KR20160074604A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent capable of forming a liquid crystal alignment film excellent in adhesion to a sealing agent and a base substrate while suppressing afterimage due to AC driving, a liquid crystal alignment film formed from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film Lt; / RTI > A liquid crystal aligning agent containing the following components (A) and (B). Component (A): a polymer containing at least one member selected from a polyimide precursor having a protective group substituted with a hydrogen atom by heat and polyimide. Component (B): A polymer containing at least one member selected from polyimide precursors having urea and / or thiourea groups and polyimide.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

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

In a liquid crystal display device used for a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the arrangement of liquid crystals (also called orientation) is usually formed in the device.

At present, the most widely used liquid crystal alignment film has a structure in which the surface of a resin film composed of a polyimide precursor formed on an electrode substrate, for example, polyamide acid or polyimide imidized thereon is used as a surface, nylon, polyester Rubbing in one direction with a cloth such as a so-called rubbing treatment method.

In the step of controlling the alignment state of the liquid crystal alignment film (also referred to as liquid crystal alignment treatment), the rubbing treatment of the surface of the resin film is an industrially useful method which is simple and excellent in productivity. However, the demand for higher performance, higher definition, and larger size of the liquid crystal display element is further increased, and the surface of the liquid crystal alignment film caused by the rubbing process is affected by scratches, oscillation, mechanical force or static electricity, And the like.

As a method for replacing the rubbing treatment method, there is known a photo-alignment treatment for controlling the alignment state of the liquid crystal by irradiating polarized ultraviolet rays. A liquid crystal alignment treatment method using a photo alignment treatment has been proposed by using a photoisomerization reaction, a photo-crosslinking reaction, and a photo-decomposition reaction (see Non-Patent Document 1).

Further, in Patent Document 1, it has been proposed to use a resin coating made of a polyimide resin having an alicyclic structure such as a cyclobutane ring in the main chain for optical alignment treatment. Particularly, when a polyimide-based resin is used for a liquid crystal alignment film of a photo alignment method, its usefulness is expected because it has higher heat resistance than those of other resins.

The above-described photo-alignment treatment is advantageous in that it can be produced by an industrially easy manufacturing process as a liquid-crystal alignment treatment of a rubbing-less. Further, in a liquid crystal display device using an IPS (In-Plane Switching) driving method or an FFS (Fringe Field Switching) driving method, when a liquid crystal alignment film obtained by the above-described photo alignment treatment is used, compared with a liquid crystal alignment film obtained by a rubbing treatment method , It is possible to improve the contrast and viewing angle characteristics of the liquid crystal display element, and it is possible to improve the performance of the liquid crystal display element. For this reason, the photo alignment treatment method has attracted particular attention as a liquid crystal alignment treatment method in the future.

On the other hand, as the liquid crystal alignment film used in the IPS drive method or the FFS drive type liquid crystal display device, in addition to the basic characteristics such as excellent liquid crystal alignment property (liquid crystal orientation property, liquid crystal alignment control ability) and electric characteristics, It is necessary to suppress the residual image caused by the AC drive which occurs in the liquid crystal display device of the driving type and to have the characteristics such as the quick relaxation of the residual charge accumulated by the DC voltage. However, the liquid crystal alignment film obtained by the photo alignment treatment method has insufficient liquid crystal alignability, electrical characteristics as a liquid crystal display element, and furthermore, stability of these characteristics, and it is difficult to satisfy the above characteristics.

Further, in recent years, in order to make a liquid crystal display thinner and to enlarge a display area, application of a narrowing-down softening that narrows a frame edge area on a substrate is examined. In the LCD panel to which the tightening and softening is applied, a sealant is applied on the liquid crystal alignment film and the liquid crystal alignment film is bonded. Therefore, a shortage of adhesion strength to the liquid crystal alignment film, the sealant and the substrate is a serious problem. In general, it is known that the adhesive strength (also referred to as adhesiveness) of the organic film-sealing agent and the organic film-base substrate tends to be weaker than that of the interface with the underlying substrate-sealing agent. , The liquid crystal alignment film-sealant, and the liquid crystal alignment film-substrate.

However, there is no example in which the adhesion strength of the liquid crystal alignment film-sealant is examined. Particularly, adhesion between the liquid crystal alignment film and the sealant is improved and suppression of the residual image and early relaxation of the residual charge occur in the liquid crystal display element. The example of the report that was examined for

Japanese Patent Application Laid-Open No. 9-297313

 &Quot; Liquid crystal photo alignment layer " Kiyohito, Ichimura Functional Materials, Nov. 1997, Vol. 17, No. 11, pages 13-22

Means for Solving the Problems The present inventors have found that a method for suppressing afterimage due to AC driving generated in an IPS driving method or an FFS driving type liquid crystal display device and obtaining a liquid crystal alignment film having high adhesion to a sealing agent, (Hereinafter referred to as a liquid crystal aligning component) and a component having excellent adhesiveness between a sealant and a base substrate (hereinafter, an adhesive component) were blended. However, such a liquid crystal aligning agent does not necessarily solve the above-described problems, especially in the photo-alignment treatment method.

That is, in the liquid crystal alignment film obtained from the liquid crystal aligning agent containing the two components, adhesion between the sealant and the base substrate is improved by the presence of the adhesive component, but this leads to inhibition of the alignment control force of the liquid crystal, And therefore, the two characteristics can not always be compatible with each other.

An object of the present invention is to provide a liquid crystal aligning agent which blends a liquid crystal aligning component having a liquid crystal alignability, that is, a liquid crystal aligning component having a strong alignment control force of liquid crystal, and an adhesive component having excellent adhesiveness between a sealant and a base substrate, And a liquid crystal alignment film capable of achieving both adhesion between the sealant and the base substrate.

In addition, the present invention provides a liquid crystal display element having the liquid crystal alignment film and a liquid crystal aligning agent capable of providing the liquid crystal alignment film.

As a result of intensive studies, the inventor of the present invention has found that a liquid crystal aligning agent having a polymer having a specific structure is very effective for achieving the above object, and has completed the present invention.

That is, the present invention has the following points.

(1) A liquid crystal aligning agent containing the following components (A) and (B).

(A): a poly (oxyalkylene) polymer having at least one structure selected from structures represented by the following formula [1A] (also referred to as specific structure (1A)) and formula [1B] At least one polymer selected from a polyimide precursor and a polyimide (also referred to as a specific polymer (A)).

(B): At least one polymer selected from a polyimide precursor having a structure represented by the following formula [2] (also referred to as a specific structure (2)) and a polyimide (also referred to as a specific polymer (B) .

[Chemical Formula 1]

(In the formula [1A] and the formula [1B], X ^A and X ^C each independently represent a protecting group substituted by a hydrogen atom by heat, and X ^B represents a single bond or an organic Group, wherein the atom to which the ester group (-COO- group) is bonded is a carbon atom.

(2)

Y ¹ and Y ⁷ each independently represent 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-, provided that each of R ¹ , R ² and R ³ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms Y ² and Y ⁶ each independently represent an alkylene group of 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, Y ⁴ represents an alkyl group of 1 to 10 carbon atoms, An oxygen atom or a sulfur atom).

(2) The resin composition according to the above (1), wherein the structure represented by the above formula [1A] and the structure represented by the formula [1B] is at least one structure selected from the structures represented by the following formulas [1a], [ Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.

(3)

(In the formula [1a], X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^b represents a protecting group substituted by a hydrogen atom by heat, and m represents an integer of 1 or 2, 1a] in has no substituent of X ^a and m is 2, the formula [1b] of, X ^c denotes a protective group which is substituted with hydrogen atoms by heat, formula [1c] of, X ^d is a single bond or a c 1 -C X ^e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^f represents a protecting group substituted by a hydrogen atom by heat, and n represents an integer of 1 to 4).

(3) The polymer of component (A) is obtained by using a diamine component containing a diamine having at least one structure selected from the structures represented by the above formulas [1a], [1b] and [1c] A liquid crystal aligning agent according to claim 2, which is a polymer containing at least one kind selected from polyimide precursors and polyimides.

(4) The liquid crystal aligning agent according to (3), wherein the diamine is a diamine represented by the following formula [1-1].

[Chemical Formula 4]

(In the formula [1-1], X ^D represents an organic group having 5 to 50 carbon atoms and at least one structure selected from the structures represented by the formulas [1a], [1b] and [ ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

(5) The liquid crystal aligning agent according to (4), wherein the diamine is at least one diamine selected from the diamines represented by the following formulas [1a-1] to [1c-1].

[Chemical Formula 5]

X ¹ represents 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-, provided that R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, represents. X ² represents a single bond, an alkylene group of carbon number 1 ~ 10, X ^a represents an organic group of a hydrogen atom or a carbon number 1 ~ 20, X ^b represents a protecting group which is substituted with hydrogen atoms by the heat. m is 1 or P represents an integer of 1 to 4, and q represents an integer of 1 to 4, provided that when m is 2, X represents ^a hydrogen atom.

In formula [1b-1], X ³ and X ⁷ each independently represent 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-. 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 of 1 to 10 carbon atoms, X ⁵ represents a single bond or an alkylene group of 1 to 10 carbon atoms, X ^c represents a protecting group substituted by a hydrogen atom And r represents an integer of 1 to 4.

In formula [1c-1], X ⁸ represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ ) -, -CON (R ² ) -, -N (R ³ ) , -CH ₂ O-, -COO-, and OCO-. 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, an alkylene group of carbon number 1 ~ 10, X ^d represents an organic group of a single bond or a carbon number of 1 ~ 20, X ^e represents an organic group of a hydrogen atom or a carbon number 1 ~ 20, X ^f is a column, N is an integer of 1 to 4, s is an integer of 1 to 4, t is an integer of 1 to 4, and the formula [1a-1] to the formula [1c- 1], A ¹ to A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

(6) The liquid crystal aligning agent according to (5), wherein the diamine is at least one diamine selected from diamines represented by the following formulas [1d-1] to [1d-5].

[Chemical Formula 6]

(In the formulas [1d-1] to [1d-5], R ¹ to R ⁷ each independently represent at least one selected from the structures represented by the following formulas [a-1] to [ A ¹ to A ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In formulas (1d-1) to (1d-5), A ¹ to A ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

(7)

(In the formula [a-2], R ¹ represents an alkylene group having 1 to 5 carbon atoms).

(7) The polyimide precursor as described in the above item (1), wherein the polymer of component (B) is a polymer containing at least one polyimide precursor obtained by using a diamine component containing a diamine having a structure represented by the formula [ The liquid crystal aligning agent according to any one of (1) to (6).

(8) The liquid crystal aligning agent according to (7), wherein the diamine is a diamine represented by the following formula [2-1].

[Chemical Formula 8]

(In the formula [2-1], Y ^A represents an organic group having 10 to 50 carbon atoms having the structure represented by the above formula [2], A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms .

(9) The liquid crystal aligning agent according to (8), wherein the diamine is a diamine represented by the following formula (2a).

[Chemical Formula 9]

(In formula [2a], Y ¹ and Y ⁷ each independently represent 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-, provided that each of R ¹ , R ² and R ³ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms Y ² and Y ⁶ each independently represent an alkylene group of 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, Y ⁴ represents an alkyl group of 1 to 10 carbon atoms, An oxygen atom or a sulfur atom; and A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

(10) The liquid crystal aligning agent according to (9), wherein the diamine is at least one kind of diamine selected from the following formulas [2a-1] to [2a-3].

[Chemical formula 10]

(In formulas (2a-1) to (2a-3), A ¹ to A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

(11) The polymer according to the above (1), wherein the polymer of the component (A) is a polymer containing at least one member selected from a polyimide precursor and a polyimide obtained by using a diamine represented by the following formula [3-1] ) To (10).

(11)

(In the formula [3-1], X ^E represents at least one structure selected from the structures represented by the following formulas [3a-1] to [3a-9], and A ¹ and A ² each independently And represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[Chemical Formula 12]

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

(12) The polymer of the component (A) and the polymer of the component (B) are at least one polymer selected from a polyimide precursor obtained by using a tetracarboxylic acid component represented by the following formula [4] Is the liquid crystal aligning agent according to any one of (1) to (11).

[Chemical Formula 13]

(In the formula [4], Z represents at least one structure selected from the following formulas [4a] to [4q].

[Chemical Formula 14]

[Chemical Formula 15]

Z ¹ and 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], each of Z ⁵ and Z ⁶ independently represents , A hydrogen atom or a methyl group.

(13) The method according to any one of the above (1) to (4), wherein the tetracarboxylic acid component is at least one compound selected from the group consisting of compounds represented by the formula [4a], formula [4e] to formula [4g], formula [4l] (12), wherein the liquid crystal aligning agent is a tetracarboxylic acid component having at least one structure selected from the group consisting of a tetracarboxylic acid component and a tetracarboxylic acid component.

(14) The polymer of component (A), wherein the diamine represented by the formula [1a-1], the formula [1b-1] and the formula [ In terms of% by mole, of the liquid crystal aligning agent according to any one of (5) to (13).

(15) The polymer according to any one of the above (9) to (14), wherein the diamine represented by the formula (2a) is 20 to 100 mol% in 100 mol% ≪ / RTI >

(16) The liquid crystal aligning agent according to any one of (1) to (15), wherein the polymer of the component (B) is 40 to 250 parts by mass based on 100 parts by mass of the polymer of the component (A).

(17) The liquid crystal aligning agent according to any one of (1) to (16), wherein at least one polymer of the component (A) and the polymer of the component (B) is a polyamide acid alkyl ester.

(18) The liquid crystal aligning composition according to the above (1), wherein the liquid crystal aligning agent is at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N- To (17) above.

(19) As the solvent of the liquid crystal aligning agent, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether (1) to (18) above, wherein the liquid crystal aligning agent contains at least one kind of solvent selected from the group consisting of the following.

(20) The liquid crystal aligning agent according to any one of the above items (1) to (3), wherein the liquid crystal aligning agent is a crosslinking compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinking compound having at least one substituent selected from the group consisting of a hydroxyl group, The liquid crystal aligning agent according to any one of (1) to (19) above, which contains at least one crosslinkable compound selected from a crosslinkable compound having a polymerizable unsaturated bond and a crosslinkable compound having a polymerizable unsaturated bond.

(21) A liquid crystal alignment film obtained from the liquid crystal aligning agent described in any one of (1) to (20) above.

(22) A liquid crystal alignment film obtained by an ink-jet method using the liquid crystal aligning agent according to any one of (1) to (20).

(23) A liquid crystal alignment film obtained by irradiating the liquid crystal alignment film according to (21) or (22) above with polarized radiation.

(24) A liquid crystal display element having the liquid crystal alignment film according to any one of (21) to (23).

A liquid crystal aligning agent containing two types of at least one kind of polymer selected from a polyimide precursor having a specific structure or polyimide is preferable because it suppresses the afterimage due to the AC driving and also has both the sealing agent and the adhesiveness with the base substrate A liquid crystal alignment film can be obtained. Particularly, it is useful for a liquid crystal alignment film for photo-alignment treatment obtained by irradiating polarized radiation. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television of a large size on a large screen, a car navigation system for small and medium size, or a smart phone.

Whether or not the problem of the present invention is solved in the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is considered to be almost as follows although it is not necessarily clear.

The specific structure (1A) and the specific structure (1B) are structures capable of increasing the liquid crystal alignment property. Therefore, a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer having these structures becomes a liquid crystal alignment film excellent in liquid crystal alignability, and it is possible to suppress afterimage by AC driving in a liquid crystal display element. The specific structure 1A and the specific structure 1B also have an effect of enhancing the adhesion with the sealant.

The specific structure 2 can increase adhesion with a base substrate, for example, an ITO (Indium Tin Oxide) substrate or the like. Therefore, a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer having these structures becomes a liquid crystal alignment film having excellent adhesion with a base substrate. However, the effect of each specific structure can not be obtained due to the presence position in the liquid crystal alignment film. That is, it is necessary that the specific structure 1A and the specific structure 1B are present in the vicinity of the interface of the liquid crystal alignment film, and that the specific structure 2 exists in the liquid crystal alignment film and the interface of the base substrate .

In general, when two components having different surface free energies are blended, it is known that a component having a low surface free energy is localized on the surface of the film, and a component having a high surface free energy is localized in the interface between the film and the substrate have. Since the specific polymer (A) has a specific structure (1A) or specific structure (1B) with low polarity, it becomes a component having a low surface free energy. On the other hand, since the specific polymer (B) has the specific structure (1) having a higher polarity than the specific structure (1A) and the specific structure (1B), it becomes a component having a higher surface free energy than the specific polymer (A). Therefore, in the liquid crystal alignment film obtained from the liquid crystal alignment film obtained from the liquid crystal aligning agent containing the specific polymer (A) and the specific polymer (B), that is, the liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent, the specific polymer (A) It is believed that the specific polymer (B) is unevenly distributed in the interface between the liquid crystal alignment film and the substrate.

Particularly, when the specific structure 1A, the specific structure 1B, and the specific structure 2 are used, each specific polymer tends to be unevenly distributed as described above. Accordingly, in the liquid crystal alignment film of the present invention, it is considered that the liquid crystal alignability, the sealant, and the adhesion with the base substrate can be compatible with each other.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view simply showing a test sample substrate used in evaluation of adhesion between a sealant and a base substrate. FIG.

≪ Specific structure (1A) Specific structure (1B) >

The specific polymer (A) of the present invention is a polymer comprising at least one kind of polyimide precursor having at least one structure selected from the structures represented by the following formulas [1A] and [1B] to be.

[Chemical Formula 16]

In the formula [1A], X ^A represents a protecting group substituted by a hydrogen atom by heat. This group is referred to as a protecting group in that it bonds to a nitrogen atom, is eliminated by heat and is substituted with a hydrogen atom, and forms an amino group. The temperature at which such protective groups are eliminated by heat and substituted with hydrogen atoms is preferably 150 to 300 占 폚, more preferably 200 to 270, which is a firing temperature in the production of a liquid crystal alignment film. Such a protecting group is not particularly limited as long as it is eliminated by heat and is substituted by a hydrogen atom. Specifically, at least one kind selected from the group consisting of the following formulas [a-1] to [a-6] The protecting group represented by [a-1] or [a-6] is preferable.

[Chemical Formula 17]

(In the formula [a-2], R ¹ represents an alkylene group having 1 to 5 carbon atoms).

Among them, it is preferable to use a protecting group having a structure represented by the formula [a-1] or the formula [a-6].

The above formula [1A] is preferably a structure represented by the following formulas [1a] and [1b].

[Chemical Formula 18]

In the formula [1a], X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Among them, a hydrogen atom or an organic group having 1 to 10 carbon atoms is preferable.

In the formula [1a], X ^b represents a protecting group of a carboxyl group and is a group substituted by a hydrogen atom by heat. The same as X ^A described above, and the preferred examples thereof are also the same. m represents an integer of 1 or 2, and when m is 2, there is no substituent of X ^a . Among them, 1 is preferable.

In the formula [1b], X ^c is a protecting group of a carboxyl group, represents a hydrogen atom is substituted by the heat. Are the same as the definitions of X ^A and X ^b , and the preferred examples thereof are also the same.

Specific examples of the structures represented by the formulas [1a] and [1b] include the following formulas [XA-1] to [XA-12].

[Chemical Formula 19]

(In the formulas [XA-1] to [XA-6], A ¹ to A ⁶ each independently represent at least one kind selected from the structures represented by the above formulas [a-1] to [ Wherein n1 represents an integer of 0 to 10, and n2 to n6 of the formula [XA-2] to the formula [XA-6] represent an integer of 1 to 10.

[Chemical Formula 20]

(Wherein [XA-7] ~ formula [XA-12] of, A ⁷ ~ A ¹⁸ is at least one member, each independently, selected from the structures represented by the formula [a-1] ~ formula [a-6] , N7 in the formula [XA-7] represents an integer of 0 to 10, and n8 to n12 in the formula [XA-8] to the formula [XA-12] represent an integer of 1 to 10.

In the formula [1B], X ^B represents a single bond or an organic group having 1 to 40 carbon atoms. 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-), a thioether bond (-S-) Or an alkylene group, an arylene group or a combination thereof, which may contain a thioester bond (-S (= O) ₂ -). At that time, the atom to which the ester group (-COO-) in the formula [1B] is bonded is a carbon atom.

In the formula [1B], X ^C represents a protecting group of a carboxyl group and is a group substituted by a hydrogen atom by heat. This group is the same as X ^A described above, and the preferred examples thereof are also the same. The structure represented by the above formula [1B] is preferably a structure having a structure represented by the following formula [1c].

[Chemical Formula 21]

In the formula [1c], X ^d represents a single bond or an organic group having 1 to 20 carbon atoms, and when X ^d is a single-bond, there is no substituent of X ^e . Among them, a single bond or an organic group having 1 to 10 carbon atoms is preferable.

In the formula [1c], ^Xe represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Among them, a hydrogen atom or an organic group having 1 to 10 carbon atoms is preferable. X ^f represents a protecting group of a carboxyl group and a group substituted by a hydrogen atom by heat. This group is the same as X ^A described above, and the preferred examples thereof are also the same. n represents an integer of 1 to 4; Among them, 1 or 2 is preferable.

Specific examples of the structure represented by the formula [1c] include the structures represented by the following formulas [XC-1] to [XC-12].

[Chemical Formula 22]

(Wherein [XC-1] ~ formula ^{[XC-6], B 1} ~ B 6 is at least one member, each independently, selected from the structures represented by the formula [a-1] ~ formula [a-6] Wherein n1 represents an integer of 0 to 10 and n2 to n6 represent an integer of 1 to 10 in the formulas [XC-2] to [XC-6].

(23)

(Wherein [XC-7] ~ formula ^{[XC-12], B 7} ~ B 18 is at least one member, each independently, selected from the structures represented by the formula [a-1] ~ formula [a-6] And n7 in the formula [XC-7] represents an integer of 0 to 10, and n8 to n12 in the formula [XC-8] to the formula [XC-12] represent an integer of 1 to 10.

<Specific structure (2)>

The specific polymer (B) of the present invention is a polymer containing at least any one selected from a polyimide precursor having a specific structure (2) represented by the following formula [2] and a polyimide.

&Lt; EMI ID =

In formula [2], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N (R ¹ ) -, -CON (R ² ) , -N (R ³ ) CO-, -CH ₂ O-, -COO- and OCO-. 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-, -S-, -OCO- or COO- is preferable. More preferably, it is a single bond, -O- or S- in view of the liquid crystal alignability and the film hardness of the liquid crystal alignment film.

In the formula [2], Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms. Among them, an alkylene group having 1 to 3 carbon atoms is preferable, and the structure thereof may be either a linear chain or a branched chain. Specifically, from the viewpoints of the liquid crystal alignability and the film hardness of the liquid crystal alignment film, a methylene group (-CH ₂ -), an ethylene group (-CH ₂ CH ₂ -), a propylene (- (CH ₂ ) ₃ -) or an isopropyl group (-C (CH ₂ ) ₂ -).

In the formula [2], Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.

In the formula [2], Y ⁴ represents an oxygen atom or a sulfur atom. Of these, oxygen atoms are preferable from the viewpoint of the film hardness of the liquid crystal alignment film.

Specific polymer (A) Specific polymer (B)

The specific polymer (A) and the specific polymer (B) are at least one kind of polymer selected from a polyimide precursor and a polyimide (collectively referred to as a polyimide polymer). Among them, the polyimide polymer of the present invention is preferably a polyimide precursor or polyimide obtained by reacting a diamine component with a tetracarboxylic acid component.

The polyimide precursor is a structure represented by the following formula [A].

(25)

(Wherein [A] of, R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² are, each independently, a hydrogen atom or an alkyl group having a carbon number of 1 ~ 5, A ^3, and A ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, and n represents a positive integer).

Examples of the diamine component include diamines having two primary or secondary amino groups in the molecule.

Examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds and tetracarboxylic acid dialkyl ester dihalide compounds. have.

In order to obtain a polyamic acid in which A ¹ and A ² in the formula [A] are hydrogen atoms, a diamine having two primary or secondary amino groups in the molecule and a tetracarboxylic acid compound or a tetracarboxylic acid anhydride .

In order to obtain a polyamide acid alkyl ester wherein A ¹ and A ² in the formula [A] are alkylene groups of 1 to 5 carbon atoms, the diamine is reacted with a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid And then reacting it with a di-alkyl di-halide compound. In addition, it may be introduced into a polyamic acid obtained by the above method, the expression [A] to represent A ¹ and A ² C 1 -C 5 alkylene group of the.

The specific polymer (A) is a polymer having at least one structure selected from the specific structure (1A) and the specific structure (1B).

The method of introducing the specific structure (1A) or the specific structure (1B) into the specific polymer (A) is not particularly limited, but it is preferable to use a diamine having the specific structure (1A) or the specific structure (1B) as the diamine component Do. Particularly preferred is a diamine having a structure represented by the above formula [1a], formula [1b] or formula [1c].

Specifically, it is preferable to use a diamine (also referred to as a specific diamine (1)) represented by the following formula [1-1].

(26)

In the formula [1-1], X ^D represents an organic group having 5 to 50 carbon atoms and having at least one structure selected from the structures represented by the formulas [1a], [1b] and [1c] In the formula [1-1], A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

More specifically, diamines represented by the following formulas [1a-1] to [1c-1] are preferably used.

(27)

X ¹ represents 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-. R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In particular, a single bond, -O-, -CONH-, -NHCO-, -COO- or OCO- is preferable.

In the formula [1a-1], X ² represents a single bond or an alkylene group having 1 to 10 carbon atoms. Among them, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable. X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms. As the organic group having 1 to 10 carbon atoms, it is preferable that - (CH ₂ ) _n -COO-tBu (n represents an integer of 1 to 5, and tBu represents a tert-butyl group).

In the formula [1a-1], X ^b is a group which is eliminated by heating and is substituted with a hydrogen atom, and is a protecting group of a carboxyl group. Specific examples of the groups are the same as above, and X ^A, and the preferred examples are the same as the aforementioned X ^A.

In the formula [1a-1], m represents an integer of 1 or 2, and when m in the formula [1a] is 2, there is no substituent of X ^a . p represents an integer of 1 to 4; Among them, 1 to 3 are preferable from the viewpoint of availability of raw materials and easiness of synthesis. More preferred is 1 to 2. q represents an integer of 1 to 4; Among them, 1 to 3 are preferable from the viewpoint of availability of raw materials and easiness of synthesis. More preferred is 1 to 2.

In formula [1b-1], X ³ and X ⁷ each independently represent 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- or OCO-. 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 the formula [1b-1], X ⁴ and X ⁶ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. In particular, a single bond or an alkyl group having 1 to 5 carbon atoms is preferable.

X ⁵ represents a single bond or an alkylene group having 1 to 10 carbon atoms. Among them, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable. X ^c is a protecting group of a carboxyl group, is the same as X ^b described above, and the preferred examples thereof are also the same.

In the formula [1b-1], r represents an integer of 1 to 4. Among them, 1 to 3 are preferable from the viewpoint of availability of raw materials and easiness of synthesis. More preferred is 1 to 2.

In formula [1c-1], X ⁸ represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ ) -, -CON (R ² ) -, -N (R ³ ) , -CH ₂ O-, -COO-, or OCO-. R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In particular, a single bond, -O-, -CONH-, -NHCO-, -COO- or OCO- is preferable.

In the formula [1c-1], X ⁹ represents a single bond or an alkylene group having 1 to 10 carbon atoms, and is preferably a single bond or an alkylene group having 1 to 5 carbon atoms. X ^d represents a single bond or an organic group having 1 to 20 carbon atoms. Among them, a single bond or an organic group having 1 to 10 carbon atoms is preferable. More preferably, it is a single bond or a carbon atom (&gt; CH-). And X ^e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. At that time, when X ^d is a single-bond sum, X ^e does not exist. Among them, a hydrogen atom or NH-COO-tBu (tBu represents a tert-butyl group) is preferable.

In the formula [1c-1], X ^f is a protecting group of a carboxyl group, as defined above a X ^b, X ^b, and further, it is preferred that the same examples. n represents an integer of 1 to 4; Among them, 1 to 3 is preferable, and 1 to 2 is more preferable in view of the availability of raw materials and easiness of synthesis. s represents an integer of 1 to 4, and is preferably 1 to 3, and more preferably 1 to 2, from the viewpoints of availability of the raw material and ease of synthesis. t represents an integer of 1 to 4, and is preferably 1 to 3, and more preferably 1 to 2, from the viewpoints of availability of raw materials and ease of synthesis.

In formulas [1a-1] to [1c-1], A ¹ to A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Specific diamines of the specific diamine (1) of the present invention include diamines represented by the following formula [1d].

(28)

(In the formula [1d], D represents at least one structure selected from the structures represented by the formulas [XA-1] to [XA-12] and the formulas [XC-1] to [XC-12] , and n represents an integer of 1 to 4).

Specific examples of the diamine include diamines represented by the following formulas [1d-1] to [1d-11].

[Chemical Formula 29]

(Formula [1d-1] ~ formula [1d-5] of, R ¹ ~ R ⁷ are each independently selected from the formula [a-1] ~ type indicates at least a structure of one type of compound selected from [a-6] , And A ¹ to A ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, in formulas [1d-1] to [1d-5].

(30)

(Wherein [1d-6] ~ formula ^{[1d-9], R 8} ~ R 14 is at least one member, each independently, selected from the structures represented by the formula [a-1] ~ formula [a-6] , And A ¹¹ to A ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, in the formulas [1d-6] to [1d-9].

Among them, as the specific diamine (1) of the present invention, it is preferable to use diamines represented by the above-mentioned formulas [1d-1] to [1d-5].

As the specific diamine (1) of the present invention, diamines represented by the following formulas [1d-10] and [1d-11] may also be used.

(31)

(Formula [1d-10] and formula [1d-11] of, R ¹⁵ ~ R ¹⁸ is at least one member, each independently, selected from the structures represented by the formula [a-1] ~ formula [a-6] , And A ¹⁹ and A ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms in the formula [1d-11].

The specific diamine (1) in the specific polymer (A) is preferably 5 to 40 mol% in 100 mol% of all the diamine components. Among them, it is preferably 5 to 30 mol%. More preferred is 5 to 20 mol%.

The specific diamine (1) of the present invention is preferably used in a specific diamine (1), depending on the solubility of the specific polymer (A) in a solvent, the application property of a liquid crystal aligning agent, the liquid crystal alignment property in the case of a liquid crystal alignment film, One or more of them may be used in combination.

Specific polymer (B) is a polymer having specific structure (2).

The method of introducing the specific structure (2) into the specific polymer (B) is not particularly limited, but it is preferable to use a diamine having the specific structure (2) as the diamine component. Particularly preferred is the use of a diamine having the structure represented by the above formula [2].

Specifically, it is preferable to use a diamine (also referred to as a specific diamine (2)) represented by the following formula [2-1].

(32)

In the formula [2-1], Y ^A represents an organic group having 10 to 50 carbon atoms and having the structure represented by the formula [2]. A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. More specifically, it is preferable to use a diamine represented by the following formula [2a].

(33)

In formula [2a], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N (R ¹ ) -, -CON (R ² ) , -N (R ³ ) CO-, -CH ₂ O-, -COO- and OCO-. 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-, -S-, -OCO- or COO- is preferable. More preferably, it is a single bond, -O- or S-, which is as flexible as possible and less steric hindrance in view of liquid crystal alignability and film hardness.

In formula [2a], Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms. Among them, an alkylene group having 1 to 3 carbon atoms is preferable, and the structure thereof may be either a linear chain or a branched chain. Specifically, from the viewpoints of the liquid crystal alignability and the film hardness of the liquid crystal alignment film, a methylene group (-CH ₂ -), an ethylene group (-CH ₂ CH ₂ -), a propylene (- (CH ₂ ) ₃ -) or an isopropyl group (-C (CH ₂ ) ₂ -).

In formula [2a], Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.

In formula [2a], Y ⁴ represents an oxygen atom or a sulfur atom. Of these, oxygen atoms are preferable from the viewpoint of the film hardness of the liquid crystal alignment film.

Preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Y ^{7 in} the formula [2a] are as shown in Table 1 below.

Among them, the combination represented by the formula [2-1a], the formula [2-2a], the formula [2-4a], the formula [2-5a], the formula [2-7a] and the formula [2-8a] .

In formula [2a], A1 and A2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Specific diamines of the specific diamine (2) include diamines represented by the following formulas [2a-1] to [2a-3].

(34)

(In formulas (2a-1) to (2a-3), A ¹ to A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

The specific diamine (2) in the specific polymer (B) is preferably 10 to 100 mol% in 100 mol% of all the diamine components. Among them, 20 to 100 mol% is preferable. More preferred is 30 to 100 mol%.

The specific diamine (2) is preferably one or more selected from the group consisting of one kind or a combination of two or more kinds, depending on the solubility of the specific polymer (B) in the solvent, the application property of the liquid crystal aligning agent, the liquid crystal alignment property in the case of the liquid crystal alignment film, Two or more species may be used in combination.

It is preferable to use other diamine (also referred to as a specific second diamine) represented by the following formula [3-1] together with the specific diamine (1) for the diamine component in producing the specific polymer (A).

(35)

In the formula [3-1], Y ^A represents at least one structure selected from the structures represented by the following formulas [3a-1] to [3a-9].

(36)

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

In the formula [3-1], A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Among them, diamines represented by the formulas [3a-1] to [3a-4], formula [3a-6], formula [3a-8] or formula [3a-9] are preferable as specific second diamines. More preferred are the formulas [3a-1] to [3a-3], the formula [3a-8] or the formula [3a-9]. Particularly preferred are the formula [3a-1], the formula [3a-2] or the formula [3a-9].

The specific second diamine in the specific polymer (A) is preferably 50 to 95 mol% in 100 mol% of all the diamine components. More preferably, it is 60 to 95 mol%. Especially preferred is 80 to 95 mol%.

The specific second diamine may be one or two or more (preferably two or more) diamines, depending on the solubility of the specific polymer (A) in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal alignment property in the case of using the liquid crystal alignment film, More than one species may be mixed and used.

As the diamine component of the specific polymer (A) and the specific polymer (B), as long as the effect of the present invention is not impaired, other diamines (1), specific diamines (2) (Also known as other diamines) may be used.

Specific examples include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4'- -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy- 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl- 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 Aminodiphenyl ether, 4,4'-sulfonyldiamine, 3,3'-sulfonyldiamine, bis (4-aminophenyl) silane, (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'- 4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodi (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl , N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, Benzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8- Diaminonaphthalene, 1,2-bis (4-amyl Bis (4-aminophenyl) propane, 1, 3-bis (3-aminophenyl) propane, 1,4-bis Aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl- (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, , 4,4 '- [1,4-phenylenebis (methylene)] dianiline, 4,4' - [1,3-phenylenebis )]] Dianiline, 3,4 '- [1,4-phenylenebis (methylene)] dianiline, 3,4' - [ Phenylenes such as [1,4-phenylenebis (methylene)] dianiline, 3,3 '- [1,3-phenylenebis (methylene)] dianiline, Phenylene] methanone], 1,3-phenylenebis [(3-aminophenyl) methanone] (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4- Aminobenzoate), bis (4-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis Bis (4-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminophenyl) isophthalate, Aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide) N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) terephthalamide, (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'- 4-aminophenoxy) phenyl] Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (Aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'- 3-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, Propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5- Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, Bis (4-aminophenoxy) octane, 1,8-bis (4-aminophenoxy) octane, 1,9- Phenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- , 10- (3-aminophenoxy) undecane, 1,11- (4-aminophenoxy) undecane, 1,11- Dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- , 10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane, and diamines whose amino group is a secondary amino group.

The other diamine is preferably used in an amount of from 0.1 to 50 parts by weight based on the solubility of the specific polymer (A) and the specific polymer (B) in a solvent, the coating property of a liquid crystal aligning agent, the liquid crystal alignability in the case of a liquid crystal alignment film, One or more of them may be used in combination.

As the tetracarboxylic acid component for producing the specific polymer (A) and the specific polymer (B), that is, the polyimide polymer thereof, it is preferable to use tetracarboxylic acid dianhydride represented by the following formula [4] Do. At this time, not only the tetracarboxylic acid dianhydride represented by the formula [4] but also the tetracarboxylic acid derivatives thereof, such as tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid di- An ester dihalide compound can also be used (tetracarboxylic acid dianhydride represented by the formula [4] and derivatives thereof are collectively referred to as a specific tetracarboxylic acid component).

(37)

(In the formula [4], Z represents at least one structure selected from the following formulas [4a] to [4q].

(38)

[Chemical Formula 39]

In the 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. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.

Among the Z ¹ in the formula [4], the formula [4a], the formula [4c] to the formula [4g], the formula [4k] to the formula [4m] from the viewpoint of ease of synthesis or ease of polymerization reactivity in the production of the polymer, ] Or the tetracarboxylic acid dianhydride having the structure represented by the formula [4p] and tetracarboxylic acid derivatives thereof are preferable. More preferred is a structure represented by the formula [4a], the formula [4e] to the formula [4g], the formula [4l], the formula [4m] or the formula [4p]. Especially preferred are tetracarboxylic acid dianhydrides and tetracarboxylic acid derivatives thereof having a structure represented by the formula [4a], the formula [4e], the formula [4f], the formula [4l], the formula [4m] or the formula [4p] .

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

(40)

, The specific tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B) in the tetracarboxylic acid component is preferably 50 to 100 mol% in 100 mol% of all the tetracarboxylic acid components. Among them, 70 to 100 mol% is preferable. More preferred is 80 to 100 mol%.

The specific tetracarboxylic acid component is preferably selected from the group consisting of solubility of the specific polymer (A) and the specific polymer (B) in a solvent, coating property of the liquid crystal aligning agent, orientation of liquid crystal in the case of a liquid crystal alignment film, They may be used alone or in combination of two or more.

Other tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used in the polyimide polymer of the specific polymer (A) and the specific polymer (B) as long as the effect of the present invention is not impaired.

As other tetracarboxylic acid components, tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds shown below may be used .

That is, other tetracarboxylic acid components include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-biphenyltetracarboxylic acid, Bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-di Carboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) Bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) , 4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, .

The other tetracarboxylic acid component is preferably selected from the group consisting of the solubility of the specific polymer (A) and the specific polymer (B) in a solvent, the coating property of the liquid crystal aligning agent, the liquid crystal alignability in the case of a liquid crystal alignment film, They may be used alone or in combination of two or more.

&Lt; Specific polymer (A) - Production method of specific polymer (B)

In the present invention, the method for producing the specific polymer (A) and the specific polymer (B), that is, the method for producing the polyimide polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. In general, a tetracarboxylic acid dianhydride is reacted with at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid dianhydride and a derivative of the tetracarboxylic acid and a diamine component composed of one or more diamines, And a method of obtaining a polyamic acid. Specifically, there are a method of polycondensing a tetracarboxylic acid dianhydride and a primary or secondary diamine to obtain a polyamic acid, a method of dehydrating and polycondensating a tetracarboxylic acid and a primary or secondary diamine to form a polyamic acid Or a method of polycondensing a tetracarboxylic acid dihalide with a primary or secondary diamine to obtain a polyamic acid is used.

To obtain the polyamide acid alkyl ester, a method of polycondensation of a tetracarboxylic acid in which a carboxylic acid group is dialkyl esterified with a primary or secondary diamine, a method of polycondensation of a tetracarboxylic acid dihalide having a carboxylic acid group to a dialkyl ester, A method of polycondensation of a primary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the above polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent in the presence of a diamine component and a tetracarboxylic acid component. The solvent to be used at this time is not particularly limited as long as the resultant polyimide precursor dissolves. Specific examples of the solvent to be used in the reaction include, but are not limited to, the following examples.

For example, there may be mentioned N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or gamma -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-imidazolidinone. When the solvent solubility of the polyimide precursor is high, it is preferable to use methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D- D-3] can be used.

(41)

(D-1), D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² in the formula [D-2] represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms).

These solvents may be used alone or in combination. The solvent may be a solvent that does not dissolve the polyimide precursor, or may be mixed with the solvent to the extent that the resulting polyimide precursor does not precipitate. In addition, the moisture in the solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor. Therefore, it is preferable that the solvent is dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, a method in which a solution in which a diamine component is dispersed or dissolved in a solvent is stirred to add the tetracarboxylic acid component as it is or after dispersed or dissolved in a solvent, A method of adding a diamine component to a solution in which a carboxylic acid component is dispersed or dissolved in a solvent, and a method of alternately adding a diamine component and a tetracarboxylic acid component. Any of these methods may be used. When a plurality of diamine components or tetracarboxylic acid components are used in the reaction, they may be reacted in a preliminarily mixed state, or they may be reacted individually in sequence, or the low molecular weight compounds reacted individually may be mixed and reacted, . The polymerization temperature at that time may be any temperature within the range of -20 to 150 ° C, preferably -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then a solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by ring closure of the above-mentioned polyimide precursor. In this polyimide, the closed rate (also referred to as imidization rate) of the amide acid group does not necessarily have to be 100% Can be adjusted arbitrarily.

Examples of the method of imidizing the polyimide precursor include heat imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

The temperature when the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferable to carry out the removal while removing the water generated by the imidation reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine, and among them, pyridine is preferable since it has a basicity suitable for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the polyimide precursor or the polyimide is recovered from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used in the 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 charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, when the polymer precipitated and recovered is redissolved in a solvent and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more solvents selected from these solvents are used, the purification efficiency is further increased, which is preferable.

For the specific polymer (A) and the specific polymer (B), it is preferable to use a polyamide acid alkyl ester.

More specific methods for producing the polyamide acid alkyl ester of the present invention are shown in the following (1) to (3).

(1) a method of producing by the esterification reaction of polyamic acid

A polyamide acid is prepared by preparing a polyamic acid with a diamine component and a tetracarboxylic acid component and then subjecting the carboxyl group (COOH group) to a chemical reaction, that is, an esterification reaction.

Specific examples of the esterification reaction include a method in which the polyamic acid and the 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) .

As the esterifying agent, those which can be easily removed after the esterification reaction are preferable, and N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N- dimethylformamide dipropyl Acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, Triazine, 1-propyl-3-p-tolyltriazine, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4- methylmorpholinium chloride. have. The amount of the esterifying agent to be used is preferably 2 to 6 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid. Among them, 2 to 4 molar equivalents are preferred.

Examples of the solvent used in the esterification reaction include solvents used for the reaction of the diamine component and the tetracarboxylic acid component in view of the solubility of the polyamic acid in a solvent. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are preferable. These solvents may be used alone or in combination of two or more.

The concentration of the polyamic acid in the solvent in the esterification reaction is preferably 1 to 30% by mass in view of difficulty of precipitation of the polyamic acid. Among these, 5 to 20% by mass is preferable.

(2) a method of producing by the reaction of a diamine component with a tetracarboxylic acid diester dichloride

Diamine component and a tetracarboxylic acid diester dichloride.

Specifically, the reaction is carried out by reacting the diamine component and the tetracarboxylic acid diester dichloride 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 For 1 to 4 hours).

Examples of the base include pyridine, triethylamine, 4-dimethylaminopyridine and the like. Among them, pyridine is preferable for the reaction to proceed mildly. The amount of the base to be used is preferably such that it can be easily removed after the reaction, and is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride. Among them, a molar ratio of 2-fold to 3-fold is more preferable.

The solvent used in the above reaction may be a solvent used for the reaction of the diamine component and the tetracarboxylic acid component in view of the solubility of the resulting polymer, that is, the polyamide acid alkyl ester in a solvent. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are preferable. These solvents may be used alone or in combination of two or more.

The concentration of the polyamic acid alkyl ester in the solvent in the above reaction is preferably 1 to 30% by mass in view of difficulty of precipitation of the polyamic acid alkyl ester. Among these, 5 to 20% by mass is preferable. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable that the solvent used for the production of the polyamide acid alkyl ester is as dehydrated as possible. Further, it is preferable that the reaction is carried out in a nitrogen atmosphere to prevent mixing of outside air.

(3) a method in which the diamine component is reacted with a tetracarboxylic acid diester

And a polycondensation reaction of a diamine component and a tetracarboxylic acid diester.

Specifically, the polycondensation reaction is carried out by reacting the diamine component and the tetracarboxylic acid diester in the presence of a condensing agent, a base and a solvent at 0 to 150 ° C (preferably 0 to 100 ° C) for 30 minutes to 24 hours (Preferably 3 to 15 hours).

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) . The amount of the condensing agent to be used is preferably 2 to 3 times, more preferably 2 to 2.5 times, the mole of the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base to be used is preferably such that it can be easily removed after the polycondensation reaction, and is preferably 2 to 4 times, particularly preferably 2 to 3 times, the molar amount with respect to the diamine component.

The solvent used in the polycondensation reaction may be a solvent used for the reaction of the diamine component and the tetracarboxylic acid component in view of the solubility of the resulting polymer, that is, the polyamide acid alkyl ester in a solvent. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are preferable. These solvents may be used alone or in combination of two or more.

In addition, in the polycondensation reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The amount of the Lewis acid to be used is preferably from 0.1 to 10 times the molar amount of the diamine component. More preferably 2.0 to 3.0 times.

When the polyamide acid alkyl ester is recovered from the solution of the polyamide acid alkyl ester obtained by the above methods (1) to (3), the reaction solution may be put into a solvent and precipitated. Examples of the solvent used in the precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, and toluene. It is preferable that the polymer which has been put into a solvent by being introduced into a solvent is subjected to a cleaning operation plural times with the above-mentioned solvent for the purpose of removing the additives and catalysts used in the above. After filtration and recovery, it can be dried at room temperature or under reduced pressure or at normal pressure. In addition, when the polymer precipitated and recovered is redissolved in a solvent and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, a solvent in which the polymer is dissolved may be mentioned.

The polyamide acid alkyl ester of the present invention is preferably produced by the above-mentioned method (1) or (2) among the methods for producing the polyamide acid alkyl ester represented by the above (1) to (3).

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and is a coating solution for forming a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B) and a solvent.

The proportion of the specific polymer (B) in the liquid crystal aligning agent is preferably 10 to 900 parts by mass, more preferably 25 to 400 parts by mass, and particularly preferably 40 to 250 parts by mass, relative to 100 parts by mass of the specific polymer (A) And most preferably 60 to 160 parts by mass.

All the polymer components in the liquid crystal aligning agent of the present invention may be all the specific polymer (A) and specific polymer (B), or may be mixed with other polymers. Examples of other polymers include polyimide precursors and polyimides having no specific structure (1A), specific structure (1B), and specific structure (2). Further, cellulose-based polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, polysiloxanes and the like can be mentioned. At this time, the content of the other polymer is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the specific polymer (A) and the specific polymer (B).

The content of the solvent in the liquid crystal aligning agent is preferably 70 to 99.9% by mass. This content can be appropriately changed depending on the application method of the liquid crystal aligning agent and the thickness of the intended liquid crystal alignment film.

The solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) for dissolving the specific polymer (A) and the specific polymer (B). Specific examples of the good solvent are shown below, but the present invention is not limited to these examples.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, or 4-hydroxy-4-methyl-2-pentanone. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and? -Butyrolactone are preferable.

When the solubility of the specific polymer (A) and the specific polymer (B) in the solvent is high, the solvent represented by the above formulas [D-1] to [D-3] is preferable.

The amount of the both solvents in the liquid crystal aligning agent is preferably 20 to 99% by mass of the total solvent contained in the liquid crystal aligning agent. Among them, 20 to 90% by mass is preferable. More preferred is 30 to 80 mass%.

As long as the effect of the present invention is not impaired, the liquid crystal aligning agent of the present invention can be used as a solvent (also referred to as a poor solvent) for improving the film property and surface smoothness of the liquid crystal alignment film when the liquid crystal aligning agent is applied. Specific examples of the poor solvent are shown below, but the present invention is not limited to these examples.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, 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, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- (2-ethylhexyl) acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl Propylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- , Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate , Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid, 3-methoxy D-1] to [D-1] to [D-1] to [D- 1] to [D- 3], and the like.

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.

These poor solvents are preferably contained in an amount of 1 to 80 mass%, more preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass%, based on the entire solvent contained in the liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention is preferably a crosslinking compound having at least one substituent selected from the group consisting of a hydroxyl group, It is preferable to introduce a crosslinkable compound having a polymerizable unsaturated bond or a compound having a polymerizable unsaturated bond. These substituent groups and polymerizable unsaturated bonds need to have two or more in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, (Aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate di Glycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylphenyl) Bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3- ) Phenyl) -1- ( 1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol, and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4A].

(42)

Specifically, there can be mentioned the crosslinkable compounds represented by the formulas [4a] to [4k] listed in 58 to 59 of WO2011 / 132751 (published on October 27, 2011).

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].

(43)

Specifically, there can be mentioned the crosslinkable compounds represented by the formulas [5-1] to [5-42] listed on pages 76 to 82 of International Publication WO2012 / 014898 (published on Feb. 2, 2012).

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, Formaldehyde resin, succinamide-formaldehyde resin or ethylene urea-formaldehyde resin, and the like. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group, or a benzoguanamine derivative or glycoluril can be used. The melamine derivative or the benzoguanamine derivative may be present as a dimer or trimer. These groups preferably have 3 to 6 on average of methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750 in which a methoxymethyl group is substituted on average 3.7 per 1 triazine ring of a commercial product, MW- (Meth) acrylates such as methoxymethylated melamine, Cymel 235, 236, 238, 212, 253 and 254 such as Cymel 30 (manufactured by Sanwa Chemical Co.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703 and 712 Methoxymethylated butoxymethylated melamines, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, methoxymethylated ethoxymethylated benzoguanamines such as Cymel 1123, Methoxymethylated butoxymethylated benzoguanamines such as Mel 1123-10, butoxymethylated benzoguanamines such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoates such as Cymel 1125-80 Ana min can be given (or more, between the mid-Mitsui Ana Company). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluryl such as Cymel 1172, and methoxymethylolglycoluril such as Powderlink 1174, and the like.

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, 4-bis (sec-butoxymethyl) benzene, or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, International Publication No. WO2011 / 132751. (6-1) to (6-48), which are published on pages 62 to 66 of the publication (published on October 27, 2011).

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) Acryloyloxyethoxy trimethylol propane or glycerin polyglycidyl ether poly (meth) acrylate, and also crosslinking compounds having three polymerizable unsaturated groups in the molecule, such as ethylene glycol di (meth) acrylate, diethylene Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene (Meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (Meth) acrylate such as di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neopentyl glycol di (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxypropyl , 2- ( (Meth) acryloyloxyethyl phosphoric acid ester or N-methylol (meth) acrylamide, and the like.

In addition, a compound represented by the following formula [7A] may be used.

(44)

(Wherein E ₁ represents a group 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 or a phenanthrene ring) And E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

[Chemical Formula 45]

The above compound is an example of a crosslinkable compound, but is not limited thereto. The crosslinkable compound used in the liquid crystal aligning agent of the present invention may be one kind or two or more kinds.

The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Among them, 0.1 to 100 parts by mass is preferable in relation to 100 parts by mass of all the polymer components in order for the cross-linking reaction to proceed and to exhibit the intended effect. More preferably, it is 1 to 50 parts by mass.

As long as the effect of the present invention is not impaired, the liquid crystal aligning agent of the present invention can use a compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film when the liquid crystal aligning agent is applied.

Examples of the compound that improves the uniformity of the thickness of the liquid crystal alignment film and the surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EF Top EF301, EF303 and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafox F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals Inc.), FLORAD FC430 and FC431 (Available from Asahi Glass Co., Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.).

The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention is a compound which accelerates the charge transfer in the liquid crystal alignment film to promote the charge leakage of the device and is disclosed in International Patent Publication No. WO2011 / 132751 (published on October 27, 2011) , Nitrogen-containing heterocyclic amines represented by the formulas [M1] to [M156] may also be added. The amine may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine in an appropriate solvent at a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. This solvent is not particularly limited as long as it is a solvent for dissolving the above-mentioned specific polymer (A) and specific polymer (B).

The liquid crystal aligning agent of the present invention may contain, in addition to the above-described poor solvent, a compound capable of improving the uniformity of the film thickness of the poor solvent, the crosslinkable compound, the resin film or the liquid crystal alignment film, A dielectric material or a conductive material may be added for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent to a substrate, followed by drying and firing. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency. A plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to a glass substrate and a silicon nitride substrate. At this time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed from the viewpoint of simplifying the process. In a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is a substrate on only one side. In this case, a material that reflects light such as aluminum can also be used as the electrode in this case.

The method of applying the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, or inkjet printing is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal aligning agent is coated on the substrate, the liquid crystal alignment film can be formed by evaporating the solvent by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. The drying and firing steps after the application of the liquid crystal aligning agent of the present invention can be carried out at arbitrary temperature and time. Usually, there is a condition of firing at 50 to 120 ° C for 1 minute to 10 minutes and then firing at 150 to 300 ° C for 5 minutes to 120 minutes in order to sufficiently remove the contained solvent. The thickness of the liquid crystal alignment layer after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, it is preferably 5 nm to 300 nm. Among them, 10 nm to 200 nm is preferable.

Examples of the alignment treatment of the obtained liquid crystal alignment film include the rubbing treatment and the photo alignment treatment.

As a specific example of the photo-alignment treatment method, the surface of the liquid crystal alignment film is irradiated with radiation deflected in a predetermined direction, and if necessary, further subjected to heat treatment at a temperature of 150 to 250 ° C to obtain liquid crystal alignability (also referred to as liquid crystal alignability ) Is imparted to the compound. As the radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are more preferable.

In addition, in order to improve the liquid crystal alignment property, the substrate coated with the liquid crystal alignment film may be irradiated with radiation while heating at 50 to 250 ° C. The irradiation dose of the radiation is preferably 1 to 10,000 mJ / cm 2. Among them, 100 to 5,000 mJ / cm 2 is preferable. The liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a certain direction.

Further, in the above-mentioned technique, the liquid crystal alignment film irradiated with polarized radiation may be subjected to a contact treatment using water or a solvent. The solvent used in the contact treatment is not particularly limited so long as it is a solvent that dissolves decomposition products produced from the liquid crystal alignment film by irradiation of radiation. Specific examples thereof include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, Acetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate or cyclohexyl acetate. Among them, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferred in view of versatility and safety of the solvent. More preferred are water, 1-methoxy-2-propanol or ethyl lactate. These solvents may be used singly or in combination of two or more.

The contact treatment in the present invention, that is, immersing treatment or spraying treatment (also referred to as spray treatment) for treatment of water or a solvent in a liquid crystal alignment film irradiated with polarized radiation may be mentioned. The treatment time in these treatments is preferably 10 seconds to 1 hour in order to dissolve the decomposition products produced from the liquid crystal alignment film by the radiation efficiently. Among them, it is preferable to perform the immersion treatment for 1 minute to 30 minutes. The solvent at the time of the contact treatment may be room temperature or warmed, but is preferably 10 to 80 占 폚. Among them, 20 to 50 ° C is preferable. In addition, from the viewpoint of solubility of the degradation product, ultrasonic treatment or the like may be carried out if necessary.

After the contact treatment, rinsing (also called rinsing) with a low boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone or baking of the liquid crystal alignment film is preferably performed. At this time, either one of rinsing and firing may be performed, or both of them may be performed. The firing temperature is preferably 150 to 300 ° C. Among them, 180 to 250 ° C is preferable. More preferably, it is 200 to 230 ° C. The firing time is preferably 10 seconds to 30 minutes. Among them, 1 to 10 minutes is preferable.

The liquid crystal alignment film of the present invention is preferably used as a liquid crystal alignment film of a liquid crystal display element of a transverse electric field system such as an IPS system or an FFS system, and is particularly useful as a liquid crystal alignment film of a liquid crystal display element of an FFS system.

The liquid crystal display element of the present invention is obtained by preparing a substrate on which a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is formed and then manufacturing a liquid crystal cell by a known method and using the liquid crystal cell as a liquid crystal display element.

As an example of a method of manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Further, the liquid crystal display element may have an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is formed in each pixel portion constituting the image display.

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, for example, ITO electrodes and are patterned so that 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 alignment film is formed on each substrate under the above-described conditions, and the other substrate is superimposed on the other substrate such that the liquid crystal alignment film faces thereof face each other, and the periphery is sealed with a sealant. For the sealing agent, a spacer is usually mixed in order to control the substrate gap. It is also preferable that a spacer for controlling the gap between the substrates be scattered on the in-plane portion where the sealant is not formed. In the part of the sealant, an opening capable of filling the liquid crystal from the outside is formed.

Then, the liquid crystal material is injected into the spaces surrounded by the two substrates and the sealant through the openings formed in the sealant. Thereafter, this opening is sealed with an adhesive. For the injection, a vacuum injection method may be used, or a method using capillary phenomenon in the 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, the polarizing plate is installed. Specifically, a pair of polarizers is attached to a surface of the two substrates opposite to the liquid crystal layer.

As described above, by using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film capable of suppressing afterimage by alternating current drive and having both adhesiveness to the sealing agent and base substrate. Particularly, it is useful for a liquid crystal alignment film for photo-alignment treatment obtained by irradiating polarized radiation.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The abbreviations used below are as follows.

(Specific diamine (1))

1A: diamine represented by the following formula [1A]

(46)

(Specific diamine (2))

2A: diamine represented by the following formula [2A]

(47)

(Specific secondary diamine)

3A: p-phenylenediamine

3B: diamine represented by the following formula [3B]

(48)

(Other diamines)

4A: p-phenylenediamine

(49)

(Specific tetracarboxylic acid component)

C1: 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride

C2: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

C3: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride

C4: tetracarboxylic acid dialkyl ester dihalide compound represented by the following formula [C4]

(50)

(menstruum)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -butyrolactone

BCS: butyl cellosolve

PB: Propylene glycol monobutyl ether

&Quot; Measurement of molecular weight of polyimide polymer &quot;

The molecular weights of the polyimide precursor and polyimide were measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) , And measurement was carried out as follows.

Column temperature: 50 ° C

Eluent: 30 mmol / l (liter) of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid) as an additive, N, N'-dimethylformamide 10 ml / l of hydrofuran (THF)

Flow rate: 1.0 ml / min

Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000 manufactured by Polymer Laboratories).

&Quot; Measurement of imidization rate of polyimide &quot;

The imidization rate of the polyimide was measured in the following manner. (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, Product) (0.53 ml) was added, and completely dissolved by ultrasonic wave. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Denshoku KK). A proton originating from a structure which does not change before and after imidization is defined as a reference proton and the peak value of the proton is calculated by integrating the proton peak derived from the NH group of the amide acid appearing in the vicinity of 9.5 ppm to 10.0 ppm By using the following equation.

Imidization ratio (%) = (1 -? X / y) x 100

Wherein x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH group of the amide acid in the case of the polyamic acid (imidization ratio is 0%) The ratio of the number of reference protons to one proton.

&Quot; Synthesis of polyimide polymer &quot;

&Lt; Synthesis Example 1 &

3A (2.92 g, 27.0 mmol) and 1A (0.71 g, 2.99 mmol) were added to a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, NMP (81.8 g) was added, And dissolved by stirring. C1 (6.46 g, 28.8 mmol) was added while stirring the diamine solution, NMP was added so that the solid concentration became 10% by weight, and the mixture was stirred at 25 占 폚 for 4 hours to obtain a polyamic acid solution (1) . The viscosity of this polyamic acid solution at 25 캜 was 230 mPa.. The polyamic acid had a number average molecular weight (Mn) of 11,100 and a weight average molecular weight (Mw) of 30,000.

&Lt; Synthesis Example 2 &

4A (2.27 g, 21.0 mmol) and 2A (2.69 g, 9.02 mmol) were taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube and NMP (61.9 g) And dissolved by stirring. C2 (5.59 g, 28.5 mmol) was added while stirring the diamine solution, NMP was added so that the solid concentration became 12% by weight, and the mixture was stirred at 25 占 폚 for 4 hours to obtain a polyamic acid solution (2). The viscosity of this polyamic acid solution at 25 캜 was 410 mPa.. The polyamic acid had Mn of 9,000 and Mw of 20,000.

&Lt; Synthesis Example 3 &

2A (5.97 g, 20.0 mmol) was taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen-introducing tube, NMP (75.9 g) was added and dissolved with stirring while nitrogen was being supplied. C3 (5.53 g, 18.8 mmol) was added with stirring the diamine solution, NMP was added so that the solid concentration became 12% by weight, and the mixture was stirred at 25 占 폚 for 4 hours to obtain a polyamic acid solution (3). The viscosity of this polyamic acid solution at 25 캜 was 400 mPa.. The polyamic acid had an Mn of 11,500 and an Mw of 24,400.

&Lt; Synthesis Example 4 &

(1.45 g, 6.47 mmol) was added to the 500 mL four-necked flask equipped with a stirrer and nitrogen atmosphere. 3A (2.80 g, 25.9 mmol) was added thereto and NMP (111 g) and pyridine 78.1 mmol) was added and dissolved by stirring. Next, while stirring the diamine solution, C4 (9.89 g, 30.4 mmol) was added and the mixture was reacted at 15 DEG C for 15 hours. Then, acryloyl chloride (0.38 g, 4.21 mmol) was added, and the reaction was allowed to proceed at 15 占 폚 for 4 hours. The obtained polyamic acid alkyl ester solution was added to water (1230 g) with stirring. The precipitated white precipitate was collected by filtration, washed with IPA (isopropyl alcohol) (1230 g) five times and dried to obtain white Of a polyamide acid alkyl ester powder (10.2 g) was obtained. The polyamic acid alkyl ester had Mn of 20,800 and Mw of 41,000.

The obtained polyamic acid alkyl ester powder (0.80 g) was taken in a 100 ml Erlenmeyer flask, and γ-BL (7.18 g) was added and dissolved by stirring at 25 ° C for 24 hours to obtain a polyamic acid alkyl ester solution (4) .

&Lt; Synthesis Example 5 &

1A (0.47 g, 2.00 mmol) and 3B (4.40 g, 18.0 mmol) were taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, NMP (59.5 g) And dissolved by stirring. C1 (4.15 g, 18.5 mmol) was added while stirring the diamine solution, NMP was added so that the solid concentration became 10% by weight, and the mixture was stirred at 25 占 폚 for 4 hours to obtain a polyamic acid solution (5). The viscosity of this polyamic acid solution at 25 캜 was 210 mPa.. The polyamic acid had an Mn of 11,200 and an Mw of 23,400.

&Lt; Synthesis Example 6 &

NEP was added to the polyamic acid solution (5) (66.0 g) obtained by the synthetic method of Synthetic Example 5 to dilute it to 9 mass%, acetic anhydride (5.38 g) and pyridine (1.39 g) And the mixture was reacted at 60 DEG C for 3 hours. The reaction solution was poured into methanol (360 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 캜 to obtain a polyimide powder (6). The imidization ratio of the polyimide was 75%, Mn was 10,100, and Mw was 20,500.

&Lt; Synthesis Example 7 &

3A (2.16 g, 20.0 mmol) was taken in a 100 mL four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and NMP (31.6 g) was added and dissolved by stirring while nitrogen was being supplied. C1 (4.21 g, 18.8 mmol) was added while stirring the diamine solution, NMP was added so that the solid concentration became 10% by weight, and the mixture was stirred at 25 占 폚 for 4 hours to obtain a polyamic acid solution (7). The viscosity of this polyamic acid solution at 25 캜 was 250 mPa.. The polyamic acid had an Mn of 11,500 and an Mw of 24,400.

&Lt; Synthesis Example 8 &

C2 (3.92 g, 20.0 mmol) was taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, NMP (55.8 g) was added, and 4A (2.09 g, 19.3 mmol) NMP was added so that the solid concentration became 8% by weight, and the mixture was stirred at 25 캜 for 4 hours to obtain a polyamic acid solution (8). The viscosity of this polyamic acid solution at 25 캜 was 300 mPa.. The polyamic acid had an Mn of 11,000 and an Mw of 23,200.

The polyimide-based polymer is shown in Table 2.

* 1: Polyamide acid * 2: Polyamide acid alkyl ester

&Quot; Production of liquid crystal aligning agent &quot;

In the following Examples 1 to 5 and Comparative Examples 1 to 4, production examples of a liquid crystal aligning agent are described. This liquid crystal aligning agent is also used for evaluation. Liquid crystal aligning agents are shown in Tables 3 and 4.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion between a sealing agent and a base substrate &quot; were carried out using the liquid crystal aligning agent obtained in Examples and Comparative Examples.

Evaluation of afterimage by AC drive (FFS type liquid crystal cell)

After filtering the liquid crystal aligning agent obtained in Examples and Comparative Examples with a filter of 1.0 占 퐉, an ITO electrode having a film thickness of 50 nm as an electrode in the first layer and an ITO electrode in the form of an insulating film in the second layer were formed on a glass substrate A silicon nitride film having a film thickness of 500 nm was formed on a glass substrate having an FFS driving electrode having a comb-shaped ITO electrode (electrode width: 3 mu m, electrode pitch: 6 mu m, electrode height: 50 nm) , A liquid crystal aligning agent was applied by spin coating. Thereafter, the film was dried on a hot plate at 80 DEG C for 5 minutes, and then fired in a hot air circulating oven at 250 DEG C for 60 minutes to form a coating film having a film thickness of 100 nm. This coating film was irradiated with ultraviolet rays of 254 nm through a polarizing plate at 600 mJ / cm 2 to obtain a substrate on which a liquid crystal alignment film was formed. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, and the alignment treatment was carried out.

The two substrates were set as one set, a sealant was printed on the substrate, and another substrate was adhered to the liquid crystal alignment film so that the alignment direction was 0 ° as viewed from the face of the liquid crystal alignment film, and then the sealant was cured To make an empty cell. A liquid crystal MLC-2041 (manufactured by Merck Japan Co.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

Using this FFS-driven liquid crystal cell, an AC voltage of ± 10 V was applied for 120 hours at a frequency of 60 Hz under a constant temperature environment of 60 ° C. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for one day.

After leaving the liquid crystal cell, the liquid crystal cell was placed between two polarizing plates arranged so that the polarization axis thereof was orthogonal to each other. The backlight was turned on in a voltage unapplied state, and the angle of arrangement of the liquid crystal cells was adjusted so that the luminance of transmitted light was minimized. The rotation angle at which the liquid crystal cell was rotated from the angle at which the second area of the first pixel was darkest to the angle at which the first area became darkest was calculated as an angle DELTA (DEG). Similarly, in the second pixel, the second region and the first region were compared to calculate the same angle DELTA (DEG). Then, the average value of the angles DELTA (DEG) between the first pixel and the second pixel was calculated as the angle DELTA (DEG) of the liquid crystal cell.

The evaluation showed that the smaller the value of the angle DELTA (DEG) of the liquid crystal cell was, the better the afterglow characteristics by the AC drive (the values of the angle DELTA (DEG) of the liquid crystal cell are shown in Tables 5 and 6) .

Table 5 and Table 6 show the results obtained in Examples and Comparative Examples.

&Quot; Evaluation of adhesion between a sealant and a base substrate &quot;

The liquid crystal aligning agent obtained in Examples and Comparative Examples was filtered with a filter of 1.0 mu m and then applied to an ITO substrate of 30 mm x 40 mm by spin coating. Thereafter, the resultant was dried on a hot plate at 80 DEG C for 2 minutes, and then fired in a hot air circulating oven at 230 DEG C for 14 minutes to form a coating film having a film thickness of 100 nm. This coating film was irradiated with ultraviolet light of 254 nm through a polarizing plate at 500 mJ / cm 2 to obtain a substrate on which a liquid crystal alignment film was formed. Two substrates on which this liquid crystal alignment film was formed were produced.

A sealant (XN-1500T, manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of the other substrate on the other side of the substrate, and the overlapping width of the substrate was set to 1 cm. &lt; / RTI &gt; At that time, the amount of the sealant was adjusted so that the diameter of the sealant after the fusion was 3 mm. Two assembled substrates were fixed with a clip and then thermally cured at 150 DEG C for one hour to prepare a test sample substrate for evaluation.

Thereafter, this test sample substrate was fixed with a table type precision universal testing machine (AGS-X500N) (manufactured by Shimadzu Corporation), and the upper and lower ends of the substrate were fixed by pressing from the upper part of the central portion of the substrate, (N), i.e., the peeling pressure (N), was measured.

In the evaluation, the larger the value of the peeling stress (N), the better the adhesion between the sealing agent and the base substrate. (Tables 5 and 6 show values of peeling stress (N)).

Table 5 and Table 6 show the results obtained in Examples and Comparative Examples.

&Lt; Example 1 &gt;

The polyamic acid solution (1) (4.95 g) obtained by the synthetic method of Synthesis Example 1 and the polyamic acid solution (2) (2.68 g) obtained by the synthetic method of Synthesis Example 2 were taken in a 20 ml sample tube containing the stirrer , NMP (4.37 g) and BCS (3.00 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion between a sealing agent and a base substrate &quot; were carried out using the obtained liquid crystal aligning agent (1).

&Lt; Example 2 &gt;

The polyamic acid solution (1) (4.98 g) obtained by the synthetic method of Synthesis Example 1 and the polyamic acid solution (3) (2.72 g) obtained by the synthetic method of Synthesis Example 3 were taken in a 20 ml sample tube containing the stirrer , NEP (4.29 g) and BCS (3.00 g) were added and stirred for 30 minutes by a magnetic stirrer to obtain liquid crystal aligning agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion between a sealing agent and a base substrate &quot; were carried out using the obtained liquid crystal aligning agent (2).

&Lt; Example 3 &gt;

The polyamic acid solution (1) (3.50 g) obtained by the synthetic method of Synthesis Example 1 and the polyamic acid solution (2) (2.33 g) obtained by the synthetic method of Synthesis Example 2 were taken in a 50 ml sample tube containing the stirrer , NMP (12.8 g) and PB (4.66 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (3).

The resulting liquid crystal aligning agent (3) was pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉 to evaluate the ink-jet applicability. For the ink-jet applicator, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The coating was carried out on a substrate cleaned with pure water and IPA on a substrate having a coating area of 70 mm x 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 mm / sec, 60 seconds, drying was carried out on a hot plate at 70 DEG C for 5 minutes. In addition, on the substrate, the substrate under the conditions of "Evaluation of afterimage by AC drive (FFS type liquid crystal cell)" and "Evaluation of adhesion between the sealant and base substrate" was used.

The film property of the substrate on which the obtained liquid crystal alignment film was formed was confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence of pinholes. As a result, no pinhole was seen on the coating film, and a liquid crystal alignment film excellent in coating film property was obtained.

Evaluation was carried out using the substrate on which the obtained liquid crystal alignment film was formed under the conditions of "Evaluation of afterimage by AC drive (FFS type liquid crystal cell)" and "Evaluation of adhesion between the sealant and base substrate" did.

<Example 4>

The polyamide acid alkyl ester solution (4) (3.75 g) obtained by the synthetic method of Synthesis Example 4 and the polyamic acid solution (2) (2.50 g) obtained by the synthetic method of Synthesis Example 2 were added to a 20 ml sample tube containing the stirrer, , NMP (2.72 g), γ-BL (0.87 g) and BCS (2.46 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion between a sealing agent and a base substrate &quot; were carried out using the obtained liquid crystal aligning agent (4).

&Lt; Example 5 &gt;

NMP (2.12 g) and NEP (4.60 g) were added to the polyimide powder (6) (0.38 g) obtained by the synthetic method of Synthesis Example 6, and the mixture was stirred at 70 캜 for 24 hours Lt; / RTI &gt; To this solution, the polyamic acid solution (3) (2.10 g) and BCS (2.30 g) obtained by the synthetic method of Synthesis Example 3 were added and stirred at 40 占 폚 for 4 hours to obtain liquid crystal aligning agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion between a sealing agent and a base substrate &quot; were carried out using the liquid crystal aligning agent 5 thus obtained.

&Lt; Comparative Example 1 &

NMP (3.74 g) and BCS (3.00 g) were taken in a 20 ml sample tube equipped with a stirrer, and the polyamic acid solution (1) (8.26 g) obtained by the synthetic method of Synthesis Example 1 was added thereto. Followed by stirring for 30 minutes to obtain liquid crystal aligning agent (6). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion between a sealing agent and a base substrate &quot; were carried out using the liquid crystal aligning agent 6 thus obtained.

&Lt; Comparative Example 2 &

NMP (3.75 g) and BCS (3.00 g) were taken in a 20 ml sample tube containing the stirrer and the polyamic acid solution (2) (8.26 g) obtained by the synthetic method of Synthesis Example 2 was added thereto. Followed by stirring for 30 minutes to obtain liquid crystal aligning agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion between a sealing agent and a base substrate &quot; were carried out using the obtained liquid crystal aligning agent 7.

&Lt; Comparative Example 3 &

The polyamic acid solution (2) (2.66 g) obtained by the synthetic method of Synthesis Example 2 and the polyamic acid solution (7) (4.97 g) obtained by the synthetic method of Synthesis Example 7 were taken in a 20 ml sample tube containing the stirrer , NMP (4.36 g) and BCS (3.00 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC drive (FFS type liquid crystal cell) &quot; and &quot; evaluation of adhesion between a sealant and a base substrate &quot; were carried out using the obtained liquid crystal aligning agent (8).

&Lt; Comparative Example 4 &

The polyamic acid solution (1) (4.97 g) obtained by the synthetic method of Synthesis Example 1 and the polyamic acid solution (5) (2.66 g) obtained by the synthetic method of Synthesis Example 5 were taken in a 20 ml sample tube containing the stirrer , NMP (4.36 g) and BCS (3.00 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of afterimage by AC driving (liquid crystal cell of FFS system) &quot; and &quot; evaluation of adhesion with a sealing agent and a base substrate &quot; were carried out by using the obtained liquid crystal aligning agent 9.

* 1: represents the ratio (parts by mass) of the specific polymer (A) to 100 parts by mass of the whole polymer.

* 2: The ratio (parts by mass) of the specific polymer (B) to 100 parts by mass of the total polymer.

* 3: represents the ratio (parts by mass) of other polymer to 100 parts by mass of the total polymer.

* 4: represents the ratio (parts by mass) of each solvent to 100 parts by mass of the total solvent.

* 5: Represents the proportion of the whole polymer in the liquid crystal aligning agent.

The meanings of * 1 to * 5 are the same as those in Table 3.

As can be seen from the above results, the liquid crystal aligning agent of the Examples had an excellent afterimage characteristic by alternating current drive as compared with the liquid crystal aligning agent of the comparative example, and also had a high adhesion with the sealing agent and the base substrate .

Specifically, it is a comparison between Example 1 and Comparative Example 1 or Comparative Example 2. Comparative Example 1 using only the specific polymer (A) had a poor adhesion to the sealing agent and the base substrate, as compared with the corresponding examples. In Comparative Example 2 using only the specific polymer (B), the after-image characteristic due to the AC driving was bad. On the other hand, in Example 1, both of these characteristics were excellent.

It is also a comparison between Example 1 and Comparative Example 3 or Comparative Example 4. Comparative Example 3 using a polymer containing no specific diamine (1) had bad afterglow characteristics due to AC driving as compared with the corresponding examples. In Comparative Example 4 using a polymer containing no specific diamine (1), adhesion between the sealing agent and the base substrate was poor.

Industrial availability

The liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is excellent in reliability and is preferably used for a liquid crystal television of a high precision on a large screen, a car navigation system of a small or medium size or a smart phone.

The entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2013-219841 filed on October 23, 2013 are incorporated herein by reference and are hereby incorporated by reference.

Claims (24)

A liquid crystal aligning agent containing the following components (A) and (B).
(A): a polyimide precursor having at least one structure selected from the group consisting of the following formulas [1A] and [1B], and a polyimide imidized with the polyimide precursor At least one kind of polymer.
Component (B): at least one polymer selected from the group consisting of a polyimide precursor having the structure of the following formula [2] and a polyimide in which the polyimide precursor is imidized.
[Chemical Formula 1]

(In the formulas [1A] and [1B], X ^A and X ^C each independently represent a protecting group substituted by a hydrogen atom by heat X ^B represents a single bond or an organic group having 1 to 40 carbon atoms, And the atom to which the ester group (-COO- group) is bonded is a carbon atom.
(2)

Y ¹ and Y ⁷ each independently represent 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-, provided that each of R ¹ , R ² and R ³ independently represents a hydrogen atom or a carbon number Y ² and Y ⁶ represent an alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Y ⁴ represents oxygen Atom or sulfur atom). The method according to claim 1,
Wherein at least one structure selected from the group consisting of the formulas [1A] and [1B] is a structure represented by the following formula [1a], formula [1b] or formula [1c].
(3)

(In the formula [1a], X ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^b represents a protecting group substituted by a hydrogen atom by heat, and m represents an integer of 1 or 2. However, ] Is ^a hydrogen atom of X ^a when m is 2. In the formula [1b], X ^c represents a protecting group substituted with a hydrogen atom by a heat. In the formula [1c], X ^d represents a single bond or a C 1-20 X ^e is a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ^f is a protecting group substituted by a hydrogen atom by heat, and n is an integer of 1 to 4). 3. The method of claim 2,
The component (A) is obtained by polycondensing a diamine component and a tetracarboxylic acid component containing a diamine having at least one structure selected from the structures represented by the above formulas [1a], [1b] and [1c] Wherein the liquid crystal aligning agent is at least one polymer selected from the polyimide precursor obtained and the polyimide obtained by imidizing the polyimide precursor. The method of claim 3,
Wherein the diamine is a diamine represented by the following formula [1-1].
[Chemical Formula 4]

(In the formula [1-1], X ^D represents an organic group having 5 to 50 carbon atoms and at least one structure selected from the group consisting of the formulas [1a], [1b] and [1c] ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 5. The method of claim 4,
Wherein the diamine is at least one diamine selected from the group consisting of the following formulas [1a-1] to [1c-1].
[Chemical Formula 5]

X ¹ represents 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-, provided that R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, represents. X ² represents a single bond, an alkylene group of carbon number 1 ~ 10, X ^a represents an organic group of a hydrogen atom or a carbon number 1 ~ 20, X ^b represents a protecting group which is substituted with hydrogen atoms by the heat. m is 1 or P represents an integer of 1 to 4, and q represents an integer of 1 to 4, provided that when m is 2, X represents ^a hydrogen atom.
In formula [1b-1], X ³ and X ⁷ each independently represent 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-. 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 of 1 to 10 carbon atoms, X ⁵ represents a single bond or an alkylene group of 1 to 10 carbon atoms, X ^c represents a protecting group substituted by a hydrogen atom And r represents an integer of 1 to 4.
In formula [1c-1], X ⁸ represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ ) -, -CON (R ² ) -, -N (R ³ ) , -CH ₂ O-, -COO-, and OCO-. 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, an alkylene group of carbon number 1 ~ 10, X ^d represents an organic group of a single bond or a carbon number of 1 ~ 20, X ^e represents an organic group of a hydrogen atom or a carbon number 1 ~ 20, X ^f is a column, N is an integer of 1 to 4, s is an integer of 1 to 4, t is an integer of 1 to 4, and the formula [1a-1] to the formula [1c- 1], A ¹ to A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 6. The method of claim 5,
Wherein the diamine is at least one diamine selected from the group consisting of the following formulas [1d-1] to [1d-5].
[Chemical Formula 6]

(In formulas (1d-1) to (1d-5), R ¹ to R ⁷ each independently represent at least one member selected from the group consisting of the following formulas [a- 1] to [ A ¹ to A ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In formulas (1d-1) to (1d-5), A ¹ to A ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
(7)

(In the formula [a-2], R ¹ represents an alkylene group having 1 to 5 carbon atoms). 7. The method according to any one of claims 1 to 6,
Wherein the polymer of the component (B) is a polyimide precursor obtained by polycondensation of a diamine component containing a diamine having the structure of the formula [2] and a tetracarboxylic acid component, and a polyimide precursor obtained by imidizing the polyimide precursor Wherein the liquid crystal aligning agent is at least one kind of polymer selected from the group consisting of 8. The method of claim 7,
Wherein the diamine is a diamine represented by the following formula [2-1].
[Chemical Formula 8]

(In the formula [2-1], Y ^A represents an organic group having 10 to 50 carbon atoms having the structure represented by the above formula [2], A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms . 9. The method of claim 8,
Wherein the diamine is a diamine represented by the following formula [2a].
[Chemical Formula 9]

(Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ ) -, -CON (R ² ) -, -N (R ³ ) , -CH ₂ O-, -COO- and OCO-, provided that R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Y ⁴ represents an oxygen atom or a sulfur atom, And A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 10. The method of claim 9,
Wherein the diamine is at least one diamine selected from the group consisting of the following formulas [2a-1] to [2a-3].
[Chemical formula 10]

(In formulas (2a-1) to (2a-3), A ¹ to A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). 11. The method according to any one of claims 1 to 10,
Wherein the polymer of component (A) is a polyimide precursor obtained by polycondensation of a diamine component containing a diamine represented by the following formula [3-1] and a tetracarboxylic acid component, and a polyimide precursor obtained by imidizing the polyimide precursor Wherein the liquid crystal aligning agent is at least one kind of polymer selected.
(11)

(In the formula [3-1], X ^E represents at least one structure selected from the group consisting of the following formulas [3a-1] to [3a-9], and A ¹ and A ² each independently And represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
[Chemical Formula 12]

(In the formula [3a-9], n represents an integer of 1 to 5). 12. The method according to any one of claims 3 to 11,
Wherein the tetracarboxylic acid component is a tetracarboxylic acid compound represented by the following formula [4].
[Chemical Formula 13]

(Z represents at least one structure selected from the group consisting of the following formulas [4a] to [4q]).
[Chemical Formula 14]

[Chemical Formula 15]

Z ¹ and 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], each of Z ⁵ and Z ⁶ independently represents , A hydrogen atom or a methyl group. 13. The method of claim 12,
Wherein the tetracarboxylic acid component is selected from the group consisting of the formula [4a], the formula [4e] to the formula [4g], the formula [4l], the formula [4m] or the formula [4p] Wherein the liquid crystal aligning agent is a tetracarboxylic acid compound. 14. The method according to any one of claims 5 to 13,
The diamine represented by the formula [1a-1], the formula [1b-1] and the formula [1c-1] in the polymer of the component (A) is preferably 5 to 30 mol% Liquid crystal aligning agent. 15. The method according to any one of claims 9 to 14,
In the polymer of the component (B), the diamine represented by the formula (2a) is 20 to 100 mol% in 100 mol% of the total diamine component. 16. The method according to any one of claims 1 to 15,
Wherein the polymer of the component (B) is contained in an amount of 40 to 250 parts by mass based on 100 parts by mass of the component (A). 17. The method according to any one of claims 1 to 16,
Wherein at least one of the polymer (A) and the polymer (B) is a polyamide acid alkyl ester. 18. The method according to any one of claims 1 to 17,
A liquid crystal aligning agent containing at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and? -Butyrolactone. 18. The method according to any one of claims 1 to 17,
At least one member 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. 20. The method according to any one of claims 1 to 19,
A crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, and a crosslinkable compound having a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group, and a crosslinkable compound having a polymerizable unsaturated bond Wherein the liquid crystal aligning agent is a liquid crystal aligning agent. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 20. A liquid crystal alignment film obtained by the ink jet method using the liquid crystal aligning agent according to any one of claims 1 to 20. 22. A liquid crystal alignment film obtained by irradiating polarized radiation onto the liquid crystal alignment film according to claim 21 or 22. A liquid crystal display element having the liquid crystal alignment film according to any one of claims 21 to 23.

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