TWI422616B - 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, a liquid crystal alignment film using the same, and a liquid crystal display element. In particular, the liquid crystal alignment film used for the liquid crystal display element produced by the rubbing treatment step uses a liquid crystal alignment film and a liquid crystal display element.

The liquid crystal display element is a structure in which liquid crystal molecules are sandwiched by a liquid crystal alignment film formed on a substrate, and a display element that responds to the liquid crystal molecules via a voltage. The liquid crystal alignment film has an important task of controlling the alignment direction and the pretilt angle of the liquid crystal molecules in an arbitrary state.

The liquid crystal alignment film is generally produced by applying a pressure to a surface of a polyimide film formed on a substrate by rubbing or lining, or the like, by performing a so-called "friction treatment". This rubbing treatment determines the alignment direction of the liquid crystal molecules.

As means for increasing the pretilt angle of the liquid crystal, a means for introducing a long-chain alkyl group into a structure of a polyimide having a liquid crystal alignment film is known (for example, see Patent Document 1).

As a means for forming a polyimide film on a substrate, there are a method of coating a solution of polyacrylic acid, a method of imidating ruthenium on a substrate, and a method of applying a solution of soluble polyimine.

Among them, the method of using a solution of soluble polyimine can form good characteristics even when it is used as a liquid crystal alignment film even for relatively low-temperature baking. The polyimide film has a low strength, and the friction treatment tends to cause damage to the surface of the film and peeling of the film.

Further, in the production of a liquid crystal alignment film, as a means for applying a polymer solution to a substrate, an offset printing method is now widely used industrially. However, since a solution of a soluble polyimine having a high ruthenium iodide ratio is inferior in printability, it is necessary to mix polylysine or a soluble polyimine having a low ruthenium amination ratio, etc. (for example, Refer to Patent Document 2). Further, in order to impart a large pretilt angle to the liquid crystal, when a long-chain alkyl group is introduced into the structure of the soluble polyimine, the printability tends to be deteriorated.

As a means for improving the printability of the polymer solution to the substrate, a method of adding a solvent such as butyl cellosolve is known (for example, see Patent Document 3). However, in general, in comparison with soluble polyimine and polylysine, a large amount of a solvent such as butyl cellosolve cannot be used because of low solubility.

Patent Document 1: JP-A-2-282726 Patent Document 2: Japanese Patent Publication No. 9-297312 Patent Document 3: JP-A-2-037324

An object of the present invention is to provide a liquid crystal alignment film having a large pretilt angle of a liquid crystal (for example, 4 Å or more), and a polyimide having a high imidization ratio and excellent printability. The liquid crystal alignment treatment agent.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have finally completed the present invention. That is, the present invention has the following points.

(1) A liquid crystal alignment treatment agent comprising the following polyimine (A) and the following polyimine (B), polyimine (A): (i) from formula (1) a diamine component consisting of the diamine shown, or (ii) a diamine represented by the formula (1) and a group consisting of the formula (2), the formula (3), the formula (4), and the formula (5) a diamine component composed of at least one selected diamine, a polyamidimide obtained by reacting a polyamic acid obtained by reacting a tetracarboxylic dianhydride component with a tetracarboxylic acid dianhydride component; and a polyimine (B): (iii) a diamine component consisting of a diamine represented by the formula (1) and a diamine represented by the formula (6), or (iv) a diamine represented by the formula (1) and a formula (6) The amine is reacted with a diamine component composed of at least one diamine selected from the group consisting of formula (2), formula (3), formula (4), and formula (5), and reacted with a tetracarboxylic dianhydride component. a polyamidimide obtained by hydrazylation of a polyamic acid; (In the formula (2), X ₁ represents a single bond, or a bond group selected from a group consisting of ether, ester, and decylamine, and X ₂ represents a linear alkyl group having 1 to 12 carbon atoms; Wherein n is 1 or 2; in the formula (5), X ₃ represents a single bond, or a bond group selected from the group consisting of -O-, -CH ₂ -, -NH-, and -CONH-, R is a hydrogen atom or a methyl group) (In the formula (6), X ₄ represents a single bond, or a bond group selected from the group consisting of ether, ester, methylene ether, and decylamine, and X ₅ is a linear alkane having 14 to 20 carbon atoms. a group or a monovalent organic group represented by the following formula (7) (In the formula (7), X ₆ is a phenyl group or a cyclohexyl group, and X ₇ is a cyclohexyl group having a linear alkyl group having 1 to 12 carbon atoms).

(2) The liquid crystal alignment treatment agent according to the above (1), which comprises a polyimine (A) and a polyimine (B) in a mass ratio of 50:50 to 90:10.

(3) The liquid crystal alignment treatment agent according to the above (1) or (2), wherein the polyamidene (A) and the polyimine (B) have a sulfhydrylation ratio of 40% or more.

The liquid crystal alignment treatment agent according to any one of the above aspects (1), wherein the amount of the total diamine in 100 mol% of the polyimine (A) is 20 to 100. More% of the diamine represented by the formula (1), and when the diamine content of the formula (1) is less than 100 mol%, the remaining diamine is from the formula (2), the formula (3), and the formula (4). And at least one diamine selected from the group consisting of formula (5).

The liquid crystal alignment treatment agent according to any one of the above aspects (1), wherein the amount of the total diamine in 100 mol% of the polyimine (B) is 20 to 90. Mole % of the diamine represented by the formula (1), 5 to 40 mol% of the diamine represented by the formula (6), and the total content of the diamine of the formula (1) and the diamine of the formula (6) is low. At 100 mol%, the remaining diamine is at least one selected from the group consisting of formula (2), formula (3), formula (4), and formula (5).

(6) The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), which further contains an organic solvent component.

(7) The liquid crystal alignment treatment agent according to the above (6), wherein the organic solvent component contains γ-butyl propyl ester, butyl cellosolve, dipropylene glycol monomethyl ether or diethylene glycol diethyl ether.

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent is a liquid crystal alignment film which is subjected to rubbing treatment.

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

(10) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of the above (1) to (8) to a substrate on which an electrode is attached. It is obtained by baking and rubbing treatment.

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

The liquid crystal alignment treatment agent of the present invention is excellent in printability when applied to a substrate, and has less damage to the surface of the film and peeling of the film during rubbing treatment, and a liquid crystal alignment film having a large pretilt angle of liquid crystal is obtained, so that display defects are small. A liquid crystal display element having good characteristics. Moreover, although the liquid crystal alignment treatment agent of the present invention may increase the ruthenium imidization ratio of the polyimine contained therein, it has the above characteristics, so that a highly reliable liquid crystal display element can be obtained.

Best form for implementing the invention

The invention is described in detail below.

The liquid crystal alignment treatment agent of the present invention contains two polyimines of the following polyimine (A) and the following polyimine (B), and contains a mass ratio of 50:50 to 90:10. Indole (A) and polyimine (B). The liquid crystal alignment treatment agent of the present invention is particularly suitable for use as a liquid crystal alignment film for rubbing treatment. That is, the liquid crystal alignment treatment agent of the present invention is applied onto a substrate on which an electrode is attached and baked, and is used as a liquid crystal alignment film which is subjected to rubbing treatment.

<Polyimine (A)> The polyimine (A) used in the present invention is a polyimine obtained by reacting a polyamine derivative obtained by reacting a diamine component with a tetracarboxylic dianhydride component. The polyimine (A) is soluble in the organic solvent contained in the liquid crystal alignment treatment agent of the present invention, and the reaction of the polyimine (A) obtained by reacting the diamine component with the tetracarboxylic dianhydride component It is also soluble in the organic solvent used.

[Diamine component] The diamine component for obtaining the polyimine (A) is a diamine represented by the following formula (1) as an essential component.

In the diamine represented by the formula (1), the position of each substituent on the benzene ring is not particularly limited, but the positional relationship of the two amine groups is preferably a meta or para position. Preferred specific examples of the diamine are listed below, but are not limited thereto.

The use of the diamine represented by the formula (1) is effective for suppressing damage to the surface of the film and peeling of the film during the rubbing treatment, and further, the solubility of the polyimine (A) in the organic solvent is also high. The diamine represented by the formula (1) may be used singly or in combination of plural kinds.

The content of the diamine represented by the formula (1) is 20 to 100 mol%, preferably 30 to 100 mol%, more preferably 40 to 100 mol% of the entire diamine component in the polyimine (A). 100% by mole. The more the ratio of the diamine represented by the formula (1), the higher the effect of suppressing the damage of the surface of the alignment film and the peeling of the film during the rubbing treatment, and the higher the solubility of the polyimine in the organic solvent.

When the diamine represented by the formula (1) is less than 100 mol%, the remaining diamine is composed of the following group (2), formula (3), formula (4), and formula (5). At least one of the selected ones. The content of at least one diamine selected from the group consisting of formula (2), formula (3), formula (4), and formula (5) is the entire diamine component of the polyimine (A). 0 or more to 80% by mole, preferably 5 to 70% by mole, more preferably 10 to 60% by mole. In particular, the content of the diamine represented by the formula (2) is preferably from 0 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 30 mol%, and the remaining content is At least one diamine selected from the group consisting of formula (3), formula (4), and formula (5).

In the formula (2), X ₁ represents a single bond or a bond group selected from the group consisting of ether, ester, and decylamine, and X ₂ represents a linear alkyl group having 1 to 12 carbon atoms.

In the formula (3), n is 1 or 2, preferably 1.

In the formula (5), X ₃ represents a single bond, or a bond group selected from the group consisting of -O-, -CH ₂ -, -NH-, and -CONH-, and R is a hydrogen atom or a methyl group. Good is a hydrogen atom.

When the diamine of the formula (2) is used, there is an effect of increasing the solubility and the pretilt angle of the liquid crystal. Further, when the diamine represented by the formula (3) to the formula (5) is used, there is an effect of improving the alignment property of the liquid crystal.

Specific examples of the diamine represented by the formulae (2) to (5) are exemplified below, but are not limited thereto.

Examples of the diamine represented by the formula (2) include a diamine of the following formulas (11) to (14).

In the formulae (11) to (14), m is an integer of 0 to 11, preferably 5 to 11.

Examples of the diamine represented by the formula (3) include 2-aminobenzylamine, 3-aminobenzylamine, 4-aminobenzylamine, and 2-(2-aminophenyl)ethylamine. 2-(3-Aminophenyl)ethylamine, 2-(4-aminophenyl)ethylamine, and the like.

Examples of the diamine represented by the formula (4) include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and the like.

Examples of the diamine represented by the formula (5) include 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, and 4,4. '-Diamino-3,3'-dimethylbiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 4,4'-diamine Diphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-diaminodi Phenyl decylamine and the like.

Among them, 3-aminobenzylamine or 4-aminobenzylamine is particularly preferable because it has high solubility as a polyimine.

[tetracarboxylic dianhydride component] In order to obtain polyimine (A), a tetracarboxylic acid which reacts with the above diamine component The acid dianhydride component is not limited to the problems of improving the printability at the time of coating the substrate, the damage of the surface of the liquid crystal alignment film caused by the rubbing treatment, and the peeling of the film, and of course, various options can be selected depending on other characteristics. In the present invention, the tetracarboxylic dianhydride to be used may be used alone or in combination of plural kinds.

For example, even a polyimine having a high sulfonium imidization ratio is preferably used from the viewpoint of easily obtaining a polyimide having a relatively high solubility and a voltage holding ratio of the liquid crystal cell. An alicyclic structure or an aliphatic structure of tetracarboxylic dianhydride.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3. , 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 - naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3, 3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-di Alkene-1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.0 ^2,5 ]-nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8- Diacetate, hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11, 12-dianhydride and the like.

In particular, when aromatic tetracarboxylic dianhydride is used in combination, the liquid crystal alignment property can be improved, and the accumulated charge of the liquid crystal cell can be reduced.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride. 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyl Tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4-benzophenonetetracarboxylic dianhydride, double (3,4 -dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfonahydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Carboxylic dianhydride and the like.

When considering the balance between the solubility of the polyimine (A), the alignment property of the liquid crystal, the voltage holding ratio, and the accumulated charge characteristics, the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure is used. The ratio of the combined use of the aromatic tetracarboxylic dianhydride to the molar ratio of the former/the latter is preferably from 90/10 to 60/40, more preferably from 80/20 to 70/30. A particularly preferred combination of tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride.

[Method for producing polylysine] The reaction of reacting the above diamine component with a tetracarboxylic dianhydride component to obtain polyglycine is usually carried out by mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent.

The method of mixing the tetracarboxylic dianhydride component and the diamine component in an organic solvent is not particularly limited. For example, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and a tetracarboxylic dianhydride component is added as it is, or is dispersed or dissolved in an organic solvent, is dispersed in a tetracarboxylic dianhydride component or A method of adding a diamine component to a solution dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride component and a diamine component, and the like. Further, when the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of compounds, the plurality of components may be polymerized in a state of being preliminarily mixed. The polymerization can be carried out individually and sequentially.

When the tetracarboxylic dianhydride component and the diamine component are polymerized in an organic solvent, the temperature is usually from 0 to 150 ° C, preferably from 5 to 100 ° C, more preferably from 10 to 80 ° C.

When the temperature at the time of the polymerization reaction is high, the polymerization reaction is rapidly completed, but if it is too high, a polymer having a high molecular weight is not obtained.

Further, the polymerization reaction can be carried out at any concentration of the produced polymer. If the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction liquid becomes excessively high, and it is difficult to uniformly Stir. Therefore, the concentration at the time of carrying out the polymerization reaction is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. Further, it is also possible to use a method in which the polymerization reaction is carried out at a high concentration in the initial stage of the polymerization, and then the organic solvent is added to lower the concentration.

The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the produced polyamic acid. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and dimethylene are mentioned. Anthracene, tetramethylurea, pyridine, dimethyl hydrazine, hexamethylene hydrazine, γ-butyl propyl ester, and the like.

These organic solvents may be used singly or in combination of plural kinds. In addition, even if it is an organic solvent which does not melt|dissolve poly-prolinic acid, it can mix with the said organic solvent, and can use it as the range which the poly-

Further, since the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polyamic acid, the organic solvent is preferably dried as much as possible.

The ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization of polyamic acid is preferably from 0.8:1 to 1.2:1, more preferably from 0.9:1 to 1:1, in terms of molar ratio. The closer the molar ratio is to 1:1, the greater the molecular weight of the polylysine obtained. By controlling the molecular weight of the polyaminic acid, the molecular weight of the polyimine obtained after the imidization can be adjusted.

In the present invention, the molecular weight of the polylysine is not particularly limited, but particularly, as a precursor for obtaining a polyimine (A) suitable for the present invention, the weight average molecular weight is preferably 2,000 to 200,000, more Good for 5,000~50,000.

[Method for producing polyimine (A)] The ruthenium imidization of the polylysine obtained as described above can be carried out by stirring in an organic solvent in the presence of a basic catalyst and an acid anhydride for 1 to 100 hours.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because the reaction can be moderately alkaline.

Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because the obtained polyimine can be easily purified after the imidization of hydrazine.

As the organic solvent used for the ruthenium imidization of the polyamic acid, the same organic solvent as the organic solvent used in the polymerization reaction of the above polyamic acid can be used.

The ruthenium imidization ratio of the polyimine (A) can be adjusted by the amount of the catalyst, the reaction temperature, the reaction time, and the like. The amount of basic catalyst is preferably amidino-based 0.2 to 10 times Mo, more preferably 0.5 to 5 times Mo. Further, the amount of the acid anhydride is preferably from 1 to 30 moles, more preferably from 1 to 10 moles, per mole of the guanamine group. The reaction temperature is preferably -20 to 250 ° C, more preferably 0 to 180 ° C. The reaction time is from 1 to 100 hours, preferably from 1 to 10 hours.

The ruthenium imidization ratio of the polyimine (A) is not particularly limited, but is preferably 40% or more, and more preferably 60% or more, and particularly preferably 80% or more in order to obtain a high voltage holding ratio.

In the solution of the obtained polyimine (A), since the catalyst or the like remaining remains, it is preferred to use the liquid crystal alignment treatment agent of the present invention after recovering and washing the polyimide.

The polyimine (A) can be recovered by subjecting the ruthenium-imided solution to a stirred weak solvent to precipitate a polyimine and then filtering. Examples of the weak solvent include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. The washing of the recovered polyimine is also carried out by the weak solvent. The recovered and washed polyimine is subjected to normal temperature or heat drying under normal pressure or reduced pressure to form a powder.

The molecular weight of the polyimine (A) contained in the liquid crystal alignment agent of the present invention is not particularly limited, but the weight average molecular weight is preferred from the viewpoints of coating film strength and ease of handling as a liquid crystal alignment treatment agent. It is 2,000 to 200,000, more preferably 5,000 to 50,000.

<polyimine (B)> Polyimine (B) is a reaction of a diamine component with a tetracarboxylic dianhydride component. The obtained polyamic acid is subjected to quinone imidization of polyimine. The polyimine (B) is soluble in the organic solvent contained in the liquid crystal alignment treatment agent of the present invention, and the reaction of the polyimine (B) obtained by reacting the diamine component with the tetracarboxylic dianhydride component It is also soluble in the organic solvent used.

[Diamine component] The diamine component for obtaining the polyimine (B) is a diamine represented by the formula (1) and a diamine represented by the formula (6) as an essential component.

In the formula (6), X ₄ represents a single bond, or a bond group selected from the group consisting of ether, ester, methylene ether, and decylamine, and X ₅ is a linear alkyl group having 14 to 20 carbon atoms. Or a monovalent organic group represented by the following formula (7).

In the formula (7), X ₆ is a phenyl group or a cyclohexyl group, and X ₇ is a cyclohexyl group having a linear alkyl group having 1 to 12 carbon atoms.

The diamine represented by the formula (1) is the same as the specific example of the [diamine component] described in the above polyimine (A).

In the polyimine (B), not only the diamine represented by the formula (1) but also the diamine represented by the formula (6) is also required as the diamine component. The content of the diamine represented by the formula (1) is 20 to 90 mol%, preferably 30 to 60 mol%, more preferably 30 to 50, based on the entire diamine component in the polyimine (B). Moer%.

On the other hand, the diamine represented by the formula (6) preferably contains 5 to 40 mol% of the entire diamine component in the polyimine (B), which increases the pretilt angle of the liquid crystal. The content of the diamine represented by the formula (6) is particularly preferably from 10 to 40 mol%, more preferably from 10 to 30 mol%. In particular, the more the ratio of the diamine represented by the formula (6), the more the pretilt angle of the liquid crystal is larger, which is preferable. The diamine represented by the formula (6) may be used alone or in combination of plural kinds.

Further, in the entire diamine component of the polyimine (B), when the total content of the diamine of the formula (1) and the diamine of the formula (6) is less than 100 mol%, the remaining diamine is from At least one selected from the group consisting of the above formula (2), formula (3), formula (4), and formula (5). It is preferably at least one diamine selected from the group consisting of the formula (3), the formula (4), and the formula (5), and these diamines can achieve an effect of maintaining good liquid crystal alignment. The content of these diamines is from 0 to 75 mol%, preferably from 5 to 75 mol%, preferably from 10 to 60 mol%, based on the diamine component in the polyimine (B). .

Specific examples of the diamine represented by the formula (6) are given below, but are not limited thereto.

In the formulae (15) to (19), p is an integer of 13 to 19, preferably 13 to 17.

In the formulae (20) to (24), q is an integer of 0 to 11, preferably 2 to 6.

In the formulae (25) to (29), b is an integer of 0 to 11, preferably 2 to 6.

[tetracarboxylic dianhydride component] In order to obtain polyimine (B), a tetracarboxylic acid which reacts with the above diamine component The acid dianhydride component is not limited to the problems of improving the printability at the time of coating the substrate, the damage of the surface of the liquid crystal alignment film caused by the rubbing treatment, and the peeling of the film, and of course, various options can be selected depending on other characteristics. The tetracarboxylic dianhydride to be used may be used alone or in combination of plural kinds. A preferred example of the tetracarboxylic dianhydride exemplified as the [tetracarboxylic dianhydride component] of the polyimine (A).

[Method for producing polyaminic acid and polyimine (B)] a reaction operation in which the diamine component and the tetracarboxylic dianhydride component are reacted to obtain a poly-proline, and the obtained polyaminic acid oxime imidization and polyimine recovery operation are the same as the above-mentioned poly The above-mentioned method of producing a polyimine (A method for producing a polyaminic acid) and [Method for producing a polyimine (A)] are carried out in the same manner.

The molecular weight of the precursor of the polyimine (B), that is, the polyamic acid is not particularly limited, but particularly, as a precursor for obtaining the polyimine (B) suitable for the present invention, the weight average molecular weight is preferred. It is 2,000 to 200,000, more preferably 5,000 to 50,000.

Further, the molecular weight of the polyimine (B) is not particularly limited, but the weight average molecular weight is preferably from 2,000 to 200,000, more preferably from the viewpoint of coating film strength and ease of handling as a liquid crystal alignment treatment agent. 5,000~50,000.

The ruthenium imidization ratio of the polyimine (B) is not particularly limited, but is preferably 40% or more in the same manner as the polyimine (A), and more preferably 60 in order to obtain a high voltage holding ratio. More than %, especially better than 80%.

<Liquid alignment treatment agent> The liquid crystal alignment treatment agent of the present invention is a solution containing a suitable ratio of polyimine (A) and polyimine (B). For example, the powders of the polyimine (A) and the polyimine (B) are dissolved in an organic solvent to form a polyimine solution, and after mixing the solutions, the solution is diluted to a desired concentration. The solution or a solution of each polyimine is diluted to a desired concentration, and then mixed to form a solution. In the above-mentioned dilution step, in order to control the coating property to the substrate, adjustment of the organic solvent composition, addition of an additive for improving coating film properties, and the like can be performed.

The ratio of the polyimine (A) to the polyimine (B) contained in the liquid crystal alignment agent of the present invention, for the total content of the polyimine (A) and the polyimine (B), The content of the polyimine (A) is from 50 to 90% by mass, and good printability and a large pretilt angle can be easily obtained. The content of the polyimine (A) is preferably from 60 to 80% by mass.

That is, the polyimine (A) and the polyimine (B), the mass ratio of the former to the latter, are 50:50 to 90:10, preferably 60:40 to 80:20.

Examples of the organic solvent for redissolving the powder of the polyimine (A) and/or the polyimide (B) include N,N-dimethylformamide and N,N-dimethyl. Acetamine, N-methyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, Tetramethylurea, dimethylhydrazine, hexamethylarylene, γ-butylpropyl ester, 1,3-dimethyl-imidazolidinone, and the like. Among them, γ-butyl propyl ester is preferred because it is not easily hygroscopic.

Examples of the solvent to be added for controlling the coating property to the substrate include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, and B. Kikabi alcohol acetate, ethylene glycol, diethylene glycol diethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2- Propyl alcohol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate Ester, dipropylene glycol, dipropylene glycol monomethyl ether, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. .

The solvent may not contain a solvent which cannot dissolve the polyimine (A) or the polyimine (B) alone, and may be mixed into the liquid crystal alignment of the present invention in a range in which the polyimide does not precipitate. In the treatment agent. In particular, it is known that the uniformity of the coating film can be improved at the time of coating the substrate by appropriately mixing a solvent having a low surface tension, and is also applicable to the liquid crystal alignment treatment agent of the present invention.

Among the above combinations of solvents, in addition to γ-butyl propionate and butyl cellosolve, it is preferred to also contain dipropylene glycol monomethyl ether or diethylene glycol diethyl ether, particularly preferably γ-butyl propyl ester, butyl solution. A combination of a fiber and a dipropylene glycol monomethyl ether. The ratio of each solvent is 40 to 80% by mass, preferably 40 to 70% by mass, and 10 to 30% by mass, preferably 10 to 20% by mass, based on the total solvent. The dipropylene glycol monomethyl ether or diethylene glycol diethyl ether is 10 to 30% by mass, preferably 10 to 20% by mass. By using the liquid crystal alignment agent of the present invention having such a composition, unevenness and pinholes due to changes in film thickness are less likely to occur during printing.

As an additive for improving the characteristics of the coating film, 3-aminopropylmethyldiethoxydecane, 3-phenylaminopropyltrimethoxydecane, and 3-amine are mentioned. A decane coupling agent such as propyltriethoxysilane or (aminoethylaminomethyl)phenethyltrimethoxydecane. By adding a decane coupling agent, the adhesion of the coating film to the substrate can be further improved.

The content (concentration) of the polyimine contained in the liquid crystal alignment agent of the present invention can be appropriately changed depending on the setting of the thickness of the liquid crystal alignment film to be formed. In general, the total content of the polyimine (A) and the polyimine (B) is preferably from 1 to 10% by mass, particularly preferably from 2 to 6% by mass, in which case it is easy to form a uniform defect-free The coating film can further improve the storage stability of the liquid crystal alignment treatment agent. Further, the liquid crystal alignment agent of the present invention is preferably filtered before being applied onto a substrate, as the case may be.

<Liquid alignment film> The liquid crystal alignment film of the present invention can be obtained by applying the liquid crystal alignment treatment agent onto a substrate, drying it, baking it, and curing it as a coating film, and applying a rubbing treatment or the like to the coating film surface.

The substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.

Further, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed, from the viewpoint of simplification of the process, and in the case of a reflective liquid crystal display device, it is also possible to use only a single-sided substrate. For an opaque substrate such as a wafer, a material such as aluminum that reflects light can be used as the electrode.

Examples of the coating method of the liquid crystal alignment treatment agent include a spin coating method, a printing method, an inkjet method, and the like. In terms of productivity, industrially widely used offset plates The printing method is also applicable to the liquid crystal alignment treatment agent of the present invention.

The drying step after the application of the liquid crystal alignment agent is not necessarily required. However, it is preferred to carry out a drying step when the time from the application to the baking is not necessarily the case, or when the baking is not performed immediately after application. The degree of drying is not particularly limited as long as the shape of the coating film is not deformed by the conveyance of the substrate, and the solvent can be evaporated. For example, a method of drying for 0.5 to 30 minutes, preferably 1 to 5 minutes, on a hot plate having a temperature of 50 to 150 ° C, preferably 80 to 120 ° C, may be mentioned.

The baking of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of 100 to 350 ° C, preferably 150 ° C to 300 ° C, more preferably 180 ° C to 250 ° C. When the proline group is present in the polyimide, the rate of oxime imidization of the polyimide film obtained at the calcination temperature may vary, but in the present invention, the yield of oxime may not necessarily be 100%. .

If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element is lowered, so it is preferably 10 to 200 nm, more preferably 50. ~100 nm.

As described above, the rubbing treatment of the coating film surface formed on the substrate can be performed using an existing friction device. Examples of the material of the rubbing cloth at this time include cotton, enamel, and nylon.

The liquid crystal alignment film of the present invention can be obtained by a method.

<Liquid crystal display element> The liquid crystal display element of the present invention is obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method. The method produces a liquid crystal cell and becomes a liquid crystal display element.

For the production of a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is generally used, and a spacer of 1 to 30 μm is preferably sandwiched, and a spacer of 2 to 10 μm is preferably sandwiched, and the rubbing direction is 0 to 270. Set at any angle of the crucible, seal the surrounding with a sealant, inject liquid crystal and close the method. The method of encapsulating the liquid crystal is not particularly limited, and a vacuum method in which the liquid crystal cell to be produced is depressurized, a liquid crystal is injected thereinto, a liquid crystal is dropped, and a dropping method is performed.

Example

The invention is illustrated in more detail below by the examples, but the invention is not construed as limited.

The abbreviations used in the examples and comparative examples are as follows.

<tetracarboxylic dianhydride> CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride PMDA: pyromellitic dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

<Diamine> 2,4-DAA: 2,4-diamino-N,N-diallylaniline PCH7AB: 4-{4-(4-heptylcyclohexyl)phenoxy}1,3-diaminobenzene C12DAB: 4-dodecyloxy-1,3-diaminobenzene C14DAB: 4-tetradecyloxy-1,3-diaminobenzene C16DAB: 4-hexadecyloxy-1,3-diaminobenzene 4-ABA: 4-aminobenzylamine 3-ABA: 3-aminobenzylamine

<organic solvent> NMP: N-methyl-2-pyrrolidone γBL: γ-butyl propyl ester BS: butyl cellosolve DPM: dipropylene glycol monomethyl ether

<Structure>

<Measurement of molecular weight> The molecular weight of polyimine is determined by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight and weight average are calculated as polyethylene glycol and polyethylene oxide equivalent values. Molecular weight.

GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: manufactured by Shodex Co., Ltd. (series of KD803, KD805) Column temperature: 50 °C Eluent: N,N-dimethylformamide (as additive, lithium bromide) Monohydrate (LiBr.H ₂ O) was 30 mmol/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) was 30 mmol/L, tetrahydrofuran (THF) was 10 ml/L. Flow rate: 1.0 ml/min calibration curve was prepared. Standard samples were used: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

<Measurement of the imidization ratio of oxime> The ruthenium iodide ratio of the polyimine was measured as follows. 20 mg of the polyimine powder was placed in an NMR sample tube, and 0.536 ml of a hydrogenated dimethyl hydrazine (DMSO-d ₆ , 0.05% TMS mixture) was added to completely dissolve. This solution was measured by a proton NMR at 500 MHz by a NMR analyzer (JNM-ECA500) manufactured by Japan Electronic Data Co., Ltd. The ruthenium imidization rate is determined by using a proton that has not changed before and after imidization as a reference proton. The peak value of the proton is used and the NH group of proline is present near 9.5 to 10.0 ppm. The cumulative value of the proton spike is obtained by the following formula.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is a cumulative value of proton spikes derived from the NH group of proline, y is the peak cumulative value of the reference proton, and α is a poly-proline (the imidization ratio is 0%). For an NH proton of proline, the ratio of the number of reference protons.

(Synthesis Example 1)

As the tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 8.13 g (0.040 mol) of 2,4-DAA and 3.67 g (0.030 mol) of 4 were used. - ABA, 8.77 g (0.030 mol) of C12DAB, and reacted at room temperature for 24 hours in 161.8 g of NMP to obtain a polyaminic acid solution.

To 34.81 g of this polyaminic acid solution, 62.65 g of NMP was added for dilution, 5.15 g of acetic anhydride and 2.19 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was charged 366.8 m. The precipitated solids were recovered from the liter of methanol. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-1). The polyimine had a number average molecular weight of 12,016 and a weight average molecular weight of 35,126. Further, the hydrazine imidation ratio was 90%.

To 1.99 g of the polyimine obtained above, 17.91 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 7.53 g of γBL, 4.82 g of BS, and 4.82 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 2)

As the tetracarboxylic dianhydride component, 13.43 g (0.0685 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 8.13 g (0.040 mol) of 2,4-DAA and 5.50 g (0.045 mol) of 4 were used. - ABA, 4.39 g (0.015 mol) of C12DAB, and reacted at room temperature for 24 hours in 152.0 g of NMP to obtain a polyaminic acid solution.

To 32.39 g of this polyaminic acid solution, 72.88 g of NMP was added for dilution, 5.09 g of acetic anhydride and 2.17 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 393.9 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-2). The polyimine had a number average molecular weight of 12,616 and a weight average molecular weight of 39,703. Further, the sulfhydrylation rate is 90%.

To 3.01 g of the polyimine obtained above, 27.09 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 10.09 g of γBL, 8.21 g of BS, and 8.21 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 3)

As the tetracarboxylic dianhydride component, 13.33 g (0.068 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 8.13 g (0.040 mol) of 2,4-DAA and 7.33 g (0.060 mol) of 4 were used. -ABA, the reaction was allowed to proceed for 24 hours at room temperature in 141.4 g of NMP to obtain a polyaminic acid solution.

To 30.15 g of this polyaminic acid solution, 67.84 g of NMP was added for dilution, 5.11 g of acetic anhydride and 2.18 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 368.5 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-3). The polyimine had a number average molecular weight of 12,899 and a weight average molecular weight of 39,984. Further, the sulfhydrylation rate was 85%.

To 3.06 g of the polyimine obtained above, 27.54 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to room temperature, add 10.14 g. γBL, 8.24 g of BS, and 8.24 g of DPM were thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 4)

As the tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 6.10 g (0.030 mol) of 2,4-DAA and 4.89 g (0.040 mol) of 3 were used. - ABA, 9.62 g (0.030 mol) of C14DAB, and reacted at room temperature for 24 hours in 162.7 g of NMP to obtain a polyaminic acid solution.

To 35.79 g of this polyaminic acid solution, 63.91 g of NMP was added for dilution, 5.16 g of acetic anhydride and 2.20 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 374.7 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-4). The polyimine had a number average molecular weight of 13,472 and a weight average molecular weight of 35,859. Further, the hydrazine imidation ratio was 89%.

To 2.17 g of the polyimine obtained above, 15.91 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 6.37 g of γBL, 7.38 g of BS, and 7.38 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 5)

As the tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 6.10 g (0.030 mol) of 2,4-DAA and 6.11 g (0.050 mol) of 3 were used. - ABA, 6.97 g (0.020 mol) of C16DAB, and reacted at room temperature for 24 hours in 157.0 g of NMP to obtain a polyaminic acid solution.

To 23.20 g of this polyaminic acid solution, 32.77 g of NMP was added for dilution, 3.49 g of acetic anhydride and 1.49 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 213.3 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-5). The polyimine had a number average molecular weight of 12,498 and a weight average molecular weight of 34,121. Further, the hydrazine imidation ratio was 89%.

To 1.59 g of the polyimine obtained above, 11.66 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 4.99 g of γBL, 5.78 g of BS, and 5.78 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 6)

As the tetracarboxylic dianhydride component, 13.33 g (0.068 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 8.13 g (0.040 mol) of 2,4-DAA and 6.11 g (0.040 mol) of 4 were used. - ABA, 3.81 g (0.010 mol) PCH7AB, in 151.7 g NMP, react at room temperature 24 A polyamine solution was obtained in an hour.

To 33.38 g of this polyaminic acid solution, 59.61 g of NMP was added for dilution, 5.26 g of acetic anhydride and 2.24 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 351.7 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-6). The polyimine had a number average molecular weight of 10,877 and a weight average molecular weight of 34,898. Further, the hydrazine imidation ratio was 90%.

To 1.91 g of the polyimine obtained above, 17.19 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 2.37 g of γBL, 4.35 g of BS, and 4.35 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 7)

As the tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 6.10 g (0.030 mol) of 2,4-DAA and 3.67 g (0.030 mol) of 3 were used. - ABA, 12.82 g (0.040 mol) of C14DAB, and reacted at room temperature for 24 hours in 170.6 g of NMP to obtain a polyaminic acid solution.

To 58.20 g of this polyaminic acid solution, 102.3 g of NMP was added for dilution, and 8.06 g of acetic anhydride and 3.44 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 601.9 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-7). The polyimine had a number average molecular weight of 11,013 and a weight average molecular weight of 36,721. Further, the hydrazine imidation ratio was 89%.

To 3.27 g of the polyimine obtained above, 23.98 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 7.75 g of γBL, 11.95 g of BS, and 11.95 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 8)

As the tetracarboxylic dianhydride component, 19.36 g (0.099 mol) of CBDA was used; as the diamine component, 6.10 g (0.030 mol) of 2,4-DAA, 4.89 g (0.040 mol) of 3-ABA, and 9.62 g (0.030 mol) were used. C14DAB was reacted in 159.8 g of NMP at room temperature for 24 hours to obtain a polyaminic acid solution.

To 74.94 g of this polyaminic acid solution, 131.68 g of NMP was added for dilution, 11.09 g of acetic anhydride and 4.73 g of pyridine were added, and the reaction was carried out at a temperature of 50 ° C for 3 hours to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 778.5 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-8). The number average molecular weight of the polyimine is 16,241, weight average molecular weight of 40,259. Further, the hydrazine imidation ratio was 89%.

To 4.80 g of the polyimine obtained above, 43.20 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 3.60 g of γBL, 18.05 g of BS, and 18.05 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 9)

As the tetracarboxylic dianhydride component, 9.61 g (0.049 mol) of CBDA and 15.02 g (0.050 mol) of TDA were used; as the diamine component, 6.10 g (0.030 mol) of 2,4-DAA and 4.89 g (0.040 mol) of 3 were used. - ABA, 9.62 g (0.030 mol) of C14DAB, and reacted at room temperature for 24 hours in 180.9 g of NMP to obtain a polyaminic acid solution.

To 40.54 g of this polyaminic acid solution, 70.66 g of NMP was added for dilution, 5.27 g of acetic anhydride and 2.24 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 415.5 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-9). The polyimine had a number average molecular weight of 14,756 and a weight average molecular weight of 35,977. Further, the hydrazine imidation ratio was 90%.

To 4.07 g of the polyimine obtained above, 36.63 g of γBL was added. Stir at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 2.44 g of γBL, 14.16 g of BS, and 14.16 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 10)

19.41 g (0.099 mol) of CBDA was used as the tetracarboxylic dianhydride component, and 20.33 g (0.100 mol) of 2,4-DAA was used as the diamine component, and the reaction was carried out for 24 hours at room temperature in 159.00 g of NMP. Polylysine solution.

To 25.13 g of this polyaminic acid solution, 38.79 g of NMP was added for dilution, 3.94 g of acetic anhydride and 1.68 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 243.4 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-10). The polyimine had a number average molecular weight of 10,122 and a weight average molecular weight of 21,004. Further, the hydrazine imidation ratio was 97%.

To 2.50 g of the polyimine obtained above, 22.50 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved.

(Synthesis Example 11)

As the tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 8.13 g (0.040 mol) of 2,4-DAA and 3.67 g (0.030 mol) of 4 were used. - ABA, 8.77 g (0.030 mol) of C12DAB, and reacted at room temperature for 24 hours in 162.6 g of NMP to obtain a polyaminic acid solution.

To 38.33 g of this polyaminic acid solution, 68.99 g of NMP was added for dilution, 5.67 g of acetic anhydride and 2.42 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 45 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 403.9 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-11). The polyimine had a number average molecular weight of 13,513 and a weight average molecular weight of 47,948. Further, the sulfhydrylation rate was 76%.

To 5.21 g of the polyimine obtained above, 46.89 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 14.49 g of γBL, 14.49 g of BS, and 14.49 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Synthesis Example 12)

As the tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 6.10 g (0.030 mol) of 2,4-DAA and 4.89 g (0.040 mol) of 3 were used. -ABA, 9.62 g (0.030 mol) C14DAB was reacted in 162.7 g of NMP at room temperature for 24 hours to obtain a polyaminic acid solution.

To 39.77 g of this polyaminic acid solution, 69.88 g of NMP was added for dilution, 5.79 g of acetic anhydride and 2.47 g of pyridine were added, and the reaction was allowed to proceed for 1 hour at a temperature of 50 ° C to imidize.

After the reaction solution was cooled to about room temperature, it was poured into 412.7 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-12). The polyimine had a number average molecular weight of 10,734 and a weight average molecular weight of 28,190. Further, the sulfhydrylation rate was 79%.

To 4.8 g of the polyimine obtained above, 43.2 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 3.6 g of γBL, 18.05 g of BS, and 18.05 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution.

(Reference example 1)

As a tetracarboxylic dianhydride component, 22.59 g (0.115 mol) of CBDA was used; as a diamine component, 14.66 g (0,120 mol) of 4-ABA was used, and in 211.10 g of NMP, the reaction was allowed to proceed at room temperature for 24 hours to obtain a polyfluorene. Amino acid solution.

To 21.22 g of this polyaminic acid solution, 22.74 g of NMP was added for dilution, 10.12 g of acetic anhydride and 4.71 g of pyridine were added, and the reaction was carried out at a temperature of 50 ° C. As a result, gelation was carried out at 30 minutes, and polyimine was not obtained.

Next, the reaction temperature was lowered to 35 ° C, and the same dissolution as described above was carried out. The liquid was imidized for 3 hours.

After cooling the reaction solution to about room temperature, it was poured into 205.7 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine. The polyimine had a number average molecular weight of 12,994 and a weight average molecular weight of 30,081. Further, the sulfhydrylation rate was 78%.

To 1.64 g of the polyimine obtained above, 14.76 g of γBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours, but at the end of the stirring, the undissolved polyimine remained, and it was confirmed that 2, 4 was not used. -DAA is a diamine component, and the solubility of polyimine is poor.

Table 1 shows the results of Synthesis Examples 1 to 12 and Reference Example 1.

(Example 1)

The polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4 was used as SPI- The mass ratio of 1 to SPI-4 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

<Printability evaluation> The liquid crystal alignment treatment agent was offset-printed onto the washed Cr plate using an alignment film printer ("Angstromer" manufactured by Nippon Photographic Co., Ltd.). The printed substrate was placed on a hot plate at 70 ° C for 5 minutes to temporarily dry the coating film.

In the optical microscope ("ECLIPSE ME600" manufactured by NIKON Co., Ltd.), the surface of the film after the temporary drying was observed 50 times, and as a result, unevenness due to the change in film thickness did not occur, and pinholes (concave spots of the film) were not observed. .

<Evaluation of friction resistance> The liquid crystal alignment treatment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C for 5 minutes, and then fired on a hot plate at 230 ° C for 15 minutes to form a coating having a film thickness of 100 nm. membrane. Using a rubbing device with a roll diameter of 120 mm, using a crepe cloth, the film surface was rubbed under the conditions of a roller rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.3 mm to obtain a liquid crystal alignment film. Substrate.

In the confocal laser microscope, the film surface of the liquid crystal alignment film was observed at 2000 times, and no damage or peeling of the film was observed.

Further, the observation of the surface of the film was performed by a laser scanning microscope 1LM21D manufactured by LASERTEC.

(Example 2)

Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 5, the mass ratio of SPI-1 to SPI-5 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 3)

Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 6, the mass ratio of SPI-1 to SPI-6 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 4)

Using the polyimine solution obtained in Synthesis Example 2 and Synthesis Example 4, the mass ratio of SPI-2 to SPI-4 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 5)

Using the polyimine solution obtained in Synthesis Example 3 and Synthesis Example 4, the mass ratio of SPI-3 to SPI-4 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 6)

The polyimine solution obtained in Synthesis Example 1 and Synthesis Example 7 was mixed at a mass ratio of SPI-1 to SPI-7 at 7:3 to obtain a liquid crystal alignment treatment agent of the present invention.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 7)

The polyimine solution obtained in Synthesis Example 1 and Synthesis Example 8 was mixed at a mass ratio of SPI-1 to SPI-8 at 7:3 to obtain a liquid crystal alignment treatment agent of the present invention.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 8)

The polyimine solution obtained in Synthesis Example 1 and Synthesis Example 9 was mixed at a mass ratio of SPI-1 to SPI-9 at 7:3 to obtain a liquid crystal alignment treatment agent of the present invention.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 9)

Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4, the mass ratio of SPI-1 to SPI-4 was 6:4, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Embodiment 10)

Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4, the mass ratio of SPI-1 to SPI-4 was 9:1, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 11)

Using the polyimine solution obtained in Synthesis Example 10 and Synthesis Example 4, the mass ratio of SPI-10 to SPI-4 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Embodiment 12)

Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 12, the mass ratio of SPI-1 to SPI-12 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Example 13)

Using the 2:polyimine solution obtained in Synthesis Example 11 and Synthesis Example 4, the mass ratio of SPI-11 to SPI-4 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

(Comparative Example 1)

The polyimine solution obtained in Synthesis Example 4 was used as a liquid crystal alignment treatment agent, and the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, the unevenness caused by the change in film thickness was severe, and most of the pinholes were also observed. No damage or peeling of the film was observed.

(Comparative Example 2)

The polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4 was mixed at a mass ratio of SPI-1 to SPI-4 to 4:6 to obtain a liquid crystal alignment treatment agent of the present invention.

Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, the unevenness caused by the change in film thickness was severe, and most of the pinholes were also observed. No damage or peeling of the film was observed.

(Comparative Example 3)

The polyimine solution obtained in Synthesis Example 1 was used as a liquid crystal alignment treatment agent, and the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, unevenness due to the change in film thickness did not occur, pinholes were not observed, and no damage or peeling of the film was observed.

<Evaluation of pretilt angle> The liquid crystal alignment treatment agents used in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated for the pretilt angle of the liquid crystal cell as follows.

Spin-coating the liquid crystal alignment treatment agent on the glass substrate with the transparent electrode, After drying on a hot plate at 70 ° C for 5 minutes, it was baked on a hot plate at 230 ° C for 15 minutes to form a coating film having a film thickness of 100 nm. Using a rubbing device with a roll diameter of 120 mm, using a crepe cloth, the film surface was rubbed under the conditions of a roller rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.3 mm to obtain a liquid crystal alignment film. Substrate.

Two sheets of the substrate were prepared, and a spacer of 6 μm was spread on one of the liquid crystal alignment film surfaces, and a sealant was printed thereon, and the other substrate was bonded in a reverse direction to the opposite rubbing direction of the liquid crystal alignment film surface. Thereafter, the sealant is hardened to prepare a hollow cell. In this empty cell, liquid crystal MLC-2003 (manufactured by MERCK Japan Co., Ltd.) was injected by a vacuum injection method, and the injection port was closed to obtain an antiparallel nematic liquid crystal cell.

Using this liquid crystal cell, the measurement of the pretilt angle at a temperature of 23 ° C was performed. For the measurement, TBA107 manufactured by Autronic Corporation was used. The evaluation results are shown in Table 2.

<Evaluation of Voltage Retention Rate> Two sheets of the liquid crystal alignment film prepared in the same manner as described above were used, and a spacer of 6 μm was spread on one of the liquid crystal alignment film surfaces to print a sealant, and the other substrate was subjected to relative rubbing of the liquid crystal alignment film surface. After the directions are bonded in a straight line, the sealant is hardened to form a hollow cell. In this empty cell, liquid crystal MLC-2003 (C080, manufactured by MERCK Japan Co., Ltd.) was injected by a vacuum injection method, and the injection port was closed to obtain a twisted nematic liquid crystal cell.

For this liquid crystal cell, a voltage of 4 V for 60 microseconds was applied at a temperature of 23 ° C, and the voltage after 16.67 msec was measured to calculate how much the voltage can be maintained as a voltage holding ratio. Further, the same measurement was carried out at a temperature of 90 °C. Further, the voltage holding ratio was measured by using a VHR-1 voltage holding ratio measuring device manufactured by Dongyang Technology Co., Ltd.

Table 2 shows the evaluation results of the respective characteristics in Examples 1 to 13 and Comparative Examples 1 to 3.

Further, the rubbing resistance was regarded as ○ in the case where the surface of the liquid crystal alignment film was observed, and no damage was observed and the film was peeled off.

From the above evaluation results, it was confirmed that the liquid crystal alignment treatment agent of the present invention The printability is excellent, and the liquid crystal of the obtained liquid crystal alignment film has a large pretilt angle and is excellent in abrasion resistance.

On the other hand, in the liquid crystal alignment treatment agent of the comparative example, it was confirmed that the obtained liquid crystal alignment film had a large pretilt angle of the liquid crystal, but the printability was poor (Comparative Example 1), or the liquid crystal alignment was obtained even if there was no problem in printability. The pretilt angle of the liquid crystal of the film was also small (Comparative Example 3).

Industrial utilization possibility

The liquid crystal alignment treatment agent of the present invention can form a liquid crystal alignment film which contains a polyimide having a high yield of ruthenium iodide and which is less likely to cause damage to the surface of the film during the rubbing treatment and peeling of the film. Moreover, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is applied to a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, an OCB liquid crystal display element, etc. which are highly reliable liquid crystal display devices. .

Further, the specification of the Japanese Patent Application No. 2006-317529 filed on Nov. 24, 2006, and the Japanese Patent Application No. 2006-322397 filed on Nov. 29, 2006, the scope of the patent application, and the abstract The entire contents of this specification are hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety

Claims (10)

A liquid crystal alignment treatment agent characterized by comprising the following polyimine (A) and polyimine (B), polyimine (A): (i) represented by formula (1) An amine component composed of an amine, or (ii) a diamine component composed of a diamine represented by the formula (1) and at least one diamine selected from the group consisting of the formulas (2) and (3), and a polyamidimide obtained by reacting a polycarboxylic acid with a tetracarboxylic dianhydride component; a polyimine (B): (iii) a diamine represented by the formula (1) (6) a diamine component composed of a diamine, or (iv) a diamine represented by the formula (1) and a diamine represented by the formula (6) and a group consisting of the formula (2) and the formula (3) a selected polyamine component obtained by reacting at least one diamine component and a polyphthalic acid obtained by reacting a tetracarboxylic dianhydride component with a tetracarboxylic acid dianhydride component; (In the formula (2), X ₁ represents a single bond, or a bond group selected from a group consisting of ether, ester, and decylamine, and X ₂ represents a linear alkyl group having 1 to 12 carbon atoms; ), n series 1 or 2) (In the formula (6), X ₄ represents a single bond, or a bond group selected from the group consisting of ether, ester, methylene ether, and decylamine, and X ₅ is a linear alkane having 14 to 20 carbon atoms. a group or a monovalent organic group represented by the following formula (7): [Chemical Formula 4]-X ₆ -X ₇ (7) (In the formula (7), the X ₆ -phenyl group or the cyclohexyl group, the X ₇ system has a cyclohexyl group of a linear alkyl group having 1 to 12 carbon atoms). The liquid crystal alignment treatment agent of claim 1, which comprises a polyimine (A) and a polyimine (B) in a mass ratio of 50:50 to 90:10. The liquid crystal alignment treatment agent of claim 1, wherein the polyamidene (A) and the polyimine (B) have a sulfhydrylation ratio of 40% or more. The liquid crystal alignment treatment agent of claim 1, wherein the amount of the total diamine of 100 mol% in the polyimine (A) is 20% to 100 mol%, represented by the formula (1) The diamine, and when the diamine content of the formula (1) is less than 100 mol%, the remaining diamine is at least one diamine selected from the group consisting of the formulas (2) and (3). The liquid crystal alignment treatment agent of claim 1, wherein the amount of the total diamine of 100 mol% in the polyimine (B) is 20~ 90 mol% of the diamine represented by the formula (1), 5 to 40 mol% of the diamine represented by the formula (6), and the total content of the diamine of the formula (1) and the diamine of the formula (6) When it is less than 100% by mole, the remaining diamine is at least one selected from the group consisting of the formulas (2) and (3). The liquid crystal alignment treatment agent according to any one of claims 1 to 5, which further comprises γ-butyl propionate, butyl cellosolve, dipropylene glycol monomethyl ether or diethylene glycol diethyl ether as an organic solvent. ingredient. The liquid crystal alignment treatment agent according to claim 1, wherein the liquid crystal alignment treatment agent is a rubbed liquid crystal alignment film. A liquid crystal alignment film obtained by using a liquid crystal alignment treatment agent according to any one of claims 1 to 7. A liquid crystal alignment film obtained by applying a liquid crystal alignment treatment agent according to any one of claims 1 to 7 to a substrate on which an electrode is attached, and performing baking and rubbing treatment. A liquid crystal display element having a liquid crystal alignment film according to claim 8 or 9.