TWI486377B - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent containing a polyimide and/or a polyimide precursor, a liquid crystal alignment film, and a liquid crystal display element.

Liquid crystal display elements have been widely used in today's applications as thin and light display devices. In the liquid crystal display device, a liquid crystal alignment film is used to determine the alignment state of the liquid crystal. Further, in addition to a part of the vertical alignment type liquid crystal display element or the like, the liquid crystal alignment film is produced by applying a certain alignment treatment to the surface of the polymer film formed on the electrode substrate.

As the polymer used for the liquid crystal alignment film, polyimine, polyamine, polyamidimine or the like is known, and a liquid crystal alignment agent which dissolves these polymers or the precursor in a solvent is generally used. As a precursor of polyimine, polylysine is generally used.

As a method of aligning the polymer film formed on the electrode substrate, the most popular method is to apply a rubbing treatment by applying a pressure to the surface of the film by a cloth such as a crucible. However, in the step of the rubbing treatment, a part of the film may be peeled off, or a scratch caused by the rubbing treatment may occur on the surface of the liquid crystal alignment film, causing a problem of so-called "film reduction", which may become a characteristic of the liquid crystal display element. One of the reasons for the decrease or the decrease in yield.

For the problem of film reduction caused by the rubbing treatment, there has been proposed a method of using a liquid crystal alignment agent containing a specific heat crosslinkable compound while using at least one polymer of polyaminic acid or polyimine (for example, Patent Document 1) or a method of using a liquid crystal alignment agent containing an epoxy group-containing compound (for example, refer to Patent Document 2) or the like, or a method of improving frictional resistance by using a curing agent.

Further, in recent years, large-screen and high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements in such applications are required to have characteristics that can withstand long-term use in a severe use environment. Therefore, the liquid crystal alignment film used herein must have higher reliability than in the past, and the electrical characteristics of the liquid crystal alignment film are required to be excellent in initial characteristics. For example, it is required to have excellent light resistance for long-term backlight exposure.

[Advanced technical literature]

[Patent Literature]

[Patent Document 1] JP-A-9-185065

[Patent Document 2] JP-A-9-146100

The present invention has been made in view of the above circumstances.

That is, the problem to be solved by the present invention is to provide a liquid crystal alignment agent which is less cut by a rubbing treatment and which has a small decrease in voltage holding ratio even after long-time exposure to a backlight, and further provides durability. A highly reliable liquid crystal display element for long-term use in harsh environments.

The gist of the present invention is as follows.

(1) A liquid crystal alignment agent characterized by containing a compound having a structure in which a group represented by the formula [i] is bonded to an aromatic ring and a component (B) selected from the group consisting of poly(imine) and poly(a) At least one polymer compound in the group of amine precursors.

(X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(2) The liquid crystal alignment agent according to the above (1), wherein X in the formula [i] is a hydrogen atom.

(3) The liquid crystal alignment agent according to the above (1), wherein the component (A) is at least one selected from the group consisting of a compound represented by the following formula [1] and a compound represented by the formula [2]. .

In the formula, X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ₁ , Y ₂ and Y ₃ each independently represent an aromatic ring, and any hydrogen of the aromatic ring The atom may be substituted by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group. Z ₁ represents a single bond, all or a part of which may be bonded to form a cyclic structure of a saturated hydrocarbon group having 1 to 10 carbon atoms, and any hydrogen atom may be substituted by a fluorine atom -NH-, -N(CH ₃ )- or a group represented by the formula [3].

(In the formula, P ₁ and P ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring.)

t ₁ is an integer of 2 to 4, and t ₂ and t _{3 are} each independently an integer of 1 to 3, and a and b are each independently an integer of 1 to 3. ]

(4) The liquid crystal alignment agent according to the above (3), wherein X ₁ in the formula [1] and X ₂ and X ₃ in the formula [2] are a hydrogen atom.

(5) The liquid crystal alignment agent according to the above (3) or (4), wherein Y ₁ in the formula [1] and Y ₂ and Y ₃ in the formula [2] are each independently a benzene ring or a pyridine ring.

(6) The liquid crystal alignment agent according to any one of the above-mentioned (1), wherein the component (A) is at least one compound selected from the group consisting of the following compounds.

The liquid crystal alignment agent of any one of the above-mentioned (1), wherein the component (A) is at least one compound selected from the group consisting of the following compounds.

The liquid crystal alignment agent of any one of the above (1), wherein the component (B) is selected from the group consisting of polyamines obtained by reacting a diamine component with a tetracarboxylic dianhydride component. And at least one polymer compound in a group of the polyamidene obtained by subjecting the polyamic acid to dehydration ring closure.

The liquid crystal alignment agent of any one of the above-mentioned (1) to (8) further containing an organic solvent.

(10) The liquid crystal alignment agent according to any one of the above (1) to (9), wherein the mass (solid content concentration) other than the organic solvent is 1 to 20% by mass.

(11) A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to any one of the above (1) to (10).

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

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment film which is less resistant to film reduction by rubbing treatment and which has a small decrease in voltage holding ratio even after exposure to a backlight for a long period of time. In this way, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can be excellent in reliability, and can be applied to a liquid crystal television or the like which is high-definition on a large screen.

The liquid crystal alignment agent of the present invention is a compound having a structure in which a group represented by the formula [i] is bonded to an aromatic ring (hereinafter also referred to as a specific compound), and a component (B) is selected from the group consisting of poly(A). At least one polymer compound (hereinafter also referred to as a specific polymer) in which the amine and the polyimide precursor are grouped.

In the formula [i], X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Further, when X is a hydrogen atom, it is preferable to maintain a uniform liquid crystal distribution downward, to increase the pretilt angle of the liquid crystal, and to simultaneously remove the charge accumulated in the liquid crystal display element at the same time.

The liquid crystal alignment agent of the present invention generally contains the components (A) and (B), which are in a solution state in which these are dissolved in an organic solvent.

<(A) component>

The specific compound of the component (A) has a structure in which a group represented by the above formula [i] is bonded to an aromatic ring, and a group represented by the formula [i] (-CH ₂ -OX group) is directly bonded to an aromatic ring, so that It is easy to combine with polyimine and polylysine, and it is easy to react with specific compounds by themselves. This is presumed to be the cause of the effect of the present invention.

Among the specific compounds, at least one compound which is a group of the compound represented by the following formula [1] and the compound represented by the formula [2] is also preferred.

In the formula, X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ₁ , Y ₂ and Y ₃ each independently represent an aromatic ring. Any hydrogen atom of the aromatic ring may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group. Z ₁ represents a single bond, all or a part may be bonded to form a cyclic structure of a divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and any hydrogen atom may be substituted by a fluorine atom -NH-, -N ( CH ₃ )-, a group represented by the formula [3]. t ₁ is an integer of 2 to 4, and t ₂ and t _{3 are} each independently an integer of 1 to 3, and a and b are each independently an integer of 1 to 3.

In the formula [3], P ₁ and P ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring.

The -CH ₂ -OX ₁ group, the -CH ₂ -OX ₂ group and the -CH ₂ -OX ₃ gene of the formula [1] and the formula [2] are directly bonded to the aromatic ring, so Y ₁ , Y ₂ , and Y ₃ each independently represents an aromatic ring.

Examples of the specific examples thereof include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a benzonaphthalene ring, a pyrrole ring, an imidazole ring, and an oxazole ring. Thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazoline Alkane ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thiline ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, anthracene A pyridine ring, an oxazole ring, and the like. Specific examples of the preferred aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, and an anthracene ring. An azole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, an anthracene ring, a quinoxaline ring, an acridine ring or the like. More preferred are a benzene ring, a naphthalene ring, a pyridine ring or an oxazole ring, and most preferably a benzene ring or a pyridine ring.

Further, the hydrogen atom of these aromatic rings may be substituted by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group.

t ₂ and t ₃ in the formula [2] are preferably an integer of 1 or 2. Also, a and b are preferably 1 or 2.

X ₁ in the formula [1] and X ₂ and X ₃ in the formula [2] each independently represent a group selected from a hydrogen atom, CH ₃ , C ₂ H ₅ , and C ₃ H ₇ , and the carbon number is preferably The less the binding reaction with polyimine and polylysine is easier, or the ease with which the compounds react with each other is excellent. On the other hand, when the carbon number is large, the reactivity of the -CH ₂ -OX ₁ group, the -CH ₂ -OX ₂ group, and the -CH ₂ -OX ₃ group is lowered, and the storage stability of the solution containing the compound is increase. In the case where X ₁ in the formula [1] and X ₂ and X ₃ in the formula [2] are hydrogen atoms, the uniform liquid crystal can be kept downward, and the pretilt angle of the liquid crystal can be improved, and the liquid crystal can be quickly adjusted. It is preferable that the charge accumulated in the liquid crystal display element is removed.

When all or a part of Z ₁ in the formula [2] is bonded to form a divalent saturated hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms in the cyclic structure, any hydrogen atom which may be possessed may be Replaced by a fluorine atom.

Examples of Z ₁ include an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an alkylene group and an alicyclic hydrocarbon group, and having 1 to 10 carbon atoms. Base. Further, a group in which any hydrogen atom of the above-mentioned group is substituted by a fluorine atom may be mentioned.

Q ₁ in the formula [3] is an aromatic ring, but examples of the specific examples include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, and a benzophenone. Naphthalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole Ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thiline ring, phenanthroline ring, anthracene ring, quinoxaline Ring, benzothiazole ring, phenothiazine ring, acridine ring, oxazole ring and the like. Specific examples of the preferred aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, and an anthracene ring. An azole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, an anthracene ring, a quinoxaline ring, an acridine ring or the like. More preferably, a benzene ring, a naphthalene ring, a pyridine ring, an indazole ring, an anthracene ring, etc. are mentioned.

In the present invention, at least one compound selected from the group consisting of the formula [1] and the formula [2] can be used.

Specific examples of the specific compound to be used in the present invention include compounds of [P1] to [P45], but are not limited thereto.

The specific compound of the above component (A) is preferably a compound represented by [P15], [P17], [P19], [P29], [P31], [P41], and also [P15], [P17], [ Compounds represented by P29], [P31], and [P41] are preferred.

<(B) component>

The component (B) is a specific polymer, and the specific polymer is as defined above. The polyimine precursor in the present invention means polyamic acid and/or polyphthalate. As the specific polymer, polyimide and polyglycolic acid are preferred.

In the present invention, a method of synthesizing a specific polymer is not particularly limited.

The specific polymer is generally obtained by reacting a diamine component with a tetracarboxylic dianhydride component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and a derivative thereof is reacted with a diamine component of one or a plurality of diamine compounds to obtain a repeating unit represented by the formula [5]. The structural poly-proline. To obtain a polyamine amide, a method of converting a carboxyl group of polylysine to an ester is used. Further, in order to obtain a polyimine, a method of imidizing the above polyamic acid into a polyimine is used.

In the formula [5], R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and n represents a positive integer.

The tetracarboxylic acid component and the diamine component of the raw material can be appropriately selected depending on the necessity. The tetracarboxylic acid and its derivatives are tetracarboxylic acid, tetracarboxylic acid dihalide and tetracarboxylic dianhydride. Among them, tetracarboxylic dianhydride is also preferred because it has high reactivity with a diamine compound.

Specific examples of the above R ₁ include the following structures A-1 to A-46.

Further, specific examples of R ₂ include the structures of B-1 to B-113 which will be described later.

In the above B-112 and B-113, Q represents any of -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-.

The method of producing the specific polymer is, for example, a tetracarboxylic acid component containing at least one of the tetracarboxylic dianhydrides represented by the formula [6] and at least one of the diamine compounds containing the formula [7]. The amine component is subjected to a polycondensation reaction in an organic solvent such as N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide or γ-butyl lactone. method.

Further, R ₁ in the formula [6] has the same meaning as defined in the formula [5], and specific examples thereof are the above A-1 to A-46. Further, R ₂ in the formula [7] has the same meaning as defined in the formula [5], and specific examples thereof are the above B-1 to B-113.

The tetracarboxylic dianhydride and its derivative used for obtaining a specific polymer are not particularly limited. The tetracarboxylic dianhydride may be used alone or in combination of two or more. Among them, when the voltage holding property is emphasized, it is preferred to use a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure such as A-1 to A-25 and A-46. In particular, it is preferred to use at least one selected from the group consisting of A-1 to A-6, A-8, A-16, A-18 to A-24, and A-46.

Further, when at least 10 to 100% by mole of the tetracarboxylic dianhydride component is a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, it is effective for voltage holding characteristics.

Further, when the liquid crystal alignment property or the accumulated charge is decreased, it is preferred to use an aromatic acid dianhydride such as A-26 to A-45. In particular, it is preferred to use at least one selected from the group consisting of 27, A-32, A-34, and A-39 to A-43.

Further, when at least 20 to 100 mol% of the dianhydride component is an aromatic acid dianhydride, it is effective for liquid crystal alignment or storage charge reduction.

In a preferred composition ratio (mol%) of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure in combination with an aromatic acid dianhydride, the former is 10 to 80 mol%. The latter is 20 to 90 mol%.

Particularly, in the tetracarboxylic dianhydride, when at least one selected from the group consisting of A-6, A-16, A-18, A-19 to A-22, and A-46 is used, the specific polymer is used. The solubility is increased, and the polymer is subjected to dehydration ring closure to obtain solubility in the case of soluble polyimine.

The diamine represented by the formula [7] is not particularly limited, and only one type may be used in the present invention, but a plurality of types may be used. Among them, when a part or all of the diamine component used for obtaining a specific polymer is B-80 to B-101 or the like, the pretilt angle of the liquid crystal can be improved. Further, as the diamine component for increasing the pretilt angle of the liquid crystal, a diamine compound represented by the following formula can be exemplified.

Further, in the formula, A ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₃ is a 1,4 cyclohexyl group, or a 1,4-phenyl group, and A ₂ is an oxygen atom, or -COO-* (However, the bonding position with "*" is combined with A ₃ ), A ₁ is an oxygen atom, or -COO-* (however, the bonding position with "*" is attached with (CH ₂ ) a2 combined). Further, a ₁ is an integer of 0 or 1, and a2 is an integer of 2 to 10, and a3 is an integer of 0 or 1.

When the liquid crystal is particularly vertically aligned, the diamine component is preferably used in an amount of 5 to 100 mol%, more preferably 10 to 80 mol% of B-80 to B-101.

When the tetracarboxylic acid component and the diamine component are polymerized, the reaction temperature may be any temperature of from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C.

The degree of polymerization of a particular polymer is affected by the feedstock loading ratio. Therefore, the ratio of the total number of moles of the compound constituting the tetracarboxylic acid component to the total number of moles of the diamine compound constituting the diamine component is preferably from 0.8 to 1.2, more preferably from 0.9 to 1.1. The closer the molar ratio is to 1.0, the greater the degree of polymerization of the resulting polymer.

As a method for imidizing polylysine, it is generally a thermal imidization by heating and a catalyst imidization using a catalyst, but the imidization of the imidization reaction at a relatively low temperature is carried out. It is preferred that the molecular weight of the obtained polyimine is less likely to occur.

The imidization of the catalyst can be carried out by stirring the polyglycolic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 ° C to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but when it is too high, the molecular weight of the polyimide may be lowered. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. When the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently, and if it is too large, it is difficult to completely remove it after the completion of the reaction. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity in the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is easily carried out, which is preferable. The organic solvent is not particularly limited as long as it is soluble in polylysine, and specific examples thereof include N,N'-dimethylformamide and N,N'-di. Methylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl fluorene, γ-butane Ester and the like. The imidization ratio by the imidization of the catalyst can be controlled by the amount of the catalyst and the reaction temperature and reaction time.

The produced polyimine can be obtained by recovering a precipitate obtained by putting the above reaction solution into a poor solvent. In this case, the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. , water, etc. The polyimine which is precipitated by the lean solvent is filtered, and after being filtered under normal pressure or reduced pressure, it may be a powder after being heated or dried by heating. When the polyimine powder is further dissolved in an organic solvent, and the reprecipitation operation is repeated 2 to 10 times, the polyimine can be purified. This purification step may preferably be carried out when the precipitation recovery operation cannot remove impurities.

The molecular weight of the specific polyimine used in the present invention is not particularly limited, and the weight average molecular weight is preferably 2,000 to 200,000, preferably 4,000, from the viewpoints of ease of handling and stability of properties at the time of film formation. ~ 50,000. The molecular weight can be determined by GPC (gel permeation chromatography).

<Liquid alignment treatment agent>

The liquid crystal alignment agent of the present invention is generally obtained by mixing a specific compound of the component (A) and a specific polymer of the component (B) in an organic solvent as required. The specific compound may be of one type or may be combined with a plurality of types.

The mixing method may, for example, be a method in which the component (B) is dissolved in a solution of an organic solvent, and the component (A) and the other components described later are added. The organic solvent to be used in this case is not particularly limited as long as it is a solvent for dissolving polyimine. This specific example is as follows.

For example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 1,3-dimethyl- Imidazolinone, dipentene, ethylpentyl ketone, methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, cyclohexanone, ethyl carbonate, ethyl carbonate Ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents can be used in combination of two or more types.

When the polyimine is dissolved in an organic solvent, heating can be performed for the purpose of promoting the dissolution of the polyimide. When the heating temperature is high, the molecular weight of the polyimide may be lowered. Therefore, the temperature is preferably from 30 to 100 ° C, preferably from 50 to 90 ° C. The concentration of the polyimine solution is not particularly limited, and the concentration of the polyimine in the solution is preferably from 1 to 20% by mass, preferably from 3 to 15% by mass, particularly preferably from 3 to 10% by mass.

The specific compound may be directly added to the solution of the polylysine and the solvent-soluble polyimine, but it is preferably added in a suitable solvent to a solution having a concentration of 0.1 to 50% by mass, preferably 5 to 20% by mass. The solvent of the above polyimine is mentioned as this solvent.

<Other ingredients>

The liquid crystal alignment treatment agent of the present invention may contain a specific polymer or a specific compound, or may contain a solvent or a substance which can improve the film thickness uniformity or surface smoothness when the liquid crystal alignment treatment agent is applied as another component. A substance that improves the adhesion between the liquid crystal alignment film and the substrate. These components may be added in the middle of mixing a specific polymer with a specific compound, or these may be added after being a mixed solution.

[Solvent for increasing film thickness uniformity or surface smoothness]

Specific examples of the solvent for improving the film thickness uniformity or the surface smoothness include the following.

For example, isopropyl alcohol, methoxymethylpentanone, methyl glycol, ethyl glycol, butyl sirlo, methyl sarbuta acetate, ethyl sirolimus acetate , butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Ethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol single B Acid monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n- Pentane, n-octane, diethyl ether, methyl lactate Ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxyl Methyl ethyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropionic acid Butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoethyl Acid ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxyl) A solvent having a low surface tension such as propoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate.

These solvents can be used after using one type or a mixture of plural types. When the solvent is used, the amount of the solvent contained in the liquid crystal alignment agent is preferably from 5 to 80% by mass, preferably from 20 to 60% by mass.

[Substances that increase film thickness uniformity or surface smoothness]

Examples of the material having uniform film thickness or surface smoothness include a fluorine-based surfactant, a polyoxyn-based surfactant, and a nonionic surfactant.

More specifically, for example, F-topEF301, EF303, EF352 (manufactured by Dokampa Co., Ltd.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, and FC431 (manufactured by Sumitomo 3M Co., Ltd.) Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of these materials is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (B) contained in the liquid crystal alignment agent.

[Substance that improves the adhesion between the liquid crystal alignment film and the substrate]

Specific examples of the substance which improves the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or a compound containing an epoxy group.

Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymethane alkyl propyl triethylamine, N-trimethoxymethyl propyl propyl triethylamine, 10-trimethoxy carboxyalkyl -1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxycarbamido-3,6-diaza Heteroalkyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzene Methyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N- Bis(oxyethyl)-3-aminopropyltrimethoxy Decane, N-bis(oxyethyl)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol Glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol Glycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane Wait.

When 100% by mass of the specific polymer component contained in the liquid crystal alignment agent is added, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the amount is less than 0.1 part by mass, the adhesion improving effect is not obtained, and when it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

In the liquid crystal alignment treatment agent of the present invention, in addition to the above, the polymer component other than the specific polymer or the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film can be added without impairing the range of the effect of the present invention. Further, a substance to be changed (such as a dielectric or a conductive material) may be added to improve the film hardness or density when the liquid crystal alignment film is used.

[Substances that change electrical characteristics]

Specific examples of the substance which promotes the charge transfer in the liquid crystal alignment film and promotes the removal of the charge of the liquid crystal cell using the liquid crystal alignment film include an amine such as M1 to M158 (hereinafter also referred to as an added amine). The amine may be added directly to the solution of the specific polymer, and it is preferably added in a suitable solvent to a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent of the above polyimine is mentioned as this solvent.

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

<Liquid alignment film ‧ Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film by performing coating treatment after baking on a substrate, baking treatment, rubbing treatment, light irradiation, or the like, or performing alignment treatment in a vertical alignment application or the like. The substrate 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. In particular, when a substrate such as an ITO electrode to be driven by a liquid crystal is used, it is preferable from the viewpoint of simplifying the process. Further, when the reflective liquid crystal display device is only a single-sided substrate, an opaque such as a germanium wafer may be used, and in this case, a material that reflects light such as aluminum may be used as the electrode.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, it is generally a method of performing screen printing, offset printing, letterpress printing, spraying, or the like. As other coating methods, there are dipping, roll coating, slit coating, rotor, etc., and these can be used for the purpose.

After the liquid crystal alignment agent is applied onto the substrate, the film can be formed by heating at a temperature of 50 to 300 ° C, preferably 80 to 250 ° C, by a heating means such as a hot plate. When the thickness of the coating film after firing is too thick, it is disadvantageous on the power-consuming surface of the liquid crystal display element. When it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm. Good is 10 ~ 100nm. When the liquid crystal is horizontally aligned or obliquely aligned, the coating film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above method, and a liquid crystal cell is produced by a known method as a component.

An example of a method for producing a liquid crystal cell is a pair of substrates on which a liquid crystal alignment film is to be formed, a spacer is spread on a liquid crystal alignment film of a single substrate, and a liquid crystal alignment film surface is formed inside, and another single substrate is 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 onto a liquid crystal alignment film surface of a spacer, and a substrate is bonded to each other to be closed. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

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

[Examples]

The present invention will be described in more detail below with reference to examples (synthesis examples) and comparative examples, but the present invention is not construed as being limited thereto.

<Synthesis Examples 1 to 14, Examples 1 to 27, and Comparative Examples 1 to 6>

The abbreviations symbols used in the examples (synthesis examples) and comparative examples are as follows. Further, the measurement of the molecular weight of the polyimine and the measurement of the imidization ratio were carried out according to the following methods.

<tetracarboxylic dianhydride>

A-1: 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

A-2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

A-3: pyromellitic dianhydride

A-4: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride A-5: 2,3,5-tricarboxycyclopentyl acetic acid-1,4:2 3-dianhydride

<Diamine>

B-2: 1,3-diamino-4-octadecyloxybenzene

B-4: p-phenylenediamine

B-5: 4-{4-(4-Heptylcyclohexyl)phenoxy}-1,3-diaminobenzene

B-8: 4,4'-diaminodiphenylmethane

B-13: 3,5-diamino benzoic acid

B-14: m-phenylene diamine

B-15: a diamine compound represented by the following formula B-15

B-16: 1,3-diamino-5-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene

(specific compound)

The meanings of P15, P17, P29, P31 and P41 are as described above.

<amine compound>

C-1: 3-aminomethylpyridine

C-2: 3-aminopropyl imidazole

(Organic solvents)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cyrus

GBL: γ-butyrolactone

<Measurement of molecular weight of polyimine]

The molecular weight of the polyimine in the synthesis example can be determined by using a room temperature colloidal permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd., and a pipe column (KD-803, KD-805) manufactured by Shodex Co., Ltd. as follows. Determination.

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr ‧ H2O) is 30 mmol / L, phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) 10ml/L)

Flow rate: 1.0ml/min

A standard sample was prepared as a standard sample: TSK standard polyethylene oxide (molecular weight: about 9,000, 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 Laboratory.

<Measurement of imidization rate>

The imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR sampling tube standard Φ 5 manufactured by Kusano Scientific Co., Ltd.), and 0.53 ml of dimethyl hydrazine (DMSO-d ₆ , 0.05% TMS mixture) was added thereto, and ultrasonic waves were applied thereto. Make it completely soluble. This solution was measured for proton NMR at 500 MHz by an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Ltd. The imidization ratio is identified by using protons having a structure unchanged before and after imidization as a reference proton, and the cumulative value of the peak of the proton and the proton peak cumulative value of the NH group derived from proline from 9.5 to 10.0 ppm are used. It is obtained by the following formula.

Amination rate (%) = (1-α‧x/y) × 100

In the above formula, x is the proton peak cumulative value from the NH group of the proline, y is the peak cumulative value of the reference proton, and α is the indoleamine in the case of polyproline (the imidization rate is 0%). The ratio of the number of reference protons of one proton of the acid NH group.

(Synthesis Example 1)

A-4 (13.5 g, 54 mmol), B-4 (5.4 g, 50 mmol), and B-5 (8.2 g, 22 mmol) were mixed in NMP (80.1 g), and after reacting at 40 ° C for 3 hours, A-2 (3.3 g, 17 mmol) and NMP (41.8 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After the NMP was diluted to 6% by mass in the polyamic acid solution (104.2 g), acetic anhydride (12.5 g) and pyridine (9.7 g) as an imidization catalyst were added, and the reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (1300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine had an imidization ratio of 55%, a number average molecular weight of 19,100, and a weight average molecular weight of 54,300.

(Synthesis Example 2)

A-4 (127.6 g, 510 mmol), B-13 (51.8 g, 340 mmol), and B-5 (129.4 g, 340 mmol) were mixed in NMP (1096 g), and reacted at 80 ° C for 5 hours, and then added. A-2 (33.0 g, 168 mmol) and NMP (272 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After the NMP was diluted to 6 mass% with the polyaminic acid solution (510.2 g), acetic anhydride (54.3 g) and pyridine (42.2 g) were added as an imidization catalyst, and the reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (6500 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyimine had an imidization ratio of 57%, a number average molecular weight of 22,800, and a weight average molecular weight of 79,200.

(Synthesis Example 3)

A-4 (127.6 g, 510 mmol), B-13 (51.8 g, 340 mmol), and B-5 (129.4 g, 340 mmol) were mixed in NMP (1096 g), and reacted at 80 ° C for 5 hours, and then added. A-2 (33.0 g, 168 mmol) was reacted with NMP (272 g) at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (101.2 g) and diluting to 6 mass%, acetic anhydride (21.4 g) and pyridine (16.0 g) were added as an imidization catalyst, and the reaction was carried out at 90 ° C for 3 hours. The reaction solution was poured into methanol (650 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyimine had an imidization ratio of 81%, a number average molecular weight of 21,400, and a weight average molecular weight of 65,400.

(Synthesis Example 4)

A-4 (37.3 g, 148.8 mmol), B-13 (21.1 g, 138.9 mmol), and B-16 (25.9 g, 59.5 mmol) were mixed in NMP (203.5 g), and carried out at 80 ° C for 5 hours. After the reaction, A-2 (9.5 g, 48.3 mmol) and NMP (171.4 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (125.6 g) and diluting to 6 mass%, acetic anhydride (27.0 g) and pyridine (20.9 g) were added as an imidization catalyst, and the reaction was carried out at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (1600 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyamidimide had an imidization ratio of 80%, a number average molecular weight of 21,200, and a weight average molecular weight of 64,500.

(Synthesis Example 5)

A-1 (30.3 g, 100.0 mmol), B-4 (9.7 g, 90.0 mmol), and B-2 (3.8 g, 10.0 mmol) were mixed in NMP (246.7 g), and the mixture was carried out at 50 ° C for 24 hours. After the reaction, a polyaminic acid solution was obtained. After adding NMP to the polyamic acid solution (120.8 g) and diluting to 6 mass%, acetic anhydride (35.0 g) and pyridine (16.2 g) were added as an imidization catalyst, and the reaction was carried out at 35 ° C for 3 hours. . The reaction solution was poured into methanol (1420 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (E). The polyimine had an imidization ratio of 83%, a number average molecular weight of 12,700, and a weight average molecular weight of 29,200.

(Synthesis Example 6)

A-2 (11.8 g, 60.0 mmol), A-3 (11.5 g, 52.8 mmol), and B-8 (23.8 g, 120.0 mmol) were mixed in NMP (266.4 g), and allowed to proceed at room temperature. The polyaminic acid solution (F) was prepared by a reaction for 5 hours. The polyamic acid had a number average molecular weight of 11,700 and a weight average molecular weight of 29,400.

(Synthesis Example 7)

A-2 (39.2 g, 200.0 mmol) and B-4 (20.5 g, 190.0 mmol) were mixed in NMP (537.9 g), and the reaction was carried out for 5 hours at room temperature to prepare a polyamine acid solution (G). The polyamic acid had a number average molecular weight of 13,600 and a weight average molecular weight of 38,400.

(Synthesis Example 8)

A-5 (22.2 g, 99.0 mmol) and B-8 (19.8 g, 100.0 mmol) were mixed in NMP (168.1 g), and the reaction was carried out at 40 ° C for 15 hours to obtain a polyaminic acid solution (H). The polyamic acid had a number average molecular weight of 25,500 and a weight average molecular weight of 92,100.

(Synthesis Example 9)

A-5 (22.2 g, 99.0 mmol) and B-8 (19.8 g, 100.0 mmol) were mixed in NMP (168.1 g), and the reaction was carried out at 40 ° C for 15 hours to obtain a polyamine acid solution. After adding NMP to the polyamic acid solution (50.0 g) and diluting it to 4.5% by mass, acetic anhydride (6.0 g) and pyridine (4.7 g) were added as an imidization catalyst, and the mixture was reacted at 100 ° C for 3 hours. . The reaction solution was poured into methanol (620 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (I). The polyimine had an imidization ratio of 64%, a number average molecular weight of 21,200, and a weight average molecular weight of 75,900.

(Synthesis Example 10)

A-5 (3.3 g, 15 mmol), B-4 (1.3 g, 12 mmol), B-15 (1.5 g, 3 mmol) were mixed in NMP (24.5 g), and reacted at 40 ° C for 8 hours to obtain a poly Proline solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.5 g) and pyridine (1.9 g) were added as an imidization catalyst, and the reaction was carried out at 90 ° C for 3 hours. The reaction solution was poured into methanol (330 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (J). The polyimine had an imidization ratio of 50%, a number average molecular weight of 18,100, and a weight average molecular weight of 52,300.

(Synthesis Example 11)

A-5 (4.5 g, 20 mmol), B-14 (1.5 g, 14 mmol), B-5 (2.3 g, 6 mmol) were mixed in NMP (33.0 g), and reacted at 40 ° C for 8 hours to obtain a poly Proline solution. After adding NMP to the polyamic acid solution (30.0 g) and diluting it to 6 mass%, acetic anhydride (3.7 g) and pyridine (2.9 g) were added as an imidization catalyst, and the reaction was carried out at 90 ° C for 3 hours. The reaction solution was poured into methanol (370 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (K). The polyamidimide had an imidization ratio of 51%, a number average molecular weight of 18,600, and a weight average molecular weight of 72,600.

(Synthesis Example 12)

A-4 (85.1 g, 340 mmol), B-13 (39.6 g, 260 mmol), B16 (60.9 g, 140 mmol) were mixed in NMP (556.3 g), and after reacting at 80 ° C for 5 hours, A- was added. 2 (11.5 g, 58 mmol) and NMP (231.4 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (200.0 g) and diluting to 6 mass%, acetic anhydride (26.4 g) and pyridine (13.7 g) were added as an imidization catalyst, and the reaction was carried out at 100 ° C for 2.5 hours. The reaction solution was poured into methanol (2500 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (L). The polyamidimide had an imidization ratio of 71%, a number average molecular weight of 21,300, and a weight average molecular weight of 54,700.

(Synthesis Example 13)

A-4 (112.6 g, 450 mmol), B-4 (19.5 g, 180 mmol), B-13 (18.3, 120 mmol), B-5 (114.2 g, 300 mmol) were mixed in NMP (793.5 g). After reacting at 80 ° C for 5 hours, A-2 (28.6 g, 145 mmol) and NMP (378.5 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (300.0 g) and diluting to 6 mass%, acetic anhydride (31.3 g) and pyridine (24.2 g) were added as an imidization catalyst, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (3700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (M). The polyimine had an imidization ratio of 52%, a number average molecular weight of 19,800, and a weight average molecular weight of 53,800.

(Synthesis Example 14)

A-4 (138.2 g, 552 mmol), B-13 (39.6 g, 260 mmol), B-5 (74.2 g, 195 mmol) were mixed in NMP (819 g), and after reacting at 80 ° C for 5 hours, A was added. -2 (18.1 g, 92 mmol) and NMP (346 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (500.0 g) and diluting it to 6 mass%, acetic anhydride (68.1 g) and pyridine (35.2 g) were added as an imidization catalyst, and the reaction was carried out at 100 ° C for 2.5 hours. The reaction solution was poured into methanol (6200 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (N). The polyimine had an imidization ratio of 68%, a number average molecular weight of 22,100, and a weight average molecular weight of 77,200.

The liquid crystal alignment treatment agents (1) to (27) were prepared as follows, and for each of the liquid crystal alignment treatment agents, the friction resistance was evaluated as follows. The results of the induction are shown in Table 1.

[Evaluation of friction resistance]

The liquid crystal alignment agent of the present invention obtained above was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating oven at 220 ° C for 30 minutes. A coating film having a film thickness of 100 nm was formed. This coating film surface was rubbed by a rubbing apparatus having a roll diameter of 120 mm, and rubbed under the conditions of a roll rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a pushing amount of 0.4 mm to obtain a substrate with a liquid crystal alignment film.

The surface of the liquid crystal alignment film in the vicinity of the center of the substrate was observed at a random laser microscope at a magnification of 100 times, and the observation field of view was about 6.5 mm square, and it was confirmed as a frictional flaw and a friction slag (attachment). The average of the amounts is used to evaluate the frictional resistance. The results are shown in Table 1 which will be described later. And the evaluation criteria are as follows.

Evaluation basis

A: 20 or less of frictional or frictional slag

B: 20 to 40 friction or friction slag

C: 40 to 60 friction or friction slag

D: 60 or more friction or friction slag

(Example 1)

In the polyimine powder (A) (5.2 g) obtained in Synthesis Example 1, NMP (29.5 g) was added, and the mixture was stirred at 80 ° C for 30 hours to be dissolved. To the solution, a P0.0 solution of 10.0% by mass of NMP (5.2 g) (0.52 g as P15), NMP (3.4 g), and BCS (43.3 g) were added, and liquid crystal alignment treatment was carried out by stirring at room temperature for 2 hours. Agent (1).

(Example 2)

NMP (27.3 g) was added to the polyimine powder (B) (5.6 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (5.6 g) of P15 (0.56 g as P15) was added, and the liquid crystal alignment treatment agent (2) was obtained by stirring at room temperature for 2 hours.

(Example 3)

NMP (27.3 g) was added to the polyimine powder (B) (5.6 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (3.9 g) of P15 (0.39 g as P15) was added, and the liquid crystal alignment treatment agent (3) was obtained by stirring at room temperature for 2 hours.

(Example 4)

NMP (27.3 g) was added to the polyimine powder (B) (5.6 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (2.8 g) of P15 (0.28 g as P15) was added, and the liquid crystal alignment treatment agent (4) was obtained by stirring at room temperature for 2 hours.

(Example 5)

NMP (27.3 g) was added to the polyimine powder (B) (5.6 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (1.7 g) of P15 (0.17 g as P15) was added, and the liquid crystal alignment treatment agent (5) was obtained by stirring at room temperature for 2 hours.

(Example 6)

NMP (35.2 g) was added to the polyimine powder (C) (7.2 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (7.2 g) of C-1 (0.36 g as C-1), NMP (10.4 g), and BCS (60.0 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (7.2 g) of P15 (0.72 g as P15) was added, and the liquid crystal alignment treatment agent (6) was obtained by stirring at room temperature for 2 hours.

(Example 7)

NMP (25.4 g) was added to the polyimine powder (D) (5.2 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (5.2 g) of C-1 (0.26 g as C-1), NMP (7.5 g), and BCS (43.4 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (5.2 g) of P15 (0.52 g as P15) was added, and the liquid crystal alignment treatment agent (7) was obtained by stirring at room temperature for 2 hours.

(Example 8)

A liquid crystal alignment treatment agent (8) was obtained in the same manner as in Example 7 except that P15 was changed to P31.

(Example 9)

NMP (5.0 g) and BCS (5.0 g) were added to the polyamic acid (G) (15.0 g) obtained in Synthesis Example 7, and stirred at room temperature for 2 hours. To the solution, a 10.0% by mass NMP solution (1.5 g) of P15 (0.15 g as P15) was added, and the liquid crystal alignment treatment agent (9) was obtained by stirring at room temperature for 2 hours.

(Embodiment 10)

A liquid crystal alignment treatment agent (10) was obtained in the same manner as in Example 9 except that P15 was changed to P17.

(Example 11)

A liquid crystal alignment treatment agent (11) was obtained in the same manner as in Example 9 except that P15 was changed to P29.

(Embodiment 12)

A liquid crystal alignment treatment agent (12) was obtained in the same manner as in Example 9 except that P15 was changed to P41.

(Example 13)

GBL (45.0 g) was added to the polyimine powder (E) (5.0 g) obtained in Synthesis Example 5, and the mixture was stirred at 50 ° C for 20 hours to be dissolved. GBL (33.3 g) was added to the solution, and the mixture was stirred at room temperature for 2 hours to obtain a polyimine solution. Next, GBL (112.5 g) and BCS (37.5 g) were added to the polyamic acid solution (F) (100.0 g) obtained in Synthesis Example (6), and stirred at room temperature for 2 hours to obtain a polyaminic acid solution. . Further, the polyiminoimine solution (20.0 g) was mixed with a polyaminic acid solution (80.0 g), and the mixture was stirred at room temperature for 20 hours to obtain a polyimine and a polyaminic acid mixed solution. Finally, a 10.0% by mass GBL solution (6.0 g) of P15 (0.6 g as P15) was added to the mixed solution, and the liquid crystal alignment treatment agent (13) was obtained by stirring at room temperature for 2 hours.

(Example 14)

To the polyamic acid (H) (20.0 g) obtained in Synthesis Example 8, NMP (8.5 g), P17 10.0 mass% NMP solution (1.5 g) (0.15 g as P17), and BCS (20.0 g) were added. The liquid crystal alignment treatment agent (14) was obtained by stirring at room temperature for 2 hours.

(Example 15)

NMP (28.3 g) was added to the polyimine powder (I) (5.0 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a P0.0 solution of 10.0% by mass of NMP (2.5 g) (0.25 g as P17), NMP (11.7 g), and BCS (33.3 g) were added, and a liquid crystal alignment treatment agent was obtained by stirring at room temperature for 2 hours. (15).

(Embodiment 16)

NMP (28.3 g) was added to the polyimine powder (J) (5.0 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a P0.0 solution of 10.0% by mass of NMP (2.5 g) (0.25 g as P17), NMP (11.7 g), and BCS (33.3 g) were added, and a liquid crystal alignment treatment agent was obtained by stirring at room temperature for 2 hours. (16).

(Example 17)

NMP (28.3 g) was added to the polyimine powder (K) (5.0 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a P0.0 solution of 10.0% by mass of NMP (2.5 g) (0.25 g as P17), NMP (11.7 g), and BCS (33.3 g) were added, and a liquid crystal alignment treatment agent was obtained by stirring at room temperature for 2 hours. (17).

(Embodiment 18)

NMP (48.8 g) was added to the polyimine powder (L) (10.0 g) obtained in Synthesis Example 12, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0 mass% NMP solution (10.0 g) of C-1 (0.5 g as C-1), NMP (22.8 g), and BCS (75.0 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (5.0 g) of P17 (0.5 g as P17) was added, and the liquid crystal alignment treatment agent (18) was obtained by stirring at room temperature for 2 hours.

(Embodiment 19)

NMP (48.8 g) was added to the polyimine powder (M) (10.0 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0 mass% NMP solution (10.0 g) of C-2 (0.5 g as C-2), NMP (22.8 g) and BCS (75.0 g) were added, and the mixture was stirred at 50 ° C for 20 hours. To the solution, a 10.0% by mass NMP solution (5.0 g) of P17 (0.5 g as P17) was added, and the polyimine solution (O) was obtained by stirring at room temperature for 2 hours. Next, NMP (48.8 g) was added to the polyimine powder (N) (10.0 g) obtained in Synthesis Example 14, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0 mass% NMP solution (5.9 g) of C-2 (0.6 g as C-2), NMP (26.9 g), and BCS (75.0 g) were added, and the mixture was stirred at 50 ° C for 20 hours. To the solution, a 10.0% by mass NMP solution (5.0 g) of P17 (0.5 g as P17) was added, and the mixture was stirred at room temperature for 2 hours to obtain a polyimine solution (P). Further, the above polyimine solution (O) (30.0 g) and polyimine solution (P) (30.0 g) were mixed, and the liquid crystal alignment treatment agent (19) was obtained by stirring for 20 hours.

(Embodiment 20)

NMP (9.8 g) was added to the polyimine powder (A) (2.0 g) obtained in Synthesis Example 1, and the mixture was stirred at 80 ° C for 30 hours to be dissolved. To the solution, a 10.0% by mass NMP solution (1.0 g) of P17 (0.1 g as P17), NMP (3.9 g), and BCS (16.7 g) were added, and a liquid crystal alignment treatment agent was obtained by stirring at room temperature for 2 hours. (20).

(Example 21)

NMP (9.8 g) was added to the polyimine powder (B) (2.0 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. NMP (2.9 g) and BCS (16.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (2.0 g) of P17 (0.2 g as P17) was added, and the liquid crystal alignment treatment agent (21) was obtained by stirring at room temperature for 2 hours.

(Example 22)

NMP (9.8 g) was added to the polyimine powder (B) (2.0 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (1.5 g), and BCS (16.7 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (1.4 g) of P17 (0.14 g as P17) was added, and the liquid crystal alignment treatment agent (22) was obtained by stirring at room temperature for 2 hours.

(Example 23)

To the polyimine powder (B) (2.0 g) obtained in Synthesis Example 2, NMP (9.8 g) was added, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. NMP (2.9 g) and BCS (16.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (1.0 g) of P17 (0.1 g as P17) was added, and the liquid crystal alignment treatment agent (23) was obtained by stirring at room temperature for 2 hours.

(Example 24)

To the polyimine powder (B) (2.0 g) obtained in Synthesis Example 2, NMP (9.8 g) was added, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0% by mass NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (2.3 g), and BCS (16.7 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (0.6 g) of P17 (0.06 g as P17) was added, and the liquid crystal alignment treatment agent (24) was obtained by stirring at room temperature for 2 hours.

(Embodiment 25)

To the polyimine powder (C) (2.0 g) obtained in Synthesis Example 3, NMP (9.8 g) was added, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0 mass% NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (1.9 g), and BCS (16.7 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (1.0 g) of P17 (0.1 g as P17) was added, and the liquid crystal alignment treatment agent (25) was obtained by stirring at room temperature for 2 hours.

(Example 26)

To the polyimine powder (D) (2.0 g) obtained in Synthesis Example 4, NMP (9.8 g) was added, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution, a 5.0 mass% NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (1.9 g), and BCS (16.7 g) were added, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (1.0 g) of P17 (0.1 g as P17) was added, and the liquid crystal alignment treatment agent (26) was obtained by stirring at room temperature for 2 hours.

(Example 27)

The polyimine powder (E) (2.0 g) obtained in Synthesis Example 5 was added to GBL (18.0 g), and stirred and dissolved at 50 ° C for 20 hours. GBL (13.3 g) was added to the solution, and the mixture was stirred at room temperature for 2 hours to obtain a polyimine solution. Next, GBL (112.5 g) and BCS (37.5 g) were added to the polyamic acid solution (F) (100.0 g) obtained in Synthesis Example (6), and the mixture was stirred at room temperature for 2 hours to obtain a polyaminic acid solution. Further, the above polyimine solution (20.0 g) and polylysine solution (80.0 g) were mixed, and the mixture was stirred at room temperature for 20 hours to obtain a mixed solution of polyimine and polyamine. Finally, a 10.0% by mass GBL solution (6.0 g) of P17 (0.6 g as P17) was added to the mixed solution, and the liquid crystal alignment treatment agent (27) was obtained by stirring at room temperature for 2 hours.

(Comparative Example 1)

In the polyimine powder (A) (6.6 g) obtained in Synthesis Example 1, NMP (32.2 g) was added, and the mixture was stirred and dissolved at 80 ° C for 30 hours. NMP (16.1 g) and BCS (55.0 g) were added to the solution, and the liquid crystal alignment treatment agent (28) was obtained by stirring at room temperature for 2 hours.

(Comparative Example 2)

To the polyimine powder (B) (4.6 g) obtained in Synthesis Example 2, NMP (22.5 g) was added, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To this solution, a 5.0% by mass NMP solution (4.6 g) of C-1 (0.23 g as C-1), NMP (6.7 g), and BCS (38.4 g) were added, and the mixture was stirred at 50 ° C for 15 hours. A liquid crystal alignment treatment agent (29) was obtained.

(Comparative Example 3)

The liquid crystal alignment treatment agent (30) was prepared in the same manner as in Comparative Example 2 except that the polyimine powder (C) obtained in Synthesis Example 3 was used.

(Comparative Example 4)

The liquid crystal alignment treatment agent (31) was prepared in the same manner as in Comparative Example 2 except that the polyimine powder (D) obtained in Synthesis Example 4 was used.

(Comparative Example 5)

γ-BL (18.0 g) was added to the polyimine powder (E) (2.0 g) obtained in Synthesis Example 5, and the mixture was stirred and dissolved at 50 ° C for 20 hours. To the solution, GBL (8.3 g) and BCS (5.0 g) were added, and the liquid crystal alignment treatment agent (32) was obtained by stirring at room temperature for 2 hours.

(Comparative Example 6)

To the poly-proline (G) (15.0 g) obtained in Synthesis Example 7, NMP (5.0 g) and BCS (5.0 g) were added, and the liquid crystal alignment treatment agent (33) was obtained by stirring at room temperature for 2 hours.

(Examples 28 to 38 and Comparative Examples 7 and 8)

Each of the liquid crystal alignment treatment agents obtained in the above examples and comparative examples was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C for 5 minutes, and then subjected to a hot air circulating oven at 210 ° C. After firing in an hour, a liquid crystal alignment film having a film thickness of 100 nm was produced. Two sheets of the liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the surface of the liquid crystal alignment film. Then, a sealant was printed thereon, and after bonding, the sealant was cured to form a cell. In the empty cell, liquid crystal MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected by a reduced pressure injection method, and the inlet port was closed to obtain a nematic liquid crystal cell.

When each liquid crystal cell was observed by a polarizing microscope, the liquid crystal exhibited uniform vertical alignment, and no alignment defects were observed. The voltage holding ratio at the time of production of the liquid crystal cell and the voltage holding ratio after UV-vis irradiation (light resistance) were evaluated for each liquid crystal cell, and the results are summarized in Table 2.

<Voltage retention rate when liquid crystal cell is produced>

The liquid crystal cell produced above was subjected to a voltage of 1 V for 60 μs at a temperature of 80 ° C, and the voltage after 16.67 ms and after 50 ms was measured, and the voltage was maintained as a voltage holding ratio. As a result, the voltage holding ratio at 16.67 ms was 97.0%, and the voltage holding ratio at 50 ms was 94.2%.

Further, the measurement was carried out by using a VHR-1 voltage holding ratio measuring apparatus manufactured by Dongyang Technica Co., Ltd., and setting at a voltage of ±1 V, Pulse Width: 60 μs, and a Flame Period: 16.67 ms or 50 ms.

<Voltage retention after UV-vis irradiation>

The same measurement was carried out after each liquid crystal cell having the above voltage holding ratio measurement was irradiated with light of 50 J/cm ² in terms of 365 nm. Further, UV-vis (high pressure mercury lamp) irradiation was carried out using a desktop UV curing device (HCT3B28HEX-1) manufactured by SEN LIGHT CORPORATION. As a result, the voltage holding ratio at 16.67 ms was 92.3%, and the voltage holding ratio at 50 ms was 88.9%.

<Examples 39 to 54 and Comparative Examples 9 to 20>

Each liquid crystal alignment treatment agent was prepared as follows. The composition of each of the obtained liquid crystal alignment treatment agents is summarized in Table 3. Further, liquid crystal cells were produced using each liquid crystal alignment treatment agent, and each inclination angle, friction resistance, and RDC were evaluated as follows. The results of the induction are shown in Table 4.

Further, the abbreviations used in the examples and comparative examples are as follows. Further, the abbreviation unless otherwise specified is as described above.

(specific compound)

P13, P17, P46, P47, P31 and P49 have the meanings as described above.

(diamine)

B-1: 2,4-diamino-N,N-diallylaniline

B-3: 4-(trans-4-pentylcyclohexyl)benzamide-2',4'-phenylenediamine

B-6: 4-aminobenzylamine

B-7: 3-aminobenzylamine

B-9: 1,3-diamino-4-dodecyloxy-benzene

B-10: 1,3-diamino-4-tetradecyloxybenzene

B-11: 1,4-bis(4-aminophenoxy)pentane

B-12: 4,4'-diaminodiphenylamine

<Production of liquid crystal cell>

The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C for 5 minutes, and then fired on a hot plate at 210 ° C for 10 minutes to form a film having a film thickness of 70 nm. . The coating film was rubbed on a rubbing apparatus having a roll diameter of 120 mm, and rubbed under the conditions of a roll rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film. Two substrates with a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the liquid crystal alignment film surface of the one film, and the other substrate was bonded to the surface of the liquid crystal alignment film by the upper printing sealant. After the direction is straight, the sealant is hardened to produce a hollow cell. In the 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 a twisted nematic liquid crystal cell.

<Measurement of pretilt angle>

The prepared twisted nematic liquid crystal cell was heated at 105 ° C for 5 minutes, and then the pretilt angle was measured. The pretilt angle was measured using a crystal rotation method.

<Measurement of accumulated charge (RDC)>

The twisted nematic liquid crystal cell produced by the method described in the above <Production of Liquid Crystal Cell> was applied at a temperature of 23 ° C at a temperature of 0 V to 0.1 V to 1.0 V, and the flicker amplitude at each voltage was measured. Level, made into a standard curve. After 5 minutes of grounding, after adding an alternating voltage of 3.0 V for 1 hour and a DC voltage of 5.0 V, the flashing amplitude level after only the DC voltage was 0 N was measured, and the RDC was estimated against the previously prepared standard curve. (The estimated method of this RDC is called the scintillation reference method.)

Here, RDC (before OFF) indicates a value obtained by adding an AC voltage of 3.0 V for 1 hour and a DC voltage of 5.0 V, and RDC (after 10 minutes) indicates a value of accumulated charge 10 minutes after the AC voltage is set to OFF.

<Evaluation of friction resistance>

The liquid crystal alignment agent of the present invention obtained as described above was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating oven at 210 ° C for 10 minutes to form a glass substrate. A film having a film thickness of 100 nm. This coating film surface was rubbed by a rubbing apparatus having a roll diameter of 120 mm at a roller rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.5 mm to obtain a substrate with a liquid crystal alignment film.

The liquid crystal of the vicinity of the center of the substrate was aligned on the surface of the film, and observed at a random laser microscope set at a magnification of 100 times, and the frictional damage and the friction slag (attachment) confirmed in the square of the observation field of about 6.5 mm were observed. The average of the amounts is used to evaluate the frictional tolerance. And the evaluation criteria are determined as follows.

Evaluation basis

○: 20 or less frictional or frictional slag

△: 20 to 60 frictional or friction slag

×: 60 or more frictional or friction slag

(Example 39)

As the acid dianhydride component, 30.03 g (100 mmol) of A-1 was used, and as the diamine component, 9.73 g (90 mmol) of B-4, 3.77 g (10 mmol) of B-2, and NMP247g were used at 40 degrees. After the hour reaction, a polyaminic acid solution was obtained.

50 g of the polyaminic acid solution was diluted to 5 wt% with NMP, and 17.6 g of acetic anhydride as an imidization catalyst was added thereto, and 8.2 g of pyridine was added thereto, and the reaction was carried out at 40 ° C for 3 hours to prepare a soluble polyimine. Resin solution. This solution was poured into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to give white-soluble polyimine (SPI-1). The molecular weight of the soluble polyimine was measured, and the number average molecular weight was 13,430, and the weight average molecular weight was 26,952. The imidization ratio was 85%.

1 g of this polyimine powder was dissolved in 11.8 g of GBL and 4.8 g of BCS to obtain a uniform polyimine solution. To 10 g of this solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours as a liquid crystal alignment treatment agent.

(Embodiment 40)

As the tetracarboxylic dianhydride component, 9.80 g (50 mmol) of A-2 and 9.60 g (44 mmol) of A-3 were used, and 19.8 g (100 mmol) of B-8 and NMP 222 g were used as a diamine component, and it was carried out at room temperature. A polyamine acid solution (PAA-1) was obtained after 5 hours of reaction. The polyamine had a number average molecular weight of 11,153 and a weight average molecular weight of 29,487. To 10 g of this solution, 10.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent.

For 10 g of a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 41)

For 10 g of a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 0.03 g of P19 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 42)

For 10 g of a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 0.03 g of P13 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 43)

To 10 g of a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 0.03 g of P49 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 44)

For 10 g of a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 0.03 g of P48 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 45)

For 10 g of a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 0.03 g of P46 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 46)

For 10 g of a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 0.03 g of P47 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 47)

30.03 g (100 mmol) of A-1, 8.56 g (80 mmol) of B-4, and 5.85 g (20 mmol) of B-9, NMP 252 g were reacted at 50 ° C for 24 hours to prepare a polyaminic acid solution. 50 g of this polyaminic acid solution was diluted to 5 mass% by NMP, and 8.0 g of pyridine as an imidization catalyst and 17.2 g of acetic anhydride were further added, and the reaction was carried out at 40 ° C for 3 hours. This solution was poured into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to give a white polyimine powder (SPI-2). The solvent-soluble polyimine obtained had a number average molecular weight of 9,111 and a weight average molecular weight of 18,045. Further, the imidization ratio was 83%.

To 10 g of a solution having a mass ratio of SPI-2- to PAA-1 of 2:8, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 48)

As the tetracarboxylic dianhydride component, 8.18 g (42 mmol) of A-2, 1.63 g (7.5 mmol) of A-3, 1.22 g (10 mmol) of B-7 as a diamine component, and 5.08 g (25 mmol) were used. B-1, 6.11 g (15 mmol) of B-3, and NMP 88.96 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution. To 95.8 g of the polyaminic acid solution, 228.5 g of NMP was added and diluted, and 15.1 g of acetic anhydride and 6.4 g of pyridine were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours. The reaction solution was cooled to room temperature, and then poured into 1259.1 ml of methanol to recover a precipitated solid. 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 soluble polyimine (SPI-3). The polyimine had a number average molecular weight of 18,195 and a weight average molecular weight of 57,063. Further, the imidization ratio was 93%. 1.2 g of GBL was added to 1.2 g of the polyimide pigment, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent.

To 10 g of this solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 49)

As the tetracarboxylic dianhydride component, 13.53 g (69 mmol) of A-2, 6.54 g (30 mmol) of A-3 was used, and 8.13 g (40 mmol) of B-1 and 3.67 g (30 mmol) of B were used as the diamine component. -6, 8.77 g (30 mmol) of B-9, NMP 161.8 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution.

To 18.81 g of the polyamic acid solution, 62.65 g of NMP was added and diluted, and 5.15 g of acetic anhydride and 2.19 g of pyridine were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours.

After the reaction solution was cooled to room temperature, it was poured into 366.8 ml of methanol, and the precipitated solid matter was collected. The solid matter was washed several times with methanol, 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 12,016 and a weight average molecular weight of 35,126. Further, the imidization ratio was 90%.

1.2 g of GBL was added to 1.2 g of the polyimide pigment, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent.

To 10 g of this solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 50)

As the tetracarboxylic dianhydride component, 13.33 g (68 mmol) of A-2 and 6.54 g (30 mmol) of A-3 were used, and as the diamine component, 3.81 g (10 mmol) of B-5 and 8.13 g (40 mmol) of B were used. -1, 7.64 g (50 mmol) of B-6 and NMP 151.7 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution. To 33.38 g of the polyamic acid solution, 59.61 g of NMP was added and diluted, and 5.26 g of acetic anhydride and 2.24 g of pyridine were added, and the reaction was carried out at a temperature of 50 ° C for 3 hours to imidize.

After cooling the reaction solution to room temperature, it was poured into 351.7 ml of methanol, and the precipitated solid matter was collected. The solid matter was washed several times with methanol, 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 10,111 and a weight average molecular weight of 33,653. Further, the imidization ratio was 90%.

1.2 g of GBL was added to 1.2 g of the polyimide pigment, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent.

To 10 g of this solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 51)

6.86 g (35 mmol) of A-2 and 3.27 g (15 mmol) of A-3 were used as the tetracarboxylic dianhydride component, and 2.44 g (20 mmol) of B-7 and 3.04 g (15 mmol) of B were used as the diamine component. -1, 6.11 g (15 mmol) of B-3, NMP 87.0 g was reacted at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-2). The polyamic acid had a number average molecular weight of 15,539 and a weight average molecular weight of 47,210. To 10 g of this solution, 10.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent.

To 10 g of this solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 52)

For 10 g of a solution having a mass ratio of SPI-3- to PAA-4 of 3:7, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 53)

4.05 g (18 mmol) of A-3 was used as the tetracarboxylic dianhydride component, and 5.15 g (18 mmol) of B-11 and 0.75 g (2 mmol) of B-2 and NMP 73.07 g were used as the diamine component. After heating for 16 hours, a 12% by mass polyamine solution was obtained. The polyamic acid had a number average molecular weight of 12,180 and a weight average molecular weight of 25,160. 50 g of this polyaminic acid solution was diluted with NMP 115 g and BCS 50 g to obtain a polyaminic acid solution (PAA-3).

To 10 g of this solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Example 54)

As the tetracarboxylic dianhydride component, 7.15 g (37 mmol) of A-2 and 3.00 g (10 mmol) of A-1 were used, and 7.97 g (40 mmol) of B-12 and 1.98 g (10 mmol) were used as the diamine component. In B-8 and NMP181g, after 10 hours of reaction at room temperature, a 10 mass% polyamic acid solution was obtained. The polyaminic acid had a number average molecular weight of 12,180 and a weight average molecular weight of 30,160. 100.0 g of this polyaminic acid solution was diluted with NMP 230 g and BCS 100 g to obtain a polyaminic acid solution (PAA-4).

To 10 g of a solution in which the mass ratio of PAA-3- and PAA-4 was 2:8, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Comparative Example 9)

30.03 g (100 mmol) of A-1 was used as the tetracarboxylic dianhydride component, and 9.73 g (90 mmol) of B-4 and 3.77 g (10 mmol) of B-2 and NMP 247 g were used as the diamine component, and the temperature was 40 degrees. A polyaminic acid solution was obtained after 3 hours of reaction.

50 g of the polyaminic acid solution was diluted to 5 wt% by NMP, and then 17.6 g of acetic anhydride and 8.2 g of pyridine were added as an imidization catalyst, and the reaction was carried out at 40 ° C for 3 hours to prepare a soluble polyimine resin. Solution. This solution was poured into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to give white soluble polyimine (SPI-1). As a result of measuring the molecular weight of the soluble polyimine, the number average molecular weight was 13,430 and the weight average molecular weight was 26,952. Further, the imidization ratio was 85%. 1 g of this polyimine powder was dissolved in 11.8 g of GBL and 4.8 g of BCS to obtain a uniform polyimine solution.

(Comparative Example 10)

The mass ratio of SPI-1 to PAA-1 was mixed to 2:8, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Comparative Example 11)

The mass ratio of SPI-2 to PAA-1 was mixed to 2:8, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Comparative Example 12)

As the tetracarboxylic dianhydride component, 8.18 g (42 mmol) of A-2 and 1.63 g (7.5 mmol) of A-3 were used, and as the diamine component, 1.22 g (10 mmol) of B-7 and 5.08 g (25 mmol) were used. In B-1, 6.11 g (15 mmol) of B-3 and NMP 88.96 g, a polyamine acid solution was obtained after 24 hours of reaction at room temperature. To 95.8 g of this polyaminic acid solution, 228.5 g of NMP was added and diluted, and 15.1 g of acetic anhydride and 6.4 g of pyridine were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours. The reaction solution was cooled to room temperature, and then poured into 1259.1 ml of methanol to recover a precipitated solid. The solid matter was washed several times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of soluble polyimine (SPI-3). The polyimine had a number average molecular weight of 18,195 and a weight average molecular weight of 57,063. Further, the imidization ratio was 93%. 1.2 g of GBL was added to 1.2 g of the polyimide pigment, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent.

(Comparative Example 13)

As the tetracarboxylic dianhydride component, 13.53 g (69 mmol) of A-2 and 6.54 g (30 mol) of A-3 were used, and as the diamine component, 8.13 g (40 mmol) of B-1 and 3.67 g (30 mmol) of B were used. -6, 8.77 g (30 mmol) of B-9, NMP 161.8 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution.

To 18.81 g of the polyamic acid solution, 62.65 g of NMP was added and diluted, and 5.15 g of acetic anhydride and 2.19 g of pyridine were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours.

After the reaction solution was cooled to room temperature, it was poured into 366.8 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 12,016 and a weight average molecular weight of 35,126. Further, the imidization ratio was 90%.

1.2 g of GBL was added to 1.2 g of the polyimide pigment, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent.

(Comparative Example 14)

As the tetracarboxylic dianhydride component, 13.33 g (68 mmol) of A-2 and 6.54 g (30 mmol) of A-3 were used, and as the diamine component, 3.81 g (10 mmol) of B-5 and 8.13 g (40 mmol) of B were used. -1, 7.64 g (50 mmol) of B-6 and NMP 151.7 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution. To the 33.38 g of the polyamic acid solution, 59.61 g of NMP was added and diluted, and 5.26 g of acetic anhydride and 2.24 g of pyridine were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours.

After cooling the reaction solution to room temperature, it was poured into 351.7 ml of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed several times with methanol, 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 10,111 and a weight average molecular weight of 33,653. Further, the imidization ratio was 90%.

1.2 g of GBL was added to 1.2 g of the polyimide pigment, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent.

(Comparative Example 15)

As the tetracarboxylic dianhydride component, 6.86 g (35 mmol) of A-2 and 3.27 g (15 mmol) of A-3 were used, and as the diamine component, 2.44 g (20 mmol) of B-7 and 3.04 g (15 mmol) were used. B-1, 6.11 g (15 mmol) of B-3, and NMP 87.0 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-2). The polyamic acid had a number average molecular weight of 15,539 and a weight average molecular weight of 47,210. To 10 g of this solution, 10.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent.

(Comparative Example 16)

The mass ratio of SPI-3 to PAA-4 was mixed to 3:7, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Comparative Example 17)

4.05 g (18 mmol) of A-3 was used as the tetracarboxylic dianhydride component, and 5.15 g (18 mmol) of B-11 and 0.75 g (2 mmol) of B-2, NMP 73.07 g were used as the diamine component at room temperature. After 16 hours of reaction, a 12% by mass polyamine solution was obtained. The polyamic acid had a number average molecular weight of 12,180 and a weight average molecular weight of 25,160. 50 g of this polyaminic acid solution was diluted with 115 g of NMP and 50 g of BCS to obtain a polyaminic acid solution (PAA-3).

(Comparative Example 18)

As the tetracarboxylic dianhydride component, 9.80 g (50 mmol) of A-2 and 9.60 g (44 mmol) of A-3 were used, and as the diamine component, 19.8 g (100 mmol) of B-8 and NMP 222 g were used for 5 hours at room temperature. The reaction gave a polyaminic acid solution (PAA-1). The polyamine had a number average molecular weight of 11,153 and a weight average molecular weight of 29,487. To 10 g of this solution, 10.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent.

To 10 g of this solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Comparative Example 19)

As the tetracarboxylic dianhydride component, 7.15 g (37 mmol) of A-2 and 3.00 g (10 mmol) of A-1 were used, and as the diamine component, 7.97 g (40 mmol) of B-12 and 1.98 g (10 mmol) of B were used. -8, NMP181g was subjected to a reaction at room temperature for 16 hours to obtain a 10 mass% polyamine acid solution. The polyaminic acid had a number average molecular weight of 12,180 and a weight average molecular weight of 30,160. 100.0 g of this polyaminic acid solution was diluted with NMP 230 g and BCS 100 g to obtain a polyaminic acid solution (PAA-4).

To 10 g of the solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

(Comparative Example 20)

The mass ratio of PAA-3 to PAA-4 was mixed to 2:8, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent.

[Industrial availability]

By using the liquid crystal alignment agent of the present invention, the film subjected to the rubbing treatment is less cut, and even after exposure for a long period of time, a liquid crystal alignment film having a small voltage retention ratio can be obtained, and the liquid crystal of the obtained liquid crystal alignment film can be obtained. The display element is excellent in reliability, and can be used for LCDs such as large-screen and high-definition LCD TVs and screens.

The entire disclosure of Japanese Patent Application No. 2008-334248, filed on Dec. 26, 2008, the entire content of

Claims (8)

A liquid crystal alignment agent characterized by containing at least one compound selected from the group consisting of the compound represented by the formula [2] and (B) selected from the group consisting of polyimine and polyimine precursors. At least one polymer compound in a group; [wherein, X ₂ and X ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ₂ and Y ₃ each independently represent an aromatic ring, and any hydrogen atom of the aromatic ring may be a hydroxyl group or a carbon atom number of 1. ~3 of an alkyl group, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group; Z ₁ is a single bond, all or a combination of carbon atoms having a ring structure of 1 to 10 a saturated hydrocarbon group, an arbitrary hydrogen atom may be substituted by a fluorine atom -NH-, -N(CH ₃ )- or a group of the formula [3]; -P ₁ -Q ₁ -P ₂ - [3] (wherein, P ₁ and P ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, Q ₁ represents an aromatic ring), and t ₂ and t _{3 are} each independently an integer of 1 to 3, and a and b are each independently an integer of 1 to 3. The liquid crystal alignment agent of claim 1, wherein the component (A) is at least one compound selected from the group consisting of the following compounds, The liquid crystal alignment agent of claim 1, wherein the component (A) is at least one compound selected from the group consisting of compounds represented by the above formula [P15], formula [P17], formula [P29] or formula [P31]. . The liquid crystal alignment agent according to any one of the items 1 to 3, wherein the component (B) is selected from the group consisting of polyamines obtained by reacting a diamine component with a tetracarboxylic dianhydride component and Polylysine for dehydration At least one polymer compound in a group of polyimine obtained by the ring. The liquid crystal alignment agent of claim 4, which further contains an organic solvent. The liquid crystal alignment agent of claim 5, wherein the mass of the organic solvent to be removed (the concentration of the solid component) is 1 to 20% by mass. A liquid crystal alignment film which is obtained by using a liquid crystal alignment agent according to any one of claims 1 to 6. A liquid crystal display element comprising the liquid crystal alignment film of claim 7 of the patent application.