WO2008013285A1

WO2008013285A1 - Liquid crystal aligning agent and liquid crystal displays made by using the same

Info

Publication number: WO2008013285A1
Application number: PCT/JP2007/064814
Authority: WO
Inventors: Kohei Goto; Noritoshi Miki; Kazuyoshi Hosaka
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-07-28
Filing date: 2007-07-27
Publication date: 2008-01-31
Also published as: CN101495915B; JP5003682B2; KR20090052317A; TW200831611A; TWI437045B; JPWO2008013285A1; CN101495915A; KR101426102B1

Abstract

The invention provides a liquid crystal alignment layer which has a high voltage holding ratio and permits speedy relaxation of a residual charge accumulated by the application of DC voltage even after long-time exposure to high temperature. A liquid crystal aligning agent containing the following components (A) and (B): (A) a polymer which is obtained by subjecting a polyamic acid composed of repeating units represented by the structural formula [1] to imidation and which contains 0.1 to 3 carboxyl groups per repeating unit on the average: [1] (wherein R1 is a tetravalent organic group; R2 is a divalent organic group; and n is a positive integer) and (B) an amine compound having one primary amino group and a nitrogenous aromatic heterocycle in the molecule in which the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Description

Specification

Liquid crystal alignment treatment agent and liquid crystal display element using the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.

Background art

[0002] Currently, as a liquid crystal alignment film of a liquid crystal display element, a liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution is applied to a glass substrate or the like. A so-called polyimide-based liquid crystal alignment film that has been fired and baked is mainly used.

[0003] The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, as liquid crystal display elements are becoming more precise, the liquid crystal alignment film used in the liquid crystal alignment film has a high voltage holding ratio due to demands for suppressing the decrease in contrast and reducing the afterimage phenomenon. The characteristics that the residual charge when applying a DC voltage is small and / or the residual charge accumulated by the DC voltage is relaxed are becoming increasingly important.

[0004] In a polyimide-based liquid crystal alignment film, the time until the afterimage generated by the direct current voltage disappears is short, and it includes a tertiary amine having a specific structure in addition to polyamic acid and imide group-containing polyamic acid. Those using a liquid crystal aligning agent (for example, see Patent Document 1) and those using a liquid crystal aligning agent containing a soluble polyimide using a specific diamine having a pyridine skeleton or the like as a raw material (for example, see Patent Document 2) It has been known. In addition to a polyamic acid and its imidized polymer, it contains one carboxylic acid group in the molecule, assuming that the voltage retention rate is high and the time until the afterimage generated by the DC voltage disappears is short. Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (For example, see Patent Document 3) is known!

[0005] However, in recent years, large-screen, high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements for such applications mainly display characters and still images up to that point. Compared to display applications, demands for afterimages are becoming stricter, and characteristics that can withstand long-term use in harsh usage environments are required. Therefore, the liquid crystal alignment film used there is required to be more reliable than before, and the electrical characteristics of the liquid crystal alignment film are not only good in initial characteristics, but also, for example, at high temperatures. It is required to maintain good characteristics even after long-term exposure.

Patent Document 1: Japanese Patent Application Laid-Open No. 9 316200

Patent Document 2: JP-A-10-104633

Patent Document 3: JP-A-8-76128

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention has been made in view of the above circumstances. That is, the problem to be solved by the present invention is to obtain a liquid crystal alignment film that has a high voltage holding ratio and has a fast relaxation of residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. It is in providing the liquid-crystal aligning agent which can be performed. It is another object of the present invention to provide a highly reliable liquid crystal display device that can withstand long-term use in harsh usage environments.

Means for solving the problem

[0008] As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a liquid crystal alignment treatment agent containing a specific polyimide and a specific amine compound, more specifically, a specific polyimide and The present inventors have found that the above problems can be solved by using a liquid crystal aligning agent obtained by mixing a specific amine compound in an organic solvent, and have completed the present invention. That is, the present invention has the following characteristics.

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

Component (A): a polyimide having a carboxyl group in the molecule.

Component (B): has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Amine compound.

(2) The component (A) is a polymer obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the following formula [1], and the amount of carboxyl groups in the polymer is Combined repetition The liquid crystal aligning agent according to the above (1), wherein the average value with respect to the repeating unit is 0.3.

[Chemical 1]

(Wherein R is a tetravalent organic group, R is a divalent organic group, and n represents a positive integer)

1 2

(3) From the structural formula in which the component (A) is a structural unit of the repeating unit represented by the above formula [1], a part or all of the repeating unit has a unit represented by the following formula [2] The polyamic acid is imidized, and the amount of carboxyl groups of the polymer is 0.;! To 3 in average value with respect to the repeating unit of the polymer. Liquid crystal alignment treatment agent.

[Chemical 2]

[2]

(In the formula, R is a tetravalent organic group, R is a divalent organic group, and at least R or R is

3 4 3 4

Has a carboxyl group)

(4) The liquid crystal aligning agent according to any one of the above (1) to (3), wherein the component (B) is an amine compound represented by the following formula [3].

[Chemical 3]

(Wherein X is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X is a nitrogen-containing aromatic heterocyclic ring)

2 (5) The liquid crystal aligning agent according to any one of the above (1) to (4), wherein the component (B) is an amine compound represented by the following formula [4].

[0012] [Chemical 4]

(In the formula, X is an aliphatic hydrocarbon group having 10 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group;

Three

Yes, X is a single bond, 〇, —NH—, —S—, —SO or divalent having 1 to 19 carbon atoms

4 2

Is an organic group. The total number of carbon atoms in X and X is 1-20. X is replacement

With 3 4 5 groups! /, May! /, Nitrogen-containing aromatic heterocycles)

(6) The component (B) is a group represented by the following formulas [4], X, X, and X force:

3 4 5

The liquid crystal alignment treatment agent according to the above (5), which is an amine compound comprising a combination selected from rings.

[0013] However, X is a straight chain or branched alkyl group having carbon number;! -10, carbon number;

Three

Alkyl group, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, Cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, A group consisting of a calebornene ring and an adamantane ring;

X force, single bond, O, 1 NH, 1 S, 1 SO—, carbon number;! ~ 19 hydrocarbon group

4 2

,-CO-0-.101 C001, 1 C001 NH, 1 NH— C001, 1 C001, 1 CF —

2

,-C (CF) One, one CH (〇H) —,-C (CH) One,-Si (CH) One, ten thousand Si (CH)

3 2 3 2 3 2 3

―, 1 Si (CH) ○ 1, ○ 1 Si (CH) — ○ 1, cyclopropane ring, cyclobutane

2 3 2 3 2

Ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane Ring, cycloheptadecane ring, cyclotadecane ring, cyclononadecane ring, cycloicosane ring, tricycloe Icosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, calebornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, funoleic len ring, anthracene ring, Phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridin ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, force rubazole ring, purine ring, thiadiazole ring, pyridazine ring, Triazine ring, Virazolidine ring, Triazole ring, Pyrazine ring, Benzimidazole ring, Benzimidazole ring, Tinoline ring, Phenanthroline ring, Indole ring, Quinoxaline ring, Benzothiazole ring, Phenothiazine ring, Oxadia Lumpur ring, is Atarijin ring, Okisazoru ring, piperidines Rajin ring, piperidine ring, Jiokisa down ring, and consists of one or more combinations selected from the group consisting of Morufuorin ring group;

X 1S pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring

Five

, Pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, force rubazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole Ring, tinolin ring, phenantorin ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, atalidine ring, and any of these, and having a substituent! /, It's one type selected from the group consisting of groups!

(7) The above-mentioned (1) to (6) containing (B) component at a ratio of 0 · 0;! To 2 mol times the amount of 1 mol of the carboxyl group contained in the polyimide of component (A). ) The liquid crystal alignment treatment agent according to any one of

(8) Any of the above (1) to (7) obtained by mixing the polyimide of component (A) and the amine compound of component (B) with heating in an organic solvent or heating after mixing. A liquid crystal alignment treatment agent according to claim 1.

(9) A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of (1) to (8).

(10) A liquid crystal display device having the liquid crystal alignment film according to (9).

The invention's effect

The liquid crystal aligning agent of the present invention can be obtained by a relatively simple method. In addition, the present invention This liquid crystal alignment treatment agent can provide a liquid crystal alignment film that has a high voltage holding ratio and has a fast relaxation of residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

FIG. 1 is a graph showing a change in potential when a relaxation evaluation of residual charge is performed in Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The liquid crystal aligning agent of the present invention comprises (A) component, a polyimide having a carboxyl group in the molecule (hereinafter also referred to as a specific polyimide), and (B) component, in the molecule. An amino group (one NH) and a nitrogen-containing aromatic heterocycle, and the amino group is aliphatic

2

A liquid crystal aligning agent containing a amine compound (hereinafter sometimes referred to as a specific amine compound) bonded to a hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Specifically, it is a liquid crystal aligning agent obtained by mixing a specific polyimide as the component (A) and a specific amine compound as the component (B) in an organic solvent.

In the present specification, the amino group (one NH 3) is synonymous with the primary amino group, and the following 1

2

Also called a grade amino group.

In the liquid crystal aligning agent of the present invention, the primary amino group in the specific amine compound has the ability to form a salt with the carboxyl group in the specific polyimide, and the carboxyl group or carboxy ester group in the specific polyimide. It is considered that a bonding reaction accompanied by ring opening of an imide group is carried out with respect to an amide bond with elimination of water or alcohol and an imide group in a specific polyimide. Furthermore, it is considered that the primary amino group that forms a salt with the carboxyl group in the specific polyimide forms an amide bond by elimination of water by the baking step in producing the liquid crystal alignment film. As a result, the liquid crystal aligning agent of the present invention is efficiently combined with the specific amine compound and the specific polyimide in the liquid crystal alignment film obtained from the simple alignment means of mixing in an organic solvent. I think.

On the other hand, the nitrogen-containing aromatic heterocycle in the specific amine compound has an electron due to its conjugated structure. Since it functions as a hopping site, the movement of charges in the liquid crystal alignment film is promoted. In addition, when a liquid crystal alignment film is formed, the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the specific polyimide are linked by salt formation, hydrogen bonding,! /, And electrostatic interaction. A charge transfer occurs between the carboxyl group in the cage and the nitrogen-containing aromatic heterocycle in the specific amine compound. Furthermore, since the specific amine compound is chemically bonded to the specific polyimide, the charge transferred to the nitrogen-containing aromatic heterocyclic moiety can efficiently move within and between the polyimide molecules.

[0019] As described above, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is able to accelerate the relaxation of the residual charges accumulated by the DC voltage, and after being exposed to a high temperature for a long time. Also maintain this property.

[0020] <(A) component / specific polyimide>

In the present invention, the specific polyimide as the component (A) is not particularly limited as long as it is a polyimide having a carboxyl group in the molecule. Such a polyimide is composed of a structural unit of a repeating unit represented by the following formula [1] because it can be obtained relatively easily by using tetraforce rubonic acid dianhydride and diamine as raw materials. A polymer obtained by imidizing polyamic acid is preferred.

[0021] [Chemical 5]

1 2

In the formula [1], R and R are different even if they are one kind each.

1 2

A combination of a plurality of different types having R and R as repeating units may be used.

1 2

The specific polyimide can be obtained by limiting the imidation ratio when imidizing the polyamic acid to usually less than 100%.

The specific polyimide has a repeating unit in the structural formula of the repeating unit represented by the formula [1]. It can also be obtained by imidizing a polyamic acid containing a structural unit represented by the following formula [2].

[0023] [Chemical 6]

(Wherein R is a tetravalent organic group, R is a divalent organic group, and R or at least one of R

3 4 3 4

Has a carboxyl group)

In that case, the imidization rate may be 100%.

[0024] The imidization ratio of the specific polyimide is preferably 20% or more for the reason that a high voltage holding ratio can be obtained. S is preferably 40% or more.

The amount of the carboxyl group in the specific polyimide (average value with respect to the repeating unit of the structural formula as polyimide) is 0 as the average value with respect to the repeating unit of the structural formula as polyimide because the effect of the present invention can be obtained efficiently. ! ~ 3 is more preferable, 0.3 to 2.0 is more preferable, and 0.5 to 1.8 is particularly preferable. The repeating unit at this time is a combination of units containing a non-imidized amic acid group. For example, in the case of a polyimide obtained by imidizing a polyamic acid composed of a repeating unit represented by the formula [1], a combination of the structures of the following formulas [5a] to [5d] when the imidization rate is less than 100%. The force that can be considered to be composed of the above The repeating unit for calculating the amount of carboxynole group includes all of the formulas [5a] to [5d].

[0025] [Chemical 7]

[5c] [5d] In the present invention, the amount of the carboxyl group in the specific polyimide (also referred to as the average value of the carboxyl group) is obtained as the sum of P in (i) below and Q in (ii) below. .

(i) Average value of carboxyl group derived from non-imidized amic acid with respect to repeating unit of structural formula as polyimide: P

(ii) Repeating the structural formula as a polyimide of the carboxyl group contained in R and R in the formula [2]

3 4

Average value for repeat unit: Q.

[0026] P in the above (i) can be calculated from the following (formula 1) using the imidization ratio (z). The imidization rate (z) can be obtained from, for example, measurement of imidization rate described later.

P = 2 X (1 -z / lOO) (Formula 1) On the other hand, Q in the above (ii) is a polyimide of the carboxyl group contained in R of the formula [2].

Three

Average values for all repeating units of the structural formulas: Q and the carboxyl group contained in R

14

Average value for repeating unit of structural formula as polyimide: It is obtained by summing with Q.

2

[0027] Each of the above R and R is a part or all of the raw material used to obtain the specific polyimide.

3 4

These are tetracarboxylic dianhydride residue (R) and diamine residue (R).

3 4

Therefore, the above Q is tetracarboxylic dianhydride used to obtain specific polyimide Is calculated from the following formula (3) using the molar fraction of the tetracarboxylic dianhydride represented by the following formula [VI] in the total molar amount.

[0028] [Chemical 8]

Q = β XW / W (Formula 3) where 13 represents the number of carboxyl groups contained in R, and W represents the tet of formula (VI).

1 3 1

Is the molar amount of lacarboxylic dianhydride, W is the total mole of tetracarboxylic dianhydride

2

Represents an amount.

[0029] The above Q is the total molar amount of diamine used for obtaining the specific polyimide.

2

It is calculated from the following formula (4) using the mole fraction of diamine represented by the following formula [V2].

[0030] [Chemical 9]

H ₂ N— R ₄ — NH ₂ [V2]

Q = β XW / W (Equation 4)

2 2 3 4 where 13 represents the number of carboxyl groups contained in R, and W is represented by the formula [V2].

2 4 3

Is the molar amount of diamine, and W represents the total molar amount of diamine.

Four

[0031] The amount of the carboxyl group can be obtained by the following (formula 5). Amount of carboxyl group in specific imide

= P + Q + Q = 2 X (l-z / 100) + / 3 XW / W + β XW / W (Formula 5) In the present invention, the amount of the carboxyl group in the specific polyimide is adjusted by (1) means for adjusting by controlling the imidization rate, (2) R in the formula [2] or the carboxyl group contained in R

3 4

Any of the number and means for adjusting by the ratio of the formula [2] in the structural formula of the repeating unit represented by the formula [1] may be used. In addition, (1) and (2) can be used in combination.

[0032] From the viewpoint of the degree of freedom of selection of R and R in the formula [1], the means (1) is preferable.

1 2

From the viewpoint of the degree of freedom in selecting the imidization ratio of the specific polyimide, the means (2) is preferable. In addition, when the specific amine compound is eliminated or the polyimide chain is cleaved due to the imidization reaction in the baking step when the liquid crystal alignment film is produced, there is little possibility of! From the viewpoint of (2), the means (2) is preferable.

[0033] When adjusting the amount of the carboxyl group in the specific polyimide by the means (1), R and R in the formula [1] are not particularly limited. R and R are in the formula [1]

1 2 1 2

Even if there is only one type each, they have different R and R structures,

1 2

A combination of a plurality of different types of positions may be used.

Specific examples of R in formula [1] are as follows.

[0034] [Chemical 10]

[ΐΐ¾] [9εοο]

l8 90 / L00ZdT / 13d S8 difficult 00Z OAV

Of these, A-6, A-16, A-18 to A-22, A-25, A-37, A-38, and A46 are soluble in organic solvents even if they have a high imidization ratio. It is preferable because of its high properties.

[0036] Further, a force of 10 mol% or more of R A- ;! to A-25 and A-46 having an alicyclic structure or an aliphatic structure is preferable because the voltage holding ratio is improved. In particular, it is preferable to use R in combination of two types selected from A-1, A-16, and A-19 because a liquid crystal alignment film can be obtained in which charge relaxation is faster.

Specific examples of R in formula [1] are as follows.

2

[0037] [Chemical 12]

l8 90 / L00ZdT / 13d S8 difficult OOZ OAV

[ετ¾] [8εοο] l8 90 / L00ZdT / 13d 91- S8 Difficulty 00Z OAV

15]

[0041] [Chemical 16]

[0042] [Chemical 17]

(In B-112 and B-113, Q represents one of COO—, one OCO—, one CONH—, one NH CO—, —CH—O—, —CO—, —NH—)

2

Among these, when part or all of R is B-80 to B-101, etc., the liquid crystal

2

The retilt angle can be increased. When aligning the liquid crystal vertically, R is preferably 5

2

~; 100 Monore ^_0/0, more preferably ί or 10-80 Monore ^_0/0 B- 80 to: B- 101 Structure ί rubbing Bayoi such.

When the amount of the carboxyl group in the specific polyimide is adjusted by the means of (2) above, the structure is not particularly limited as long as R or R has a carboxyl group!ヽ

3 4

. The number of carboxyl groups is 0 to 2 for R and R (however, R or R Either one has at least one carboxyl group).

[0044] From the viewpoint of easy synthesis of polyimide and availability of raw materials, a carboxyl group is added to R.

Four

It is preferable to have it. As R having a carboxyl group, B-102 to B-113 are

Four

Can be mentioned. At that time, even if there is only one type of R having a carboxyl group,

Four

You may use it. In addition, when R has a carboxyl group, the structure of R is particularly

4 3

Without being limited thereto, specific examples include A— ;! to A-46.

[0045] <Method for producing specific polyimide>

The method for producing the specific polyimide as the component (A) used in the present invention is not particularly limited! /, But in general, a tetracarboxylic acid component composed of one or more selected from tetracarboxylic acids and derivatives thereof And a diamine component composed of one or more diamine compounds to obtain a polyamic acid having a structural formula of a repeating unit represented by the formula [1], and imidating the polyamic acid to obtain a polyimide and Is used.

In that case, the polyamic acid obtained is controlled by the force S to make a homopolymer or copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component as raw materials.

The term “tetracarboxylic acid” and its derivatives as used herein refers to tetracarboxylic acid, tetra force sulfonic acid dihalide, and tetracarboxylic dianhydride. Of these, tetracarboxylic dianhydride is preferred because of its high reactivity with diamine compounds! /.

[0046] Specific examples of the method for producing the specific polyimide are shown below.

For example, a tetracarboxylic acid component containing at least one selected from tetracarboxylic dianhydrides represented by the formula [6] and a diamine component containing at least one selected from diamines represented by the formula [7] Can be subjected to a polycondensation reaction in an organic solvent such as N-methylpyrrolidone, N, N, -dimethylacetamide, N, N'-dimethylformamide, or γ_butyllatataton to obtain a polyamic acid.

[0047] [Chemical 18]

Note that the formula [6] has the same meaning as the definition in the formula [1], and specific examples of 1 ^ are as described in A— ;! to A-46 described in detail above. .

[Chemical 19]

H ₂ N—R ₂ —NH ₂ [7] In the formula [7], R has the same meaning as defined in the formula [1], and specific examples of R are as follows:

twenty two

It is as described in B- ;! to B-113 detailed above.

[0049] In this case, the reaction temperature is a force capable of selecting any temperature from 20 ° C to 150 ° C, preferably in the range of 5 ° C to 100 ° C.

The ratio between the total number of moles of the compound constituting the tetracarboxylic acid component and the total number of moles of the diamine compound constituting the diamine component is from 0.8 to 1.2; The closer this molar ratio is to 1.0, the greater the degree of polymerization of the polymer produced.

In order to obtain a polyamic acid having a unit represented by the formula [2] in part or all of the repeating unit in the structural formula of the repeating unit represented by the formula [1], a carboxyl group is added to R. Tetracarboxylic dianhydride and / or diamond having a carboxyl group at R

2

Can be used.

As a method for imidizing polyamic acid, thermal imidization by heating, catalytic imidization using a catalyst is generally used, and catalyst imidation in which an imidization reaction proceeds at a relatively low temperature is obtained. It is preferable that the molecular weight does not decrease.

[0050] Catalytic imidation can be carried out by stirring the polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is 120 to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but it is too high And the molecular weight of polyimide may decrease. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times that of the amic acid group, and the amount of the acid anhydride is !! to 50 mol times, preferably 3 to 30 mole times. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it is difficult to completely remove the reaction after the reaction is completed. Examples of the basic catalyst used at this time include pyridine, triethylamine, trimethylamine, triptynoleamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The organic solvent is not limited as long as it can dissolve polyamic acid. Specific examples thereof include N, N'-dimethylformamide, N, N, monodimethylacetamide, N-methyl 2-pyrrolidone, N-methylcaprolatatam, dimethyl sulfoxide, tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide, γ-petit-mouth ratatone, etc. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0051] The produced polyimide can be obtained by charging the reaction solution into a poor solvent and collecting the produced precipitate. In this case, the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polyimide deposited in a poor solvent and filtered can be powdered by filtering at normal temperature or reduced pressure at room temperature or by heating. The polyimide powder can also be purified by repeating the steps of dissolving the polyimide powder in an organic solvent and reprecipitating 2 to 10 times. It is preferable to carry out this purification process when impurities cannot be removed by a single precipitation recovery operation!

Yes

The molecular weight of the specific polyimide used in the present invention is not particularly limited! /, But is easy to handle! /, And the weight average molecular weight is 2,000 to 200,000 from the viewpoint of the stability of characteristics when the film is formed. Preferably, it is 4,000-50, 000. It is determined by molecular weight (also GPC (generome chromatography).

[0052] <(Β) component / specific amine compound> The specific amine compound as component (B) used in the present invention has an amino group (one NH) in the molecule.

2

An amine compound having one and a nitrogen-containing aromatic heterocyclic ring, and wherein the amino group (primary amino group) is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Since this specific amine compound is only the primary amino group contained in the molecule, polymer precipitation or gelation may occur during preparation of the liquid crystal alignment treatment agent or during storage of the liquid crystal alignment agent.

V, avoiding the possibility of problems.

The primary amine group contained in the specific amine compound does not contain an aliphatic hydrocarbon group or aromatic hydrocarbon in the molecule from the viewpoint of salt formation with a specific polyimide and ease of bonding reaction. It must be bonded to an aromatic cyclic hydrocarbon group!

Specific examples of the aliphatic hydrocarbon group include a linear alkyl group, an alkyl group having a branched structure, and a hydrocarbon group having an unsaturated bond. The carbon number is preferably S;! To 20, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.

[0053] Specific examples of the non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan Ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like. Preferably, it is a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, more preferably a non-aromatic cyclic hydrocarbon group having a ring having 3 to 10 carbon atoms. It is.

The nitrogen-containing aromatic heterocycle contained in the specific amine compound is an aromatic cyclic carbonization containing at least one structure selected from the group consisting of the following formulas [8a], [8b] and [8c]. Hydrogen, more preferably 1 to 4.

[0054] [Chemical 20]

[8 a] [8 b] [8 c]

(Wherein is a linear or branched alkyl group having 1 to 5 carbon atoms)

[0055] Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring , Pyridazine ring, pyrazoline ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thioline ring, phenanthorin ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazo Examples thereof include a single ring and an ataridin ring. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.

More preferred specific amine compounds are amine compounds represented by the following formula [3]: [0056] [Chemical Formula 21] H ₂ N ZZ ^Xl \, χ ₂ [3]

2

In the formula [3], X is not particularly limited as long as X is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group! /.

[0057] Preferred X in the formula [3] is a divalent divalent having one type selected from an aliphatic hydrocarbon group having a carbon number of !!-20 and a non-aromatic cyclic hydrocarbon group having a carbon number of 3-20. It is an organic group. As the non-aromatic cyclic hydrocarbon group, the above-described structure can be cited. More preferably, it is an aliphatic hydrocarbon group having 1 to 15 carbon atoms such as a cyclopropane ring and a cyclobutane ring. , Cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring, etc. It is done. Particularly preferred is a linear or branched alkyl group having 1 to 10 carbon atoms.

[0058] In addition, X is not adjacent to the amino group! /, —CH— in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group is —O— —NH— —CO — O— -0-CO-

2

CO— NH NH— CO CO S S (O) CF C (

twenty two

CF) C (CH) Si (CH) O— Si (CH) Si (CH) O

3 2 3 2 3 2 3 2 3 2 O—Si (CH 2) O—, may be replaced by a cyclic hydrocarbon group and a heterocyclic ring

3 2

. In addition, a hydrogen atom bonded to an arbitrary carbon atom is a linear or branched alkyl group having 120 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, or fluorine. An atom or a hydroxyl group may be substituted.

[0059] Specific examples of the cyclic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a funolene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a cyclopropane ring, a cyclobutane ring, Cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, Examples include cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, and adamantane ring. .

[0060] Specific examples of the heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, force rubazole ring, purine ring. , Thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthorin ring, indole ring, quinoxaline ring, benzothiazole ring, Examples include phenothiazine ring, oxadiazole ring, and atrazine ring.

[0061] X in the formula [3] is a nitrogen-containing aromatic heterocycle, and in the same manner as described above, the formula [8a] An aromatic cyclic hydrocarbon containing at least one structure selected from the group consisting of formula [8b] and formula [8c]. Specific examples thereof include the structure described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, A naphthyridine ring, a phenazine ring and a phthalazine ring are preferred.

[0062] In addition, X is a formula included in X from the viewpoint of the weakness of electrostatic interaction such as salt formation and hydrogen bonding between the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide [8a]

1 2

It is preferred that the formula [8b] and the formula [8c] are adjacent to each other! /, And that they are combined with a substituent! /,! /.

Furthermore, the carbon atom of the nitrogen-containing aromatic heterocycle represented by X in the formula [3] is a halogen atom and

2

And / or the organic group may have a substituent such as an oxygen atom, a sulfur atom, or a nitrogen atom.

[0063] A preferable combination of X and X in the formula [3] is X, an aliphatic group having from 20 to 20 carbon atoms;

1 2 1

A divalent organic group having one kind selected from a hydrocarbon group and a non-aromatic cyclic hydrocarbon group having 320 carbon atoms, X force pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimid

2

It is selected from gin ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring and phthalazine ring. X of the nitrogen-containing aromatic heterocycle of X

2

The carbon atom may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.

A more preferred specific amine compound is an amine compound represented by the following formula [4].

[0064] [Chemical 22]

Three

Yes, X is a single bond, 〇 —ΝΗ— —S— — SO one or divalent with 1 to 19 carbon atoms

4 2

Is an organic group. The total number of carbon atoms X and X have is 120. X is nitrogen Containing aromatic heterocycle)

[0065] X in the formula [4] is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic carbon.

Three

It is a hydrogen fluoride group. Specific examples thereof include straight-chain or branched alkyl groups having from 10 to 10 carbon atoms, unsaturated alkyl groups having from 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclohexane Heptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclodecane ring, And cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like. More preferably, it is a C1-C10 linear or branched alkyl group, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cyclo Examples include an undecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a calebornene ring, and an adamantane ring. Particularly preferred is a linear or branched alkyl group having 1 to 10 carbon atoms.

[0066] Any aliphatic hydrocarbon group or non-aromatic cyclic group that is not adjacent to the amino group in X

Three

CH— in the hydrocarbon group is: 01, NH C 0101, 0 1 C 0 1,-C

2

○ 1 NH, 1 NH— C 0 1, 1 C 0 1, 1 S, 1 S (0) 1,-CF 1 C (CF)

2 2 3 2-C (CH)-Si (CH)-0-Si (CH)-Si (CH) 〇 100

3 2 3 2 3 2 3 2

-Si (CH) —O—, a cyclic hydrocarbon group and a heterocyclic ring may be substituted. Also,

3 2

The hydrogen atom bonded to any carbon atom is a straight or branched alkyl group having 120 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group. The cyclic hydrocarbon group and the heterocycle mentioned here have the same meaning as defined for X in the formula [1].

X in Formula [4] is a single bond, —O— —NH— —S— — SO, or one carbon number;! ~ 1

4 2

9 is a divalent organic group. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having! To 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. . Specific examples of such X are given below.

Four

[0067] For example, a single bond, 〇 NH S——SO hydrocarbon having 1 19 carbon atoms CO— OO— CO CO— NH NH— CO CO CF

C (CF)-CH (OH) — C (CH)-Si (CH)-0-Si (CH

-Si (CH) — O O— Si (CH) — O, cyclopropane ring,

3 2 3 2

'Clopentane, cyclohexane, cycloheptane, cyclooctane, cyclo, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptane Tadecane ring, cyclotadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, no ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, Ring, indene ring, funolenic ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazol Down ring, an isoquinoline ring, a force carbazole ring, purine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, Birazorijin ring, Toriazoru ring

, Pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthorin ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxazazole ring, atalidine ring, oxazole ring, piperazine ring, piperazine ring A peridine ring, a dioxane ring, a morpholine ring, etc. are mentioned. X may contain two or more of these.

Specific examples including two or more types include: -NH NH-C H-NH-C H

2 4 3

NH-C H S-CH ― -S-C H -S-C H--S-C H

2 4 3 6

O-CH O-C H -O-C H -O-C H NH-CO-

3 6

CH NH-CO-C H NH-CO-C H-NH-CO-C H

3 6

CO-CH CO— C H CO— C H CO— C H CO— N

H-CH -CO-NH-C H CO— NH— C H CO— NH— C H -NH-CH —CH (CH) -NH-C H CH (CH) NH— C H

2 3 2 4 3 3 6

CH (CH) -NH-C H -CH (CH) S— CH — CH (CH) S— C

3 4 8 3 2 3

H -CH (CH) -S-C H -CH (CH) S- C H CH (CH)

3 6

O-CH -CH (CH) O-C H -CH (CH) O-C H -CH (CH)

3 6 3 O— CH 2 —CH (CH 2) —NH—CO—CH 2 CH (CH 2) NH— CO

4 8 3 2 3

C H -CH (CH) NH— CO— C H CH (CH) NH— CO— C H

2 4 3 3 6 3 4

-CH (CH) -CH (OH) -CH CH (OH) — C H CH (OH) —

8 3 2 2 4

C H -CH (OH) -C H -CH (CH OH)-CH CH (CH OH) —

3 6 4 8 2 2 2

C H -CH (CH OH) — C H CH (CH OH) — C H NH— CH (

2 4 2 3 6 2 4 8

CH OH)-CH CO— NH— CH—CH (CH OH)-CH NH— CO— CH (

2 2 2 2

CH OH)-CH CO— CH (CH OH)-CH S— CH (CH OH)-CH

2 2 2 2 2 O— CH (CH OH)-CH -CH (N (CH)) C H O C

2 2 2 3 2 6 4 6

H NH C H CO— NH C H NH— CO C H CO

4 6 4 6 4 6 4

C H—CH 2 — —C H S and the like can be mentioned.

6 4 6 4

[0069] X in the formula [4] is a nitrogen-containing aromatic heterocyclic ring, and is the same as X in the formula [3].

Therefore, X is equivalent to the definition of X. A specific example is the same as X described above.

5 2 2 Can raise power. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, A naphthyridine ring, a phenazine ring and a phthalazine ring are preferred.

[0070] In addition, X is a formula included in X from the viewpoint of the weakness of electrostatic interaction such as salt formation and hydrogen bonding between the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide [8a]

4 5

Adjacent to the formula [8b] and the formula [8c]! /, Combined with a carbon atom! /, The power S preferred.

Furthermore, the carbon atom of the nitrogen-containing aromatic heterocycle represented by X in the formula [4] is a halogen atom and

Five

The organic group which may have a substituent of the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom! /.

[0071] A preferable combination of X X and X in the formula [4] is X, the number of carbons;

3 4 5 3

Chain or branched alkyl group, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, Cyclotetradecane ring, norbornene ring, adamantane ring, X force single bond, 1 to 10 carbon atoms;

Four

NH CCC NH— -NH- CO CO S SO -CF C (CF) Si (CH)

2 2 3 2 3 2

O— Si (CH) Si (CH) — O O— Si (CH) — O CH (OH)

3 2 3 2 3 2

-NH-CH -NH-C H NH— C H NH— C H S— CH

2 2 4 3 6 4 8 -S-C H -S-C H -S-C H -O-CH O— C H

2 2 4 3 6 4 8 2 2 4

, -O-C H -O-C H -NH-CO-CH NH— CO— C H

3 6 4 8 2 2 4

-NH-CO-C H -NH-CO-C H CO— CH CO— C H

3 6 4 8 2 2 4 CO— C H CO— C H -CO-NH-CH CO— NH— C H

3 6 4 8 2 2 4 -CO-NH-C H -CO-NH-C H NH— CH — CH (CH) —

3 6 4 8 2 3

, -NH-C H -CH (CH) -NH-C H CH (CH) NH— C H

2 4 3 3 6 3 4 8

CH (CH) -S-CH -CH (CH) S— C H —CH (CH) S— C

3 2 3 2 4 3 3

H -CH (CH) -S-C H -CH (CH) O— CH — CH (CH) O

6 3 4 8 3 3 3

C H -CH (CH) -O-C H -CH (CH) O— C H CH (CH) —

2 4 3 3 6 3 4 8 3

, -NH-CO-CH -CH (CH) -NH-CO-C H CH (CH) NH

2 3 2 4 3

CO— C H -CH (CH) -NH-CO-C H CH (CH) CH (OH)

3 6 3 4 8 3

CH -CH (OH) -C H CH (OH) — C H CH (OH) — C H

2 2 4 3 6 4 8

, -CH (CH OH)-CH -CH (CH OH) — C H CH (CH OH) — C

2 2 2 2 4 2 3

H -CH (CH OH) — C H NH— CH (CH OH)-CH CO— N

6 2 4 8 2 2

H-CH (CH OH)-CH NH— CO— CH (CH OH)-CH CO— C

2 2 2 2

H (CH OH)-CH S— CH (CH OH)-CH O— CH (CH OH) — C

2 2 2 2 2

H -CH (N (CH)) C H O C H NH C H CO— N

2 3 2 6 4 6 4 6 4

H C H NH— CO C H CO C H CH2 C H S—

6 4 6 4 6 4 6 4

, Cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclodecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring , Tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, X force s, pyrrole ring, imidazole ring, pyrazole ring, pyridi

Five

Ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, na A ring, a phenazine ring, and a phthalazine ring. X nitrogen-containing aromatic heterocycle

Five

These carbon atoms may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.

[0072] A more preferable combination of X X and X in the formula [4] is X 1 carbon number;

3, 4 5 3

Linear or branched alkyl group, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, X 1 single bond,

Four

Straight or branched alkyl group having 1 to 5 carbon atoms, 101, 1 NH—, —CO—Ο—, 10 1 C 0 1, C 0 1 NH 1, NH 3 — C 0 1, C 0 1, S, 1 S (〇) 1, CH (〇

2

H)-, -NH-CH 1, -S -CH 1, -O-CH 1, -0 ~ C H 1, NH- C

2 2 2 2 4

O-CH I, -CO-CH -CO-NH-CH I, NH— CH— CH (CH)-

2 2 2 2 3

,-S -CH -CH (CH 2), -O-CH 1 CH (CH) —, 1 NH— C 0 1 CH— C

2 3 3 3 2

H (CH), 1 CH (〇H) — CH—, 1 CH (〇H) — C H 1, 1 CH (CH〇H) — C

3 2 2 4 2

H 1, -NH-CH (CH〇H) — CH —, 1 C〇1 NH— CH (CH〇H) — CH —,

2 2 2 2 2

-NH-CO-CH (CH〇H) — CH—, 1 C〇1 CH (CH〇H) — CH—, 1 S—

2 2 2 2

CH (CH〇H) — CH—, 101 CH (CH〇H) — CH—, 1 CH (N (CH)) 1,

Den ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, X, pyro

5 ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, It is selected from a phenazine ring and a phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocycle of X is a halogen atom and

Five

[0073] In a more preferred formula [4], the combination of X X and X is X 1 carbon number;

3, 4 5 3

A linear or branched alkyl group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, Cyclohexane ring, X, single bond, carbon number;! To 5 linear or branched alkyl group, -0-

Four

NH— -CO-Ο-, C C NH NH— C —CO— CH H) —NH—CH —S—CH CH NH— C C

2 2 2

H -CO-CH -CO-NH-CH NH— CH — CH (CH) S

2 2 2 2 3

-CH -CH (CH) -O-CH -CH (CH) NH— C CH — CH (C

2 3 3 3 2

H) CH H) — CH CH H) — C H CH (CH H) — CH —

3 2 2 4 2 2 -NH-CH (CH H) — CH C NH— CH (CH H) — CH N

2 2 2 2

H— C CH (CH H) — CH C CH (CH H) — CH S— CH (

2 2 2 2

CH H) — CH CH (CH H) — CH CH (N (CH)) C

2 2 2 2 3 2 6

H C H NH C H C NH C H NH— C C

4 6 4 6 4 6 4

H — C C H — CH2 C H — S—, cyclopropane ring, cyclobutane ring

6 4 6 4 6 4

, Cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, anthracene ring, X force pyrrole ring, imidazole ring, pyrazole ring, pyridine Ring, pyrimidine ring,

Five

Ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzazole ring. The carbon atom of the nitrogen-containing aromatic heterocycle of X is

Five

The organic group which may have a substituent of an atom and / or an organic group is an oxygen atom

Further, it may contain a hetero atom such as a sulfur atom or a nitrogen atom.

A particularly preferred combination of X X and X in formula [4] is X 1 carbon number;

3 4 5 3

Linear or branched alkyl group, cyclobutane ring, cyclohexane ring, X 1 single bond, o

Four

CO—O O—CO CO—NH NH—CO CH (OH) benzene ring, naphthalene ring, fluorene ring, anthracene ring, X 1 pyrrole ring, imida

Five

It is selected from a sol ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring. X contains nitrogen.

5 The carbon atom of the aromatic heterocyclic ring may have a halogen atom and / or a substituent of an organic group, and the organic group contains a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Also good.

Specific examples of the specific amine compound used in the present invention include the compound of M1 M156. [0075] [Chemical 23]

[0076] [Chemical 24]

77 M78 M79 M80

M93 94 M95 M96

M110 M112 M113 M114 115

M116 117 118 119 120 M121

M122 M123 M124 M125 7]

M130 M131 M132 M133

M134 M135 M136 M137 138

M152 M153 M154 M155 156 More preferred compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100-M103, M108-M125, M128-M137, M139-M143, M149-M156 are mentioned. More preferably, M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, MlOO -M103, M108-M112, M114-M116, M118-M121, M125, M134-M136, M139, M140, M143, M150, M152-M156.

[0081] <Liquid crystal aligning agent>

The liquid crystal aligning agent of the present invention is usually obtained by mixing the specific polyimide as the component (A) and the specific amine compound as the component (B) in an organic solvent. The specific amine compound to be mixed may be one type or a combination of two or more types.

As a mixing method, a reaction solution (a solution of a specific polyimide) obtained by imidizing a polyamic acid that is a precursor of a specific polyimide may be used. Usually, a powder of a specific polyimide obtained by purification is organically used. A method of adding a specific amine compound to a solution dissolved in a solvent is mentioned. The organic solvent used in that case is not particularly limited as long as it is a solvent that dissolves the specific polyimide. Specific examples are given below.

[0082] For example, N, N, monodimethylformamide, N, N, monodimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, 2-pyrrolidone, N-ethylpyrrolidone, N-bulupyrrolidone, Dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethinolesnoreoxide, γ-butyrolataton, 1,3-dimethylenoylimidazolidinone, dipentene, ethylamyl ketone, methylnonyl ketone, methyl ethyl ketone, Examples include methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone. These solvents can be used as a mixture of two or more.

[0083] When the specific polyimide is dissolved in the organic solvent, calorific heat may be used for the purpose of promoting the dissolution of the specific polyimide. If the heating temperature is too high, the molecular weight of the polyimide may decrease. Therefore, the temperature is preferably 30 to 100 ° C, more preferably 50 to 90 ° C. Although the concentration of the specific polyimide solution is not particularly limited, it is easy to uniformly mix with the specific amine compound. Therefore, the specific polyimide concentration in the solution is preferably 20 to 20% by mass, more preferably 3 to 15 mass. %, Particularly preferably 3 to 10% by mass.

[0084] The specific amine compound may be added directly to the solvent-soluble polyimide solution! /, But in a suitable solvent, the solution has a concentration of 0.;! To 10% by mass, preferably 1 to 7% by mass. It is preferable to add it afterwards. Examples of the solvent include the solvent of the solvent-soluble polyimide described above. It is done.

It is preferable that the specific polyimide and the specific amine compound are mixed with heating in an organic solvent or heated after mixing. By heating, the ratio of the specific amine compound and the specific polyimide that are already bonded in the state of the liquid crystal alignment treatment agent increases, and it becomes possible to move charges more efficiently when the liquid crystal alignment film is formed. . The temperature in the case of heating described above is preferably 10 to 100 ° C. force, more preferably (or 20 to 80 ° C.).

The addition amount of the specific amine compound is 0 with respect to 1 mol amount of the carboxyl group contained in the specific polyimide because the effect of the present invention can be obtained efficiently and the stability of the liquid crystal alignment treatment agent is not impaired. 0;! To 2 mole boost S preferred, more preferably 0.05 to;! Mole times, particularly preferred (or 0.0.08-0.8 monolayer times).

[0085] The liquid crystal aligning agent of the present invention includes a solvent and a compound that improve film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied as a component other than the specific polyimide and the specific amine compound, You may contain the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board | substrate. Other components may be added during the mixing of the specific polyimide and specific amine compound! /, Or may be added to these mixed solutions later! /.

Specific examples of solvents that improve film thickness uniformity and surface smoothness include the following:

[0086] For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethinoresenoresonolev, butinoreserosonoleb, methinoreserosonoleb acetate, ethinoreserosonole butyl acetate, butyl carbitol, Tyl carbitol, ethyl carbitol acetate, ethylene glycolate, ethylene glycolate monoacetate, ethyleneglycololemonoisopropinoreatenore, ethyleneglycololebutinoreatenore, propyleneglycololeate, propyleneglycololemonoacetate , Propylene glycol nomonomethino ethenore, propylene glycol no tert butino oleate nore, dipropylene glycol nomonomethino ethenore, diethylene glycol nore, diethylene glycono Monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Honoré mono-methylol Honoré ether Honoré, dipropylene glycol Honoré monomethyl E Chino les er Tenore, dipropylene glycol monoacetate monomethyl E chill ether. Di propylene glycol Monopropylene monoethanolate, dipropylene glycol monoacetate monopropenoyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyanolate , Diisobutylene, aminoacetate, butinolevylate, butinoleethenole, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n hexane, n-pentane, n-octane, jetyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 ethoxy Methylethyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-butyl methoxypropionate, 1-methoxy-2-propanol, 1 ethoxy-2-propano Nore, 1 Butoxy 2-Propanole, 1 Phenoxy 2-Propanole, Propylene Glycolol Monoacetate, Propylene Glyconoresacetate, Propylene Ginolole 1-Monomethylenoate 1-Acetate, Propylene Glycolol 1-Monoethinore 1 —Acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n propyl ester, lactate n butyl ester, lactate isoamid Such solvent having a low surface tension, such as esters.

[0087] These solvents may be used alone or in combination of two or more. When the above solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the entire solvent contained in the liquid crystal alignment treatment agent.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0088] More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (Sumitomo) 3), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Shishiko). The proportion of these surfactants used is 100% of component (A) contained in the liquid crystal aligning agent. Preferably, it is 0.0;! ~ 2 parts by mass, more preferably 0.01 ~;

Yes

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

[0089] For example, 3aminopropyltrimethoxysilane, 3aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) 3amino Propyltrimethoxysilane, N— (2 aminoethyl) 3-amino pill triethoxysilane, N ethoxycarbonyl 3-aminoaminopropyl trimethoxysilane, N-ethoxycarbonyl 3-aminopropyltriethoxysilane N-triethoxysilylpropynoletriethylenetriamine, N trimethoxysilylpropyltriethylenetriamine, 10 trimethoxysilyl-1,4,7 triazadecane, 10 triethoxysilyl-1,4,7 triazadecane, 9-trimethoxysilyl 1,3-Diazanonyl acetate, 9-triethoxysilyl 1 , 6-diazanononoleacetate, N-benzyl-3-aminopropinoretrimethoxysilane, N-benzyl-1-aminopropyltriethoxysilane, N-phenyl-2-triaminosilane, N-phenyl 3-aminopropyltriethoxysilane, N bis (oxyethylene) -3-aminomino trimethoxysilane, N-bis (oxethylene) 3-aminopropyltriethoxysilane, ethylene glycol diglycidyl Ethereol, Polyethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, Tripropylene glycol diglycidyl ether, Polypropylene glycol diglycidinoreatenore, Neopentinoreglycolinoglycidinoreatenore, 1,6-Hexane dinoresidegly Shizino reetenore, glycerin diglycidino reetenore, 2,2-jib mouth monopenyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl 2,4 Ν ', Ν', tetraglycidyl 1 m xylenediamine, 1,3-bis (N, N diglycidylaminomethinole) cyclohexane, Ν, Ν, Ν ', Ν', monotetraglycidyl 4, 4'— And diaminodiphenylmethane.

[0090] When these compounds are added, it is preferable that the amount is 0.;! To 30 parts by mass, more preferably 1 to 20 with respect to 100 parts by mass of the specific polyimide component contained in the liquid crystal aligning agent. Part by mass. If the amount is less than 1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

[0091] In the liquid crystal alignment treatment agent of the present invention, in addition to the above, as long as the effects of the present invention are not impaired, polymer components other than the specific polyimide, and the electrical properties such as dielectric constant and conductivity of the liquid crystal alignment film A dielectric material or conductive material whose properties are to be changed, and a crosslinkable compound which is intended to increase the hardness or density of the liquid crystal alignment film may be added.

The concentration of the solid content in the liquid crystal alignment treatment agent of the present invention can be appropriately changed depending on the film thickness of the target liquid crystal alignment film, a film having no defect, and suitable as a liquid crystal alignment film From the reason that a thickness can be obtained; it is preferably 20 to 20% by mass, more preferably 2 to 10% by mass.

[0092] <Liquid crystal alignment film / liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like. . In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. In particular, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed from the viewpoint of simplifying the process. In addition, the reflective liquid crystal display element can use an opaque material such as a silicon wafer as long as it is only on one side of the substrate, and the electrode in this case can be made of a material that reflects light such as aluminum.

[0093] The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used according to the purpose.

Firing after applying the liquid crystal aligning agent on the substrate may form a coating film by evaporating the solvent at 50 to 200 ° C, preferably 80 to 150 ° C, by a heating means such as a hot plate. it can. If the thickness of the coating film after baking is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm, more preferably 10 ~;! OOnm. When liquid crystal is aligned horizontally or tilted In this case, the coating film after baking is treated with rubbing or irradiation with polarized ultraviolet rays. The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then producing a liquid crystal cell by a known method.

[0094] To give an example of manufacturing a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded together, and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the surface of the liquid crystal alignment film on which the spacer is dispersed, and then the substrate is bonded and sealed. The method etc. which perform can be illustrated. The thickness of the spacer at this time is preferably;! -30 m, more preferably 2--10 μm.

As described above, the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television and the like. The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example

[0095] Abbreviations used in the examples are as follows.

(Tetracarboxylic dianhydride)

BODA: Bicyclo [3, 3, 0] octane 2, 4, 6, 8 Tetracarboxylic dianhydride

CBDA: 1, 2, 3, 4 cyclobutane tetracarboxylic dianhydride

TDA: 3,4-dicarboxy-1, 1,2,3,4-tetrahydro-1-naphthalene succinic acid dihydrate

[0096] [Chemical 28]

BODA CBDA TDA

(Jiamin)

p— PDA: p

PCH: 1,3-Diamino-4-1 [4 (4-Heptylcyclohexyl) phenoxy] benzene DBA: 3,5-Diaminobenzoic acid

DADPA: 4, 4'-diaminodiphenylamine

[Chemical 29]

DBA DADPA

(Specific amine compounds)

3-AMP: 3-aminomethyl pyridine

AEP: 4— (2 aminoethyl) pyridine

API: 1 (3-Aminopropyl) imidazole

4—AMP: 4-aminomethyl pyridine

2AMMP: 2 (aminomethyl) 1-5 methylvirazine

[Chemical 30]

H2N-CeHi3

HA

(Organic solvent)

NMP: N—Methyl-2— BCS: Butyl sorb GBL: y Butyro Rataton

[0100] <Molecular weight measurement of polyimide>

The molecular weight of the polyimide in the synthesis example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshi Kagaku Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex.

Column temperature: 50 ° C

Eluent: N, N'-dimethylformamide (as additives, lithium bromide-hydrate (LiBr-H20) 30mmol / L, phosphoric acid. Anhydrous crystals (ophosphoric acid) 30mmol / L, tetrahydrofuran) (THF) is 10ml / U

Flow rate: 1. OmL / min

Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: approx. 9000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation; Posimer Laboratories !; polyethylene glycol (molecular weight: approx. 12,000, 4,000, 1,000) ).

[0101] <Measurement of imidization ratio>

The imidation ratio of polyimide in the synthesis example was measured as follows. Put 20 mg of polyimide powder in an NMR sample tube (NMR sampling tube standard φ5, manufactured by Kusano Kagaku Co., Ltd.), deuterated dimethyl sulfoxide (DMSO-d, 0.05% TMS mixture) 0.5

6

3 ml was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined by determining the proton derived from the structure that does not change before and after imidation as a reference proton, the peak integrated value of this proton, and the proton peak integrated value derived from the NH group of amic acid that appears in the vicinity of 9.5 to 10.0 ppm. Was obtained by the following equation.

Imidization rate (%) = (1— a-x / y) X 100

In the above formula, X is the accumulated proton peak value derived from the NH group of the amic acid, y is the accumulated peak value of the reference proton, α is the proton of the anchor group of the amic acid in the case of polyamic acid (imidation rate is 0%) It is the number ratio of the reference proton to one.

[0102] <Calculation method of the amount of carboxyl groups>

It was calculated by the method described above. (Synthesis Example 1)

BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol) and PCH (10.3 g, 27 mmol) were mixed in NMP (100. lg) and reacted at 40 ° C for 3 hours. Thereafter, CBDA (4. lg, 21 mmol) and NMP (52.2 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (130.3 g) and diluting to 6% by mass, acetic anhydride (15.6 g) and pyridine (12. lg) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. I let you. This reaction solution was put into methanol (1600 ml), and the resulting precipitate was separated by filtration. This deposit was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A). The imidation ratio of this polyimide was 54%, the number average molecular weight was 18,300, and the weight average molecular weight was 45,300. The amount of carboxyl groups in this polyimide is 0.92 with respect to the repeating unit.

[0103] (Synthesis example 2)

BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol) and PCH (10.3 g, 27 mmol) were mixed in NMP (lOO.Og) and reacted at 40 ° C for 3 hours. Then, CBDA (4. lg, 2 lmmol) and NMP (52.2 g) were added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (55.4 g) and diluting to 6% by mass, acetic anhydride (2.7 g) and pyridine (2. lg) were added as imidization catalysts and reacted at 70 ° C for 1 hour. It was. This reaction solution was poured into methanol (660 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (B). The imidation ratio of this polyimide was 25%, the number average molecular weight was 19,500, and the weight average molecular weight was 47,800. The amount of carboxyl groups in this polyimide is 1.50 per repeating unit.

[Synthesis Example 3]

BODA (150.lg, 600mmol), DBA (60.9g, 400mmol), PCH (152.2g, 4OOmmol) were mixed in NMP (1290g) and reacted at 80 ° C for 5 hours, then CBDA ( 38. 8g, 198mmol) and NMP (320g) were added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (60.2 g) and diluting to 6% by mass, acetic anhydride (3.9 g) and pyridine (49.6 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours. It was. This reaction solution was poured into methanol (7700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (C). The imidation ratio of this polyimide was 57%, the number average molecular weight was 23,000, and the weight average molecular weight was 80,200. The amount of carboxyl groups in this polyimide is 1.36 per repeating unit.

[0105] (Synthesis Example 4)

BODA (50.lg, 600mmol), DBA (60.9g, 400mmol), PCH (152.2g, 40Ommol) were mixed in NMP (1290g) and reacted at 80 ° C for 5 hours, then CBDA ( 38.8 g, 198 mmol) and NMP (320 g) were prepared and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (300. lg) and diluting to 6% by mass, acetic anhydride (32. Og) and pyridine (24.8 g) were added as imidation catalysts and reacted at 90 ° for 2.5 hours. Let This reaction solution was poured into methanol (3900 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (D). The imidation ratio of this polyimide was 69%, the number average molecular weight was 22,700, and the weight average molecular weight was 69,300. The amount of carboxyl groups in this polyimide is 1.12 per repeating unit.

[0106] (Synthesis Example 5)

BODA (150.lg, 600mmol), DBA (60.9g, 400mmol), PCH (152.2g, 4OOmmol) were mixed in NMP (1290g) and reacted at 80 ° C for 5 hours, then CBDA ( 38. 8g, 198mmol) and NMP (320g) were added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (101.2 g) and diluting to 6% by mass, acetic anhydride (21.3 g) and pyridine (16.5 g) were added as an imidization catalyst and reacted at 90 ° C for 3 hours. It was. This reaction solution was poured into methanol (1300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (E). The imidation ratio of this polyimide was 81%, the number average molecular weight was 20,400, and the weight average molecular weight was 63,000. The amount of carboxyl groups in this polyimide is 0.88 with respect to the repeating unit.

[Synthesis Example 6] BODA (16. Og, 64 mmol), DADPA (11.9 g, 60 mmol) and PCH (9.7 g, 26 mmol) were mixed in NMP (126.4 g) and reacted at 40 ° C for 3 hours. CBDA (3.8 g, 19 mmol) and NMP (40 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (50.3 g) and diluting to 4% by mass, acetic anhydride (5.0 g) and pyridine (3.9 g) were added as an imidation catalyst and reacted at 50 ° C. for 2 hours. This reaction solution was poured into methanol (910 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (F). The imidization ratio of this polyimide was 25%, the number average molecular weight was 22,200, and the weight average molecular weight was 69,000. The amount of carboxyl groups in this polyimide is 1.50 per repeating unit.

[Synthesis Example 7]

BODA (7.5 g, 30 mmol), DADPA (1.6 g, 8. Ommol), DBA (2.4 g, 16 mmol), PCH (6.lg, 16 mmol) are mixed in NMP (53.2 g), After reacting at 40 ° C for 3 hours, CBDA (1.9 g, 10 mmol) and NMP (25 g) were mixed and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (60.4 g) and diluting to 5% by mass, acetic anhydride (6.3 g) and pyridine (4.9 g) were added as imidization catalysts and reacted at 90 ° C for 2 hours. It was. This reaction solution was poured into methanol (880 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (G). The imidation ratio of this polyimide was 51%, the number average molecular weight was 21,100, and the weight average molecular weight was 64,000. The amount of carboxyl groups in this polyimide is 1.38 per repeating unit.

[Synthesis Example 8]

TDA (9. Og, 30 mmol), DBA (3.2 g, 21 mmol), p-PDA (1. Og, 9. Ommol) were mixed in NMP (74.7 g) and reacted at room temperature for 24 hours to react with polyamic acid. A solution was obtained. After adding NMP to this polyamic acid solution (80. Og) and diluting to 6% by mass, acetic anhydride (29. lg) and pyridine (13.5 g) were added as imidization catalysts, and the mixture was stirred at 35 ° C for 3 minutes. Reacted for hours. This reaction solution was poured into methanol (710 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (H). This polyimi The imidation ratio of the catalyst was 91%, the number average molecular weight was 11,300, and the weight average molecular weight was 20,700. The amount of carboxyl groups in this polyimide is 0.88 with respect to the repeating unit.

[0110] (Example 1)

To the polyimide powder (A) (7.4 g) obtained in Synthesis Example 1, ΝΜΡ (41 · 9 g) was added and dissolved by stirring at 80 ° C. for 40 hours. To this solution, add 7.5% NMP solution (14.8 g) of 3-AMP (14.8 g as 3-AMP), NMP (3.7 g), BCS (55.5 g), and 50. A liquid crystal aligning agent (1) was obtained by stirring for 15 days at C.

The liquid crystal alignment treatment agent (1) obtained above is spin-coated on a glass substrate with an ITO electrode, dried on an 80 ° C hot plate for 5 minutes, and then baked in a 210 ° C hot-air circulating oven for 1 hour. A liquid crystal alignment film having a thickness of lOOnm was prepared. Prepare two substrates with this liquid crystal alignment film, spray a 6 m spacer on the surface of one liquid crystal alignment film, print and seal the sealant on it, and seal The agent was cured to produce an empty cell. Liquid crystal MLC-6608 (manufactured by Merck & Japan) was injected into this empty cell by a reduced pressure injection method, and the inlet was sealed to obtain a nematic liquid crystal cell.

When this liquid crystal cell was observed with a polarizing microscope, the liquid crystal was uniformly vertically aligned, and no alignment defects were observed.

[0111] <Evaluation of voltage holding ratio>

Apply the voltage of 4V to the liquid crystal cell manufactured above at 60 ° C at a temperature of 80 ° C, measure the voltage after 16. 67 ms and 1667 ms, and determine how much the voltage can be maintained. As calculated. As a result, the voltage holding ratio at 16. 67 ms was 97.6%, and the voltage holding ratio at 16 67 ms was 67.3%.

The measurement was carried out using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Tech Niriki Co., Ltd., with settings of Voltage: ± 4 V, Pulse Width: 60 s, Flame Period: 16. 67 ms or 1667 ms.

A DC voltage of 10V is applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and shorted for 1 second. After that, the potential generated in the liquid crystal cell was measured for 1800 seconds. Figure 1 shows the potential change at this time. As a result, the residual charge 50 seconds after the short circuit was 3.19V, and the residual charge 1000 seconds later was 0.25V. For measurement, a 6254 type liquid crystal physical property evaluation apparatus manufactured by Toyo Tech Niki Co., Ltd. was used.

The liquid crystal cell after the above measurement was left in a thermostat set at 100 ° C. for 7 days, and then the same measurement was performed. As a result, the voltage holding ratio at 16. 67 ms is 97.8%, the voltage holding ratio at 16 67 ms is 67.2%, and the residual charge after 50 seconds is 3.41 V, 100 seconds The later residual charge was 0.46V.

(Example 2 to Example 18)

Liquid crystal aligning agents (2) to (; 18) were prepared as described below, and liquid crystal cells were prepared and evaluated in the same manner as in Example 1. In all the liquid crystal cells, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. The evaluation results are shown in Tables 1 and 2 below. (Example 2)

A liquid crystal aligning agent (2) was obtained in the same manner as in Example 1 except that the polyimide powder (B) obtained in Synthesis Example 2 was used.

(Example 3)

A liquid crystal aligning agent (3) was obtained in the same manner as in Example 1 except that the polyimide powder (C) obtained in Synthesis Example 3 was used and dissolved by stirring at 70 ° C for 40 hours. .

(Example 4)

To the polyimide powder (C) (5.4 g) obtained in Synthesis Example 3, 3 (30 · 6 g) was added and dissolved by stirring at 70 ° C. for 40 hours. To this solution, add 1-C® i% NMP solution of 3-AMP (5.4 g) (0.38 g as 3 AMP), NMP (8. lg), BCS (40.5 g), and 50. The liquid crystal aligning agent (4) was obtained by stirring at C for 15 days.

(Example 5)

To the polyimide powder (C) (5.4 g) obtained in Synthesis Example 3, 3 (30 · 6 g) was added and dissolved by stirring at 70 ° C. for 40 hours. In this solution, add 7 mass ° / ^^^ solution of 3—AMP (5.4 g) (0.38 g as 3—AMP), NMP (8. lg), BCS (40.5 g), 50. 15 days at C As a result, a liquid crystal aligning agent (5) was obtained.

[0113] (Example 6)

To the polyimide powder (C) (7.4 g) obtained in Synthesis Example 3, ΝΜΡ (41.9 g) was added and dissolved by stirring at 70 ° C. for 40 hours. Add 5 mass ° / ^^^ solution of 3-AMP (7.4g) (0.37g as 3-AMP), NMP (ll. Lg), BCS (55.5g) to this solution, 50. A liquid crystal aligning agent (6) was obtained by stirring the mixture for 15 days at C.

(Example 7)

To the polyimide powder (C) (7.4 g) obtained in Synthesis Example 3, ΝΜΡ (41.9 g) was added and dissolved by stirring at 70 ° C. for 40 hours. To this solution, add 8.5% NEP solution (14.8 g) of AEP (1.26 g as AEP), NMP (3.7 g), and BCS (55.5 g). A liquid crystal aligning agent (7) was obtained by holding the temple for 15 days at C.

(Example 8)

To the polyimide powder (C) (7.4 g) obtained in Synthesis Example 3, ΝΜΡ (41.9 g) was added and dissolved by stirring at 70 ° C. for 40 hours. To this solution, add API lC®i% NMP solution (12.5 g) (1.26 g as API), NMP (5.9 g), and BCS (55.5 g). A liquid crystal aligning agent (8) was obtained by holding the temple for 15 days at C.

(Example 9)

To the polyimide powder (D) (10.2 g) obtained in Synthesis Example 4, ΝΜΡ (57.8 g) was added and dissolved by stirring at 70 ° C. for 40 hours. Add 3 mass ° / ^^^ solution (10.2g) (0.31g as 3 AMP), NMP (6.8g) and BCS (85. Og) to this solution. A liquid crystal aligning agent (9) was obtained by stirring for 15 days at C in C.

(Example 10)

To the polyimide powder (D) (10.2 g) obtained in Synthesis Example 4, ΝΜΡ (57.8 g) was added and stirred at 70 ° C. for 40 hours to dissolve. This solution contains 5 mass ° / ^^^ solution (10.2 g) of 3-AMP (0.51 g as 3 AMP), NMP (6.8 g), and BCS (85. Og). A liquid crystal aligning agent (10) was obtained by stirring the mixture for 15 days at C.

[Example 11]

Add ΝΜΡ (57.8g) to the polyimide powder (D) (10.2g) obtained in Synthesis Example 4 and add 40% at 70 ° C. Stir for hours to dissolve. In this solution, 3-AMP 7 mass ° / ^^^ solution (10.2g) (0.71g as 3 AMP), NMP (6.8g), BCS (85.0g) was calorieated, 50. A liquid crystal aligning agent (11) was obtained by stirring for 15 days at C in C.

(Example 12)

NMP (57.8 g) was added to the polyimide powder (D) (10.2 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 ° C. for 40 hours. In this solution, 3C AMP lC®i% NMP solution (10.2g) (1.0g as 3 AMP), NMP (6.8g), BCS (85.0g) was added. A liquid crystal aligning agent (12) was obtained by stirring for 15 days at C in C.

(Example 13)

To the polyimide powder (E) (8.6 g) obtained in Synthesis Example 5, ΝΜΡ (42.0 g) was added and dissolved by stirring at 70 ° C. for 40 hours. To this solution, 7% NMP solution of 3-AMP (8.6 g) (0.6 g as 3-AMP), NMP (2.4 g), and BCS (71.7 g) were added. A liquid crystal aligning agent (13) was obtained by carrying out a Zenzen temple in C for 15 days.

(Example 14)

To the polyimide powder (E) (8.6 g) obtained in Synthesis Example 5, ΝΜΡ (42.0 g) was added and dissolved by stirring at 70 ° C. for 40 hours. Add 1-C®i% NMP solution of 3-AMP (8.6 g) (0.86 g as 3 AMP), NMP (2.4 g), and BCS (71.7 g) to this solution. A liquid crystal aligning agent (14) was obtained by stirring the mixture for 15 days at C.

(Example 15)

To the polyimide powder (F) obtained in Synthesis Example 6 (7.4 g), ΝΜΡ (41.9 g) was added and stirred at 80 ° C. for 40 hours to dissolve. To this solution, add 1-C® i% NMP solution of 3-AMP (11. lg) (1 llg as 3 AMP), NMP (7.4 g), BCS (55.5 g), and 50. A liquid crystal aligning agent (15) was obtained by stirring the mixture for 15 days at C.

(Example 16)

To the polyimide powder (G) obtained in Synthesis Example 7 (7.4 g), koji (41.9 g) was added and dissolved by stirring at 80 ° C. for 40 hours. Add 50% NMP solution (7.4g) of 3-AMP (7.4g) (0.37g as 3-AMP), NMP (ll. Lg), BCS (55.5g) to this solution, 50. A liquid crystal aligning agent (16) was obtained by stirring for 15 days at C in C. (Example 17)

To the polyimide powder (E) (8.6 g) obtained in Synthesis Example 5, ΝΜΡ (42 · Og) was added and stirred at 80 ° C. for 40 hours to dissolve. In this solution, 7 mass% NMP solution (8.6 g) of 4 AMP (0.6 g as 4 AMP), NMP (2.4 g), and BCS (71.7 g) were added. A liquid crystal aligning agent (17) was obtained by holding the temple for 15 days at C.

(Example 18)

To the polyimide powder (E) (8.6 g) obtained in Synthesis Example 7, ΝΜΡ (42 · Og) was added and stirred at 80 ° C. for 40 hours to dissolve. To this solution, add 7% NMP solution (8.6 g) of 2AMMP (0.6 g as 2A MMP), NMP (2.4 g), BCS (71.7 g), and 50. A liquid crystal aligning agent (18) was obtained by holding the temple for 15 days at C.

[0116] (Comparative Example 1)

To the polyimide powder (A) (7.4 g) obtained in Synthesis Example 1, ΝΜΡ (41 · 9 g) was added and dissolved by stirring at 80 ° C. for 40 hours. NMP (18.5 g) and BCS (55.5 g) were added to this solution, and the mixture was stirred for 1 hour to obtain a liquid crystal aligning agent (19). Using this liquid crystal aligning agent, a liquid crystal cell was prepared and evaluated in the same manner as in Example 1.

[0117] <Evaluation of voltage holding ratio>

When the voltage holding ratio of the liquid crystal cell produced above was measured in the same manner as in Example 1, the voltage holding ratio at 16.667 ms was 97.4%, and the voltage holding ratio at 1667 ms was 64.1%. It was hot.

When the liquid crystal cell after the voltage holding ratio measurement was evaluated for relaxation of the residual charge in the same manner as in Example 1, the residual charge 50 seconds after the short circuit was 2.63 V, and the residual charge after 1000 seconds was 0.6 IV.

The liquid crystal cell for which the above measurement was completed was allowed to stand in a thermostat set at 100 ° C. for 7 days in the same manner as in Example 1, and then evaluated for the voltage holding ratio and the relaxation of residual charges. That As a result, the voltage holding ratio at 16.67 ms is 97.2%, the voltage holding ratio at 1667 ms is 57.7%, the residual charge after 50 seconds is 4.33 V, and the residual voltage after 1000 seconds. The charge was 2.62V.

[0118] (Comparative Example 2 to Comparative Example 8)

Liquid crystal alignment agents (20) to (26) were prepared as described below, and liquid crystal cells were produced in the same manner as in Example 1.

In all liquid crystal cells, the liquid crystal was uniformly vertically aligned, and no alignment defects were observed.

Using the produced liquid crystal cell, the voltage holding ratio, relaxation of residual charges, and evaluation after standing at high temperature were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2 below. (Comparative Example 2)

To the polyimide powder (C) (7.4 g) obtained in Synthesis Example 3, ΝΜΡ (41 · 9 g) was added and dissolved by stirring at 70 ° C. for 40 hours. NMP (18.5 g) and BCS (55.5 g) were added to this solution, and the mixture was stirred for 1 hour to obtain a liquid crystal aligning agent (20).

(Comparative Example 3)

3— The liquid crystal aligning agent (21) was prepared in the same manner as in Example 3 except that Py was used instead of AMP, and Py (0.81 g) was mixed with polyimide powder (C) (7.4 g). Obtained.

(Comparative Example 4)

3—A liquid crystal aligning agent (22) was obtained in the same manner as in Example 3 except that APMA was used instead of AMP.

(Comparative Example 5)

A liquid crystal aligning agent (23) was obtained in the same manner as in Example 3 except that Ml was used instead of 3-AMP.

[0119] (Comparative Example 6)

A liquid crystal aligning agent (24) was obtained in the same manner as in Example 3 except that VPy was used instead of 3-AMP.

(Comparative Example 7)

3— AP is used instead of AMP, polyimide (C) (7.4g) vs AP (1.26g) ) Was mixed in the same manner as in Example 3 except that a liquid crystal aligning agent (25) was obtained.

(Comparative Example 8)

3- Liquid crystal aligning agent (26) was obtained in the same manner as in Example 3 except that HA was used instead of AMP.

[0120] [Table 1] Polyimide ammine compound Voltage holding ratio (<½)

When making a liquid crystal cell After leaving at high temperature

6. 67ms, 6 / ms 16. 67ms 6o / ms Example 1 A 3—AMP 97. 6 67. 3 97. 8 67.2 Example 2 B 3—AMP 97. 0 53. 0 96. 7

Example 3 C 3—AMP 97. 8 63. 5 97. 7

Example 4 C 3— AMP 97. 8 64. 6 97. 9 64. 3 Example 5 C 3— AMP 97. 8 64. 1 97. 9

Example 6 C 3—AMP 97. 8 64. 8 97. 8 60.9 Example C AEP 97. 5 61. 0 97. 4

Example 8 C API 97. 3 62. 5 97. 3 68. 6 Example 9 D 3—AMP 98. 1 68- 3 98. 0 68.2 Example 10 D 3—AMP 98. 1 68. 2 98 1 68. 1 Example 11 D 3—AMP 98. 0 68. 0 98. 0 68. 1 Example 12 D 3—AMP 98. 1 68. 0 98. 1

Example 13 E 3—AMP 98. 0 68. 2 98. 1 68.3 Example 14 E 3—AMP 97. 8 67. 8 98. 0 67. 8 Example 15 F 3—AMP 97. 5 54. 1 97 7 56. 3 Example 16 G 3—AMP 97. 8 67. 8 98. 1

Example 17 E 4 AMP 98. 1 68. 6 98. 2

Example 18 E 2AMMP 98. 1 67. 2 98. 0 6 inch 7.4 Comparative example 1 A-97.4 4 64. 1 97.2 ω

卜 Comparative example 2 C 97. 8 62. 6 97. 6 63. o o ο 〇 1 Comparative example 3 C Py 97. 8 63. 6 97. 6

Comparative Example 4 c APMA 96. 6 31. 5 96. 7 31.6 Comparative Example 5 c MI 96. 9 50. 5 96. 8

Comparative Example 6 c VPy 97. 6 64. 0 97. 7

Comparative Example 7 c AP 97. 6 62. 4 97.5

Comparative Example 8 c HA 97. 3 64. 2 97.2

[0121] [Table 2] Polyimide Amine compound Residual charge relaxation (V)

When LCD cell is made (^ After hot water

50 seconds later 1000 seconds later 50 seconds later 1000 seconds later Example 1 A 3— AMP 3. 19 0. 25 3. 41 0. 46 Example 2 B 3 — AMP 2. 96 0. 17 1. 4 19 Example 3 C 3—AMP 2. 61 0. 25 1. 28 0. 30 Example 4 C 3—AMP 1. 54 0. 15 1. 39 0. 24 Example 5 C 3—AMP 2. 94 0 17 2. 21 0. 48 Example 6 C 3— AMP 3. 05 0. 17 2. 01 0. 41 Example 7 C AEP 1. 47 0. 14 1. 13 0. 23 Example 8 C API 2 99 0. 17 1. 26 0. 28 Example 9 D 3—AMP 3. 04 0. 34 2. F 6 1. 13 Example 10 D 3—AMP 3. 02 0. 25 2. 29 0. 64 Example 11 D 3— AMP 2. 77 0. 20 2. F 5 0. 62 Example 12 D 3— AMP 2. 87 0. 25 2. 54 0. 59 Example 13 E 3— AMP 3. 26 0 22 3. 34 1. 15 Example 14 E 3—AMP 3. 18 0. 30 2. 84 0. 80 Example 15 F 3 AMP 1. 94 0. 18 1. 62 0. 34 Example 16 G 3 — AMP 2. 29 0. 16 2. 38 0. 58 Example 17 E 4 AMP 3. 21 0. 26 3. 19 1. 07 Example 18 E 2A P 3. 15 0. 28 3. 17 0. 97 Comparative Example 1 A ― 2. 63 0. 61 4. 33 2.62 Comparative Example 2 C-2. 21 0. 66 3. 68 1. 88 Comparative Example 3 C Py 2. 18 0. 67 3. 72 1. 74 Comparative Example 4 C APMA 2. 50 0. 73 3. 90 2. 36 Comparative Example 5 C MI 2. 83 0. 65 3. 83 1. 85 Comparative Example 6 C VPy 3. 07 0. 60 3. 72 2.12 Comparative Example 7 C AP 2. 64 0. 55 3. 64 2. 42 Comparative Example 8 C HA 2. 97 0. 68 3. 91 2. 38 Industrial Applicability

The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film that has a high voltage holding ratio and can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. . For this reason, the liquid crystal display device obtained by this method can suppress display defects such as screen burn-in and display unevenness even when used for a long period of time, and has excellent reliability. It can utilize suitably for. Further, this liquid crystal display element can be suitably used for various display devices. The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2006-206617, filed on July 28, 2006, are hereby incorporated herein by reference. As it is incorporated.

Claims

The scope of the claims

[1] A liquid crystal aligning agent containing the following component (A) and component (B).

Component (A): a polyimide having a carboxyl group in the molecule.

[2] The component (A) is a polymer obtained by imidizing polyamic acid having a structural formula of a repeating unit represented by the following formula [1], and the amount of carboxyl groups in the polymer is 2. The liquid crystal aligning agent according to claim 1, wherein the average value relative to the repeating unit of coalescence is 0.

[Chemical 1]

1 2

In the structural formula of the repeating unit represented by the above formula [1], the component (A) is a polyamic acid having a structural formula in which part or all of the repeating unit has a unit represented by the following formula [2] 2. The liquid crystal alignment treatment according to claim 1, wherein the polymer is an imidized polymer, and the amount of carboxyl groups of the polymer is 0.;! To 3 in average value with respect to the repeating unit of the polymer. Agent.

[Chemical 2]

(Wherein R is a tetravalent organic group, R is a divalent organic group, R or R Has a carboxyl group)

[4] The liquid crystal aligning agent according to any one of claims 13 to 13, wherein the component (B) is an amine compound represented by the following formula [3].

[Chemical 3

2

[5] The liquid-crystal aligning agent according to any one of [1] to [4], wherein the component (B) is an amine compound represented by the following formula [4].

[Chemical 4

H ₂ N ^{/ X3}ヽ_X4 ^{/ X5} [ ⁴ ]

(In the formula, X is an aliphatic hydrocarbon group having a carbon number;! To 10 and a non-aromatic cyclic hydrocarbon group,

Three

X is a single bond, 〇 ΝΗ S—-SO, or divalent organic having 1 or 19 carbon atoms

4 2

It is a group. The total number of carbon atoms X and X have is 120. X has a substituent

3 4 5

/! Or even! /, A nitrogen-containing aromatic heterocycle)

[6] If the component (B) is X X and X in the above formula [4],

3 4 5

6. The liquid crystal aligning agent according to claim 5, which is an amine compound comprising a combination selected from the group consisting of:

X represents a straight-chain or branched alkyl group having a carbon number of! -10, and an unsaturated alkyl group having a carbon number of! -10.

Three

Alkyl group, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, Cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, Group consisting of a calebornene ring and adamantane ring It is one kind selected from power;

4 2

,-CO-0-.101 C001, 1 C001 NH, 1 NH— C001, 1 C001, 1 CF —

2

,-C (CF) One, one CH (〇H) —,-C (CH) One,-Si (CH) One, ten thousand Si (CH)

3 2 3 2 3 2 3

―, 1 Si (CH) ○ 1, ○ 1 Si (CH) — ○ 1, cyclopropane ring, cyclobutane

2 3 2 3 2

Ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane Ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloecosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, calebornene ring, adamantane ring, benzene ring, naphthalene Ring, tetrahydronaphthalene ring, azulene ring, indene ring, funolenic ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridin ring, Rimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, force rubazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thioline ring, phenanthrolin One selected from the group consisting of a ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an atalidine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxan ring, and a morpholine ring Or a group consisting of a plurality of combinations;

X 1S pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring

Five

, Pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, force rubazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, virazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole Ring, tinolin ring, phenant ring, ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, atalidine ring, and any of these, and may have a substituent. ! /, One selected from the group consisting of groups.

[7] The component (B) is added to 1 mol of the carboxyl group contained in the component (A) polyimide.

The liquid crystal alignment treatment agent according to any one of claims 1 to 6, which is contained at a ratio of 0.0 to 2 to 2 mole times.

[8] Claims obtained by mixing (A) component polyimide and (B) component amine compound with heating in an organic solvent or by heating after mixing; The liquid crystal aligning agent according to item.

[9] A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 8.

10. A liquid crystal display device having the liquid crystal alignment film according to claim 9.