the polyimide precursor described above, and in this polyimide, the ring-closure rate of the amic acid group (also referred to as the imidization rate) is not necessarily 100%, and is arbitrarily selected according to the use or purpose. Can be adjusted.

As a method of imidating a polyimide precursor, thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

The temperature in the case of thermally imidating a polyimide precursor in a solution is 100-400 degreeC, Preferably it is 120-250 degreeC, It is preferable to carry out, removing the water produced|generated by imidation reaction to the outside of a system.

Catalyst imidation of a polyimide precursor is -20-250 degreeC by adding a basic catalyst and an acid anhydride to the solution of a polyimide precursor, It is -20-250 degreeC, Preferably it can perform by stirring at 0-180 degreeC.

The amount of the basic catalyst is 0.5 to 30 mole times of the amic acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a suitable basicity for advancing the reaction.

As an acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned. Among them, the use of acetic anhydride is preferable because purification after completion of the reaction becomes easy.

The imidation rate by catalytic imidation can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When collect|recovering the produced|generated polyimide precursor or polyimide from the reaction solution of a polyimide precursor or a polyimide, what is necessary is just to inject|throw-in a reaction solution to a solvent and just to precipitate. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by putting it in a solvent can be collected by filtration, and then dried under normal pressure or reduced pressure, at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection|recovery is made to dissolve again in a solvent, and operation which carries out reprecipitation collection|recovery is repeated 2 times - 10 times, the impurity in a polymer can be decreased. As a solvent at this time, alcohol, ketones, hydrocarbon etc. are mentioned, for example. When three or more types of solvents selected from these are used, since the efficiency of refinement|purification further improves, it is preferable.

In this invention, it is preferable to use polyamic-acid alkylester for specific polymer (A) and (B).

The more specific method for producing the polyamic-acid alkylester of this invention is shown to following (1)-(3).

(1) Method for producing by esterification of polyamic acid

It is a method of manufacturing a polyamic acid alkylester by manufacturing a polyamic acid from a diamine component and a tetracarboxylic-acid component, performing a chemical reaction, ie, esterification, to the carboxyl group (COOH group).

The esterification reaction is a method in which a polyamic acid and an esterifying agent 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 4 hours). to be.

The esterifying agent is preferably one that can be easily removed after the esterification reaction, and includes N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, and N,N-dimethylformamide dipropyl. Acetal, N,N-dimethylformamidedineopentylbutylacetal, N,N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyl triazine, 1-propyl-3-p-tolyltriazine, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, and the like. have. The amount of the esterifying agent to be used is preferably 2 to 6 molar equivalents with respect to 1 mol of the repeating unit of the polyamic acid. Especially, 2-4 molar equivalent is preferable.

As a solvent used for the said esterification reaction, the solvent used for reaction of the said diamine component and a tetracarboxylic-acid component is mentioned from the soluble point with respect to the solvent of a polyamic acid. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. You may use these solvent 1 type or in mixture of 2 or more types.

As for the density|concentration of the polyamic acid in the solvent in the said esterification reaction, from the point which precipitation of a polyamic acid does not occur easily, 1-30 mass % is preferable. Especially, 5-20 mass % is preferable.

(2) Method for producing by reaction of diamine component and tetracarboxylic acid diester dichloride

Specifically, the diamine component and tetracarboxylic acid diester dichloride are reacted in the presence of a base and a solvent at -20 to 150°C (preferably 0 to 50°C) for 30 minutes to 24 hours (preferably 1 ∼ 4 hours) to react.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used. Among them, pyridine is preferable in order for the reaction to proceed mildly. As for the usage-amount of a base, the quantity which can be removed easily after reaction is preferable, and it is preferable that it is 2-4 times mole with respect to tetracarboxylic-acid diester dichloride. Especially, 2-3 times mole is more preferable.

As a solvent, the solvent used for reaction of the said diamine component and a tetracarboxylic-acid component from the soluble point with respect to the solvent with respect to the solvent of the polymer obtained, ie, polyamic-acid alkylester, is mentioned. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. You may use these solvent 1 type or in mixture of 2 or more types.

As for the density|concentration of the polyamic-acid alkylester in the solvent in reaction, 1-30 mass % is preferable at the point which precipitation of polyamic-acid alkylester does not occur easily. Especially, 5-20 mass % is preferable. Moreover, in order to prevent hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for preparation of polyamic-acid alkylester is dehydrated as much as possible. In addition, it is preferable to carry out the reaction in a nitrogen atmosphere to prevent mixing of external air.

(3) Method for producing by reaction of diamine component and tetracarboxylic acid diester

Specifically, in the presence of a condensing agent, a base, and a solvent, a diamine component and tetracarboxylic-acid diester in 0-150 degreeC (preferably 0-100 degreeC) WHEREIN: 30 minutes - 24 hours (preferably 3 to 15 hours) polycondensation reaction.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1, 3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluroniumtetrafluoroborate, O-(benzotriazole-1 -yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzooxazolyl)phosphonic acid diphenyl, etc. can be used. have. 2-3 times mole is preferable with respect to the tetracarboxylic-acid diester, and, as for the usage-amount of a condensing agent, 2-2.5 times mole is especially preferable.

As the base, tertiary amines such as pyridine and triethylamine can be used. The quantity which can be easily removed after a polycondensation reaction is preferable, as for the usage-amount of a base, 2-4 times mole is preferable with respect to a diamine component, and its 2-3 times mole is more preferable.

As for the solvent used for polycondensation reaction, the solvent used for reaction of the said diamine component and a tetracarboxylic-acid component is mentioned from the solubility point with respect to the solvent of the polymer obtained, ie, polyamic-acid alkylester. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. You may use these solvent 1 type or in mixture of 2 or more types.

Moreover, in a polycondensation reaction, reaction advances efficiently by adding a Lewis acid as an additive. As a Lewis acid, lithium halides, such as lithium chloride and lithium bromide, are preferable. As for the usage-amount of a Lewis acid, 0.1-10 times mole is preferable with respect to a diamine component. Especially, 2.0-3.0 times mole is preferable.

When recovering polyamic acid alkyl ester from the solution of polyamic acid alkyl ester obtained by the method of said (1)-(3), what is necessary is just to inject|throw-in the reaction solution to a solvent and just to precipitate. As a solvent used for precipitation, water, methanol, ethanol, 2-propanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned. For the purpose of removing the additives and catalysts used above, it is preferable that the polymer injected into the solvent and precipitated be washed several times with the solvent. After recovery by filtration, the polymer can be dried under normal pressure or reduced pressure, at room temperature or by heating. Moreover, the impurity in a polymer can be decreased by re-dissolving the polymer which carried out precipitation collection|recovery in a solvent, and repeating operation of reprecipitation collection|recovery 2 times - 10 times.

It is preferable to manufacture polyamic-acid alkylester by the method of said (1) or (2).

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film (it is also called a resin film), and contains a specific polymer (A), a specific polymer (B), and an organic solvent.

As for the ratio of the specific polymer (B) in a liquid crystal aligning agent, 10-900 mass parts is preferable with respect to 100 mass parts of specific polymers (A). Especially, 25-400 mass parts is preferable, and 40-250 mass parts is more preferable. Most preferably, it is 60-160 mass parts.

As for all the polymer components in the liquid crystal aligning agent of this invention, all may be the specific polymer (A) and (B) of this invention, and other polymers other than that may be mixed. As a polymer other than that, the polyimide precursor and polyimide which do not have a specific structure (1A), a specific structure (1B), and a specific structure (2) are mentioned. Furthermore, a cellulosic polymer, an acrylic polymer, a methacryl polymer, polystyrene, polyamide, polysiloxane, etc. are mentioned. In that case, content of other polymers other than that is 0.5-15 mass parts with respect to a total of 100 mass parts of specific polymers (A) and (B). Especially, 1-10 mass parts is preferable.

Moreover, it is preferable that content of the organic solvent in a liquid crystal aligning agent is 70-99.9 mass %. This content can be suitably changed according to the coating method of a liquid crystal aligning agent, and the film thickness of the liquid crystal aligning film made into the objective.

The organic solvent used for a liquid crystal aligning agent will not be specifically limited if it contains the solvent (it is also mentioned a good solvent) in which a specific polymer (A) and a specific polymer (B) are dissolved. Although the specific example of a good solvent is given below, it is not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, etc. are mentioned.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

Moreover, when the solubility with respect to the solvent of a specific polymer (A) and a specific polymer (B) is high, it is preferable to use the solvent shown by said formula [D-1] - a 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. Especially, 20-90 mass % is preferable. More preferably, it is 30-80 mass %.

The liquid crystal aligning agent of this invention can use the solvent (it is also mentioned a poor solvent) which improves the coating-film property and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid crystal aligning agent, unless the effect of this invention is impaired. Although the specific example of a poor solvent is given below, it 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-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 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-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl 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, ethylene glycol di Acetate, 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, methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, The solvent etc. which are shown by said Formula [D-1] - [D-3] are mentioned.

Among them, it is preferable to use 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether.

It is preferable that these poor solvents are 1-80 mass % of the whole solvent contained in a liquid crystal aligning agent. Especially, 10-80 mass % is preferable. More preferably, it is 20-70 mass %.

In the liquid crystal aligning agent of this invention, the crosslinking|crosslinked compound which has an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a crosslinking|crosslinking which has at least 1 type of substituent selected from the group which consists of a lower alkoxyalkyl group It is preferable to contain the crosslinkable compound which has a sex compound or a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and a polymerizable unsaturated bond in a crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminodiphenylene, tetraglycidyl. -m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroacetdiglycidylether , 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxy) Propoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1) ,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)- 1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol etc. are mentioned.

The crosslinkable compound which has an oxetane group is a crosslinkable compound which has at least two oxetane groups shown by a following formula [4A].

[Formula 56]

Specifically, the crosslinking|crosslinked compound shown by the formula [4a] - [4k] disclosed in the 58-59 sections of international publication WO2011/132751 (2011.10.27 publication) is mentioned.

As a crosslinkable compound which has a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups represented by a following formula [5A].

[Formula 57]

Specifically, the crosslinking|crosslinked compound shown by the formula [5-1] - [5-42] published on pages 76-82 of international publication WO2012/014898 (published on February 2, 2012) is mentioned.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, and a guar. Namine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin, etc. are mentioned. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group and/or an alkoxymethyl group can be used. This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less of a methylol group or an alkoxymethyl group per triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750, in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and MW-, in which an average of 5.8 methoxymethyl groups are substituted per triazine ring. 30 (above, manufactured by Sanwa Chemical) Ina Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated melamine, Cymel 235, 236, 238, 212, 253, Methoxymethylated butoxymethylated melamine such as 254, butoxymethylated melamine such as Cymel 506 and 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Methoxymethylated ethoxymethylated benzo such as Cymel 1123 Guanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxymethyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (above, the Mitsui cyanamide company make) is mentioned.

Moreover, as an example of a glycoluril, a butoxymethylation glycoluril like Cymel 1170, a methylolation glycoluril like Cymel 1172, Methoxymethylolation glycoluril like Powder Link 1174, etc. are mentioned.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1, 4-bis(sec-butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, etc. are mentioned.

More specifically, International Publication WO2011/132751. The crosslinking|crosslinked compound shown by Formula [6-1] - Formula [6-48] published on pages 62-66 of (2011.10.27 publication) is mentioned.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tri(meth) crosslinkable compounds having three polymerizable unsaturated groups in the molecule, such as acryloyloxyethoxytrimethylolpropane and glycerin polyglycidyl ether poly(meth)acrylate; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycol A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as cidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, and hydroxypivalate neopentyl glycol di(meth)acrylate ; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2 - (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphoric acid The crosslinkable compound etc. which have one polymerizable unsaturated group in a molecule|numerator, such as ester and N-methylol (meth)acrylamide, are mentioned.

Moreover, the compound shown by a following formula [7A] can also be used.

[Formula 58]

(In formula [7A], E ₁ is at least selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring. It represents a single ring, E ₂ is the formula [7a], and represents at least one group selected from the group consisting of [7b], n is an integer of 1 to 4).

[Formula 59]

The compound is an example of a crosslinkable compound, but is not limited thereto. Moreover, the number of the crosslinkable compounds used for the liquid crystal aligning agent of this invention may be one, and they may combine them two or more types.

It is preferable that content of a crosslinkable compound is 0.1-150 mass parts with respect to 100 mass parts of all polymer components. Especially, in order for a crosslinking reaction to advance and to express the objective effect, 0.1-100 mass parts is preferable with respect to 100 mass parts of all the polymer components. More preferably, it is 1-50 mass parts.

A liquid crystal aligning agent can contain the compound which improves the uniformity of the film thickness of a liquid crystal aligning film at the time of apply|coating a liquid crystal aligning agent, and surface smoothness, unless the effect of this invention is impaired.

As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

More specifically, for example, EFTOP EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapack F171, F173, R-30 (above, manufactured by Dainippon Ink), Florad FC430, FC431 ( As mentioned above, the product made by Sumitomo 3M), Asahigard AG710, Sufflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) etc. are mentioned.

To [ the usage ratio of these surfactant / 100 mass parts of all the polymer components contained in a liquid crystal aligning agent ], Preferably it is 0.01-2 mass parts, More preferably, it is 0.01-1 mass part.

Moreover, in the liquid crystal aligning agent of this invention, it is a compound which accelerates|stimulates the charge transfer in a liquid crystal aligning film, and accelerates|stimulates the electric charge leakage of an element, Comprising: It is published on the 69-73 pages of international publication WO2011/132751 (2011.10.27 publication). , You can also add the nitrogen-containing heterocyclic amine compound represented by a formula [M1] - a formula [M156]. Although you may add this amine compound directly to a liquid crystal aligning agent, it is 0.1-10 mass % of density|concentrations with an appropriate solvent, It is preferable to add, after setting it as the solution of preferably 1-7 mass %. It will not specifically limit, if it is a solvent in which the specific polymer (A) and the specific polymer (B) mentioned above are dissolved as these solvents.

In the liquid crystal aligning agent of this invention, the effect of this invention is inhibited other than the compound which improves the uniformity and surface smoothness of the said poor solvent, a crosslinking|crosslinked compound, a resin film or a liquid crystal aligning film, and surface smoothness, and a charge leakage If it is a range which does not do it, you may add the objective dielectric material and electrically-conductive substance of changing electrical characteristics, such as dielectric constant and electroconductivity of a liquid crystal aligning film.

<Liquid crystal alignment film and liquid crystal display element>

A liquid crystal aligning film is a film|membrane obtained by apply|coating the said liquid crystal aligning agent to a board|substrate, drying and baking.

It will not specifically limit if it is a board|substrate with high transparency as a board|substrate which apply|coats a liquid crystal aligning agent, Plastic substrates, such as an acryl board|substrate and a polycarbonate board|substrate, with a glass substrate and a silicon nitride board|substrate, etc. can also be used. In that case, it is preferable from the point of simplification of a process to use the board|substrate with which the ITO electrode etc. for driving a liquid crystal were formed. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is a single-side substrate, and a material that reflects light such as aluminum can also be used for the electrode in this case.

Although the application method of a liquid crystal aligning agent is not specifically limited, Industrially, screen printing, an offset printing, a flexographic printing, the inkjet method, etc. are common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc., You may use these according to the objective.

After apply|coating a liquid crystal aligning agent on a board|substrate, a solvent can be evaporated by heating means, such as a hot plate, heat circulation type oven, IR (infrared) type|mold oven, and it can be set as a liquid crystal aligning film.

Drying after apply|coating a liquid crystal aligning agent, and a baking process can select arbitrary temperature and time. Usually, in order to fully remove the solvent to contain, it bakes at 50-120 degreeC for 1 to 10 minutes, and the conditions which bake at 150-300 degreeC after that for 5 to 120 minutes are mentioned.

Although the thickness of the liquid crystal aligning film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is preferable that it is 5-300 nm. Especially, 10-200 nm is preferable.

As a method of orientating the obtained liquid crystal aligning film, although the said rubbing process method, the photo-alignment process method, etc. are mentioned, The photo-alignment process method is preferable.

As a specific example of the photo-alignment processing method, the surface of the said liquid crystal aligning film is irradiated with the radiation deflected in a fixed direction, in some cases, it heat-processes further at the temperature of 150-250 degreeC, and liquid-crystal orientation (it is also called liquid-crystal orientation ability) ) can be given. As the radiation, ultraviolet or visible light having a wavelength of 100 to 800 nm can be used. Especially, the ultraviolet-ray which has a wavelength of 100-400 nm is preferable, More preferably, it is an ultraviolet-ray which has a wavelength of 200-400 nm.

Moreover, in order to improve liquid-crystal orientation, you may irradiate a radiation, heating the board|substrate which has a liquid crystal aligning film at 50-250 degreeC.

The radiation dose is preferably from 1 to 10,000 mJ/cm 2 . Especially, 100-5,000 mJ/cm<2> is preferable. The liquid crystal aligning film manufactured in this way can orientate a liquid crystal molecule stably in a fixed direction.

Moreover, a contact process can also be performed for the liquid crystal aligning film which irradiated the polarized radiation using water and a solvent. It will not specifically limit, if it is a solvent which melt|dissolves the decomposition|disassembly product produced|generated from the liquid crystal aligning film by irradiation of a radiation as a solvent to be used. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, di Acetone alcohol, 3-methoxymethyl propionate, 3-ethoxy ethyl propionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. are mentioned. Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferable from the viewpoint of versatility and solvent safety. More preferred are water, 1-methoxy-2-propanol or ethyl lactate. The number of these solvents may be one, and they may combine two or more types.

As a contact process in this invention, an immersion process and a spray process (it is also mentioned a spray process) are mentioned. As for the processing time in these processes, 10 second - 1 hour are preferable at the point which melt|dissolves efficiently the decomposition|disassembly product produced|generated from the liquid crystal aligning film with a radiation. Especially, it is preferable to perform an immersion process for 1 to 30 minutes. Moreover, although the temperature of the solvent at the time of the said contact treatment may be normal temperature or it may be heated, Preferably, it is 10-80 degreeC. Especially, 20-50 degreeC is preferable. From the viewpoint of the solubility of the decomposition product, if necessary, ultrasonic treatment or the like may be further performed.

It is preferable to perform rinsing (it is also mentioned a rinse) by low boiling-point solvents, such as water, methanol, ethanol, 2-propanol, acetone, and methyl ethyl ketone, and baking of a liquid crystal aligning film after the said contact process. In that case, either rinsing and baking may be performed, or both may be implemented. It is preferable that the temperature of baking is 150-300 degreeC. Especially, 180-250 degreeC is preferable. More preferably, it is 200-230 degreeC. Moreover, as for the time of baking, 10 second - 30 minutes are preferable. Especially, 1 to 10 minutes are preferable.

The liquid crystal aligning film of this invention is preferable as a liquid crystal aligning film of the liquid crystal display element of transverse electric field systems, such as an IPS system and an FFS system, Especially useful as a liquid crystal aligning film of the liquid crystal display element of an FFS system.

After obtaining the board|substrate with the liquid crystal aligning film obtained from the said liquid crystal aligning agent, the liquid crystal display element of this invention produces a liquid crystal cell by a known method, and sets it as an element using the liquid crystal cell.

As an example of the manufacturing method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is taken as an example and demonstrated. Moreover, the liquid crystal display element of the active matrix structure in which switching elements, such as TFT (Thin Film Transistor), were formed in each pixel part which comprises an image display may be sufficient.

Specifically, a transparent glass substrate is prepared, a common electrode is formed on one substrate, and a segment electrode is formed on the other substrate. These electrodes can be set as, for example, an ITO electrode, and is patterned so that a desired image display can be performed. Next, an insulating film is formed 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, a liquid crystal aligning film is formed on each board|substrate on the same conditions as the above, and the other board|substrate is superimposed on one board|substrate so that the liquid crystal aligning film surface of each other may oppose, and the periphery is adhere|attached with a sealing compound. In order to control a board|substrate clearance gap in a sealing compound, it is preferable to mix a spacer normally. Moreover, it is preferable to spread|disperse the spacer for board|substrate gap|interval control also to the in-plane part which does not form a sealing compound. It is preferable to provide the opening part which can fill a liquid crystal from the outside in a part of sealing compound.

Then, liquid-crystal material is inject|poured in the space surrounded by the board|substrate of 2 sheets and sealing agent through the opening part provided in the sealing compound. Next, this opening is sealed with an adhesive. A vacuum injection method may be sufficient for injection|pouring, and the method which utilized the capillary phenomenon in air|atmosphere may be used.

As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material may be used. Next, a polarizing plate is installed. Specifically, it is preferable to affix a pair of polarizing plates to the surface on the opposite side to the liquid crystal layer of two board|substrates.

By using the liquid crystal aligning agent of this invention, the residual image by alternating current drive can be suppressed and the liquid crystal aligning film which is compatible with adhesiveness with a sealing compound and a base board|substrate can be obtained. In particular, it is useful about the liquid crystal aligning film for photo-alignment processing methods obtained by irradiating the polarized radiation.

Example

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited thereto. In addition, the abbreviation of the compound used below and the measuring method of each characteristic are as follows.

GBL: γ-butyllactone

BCS: Butyl Cellosolve

DA-A: Refer to the following formula (DA-A)

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

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

DA-3: Refer to the following formula (DA-3)

DA-4: Refer to the following formula (DA-4)

DE-1: Refer to the following formula (DE-1)

DAH-1: Refer to the following formula (DAH-1)

DAH-2: Refer to the following formula (DAH-2)

Additive A: N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine

[Formula 60]

[Formula 61]

[Formula 62]

^[1 H NMR]

Apparatus: Fourier transform superconducting nuclear magnetic resonance (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz

Solvent: Deuterated dimethyl sulfoxide (DMSO-d ₆ ))

Standard material: tetramethylsilane (TMS)

Integration count: 8, or 32

[ ¹³ C｛ ¹ H｝NMR]

Apparatus: Fourier transform superconducting nuclear magnetic resonance (FT-NMR) INOVA-400 (manufactured by Varian) 100 MHz

Solvent: Deuterated dimethyl sulfoxide (DMSO-d ₆ )

Standard material: tetramethylsilane (TMS)

Integration count: 256

[Measurement of melting point (DSC)]

Device: Differential scanning calorimetry device DSC1STARe system (manufactured by METTLER TOLEDO)

Fan: sealed Au fan

Temperature increase rate: 10 °C/min

Melting point: Analyze the endothermic peak temperature at the lowest temperature

[Viscosity]

Viscosity of polyamic acid ester and polyamic acid solution is measured by sample amount 1.1 ml, Conrotor TE-1 (1 °34', R24), temperature 25 degreeC using E-type viscometer TVE-22H (made by Toki Industries Co., Ltd.) did.

[Molecular Weight]

The molecular weight of polyamic acid ester was measured by GPC (normal temperature gel permeation chromatography) apparatus, and computed the number average molecular weight (Mn) and weight average molecular weight (Mw) as polyethyleneglycol and polyethyleneoxide conversion value.

GPC device: manufactured by Shodex (GPC-101)

Column: manufactured by Shodex (KD803, KD805 series)

Column temperature: 50℃

Eluent: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystals (o-phosphoric acid) are 30 mmol/L, tetrahydro furan (THF) is 10 ml/L)

Flow rate: 1.0 ml/min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories (Peaktop molecular weight (Mp) about 12,000, 4,000, and 1,000). In order to avoid overlapping peaks, the measurement was carried out separately for two samples of a sample in which four types of 900,000, 100,000, 12,000, and 1,000 were mixed, and a sample in which three types of 150,000, 30,000, and 4,000 were mixed.

[Measurement of imidization rate]

The imidation ratio of the polyimide in a synthesis example was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) (0.53 ml) ) was added, and ultrasonic wave was applied to completely dissolve it. Proton NMR of 500 MHz was measured for this solution with the NMR measuring instrument (JNW-ECA500) (made by Nippon Electronics Datum). The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and the integrated peak of this proton and the integrated value of the proton peak derived from the NH group of the amic acid appearing around 9.5 ppm to 10.0 ppm. was used and calculated|required by the following formula|equation.

Imidization rate (%) = (1 - α·x/y) × 100

In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated peak of the reference proton, and α is the NH group of the amic acid in the case of polyamic acid (imidization rate is 0%) It is the ratio of the number of reference protons to one proton.

[Inkjet Printing]

The inkjet printing described in the Examples was performed with the apparatus and conditions shown below. Device name: Fine pattern coating device by inkjet printing (Hitachi Plant Technology, HIS-200-1H)

Application substrate: 100 × 100 mm ITO substrate

Application area: 72 × 80 mm

Application conditions: Resolution 15 µm, stage speed 40 mm/sec, frequency 2000 Hz, pulse width 9.6 µsec, droplet amount 42 pl, pitch width 60 µm, pitch length 141 µm, applied voltage: 15 V, nozzle gap 0.5 mm

[Production of liquid crystal cell]

A liquid crystal cell provided with the structure of a FFS (Fringe Field Switching) mode liquid crystal display element is produced. First, the substrate on which the electrode was formed was prepared. The substrate is a glass substrate having a size of 30 mm x 50 mm and a thickness of 0.7 mm. On the board|substrate, the ITO electrode provided with the beta phase pattern which comprises a counter electrode as a 1st layer is formed. On the counter electrode of the first layer, as the second layer, a SiN (silicon nitride) film formed by the CVD method is formed. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the 2nd layer, the comb-tooth-shaped pixel electrode formed by patterning the ITO film|membrane as 3rd layer is arrange|positioned, and two pixels of a 1st pixel and a 2nd pixel are formed. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the 3rd layer has the comb-tooth-shaped shape comprised by arranging a plurality of "<"-shaped electrode elements in which the center part was bent. The width in the transverse 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 constituted by arranging a plurality of "<"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangular shape, but a thick, curved shape in the central part similarly to the electrode element. It has a shape resembling the letter 'K'. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has a 1st area|region above a bending part, and a 2nd area|region below.

Comparing the 1st area|region and 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, based on the rubbing direction of the liquid crystal alignment layer to be described later, the electrode element of the pixel electrode is formed to form an angle of +10° (clockwise) 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 to form an angle of -10° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotational operation (in-plane switching) in the substrate plane of the liquid crystal caused by the voltage application between the pixel electrode and the counter electrode are opposite to each other. Consists of.

Next, the obtained liquid crystal aligning agent was filtered with a 1.0 µm filter, and then the prepared substrate on which the electrode was formed and a glass substrate having a columnar spacer with a height of 4 µm on which an ITO film was formed on the back surface was coated by spin coating. . After drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. Orientation processing, such as rubbing and polarization|polarized-light ultraviolet irradiation, was given to this coating-film surface, and the board|substrate with a liquid crystal aligning film was obtained. Said two board|substrates are made into one set, a sealing compound is printed on a board|substrate, and after adhering the other board|substrate so that a liquid crystal aligning film surface faces and orientation direction becomes 0 degree, a sealing compound is hardened to produce empty cells. Liquid crystal MLC-2041 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, after heating the obtained liquid crystal cell at 110 degreeC for 1 hour and leaving it to stand overnight, it was used for each evaluation.

[Evaluation of afterimage by long-term AC drive]

The liquid crystal cell of the structure similar to the liquid crystal cell used for said afterimage evaluation was prepared.

Using this liquid crystal cell, the alternating voltage of +/-5V was applied in a 60 degreeC constant temperature environment at the frequency of 60 Hz for 120 hours. Then, it was set as the state made short between the pixel electrode of a liquid crystal cell, and a counter electrode, and it was left to stand at room temperature as it is for one day.

After standing, the liquid crystal cell was placed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, and the backlight was turned on in a state in which no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light was the smallest. And the rotation angle at the time of rotating a liquid crystal cell from the angle at which the 2nd area|region of a 1st pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as angle (DELTA). Similarly, in the second pixel, the second region and the first region were compared to calculate the same angle Δ. And 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, and the AC drive exposure Δ was less than 0.3 as “good”, and more as “poor”.

[Evaluation of charge accumulation by asymmetry of AC drive]

The prepared liquid crystal cell was placed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, the LED backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light was the smallest.

Next, the V-T curve (voltage-transmittance curve) was measured, applying the alternating voltage of frequency 30Hz to this liquid crystal cell, and the relative transmittance|permeability computed the alternating voltage used as 50 % as a drive voltage.

The light was shielded so that the LED light did not hit the liquid crystal cell. Furthermore, a 20 mV rectangular wave was applied to the liquid crystal cell at a frequency of 1 kHz for 30 minutes.

After that, an AC drive with a relative transmittance of 50% is performed simultaneously with the LED lighting, and the VF (voltage-flicker curve) curve immediately after lighting is measured, and the offset voltage value that eliminates charge accumulation due to asymmetry of the AC drive Calculated. After that, the minimum offset voltage value change amount was measured every 1 minute, and the maximum voltage value when it changed from immediately after lighting to 30 minutes was computed. In that case, when the change amount of the maximum offset voltage exceeded 20 mV, it defined and evaluated as "defect". Moreover, when the change amount of the maximum offset voltage did not exceed 20 mV, it defined and evaluated as "good|favorableness".

[Charge relaxation characteristics]

The liquid crystal cell was placed on a light source and the VT characteristic (voltage-transmittance characteristic) under a temperature of 45° C. was measured, and then the transmittance (Ta) of the liquid crystal cell in the state where a rectangular wave of ±1.5 V/60 Hz was applied was measured. Thereafter, a rectangular wave of ±1.5 V/60 Hz was applied at a temperature of 45°C for 10 minutes, and then 2V of DC was superimposed and driven for 120 minutes. The transmittance (Tb) of the liquid crystal cell when the DC voltage is turned off and driven again for 0 min, 5 min, 10 min, and 20 min only with a rectangular wave of ±1.5 V/60 Hz is measured, respectively, and the transmittance at each time ( From the difference (ΔT) between Tb) and the initial transmittance (Ta), the difference in transmittance caused by the voltage remaining in the liquid crystal display element was calculated.

(Synthesis Example 1)

Aromatic diamine compound (DA-A): Synthesis of N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine

The aromatic diamine compound (DA-A) was synthesize|combined by the route of 3 steps shown below. In addition, the aromatic diamine compound (DA-A) corresponds to the specific diamine compound (2) mentioned above.

First step: Synthesis of N-(2-(4-nitrophenyl)ethyl)-N-(4-nitrobenzyl)amine (DA-A-1)

[Formula 63]

2-(4-nitrophenyl)ethylamine hydrochloride (50.0 g, 247 mmol) was dissolved in water (300 g) and DMF (50.0 g), sodium carbonate (78.4 g, 740 mmol) was added, and 4-nitrobenzyl The DMF solution (200g) of bromide (53.3g, 247mmol) was dripped at 25 degreeC over 1 hour. During dripping, DMF/water = 1/1 (w/w, 100 g) was added, and the stirring defect by a precipitate was eliminated. The mixture was stirred as it was at room temperature for 20 hours, and further stirred at 40°C for 4 hours, and disappearance of the raw material was confirmed by HPLC (high performance liquid chromatography). Thereafter, the reaction solution was allowed to cool to room temperature, the precipitate was filtered, washed twice with water (150 g) and twice with 2-propanol (50.0 g), and dried under reduced pressure at 50°C, followed by N-2-( 4-nitrophenyl)ethyl-N-(4-nitrobenzyl)amine was obtained (white solid, yield: 73 g, yield: 99%).

Melting Point (DSC): 123℃

Second step: Synthesis of N-tert-butoxycarbonyl-N-(2-(4-nitrophenyl)ethyl)-N-(4-nitrobenzyl)amine (DA-A-2)

[Formula 64]

N-2-(4-nitrophenyl)ethyl-N-4-nitrobenzylamine (73 g, 0.24 mol) was dissolved in DMF (371 g), and ditert-butyl bicarbonate (54 g, 0.24 mol) was added to 2 It was dripped at -8 degreeC over 10 minutes. Then, it stirred at 20 degreeC for 4 hours, and the loss|disappearance of the raw material was confirmed by HPLC. Then, DMF was distilled off under reduced pressure, ethyl acetate (371g) was added to the reaction liquid, and it wash|cleaned 3 times with water (371g). Thereafter, the organic phase was concentrated under reduced pressure to obtain an orange oil (crude yield: 96 g, crude yield: 97%). This crude product was purified by silica gel column chromatography (hexane/ethyl acetate=7/3 (v/v, Rf=0.3) to obtain a yellow oil. (Crude yield: 82.0 g, crude yield: 82.8% (2 steps)) )).After adding methanol (118g) to this yellow oil and dissolving at 50 degreeC, it cools while stirring, and after stirring at 0-5 degreeC for 30 minutes, filtration and drying are carried out by N-tert-butoxycar Bornyl-N-2-(4-nitrophenyl)ethyl-N-4-nitrobenzylamine was obtained (white powder, yield: 74.5 g, yield: 78% (2 steps)).

Melting Point (DSC): 77℃

Third Step: Synthesis of N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine (DA-A)

[Formula 65]

N-tert-butoxycarbonyl-N-2-(4-nitrophenyl)ethyl-N-4-nitrobenzylamine (74 g, 0.18 mol) was dissolved in tetrahydrofuran (370 g), 3% by mass Platinum-carbon (7.4 g) was added, and the mixture was stirred at room temperature in a hydrogen atmosphere for 72 hours. Disappearance of the raw material was confirmed by HPLC, the catalyst was removed by filtration, and the filtrate was concentrated and dried to obtain a crude product of DA-A as a pale yellow oil (amount of raw material: 66 g, crude yield: 105%). After dissolving this in toluene (198 g) at 80 degreeC, it stirred at 2 degreeC for 1 hour, and precipitated the crystal|crystallization. The precipitated solid was filtered and dried to obtain DA-A (white powder, yield: 56 g, yield: 90%).

Melting Point (DSC): 103℃

(Synthesis Example 2)

110.47 g (452 mmol) of 1,2-bis (4-aminophenoxy) ethane and 18.94 g (79.8 mmol) of DA-2 were weighed into a 3000 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. , NMP was added 1587g, and it stirred, sending nitrogen, and it was made to melt|dissolve. 111.18 g (496 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride is added stirring this diamine solution, and NMP is added so that solid content concentration may be set to 12 mass % further. and stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-1). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 183 mPa*s.

(Synthesis Example 3)

950 g of polyamic acid solutions (PAA-1) obtained in a 2000 ml four-neck flask with a stirring device and a nitrogen introduction tube were weighed, 677.5 g of NMP was added, and the mixture was stirred for 30 minutes. 77.10 g 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 liquid was injected|thrown-in to 5177 g of methanol, stirring, and the precipitated deposit was collected by filtration, and then, it wash|cleaned 3 times with 5177 g of methanol, and wash|cleaned twice with 1726 g of methanol. The polyimide resin powder was obtained by drying the obtained resin powder at 60 degreeC for 12 hours.

The imidation ratio of this polyimide resin powder was 74 %, and molecular weight was Mn=8755, Mw=19663.

20.34 g of polyimide resin powder obtained in the 200 ml sample tube which put the stirring bar was weighed, 149.2g of NMP was added, it stirred at 40 degreeC for 24 hours, and it was made to melt|dissolve, and the polyimide solution (SPI-1) was obtained.

(Synthesis Example 4)

2.92 g (27.0 mmol) of p-phenylenediamine and 0.71 g (3.0 mmol) of DA-2 were weighed into a 100 ml four-necked flask equipped with a stirring device and a nitrogen inlet tube, and 81.76 g of NMP was added, It was dissolved by stirring while sending nitrogen. 6.46 g (28.8 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride is added, stirring this diamine solution, and NMP is added so that solid content concentration may be 10 weight%. and stirred at room temperature for 4 hours to obtain a solution of polyamic acid (PAA-2). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 230 mPa*s.

(Synthesis Example 5)

2.93 g (12.00 mmol) of 1,2-bis (4-aminophenoxy) ethane and 4.43 g (11.99 mmol) of DA-A were weighed in a 100 mL four-neck flask equipped with a stirring device and a nitrogen inlet tube. Then, 81.98g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 5.35 g (23.88 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride is added while stirring this diamine solution, and NMP is 9.11 for a solid content concentration of 12% by mass. g was added and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-3). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 205 mPa*s.

(Synthesis Example 6)

20 g of the polyamic acid solution (PAA-3) obtained in the 100 ml four necked flask with a stirring device and nitrogen introduction tube was measured, 14.29g of NMPs were added, and it stirred for 30 minutes. To the obtained polyamic acid solution, 1.48 g of acetic anhydride and 0.38 g of pyridine were added, and it heated at 60 degreeC for 3 hours, and performed chemical imidation. The obtained reaction liquid was injected|thrown-in stirring in 139 mL of methanol, the deposit which precipitated was collected by filtration, and then, it wash|cleaned 3 times with 139 mL of methanol. Polyimide resin powder (SPI-2) was obtained by drying the obtained resin powder at 60 degreeC for 12 hours.

The imidation ratio of this polyimide resin powder was 75 %, and molecular weight was Mn=8156, Mw=17408.

(Synthesis Example 7)

After making the inside of a 500 mL 4-necked flask with a stirring device into nitrogen atmosphere, 2.80 g (25.9 mmol) of p-phenylenediamine, and also adding 1.45 g (6.47 mmol) of DA-1, NMP was 111 g, and 6.18 g (78.1 mmol) of pyridine as a base were added and stirred to dissolve. Next, 9.89 g (30.4 mmol) of DE-1 was added, stirring this diamine solution, and it was made to react at 15 degreeC overnight. After stirring overnight, 0.38 g (4.21 mmol) of acryloyl chloride was added, and it was made to react at 15 degreeC for 4 hours. It injects|throws-in stirring the solution of the obtained polyamic acid ester to 1230 g of water, and the white precipitate which precipitated is filtrated, Then, it wash|cleans 5 times with 1230 g of IPA, and it is made to dry, and white polyamic acid ester resin powder 10.2 g was obtained. The yield was 83.0%. Moreover, the molecular weight of this polyamic acid ester was Mn=20,786 and Mw=40,973.

7.96 g of the obtained polyamic acid ester resin powder was taken in the 100 ml Erlenmeyer flask, 72.1g of GBL was added, it stirred at room temperature for 24 hours, it was made to melt|dissolve, and the polyamic acid ester solution (PAE-1) was obtained.

(Synthesis Example 8)

39.89 g (200.2 mmol) of 4,4'-diaminodiphenylamine and 7.60 g (49.95 mmol) of 3,5-diaminobenzoic acid were weighed into a 1000 ml four-necked flask equipped with a stirring device and a nitrogen inlet tube. Then, 282g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 14.88 g (75.10 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride is added, stirring this diamine solution, and NMP is added so that solid content concentration may be set to 15 mass %, and it is 2 hours at room temperature. stirred. Next, 283 g of NMP is added, 50.3 g (171.0 mmol) of DAH-1 is added, and NMP is added so that solid content concentration may be set to 12 mass %, and it stirs at room temperature for 24 hours, and polyamic acid (PAA-4) ) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 393 mPa*s.

(Synthesis Example 9)

In a 2000 ml four-neck flask equipped with a stirrer and nitrogen inlet tube, 63.76 g (320 mmol) of 4,4'-diaminodiphenylamine and 12.17 g (79.99 mmol) of 3,5-diaminobenzoic acid were weighed out. Then, 1094g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 112.59 g (383 mmol) of DAH-1 is added, stirring this diamine solution, and NMP is added so that solid content concentration may be set to 12 mass %, and it stirs at room temperature for 24 hours, and the solution of polyamic acid (PAA-5) got The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 384 mPa*s.

(Synthesis Example 10)

33.48 g (168.0 mmol) of 4,4'-diaminodiphenylamine and 21.48 g (71.99 mmol) of DA-3 were taken into a 1000 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube, and NMP was 803.1 g was added and stirred while sending nitrogen to dissolve. DAH-1 is added 66.73g (226.8mmol), stirring this diamine solution, and NMP is added so that solid content concentration may be set to 12 mass %, it stirs at room temperature for 24 hours, and the solution of polyamic acid (PAA-6) got The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 380 mPa*s.

(Synthesis Example 11)

In a 200 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube, 4.44 g (20.82 mmol) of 4,4'-diaminodiphenylamine and 0.79 g (5.19 mmol) of 3,5-diaminobenzoic acid were weighed out. Then, 15.71g of NMP and 73.08g of GBL were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. DAH-1 is added 7.39g (25.12mmol), stirring this diamine solution, and NMP is added so that solid content concentration may be set to 12 mass %, it stirs at room temperature for 24 hours, and the solution of a polyamic acid (PAA-7) got The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 530 mPa*s.

(Comparative Synthesis Example 1)

119.35g (400mmol) of DA-3 was measured to the 2000mL four necked flask with a stirring apparatus and nitrogen introduction tube, 1536g of NMPs were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 39.43 g (386 mmol) of DAH-1 is added, stirring this diamine solution, and NMP is added so that solid content concentration may be set to 12 mass %, it stirs at room temperature for 24 hours, and the solution of a polyamic acid (PAA-9) got The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 372 mPa*s.

(Synthesis Example 12)

In a 10 L separable flask equipped with a stirring device and a nitrogen inlet tube, 488.58 g (2 mol) of 1,2-bis(4-aminophenoxy)ethane and 184.69 g (0.5 mol) of DA-A were weighed. , 7772.47 g of NMP was added, and it was dissolved by stirring while sending nitrogen. 504.38 g (2.25 mol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride is added stirring this diamine solution, and NMP is further added so that solid content concentration may be 12 mass % and stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-10). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 192.6 mPa*s.

(Synthesis Example 13)

2400 g of the polyamic-acid solution (PAA-10) obtained in the 3000 mL four necked flask with stirring apparatus and nitrogen introduction pipe was measured, 800g of NMP was added, and it stirred for 30 minutes. To the obtained polyamic-acid solution, 186.20g and pyridine 48.1g were added to acetic anhydride, and it heated at 60 degreeC for 3 hours, and performed chemical imidation. The obtained reaction liquid was injected|thrown-in stirring in 13.21 L methanol, and the precipitated deposit was collected by filtration, and then, it wash|cleaned 3 times with 13.21 L methanol, and it wash|cleaned 2 times with 4.30 L methanol. The polyimide resin powder was obtained by drying the obtained resin powder at 60 degreeC for 12 hours.

The imidation ratio of this polyimide resin powder was 74 %, and molecular weight was Mn=6737 and Mw=14181.

20.34 g of polyimide resin powder obtained in the 200 ml sample tube which put the stirrer was taken, 149.2g of NMP was added, it stirred at 40 degreeC for 24 hours, and it was made to melt|dissolve, and the polyimide solution (SPI-3) was obtained.

(Synthesis Example 14)

0.87 g (5.8 mmol) of DA-4 and 4.62 g (23.2 mmol) of 4,4'-diaminodiphenylamine were weighed into a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, and NMP was 63.24 g was added, and it stirred while sending nitrogen to make it melt|dissolve. 4.27 g (14.5 mmol) of DAH-1 and 2.56 g (13.05 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride are added stirring this diamine solution, and solid content concentration is 12 weight% NMP was added so that it might become , and it stirred at room temperature for 4 hours, and obtained the solution of polyamic acid (PAA-11). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 593 mPa*s.

(Synthesis Example 15)

In a 100 ml four-necked flask equipped with a stirring device and a nitrogen inlet tube, 1.11 g (14.0 mmol) of 4,4'-diaminodiphenylmethane and 4.46 g (22.4 of 4,4'-diaminodiphenylamine) mmol) was measured, 62.02 g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. While stirring this diamine solution, 4.12 g (14 mmol) of DAH-1 and 2.38 g (12.18 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride are added, and solid content concentration is 12 weight%. NMP was added so that it might become , and it stirred at room temperature for 4 hours, and obtained the solution of polyamic acid (PAA-12). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 590 mPa*s.

(Synthesis Example 16)

In a 5 L separable flask equipped with a stirring device and a nitrogen inlet tube, 31.64 g (0.2 mol) of 3,5-diaminobenzoic acid and 165.78 g (0.83 mol) of 4,4'-diaminodiphenylamine were weighed. Then, 1270.36g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 95.57 g (0.31 mol) of DAH-2 was added stirring this diamine solution, and NMP was added so that solid content concentration might be set to 15 weight%, and it stirred at room temperature for 4 hours. Then, 201.95 g (0.69 mol) of DAH-1 was added, NMP was added so that solid content concentration might be set to 12 weight%, and it stirred at room temperature for 4 hours, and obtained the solution of polyamic acid (PAA-13). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 435 mPa*s.

(Synthesis Example 17)

In a 100 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube, 1.11 g (14.0 mmol) of 4,4'-diaminodiphenylmethane and 4.46 g (22.4 of 4,4'-diaminodiphenylamine) mmol) was weighed, 64.41 g of NMP was added, and it was dissolved by stirring while sending nitrogen. While stirring this diamine solution, 1.207 g (6.16 mmol) of DAH-1 is added 5.77 g (19.6 mmol) and 1,2,3,4- cyclobutane tetracarboxylic dianhydride, and solid content concentration is 12 weight%. NMP was added so that it might become , and it stirred at room temperature for 4 hours, and obtained the solution of polyamic acid (PAA-14). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 387 mPa*s.

(Synthesis Example 18)

0.84 g (5.6 mmol) of DA-4 and 4.46 g (22.4 mmol) of 4,4'-diaminodiphenylamine were weighed into a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, and NMP was 63.03 g was added, and it stirred while sending nitrogen to make it melt|dissolve. While stirring this diamine solution, 1.207 g (6.16 mmol) of DAH-1 is added 5.77 g (19.6 mmol) and 1,2,3,4- cyclobutane tetracarboxylic dianhydride, and solid content concentration is 12 weight%. NMP was added so that it might become , and it stirred at room temperature for 4 hours, and obtained the solution of polyamic acid (PAA-15). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 396 mPa*s.

(Synthesis Example 19)

In a 100 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube, 1.11 g (14.0 mmol) of 4,4'-diaminodiphenylmethane and 4.46 g (22.4 of 4,4'-diaminodiphenylamine) mmol) was measured, 67.90 g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 5.77 g (19.6 mmol) of DAH-1 and 1.89 g (6.16 mmol) of DAH-2 are added while stirring this diamine solution, and NMP is added so that solid content concentration may be 12 weight%, and it stirred at room temperature for 4 hours, A solution of polyamic acid (PAA-16) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 386.8 mPa*s.

(Synthesis Example 20)

0.81 g (5.4 mmol) of DA-4 and 4.30 g (21.6 mmol) of 4,4'-diaminodiphenylamine were weighed in a 100 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube, and NMP was calculated as 64.14. g was added and stirred while sending nitrogen to dissolve. While stirring this diamine solution, 1.81 g (5.94 mmol) of DAH-2 and 5.56 g (18.9 mmol) of DAH-1 are added, and NMP is added so that solid content concentration may be 12 weight%, and it stirred at room temperature for 4 hours, A solution of polyamic acid (PAA-17) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 304.0 mPa*s.

(Synthesis Example 21)

In a 100 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube, 3.82 g (19.2 mmol) of 4,4'-diaminodiphenylamine and 0.73 g (4.8 mmol) of 3,5-diaminobenzoic acid were weighed out. Then, 15.38g of NMP and 30.76g of GBL were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. While stirring this diamine solution, 4.51 g (15.3 mmol) of DAH-1 was added, and it stirred at room temperature for 4 hours. Furthermore, 1.41 g (7.2 mmol) of 1,2,3,4- cyclobutanetetracarboxylic dianhydride is added, GBL is added so that solid content concentration may be set to 12 mass %, and it stirs at room temperature for 24 hours, and polyamic acid ( PAA-18) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 308.4 mPa*s.

(Synthesis Example 22)

In a 100 ml four-necked flask equipped with a stirrer and nitrogen inlet tube, 3.82 g (19.2 mmol) of 4,4'-diaminodiphenylamine and 0.95 g (4.8) of 4,4'-diaminodiphenylmethane mmol) was weighed, NMP was added 16.74g, GBL 33.48g was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. DAH-1 is added 6.63 g (22.6 mmol), stirring this diamine solution, and GBL is added so that solid content concentration may be set to 12 mass %, it stirs at room temperature for 24 hours, and the solution of polyamic acid (PAA-19) got The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 324.4 mPa*s.

(Synthesis Example 23)

In a 100 ml four-neck flask equipped with a stirrer and nitrogen inlet tube, 2.86 g (14.4 mmol) of 4,4'-diaminodiphenylamine and 0.73 g (4.8 mmol) of 3,5-diaminobenzoic acid were weighed out. Then, 15.78 g of NMP and 31.55 g of GBL were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. DAH-1 is added 6.63 g (22.6 mmol), stirring this diamine solution, and GBL is added so that solid content concentration may be set to 12 mass %, it stirs at room temperature for 24 hours, and the solution of a polyamic acid (PAA-20) got The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 335.5 mPa*s.

(Synthesis Example 24)

In a 100 ml 4-neck flask equipped with a stirring device and a nitrogen inlet tube, 3.99 g (20.0 mmol) of 4,4'-diaminodiphenylamine and 0.76 g (5.0 mmol) of 3,5-diaminobenzoic acid were weighed out. Then, 15.45g of NMP and 3.86g of GBL were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. While stirring this diamine solution, 2.48 g (12.5 mmol) of 1,2,3,4- butanetetracarboxylic dianhydride was added, and it stirred at room temperature for 4 hours. Furthermore, 3.31 g (11.25 mmol) of DAH-1 was added, GBL was added so that solid content concentration might be set to 12 mass %, it stirred at room temperature for 24 hours, and the solution of the polyamic acid (PAA-21) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 285.2 mPa*s.

(Synthesis Example 25)

2.81 g (11.5 mmol) of 1,2-bis (4-aminophenoxy) ethane and 4.24 g (11.5 mmol) of DA-A were weighed into a 100 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube. , NMP was added 64.03g, and it stirred, sending nitrogen, and it was made to melt|dissolve. While stirring this diamine solution, 1.35 g (4.6 mmol) of DAH-1 was added, and it stirred at room temperature for 4 hours. Furthermore, 4.06 g (18.1 mmol) of 1, 3- dimethyl-1,2,3,4- cyclobutane tetracarboxylic dianhydride is added, NMP is added so that solid content concentration may be set to 12 mass %, and it is room temperature 24 It stirred for time, and the solution of polyamic acid (PAA-22) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 132.0 mPa*s.

(Example 1)

5.49 g of polyimide solution (SPI-1) obtained by synthesis example 3 and 5.14 g of polyamic acid solution (PAA-4) obtained by synthesis example 8 are weighed in the 50 ml Erlenmeyer flask which put the stirrer, 0.3 mass % 3- 4.14 g of NMP and 4.02g of BCS were added to the NMP solution of 1.24 g and NMP of glycidoxy propyl methyl diethoxy silane, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-1).

(Example 2)

5.50 g of polyamic acid solution (PAA-2) obtained by synthesis example 4 and 4.64 g of polyamic acid solution (PAA-5) obtained by synthesis example 9 are weighed in the 50 mL Erlenmeyer flask which put the stirrer, 0.3 mass % 3- 1.10 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 4.76 g of NMP, 4.01 g of BCS, and 0.17 g of additive A were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (AL-2) got it

(Example 3)

5.64 g of polyimide solution (SPI-1) obtained by synthesis example 3 and 5.14 g of polyamic-acid solution (PAA-6) obtained by synthesis example 10 are weighed in the 50 ml Erlenmeyer flask which put the stirrer, 0.3 mass % 3- 1.24 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 3.98 g of NMP, 4.02 g of BCS, and 0.19 g of additive A were added, stirred with a magnetic stirrer for 30 minutes, and liquid crystal aligning agent (AL-3) got

(Example 4)

5.50 g of polyimide solution (SPI-2) obtained in Synthesis Example 6 and 5.21 g of polyamic acid solution (PAA-5) obtained in Synthesis Example 9 are weighed in a 200 ml Erlenmeyer flask with a stirrer, 0.3 mass % 3- 1.24 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 4.04 g of NMP, 4.02 g of BCS, and 0.19 g of additive A were added, stirred with a magnetic stirrer for 30 minutes, and liquid crystal aligning agent (AL-4) got

(Example 5)

12.40 g of polyamic acid ester solution (PAE-1) obtained in Synthesis Example 7 and 15.5 g of polyamic acid solution (PAA-7) obtained in Synthesis Example 11 were weighed in 200 mL Erlenmeyer flask with a stirrer, and NMP was 4.96 g , GBL was added to 47.14g, PB was 20.02g, and 0.43g of additive A was added, it stirred for 30 minutes with a magnetic stirrer, and the liquid crystal aligning agent (AL-5) was obtained.

(Comparative Example 1)

5.44 g of polyimide solution (SPI-1) obtained in Synthesis Example 3 and 5.17 g of polyamic acid solution (PAA-9) obtained in Comparative Synthesis Example 1 were weighed in a 50 ml Erlenmeyer flask with a stirrer, 0.3 mass% 3 - 1.24 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 4.15 g of NMP, 4.02 g of BCS, and 0.19 g of additive A were added, stirred with a magnetic stirrer for 30 minutes, and the liquid crystal aligning agent (B-1) ) was obtained.

(Example 6)

After filtering the liquid crystal aligning agent (AL-1) obtained in Example 1 with a filter of 1.0 µm, the prepared substrate on which the electrode is formed and an ITO film on the back surface of the prepared glass substrate having a columnar spacer having a height of 4 µm, It was applied by spin coat application. After drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. 0.2 J/cm 2 of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 were irradiated to this coating film surface through a polarizing plate. This board|substrate was immersed in 25 degreeC ethyl lactate for 5 minutes, and then, it was made to immerse in 25 degreeC pure water for 1 minute, and it dried for 5 minutes on a 200 degreeC hotplate, and obtained the board|substrate with a liquid crystal aligning film. The two substrates are set as one set, a sealing compound is printed on the substrate, and the other substrate is adhered so that the liquid crystal aligning film surface is facing and the alignment direction is 0 °, and then the sealing compound is cured, An empty cell was created. Liquid crystal MLC-2041 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, and it was left to stand overnight.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.9%, 2.0%, 1.1%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 7)

After filtering the liquid crystal aligning agent (AL-2) obtained in Example 2 with a filter of 1.0 μm, the prepared substrate on which the electrode is formed and an ITO film on the back surface of the prepared glass substrate having a columnar spacer having a height of 4 μm, It was applied by spin coat application. After drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. 0.5 J/cm 2 of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 were irradiated to this coating film surface through a polarizing plate. This board|substrate was baked for 20 minutes in 230 degreeC hot-air circulation type oven, and the board|substrate with a liquid crystal aligning film was obtained. The two substrates are set as one set, a sealing compound is printed on the substrate, and the other substrate is adhered so that the liquid crystal aligning film surface is facing and the alignment direction is 0 °, and then the sealing compound is cured, An empty cell was created. Liquid crystal MLC-2041 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, and it was left to stand overnight.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.1%, 1.9%, 0.9%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 8)

The FFS drive liquid crystal cell was produced by the method similar to Example 6 except having used the liquid crystal aligning agent (AL-3) obtained in Example 3.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.7%, 0.5%, 0.3%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 9)

FFS drive by the method similar to Example 6 using the liquid crystal aligning agent (AL-4) obtained in Example 4 except having carried out the contact process for 5 minutes with 25 degreeC pure water instead of ethyl lactate after polarization|polarized-light ultraviolet irradiation A liquid crystal cell was produced.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 4.0%, 0.9%, 0.5%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 10)

Using the liquid crystal aligning agent (AL-5) obtained in Example 5, the FFS drive liquid crystal cell was produced by the method similar to Example 7 except having apply|coated the liquid crystal aligning agent by inkjet printing.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 8.4%, 1.4%, 0.9%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Comparative Example 2)

The FFS drive liquid crystal cell was produced by the method similar to Example 6 except having used the liquid crystal aligning agent (B-1) obtained by the comparative example 1.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 9.9%, 0.5%, 0.2%, and 0%, respectively. As a result of performing charge accumulation value evaluation by asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or more, and it was unsatisfactory.

(Example 11)

4.47 g of the polyimide solution (SPI-3) obtained by the polyimide solution (SPI-3) obtained by the synthesis example 13, and the polyamic acid solution (PAA-11) obtained by the synthesis example 14 was measured to the 50 ml Erlenmeyer flask which put the stirrer, 1.0 mass % 3- 0.9g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.34g of NMP, 5.4g of GBL, 3.60g of BCS were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-6). .

(Example 12)

3.18 g of polyimide solution (SPI-3) obtained by synthesis example 13, 4.10 g of polyamic acid solution (PAA-12) obtained by synthesis example 15 are weighed in the 50 ml Erlenmeyer flask which put the stirrer, 1.0 mass % 3- 0.9g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.46g of NMP, 5.4g of GBL, 3.60g of BCS were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-7). .

(Example 13)

4.05 g of the polyimide solution (SPI-3) obtained by the polyimide solution (SPI-3) obtained by the synthesis example 13, and the polyamic-acid solution (PAA-13) obtained by the synthesis example 16 was measured to the 50 mL Erlenmeyer flask which put the stirring bar, and 1.0 mass % 3- NMP solution of glycidoxypropylmethyldiethoxysilane 0.9g, NMP 150g, GBL 5.4g, BCS 3.60g were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-8). .

(Example 14)

3.99 g of polyimide solution (SPI-3) obtained by the polyimide solution (SPI-3) obtained by the synthesis example 13, 3.99 g of the polyamic-acid solution (PAA-14) obtained by the synthesis example 17 in the 50 ml Erlenmeyer flask which put the stirring bar, 1.0 mass % 3- 0.9g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.56g of NMP, 5.40g of GBL, 3.60g of BCS were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-9). .

(Example 15)

3.89 g of the polyimide solution (SPI-3) obtained by the polyimide solution (SPI-3) obtained by the synthesis example 13, 3.89 g of the polyamic-acid solution (PAA-15) obtained by the synthesis example 18 was weighed in the 50 mL Erlenmeyer flask which put the stirrer, 1.0 mass % 3- 0.9g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.66g of NMP, 5.40g of GBL, 3.60g of BCS were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-10). .

(Example 16)

3.79 g of the polyimide solution (SPI-3) obtained by the polyimide solution (SPI-3) obtained by the synthesis example 13, and the polyamic-acid solution (PAA-16) obtained by the synthesis example 19 were weighed in the 50 mL Erlenmeyer flask which put the stirrer, 1.0 mass % 3- 0.9g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.76g of NMP, 5.40g of GBL, 3.60g of BCS were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-11). .

(Example 17)

3.18 g of polyimide solution (SPI-3) obtained by synthesis example 13 and 3.96 g of polyamic acid solution (PAA-17) obtained by synthesis example 20 are weighed in the 50 ml Erlenmeyer flask which put the stirrer, 1.0 mass % 3- 0.9g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.58g of NMP, 5.40g of GBL, 3.60g of BCS were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-12). .

(Example 18)

6.02 g of the polyamic acid ester solution (PAE-1) obtained by 4.8 g and the synthesis example 21 obtained by the polyamic acid ester solution (PAE-1) obtained by the synthesis example 7 was weighed in the 50 mL Erlenmeyer flask which put the stirrer, 1.0 mass % 3 - 0.9 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 2.83 g of NMP, 9.74 g of GBL, and 6.00 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (AL-13) got it

(Example 19)

4.8 g of polyamic acid ester solution (PAE-1) obtained by synthesis example 7, 6.17 g of polyamic acid solution (PAA-19) obtained by synthesis example 22 are weighed in the 50 ml Erlenmeyer flask which put the stirring bar, 1.0 mass % 3 - 0.9 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.91 g of NMP, 9.62 g of GBL, and 6.00 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (AL-14) got it

(Example 20)

5.99g of polyamic acid ester solution (PAE-1) obtained by 4.8 g and synthesis example 23 of the polyamic acid ester solution (PAE-1) obtained by the synthesis example 7 was measured in the 50 mL Erlenmeyer flask which put the stirrer, 1.0 mass % 3 - 0.9 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.95 g of NMP, 9.77 g of GBL, and 6.00 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (AL-15) got it

(Example 21)

6.10 g of polyamic acid ester solution (PAE-1) obtained by 4.8 g and synthesis example 24 of the polyamic acid ester solution (PAE-1) obtained by the synthesis example 7 was weighed in the 50 mL Erlenmeyer flask which put the stirrer, 1.0 mass % 3 - 0.9 g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.92 g of NMP, 9.67 g of GBL, and 6.00 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (AL-16) got it

(Example 22)

6.09 g of polyamic acid solution (PAA-22) obtained by 4.8 g and synthesis example 9 of the polyamic acid solution (PAA-22) obtained by the synthesis example 25 was weighed in the 50 mL Erlenmeyer flask which put the stirrer, 1.0 mass % 3- 0.9g of NMP solution of glycidoxypropylmethyldiethoxysilane, 1.96g of NMP, 9.77g of GBL, 6.00g of BCS were added, and it stirred for 30 minutes with a magnetic stirrer, and obtained the liquid crystal aligning agent (AL-17). .

(Example 23)

After filtering the liquid crystal aligning agent (AL-6) obtained in Example 11 with a filter of 1.0 μm, the prepared substrate on which the electrode is formed and an ITO film on the back surface of the prepared glass substrate having a columnar spacer having a height of 4 μm, It was applied by spin coat application. After drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. 0.2 J/cm 2 of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 were irradiated to this coating film surface through a polarizing plate. This board|substrate was made to immerse in 25 degreeC ethyl lactate for 5 minutes, then, it was made to immerse in 25 degreeC pure water for 1 minute, it dried on a 200 degreeC hotplate for 5 minutes, and the board|substrate with a liquid crystal aligning film was obtained. The two substrates are set as one set, a sealing compound is printed on the substrate, and the other substrate is adhered so that the liquid crystal aligning film surface is facing and the alignment direction is 0 °, and then the sealing compound is cured, An empty cell was created. Liquid crystal MLC-2041 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, and it was left to stand overnight.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT at 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 4.5%, 0.8%, 0.4%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 24)

The FFS drive liquid crystal cell was produced by the method similar to Example 23 except having used the liquid crystal aligning agent (AL-7) obtained in Example 12.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.8%, 1.2%, 0.7%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 25)

The FFS drive liquid crystal cell was produced by the method similar to Example 23 except having used the liquid crystal aligning agent (AL-8) obtained in Example 13.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.9%, 1.2%, 0.8%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 26)

The FFS drive liquid crystal cell was produced by the method similar to Example 23 except having used the liquid crystal aligning agent (AL-9) obtained in Example 14.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.5%, 1.2%, 0.6%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 27)

The FFS drive liquid crystal cell was produced by the method similar to Example 23 except having used the liquid crystal aligning agent (AL-10) obtained in Example 15.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable.

As a result of evaluating the charge relaxation characteristics, ΔT at 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 5.5%, 1.1%, 0.7%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 28)

The FFS drive liquid crystal cell was produced by the method similar to Example 23 except having used the liquid crystal aligning agent (AL-11) obtained in Example 16.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT at 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 7.3%, 1.2%, 0.6%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 29)

The FFS drive liquid crystal cell was produced by the method similar to Example 23 except having used the liquid crystal aligning agent (AL-12) obtained in Example 17.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 7.8%, 1.4%, 0.7%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 30)

After filtering the liquid crystal aligning agent (AL-13) obtained in Example 18 with a filter of 1.0 µm, the prepared substrate on which the electrode is formed and an ITO film on the back surface of the prepared glass substrate having a columnar spacer having a height of 4 µm, It was applied by spin coat application. After drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. 0.5 J/cm 2 of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 were irradiated to this coating film surface through a polarizing plate. This board|substrate was baked for 20 minutes in 230 degreeC hot-air circulation type oven, and the board|substrate with a liquid crystal aligning film was obtained. The two substrates are set as one set, a sealing compound is printed on the substrate, and the other substrate is adhered so that the liquid crystal aligning film surface is facing and the alignment direction is 0 °, and then the sealing compound is cured, An empty cell was created. Liquid crystal MLC-2041 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, and it was left to stand overnight.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.5%, 0.2%, 0.2%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 31)

The FFS drive liquid crystal cell was produced by the method similar to Example 30 except having used the liquid crystal aligning agent (AL-14) obtained in Example 19.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 5.9%, 0.3%, 0.2%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 32)

The FFS drive liquid crystal cell was produced by the method similar to Example 30 except having used the liquid crystal aligning agent (AL-15) obtained in Example 20.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 4.9%, 0.6%, 0.3%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 33)

The FFS drive liquid crystal cell was produced by the method similar to Example 30 except having used the liquid crystal aligning agent (AL-16) obtained in Example 21.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 6.3%, 0.3%, 0.2%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

(Example 34)

After filtering the liquid crystal aligning agent (AL-17) obtained in Example 22 with a 1.0 µm filter, the prepared substrate on which the electrode is formed and an ITO film on the back surface of the prepared glass substrate having a columnar spacer having a height of 4 µm, It was applied by spin coat application. After drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. After rubbing this coating surface with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm/sec, indentation length: 0.3 mm), a 3/7 mixed solvent of isopropyl alcohol and pure water After performing ultrasonic irradiation for 1 minute, washing|cleaning and removing a water droplet by an air blow, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the board|substrate with a liquid crystal aligning film was obtained. The two substrates are set as one set, a sealing compound is printed on the substrate, and the other substrate is adhered so that the liquid crystal aligning film surface is facing and the alignment direction is 0 °, and then the sealing compound is cured, An empty cell was created. Liquid crystal MLC-2041 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, and it was left to stand overnight.

As a result of performing residual image evaluation by a long-term alternating current drive about this FFS drive liquid crystal cell, the value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.3 degrees or less, and was favorable. As a result of evaluating the charge relaxation characteristics, ΔT for 0 minutes, 5 minutes, 10 minutes, and 20 minutes of AC drive was 4.0%, 0.9%, 0.5%, and 0%, respectively. As a result of performing charge accumulation value evaluation by the asymmetry of alternating current drive, the change amount of the maximum offset voltage in 30-minute drive was 20 mV or less, and it was favorable.

Industrial Applicability

The liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can suppress the suppression of charge accumulation by the asymmetry of alternating current drive, rapid relaxation of the residual electric charge accumulated by a direct voltage|voltage, and also suppress the residual image by alternating current drive, It is useful as a liquid crystal aligning film of the liquid crystal display element of an IPS drive system and an FFS drive system, and a liquid crystal television which is excellent in a residual image characteristic.

In particular, the liquid crystal display element of this invention can be used suitably for a large screen, high-definition liquid crystal television, a small and medium-sized car navigation system, a smart phone, etc.

In addition, the specification of JP Patent application 2013-219840 for which it applied on October 23, 2013, a claim, and all the content of an abstract are referred here, and it takes in as an indication of the specification of this invention.

Claims (24)

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
(A) component: A polyimide precursor having at least one structure selected from the group consisting of the following formulas [1a], [1b] and [1c], and a polyimide obtained by imidizing the polyimide precursor. at least one polymer selected from

(In formula [1a], X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms when m is 1. X ^b represents a protecting group substituted with a hydrogen atom by heat. m is an integer of 1 or 2 However, when m is 2, there ^{is no substituent for X a} . In formula [1b], X ^c represents a protecting group substituted with a hydrogen atom by heat. In formula [1c], X ^d is a single bond or represents an organic group having 1 to 20 carbon atoms, X ^e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^f represents a protecting group substituted with a hydrogen atom by heat, and n represents an integer of 1 to 4)
(B) component: It is obtained by the polycondensation reaction of the tetracarboxylic-acid component containing tetracarboxylic dianhydride of following formula (B-1), and the diamine component containing the diamine of following formula (B-2) The at least 1 sort(s) of polymer chosen from the group which consists of polyimide which imidated a polyamic acid and its polyimide precursor.

(Wherein, Y ₁ represents a divalent organic group having a structure represented by the following formula (YD-14) or (YD-18). B ₁ and B ₂ each independently represent a hydrogen atom and 1 to 10 carbon atoms. represents an alkyl group, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and these groups may have a substituent.

(In formula (YD-14), j is an integer of 0-3.) The method of claim 1,
The said (A) component polycondenses the diamine component containing the diamine which has at least 1 sort(s) of structure chosen from the structure shown by the said formula [1a], a formula [1b], and a formula [1c], and a tetracarboxylic-acid component, The liquid crystal aligning agent which is an at least 1 sort(s) of polymer chosen from the polyimide which imidated the polyimide precursor obtained and this polyimide precursor. 3. The method of claim 2,
The liquid crystal aligning agent whose diamine which has an at least 1 sort(s) of structure chosen from the group which consists of said formula [1a], a formula [1b], and a formula [1c] is a diamine represented by following formula [1-1].

(wherein, X ^D represents an organic group having 5 to 50 carbon atoms and having at least one structure selected from the group consisting of formula [1a], formula [1b] and formula [1c], A ¹ and A ² are , each independently represent 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 may have a substituent. 4. The method of claim 3,
The liquid crystal aligning agent whose said diamine is at least 1 sort(s) of diamine chosen from the group which consists of a following formula [1a-1] - a formula [1c-1].

(In formula [1a-1], X ¹ is a single bond, an alkylene group having 2 to 10 carbon atoms, -O-, -N(R ¹ )-, -CON(R ² )-, -N(R ³ )CO represents at least one organic group selected from -, -CH ₂ O-, -COO- and -OCO-, with the proviso that R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ² represents a single bond or an alkylene group having 1 to 10 carbon atoms X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms when m is 1. X ^b is heat substituted with a hydrogen atom m represents an integer of 1 or 2. In that case, when m is 2, there ^{is no substituent for X a} . p represents an integer of 1 to 4, q represents an integer of 1 to 4 indicates.
In formula [1b-1], X ³ and X ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )-, -CON(R ² )-, - At least 1 type selected from N(R ³ )CO-, -CH ₂ O-, -COO-, and -OCO- is represented. However, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ⁴ and X ⁶ each independently represent a single bond or an alkylene group ^{having 2 to 10 carbon atoms, X 5} represents a single bond or an alkylene group having 2 to 10 carbon atoms, and X ^c is a protecting group substituted with a hydrogen atom by heat. and r represents the integer of 1-4.
In the formula [1c-1], X ⁸ is a single bond, an alkylene group having 2 to 10 carbon atoms, -O-, -N(R ¹ )-, -CON(R ² )-, -N(R ³ )CO- , -CH ₂ O-, -COO-, and -OCO- represent at least 1 sort(s). However, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ⁹ represents a single bond or an alkylene group having 1 to 10 carbon atoms, X ^d represents a single bond or an organic group ^{having 1 to 20 carbon atoms, X e} represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^f represents a heat represents a protecting group substituted with a hydrogen atom, n represents an integer of 1 to 4, s represents an integer of 1 to 4, t represents an integer of 1 to 4, formula [1a-1] to formula [1c- In 1], A ¹ to A ⁶ are each independently 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 may have a substituent. .) 5. The method of claim 4,
The liquid crystal aligning agent whose said diamine is at least 1 sort(s) of diamine chosen from the group which consists of a following formula [1d-1] - a formula [1d-3].

(Formula [1d-1] ~ formula [1d-3] of, R ¹ ~ R ⁴ is at least one kind selected from the group consisting of each independently represent the formula [a-1] ~ formula [a-6] below A ¹ to A ⁶ are each independently 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 may have a substituent do.)

(In formula [a-2], R<^1> represents a C1-C5 alkyl group.) 6. The method according to any one of claims 1 to 5,
The polymer of the component (A) is a polyimide precursor obtained by polycondensing a diamine component containing a diamine represented by the following formula [3-1] and a tetracarboxylic acid component, and a polyimide obtained by imidizing the polyimide precursor The liquid crystal aligning agent which is at least 1 sort(s) chosen from the group.

(In formula [3-1], X ^E represents at least one structure selected from the group consisting of the following formulas [3a-1] to [3a-10], and A ¹ and A ² are each independently , 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 may have a substituent.

(In formula [3a-9], n represents the integer of 1-5.) 6. The method according to any one of claims 2 to 5,
The liquid crystal aligning agent whose said tetracarboxylic-acid component is tetracarboxylic dianhydride represented by following formula [4].

(Z represents at least one structure selected from the group consisting of the following formulas [4a] to [4q].)

(In formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and in the formula [4g], Z ⁵ and Z ⁶ are each independently , represents a hydrogen atom or a methyl group.) 8. The method of claim 7,
The group in which the said tetracarboxylic-acid component consists of said formula [4a], a formula [4e] - a formula [4g], a formula [4l], a formula [4m], and a formula [4p], Z in said formula [4] The liquid crystal aligning agent which is at least 1 sort(s) of tetracarboxylic-acid compound chosen from. 6. The method according to claim 4 or 5,
Polymer of said (A) component WHEREIN: Diamine shown by the said formula [1a-1], a formula [1b-1], and a formula [1c-1] is 5-30 mol% in 100 mol% of all the diamine components liquid crystal aligning agent. 6. The method according to any one of claims 1 to 5,
Said (B) component WHEREIN: The liquid crystal aligning agent whose tetracarboxylic dianhydride represented by the said Formula (B-1) is 10-100 mol% with respect to 1 mol of all the tetracarboxylic-acid components. 6. The method according to any one of claims 1 to 5,
Said (B) component WHEREIN: The liquid crystal aligning agent whose diamine of the said Formula (B-2) is 10-100 mol% with respect to 1 mol of all the diamine components. 6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent whose polymer of the said (B) component is 40-250 mass parts with respect to 100 mass parts of polymers of the said (A) component. 6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent containing the at least 1 sort(s) of solvent chosen from the group which consists of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and (gamma)-butyrolactone. 6. The method according to any one of claims 1 to 5,
At least one selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether A liquid crystal aligning agent containing a solvent. 6. The method according to any one of claims 1 to 5,
A crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group, and a polymerizable unsaturated bond The liquid crystal aligning agent containing at least 1 sort(s) chosen from the group which consists of a crosslinkable compound which has. The liquid crystal aligning film obtained by apply|coating the liquid crystal aligning agent in any one of Claims 1-5, and baking. The liquid crystal aligning film obtained by the inkjet method using the liquid crystal aligning agent in any one of Claims 1-5. The liquid crystal aligning film obtained by irradiating the radiation which polarized to the liquid crystal aligning film of Claim 16. The liquid crystal display element which has the liquid crystal aligning film of Claim 16. delete delete delete delete delete