KR101671659B1 - Liquid crystal aligning agent - Google Patents

Abstract

(식 (1) 중, X 는 산소 원자 또는 황 원자이고, Y¹ 및 Y² 는 각각 독립적으로, 단결합, -O-, -S-, -OCO-, 또는 -COO- 이고, R¹ 및 R² 는 각각 독립적으로 탄소수 1 ∼ 3 의 알킬렌기이다)An object of the present invention is to provide a liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film having less scratches and scratches on the film surface during rubbing treatment, good alignment of liquid crystal, high voltage holding ratio of the liquid crystal cell and low ion density. A liquid crystal alignment treatment agent containing any one of a polyimide precursor or a polyimide obtained by reacting a diamine component and a tetracarboxylic acid derivative, wherein the diamine component comprises a diamine represented by the following formula (1) Treatment agent.

(1), X is an oxygen atom or a sulfur atom, Y ¹ and Y ² are each independently a single bond, -O-, -S-, -OCO-, or -COO-, and R ¹ and And R < ² > each independently represent an alkylene group having 1 to 3 carbon atoms)

Description

[0001] LIQUID CRYSTAL ALIGNING AGENT [0002]

The present invention relates to a liquid crystal alignment treatment agent for producing a liquid crystal alignment film. To a liquid crystal alignment treatment agent for use in a liquid crystal alignment film produced through a rubbing treatment process.

The liquid crystal alignment film is a film for controlling the alignment direction of the liquid crystal molecules to be constant in a liquid crystal display element or a phase difference plate using a polymerizable liquid crystal.

As a simple method of producing a liquid crystal alignment film, there is a method of forming a polymer film such as polyimide on a substrate and rubbing the surface with a cloth, so-called rubbing treatment, and it is widely used industrially today.

In the rubbing process, there is a problem that dust generated due to scraping of the liquid crystal alignment film and scratches generated in the liquid crystal alignment film degrade the display quality, so that rubbing resistance is one of the characteristics required for the liquid crystal alignment film.

As a method of obtaining a liquid crystal alignment film in which rubbing shrinkage or rubbing scratches do not easily occur, a method of adding various additives to a polyimide or polyimide precursor is known (see, for example, Patent Documents 1 and 2). In addition, a polyimide structure having good rubbing resistance has also been proposed (see, for example, Patent Documents 3 and 4).

In some applications of liquid crystal display elements in recent years, rubbing treatment tends to be rubbed more strongly. This is for the purpose of making the alignment state of the liquid crystal more uniform and stronger by performing strong rubbing treatment. Therefore, the requirement for rubbing resistance of the liquid crystal alignment film is also increased.

Japanese Patent Application Laid-Open No. 7-120769 Japanese Patent Application Laid-Open No. 9-146100 Japanese Patent Application Laid-Open No. 2008-90297 Japanese Patent Application Laid-Open No. 9-258229

An object of the present invention is to provide a liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film excellent in rubbing resistance and rubbing scratches and having excellent rubbing resistance.

The inventors of the present invention have conducted intensive studies in order to achieve the above object, and have found out a novel liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film excellent in rubbing resistance, and the present invention is based on this finding, and has the following points.

1. A liquid crystal alignment treatment agent containing any one of a polyimide precursor or a polyimide obtained by reacting a diamine component and a tetracarboxylic acid derivative, characterized in that the diamine component contains a diamine represented by the following formula (1) Liquid crystal alignment treatment agent.

[Chemical Formula 1]

(1), X is an oxygen atom or a sulfur atom, Y ¹ and Y ² are each independently a single bond, -O-, -S-, -OCO-, or -COO-, and R ¹ and And R < ² > each independently represent an alkylene group having 1 to 3 carbon atoms)

2. The liquid crystal alignment treatment agent as described in 1 above, wherein in Formula (1), -R ¹ -Y ¹ - and -R ² -Y ² - have the same structure.

3. The liquid crystal alignment treatment agent according to 1 or 2 above, wherein, in formula (1), Y ¹ and Y ² are single bonds.

4. The liquid crystal alignment treatment agent according to any one of 1 to 3 above, wherein X in the formula (1) is an oxygen atom.

Wherein the tetracarboxylic acid derivative is a tetracarboxylic acid dianhydride, a tetracarboxylic acid monoanhydride, a tetracarboxylic acid, a dicarboxylic acid dialkyl ester, or a dicarboxylic acid chloride dialkyl ester. The liquid crystal alignment treatment agent according to any one of the preceding claims.

6. The liquid crystal alignment treating agent according to any one of 1 to 5 above, further comprising a fluorinated surfactant, a silicone surfactant or a nonionic surfactant.

7. The liquid crystal alignment treating agent according to any one of 1 to 6 above, which further contains a functional silane-containing compound or an epoxy group-containing compound.

8. The liquid crystal alignment treatment agent according to any one of 1 to 7 above, wherein the solid content concentration in the liquid crystal alignment treatment agent is 1 to 20 mass% with respect to the total amount (100 mass%) of the liquid crystal alignment treatment agent.

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

10. A liquid crystal display element having the liquid crystal alignment film as described in 9 above.

11. Bisaminophenyl or bisaminophenoxyalkylurea represented by the following formula (1-7), formula (1-8), formula (1-b) or formula (1-c)

(2)

(1-b), R ¹² and R ²² each independently represent an alkylene group having 1 to 3 carbon atoms, and R ¹³ and R ²³ each independently represent an alkylene group having 1 to 3 carbon atoms, Lt; / RTI >

12. Bisaminophenyl or bisaminophenoxyalkylurea represented by the following formulas (1-9) to (1-11).

(3)

By using the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film having less scratches and scratches on the film surface at the time of rubbing treatment and having good alignment property of liquid crystal. The liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of the present invention has a high voltage maintaining ratio and a low ion density of the liquid crystal cell, so that a liquid crystal display device of high quality can be produced.

≪ Specific diamine compound &

The liquid crystal alignment treatment agent of the present invention is characterized by using a specific diamine represented by the following formula (1) as a diamine component containing a polyimide precursor or polyimide such as polyamic acid or polyamic acid ester, .

[Chemical Formula 4]

X 1 is an oxygen atom or a sulfur atom, Y ¹ and Y ² are each independently a single bond, -O-, -S-, -OCO-, or -COO-, R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms.

In the formula (1), when X is an oxygen atom, it is urea, and when it is a sulfur atom, thiourea (hereinafter, urea and thiourea groups may be collectively referred to as (thio) urea).

Both oxygen and sulfur atoms are highly electronegative. On the nitrogen atom, there are two hydrogen atoms having high donor. Therefore, the (thio) urea group is relatively strongly self-assembled by the non-covalent bond with the two hydrogen atoms of the other (thio) ureas. In the present invention, X in the formula (1) is preferably an oxygen atom. This is considered to be due to the fact that the urea structure is stronger than the thiourea structure due to the higher oxygen atom and therefore self-aggregation when the oxygen atom and the sulfur atom are compared with each other.

In the liquid crystal alignment treatment agent of the present invention, a (thio) urea group derived from a specific diamine having a specific structure of the formula (1) is contained in the polymer chain. Therefore, rubbing resistance is improved by electrostatic interaction between (thio) urea babies present in a polymer chain having a specific structure. In this respect, the present invention is different from the method of improving the rubbing resistance by connecting the chains of the polymer, which are generally used in the field of liquid crystal alignment films, with a crosslinking agent.

In the formula (1), R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms, and the structure may be either a linear chain or a branched chain.

Specific examples thereof include methylene, ethylene, trimethylene, 1-methylethylene and 2-methylethylene groups. From the viewpoint of the orientation and rubbing resistance of the liquid crystal, a structure having a free-rotation site as possible and a small steric hindrance is preferable, and methylene, ethylene and trimethylene are particularly preferable.

In the formula (1), Y ¹ and Y ² each independently represent a single bond, -O-, -S-, -OCO-, or -COO-. Also, with respect to the structures of Y ¹ and Y ² , from the viewpoints of alignment and rubbing resistance of the liquid crystal, a structure which is as flexible as possible and has a small steric hindrance is preferable, and a single bond, -O-, or -S- is preferable.

The structure between the (thio) urea group and the benzene ring is preferably symmetrical with respect to the (thio) urea group in the sense that a film with a high film density is formed to form a stronger liquid crystal alignment film, and -R ¹ -Y ¹ - and -R ² -Y ² - have the same structure.

Among the specific diamines represented by the formula (1), those represented by the following formulas (1-a) to (1-c) are preferable.

[Chemical Formula 5]

(In the formula (1-a), R ¹¹ and R ²¹ are each an alkylene group having 1 to 3 carbon atoms and the same carbon number)

[Chemical Formula 6]

(In the formula (1-b), R ¹² and R ²² represent an alkylene group having 1 to 3 carbon atoms,

(7)

(In the formula (1-c), R ¹³ and R ²³ each independently represent an alkylene group having 1 to 3 carbon atoms)

In the formula (1), the bonding position of the amino group on the benzene ring is not particularly limited, but from the viewpoint of the orientation of the liquid crystal, it is preferably a 3-aminophenyl structure or a 4-aminophenyl structure, Structure. Specifically, the formula (1) is preferably any one of the following formulas (1-1), (1-2), and (1-3) ) to be.

[Chemical Formula 8]

In the formulas (1-1), (1-2) and (1-3), Y ¹ , Y ² , R ¹ and R ² have the same meanings as in the formula (1).

The following formulas (1-4) to (1-15) are given as concrete examples of the formula (1).

[Chemical Formula 9]

The compounds of the formulas (1-7) to (1-11) are novel compounds originally provided in the present invention, and of course, polyimide precursors or polyimides using the compounds are novel compounds. The diamine compounds other than the formulas (1-7) to (1-11) are known compounds, and the polyimide precursor or polyimide using these diamine compounds is a novel compound.

<Synthesis method of diamine>

The diamine represented by the formula (1) can be synthesized, for example, as follows. The diamine compound represented by the formula (1) of the present invention is composed of an aniline skeleton, a spacer portion (R ¹ , R ² ), a linking group (Y ¹ , Y ² ) and a (thio) urea group, However, it can be synthesized by, for example, the method described below.

[Chemical formula 10]

X 1 is an oxygen atom or a sulfur atom, Y ¹ and Y ² are each independently a single bond, -O-, -S-, -OCO-, or -COO-, R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms. The bonding position of the amine group on the benzene ring is not particularly limited.

(11)

The diamine compound represented by the formula (1) of the present invention can be produced by reacting a dinitro compound represented by the corresponding formula (2) (wherein R ¹ , R ² , Y ¹ , Y ² , 1), and then reducing the nitro group to convert it to an amino group. The method of reducing the dinitro compound is not particularly limited and is usually carried out by using palladium-carbon, platinum oxide, Raney-nickel, iron, tin chloride, platinum black, rhodium- There is a method in which reduction is carried out by a reaction using hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride or the like in a solvent such as ethyl, toluene, tetrahydrofuran, dioxane or alcohol.

The synthesis method of the dinitro compound represented by the formula (2) is not particularly limited and can be synthesized by an arbitrary method, and specific examples thereof can be synthesized by, for example, a method represented by the following scheme (3) .

[Chemical Formula 12]

In the scheme (3), the dinitro compound represented by the formula (2) is a nitrobenzene compound (?), (? ') And (thio) carbonyl compound (collectively a carbonyl compound and a thiocarbonyl compound) beta] in an organic solvent in the presence of an alkali.

In the nitrobenzene compounds (a) and (a '), R ¹ , R ² , Y ¹ and Y ² are the same as in the formula (1), and the amino group represented by NH ₂ is a hydrochloride salt (NH ₂揃 HCl) Or the like may be formed. As specific examples thereof, nitrobenzylamine, or a hydrochloride thereof; 2- (nitrophenyl) ethylamine, or a hydrochloride thereof; 3- (nitrophenyl) propylamine, or a hydrochloride thereof; And the like. The substitution position of the nitro group on the benzene ring is appropriately selected to be the substitution position at which the aimed diamine compound is obtained. The compounds shown here are examples, and are not particularly limited.

(Thio) carbonyl compound (X), X is the same as in the formula (1), and Z is an organic group having 1 to 2 substituents. (Thio) carbonyl compound (?) Include, for example, phosgene, thiophosgene, diphenyl carbonate, diphenyl thiocarbonate, bis (nitrophenyl) carbonate, bis (nitrophenyl) thiocarbonate, dimethyl carbonate, dimethyl thiocarbonate , Diethyl carbonate, diethyl thiocarbonate, ethylene carbonate, ethylene thiocarbonate, 1,1'-carbonylbis-1H-imidazole, and 1,1'-thiocarbonylbis-1H-imidazole . Further, carbon oxide (carbon monoxide or carbon dioxide) may be used instead of the carbonyl compound (?). The compounds shown here are examples, and are not particularly limited.

In the scheme (3), in order to obtain a compound having a symmetric structure centering on (thio) urea group, the nitrobenzene compound (?) And (? ') Need to be the same. In order to obtain an asymmetric compound, The equimolar reaction of the compound (α) with respect to the (thio) carbonyl compound (β) may be followed by adding the nitrobenzene compound (α ') having a structure different from that of the nitrobenzene compound (α).

Examples of the alkali include basic organic compounds such as triethylamine, diisopropylethylamine and DMAP (4-N, N-dimethylaminopyridine); Inorganic alkaline compounds such as sodium hydroxide and potassium carbonate; Metal hydrides such as sodium hydride; And the like. The compounds shown here are examples, and are not particularly limited.

Examples of the organic solvent include solvents that do not affect the reaction, specifically, aromatic solvents such as toluene and xylene; Aliphatic hydrocarbon solvents such as hexane and heptane; Halogen-based solvents such as dichloromethane and 1,2-dichloroethane; Ether-based solvents such as tetrahydrofuran and 1,4-dioxane; Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide; May be used singly or in combination. The amount of these used is arbitrary.

The diamine thus synthesized can be used as a raw material for polyamides or polyureas in addition to polyimide precursors and polyimides such as polyamic acid and polyamic acid ester described later, and these polymers can be used as materials for various electronic materials .

<Polyimide precursor or polyimide>

The polyimide precursor contained in the liquid crystal alignment treatment agent of the present invention is obtained by a reaction of a diamine component containing the specific diamine as essential and a tetracarboxylic acid derivative.

The diamine component for obtaining the polyimide precursor may be only a specific diamine represented by the formula (1), or may be used in combination with other diamines.

When used in combination with other diamines, the proportion of the specific diamine represented by the formula (1) can be any value. In order to obtain sufficient rubbing resistance, the proportion of the specific diamine (100 mol%) is preferably 10 mol% , More preferably not less than 30 mol%, still more preferably not less than 50 mol%. On the other hand, from the viewpoint of optimization of the pretilt angle and reduction of accumulated charges, the proportion of the specific diamine component is preferably 90 mol% or less in the total diamine component.

The diamine used in combination with the specific diamine represented by the formula (1) is not particularly limited, but can be represented by the following formula (4).

[Chemical Formula 13]

In the formula (4), R ⁵ represents a divalent organic group, and R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group.

Specific examples of R &lt; ⁵ &gt; include the following divalent organic groups.

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

Formula [B-112], and expression of the [B-113], 2 of Q are, each independently, -COO-, -OCO-, -CONH-, -NHCO- , -CH 2 -, -O-, -CO-, or -NH-.

When the part or whole of R ⁵ in the formula (4) is the formula [B-80] to the formula [B-101] or the like, the pretilt angle of the liquid crystal can be increased.

When the liquid crystal is vertically aligned, it is preferable that R ⁵ in the above formula (4) used in combination is a diamine having a structure of any of the formulas [B-80] to [B-101]. When such a diamine is used, the content of the diamine in the total diamine is preferably 5 to 90 mol%, more preferably 10 to 80 mol%. On the other hand, when the pretilt angle is reduced, R ⁵ in the formula (4) is preferably selected from the group consisting of any one of the formulas [B-1] to [B-79] and [B-102] Structure is preferably used in combination. In addition, at least one of R ³ and R ⁴ in the formula (4) is preferably a monovalent organic group, more preferably a methyl group.

The tetracarboxylic acid derivative to be reacted with the specific diamine component represented by the formula (1) or the specific diamine component represented by the formula (1) containing the diamine represented by the formula (4) is not particularly limited. The tetracarboxylic acid derivative in the present invention includes tetracarboxylic acid dianhydride, tetracarboxylic acid monoanhydride, tetracarboxylic acid, dicarboxylic acid dialkyl ester (represented by the following formula (5-d)), And a dicarboxylic acid chloride dialkyl ester (represented by the following formula (5-e)), and the reaction is not limited thereto as far as the reaction with the diamine proceeds.

The tetracarboxylic acid derivatives are represented by the following formulas (5-a) to (5-e), and R ⁷ represents an alkyl group. Specific examples of R ⁶ include the following [A-1] to [A-47].

[Chemical Formula 29]

(30)

(31)

(32)

(33)

Among them, when R ⁶ is a group represented by the formula [A-6], the formula [A-16], the formula [A-18] to the formula [A-22], the formula [A- The tetracarboxylic acid derivative [A-38] is preferable because polyimide having a high imidization rate has high solubility in an organic solvent. When 10 mol% or more, preferably 20 mol% or more of the tetracarboxylic acid derivative to be used is R ⁶ having an alicyclic structure or aliphatic structure such as the formulas [A-1] to [A-25] Is preferable because the voltage holding ratio is improved. When R ⁶ is a tetracarboxylic acid derivative selected from the group consisting of the formula [A-1], the formula [A-16] and the formula [A-19] among these alicyclic structures or aliphatic structures, The charge relaxation is preferable because a liquid crystal alignment film with a higher speed can be obtained.

On the other hand, an aromatic tetracarboxylic acid derivative of 10 mol% or more, preferably 20 mol% or more, based on the total amount of the tetracarboxylic acid derivative to be used is preferable because it can improve the liquid crystal alignability and reduce the accumulated charge .

As a method for obtaining a polyimide precursor or polyimide by reacting the above-mentioned diamine component (hereinafter, simply referred to as a diamine) with a tetracarboxylic acid derivative component (hereinafter, simply referred to as a tetracarboxylic acid derivative) . The case where a tetracarboxylic acid dianhydride is used is described below as an example.

The polymerization reaction method of the tetracarboxylic acid derivative and the diamine used in the production of the liquid crystal alignment treatment agent of the present invention is not particularly limited. Generally, a polyamic acid can be obtained by a polymerization reaction by mixing in an organic solvent. Polyamic acid esters can be obtained by esterifying a carboxylic acid group with polyamic acid using a known esterifying agent. The resulting polyamic acid and polyamic acid ester can be converted into polyimide by dehydration ring closure.

As a method for mixing the tetracarboxylic acid derivative and the diamine component in an organic solvent, a method in which a solution in which a diamine is dispersed or dissolved in an organic solvent is stirred to disperse or dissolve the tetracarboxylic acid derivative component in that state or in an organic solvent A method of adding a diamine to a solution in which a tetracarboxylic acid derivative is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid derivative and a diamine, and the like. When at least one of the tetracarboxylic acid derivative component and the diamine is composed of a plurality of compounds, the plural kinds of components may be polymerized in advance in a mixed state, or they may be subjected to polymerization reaction sequentially.

The temperature at which the tetracarboxylic acid derivative and the diamine are polymerized in an organic solvent is generally 0 to 150 占 폚, preferably 5 to 100 占 폚, more preferably 10 to 80 占 폚. When the temperature is high, the polymerization reaction is terminated quickly, but when the temperature is too high, a polymer having a high molecular weight may not be obtained. The polymerization reaction can be carried out at an arbitrary injection concentration. However, if the injection concentration is too low, a high molecular weight polymer can not be obtained well. If the injection concentration is too high, the viscosity of the reaction solution becomes too high, , Preferably from 1 to 50 mass%, and more preferably from 5 to 30 mass%. The polymerization is carried out at a high concentration in the initial stage, and then an organic solvent may be added. Herein, the injection concentration refers to the concentration of the total mass of the tetracarboxylic acid dianhydride component and the diamine component.

The organic solvent used in the reaction is not particularly limited as long as it dissolves the resulting polyamic acid and polyamic acid ester (hereinafter sometimes referred to as polyamic acid (ester)). Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Sulfoxide,? -Butyrolactone, and the like. These may be used alone or in combination. In addition, even a solvent which does not dissolve the polyamic acid (ester) may be used in combination with the solvent insofar as the produced polyamic acid (ester) does not precipitate.

In addition, the water content in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyamic acid (ester). Therefore, it is preferable to use an organic solvent which is dehydrated and dried as much as possible.

The molar ratio of the tetracarboxylic acid derivative to the diamine used in the polymerization reaction for obtaining the polyamic acid is preferably 1: 0.8 to 1: 1.2, and the molecular weight of the obtained polyamic acid becomes closer to 1: It grows. If the molecular weight of the polyamic acid (ester) is too small, the strength of the coating film obtained therefrom may become insufficient. Conversely, if the molecular weight of the polyamic acid (ester) is excessively high, the viscosity of the liquid crystal alignment treatment agent produced there becomes excessively high, The workability at the time of formation and the uniformity of the coating film may be deteriorated. Therefore, the weight average molecular weight of the polyamic acid (ester) used in the liquid crystal alignment treatment agent of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000.

In order to obtain a polyamic acid in the present invention, a tetracarboxylic acid derivative and a diamine are used. As the diamine, a specific diamine represented by the above formula (1) and a diamine represented by the above formula (4) are optionally used. When a diamine represented by the formula (4) is used, the tetracarboxylic acid derivative preferably used is a compound represented by the formula (5) wherein R ^{6 in} the formula (5-a) A-2], [A-16], A [A-18], A-19, A- As the diamine of the formula (4) used in combination with a specific diamine, the diamine of the formula (A-32), the formula [A-35], the formula [A- B- ⁵ , and the formula [B-6], the formula [B-7], the formula [B-8], the formula [B-16] B-45], the formula [B-40], the formula [B-44], the formula [B-45] B-62], the formula [B-62], the formula [B-56], the formula [B- B-84], the formula [B-80], the formula [B-80] [B-87], the formula [B-93], the formula [B-104], the formula [B-114], the formula [B-115] or the formula [B-118] are used. Among them, as the tetracarboxylic acid derivative, R ⁶ in the formula (5-a) is preferably a tetracarboxylic acid derivative represented by the formula [A-1], the formula [A- A-32] is preferable, and as the diamine of the formula (4), R &lt; 1 &gt; B- ⁵ , and the formula [B-7], the formula [B-8], the formula [B-17], the formula [B-20], the formula [B- B-84], the formula [B-32], the formula [B-61], the formula [B- , The formula [B-85], the formula [B-104], the formula [B-114], the formula [B-115] or the formula [B-118].

The polyamic acid thus obtained may be represented by the repeating unit represented by the following formula (6), and the polyamic acid ester may be represented by the following formula (7).

(34)

R ^a , R ^b and R ^c in the formulas (6) and (7), when a diamine represented by the formula (1) is used as a group derived from a diamine represented by the formula (1) ^a and R ^b are hydrogen and R ^c is -phenylene- Y ¹ -NH-CX-HN-R ² -Y ² -phenylene-, and when a diamine represented by formula (4) is used, R ^a is R ³ , R ^b is R ⁴ , and R ^c is R ⁵ . R ⁶ has the same meaning as R ⁶ in the tetracarboxylic acid derivative represented by the above formulas (5-a) to (5-e). R in the formula (7) is a group derived from the esterifying agent used.

The polyamic acid or polyamic acid ester thus obtained may be used in the liquid crystal alignment treatment agent of the present invention in this state, but it may be used as a dehydrated ring-closed polyimide. However, depending on the structure of the polyamic acid (ester), insolubilization by imidization reaction may be difficult to use in a liquid crystal alignment treatment agent. In this case, all of the amic acid (ester) groups in the polyamic acid (ester) may be imidized to such an extent that proper solubility can be maintained without being imidized.

The imidization reaction in which the polyamic acid (ester) is dehydrocondensed is generally a thermal imidization in which a solution of a polyamic acid is heated in that state, and a chemical imidization in which a catalyst is added to a solution of a polyamic acid (ester) The chemical imidization in which the imidization reaction progresses is not preferable because the molecular weight of the obtained polyimide is not sufficiently lowered.

The chemical imidization can be carried out by stirring the polyamic acid (ester) in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature in this case is -20 to 250 ° C, preferably 0 to 180 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the polyamic acid (ester), and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the polyamic acid (ester). If the amount of the basic catalyst or the acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it is difficult to completely remove the catalyst after completion of the reaction.

Examples of the basic catalyst used for imidization include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferred since it has a basicity suitable for proceeding the reaction.

As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy. As the organic solvent, a solvent used in the above-mentioned polyamic acid polymerization reaction can be used. The imidization rate by chemical imidization can be controlled by controlling the amount of catalyst, reaction temperature, and reaction time.

In the polyimide solution thus obtained, the added catalyst remains in the solution. Therefore, in order to use the polyimide solution in the liquid crystal alignment treatment agent of the present invention, the polyimide solution is poured into a stirred poor solvent, It is preferable that the precipitate is recovered and used. Examples of the poor solvent used for the precipitation and recovery of polyimide include, but are not limited to, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene and benzene. The precipitated polyimide may be recovered by filtration and washing by pouring into a poor solvent, and then recovered as a powder at room temperature or under reduced pressure or by heating and drying. The polyimide may be purified by dissolving the powder in a good solvent again and repeating the operation for reprecipitation 2 to 10 times. When the impurities can not be removed by one settling recovery operation, it is preferable to repeat this purifying step. As a poor solvent for carrying out the repeated purification process, for example, three or more poor solvents such as alcohols, ketones and hydrocarbons may be mixed or used sequentially, which is preferable because the purification efficiency is further increased.

The polyamic acid (ester) may also be subjected to precipitation and purification by the same procedure. When the solvent used for the polymerization of the polyamic acid is not contained in the liquid crystal alignment treatment agent, or when unreacted monomer components or impurities are present in the reaction solution, this precipitation recovery and purification may be carried out.

The imidization rate of the polyimide contained in the liquid crystal alignment treatment agent of the present invention is not particularly limited. It may be set to an arbitrary value in consideration of the solubility of the polyimide. The molecular weight of the polyimide contained in the liquid crystal alignment treatment agent of the present invention is not particularly limited. However, if the molecular weight of the polyimide is too small, the strength of the resulting coating film may be insufficient. Conversely, if the molecular weight of the polyimide is excessively large, The viscosity of the liquid crystal alignment treatment agent becomes excessively high, and the workability at the time of forming a coating film and the uniformity of the coating film may be deteriorated. Accordingly, the weight average molecular weight of the polyimide used in the liquid crystal alignment treatment agent of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention contains any one of the polyimide precursors or polyimides obtained as described above and is usually a coating liquid in which these polymers are dissolved in an organic solvent. The polymer contained in the liquid crystal alignment treatment agent of the present invention may contain, in addition to the polyimide precursor or polyimide, a polymer having another structure. The organic solvent contained in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it dissolves the polymer contained therein.

Specific examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, There may be mentioned, for example, norbornylidene, lauridone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide,? -Butyrolactone and 1,3-dimethyl-imidazolidinone. These may be used alone or in combination of two or more.

In addition, even a solvent that does not dissolve the polymer alone can be mixed with the liquid crystal alignment treatment agent of the present invention as far as the polymer does not precipitate. Particularly, it is preferable to use ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1- Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- A solvent having a low surface tension such as dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid N-propyl ester, lactic acid N-butyl ester, lactic acid Iso- , It is known that the uniformity of the coating film on the substrate is improved by mixing them. Therefore, these solvents may be used alone or in combination.

In the liquid crystal alignment treatment agent of the present invention, a solvent having a low surface tension is preferably used. The amount of the solvent to be used is preferably 5 to 80 mass%, more preferably 20 to 80 mass% 60% by mass.

The liquid crystal alignment treatment agent of the present invention may contain various additives in addition to the above polymer and organic solvent.

Examples of the additive for improving film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant.

(Manufactured by TOKEM PRODUCTS CO., LTD.), MEGA PARK F171, F173, R-30 (manufactured by Dainippon Ink & Chemicals, Inc.), FLORAD FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.) SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Kagaku Co., Ltd.), and the like. The use ratio of these surfactants 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 polymer component contained in the liquid crystal alignment treatment agent.

Specific examples of the additive for improving the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (3-aminopropyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When these compounds are added, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may contain, in addition to the above, a dielectric substance or a conductive substance for the purpose of changing electrical properties such as dielectric constant and conductivity of a polymer component other than the polymer, a liquid crystal alignment film, , And a crosslinkable compound for increasing the hardness and density of the film when the liquid crystal alignment film is used.

The concentration of the solid content in the liquid crystal alignment treatment agent of the present invention can be appropriately changed in accordance with the film thickness of the liquid crystal alignment film to be desired. However, the reason that the film thickness without defects can be formed and an appropriate film thickness can be obtained as the liquid crystal alignment film Is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass.

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without rubbing treatment, light irradiation or the like, or with a liquid crystal alignment film without vertical alignment treatment after application and baking on a substrate. Here, the substrate to be used is not particularly limited as long as it is a substrate having high transparency. A glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used, and a substrate on which an ITO electrode or the like for liquid crystal driving is formed is used Is preferable from the viewpoint of simplification of the process. In a reflection type liquid crystal display device, an opaque material such as a silicon wafer may be used only on one side of the substrate. In this case, a material that reflects light such as aluminum can also be used as the electrode in this case.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. As other coating methods, there are dip, roll coater, slit coater, spinner and the like, and they may be used depending on the purpose.

The baking of the substrate coated with the liquid crystal alignment treatment agent can be carried out at any temperature of 100 to 350 ° C, preferably 150 to 300 ° C, more preferably 180 to 250 ° C. When polyamic acid or polyamic acid ester is contained in the liquid crystal alignment treatment agent, the conversion rate to polyimide varies depending on the firing temperature. However, the liquid crystal alignment treatment agent of the present invention does not necessarily require 100% imidization. For this reason, the firing time can be set to any time. If the firing time is too short, display defects may occur due to the influence of the residual solvent, and therefore, the firing time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes .

When the thickness of the coated film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 To 100 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.

The liquid crystal display element of the present invention is obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

For example, a pair of substrates on which liquid crystal alignment films are formed are prepared, and spacers are dispersed on the liquid crystal alignment films of the substrates of the individual substrates to make the liquid crystal alignment film surfaces inward, and the substrates of the other substrates are bonded A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed by sealing. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

As described above, the liquid crystal display element manufactured using the liquid crystal alignment treatment agent of the present invention is excellent in reliability and can be preferably used for a liquid crystal television of high precision on a large screen.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited thereto.

Abbreviations used in the following Examples and Comparative Examples are as follows.

BABU: 1,3-bis (4-aminobenzyl) urea

BAPU: 1,3-bis (4-aminophenethyl) urea

DA-3: 1,3-bis (3-aminobenzyl) urea

DA-4: 1- (4-aminobenzyl) -3- (4-aminophenetyl) urea

DA-5: 1,3-bis (2- (4-aminophenoxy) ethyl) urea

DA-6: 1,3-bis (3- (4-aminophenoxy) propyl) urea

DA-7: 1,5'-bis (4-aminophenoxy) pentane

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

PMDA: pyromellitic acid dianhydride

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

CA-4: 1,3-Dicarbomethoxy-2,4-bis (chlorocarbonyl) cyclobutane

CA-5: 2,5-dicarbomethoxyterephthalic acid dichloride

p-PDA: Para-phenylenediamine

In the synthesis examples, &quot; ¹ H-NMR &quot; means a nuclear magnetic resonance spectrum of a hydrogen atom in a molecule.

[Synthesis Example 1]

Synthesis of 1,3-bis (4-aminophenetyl) urea [BAPU]

(35)

(52.5 g, 259 mmol) and bis (4-nitrophenyl) carbonate [D] (37.53 g, 123 m) in a four-necked flask under nitrogen atmosphere (74.90 g, 740 mmol) and 4-N, N-dimethylaminopyridine (3.01 g, 24.7 mmol) were added to the mixture, and THF (tetrahydrofuran) And the mixture was stirred with a mechanical stirrer. The reaction was followed by HPLC (high performance liquid chromatography). After completion of the reaction, the reaction solution was added to pure water (9 L) and stirred for 30 minutes. Thereafter, filtration was performed, and the filtrate was washed with pure water (1 L) to obtain a crude product of a white solid. The resultant white solid was dispersed and washed with methanol (488 g) using an ultrasonic device, followed by filtration and drying to obtain a dinitro compound [E] as a white solid (Yield 42.3 g, yield: 96%).

A mixture of compound [E] (42.32 g, 118 mmol), 5% palladium carbon (5% Pd / C) (4.23 g), and 1,4-dioxane (2031 g) , And the mixture was stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC and after completion of the reaction, the catalyst was filtered with celite. Thereafter, the solvent of the liquid was distilled off under reduced pressure to obtain the crude product of a white solid. 2-propanol (85 g) was added to the obtained crude product, followed by dispersion washing with an ultrasonic device, followed by filtration and drying to obtain a white solid diamino compound [BAPU] (Yield 31.9 g, yield: 91% .

[Synthesis Example 2]

Synthesis of 1,3-bis (4-aminobenzyl) urea [BABU]

(36)

Nitrobenzylamine hydrochloride [F] (25.00 g, 133 mmol), bis (4-nitrophenyl) carbonate [D] (19.20 g, 63.1 mmol) in THF 750 g) was added, and triethylamine (38.32 g, 379 mmol) and 4-N, N-dimethylaminopyridine (1.54 g, 12.6 mmol) were added thereto and stirred with a mechanical stirrer. The reaction was followed by HPLC, and after completion of the reaction, the reaction solution was added to pure water (4.5 L) and stirred for 30 minutes. Thereafter, filtration was carried out, and the filtrate was washed with pure water (500 ml) to obtain a crude product of a pale yellowish white solid. The obtained pale yellowish white solid was dispersed and washed with methanol (300 g) using an ultrasonic device, followed by filtration and drying to obtain a pale yellowish white solid dinitro compound [G] (Yield 19.01 g, yield: 91%).

After replacing the mixture of compound [G] (16.00 g, 48.4 mmol), 5% palladium carbon (5% Pd / C) (1.60 g) and 1,4-dioxane (800 g) , And the mixture was stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC and after completion of the reaction, the catalyst was filtered with celite. Thereafter, the solvent of the liquid was distilled off under reduced pressure to obtain a crude product of a white solid. 2-Propanol (128 g) was added to the obtained crude product, followed by dispersion washing with an ultrasonic device, followed by filtration and drying to obtain a diamino compound [BABU] as a white solid (Yield 12.19 g, yield 93%). .

[Synthesis Example 3]

Synthesis of 1,3-bis (3-aminobenzyl) urea [DA-3]

(37)

Nitrobenzylamine hydrochloride [H] (10.00 g, 53.0 mmol), bis (4-nitrophenyl) carbonate [D] (7.68 g, 25.3 mmol) and THF 384 g) was added, and triethylamine (15.33 g, 152 mmol) and 4-N, N-dimethylaminopyridine (0.62 g, 5.05 mmol) were added thereto and stirred. The reaction was followed by HPLC and after completion of the reaction, the reaction solution was added to pure water (2.3 L) and stirred for 30 minutes. Thereafter, filtration was carried out, and the filtrate was washed with pure water (500 ml) to obtain crude white solid. The resultant white solid was dispersed and washed with 2-propanol (50 g) using an ultrasonic device, followed by filtration and drying to obtain dinitro compound [I] as a white solid (Yield 7.04 g, yield 84%).

After replacing the mixture of the compound [I] (7.04 g, 21.3 mmol), 5% palladium carbon (5% Pd / C) (0.7 g) and 1,4-dioxane (350 g) , And the mixture was stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC and after completion of the reaction, the catalyst was filtered with celite. Thereafter, the liquid was distilled off under reduced pressure to obtain the crude product of a white tea solid. 2-propanol (60 g) was added to the crude product, followed by dispersion washing with an ultrasonic device, followed by filtration and drying to obtain a diamino compound [DA-3] as a white solid (yield: 4.04 g, 81%).

[Synthesis Example 4]

Synthesis of 1- (4-aminobenzyl) -3- (4-aminophenethyl) urea [DA-4]

(38)

4-nitrobenzylamine hydrochloride [F] (50.00 g, 265 mmol), pyridine (20.97 g, 265 mmol) and dichloromethane (750 g) were added to a four-necked flask under nitrogen atmosphere at room temperature, And cooled to less than 10 degrees. Thereafter, a dichloromethane (150 g) solution of 4-nitrophenyl chloroformate [J] (53.43 g, 265 mmol) was added thereto, and the reaction temperature was elevated to 23 ° C. and stirred for 1 hour. Respectively. After completion of the reaction, the reaction solution was cooled to room temperature, and dichloromethane (500 g) and an aqueous hydrochloric acid solution (1000 g) diluted to 10 mass% were added to perform filtration. The liquid was stirred at room temperature, and the precipitated solid was filtered. The solid was washed with methanol (200 g) and dried to obtain a white solid compound [K] (Yield 33.26 g, yield 40%). On the other hand, a saturated aqueous solution of sodium hydrogencarbonate (500 g) was added to the liquid and the organic layer was washed with saturated saline (500 g) and dried with magnesium sulfate. Thereafter, the mixture was filtered and the solvent was distilled off to obtain white crude product. The crude product was recrystallized from methanol (200 g) to obtain a white solid compound [K] (gain 16.6 g, yield 20%).

To a four-necked flask under nitrogen purging at room temperature, 2- (4-nitrophenyl) ethylamine hydrochloride

(45.28 g, 142 mmol) and THF (2260 g) were added, followed by addition of triethylamine (43.23 g, 427 mmol) and 4- N, N-dimethylaminopyridine (1.74 g, 14.2 mmol) was added to carry out the reaction. The reaction was followed by HPLC, and after completion of the reaction, the reaction solution was added to pure water (10 L) and stirred for 30 minutes. Thereafter, filtration was performed, and the filtrate was washed with pure water (2 L) to obtain a crude product of a white solid. The obtained white solid was washed with 2-propanol (300 g), followed by filtration and drying to obtain a dinitro compound [L] as a white solid (gain: 43.9 g, yield 90%).

After replacing the mixture of compound [L] (50.00 g, 145 mmol), 5% palladium carbon (5% Pd / C) (5.0 g) and 1,4-dioxane (1000 g) with nitrogen, , And the mixture was stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC and after completion of the reaction, the catalyst was filtered with celite. Thereafter, the liquid was distilled off under reduced pressure to obtain the crude product of a white tea solid. 2-propanol (330 g) was added to the crude product, followed by dispersion washing with an ultrasonic device, followed by filtration and drying to obtain a diamino compound [DA-4] 90%).

[Synthesis Example 5]

Synthesis of 1,3-bis (2- (4-aminophenoxy) ethyl) urea [DA-5]

[Chemical Formula 39]

Synthesis of Compound [P] by Reaction Process A

Nitrophenol (27.69 g, 199 mmol), potassium carbonate (55.01 g, 398 mmol) and N, N-dimethylformamide (hereinafter referred to as DMF) 140 g) was added and heated to 65 占 폚. Thereto was added dropwise a solution of N- (2-bromoethyl) phthalimide (50.57 g, 199 mmol) in DMF (140 g). After completion of the reaction, the reaction solution was added to ice water (2240 g) to obtain a yellow solid. This was filtered, washed with water and then dried to obtain Compound [O] as a white solid (Yield 44.2 g, yield 71%).

Hydrazine hydrate (81.00 g, 1.28 mol) was added to a solution of the compound [O] (40.00 g, 128 mmol) in ethanol (930 g) in a four-necked flask under a nitrogen atmosphere at room temperature, . After completion of the reaction, the precipitated solid was dissolved in distilled water (930 g) and extracted four times with 1,2-dichloroethane (500 g). The organic layer was combined, washed with water (500 g) twice, dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain Compound [P] as a yellow solid (Yield 16.5 g, yield 51%).

Synthesis of Compound [P] by Reaction Process B

1,2-dimethoxyethane (hereinafter referred to as DME) (150 g) was placed in a four-necked flask under nitrogen flow at room temperature, and 60% sodium hydride (16.24 g, 372 mmol) was added thereto. Then, a solution of 2-ethanolamine (22.73 g, 372 mmol) in DME (50 g) was slowly added dropwise. Next, a DME (50 g) solution of 1-fluoro-4-nitrobenzene (50.00 g, 354 mmol) was added dropwise. After completion of the reaction, the reaction solution was added to distilled water (1250 g) and extracted three times with dichloromethane (400 g). The organic layers were combined, dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain a compound [P] as a yellow solid (Yield 46.1 g, yield 71%).

N, N-dimethylamino (4-nitrophenyl) [D] (7.95 g, 26.1 mmol), triethylamine (15.87 g, 157 mmol) Pyridine (0.64 g, 5.23 mmol), and THF (280 g) were added and stirred. Thereto, a solution of the compound [P] (10.00 g, 54.9 mmol) in THF (40 g) was further added to carry out the reaction. The reaction was followed by HPLC and after completion of the reaction, the reaction solution was added to pure water (1.9 L) and stirred for 30 minutes. Thereafter, filtration was carried out and the filtrate was washed with pure water (500 ml) to obtain a crude product of a yellow solid. The obtained crude product was washed with 2-propanol (60 g) and then dried to obtain a dinitro compound [Q] as a yellow solid (gain: 6.98 g, yield: 68%).

A four-necked flask containing a mixture of compound [Q] (6.73 g, 17.2 mmol), 5% palladium carbon (5% Pd / C) (0.67 g), and 1,4- Substituted with nitrogen, replaced again with hydrogen, and stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC and after completion of the reaction, the catalyst was filtered with celite. Thereafter, the liquid was distilled off under reduced pressure to obtain the crude product of a pale yellow solid. 2-propanol (48 g) was added to the crude product, followed by dispersion washing with an ultrasonic device, followed by filtration and drying to obtain a diamino compound [DA-5] 60%).

[Synthesis Example 6]

Synthesis of 3-bis (3- (4-aminophenoxy) propyl) urea [DA-6]

(40)

Synthesis of compound [T] by reaction step C

4-Nitrophenol (25.79 g, 185 mmol), potassium carbonate (49.70 g, 185 mmol) and DMF (130 g) were added to a four-necked flask under nitrogen atmosphere at room temperature and heated to 65 占 폚. Thereto was added dropwise a solution of N- (3-bromopropyl) phthalimide (49.7 g, 185 mmol) in DMF (130 g). After completion of the reaction, the reaction solution was added to ice water (2080 g) to obtain a yellow solid. This was filtered, washed with water and then dried to obtain compound [S] as a yellowish white solid (Yield: 59.5 g, yield: 98%).

Hydrazine-hydrate (116.0 g, 1.85 mol) was added to a solution of the compound [S] (60.50 g, 185 mmol) in ethanol (908 g) in a four-necked flask at room temperature and under nitrogen atmosphere, . After completion of the reaction, the precipitated solid was dissolved in distilled water (908 g) and extracted four times with 1,2-dichloroethane (500 g). The organic layers were combined, washed with water (500 g) twice, and dried over magnesium sulfate. Thereafter, the mixture was filtered and the solvent was distilled off to obtain Compound [T] as a pale yellow oil (Yield: 36.0 g, yield: 99%).

Synthesis of compound [T] by reaction step D

1,2-dimethoxyethane (hereinafter referred to as DME) (188 g) was placed in a four-necked flask under nitrogen flow at room temperature, and 60% sodium hydride (14.52 g, 333 mmol) was added thereto. Then, a solution of 3-amino-1-propanol (25.00 g, 333 mmol) in DME (94 g) was slowly added dropwise. Next, a DME (94 g) solution of 1-fluoro-4-nitrobenzene (46.96 g, 333 mmol) was added dropwise. After completion of the reaction, the reaction solution was added to distilled water (564 g) and extracted three times with dichloromethane (500 g). The organic layers were combined, dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain a compound [T] (yield 60.72 g, yield 93%) as a yellow oil.

(60.72 g, 310 mmol), bis (4-nitrophenyl) [D] (35.87 g, 118 mmol) and triethylamine (47.72 g, 472 mmol), 4-N, N-dimethylaminopyridine (1.44 g, 11.8 mmol), and THF (720 g). The reaction was followed by HPLC, and after completion of the reaction, the reaction solution was added to pure water (4.3 L) and stirred for 30 minutes. Thereafter, filtration was performed, and the filtrate was washed with pure water (1 L) to obtain a crude solid of a yellow solid. The obtained crude product was washed with 2-propanol (400 g) and then dried to obtain a dinitro compound [U] having a yellow solid (gain: 38.1 g, yield: 77%).

A mixture of compound [U] (26.00 g, 62.1 mmol), 5% palladium carbon (5% Pd / C) (2.6 g), and 1,4-dioxane (160 g) / ethanol The inside of the four-necked flask was purged with nitrogen, replaced again with hydrogen, and stirred at room temperature in the presence of hydrogen. After the completion of the reaction, the reaction was monitored by HPLC. After completion of the reaction, the solution was purged with nitrogen to dissolve the precipitated solid, and then acetonitrile (1500 g) and DMF (150 g) were added and heated to dissolve completely. The catalyst was then filtered with celite. Thereafter, the liquid was distilled off under reduced pressure to obtain the crude product of a white tea solid. 2-Propanol (160 g) was added to the crude product, and the dispersion was washed with an ultrasonic device. Thereafter, filtration and drying were carried out to obtain a diamino compound [DA-6] as a white solid (Yield: 17.7 g, yield: 79%).

[Example 1]

0.60 g (2.0 mmol) of BAPU and 1.95 g (18.0 mmol) of p-PDA were placed in a 50 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, and N-methyl-2-pyrrolidone 30 g, and dissolved with stirring while nitrogen was being supplied. To this diamine solution, 3.70 g (18.9 mmol) of CBDA was added while stirring, and N-methyl-2-pyrrolidone was further added thereto so as to have a solid content concentration of 12 mass%, and the mixture was stirred at room temperature for 4 hours To obtain a solution of polyamic acid (P1). The viscosity of this polyamic acid solution at 25 占 폚 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) to be 316 mPa 占 퐏.

9.94 g of N-methyl-2-pyrrolidone and 6.54 g of butyl cellosolve were added to 16.24 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a concentration of P1 of 6.0% by mass.

(Rubbing resistance)

The liquid crystal alignment treatment agent obtained above was filtered with a filter of 1.0 占 퐉 and then spin-coated on a glass substrate on which a transparent electrode was formed and dried on a hot plate at 80 占 폚 for 5 minutes and then baked at 230 占 폚 for 30 minutes to give a film thickness of 100 nm Of a polyimide film was obtained. This polyimide film was rubbed with a rayon cloth (roll diameter 120 mm, rotation number 1000 rpm, moving speed 20 mm / sec, indentation amount 0.4 mm). The surface state of this film surface was observed by using a focal laser microscope, and the presence or absence of scraps and the presence of scratches were observed at a magnification of 10 times. The results are shown in Table 2.

(Production of liquid crystal cell)

The liquid crystal alignment treatment agent obtained above was filtered with a filter of 1.0 占 퐉 and then spin-coated on a glass substrate on which a transparent electrode was formed and dried on a hot plate at 80 占 폚 for 5 minutes and then baked at 230 占 폚 for 30 minutes to give a film thickness of 100 nm Of a polyimide film was obtained. This polyimide film was subjected to ultrasonic irradiation for 1 minute in pure water after rubbing with a rayon cloth (roll diameter 120 mm, rotation speed 300 rpm, moving speed 20 mm / sec, indentation amount 0.2 mm), dried at 80 캜 for 10 minutes . Two substrates each having such a liquid crystal alignment film formed thereon were prepared, spacers having a size of 6 mu m were provided on the liquid crystal alignment film surface of one of the substrates, and the rubbing directions of the two substrates were combined so as to be antiparallel to each other. And a hollow cell having a cell gap of 6 탆 was prepared. A liquid crystal (MLC-2041, manufactured by MULKS) was vacuum-injected into the cell at room temperature, and the injection port was sealed to obtain an anti-parallel liquid crystal cell.

(Liquid crystal alignment property)

The alignment state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that the alignment was uniform without any defects.

(Pretilt angle)

The pretilt angle of the liquid crystal after heating at 110 DEG C for 30 minutes was measured for the liquid crystal cell using a measuring apparatus (TBA107, autroNic-MELCHERS GmbH) by a crystal rotation method.

(Voltage holding ratio)

A voltage of 4 V was applied to the liquid crystal cell manufactured in the same manner as in the above (production of liquid crystal cell) for 60 seconds, and the voltage after 16.67 ms was measured, and the variation from the initial value was calculated as the voltage holding ratio. At the time of measurement, the temperature of the liquid crystal cell was set at 90 占 폚 and measurement was performed at each temperature.

(Ion density)

Using a liquid crystal cell manufactured in the same manner as in the above (production of a liquid crystal cell), the ion density was measured using a 6254-type liquid crystal physical property evaluation apparatus manufactured by Toyota Technica. The measurement was carried out by applying a triangular wave of 10 V and 0.01 Hz and calculating the area corresponding to the ion density of the obtained waveform by the triangular approximation method to obtain the ion density. At the time of measurement, the temperature of the liquid crystal cell was measured at 60 캜.

[Example 2]

2.39 g (8.0 mmol) of BAPU and 0.87 g (8.0 mmol) of p-PDA were placed in a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, g, and dissolved with stirring while nitrogen was being supplied. To this diamine solution, 2.92 g (14.9 mmol) of CBDA was added while stirring, and N-methyl-2-pyrrolidone was added again so as to have a solid content concentration of 12 mass%, and the mixture was stirred at room temperature for 2 hours To obtain a polyamic acid (P2) solution. The viscosity of this polyamic acid solution at 25 캜 was confirmed to be 281 mPa s by an E-type viscometer (manufactured by Toki Industry Co., Ltd.).

9.61 g of N-methyl-2-pyrrolidone and 6.43 g of butyl cellosolve were added to 16.12 g of this polyamic acid solution to obtain a liquid crystal alignment treating agent having a concentration of P2 of 6.0% by mass.

[Example 3]

2.68 g (9.0 mmol) of BAPU and 30 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved with stirring while nitrogen was supplied . 1.69 g (8.6 mmol) of CBDA was added while stirring the diamine solution, N-methyl-2-pyrrolidone was further added thereto so that the solid concentration became 12 mass%, and the mixture was stirred at room temperature for 6 hours Thereby obtaining a polyamic acid (P3) solution. The viscosity of the polyamic acid solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.), and found to be 206 mPa 占 퐏.

5.10 g of N-methyl-2-pyrrolidone and 4.94 g of butyl cellosolve were added to 14.65 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P3 concentration of 6.0% by mass.

[Example 4]

2.69 g (9.7 mmol) of BABU and 25 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolved with stirring while nitrogen was supplied . 1.85 g (9.4 mmol) of CBDA was added while stirring the diamine solution, N-methyl-2-pyrrolidone was added again to a solids concentration of 10% by mass, and the mixture was stirred at room temperature for 2 hours Thereby obtaining a polyamic acid (P4) solution. The viscosity of the polyamic acid solution at 25 캜 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.), and found to be 173 mPa s.

5.90 g of N-methyl-2-pyrrolidone and 4.75 g of butyl cellosolve were added to 13.90 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P4 concentration of 6.0% by mass.

[Example 5]

2.54 g (8.5 mmol) of BAPU and 30 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolved with stirring while nitrogen was supplied . 1.69 g (7.7 mmol) of PMDA was added while stirring the diamine solution, and N-methyl-2-pyrrolidone was added thereto so as to have a solid content concentration of 10 mass%, and the mixture was stirred at room temperature for 4 hours To obtain a polyamic acid (P5) solution. The viscosity of this polyamic acid solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 138.6 mPa 占 퐏.

5.64 g of N-methyl-2-pyrrolidone and 4.94 g of butyl cellosolve were added to 15.13 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P5 concentration of 6.0% by mass.

[Example 6]

2.43 g (9.0 mmol) of BABU and 30 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolved with stirring while nitrogen was supplied . While stirring the diamine solution, 1.88 g (8.6 mmol) of PMDA was added, and N-methyl-2-pyrrolidone was further added thereto so as to have a solid content concentration of 10% by mass and stirred at room temperature for 3 hours To obtain a polyamic acid (P6) solution. The viscosity of this polyamic acid solution at 25 占 폚 was 276 mPa 占 퐏, as determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.).

To 10.75 g of this polyamic acid solution, 8.56 g of N-methyl-2-pyrrolidone and 4.83 g of butyl cellosolve were added to obtain a liquid crystal alignment treating agent having a P6 concentration of 4.5% by mass.

[Example 7]

3.58 g (12.0 mmol) of BAPU and 30 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolved with stirring while nitrogen was supplied . While the diamine solution was stirred, 2.86 g (11.4 mmol) of BODA was added, N-methyl-2-pyrrolidone was added thereto so that the solid concentration became 12 mass%, and the mixture was stirred at 50 deg. To obtain a polyamic acid (P7) solution. The viscosity of this polyamic acid solution at 25 캜 was confirmed to be 630 mPa s by an E-type viscometer (manufactured by Toki Industries Co., Ltd.).

12.80 g of the polyamic acid solution, 12.80 g of N-methyl-2-pyrrolidone and 6.32 g of butyl cellosolve were added to obtain a liquid crystal alignment treating agent having a P7 concentration of 6.0% by mass.

[Example 8]

3.24 g (12.0 mmol) of BABU and 25 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and dissolved with stirring while nitrogen was supplied . While stirring the diamine solution, 2.99 g (11.9 mmol) of BODA was added, and N-methyl-2-pyrrolidone was added thereto so that the solid concentration became 15% by mass. To obtain a polyamic acid (P8) solution. The viscosity of this polyamic acid solution at 25 캜 was confirmed to be 498 mPa s by an E-type viscometer (manufactured by Toki Industries Co., Ltd.).

12.0 g of N-methyl-2-pyrrolidone and 5.50 g of butyl cellosolve were added to 9.95 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P8 concentration of 6.0% by mass.

[Example 9]

2.31 g (8.54 mmol) of DA-3 and 24.3 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, . While stirring the diamine solution, 1.66 g (8.46 mmol) of CBDA was added, and N-methyl-2-pyrrolidone was further added thereto so as to have a solid content concentration of 10% by mass and stirred at room temperature for 4 hours To obtain a polyamic acid (P9) solution. The viscosity of this polyamic acid solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 155 mPa 占 퐏.

7.57 g of N-methyl-2-pyrrolidone and 6.09 g of butyl cellosolve were added to 16.80 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P9 concentration of 6.0% by mass.

[Example 10]

2.84 g (9.98 mmol) of DA-4 and 29.5 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, . While stirring the diamine solution, 1.66 g (9.53 mmol) of CBDA was added, and N-methyl-2-pyrrolidone was added thereto so that the solid concentration became 10% by mass, and the mixture was stirred at room temperature for 4 hours To obtain a polyamic acid (P10) solution. The viscosity of the polyamic acid solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.), and found to be 206 mPa 占 퐏.

7.75 g of N-methyl-2-pyrrolidone and 6.22 g of butyl cellosolve were added to 17.12 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P10 concentration of 5.5% by mass.

[Example 11]

3.40 g (9.48 mmol) of DA-6 and 29.5 g of N-methyl-2-pyrrolidone were added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, . 1.76 g (8.97 mmol) of CBDA was added while stirring the diamine solution, N-methyl-2-pyrrolidone was added again to a solids concentration of 10% by mass, and the mixture was stirred at room temperature for 4 hours To obtain a polyamic acid (P11) solution. The viscosity of the polyamic acid solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 150 mPa 占 퐏.

5.26 g of N-methyl-2-pyrrolidone and 6.03 g of butyl cellosolve were added to 18.88 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P11 concentration of 6.0% by mass.

[Example 12]

0.53 g (1.6 mmol) of DA-5 and 1.56 g (14.4 mmol) of p-PDA were placed in a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 30.9 g of lauridol was added and dissolved by stirring while nitrogen was being fed. While stirring the diamine solution, 2.82 g (15.4 mmol) of CBDA was added, and N-methyl-2-pyrrolidone was further added thereto so as to have a solid content concentration of 10% by mass and stirred at room temperature for 4 hours To obtain a solution of polyamic acid (P12). The viscosity of the polyamic acid solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 160 mPa 占 퐏.

6.03 g of N-methyl-2-pyrrolidone and 6.11 g of butyl cellosolve were added to 18.41 g of the polyamic acid solution to obtain a liquid crystal alignment treating agent having a P12 concentration of 6.0% by mass.

[Example 13]

7.00 g (24.44 mmol) of DA-7 and 3.13 g (10.48 mmol) of BAPU were placed in a 1000 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and the inside of the flask was replaced with nitrogen. Next, 359.90 g of dehydrated N-methyl-2-pyrrolidone and 6.63 g of pyridine were charged into a syringe and stirred with a magnetic stirrer at 25 캜 to completely dissolve BAPU and DA-7. Thereafter, the reaction solution was cooled, and 9.34 g (31.44 mmol) of CA-4 was added while stirring with a magnetic stirrer. The addition was carried out for 30 seconds using a funnel. Thereafter, the funnel used for the addition was washed with dehydrated N-methyl-2-pyrrolidone (10.00 g), the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under water cooling. Next, while stirring 5 times the weight of methanol in the reaction solution, the reaction solution was gradually stirred for 1 hour. Thereafter, the precipitate obtained by filtration was stirred together with methanol five times by weight for 1 hour, and then the precipitate was collected by filtration. Thereafter, the same operation was carried out using 5 times the weight of methanol, and the resulting precipitate was dried at 100 캜 under reduced pressure for 24 hours to obtain 14.59 g of polyamic acid ester (P13). 2.26 g of the resulting solid was completely dissolved with 20.36 g of N-methyl-2-pyrrolidone. Next, 2.12 g of N-methyl-2-pyrrolidone and 10.60 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment treatment agent having a P13 concentration of 6.0% by mass.

[Example 14]

4.00 g (13.97 mmol) of DA-7 and 1.78 g (5.99 mmol) of BAPU were placed in a 300 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and the inside of the flask was replaced with nitrogen. Next, 202.93 g of dehydrated N-methyl-2-pyrrolidone and 3.79 g of pyridine were injected into a syringe and stirred with a magnetic stirrer at 25 캜 to completely dissolve BAPU and DA-7. Thereafter, the reaction solution was cooled, 1.27 g (3.99 mmol) of CA-5 and 4.15 g (13.96 mmol) of CA-4 were added while stirring with a magnetic stirrer. The addition was carried out for 30 seconds using a funnel. Thereafter, the funnel used for the addition was washed with dehydrated N-methyl-2-pyrrolidone (10.00 g), the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under water cooling. Next, while stirring 5 times the weight of methanol in the reaction solution, the reaction solution was gradually stirred for 1 hour. Thereafter, the precipitate obtained by filtration was stirred together with methanol five times by weight for 1 hour, and then the precipitate was collected by filtration. Thereafter, the same operation was carried out again using 5 times the weight of methanol, and the resulting precipitate was dried at 100 캜 under reduced pressure for 24 hours to obtain 8.87 g of polyamic acid ester (P14). 2.27 g of the solid obtained was completely dissolved with 20.45 g of N-methyl-2-pyrrolidone. Next, 2.13 g of N-methyl-2-pyrrolidone and 10.65 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment treating agent having a P14 concentration of 6.0% by mass.

[Comparative Example 1]

2.17 g (20.0 mmol) of p-PDA was added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and 25 g of N-methyl-2-pyrrolidone was further added thereto. Lt; / RTI &gt; While stirring the diamine solution, 3.77 g (19.2 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, and again, N-methyl-2-pyrrolidone And the mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution. The viscosity of this polyamic acid solution at 25 占 폚 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) to be 602.3 mPa 占 퐏.

7.89 g of the resulting polyamic acid solution was collected into a 50 ml Erlenmeyer flask containing an agitator, 6.29 g of N-methyl-2-pyrrolidone and 3.55 g of butyl cellosolve were added and stirred for 30 minutes by a magnetic stirrer to obtain polyamic acid To obtain a liquid crystal alignment treatment agent having a concentration of 5.5% by mass.

[Comparative Example 2]

10.00 g (34.92 mmol) of DA-7 was placed in a 1000 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and the inside of the flask was replaced with nitrogen. Next, 304 g of dehydrated N-methyl-2-pyrrolidone and 6.1 g of pyridine were charged into a syringe and stirred with a magnetic stirrer at 25 캜 to completely dissolve DA-7. Thereafter, the reaction solution was cooled, and 9.34 g (31.43 mmol) of CA-4 was added while stirring with a magnetic stirrer. The addition was carried out for 30 seconds using a funnel. Thereafter, the funnel used for the addition was washed with 20 g of dehydrated N-methyl-2-pyrrolidone, the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under cooling with water. Next, while stirring the distilled water five times the weight of the reaction solution, the reaction solution was gradually stirred for 1 hour. Thereafter, the precipitate obtained by filtration was stirred for 1 hour with distilled water having a weight of 5 times, and the precipitate was recovered by filtration. Thereafter, the same operation was carried out again using a 5-fold weight of ethanol, and the resulting precipitate was dried at 100 캜 under reduced pressure for 24 hours to obtain 14.82 g of a solid. 3.99 g of the obtained solid was completely dissolved with 35.90 g of N-methyl-2-pyrrolidone. Next, 6.91 g of N-methyl-2-pyrrolidone and 19.36 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment treating agent having a polyamic acid ester concentration of 5.5% by mass.

[Comparative Example 3]

7.00 g (24.44 mmol) of DA-7 was placed in a 1000 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and the inside of the flask was replaced with nitrogen. Next, 249.3 g of dehydrated N-methyl-2-pyrrolidone and 4.6 g of pyridine were charged into a syringe and stirred with a magnetic stirrer at 25 캜 to completely dissolve DA-7. Thereafter, the reaction solution was cooled and 1.56 g (4.88 mmol) of CA-5 and 6.08 g (17.12 mmol) of CA-4 were added while stirring with a magnetic stirrer. The addition was carried out for 30 seconds using a funnel. Thereafter, the funnel used for the addition was washed with 10 g of dehydrated N-methyl-2-pyrrolidone, the inside of the reaction vessel was purged with nitrogen, and stirring was continued for 3 hours under water cooling. Next, while stirring 5 times the weight of methanol in the reaction solution, the reaction solution was gradually stirred for 1 hour. Thereafter, the precipitate obtained by filtration was stirred together with methanol five times by weight for 1 hour, and then the precipitate was collected by filtration. Thereafter, the same operation was repeated using 5 times the weight of methanol, and the obtained precipitate was dried at 100 캜 under reduced pressure for 24 hours to obtain 11.15 g of a solid. 10.06 g of the obtained solid was completely dissolved with 90.54 g of N-methyl-2-pyrrolidone. Next, 5.63 g of N-methyl-2-pyrrolidone and 44.97 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment treating agent having a polyamic acid ester concentration of 6.0% by mass.

Table 1 shows the amounts of the raw materials (diamine and the like) used in Examples 1 to 14 and Comparative Examples 1 to 3, the abbreviations of the obtained polyamic acid (P1 and the like) and the polyamic acid of N-methyl-2-pyrrolidone The viscosity of the solution is summarized. In addition, no abbreviations were given to the polyamic acid and the polyamic acid ester of Comparative Examples 1 to 3 (indicated by a blank in Table 1).

In Table 1, "-" indicates that the viscosity is not measured.

A liquid crystal cell was prepared using the liquid crystal alignment film treatment agents obtained in Examples 2 to 4, Examples 7 to 13, and Comparative Example 1 and Comparative Example 2 in the same manner as in Example 1, and rubbing resistance, liquid crystal orientation , The pretilt angle, the voltage holding ratio and the ion density were measured. In addition, the rubbing resistance and the liquid crystal alignability of Example 5, Example 6, Example 14, and Comparative Example 3 were measured in the same manner as in Example 1. The obtained results are shown in Table 2.

By using the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film which is excellent in rubbing resistance, good in orientation of liquid crystal and strong rubbing treatment. Further, since the liquid crystal alignment film of the present invention has a high voltage holding ratio and low ion density of the liquid crystal cell, it can be used as a liquid crystal display device which does not require rubbing treatment and which is optically oriented.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2008-285860 filed on November 6, 2008 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

Claims (2)

A bisaminophenoxyalkylurea represented by the following formula (1-c).

(In the formula (1-c), R ¹³ and R ²³ each independently represent an alkylene group having 1 to 3 carbon atoms) Bisaminophenoxyalkylurea represented by the following formula (1-10) or formula (1-11).