TWI437045B - A liquid crystal alignment agent and a liquid crystal display device using the liquid crystal display device - Google Patents

Description

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

The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal alignment film and a liquid crystal display element using the same.

At present, a liquid crystal alignment film of a liquid crystal display element is mainly coated with a liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) which is a solution of a polyamidene precursor such as polylysine or a solution of a soluble polyimine. It is baked on a glass substrate and is called a polyimine-based liquid crystal alignment film.

The liquid crystal alignment film is intended for the purpose of controlling the alignment state of the liquid crystal. However, with the high definition of the liquid crystal display element, it is required to control the contrast of the liquid crystal display element to reduce or reduce the afterimage phenomenon, so that the voltage retention ratio in the liquid crystal alignment film used therein is high, or the residual charge is small when a DC voltage is applied. It is important that the mitigation of the residual charge accumulated by the DC voltage is fast.

In the polyimine-based liquid crystal alignment film, the time until the disappearance of the afterimage due to the DC voltage is short, and the polyamine or the ruthenium-containing polyamine is added to the specific structure. A liquid crystal alignment agent containing a soluble amine, which is used as a raw material having a specific diamine such as a pyridine structure, is used as a liquid crystal alignment agent of a tertiary amine (for example, refer to Patent Document 1). ), etc., is known. Further, the voltage holding ratio is high, and the time until the afterimage due to the DC voltage disappears is short, except that polyphosphoric acid or its quinone imidized polymer or the like is used, and a very small amount is selected from the molecule. A liquid crystal alignment agent containing a compound having one carboxylic acid group, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (see, for example, Patent Document 3) is known. .

However, in recent years, large-screen, high-definition liquid crystal televisions have been widely put into practical use, and the liquid crystal display elements of this use have more requirements for afterimages than the display devices that have been mainly displayed by characters or still pictures. It is rigorous and requires long-term durability in harsh environments. Therefore, the liquid crystal alignment film used therein must have higher reliability than the conventional one, and the electrical characteristics of the liquid crystal alignment film not only require good initial characteristics, but also maintain good characteristics after long-term exposure, for example, at a high temperature.

Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei.

The present invention has been made in view of the above circumstances. In other words, the problem to be solved by the present invention is to provide a liquid crystal alignment treatment of a liquid crystal alignment film which has a high voltage holding ratio and can be quickly neutralized by a residual voltage accumulated by a DC voltage even after exposure for a long time at a high temperature. Agent. Further, it is possible to provide a liquid crystal display element which is resistant to long-term use and has high reliability in a severe use environment.

In order to solve the above problems, the inventors of the present invention have further intensively studied and found that a specific polymerization is mixed in an organic solvent by a liquid crystal alignment treatment agent containing a specific polyimine and a specific amine compound. The liquid crystal alignment treatment agent obtained by the sulfimine and a specific amine compound can solve the above problems, and the present invention has been completed. In other words, the present invention has the following features as the gist.

(1) A liquid crystal alignment treatment agent comprising the following (A) component and (B) component, (A) component: a polyimine having a carboxyl group in a molecule; and (B) component: having a molecule One primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the primary amine group is bonded to an aliphatic hydrocarbon group or an amine compound of a non-aromatic cyclic hydrocarbon group.

(2) The liquid crystal alignment treatment agent according to (1), wherein the component (A) is a polymerization in which a polyamine acid obtained by a structural formula having a repeating unit represented by the following formula [1] is imidized. The amount of carboxyl groups of the polymer is 0.1 to 3, and the average value of the repeating unit of the polymer is 0.1 to 3. (wherein R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and n is a positive integer).

(3) The liquid crystal alignment treatment agent according to (1), wherein the component (A) is such that, in the structural formula of the repeating unit represented by the formula [1], a part or all of the repeating unit has the following formula [2] The polyamine acid formed by the structural formula of the unit is a ruthenium imidized polymer, and the carboxyl group amount of the polymer is 0.1 to 3, and the average value of the repeating unit of the polymer is 0.1 to 3. (wherein R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R ₃ or R ₄ has a carboxyl group).

(B) The liquid crystal alignment treatment agent according to any one of (1), wherein the component (B) is an amine compound represented by the following formula [3]. (In the formula, X ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X ₂ is a nitrogen-containing aromatic heterocyclic ring).

The liquid crystal alignment treatment agent according to any one of the above aspects, wherein the component (B) is an amine compound represented by the following formula [4]. (wherein X ₃ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a non-aromatic cyclic hydrocarbon group, and X ₄ is a single bond, -O-, -NH-, -S-, -SO ₂ - or carbon The valent organic group having 1 to 19 carbon atoms, and the total of carbon atoms of X ₃ and X ₄ is 1 to 20, and X ₅ is a nitrogen-containing aromatic heterocyclic ring which may have a substituent.

(6) The liquid crystal alignment treatment agent according to (5), wherein the component (B) is an amine selected from the group consisting of X ₃ , X ₄ and X _{5 of} the formula [4] selected from the group or ring combination described below. a compound wherein X ₃ is one linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, and a cyclopentane ring. a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, Cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring , a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring; the X ₄ system is one selected from the group consisting of a single bond, -O-, -NH-, -S-, - SO ₂ -, hydrocarbon group of 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF ₂ -, -C (CF _{3 2} -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O- _{, -O-Si (CH 3)} 2 -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane Ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring sixteen Alkane ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, decahydrogen Naphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, phenanene ring, pyrrole ring, imidazole Ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, three a azine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a metadiazonium ring, a tennoline ring, a phenanthroline ring, an anthracene ring, a quinoxaline ring, a benzothiazole ring. a group formed by a group or a combination of a phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, and a morpholine ring; X ₅ The system is selected from the group consisting of a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, Oxazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazole Alkane ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, tenox ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring An oxadiazole ring, an acridine ring, or a group in which any of these may have a substituent.

(7) The liquid crystal alignment treatment agent according to any one of (1) to (6), wherein the carboxyl group contained in the polyimine of the (A) component is 0.01 to 2 mol. The ratio of the multiple amount contains the component (B).

(A) The liquid crystal alignment treatment agent according to any one of (1), wherein the polyamine of the component (A) and the amine compound of the component (B) are heated and mixed in an organic solvent. Or the person who heats after mixing.

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

(10) A liquid crystal display element comprising the liquid crystal alignment film according to (9).

The liquid crystal alignment treatment agent of the present invention can be obtained by a relatively simple method. Further, the liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio, and a liquid crystal alignment film which is fastened by the relaxation of the residual electric charge accumulated by the direct current voltage can be obtained after prolonged exposure at a high temperature. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

[In order to implement the best form of the invention]

The liquid crystal alignment treatment agent of the present invention contains (A) a component: a polyimine having a carboxyl group in a molecule (hereinafter also referred to as a specific polyimine), and a component (B) having one in a molecule. Liquid crystal alignment of a primary amine group (-NH ₂ ) and a nitrogen-containing aromatic heterocyclic ring, and the primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group amine compound (hereinafter also referred to as a specific amine compound) Treatment agent. More specifically, it is a liquid crystal alignment treatment agent obtained by mixing a specific polyimine of the component (A) and a specific amine compound of the component (B) in an organic solvent.

In the present specification, the above-mentioned amine group (-NH ₂ ) is synonymous with a primary amine group, and is hereinafter also referred to as a primary amine group.

In the liquid crystal alignment treatment agent of the present invention, it is considered that a first-stage amine group in a specific amine compound forms a salt with a carboxyl group in a specific polyimine, or a carboxyl group or a carboxyl group in a specific polyimine. With the detachment of water or alcohol, the indoleamine bonding, or the ring-opening reaction of the quinone imine group with a ruthenium imine group in a specific polyimine. Further, depending on the firing process in the case of producing a liquid crystal alignment film, a primary amine group which forms a salt with a carboxyl group in a specific polyimine may be considered, and water may be desorbed to form a guanamine bond. As a result, regardless of the simple method of mixing the liquid crystal alignment treatment agent of the present invention, it is conceivable that the specific amine compound and the specific polyimine are effectively bonded in the liquid crystal alignment film obtained therefrom.

Further, since the nitrogen-containing aromatic heterocyclic ring in the specific amine compound has a function as an electron jumping side by the conjugated structure, the charge movement in the liquid crystal alignment film can be promoted. Further, when the liquid crystal alignment film is bonded by a static interaction of a nitrogen-containing aromatic heterocyclic ring with a carboxyl group in a specific polyimine or a hydrogen bond called a hydrogen bond, the specific polyimine is bonded. The carboxyl group in the reaction with the nitrogen-containing aromatic heterocyclic ring in the specific amine compound causes a charge shifting action. Further, since the specific amine compound is chemically bonded to a specific polyimine, the charge which moves on the nitrogen-containing aromatic heterocyclic moiety can effectively move the intramolecular or intramolecular phase of the polyimine.

According to the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention, it is considered that the relaxation of the residual charge accumulated by the direct current voltage becomes rapid, and can be maintained even after prolonged exposure at a high temperature. This feature.

<(A) component / specific polyimine >

In the present invention, the specific polyimine of the component (A) is not particularly limited as long as it is a polyimine having a carboxyl group in the molecule. The polyimine is preferably obtained by using tetracarboxylic dianhydride and a diamine as raw materials, so that the polyaminic acid formed by the structural formula of the repeating unit represented by the following formula [1] can be obtained. The polymer is preferred.

(wherein R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and n is a positive integer).

Further, in the formula [1], R ₁ and R ₂ may be the same type, or may have different types of R ₁ and R ₂ , and a plurality of different types may be combined as a repeating unit.

The specific polyimine can be usually obtained by controlling the imidization ratio of the polyamic acid to oxime imidization to less than 100%.

Further, a specific polyimine can be obtained by subjecting a polyamine contained in a repeating unit to a structural unit represented by the following formula [2] in a structural formula of a repeating unit represented by the formula [1]. Made.

(wherein R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R ₃ or R ₄ has a carboxyl group).

At this time, the ruthenium amination rate may also be 100%.

The ruthenium imidization ratio of the specific polyimine can be a high voltage retention rate, preferably 20% or more, more preferably 40% or more.

The amount of the carboxyl group in the specific polyimine (the average value of the repeating unit of the structural formula of the polyimine) can be more effectively obtained by the effect of the present invention, and the structure as the polyimine The average repeating unit is preferably 0.1 to 3, more preferably 0.3 to 2.0, and most preferably 0.5 to 1.8. The repeating unit at this time may also be a unit combining a proline group which is not imidized by hydrazine. For example, in the case of a polyimine obtained by imidating a polyamic acid formed by a repeating unit represented by the formula [1], when the ruthenium imidization ratio is less than 100%, the following may be considered. The structural combination of the formulae [5a] to [5d] comprises all the formulas [5a] to [5d] in the repeating unit in the case of the amount of the carboxyl group obtained as described above.

In the present invention, the amount of a carboxyl group (also referred to as an average value of a carboxyl group) in a specific polyimine is given by the sum of (a) P, and (ii) Q Seek.

(i) Average value for repeating units derived from the carboxyl group of proline which is not imidized by hydrazine, as a structural formula of polyimine: P

(ii) The average value of the repeating unit of the structural formula of R ₃ and R ₄ of the above formula [2] and the structural formula of the polyimine: Q ₀

Next, P in the above (i) can be obtained by the following (Formula 1) using the ruthenium imidization ratio (z). Further, the ruthenium amination ratio (z) can be determined, for example, from the measurement of the following hydrazine imidization ratio.

P=2×(1-z/100) (Equation 1)

Further, the Q of the above (ii) is the average value Q ₁ of the carboxyl group contained in R ₃ of the above formula [2], the repeating unit of the structural formula of the polyimine, and the content of R ₄ The carboxyl group is obtained as the sum of the average values Q ₂ as a repeating unit of the structural formula of the polyimine.

Each of R ₃ and R ₄ is a part or the whole of a tetracarboxylic dianhydride residue (R ₃ ) or a diamine residue (R ₄ ) which is a raw material used for producing a specific polyimine.

Therefore, in the above Q ₁ , the molar fraction of the tetracarboxylic dianhydride represented by the following formula [V1] in the total molar amount of the tetracarboxylic dianhydride used in the production of the specific polyimine is used. The following formula (3) is obtained.

Q ₁ = β ₁ × W ₁ / W ₂ (Equation 3)

Here, β ₁ represents the number of carboxyl groups contained in R ₃ , W ₁ is the molar amount of the tetracarboxylic dianhydride of the formula [V1], and W ₂ represents the total molar amount of the tetracarboxylic dianhydride. .

In addition, in the above-mentioned Q ₂ , the molar fraction of the diamine represented by the following formula [V2] in the total amount of the diamine used in the production of the specific polyimine is used, and the following formula (4) ) Seek.

[Chemical 9] H ₂ N-R ₄ -NH ₂ [V2] Q ₂ = β ₂ × W ₃ / W ₄ (Formula 4)

Here, β ₂ represents the number of carboxyl groups contained in R ₄ , W ₃ is the molar amount of the diamine of the formula [V2], and W ₄ represents the total molar amount of the diamine.

The amount of the carboxyl group is determined by the following (Formula 5).

The amount of carboxyl group in a specific quinone imine = P + Q ₁ + Q ₂ = 2 × (1 - z / 100) + β ₁ × W ₁ / W ₂ + β ₂ × W ₃ / W ₄ (Formula 5)

In the present invention, the adjustment of the amount of the carboxyl group in the specific polyimine may be (1) a method of adjusting the yield of the oxime imidization, and (2) by R ₃ or R _{4 of the} formula [2]. Any one of the methods of adjusting the ratio of the number of carboxyl groups contained in the formula and the formula (2) of the structural formula of the repeating unit shown in the formula [1]. Alternatively, the methods (1) and (2) may be used in combination.

With respect to the degree of freedom in selecting R ₁ and R _{2 in} the formula [1], the method of (1) is preferred. The method of (2) is preferred in terms of the degree of freedom in the selection of the imidization ratio of the specific polyimine. Further, in the firing process in the production of the liquid crystal alignment film, the imidization reaction is carried out to remove the specific amine compound or to reduce the possibility that the polyamidene chain is cleaved, and the method (2) is used. Preferably.

When the amount of the carboxyl group in the specific polyimine is adjusted by the method of the above (1), R ₁ and R _{2 of the} formula [1] are not particularly limited. Further, R ₁ and R ₂ may be the same type in the formula [1], or may have different types of R ₁ and R ₂ , and may be combined into several different types as repeating units.

_A specific example of R ₁ in the formula [1] is as follows.

Among them, A-6, A-16, A-18~A-22, A-25, A-37, A-38 and A-46 are polyimines with high imidization rate. It is preferred because it has high solubility in an organic solvent.

Further, when 10 mol% or more of R ₁ is an alicyclic structure or an aliphatic structure such as A-1 to A-25 and A-46, the voltage holding ratio can be improved, which is preferable. In particular, R ₁ is preferably used in combination with two kinds of liquid crystal alignment films which are selected from the group consisting of A-1, A-16 and A-19, since a charge-relaxing effect is relatively fast.

Specific examples of R _{2 in} the formula [1] are as follows.

(In B-112 and B-113, Q system means -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, -NH-)

Among these, when part or all of R ₂ is B-80 to B-101 or the like, the pretilt angle of the liquid crystal can be improved. When the liquid crystal is vertically aligned, a preferred R ₂ is a structure of B-80 to B-101 of 5 to 100 mol% (more preferably 10 to 80 mol%).

When the amount of the carboxyl group in the specific polyimine is adjusted by the method of the above (2), the structure in which either of R ₃ or R ₄ has a carboxyl group is not particularly limited. Further, the number of carboxyl groups is preferably 0 to 2 each of R ₃ and R ₄ (except that at least one of R ₃ or R ₄ has at least one carboxyl group).

The ease of synthesis of the polyimine and the availability of the raw material are preferably those having a carboxyl group in R ₄ . R ₄ having a carboxyl group is, for example, B-102 to B-113. In this case, one type of R ₄ having a carboxyl group may be used alone or two or more types may be used in combination. Further, when R ₄ has a carboxyl group, the structure of R ₃ is not particularly limited, and specifically, for example, A-1 to A-46.

<Method for producing specific polyimine]

The method for producing the specific polyimine of the component (A) used in the present invention is not particularly limited, and generally one or several tetracarboxylic acid components selected from tetracarboxylic acids and derivatives thereof are used. And reacting with a diamine component formed by one or several kinds of diamine compounds to obtain a polyaminic acid having a structural formula of a repeating unit represented by the formula [1], and subjecting the polylysine to a quinone imine Method.

At this time, the obtained polylysine can form a monomer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component of the raw material.

The tetracarboxylic acid and its derivatives referred to herein are a tetracarboxylic acid, a tetracarboxylic acid dihalide, and a tetracarboxylic dianhydride. Among them, tetracarboxylic dianhydride is preferred because it has high reactivity with a diamine compound.

Hereinafter, it is a specific example of the manufacturing method of a specific polyimine.

For example, at least one tetracarboxylic acid component selected from the group consisting of the tetracarboxylic dianhydride represented by the formula [6] and at least one diamine component selected from the diamine compound represented by the formula [7] may be contained. Polycondensation reaction is carried out in an organic solvent such as N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide or γ-butyrolactone to obtain a polyfluorene Amino acid.

Further, the R ₁ of the formula [6] is the same as the definition of the formula [1], and the specific examples of R ₁ are as described in the above-mentioned A-1 to A-46.

[19] H ₂ NR ₂ -NH ₂ [7]

Further, the R ₂ system of the formula [7] is the same as the definition of the formula [1], and the specific examples of R ₂ are as described in the above-mentioned B-1 to B-113.

In this case, the reaction temperature may be selected from any of -20 ° C to 150 ° C, preferably in the range of -5 ° C to 100 ° C.

The ratio of the total number of moles of the compound constituting the tetracarboxylic acid component to the total number of moles of the diamine compound constituting the diamine component is preferably 0.8 to 1.2. When the molar ratio is close to 1.0, the degree of polymerization of the resulting polymer becomes large.

Further, in the case where a part or all of the repeating units of the structural formula represented by the formula [1] have a polylysine having a unit of the formula [2], a tetracarboxylic acid having a carboxyl group in R ₁ may be used. An anhydride and/or a diamine having a carboxyl group in R ₂ .

A method for imidating polylysine with ruthenium by heating The imidization of a ruthenium imidization by a ruthenium imidization using a catalyst, and the imidization of a ruthenium imidization reaction at a lower temperature is less likely to cause a decrease in the molecular weight of the obtained polyimine. good.

The catalyst oxime imidization allows the polyglycolic acid to be carried out in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization is carried out, but when the temperature is too high, the molecular weight of the polyimine is lowered. The amount of the alkaline catalyst is 0.5 to 30 moles of the prolyl group, preferably 2 to 20 moles, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. When the amount of the basic catalyst or the acid anhydride is small, the reaction does not proceed sufficiently, and when it is too large, it is not easily removed completely after completion of the reaction. The basic catalyst used at this time is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has an appropriate basicity in the reaction. Further, an acid anhydride such as acetic anhydride, trimellitic anhydride, pyromellitic anhydride or the like, wherein acetic anhydride is used, is preferred because it is easily purified after completion of the reaction. The organic solvent is not particularly limited as long as it can dissolve the polylysine, and specifically, for example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-A Base-2-pyrrolidone, N-methylcaprolactone, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethylarylene, γ-caprolactone, and the like. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

The produced polyimine can be obtained by charging the above reaction solution into a poor solvent and recovering the resulting precipitate. The poor solvent to be used at this time is not particularly limited, and is, for example, methanol, acetone, hexane, butyl cellosolve, Heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The precipitated polyimine in the lean solvent can be filtered, and then dried at room temperature or under reduced pressure under normal pressure or reduced pressure to form a powder. The polyimine is also purified by re-dissolving the quinone imine powder in an organic solvent for 2 to 10 times. When the impurities cannot be completely removed by a single precipitation recovery operation, it is preferred to carry out the purification process.

The molecular weight of the specific polyimine used in the present invention is not particularly limited, and it is easy to handle, and in terms of stability of properties at the time of film formation, the weight average molecular weight is preferably 2,000 to 200,000, more preferably 4,000 to 50,000. . The molecular weight is determined by GPC (gel permeation chromatography).

<(B) component/specific amine compound>

The specific amine compound of the component (B) used in the present invention has one amine group (NH ₂ ) and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the above amine group (monoamine group 1) is bonded to An amine compound of an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

In the specific amine compound, since only one of the primary amine groups contained in the molecule is contained, the problem of causing precipitation or gelation of the polymer can be avoided in the preparation of the liquid crystal alignment treatment agent or the storage of the liquid crystal alignment agent.

The primary amine group contained in the specific amine compound is liable to form a salt or a bonding reaction with a specific polyamidiamine, and must be bonded to an aliphatic hydrocarbon or a non-aromatic ring containing no aromatic hydrocarbon in the molecule. On the hydrocarbon base.

Specific examples of the aliphatic hydrocarbon group, such as a linear alkyl group, having a branched structure An alkyl group, a hydrocarbon group having an unsaturated bond, or the like. Preferably, the carbon number is from 1 to 20, and the carbon number is preferably from 1 to 15, and the best carbon number is from 1 to 10.

Specific examples of the non-aromatic cyclic hydrocarbon group, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, Cyclodecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, ring ten A nonane ring, a cyclohexadecane ring, a tricyclohexadecane ring, a tricyclotetracosane ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring. Preferably, the ring is composed of a carbon number of 3 to 20, more preferably a ring of 3 to 15 carbon atoms, and most preferably a ring of a non-aromatic cyclic hydrocarbon group of 3 to 10 carbon atoms.

The nitrogen-containing aromatic heterocyclic ring contained in the specific amine compound is an aromatic cyclic hydrocarbon having at least one structure selected from the group consisting of the following formula [8a], formula [8b], and formula [8c]. Preferably, it is 1 to 4.

(wherein, Y ₁ is a linear or branched alkyl group having 1 to 5 carbon atoms)

Specifically, for example, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, an indazole ring, an anthracene ring, and a thiophene ring. Diazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, tinoline Ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring may have a substituent containing a hetero atom.

More preferably, the specific amine compound is an amine compound represented by the following formula [3].

(wherein X ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X ₂ is a nitrogen-containing aromatic heterocyclic ring)

In the formula [3], X ₁ is not particularly limited as long as it is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

The preferred X ₁ in the formula [3] is a divalent organic group having one type of aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. The non-aromatic cyclic hydrocarbon group is, for example, the above configuration. More preferably, it is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, or a ring. A decane ring, a cyclodecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, an adamantane ring, and the like. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms.

Further, -CH ₂ - contained in any aliphatic or non-aromatic cyclic hydrocarbon group which is not adjacent to the amine group contained in X ₁ may be -O-, -NH-, -CO-O-, -O -CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, ring Hydrocarbon group and heterocyclic ring. Further, a hydrogen atom bonded to any carbon atom may be a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, or a hydroxyl group. Replace.

Specific examples of the cyclic hydrocarbon group, such as a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a phenanene ring, a cyclopropane ring, a cyclobutane ring , cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, ring Tetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclic ring A dodecane ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like.

Further, specific examples of the heterocyclic ring include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, an indazole ring, and an anthracene ring. , thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, tenoxo ring, phenanthroline ring, hydrazine Ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like.

In the formula [3], the X ₂ is a nitrogen-containing aromatic heterocyclic ring, and in the same manner as described above, it contains at least one aromatic structure selected from the group consisting of the formula [8a], the formula [8b], and the formula [8c]. Cyclic hydrocarbons. Specifically, for example, the configuration described above. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a metadiazonium ring, The quinoxaline ring, the azepine ring, the dioxetane ring, the naphthyridine ring, the phenazine ring, and the pyridazine ring are preferred.

Further, in the case of the ease of electrostatic interaction of a nitrogen-containing aromatic heterocyclic ring with a carboxyl group in a specific polyimine or a hydrogen bond, X ₁ does not have the formula [8a] contained in X ₂ . The substituents adjacent to the formula [8b] and the formula [8c] are preferably bonded.

Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X ₂ of the formula [3] may have a substituent of a halogen atom and/or an organic group, and the organic group may further contain an oxygen atom, a sulfur atom, a nitrogen atom or the like. Hetero atom.

A preferred combination of X ₁ and X _{2 in} the formula [3], wherein X ₁ is a divalent having one aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. The organic group, X ₂ is selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a diazonium ring. Ring, quinoxaline ring, azepine ring, dioxetane ring, naphthyridine ring, phenazine ring, pyridazine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X ₂ may have a substituent of a halogen atom and/or an organic group, and the organic group may further contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

More preferably, the specific amine compound is an amine compound represented by the following formula [4].

(wherein X ₃ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a non-aromatic cyclic hydrocarbon group, and X ₄ is a single bond, -O-, -NH-, -S-, -SO ₂ - or carbon The valent organic group having 1 to 19 carbon atoms, and the total of carbon atoms of X ₃ and X ₄ is 1 to 20, and X ₅ is a nitrogen-containing aromatic heterocyclic ring which may have a substituent.

X ₃ of the formula [4] is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group. Specifically, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane. Ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring sixteen Alkane ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, decahydrogen Naphthalene ring, original norbornene ring, adamantane ring, and the like. Preferred are linear or branched alkyl groups having 1 to 10 carbon atoms, cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, cyclodecanes. Ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms.

-CH ₂ - contained in X ₃ and not in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group adjacent to the amine group, may also be -O-, -NH-, -CO-O-, -O- CO-, -CO-NH-, -NH-CO-, -CO-, S-, -S(O) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclic hydrocarbon group And a heterocyclic ring. Further, a hydrogen atom bonded to any carbon atom may be a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, or a hydroxyl group. Replace. The cyclic hydrocarbon group and the heterocyclic ring referred to herein are synonymous with those described in X _{1 of} the formula [1].

X ₄ of the formula [4] is a single bond, -O-, -NH-, -S-, -SO ₂ - or a divalent organic group having 1 to 19 carbon atoms. The bis-valent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may further contain an oxygen atom, a nitrogen atom, a sulfur atom or a ruthenium atom. The specificity of this X ₄ is as follows.

For example, a single bond, -O-, -NH-, -S-, -SO ₂ - or a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH- CO-, -CO-, -CF ₂ -, -C(CF ₃ ) ₂ -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si (CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, Cyclohexadecane ring, cycloheptadecane ring, cyclooctadecyl ring, cyclodecadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring , decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, phenanene ring, pyrrole Ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine Ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring Dialinium ring, tenoxon ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, oxazole ring, piperazine Ring, piperidine ring, dioxane ring and morpholine ring. X ₄ may contain two or more of these.

Specific examples containing two or more kinds, such as -NH-CH ₂ -, -NH-C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -S-CH ₂ -, -SC ₂ H ₄ -, -SC ₃ H ₆ -, -SC ₄ H ₈ -, -O-CH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, - NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H ₆ -, -NH-CO-C ₄ H ₈ , -CO-CH ₂ -, -CO- C ₂ H ₄ -, -CO-C ₃ H ₆ -, -CO-C ₄ H ₈ -, -CO-NH-CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH-C ₃ H ₆ -, -CO-NH-C ₄ H ₈ -, -NH-CH ₂ -CH(CH ₃ )-, -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH-C ₃ H ₆ -CH(CH ₃ )-, -NH-C ₄ H ₈ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -SC ₂ H ₄ -CH(CH ₃ )-, -SC ₃ H ₆ -CH(CH ₃ )-, -SC ₄ H ₈ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ ) -, -OC ₃ H ₆ -CH(CH ₃ )-, -OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -NH-CO-C ₂ H ₄ -CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH)- CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(OH)-C ₃ H ₆ -, -CH(OH)-C ₄ H ₈ -, -CH(CH ₂ OH)-CH ₂ -, -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH)-C ₄ H ₈ -, -NH-CH(CH ₂ OH )-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O- , -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ - , -C ₆ H ₄ -S-, and the like.

The X ₅ of the formula [4] is a nitrogen-containing aromatic heterocyclic ring, which is the same as X _{2 of the} formula [3], and therefore, X ₅ has the same meaning as X ₂ . Specifically, it is, for example, the same configuration as the above X ₂ . Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazonium ring The quinoxaline ring, the azepine ring, the dioxetane ring, the naphthyridine ring, the phenazine ring, and the pyridazine ring are preferred.

Further, in the case where the nitrogen-containing aromatic heterocyclic ring forms a salt with a carboxyl group in a specific polyimine or the ease of electrostatic interaction called a hydrogen bond, X ₄ does not have the formula [8a] contained in X ₅ . ], the carbon atom bonding adjacent to the formula [8b] and the formula [8c] is preferred.

Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X _{5 in} the formula [4] may have a substituent of a halogen atom and/or an organic group, and the organic group may further contain an oxygen atom, a sulfur atom, a nitrogen atom or the like. Hetero atom.

A preferred combination of X ₃ , X ₄ and X _{5 in} the formula [4], wherein X ₃ is a linear or branched alkyl group having a carbon number of 1 to 10, a cyclopropane ring, a cyclobutane ring or a cyclopentane ring. a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, The original norbornene ring, the adamantane ring, the X ₄ system is a single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O -Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, -CH(OH)-, -NH-CH ₂ -, -NH- C ₂ H ₄ -, -NH-C ₃ H ₆ -, -NH-C ₄ H ₈ -, -S-CH ₂ -, -SC ₂ H ₄ -, SC ₃ H ₆ -, -SC ₄ H ₈ - , -O-CH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -NH-CO-CH ₂ -, -NH-CO-C ₂ H ₄ -, - NH-CO-C ₃ H ₆ -, -NH-CO-C ₄ H ₈ -, -CO-CH ₂ -, -CO-C ₂ H ₄ -, -CO-C ₃ H ₆ -, -CO-C ₄ H ₈ -, -CO-NH-CH ₂ -, -CO-NH-C ₂ H ₄ -, -CO-NH-C ₃ H ₆ -, -CO-NH-C ₄ H ₈ -, -NH- CH ₂ -CH(CH ₃ )-, -NH-C ₂ H ₄ -CH(CH ₃ )-, -NH-C ₃ H ₆ -CH(CH ₃ )-, -NH-C ₄ H ₈ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -SC ₂ H ₄ -CH(CH ₃ )-, - SC ₃ H ₆ -CH(CH ₃ )-, -SC ₄ H ₈ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -OC ₂ H ₄ -CH(CH ₃ )- , -OC ₃ H ₆ -CH(CH ₃ )-, -OC ₄ H ₈ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -NH-CO-C ₂ H _4- CH(CH ₃ )-, -NH-CO-C ₃ H ₆ -CH(CH ₃ )-, -NH-CO-C ₄ H ₈ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(OH)-C ₃ H ₆ -, -CH(OH)-C ₄ H ₈ -, -CH(CH ₂ OH)-CH ₂ - , -CH(CH ₂ OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-C ₃ H ₆ -, -CH(CH ₂ OH)-C ₄ H ₈ -, -NH-CH (CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O -, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -, -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, Cyclodecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene Ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, pheneneene ring, X ₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine Ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, quinoxaline ring, azepine ring, dioxetane ring, naphthyridine ring, phenanthrene Pyrazine ring, pyridazine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X ₅ may have a halogen atom and/or an organic group, and the organic group may also contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

In preferred X _3, X ₄ composition formula [4] and of X _5, X ₃ is selected based 1 to 5 carbon atoms, a straight-chain or branched-chain alkyl group, a cyclopropane ring, cyclobutane ring, cyclopentane Ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, X ₄ is a linear or branched alkyl group selected from a single bond, a carbon number of 1 to 5, -O-, -NH- , -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S(O) ₂ -, -CH(OH)-, -NH -CH ₂ -, -S-CH ₂ -, -O-CH ₂ -, -OC ₂ H ₄ -, -NH-CO-CH ₂ -, -CO-CH ₂ -, -CO-NH-CH ₂ - , -NH-CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH ( CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, - S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N(CH ₃ ) ₂ )-, -C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ - , -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, Ring, a naphthalene ring, a tetrahydronaphthalene ring, azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a phenanthrene phenalene (phenalene) cycloalkyl, X ₅ is selected from pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring , pyrimidine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, quinoxaline ring, azepine ring, dioxetane ring, naphthyridine ring, phenazine ring , pyridazine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X ₅ may have a substituent of a halogen atom and/or an organic group, and the organic group may further contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

Formula [4] in a better X _3, X ₄ and X ₅ in combination, the system X ₃ is selected from C 1-4 straight-chain or branched-chain alkyl group having 1 to 5, the cyclopropane ring, cyclobutane ring, a cyclopentyl An alkane ring, a cyclohexane ring, X ₄ is a linear or branched alkyl group selected from a single bond, having a carbon number of 1 to 5, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CH(OH)-, -NH-CH ₂ -, -S-CH ₂ -, -O-CH ₂ -, -NH-CO-CH ₂ -, -CO-CH ₂ -, -CO-NH-CH ₂ -, -NH-CH ₂ -CH(CH ₃ )-, -S-CH ₂ -CH(CH ₃ )-, -O-CH ₃ -CH(CH ₃ )-, -NH-CO-CH ₂ -CH(CH ₃ )-, -CH(OH)-CH ₂ -, -CH(OH)-C ₂ H ₄ -, -CH(CH ₂ OH)-CH ₂ -, -NH-CH(CH ₂ OH)-CH ₂ -, -CO-NH-CH(CH ₂ OH)-CH ₂ -, -NH-CO-CH(CH ₂ OH)-CH ₂ -, -CO-CH(CH ₂ OH)-CH ₂ -, -S-CH(CH ₂ OH)-CH ₂ -, -O-CH(CH ₂ OH)-CH ₂ -, -CH(N( CH ₃ ) ₂ )-, C ₆ H ₄ -O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H _4- CO-, -C ₆ H ₄ -CH ₂ - , -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, raw borneol An olefin ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, and X ₅ is selected from the group consisting of pyrrole rings and microphones. An azole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a metadiazonium ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X ₅ may have a halogen atom and/or an organic group, and the organic group may also contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

The preferred combination of X ₃ , X ₄ and X _{5 in} the formula [4], wherein X ₃ is a linear or branched alkyl group having a carbon number of 1 to 5, a cyclobutane ring, a cyclohexane ring, and X ₄ It is selected from the group consisting of a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH(OH)-, a benzene ring, a naphthalene ring, an anthracene ring, An anthracene ring, X ₅ is selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X ₅ may have a substituent of a halogen atom and/or an organic group, and the organic group may further contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

Specific examples of the specific amine compound used in the present invention are, for example, compounds of M1 to M156.

Preferred compounds are, for example, M6~M8, M10, M16~M21, M31~M36, M40~M45, M47~M57, M59~M63, M68, M69, M72~M82, M95~M98, M100~M103, M108~M125 , M128~M137, M139~M143, M149~M156. More preferred are, for example, M6~M8, M16~M20, M32~M36, M40, M41, M44, M49~M54, M59~M62, M68, M69, M75~M82, M100~M103, M108~M112, M114~M116, M118~M121, M125, M134~M136, M139, M140, M143, M150, M152~M156.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is usually obtained by mixing a specific polyimine of the above component (A) with a specific amine compound of the component (B) in an organic solvent. The specific amine compound to be mixed may be one type or a combination of several types.

The mixing method may use a reaction solution (a solution of a specific polyimine) which is subjected to hydrazylation of a polylysine which is a precursor of a specific polyimine, but usually, for example, a specific polyimine obtained by refining A method in which a powder is dissolved in a solution of an organic solvent and a specific amine compound is added. The organic solvent to be used at this time is not particularly limited as long as it is a solution which can dissolve a specific polyimine. This is specifically described below.

For example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactone, 2-pyrrolidone, N-B Pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 1,3-dimethyl-imidazoledione , dipentene, ethyl pentanone, methyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4 - Hydroxy-4-methyl-2-pentanone and the like. These solvents may be used in combination of two or more kinds.

When a specific polyimine is dissolved in an organic solvent, heating may be performed for the purpose of promoting dissolution of a specific polyimine. When the heating temperature is too high, the molecular weight of the polyimine is lowered, so that the temperature is preferably 30 to 100 ° C, more preferably 50 to 90 ° C. The concentration of the solution of the specific polyimine is not particularly limited. When it is easily mixed with a specific amine compound, the concentration of the specific polyimine in the solution is preferably from 1 to 20% by mass, more preferably from 3 to 15% by mass. Good, best with 3~10% by mass.

The specific amine compound may be a solution which can be directly added to the solvent-soluble polyimine, and is preferably added in a suitable solvent in a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is, for example, a solvent of the above solvent-soluble polyimine.

It is preferred to heat and mix the specific polyimine and the specific amine compound in an organic solvent, or to heat after mixing. By heating, the ratio of the specific amine compound which has been linked in the state of the liquid crystal alignment agent to the specific polyimine is increased, and the liquid crystal alignment film is formed to more effectively perform the electrophoretic movement. The temperature during the above heating is preferably from 10 to 100 ° C, more preferably from 20 to 80 ° C.

The addition amount of the specific amine compound can more effectively obtain the effect of the present invention without impairing the safety of the liquid crystal alignment treatment agent, and the carboxyl group contained in 1 mol of the specific polyimine. It is better to use 0.01~2 moles, more preferably 0.05~1 moles, and the best is 0.08~0.8 moles.

The liquid crystal alignment treatment agent of the present invention may contain, in addition to the specific polyimine and the specific amine compound, a solvent or a compound which improves the film thickness uniformity or surface smoothness when the liquid crystal alignment treatment agent is applied. A compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate. The other components may be added during the mixing of the specific polyimine and the specific amine compound, or may be added after mixing the solutions.

Specific examples of the solvent for improving the film thickness uniformity or the surface smoothness are as follows.

For example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Acetate, propylene glycol monomethyl ether, propylene glycol - 3-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetic acid Ester monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate , butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, acetic acid Ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropane Ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol , 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1- Monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, lactic acid A solvent having a low surface tension such as n-propyl ester, n-butyl lactate or isoamyl lactate.

These solvents may be used in one or a mixture of several. When the solvent is used, it is preferably 5 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent, and more preferably 20 to 60% by mass.

A compound which improves film thickness uniformity or surface smoothness, for example, a fluorine-based surfactant, a polyoxyalkylene-based surfactant, a nonionic surfactant, and the like.

More specifically, for example, Yevtton EF301, EF303, EF352 (made by Don Kembroke Guz), Mekkafa Valley (transliteration) F171, F173, R-30 (Greater Japan) Ink company), Floraton (transliteration) FC430, FC431 (manufactured by Sumitomo 3M), Assaka Karton (transliteration) AG710, Safron (transliteration) S-382, SC101, SC102, SC103, SC104, SC105 , SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (A) contained in the liquid crystal alignment agent.

Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate are a compound containing a functional decane or an epoxy group-containing compound as described below.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxycarbamidopropyltriethylenetriamine, N-trimethoxycarbamidopropyltriethylenetriamine, 10-trimethoxycarbamimidyl-1,4,7- Triazanonane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxycarbamido-3,6-diazaindolyl acetate, 9-Triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide)-3 -Aminopropyltrimethoxydecane, N-double (oxidation) Alkyl-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibrominated neopentyl glycol Diglycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl-m-xylenediamine , 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodi Phenylmethane and the like.

When the compound is added, the specific polyimine component contained in 100 parts by mass of the liquid crystal alignment agent is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the amount is less than 0.1 part by mass, the effect of improving the adhesion is not obtained, and when it is more than 30 parts by mass, the alignment of the liquid crystal becomes poor.

In the liquid crystal alignment treatment agent of the present invention, in addition to the above, a polymer component other than the specific polyamidene or a dielectric constant or conductivity of the liquid crystal alignment film may be added within a range that does not impair the effects of the present invention. A dielectric or conductive material for the purpose of electrical changes such as properties, and a crosslinkable compound for the purpose of improving film hardness or density when forming a liquid crystal alignment film.

The concentration of the solid component in the liquid crystal alignment treatment agent of the present invention can be appropriately changed by the film thickness of the intended liquid crystal alignment film, but a coating film having no defects is formed, and it can be obtained as a suitable film thickness of the liquid crystal alignment film. It is preferably 1 to 20% by mass, more preferably 2 to 10% by mass.

<Liquid alignment film. Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used for liquid crystal alignment film after being applied to a substrate and then subjected to rubbing treatment or alignment treatment such as light irradiation, or in the case of vertical alignment or the like without alignment treatment. . In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used. In particular, when a substrate for forming an ITO electrode or the like for liquid crystal driving is used, it is preferable in terms of simplification of the process. Further, in the reflective liquid crystal display device, an opaque material such as a germanium wafer can be used only on one substrate, and in this case, a material such as alumina that reflects light can be used.

The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, there are generally methods by screen printing, off-line printing, flexible printing, inkjet, and the like. Other coating methods include dipping, roll coating, slit coating, rotators, etc., depending on the purpose.

After the liquid crystal alignment treatment agent is applied to the substrate and fired, the solvent can be evaporated at 50 to 200 ° C, preferably 80 to 150 ° C by a heating method such as a hot plate to form a coating film. The thickness of the coating film after firing is extremely unfavorable in terms of power consumption of the liquid crystal display element. When it is too thin, the reliability of the liquid crystal display element is lowered, preferably 5 to 300 nm, and 10 to 100 nm. The liquid crystal is horizontally aligned or tilted, and the film after firing is treated by rubbing or polarized ultraviolet rays.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above method, and a liquid crystal cell is produced by a conventional method to form a liquid crystal display element.

In the case of producing a liquid crystal cell, a substrate on which a pair of liquid crystal alignment films are formed is used, and a spacer is spread on a liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is inside, and the other substrate is bonded. A method in which a liquid crystal is injected under reduced pressure to seal, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and sealed. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

As described above, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be used for a large-screen, high-definition liquid crystal television or the like.

In the following, the invention will be described in more detail by way of examples, but the invention is not limited thereto.

[Examples]

The abbreviation used in the examples is as follows.

(tetracarboxylic dianhydride) BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic acid Dihydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

(Diamine) p-PDA: p-phenylenediamine PCH: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene DBA: 3,5-diamino DADPA benzoic acid: 4,4'-diaminodiphenylamine

(specific amine compound) 3-AMP: 3-aminomethylpyridine AEP: 4-(2-aminoethyl)pyridine API: 1-(3-aminopropyl)imidazole 4-AMP: 4-amino group Methylpyridine 2AMMP: 2-(Aminomethyl)-5-methylpyrazine

(Comparative compound) MI: 2-methylimidazole Py:pyridine VPy: 2-vinylpyridine APMA: N-(3-aminopropyl)-N-methylaniline AP: 3-aminopyridine HA: n-hexylamine

(organic solvent) NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve GBL: γ-butyrolactone

<Measurement of the molecular weight of the polyimine] The molecular weight of the polyimine of the synthesis example is a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Shodex Co., Ltd., manufactured by Shodex Co., Ltd. Columns (KD-803, KD805) were measured as described below.

Column temperature: 50 ° C Dissolution: N, N'-dimethylformamide (with lithium bromide monohydrate (LiBr-H ₂ O) 30 mmol / L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol / L , tetrahydrofuran (THF) is 10ml / L) as an additive)

Flow rate: 1.0 mL / min

Standard sample for calibration line preparation: TSK standard polyethylene oxide (molecular weight: about 9,000, 150,000, 100,000, 30,000) made by Dongsuo Co., Ltd., and polyethylene glycol (produced by Polymer Labrador) The molecular weight is about 12,000, 4,000, 1,000).

<Measurement of ruthenium iodization>

The ruthenium imidization ratio of polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was added to the NMR sample tube (the NMR sample tube starter manufactured by Kusano Scientific Co., Ltd.) 5), 0.53 ml of dihydrogenated dimethyl hydrazine (DMSO-d ₅ , 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve. This solution was subjected to a proton NMR of 500 MHz by a NMR measuring instrument (INW-ECA500) manufactured by JEOL. The ruthenium imidization ratio is determined by using a proton derived from a structure which has not changed before and after imidization as a reference proton, and the peak value of the proton is used, and the NH group derived from proline which is present in the vicinity of 9.5 to 10.0 ppm is used. The cumulative value of the proton peak is obtained by the following formula.

Ruthenium amination rate (%) = (1-α.x/y) x 100

In the above formula, x is the cumulative value of proton peaks derived from the NH group of proline, y is the integrated value of the peak from the reference proton, and α is the pair 1 The ratio of the number of the reference protons for the protons of the NH group of the proline in the case of poly-proline (0% imidization).

<Method for determining the amount of carboxyl groups>

It is obtained by the method described above.

(Synthesis Example 1)

BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol), PCH (10.3 g, 27 mmol) were mixed in NMP (100.1 g), and the reaction was carried out at 40 ° C for 3 hours, and then CBDA (4.1 g) was added. 21 mmol) and NMP (52.2 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (130.3 g) and diluting it to 6 mass%, acetic anhydride (15.6 g) and pyridine (12.1 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (1600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine had a ruthenium iodide ratio of 54%, a number average molecular weight of 18,300, and a weight average molecular weight of 45,300. The amount of the carboxyl group of the polyimine was 0.92 for the repeating unit.

(Synthesis Example 2)

BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol), PCH (10.3 g, 27 mmol) were mixed in NMP (100.0 g), and the reaction was carried out at 40 ° C for 3 hours, and then CBDA (4.1 g) was added. 21 mmol) and NMP (52.2 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (55.4 g), and after diluting to 6 mass%, acetic anhydride (2.7 g) and pyridine (2.1 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 70 ° C. hour. The reaction solution was poured into methanol (660 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyimine had a hydrazine imidization ratio of 25%, a number average molecular weight of 19,500, and a weight average molecular weight of 47,800. The amount of the carboxyl group of the polyimine was 1.50 for the repeating unit.

(Synthesis Example 3) BODA (150.1 g, 600 mmol), DBA (60.9 g, 400 mmol), PCH (152.2 g, 400 mmol) were mixed in NMP (1290 g), and the reaction was carried out at 80 ° C for 5 hours, and then CBDA was added ( 38.8 g, 198 mmol) and NMP (320 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (600.2 g) and diluting it to 6 mass%, acetic anhydride (63.9 g) and pyridine (49.6 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (7700 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyimine had a ruthenium iodide ratio of 57%, a number average molecular weight of 23,000, and a weight average molecular weight of 80,200. The amount of the carboxyl group of the polyimine was 1.36 for the repeating unit.

(Synthesis Example 4) BODA (50.1 g, 600 mmol), DBA (60.9 g, 400 mmol), and PCH (152.2 g, 400 mmol) were mixed in NMP (1290 g), and the reaction was carried out at 80 ° C for 5 hours, and then CBDA was added ( 38.8 g, 198 mmol) and NMP (320 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (300.1 g), and after diluting to 6 mass%, acetic anhydride (32.0 g) and pyridine (24.8 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 90 ° C. hour. The reaction solution was poured into methanol (3900 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyimine had a hydrazine imidation ratio of 69%, a number average molecular weight of 22,700, and a weight average molecular weight of 69,300. The amount of the carboxyl group of the polyimine was 1.12 for the repeating unit.

(Synthesis Example 5) BODA (150.1 g, 600 mmol), DBA (60.9 g, 400 mmol), PCH (152.2 g, 400 mmol) were mixed in NMP (1290 g), and the reaction was carried out at 80 ° C for 5 hours, and then CBDA was added ( 38.8 g, 198 mmol) and NMP (320 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (101.2 g) and diluting it to 6 mass%, acetic anhydride (21.3 g) and pyridine (16.5 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 90 ° C. hour. The reaction solution was poured into methanol (1300 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (E). The polyimine had a ruthenium iodide ratio of 81%, a number average molecular weight of 20,400, and a weight average molecular weight of 63,000. The amount of the carboxyl group of the polyimine was 0.88 for the repeating unit.

(Synthesis Example 6) BODA (16.0 g, 64 mmol), DADPA (11.9 g, 60 mmol), and PCH (9.7 g, 26 mmol) were mixed in NMP (126.4 g), and the reaction was carried out at 40 ° C for 3 hours, and then CBDA was added. (3.8 g, 19 mmol) and NMP (40 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (50.3 g) and diluting it to 4% by mass, acetic anhydride (5.0 g) and pyridine (3.9 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 50 ° C. hour. The reaction solution was poured into methanol (910 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (F). The polyimine had a hydrazine imidization ratio of 25%, a number average molecular weight of 22,200, and a weight average molecular weight of 69,000. The amount of the carboxyl group of the polyimine was 1.50 for the repeating unit.

(Synthesis Example 7) BODA (7.5 g, 30 mmol), DADPA (1.6 g, 8.0 mmol), DBA (2.4 g, 16 mmol), and PCH (6.1 g, 16 mmol) were mixed in NMP (53.2 g) at 40 ° C After the reaction was carried out for 3 hours, CBDA (1.9 g, 10 mmol) and NMP (25 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (60.4 g) and diluting it to 5% by mass, acetic anhydride (6.3 g) and pyridine (4.9 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 90 ° C. hour. The reaction solution was poured into methanol (880 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (G). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 21,100, and a weight average molecular weight of 64,000. The amount of the carboxyl group of the polyimine was 1.38 for the repeating unit.

(Synthesis Example 8) TDA (9.0 g, 30 mmol), DBA (3.2 g, 21 mmol), and p-PDA (1.0 g, 9.0 mmol) were mixed in NMP (74.7 g), and the reaction was carried out at room temperature for 24 hours. A polyaminic acid solution was prepared. After adding NMP to the polyamic acid solution (80.0 g) and diluting it to 6 mass%, acetic anhydride (29.1 g) and pyridine (13.5 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 35 ° C. hour. The reaction solution was poured into methanol (710 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (H). The polyimine had an oxime imidization ratio of 91%, a number average molecular weight of 11,300, and a weight average molecular weight of 20,700. The amount of the carboxyl group of the polyimine was 0.88 for the repeating unit.

(Example 1) NMP (41.9 g) was added to the polyimine powder (A) (7.4 g) obtained in Synthesis Example 1, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. 3-AMP 7.5% by mass NMP solution (14.8 g) (as 3-AMP, 1.11 g), NMP (3.7 g), and BCS (55.5 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (1) is obtained.

<Preparation of Liquid Crystal Cell> The liquid crystal alignment treatment agent (1) obtained above was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C for 5 minutes, and then circulated at 210 ° C. The film was fired in an oven for 1 hour to prepare a liquid crystal alignment film having a film thickness of 100 nm. Two sheets of the liquid crystal alignment film were used, and a 6 μm spacer was spread on one of the liquid crystal alignment films, and then a sealant was printed thereon, and after bonding, the sealant was cured to prepare an empty cell. Liquid crystal MLC-6608 (manufactured by Meru Valley Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a nematic liquid crystal cell.

When the liquid crystal cell is observed by a polarizing microscope, the liquid crystal is uniformly aligned vertically, and there is no alignment defect.

<Evaluation of Voltage Retention Rate> A voltage of 4 V was applied to the liquid crystal cell prepared above at a temperature of 80 ° C for 60 μs, and the voltage after 16.67 ms and after 1667 ms was measured, and how much voltage was held as a voltage holding ratio was calculated. As a result, the voltage holding ratio of 16.67 ms was 97.6%, and the voltage holding ratio of 1667 ms was 67.3%.

In addition, the measurement was carried out using a VHR-1 voltage retention ratio measuring device manufactured by Toyo Diguyika Co., Ltd., and was measured at a setting of Voltage: ±4 V, Pulse Width: 60 μs, Flame Period: 16.67 ms or 1667 ms.

<Evaluation of Residual Charge Relaxation> A DC voltage of 10 V for 30 minutes was applied to the liquid crystal cell after the measurement of the voltage holding ratio described above, and a short circuit occurred for one second, and then a potential generated in the liquid crystal cell was measured for 1800 seconds. The potential change at this time is as shown in Fig. 1. As a result, the residual charge after 50 seconds after the short circuit was 3.19 V, and the residual charge after 1000 seconds was 0.25 V. Further, the measurement system used was a 6254 liquid crystal physical property evaluation device manufactured by Toyo Digunik Co., Ltd.

<Evaluation after High Temperature Placement> The liquid crystal cell after completion of the above measurement was allowed to stand in a thermostat set at 100 ° C for 7 days, and the same measurement was performed. As a result, the voltage retention of 16.67 ms was 97.8%, the voltage retention of 1667 ms was 67.2%, the residual charge after 50 seconds was 3.41 V, and the residual charge after 1000 seconds was 0.46 V.

(Examples 2 to 18) The liquid crystal alignment agents (2) to (18) were prepared as described below, and a liquid crystal cell was produced in the same manner as in Example 1 and evaluated. In all of the unit cells, the liquid crystals are uniformly aligned vertically, with no alignment defects. The evaluation results are shown in Tables 1 and 2 below.

(Example 2) A liquid crystal alignment treatment agent (2) was prepared in the same manner as in Example 1 except that the polyimine powder (B) obtained in Synthesis Example 2 was used.

(Example 3) A liquid crystal alignment treatment agent (3) was prepared in the same manner as in Example 1 except that the polyimine powder (C) obtained in Synthesis Example 3 was stirred at 70 ° C for 40 hours. ).

(Example 4) NMP (30.6 g) was added to the polyimine powder (C) (5.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. To this solution, a 10-AMP 10 mass% NMP solution (5.4 g) (as 3-AMP, 0.38 g), NMP (8.1 g), and BCS (40.5 g) was added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (4) is obtained.

(Example 5) NMP (30.6 g) was added to the polyimine powder (C) (5.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to dissolve. To this solution, a 3-AMP 7 mass% NMP solution (5.4 g) (as 3-AMP, 0.38 g), NMP (8.1 g), and BCS (40.5 g) was added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (5) is obtained.

(Example 6) NMP (41.9 g) was added to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to dissolve. To this solution, a 5-AMP 5 mass% NMP solution (7.4 g) (as 3-AMP, 0.37 g), NMP (11.1 g), and BCS (55.5 g) were added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (6) is obtained.

(Example 7) NMP (41.9 g) was added to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. A solution of 8.5% by mass of NMP (14.8 g) (as AEP, 1.26 g), NMP (3.7 g), and BCS (55.5 g) of AEP was added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment. Agent (7).

(Example 8) NMP (41.9 g) was added to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to dissolve. 10% by mass of NMP solution (12.5 g) (as API, 1.26 g), NMP (5.9 g), and BCS (55.5 g) of API were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment. Agent (8).

(Example 9) NMP (57.8 g) was added to the polyimine powder (D) (10.2 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. 3-AMP 3 mass% NMP solution (10.2 g) (as 3-AMP, 0.31 g), NMP (6.8 g), and BCS (85.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (9) is obtained.

(Example 10) NMP (57.8 g) was added to the polyimine powder (D) (10.2 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. To this solution, a 5-AMP 5 mass% NMP solution (10.2 g) (as 3-AMP, 0.51 g), NMP (6.8 g), and BCS (85.0 g) was added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (10) is obtained.

(Example 11) NMP (57.8 g) was added to the polyimine powder (D) (10.2 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. A 3-AMP 7 mass% NMP solution (10.2 g) (as 3-AMP, 0.71 g), NMP (6.8 g), and BCS (85.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (11) is obtained.

(Example 12) NMP (57.8 g) was added to the polyimine powder (D) (10.2 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 40 hours to dissolve. To this solution, a 10-AMP 10 mass% NMP solution (10.2 g) (as 3-AMP, 1.0 g), NMP (6.8 g), and BCS (85.0 g) was added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (12) is obtained.

(Example 13) NMP (42.0 g) was added to the polyimine powder (E) (8.6 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 40 hours to dissolve. A 3-AMP 7 mass% NMP solution (8.6 g) (as 3-AMP, 0.6 g), NMP (2.4 g), and BCS (71.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (13) is obtained.

(Example 14) NMP (42.0 g) was added to the polyimine powder (E) (8.6 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 40 hours to dissolve. 3-AMP 10 mass% NMP solution (8.6 g) (as 3-AMP, 0.86 g), NMP (2.4 g), and BCS (71.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (14) is obtained.

(Example 15) NMP (41.9 g) was added to the polyimine powder (F) (7.4 g) obtained in Synthesis Example 6, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. To this solution, a 10-AMP 10 mass% NMP solution (11.1 g) (as 3-AMP, 1.11 g), NMP (7.4 g), and BCS (55.5 g) were added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (15) is obtained.

(Example 16) NMP (41.9 g) was added to the polyimine powder (G) (7.4 g) obtained in Synthesis Example 7, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. To this solution, a 5-AMP 5 mass% NMP solution (7.4 g) (as 3-AMP, 0.37 g), NMP (11.1 g), and BCS (55.5 g) were added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (16) is obtained.

(Example 17) NMP (42.0 g) was added to the polyimine powder (E) (8.6 g) obtained in Synthesis Example 5, and the mixture was stirred at 80 ° C for 40 hours to dissolve. 4-AMP 7 mass% NMP solution (8.6 g) (as 4-AMP, 0.6 g), NMP (2.4 g), and BCS (71.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (17) is obtained.

(Example 18) NMP (42.0 g) was added to the polyimine powder (E) (8.6 g) obtained in Synthesis Example 7, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. 2AMMP of a 7 mass% NMP solution (8.6 g) (as 2AMMP, 0.6 g), NMP (2.4 g), and BCS (71.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment. Agent (18).

(Comparative Example 1) NMP (41.9 g) was added to the polyimine powder (A) (7.4 g) obtained in Synthesis Example 1, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (18.5 g) and BCS (55.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (19). Using this liquid crystal alignment treatment agent, a liquid crystal cell was produced and evaluated in the same manner as in Example 1.

When the liquid crystal cell was observed with a polarizing microscope, the liquid crystal was uniformly aligned vertically, and there was no alignment defect.

<Evaluation of Voltage Retention Rate> When the voltage holding ratio was measured in the same manner as in Example 1 in the liquid crystal cell produced as described above, the voltage holding ratio of 16.67 ms was 97.4%, and the voltage holding ratio of 1667 ms was 64.1%.

<Evaluation of Residual Charge Relaxation> When the liquid crystal cell after the measurement of the voltage holding ratio was evaluated in the same manner as in Example 1, when the residual charge relaxation was evaluated, the residual charge after 50 seconds after the short circuit was 2.63 V, after 1000 seconds. The residual charge was 0.61V.

<Evaluation after High Temperature Placement> The liquid crystal cell in which the above measurement was completed was placed in a thermostat set at 100 ° C for 7 days in the same manner as in Example 1, and then the voltage holding ratio and the residual charge relaxation were evaluated. As a result, the voltage retention of 16.67 ms was 97.2%, the voltage retention of 1667 ms was 57.7%, the residual charge after 50 seconds was 4.33 V, and the residual charge after 1000 seconds was 2.62 V.

(Comparative Example 2 to Comparative Example 8) Liquid crystal alignment treatment agents (20) to (26) were prepared as described below, and a liquid crystal cell was produced in the same manner as in Example 1.

In all liquid crystal cells, the liquid crystals are uniformly aligned vertically, with no alignment defects.

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

(Comparative Example 2) NMP (41.9 g) was added to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (18.5 g) and BCS (55.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (20).

(Comparative Example 3) A liquid crystal alignment treatment agent was prepared in the same manner as in Example 3 except that Py was used instead of 3-AMP, and Py (0.81 g) was mixed with the polyimine powder (C) (7.4 g). twenty one).

(Comparative Example 4) A liquid crystal alignment treatment agent (22) was obtained in the same manner as in Example 3 except that APMA was used instead of 3-AMP.

(Comparative Example 5) A liquid crystal alignment treatment agent (23) was obtained in the same manner as in Example 3 except that MI was used instead of 3-AMP.

(Comparative Example 6) A liquid crystal alignment treatment agent (24) was obtained in the same manner as in Example 3 except that VPy was used instead of 3-AMP.

(Comparative Example 7) A liquid crystal alignment treatment agent was prepared in the same manner as in Example 3 except that AP was used instead of 3-AMP, and AP (1.26 g) was mixed with the polyimine powder (C) (7.4 g). 25).

(Comparative Example 8) A liquid crystal alignment treatment agent (26) was obtained in the same manner as in Example 3 except that HA was used instead of 3-AMP.

[industrial use value]

The liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio, and after a long time exposure at a high temperature, a liquid crystal alignment film which is relaxed by the residual electric charge accumulated by the direct current voltage can be obtained. Therefore, the liquid crystal display element obtained thereby can suppress the display failure of the screen burnt or the display spot even if it is used for a long period of time, and can be suitably used for a large-screen, high-definition liquid crystal television or the like for the reliability. Moreover, the liquid crystal display element can be suitably used for various display devices.

In addition, the entire contents of the specification, the claims, the drawings and the abstract of the Japanese Patent Application No. 2006-206617 filed on Jul.

[Fig. 1] is a graph showing a change in potential when the relaxation of residual charge is evaluated in the first embodiment.

Claims (10)

A liquid crystal alignment treatment agent comprising the following components (A) and (B), (A) component: a polyimine having a carboxyl group in a molecule, and (B) a component having one level in a molecule An amine group and a nitrogen-containing aromatic heterocyclic ring, and the primary amine group is bonded to an amine compound of an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the component (A) is a polymer obtained by imidating a polyamic acid formed by a structural formula having a repeating unit represented by the following formula [1]. The average amount of carboxyl groups of the polymer is 0.1 to 3 for the repeating unit of the polymer. (wherein R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and n is a positive integer). The liquid crystal alignment treatment agent of the first aspect of the invention, wherein the component (A) is such that, in the structural formula of the repeating unit represented by the formula [1], a part or all of the repeating unit has the following formula [2] The polyamic acid formed by the structural formula of the unit is a ruthenium imidized polymer, and the carboxyl group amount of the polymer is 0.1 to 3 averages of the repeating unit of the polymer. (wherein R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R ₃ or R ₄ has a carboxyl group). The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the component (B) is an amine compound represented by the following formula [3]. (In the formula, X ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X ₂ is a nitrogen-containing aromatic heterocyclic ring). The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the component (B) is an amine compound represented by the following formula [4]. (wherein X ₃ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a non-aromatic cyclic hydrocarbon group, and X ₄ is a single bond, -O-, -NH-, -S-, -SO ₂ - or carbon The valent organic group having 1 to 19 carbon atoms, and the total of carbon atoms of X ₃ and X ₄ is 1 to 20, and X ₅ is a nitrogen-containing aromatic heterocyclic ring which may have a substituent. The liquid crystal alignment treatment agent according to claim 5, wherein the component (B) is an amine compound obtained by selecting each of X ₃ , X ₄ and X _{5 of} the formula [4] from the group or ring combination described below. Wherein X ₃ is a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or the like. Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, ring a pentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a tricyclohexadecane ring, a tricyclotetracosane ring, a group consisting of a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring; the X ₄ system is one selected from the group consisting of a single bond, -O-, -NH-, -S-, -SO ₂ - a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF ₂ -, -C(CF ₃ ) ₂ -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane Ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane Ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecyl ring, cyclodecadecane ring, cycloecosane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane Alkane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, phenanene ring , pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, Pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, tenoxo ring, phenanthroline ring, anthracene ring, quinoxaline ring a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, and a morpholine ring, or a combination thereof the group; X ₅ is one selected based pyrrole ring, an imidazole ring, an oxazole ring, Oxazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine Ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, tenoxo ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, A phenothiazine ring, an oxadiazole ring, an acridine ring, and any one of these may have a group of substituents. The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the carboxyl group contained in the polyimine of the (A) component contains the component (B) in a ratio of 0.01 to 2 moles. . The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the polyamine of the component (A) and the amine compound of the component (B) are heated, mixed, or mixed in an organic solvent, and then heated. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 8. A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 9 of the patent application.