JP6593603B2 - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent mainly used for a liquid crystal display element of a horizontal electric field drive system, a liquid crystal alignment film using the same, and a liquid crystal display element of a horizontal electric field drive system.

  In the liquid crystal display element, the liquid crystal alignment film plays a role of aligning the liquid crystal in a certain direction. Currently, the main liquid crystal alignment films that are used industrially are formed by applying a polyimide liquid crystal aligning agent consisting of a polyimide precursor polyamic acid (also called polyamic acid) or a polyimide solution to a substrate. It is produced by doing. Further, when the liquid crystal is aligned parallel or inclined with respect to the substrate surface, a surface stretching process by rubbing is further performed after the film formation. As an alternative to the rubbing treatment, a method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays has been proposed, and in recent years, studies for industrialization have been performed.

  In order to improve the display characteristics of liquid crystal display elements, the structure of the polyamic acid and polyimide is changed and optimized, blended with resins with different characteristics, and additives are added to improve liquid crystal alignment. Various techniques have been proposed for improving the display characteristics by controlling the pretilt angle and improving the electrical characteristics. For example, in order to obtain a high voltage holding ratio, it has been proposed to use a polyimide resin having a specific repeating structure (see Patent Document 1). Further, it has been proposed to shorten the time until the afterimage is erased by using soluble polyimide having a nitrogen atom in addition to the imide group for the afterimage phenomenon (see Patent Document 2, etc.). In addition, a polyamic acid obtained from a specific diamine containing an oxazole or imidazole skeleton and tetracarboxylic dianhydride or a derivative thereof has been proposed (Patent Document 3).

  In recent years, liquid crystal display elements are often used for large-screen, high-definition liquid crystal televisions and in-vehicle applications such as car navigation systems and meter panels. In such applications, in order to obtain high luminance, a backlight with a large calorific value may be used. For this reason, the liquid crystal alignment film is required to have high reliability from another point of view, that is, high stability against light and heat from the backlight. In particular, if the voltage holding ratio, which is one of the electrical characteristics, decreases due to light irradiation from the backlight, a seizure defect (linear seizure) that is one of the display defects of the liquid crystal display element is likely to occur. As a result, a highly reliable liquid crystal display element cannot be obtained. In addition, the transverse electric field mode has a problem of image sticking (AC image sticking) due to misalignment of the orientation direction, and is particularly difficult to solve because it is easily generated by heat. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, it is also required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time.

JP-A-2-287324 JP-A-10-104633 JP 2010-54872 A WO2006-126555

  The present invention has been made in view of the above circumstances, and provides a liquid crystal aligning agent having good printability (solubility of a polymer in a solvent) on a substrate and the like, and has excellent rubbing resistance and display characteristics. In addition, it is suitable for liquid crystal display elements of lateral electric field drive system with excellent reliability when using liquid crystal with poor reliability or when exposed to high temperature or backlight for a long time An object is to provide a liquid crystal alignment film.

  As a result of intensive studies, the present inventor has found that a liquid crystal aligning agent containing a specific soluble polyimide and polyamic acid is extremely effective for achieving the above object, and has completed the present invention.

  That is, the present invention has the following gist.

  <1> Liquid crystal alignment characterized by containing a soluble polyimide obtained from a diamine component containing at least one diamine selected from the diamines of the following formulas (i) and (ii) and a tetracarboxylic dianhydride component Agent.

  In the formula, D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and D may have various substituents. E is a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, and F is a single bond or an ether bond (—O—). Represents an ester bond (—OCO—, —COO—). m is 1 or 0.

  <2> The liquid crystal aligning agent according to <1>, further comprising a polyamic acid obtained by using at least one compound represented by formulas (iii) to (vi).

  In formula (vi), R represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.

  <3> The soluble polyimide is a soluble polyimide obtained from a diamine component containing 10 to 90 mol% of at least one diamine selected from the diamines of formulas (i) and (ii) and tetracarboxylic dianhydride. <1> or <2> The liquid crystal aligning agent as described in <2>.

  <4> The liquid crystal aligning agent according to any one of <1> to <3>, wherein an imidization ratio of the soluble polyimide is 20% to 100%.

  <5> The soluble polyimide is a soluble polyimide obtained from a diamine component and a tetracarboxylic dianhydride containing at least one or more diamines selected from formulas (vii) to (x), from <1>. The liquid crystal aligning agent as described in any one of <4>.

n represents an integer of 1 to 6, R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ is a linear alkylene group having 1 to 5 carbon atoms.

  <6> The soluble polyimide and the polyamic acid are contained in a total amount of 1 to 10% by mass, and the ratio of the weight of the polyimide to the weight of the polyamic acid is 95: 5 to 5:95. The liquid crystal aligning agent as described in any one of 5>.

  <7> A liquid crystal alignment film obtained using the liquid crystal aligning agent according to <1> to <6>.

  <8> A liquid crystal display device comprising the liquid crystal alignment film according to <7>.

  The liquid crystal aligning agent of the present invention is obtained from a diamine component containing at least one diamine selected from the diamines of the above formulas (i) and (ii) (hereinafter also referred to as a specific diamine) and a tetracarboxylic dianhydride. It is characterized by containing soluble polyimide. The above-mentioned soluble polyimide has high solubility in a solvent, and the compatibility with polyamic acid when blended with polyamic acid is very good. It is possible to obtain a good quality film with excellent and less unevenness. In addition, specific diamines have the feature of generating highly active substituents when heated, some of which undergo a condensation reaction to change to a structure with good linearity, and in the portion in contact with the amic acid, Since it reacts with a specific portion of the acid, a liquid crystal alignment film having excellent liquid crystal alignment properties and excellent rubbing resistance can be obtained. Accompanying this, high-quality black display is also possible.

  Furthermore, the above-mentioned soluble polyimide is very stable to light and heat, and has the function of extremely reducing the influence of ionic impurities, etc., so the liquid crystal alignment film containing the above-mentioned soluble polyimide is not contaminated. Very high reliability can be obtained even with a very weak negative liquid crystal.

  Moreover, the polyamic acid using the compounds represented by the formulas (iii) to (vi) has a characteristic of quickly releasing the residual charges accumulated in the alignment film, thereby obtaining an alignment film having excellent image sticking characteristics. be able to. On the other hand, an alignment film using such a polyamic acid tends to be poor in reliability, but it is possible to obtain excellent reliability and excellent image sticking characteristics by combining with the soluble polyimide of the present invention.

The present invention is described in detail below.
<Soluble polyimide>
The liquid crystal aligning agent of this invention contains the soluble polyimide obtained from the diamine component containing specific diamine, and tetracarboxylic dianhydride. The specific diamine has an organic group that can be removed by heat. An amino group can be generated by elimination of the organic group.

  In the formula, D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and D may have various substituents. E is a single bond, or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and F is a single bond or an ether bond (—O -) And an ester bond (-OCO-, -COO-). m is 1 or 0.

  Although the substitution position of the amino group in the above formulas (i) and (i) is not particularly limited, from the viewpoint of synthesis difficulty and reagent availability, the meta or para position is preferred based on the amide bond, and the liquid crystal The position of para is particularly preferable from the viewpoint of orientation. Similarly, aminobenzene having no amino group (ie, —NHBoc) protected with a tertiary butoxycarbonyl group (hereinafter also referred to as Boc group) is similarly meta or para. The position is preferable, the meta position is preferable from the viewpoint of solubility, and the para position is preferable from the viewpoint of liquid crystal alignment. In addition, hydrogen of aminobenzene not having —NHBoc may be substituted with an organic group or a halogen atom such as fluorine.

  D in the formula (i) is not limited, and various structures can be selected depending on the structure of dicarboxylic acid or tetracarboxylic dianhydride used as a raw material. D is preferably a divalent hydrocarbon group from the viewpoint of solubility, and preferred examples include a linear alkylene group and a cyclic alkylene group, and this hydrocarbon group may have an unsaturated bond. . Further, from the viewpoint of liquid crystal orientation and electrical characteristics, a divalent aromatic hydrocarbon group, a heterocyclic ring, and the like are preferable. From the viewpoint of liquid crystal orientation, it is preferable that D has no substituent, but from the viewpoint of solubility, it is preferable that D be substituted with a carboxylic acid group or a fluorine atom.

  In the diamine component when synthesizing the soluble polyimide in the liquid crystal aligning agent of the present invention, the ratio of the specific diamine is not particularly limited, and the purpose is to provide various functions such as improvement of solubility and improvement of electrical characteristics. Adjusted in When used in the transverse electric field mode, very excellent liquid crystal alignment can be obtained by combining the diamines represented by the formulas (vii) to (x).

In the formulas (viii) and (ix), n represents an integer of 1 to 6, and in the formula (x), R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ has 1 carbon atom. A linear alkylene group of ˜5.

  Specifically, the ratio of the specific diamine used for this invention is 1-90 mol%, Preferably it is 1-50 mol%, More preferably, it is 5-30 mol%. Moreover, it is preferable that the diamine represented by (vii)-(x) contains at least 10 mol% or more.

  As the diamine used for the synthesis of the soluble polyimide, other diamines may be used in addition to the above diamines for the purpose of imparting various functions. Specific structures of other diamines are represented by the following general formula (3).

Y represents a divalent organic group. One example is shown below, but is not limited thereto. The portion marked with point means a moiety attached to the nitrogen of the -NH _2.

  Examples of diamines that are preferably introduced for the purpose of improving liquid crystal alignment are Y-20, Y-29, Y-30, Y-31, Y-32, Y-33, Y-40, and Y-47. Y-48, Y-53, Y-54, Y-55, Y-56, Y-58, Y-59, Y-60, Y-61, Y-64, Y-68, Y-69, Y -70, Y-71. On the other hand, many monomers having a good orientation have a linear structure, and when used for soluble polyimide, the solubility of polyimide is insufficient, and there is a possibility that it cannot be adjusted. This may be solved by selecting various structures of tetracarboxylic dianhydrides, which will be described later. Particularly preferred structures from the viewpoints of solubility and liquid crystal orientation include Y-29, Y-30, Y-31, Y-32, Y-60, and the like. In Y-29, Y-30, Y-31, and Y-32, one of the hydrogens of the aliphatic amine is replaced with a relatively small carbon number alkyl group such as a methyl group or an ethyl group, an alkenyl group, or an alkynyl group. It may be replaced, and good characteristics can be obtained, which is preferable.

  In addition, the seizure characteristics can be improved by using a heterocyclic compound or a diamine containing a nitrogen atom or a sulfur atom. An example of the preferable structure is shown below.

  For the purpose of improving the mechanical strength of the liquid crystal alignment film, improving long-term reliability, improving solubility, etc., the combined use of diamines having side chain functional groups as shown below is preferred.

  Tetracarboxylic dianhydride used for the synthesis of polyamic acid and soluble polyimide is represented by the following formula (4).

  X is a tetravalent organic group, and its structure is not particularly limited.

  The type of tetracarboxylic dianhydride used in the present invention is not particularly limited, and may be either one type depending on characteristics such as liquid crystal alignment property, pretilt angle, voltage holding characteristics, accumulated charge, etc. when the liquid crystal alignment film is formed. Two or more types can be used in combination.

  Specific examples of X are shown below, but are not limited to these structures.

  Of the above-mentioned structures, alicyclic tetracarboxylic dianhydrides as shown in X-1 to 26 are preferable from the viewpoint of solubility, and X-2, X-3, X-4, X-6, X -9, X-10, X-11, X-12, X-13, X-14, X-15, X-16, X-17, X-18, X-19, X-20, X-21 , X-22, X-23, X-24, X-25, and X-26 are preferred. On the other hand, aromatic tetracarboxylic dianhydrides such as X-27 to 46 are preferred from the viewpoint of orientation, and particularly X-27, X-28, X-33, X-34, X-35, and X-40. X-41, X-42, X-43, X-44, X-45 and X-46 are preferred.

  Particularly preferred are X-1, X-2, X-18-22, X-25, and X-26, which have moderate orientation and solubility.

<Polyamic acid>
The polyamic acid used in the liquid crystal aligning agent of the present invention plays a role of quickly releasing a residual charge (hereinafter referred to as RDC) generated in the liquid crystal aligning film, so that the raw materials in formulas (iii) to (vi) It is characterized in that at least one of the compounds represented is used. The tetracarboxylic dianhydrides represented by formulas (iii) to (v) may be used alone or in combination. When the diamine represented by the formula (vi) is used, further release of RDC can be promoted by using the tetracarboxylic dianhydrides represented by (iii) to (v) together. On the other hand, since only the diamine of formula (vi) has an excellent RDC releasing ability, good characteristics can be obtained even in combination with an aliphatic tetracarboxylic dianhydride.

  The tetracarboxylic dianhydride represented by (iii)-(v) is 20 mol%-100 mol% with respect to the whole tetracarboxylic dianhydride used for the synthesis | combination of the polyamic acid used by this invention. Is preferable, and 40 mol% to 100 mol% is more preferable. The diamine represented by the formula (vi) is preferably 20 mol% to 100 mol%, more preferably 40% to 90%, based on the entire diamine component used in the synthesis of the polyamic acid used in the present invention. preferable.

  The polyamic acid used in the present invention may be used in combination with the diamine and tetracarboxylic dianhydride described above in addition to at least one compound selected from the compounds of formulas (iii) to (vi). i) and (ii) may be used. Moreover, you may use side chain diamine as shown to Y-112-143 below as needed.

In Y-112 to Y-116, A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.

In Formulas Y-117 to Y-118, A ₂ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and A ₃ represents 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.

In formulas Y-119 to Y-121, A ₄ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH _2. -, or -CH ₂ - indicates, _{a 5} is an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group of 1 to 22 carbon atoms.

In formulas Y-122 to Y-123, A ₆ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH _2. —, —CH ₂ —, —O—, or —NH—, and A ₇ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group. .

Among Y-124 and Formula Y-125, _{A 8} is an alkyl group having 3 to 12 carbon atoms, 1,4-cyclohexylene cis - trans isomers are each trans isomer.

In the formula Y-126 and Formula Y-127, _{A 9} is an alkyl group having 3 to 12 carbon atoms, 1,4-cyclohexylene cis - trans isomers are each trans isomer.

In Formula [Y-136] to Formula [Y-141], A ₁₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or — NH— represents A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.

<Production of soluble polyimide and polyamic acid>
When manufacturing the polyimide used for this invention, the weight average molecular weight of the polyamic acid which is a precursor of a polyimide becomes like this. Preferably it is 10,000-305,000, More preferably, it is 20,000-210,000. is there. Further, the number average molecular weight is preferably 5,000 to 152,500, more preferably 10,000 to 105,000.

  The soluble polyimide and polyamic acid contained in the liquid crystal aligning agent of the present invention are produced as follows. The soluble polyimide is obtained by imidizing the precursor polyamic acid, but the difference between the polyamic acid which is the precursor of the soluble polyimide and the polyamic acid mixed with the soluble polyimide is that the former is the raw material The specific diamine is used as the diamine component.

  Both the polyamic acid mixed with the soluble polyimide and the polyamic acid which is a precursor of the soluble polyimide are produced by polycondensing a diamine component and a tetracarboxylic dianhydride component in an organic solvent.

  As a method of polycondensing a tetracarboxylic dianhydride component and a diamine component in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or A method of adding by dispersing or dissolving in an organic solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a tetracarboxylic dianhydride component and a diamine component, A method of alternately adding can be mentioned. Further, when the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of types of compounds, they may be subjected to a polycondensation reaction in a state in which these plural types of compounds are mixed in advance, or may be sequentially subjected to a polycondensation reaction individually. Good.

  The temperature at the time of polycondensation reaction of the tetracarboxylic dianhydride component and the diamine component in an organic solvent is usually 0 to 150 ° C, preferably 5 to 100 ° C, more preferably 10 to 80 ° C. The higher the temperature, the faster the polycondensation reaction will be completed, but if the temperature is too high, a high molecular weight polymer may not be obtained.

  The polycondensation reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and the total mass concentration of the tetracarboxylic dianhydride component and the diamine component is If it is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the polycondensation reaction may be performed at a high concentration, and then an organic solvent may be added.

  The organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid dissolves. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, N-methyl. Examples include caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, and γ-butyrolactone. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.

  Moreover, since water in the organic solvent inhibits the polycondensation reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.

  The ratio of the tetracarboxylic dianhydride component to the diamine component used for the polycondensation reaction of the polyamic acid is preferably 1: 0.8 to 1: 1.2 in terms of molar ratio, and this molar ratio is 1: 1. The closer the molecular weight of the polyamic acid obtained, the greater.

  The polyamic acid is produced as described above, and the polyamic acid mixed with the soluble polyimide is used as one component of the liquid crystal aligning agent of the present invention. On the other hand, polyamic acid which is a precursor of soluble polyimide is imidized. The imidization of the polyamic acid is preferably carried out in an organic solvent by stirring for 1 to 100 hours, preferably in the presence of a basic catalyst and an acid anhydride.

  Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.

  Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferable because the obtained polyimide can be easily purified after imidization. As an organic solvent, the solvent used at the time of the polycondensation reaction of the polyamic acid mentioned above can be used.

  The imidation ratio of the soluble polyimide can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. The amount of the basic catalyst at this time is preferably 0.2 to 10 times mol, more preferably 0.5 to 5 times mol of the amic acid group. Further, the amount of the acid anhydride is preferably 1 to 30 times mol, more preferably 1 to 10 times mol of the amic acid group. The reaction temperature is preferably -20 to 250 ° C, more preferably 0 to 180 ° C. The reaction time is preferably 1 to 100 hours, more preferably 1 to 20 hours.

  The imidization ratio of the soluble polyimide is not particularly limited, but is preferably 40% or more. In order to obtain a high voltage holding ratio, 60% or more is preferable, and more preferably 80% or more. Since the added catalyst or the like remains in the obtained solution of the soluble polyimide, it is preferable to recover and wash the soluble polyimide before using it for the liquid crystal aligning agent of the present invention.

  The soluble polyimide can be recovered by putting the solution after imidization into a poor solvent that is being stirred, and precipitating the polyimide, followed by filtration. Examples of the poor solvent at this time include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. The recovered soluble polyimide can be washed with this poor solvent.

  The polyimide recovered and washed in this way can be powdered by drying at normal temperature or under reduced pressure at room temperature or by heating.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains said soluble polyimide and polyamic acid in the form melt | dissolved in the organic solvent. The liquid crystal aligning agent preferably contains 3 to 10% by mass of soluble polyimide, more preferably 4 to 7% by mass. The liquid crystal aligning agent preferably contains 3 to 10% by mass of polyamic acid, more preferably 4 to 7% by mass. The total content of the soluble polyimide and the polyamic acid in the liquid crystal aligning agent is preferably 3 to 10% by mass, more preferably 4 to 7% by mass.

  Moreover, in the liquid crystal aligning agent, the polyamic acid is preferably contained in an amount of 10 to 1000 parts by mass, more preferably 10 to 800 parts by mass with respect to 100 parts by mass of the soluble polyimide.

  The organic solvent contained in the liquid crystal aligning agent is preferably 90 to 97% by mass, more preferably 93 to 96% by mass.

  In the liquid crystal aligning agent of the present invention, as an organic solvent used for dissolving the soluble polyimide and polyamic acid, the organic solvent (solvent) used for the liquid crystal aligning agent of the present invention is an organic solvent for dissolving the polymer component. If there is no particular limitation. Specific examples are given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazo Lidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone And the like. These may be used alone or in combination.

  The liquid crystal aligning agent of this invention may contain components other than said polymer component. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.

  Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and the surface smoothness include the following.

  For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, die Lenglycol dimethyl 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 monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene , Propyl ether, dihexyl ether, 1-hexanol, -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, 3-methoxy Methyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2 -Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether -2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl lactate Examples thereof include a solvent having a low surface tension such as an ester and a lactam isoamyl ester.

  These poor solvents may be used alone or in combination. When using the above solvent, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass%.

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

  More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

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

  For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N Examples include ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane.

  Furthermore, in addition to improving the adhesion between the substrate and the film, the following phenoplast additives, block isocyanates, hydroxyethylamide crosslinking agents, etc. Also good. Specific additives are shown below, but are not limited to this structure.

  When using the compound which improves adhesiveness with a board | substrate, it is preferable that the usage-amount is 0.1-30 mass parts with respect to 100 mass parts of the polymer component contained in a liquid crystal aligning agent, and more. Preferably it is 1-20 mass parts. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the liquid crystal orientation may be deteriorated.

  In addition to the above, the liquid crystal aligning agent of the present invention has a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired. Further, a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.

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

  The application method of the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, ink jet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose. Since the solubility of the polymer obtained using the diamines represented by the formulas (1) and (2) contained in the solvent is good, the liquid crystal aligning agent of the present invention is excellent in printability. Therefore, precipitation and whitening (that is, generation of agglomerates) are suppressed when applied to a substrate or the like, and coating / film forming properties are improved. In addition, a liquid crystal alignment film having excellent uniformity and transparency can be produced even if the standing time after application to a substrate or the like is increased.

  Firing after applying the liquid crystal aligning agent on the substrate can be performed at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, and the solvent can be evaporated to form a coating film. By this firing, the organic group A that can be eliminated by the heat derived from the diamine represented by the formulas (1) and (2) is eliminated from the polyamic acid, polyamic acid ester, polyimide or polyamide, and the cyclization reaction described above, Expended in intermolecular reaction. Therefore, the obtained liquid crystal alignment film is less susceptible to film scraping during the rubbing treatment and excellent in rubbing resistance, and the voltage holding ratio is less likely to be lowered even when exposed to a high temperature and high humidity or a backlight for a long time. Moreover, it is estimated that the structure of the polymer after baking changes to the structure close | similar to a liquid crystal by a cyclization reaction, Therefore, favorable liquid crystal orientation is shown.

  If the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Preferably it is 10-100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.

  The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method. For example, the two substrates disposed so as to face each other, the liquid crystal layer provided between the substrates, and the liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer. A liquid crystal display device comprising a liquid crystal cell having a liquid crystal alignment film. As a liquid crystal cell manufacturing method, a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, Examples include a method of bonding substrates and injecting liquid crystal under reduced pressure, or a method of sealing by bonding a substrate after dropping the liquid crystal on the liquid crystal alignment film surface on which spacers are dispersed. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

  As the liquid crystal, positive type liquid crystal having positive dielectric anisotropy or negative type liquid crystal having negative dielectric anisotropy, specifically, for example, MLC-2003, MLC-2041, MLC-6608 manufactured by Merck & Co., Inc. MLC-6609 or the like can be used.

  As described above, the liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is of course not limited to these examples.

  The abbreviations of the compounds used in Examples and Comparative Examples are as follows.

<Tetracarboxylic dianhydride>
A-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride
A-2: 1,2,3,4-butanetetracarboxylic dianhydride A-3: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-
Naphthalene succinic dianhydride
A-4: Pyromellitic dianhydride
A-5: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride

<Diamine>
B-1: 1,4-phenylenediamine
B-2: B-3: 4,4-diaminodiphenylmethane B-3: 4,4′-diaminodiphenylamine B-4: 3,5-diaminobenzoic acid B-5: 1,2-bis (4-aminophenoxy) ) Ethane B-6: 1,5-bis (4-aminophenoxy) pentane B-7: N1, N4-bis (2-tert-butoxycarbonylamino-4-aminophenyl) adipamide
B-8: 4-Amino-N- (2-tert-butoxycarbonylamino-4-aminophenyl) benzamide

<Organic solvent>
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: Butyl cellosolve

  Below, it shows about the evaluation method performed in the present Example.

<Viscosity measurement>
In the synthesis example or the comparative synthesis example, the viscosity of the polyamic acid solution is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), the sample amount is 1.1 mL, and the cone rotor TE-1 (1 ° 34 ′, R24). ), Measured at a temperature of 25 ° C.

<Measurement of imidization ratio>
The imidation ratio of polyimide was measured as follows. 20 mg of the polyimide powder was put in an NMR sample tube, and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixed product) was added and completely dissolved. 500 MHz proton NMR was measured for this solution with the NMR measuring device by the JEOL datum company (JNM-ECA500).

  The imidization rate was calculated by the following formula. In addition, the imidation rate of the polyimide which does not use the diamine represented by Formula (1) was calculated by setting the value of “Formula (1) Introduction amount of diamine during polyamic acid polymerization” in the following formula to zero.

Imidization rate (%) =
(100-Polyamic acid polymerization formula (1) Amount of diamine introduced (mol%) / 2) × α
In the formula, α represents a proton derived from a structure that does not change before and after imidation as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of an amic acid that appears in the vicinity of 9.5 to 10.0 ppm. It calculated | required by following Formula using the integrated value.

α = (1−α · x / y)
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%). The number ratio of the reference protons.

<Preparation of liquid crystal aligning agent>
Synthesis Example-1
Synthesis of A-3 / B-1 (70), B-8 (30) soluble polyimide and varnish adjustment B-1 was added as a diamine component to a 200 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer. 27 g (20.98 mmol), 5.00 g (8.99 mmol) of B-8 were measured, 64.3 g of NMP was added, and it was confirmed that the diamine component was completely dissolved. After adding 8.81 g (29.37 mmol) of No. 3 and stirring for 10 minutes, the mixture was heated to 50 ° C. and reacted until the viscosity was stabilized to obtain a 20% by mass polyamic acid solution [PAA-1]. The viscosity after stabilization was about 1500 mPa · s. The reaction was performed in a nitrogen atmosphere.

  60.0 g of the obtained polyamic acid solution was transferred to a 300 ml eggplant-shaped flask, and 140.0 g of NMP was added to prepare a 6.0 wt% solution. To this solution, 11.41 g (111.76 mmol) of acetic anhydride and 8.84 g (111.76 mmol) of pyridine were added and stirred at room temperature for 30 minutes, then heated to 45 ° C. and reacted for 3 hours.

  After the reaction, this solution was slowly poured into 770 g of methanol cooled to 10 ° C. or lower to precipitate a solid. The solid was collected by suction filtration, repulped with 500 g of methanol twice, and then vacuum dried at 60 ° C. to obtain the polyimide [SPI-1] of the present invention. The imidation ratio was 84%.

  Measure 2.00 g of SPI-1 in a 50 ml Erlenmeyer flask equipped with a stir bar, add 18.0 g of GBL and stir at 50 ° C. for 24 hours to confirm that it is completely dissolved. .33 g was added and stirred at room temperature for 30 minutes to obtain 6.0% by mass of SPI-1 and 94% by mass n polyimide solution [SPI-1S] of GBL.

Synthesis example 2
A-3 / B-1 (70), B-9 (30) Synthesis of soluble polyimide and varnish adjustment In a 100 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, B-1 was added as a diamine component. 95 g (27.29 mmol), 4.09 g (11.70 mmol) of B-9 were weighed, 73.64 g of NMP was added, and it was confirmed that the diamine component was completely dissolved. 3 (11.46 g, 38.21 mmol) was added, and the mixture was stirred for 10 minutes. Then, the mixture was heated to 50 ° C. and allowed to react until the viscosity was stabilized to obtain a 20% by mass polyamic acid solution [PAA-2]. The viscosity after stabilization was about 1300 mPa · s. The reaction was performed in a nitrogen atmosphere.

  70.0 g of the obtained polyamic acid solution was transferred to a 300 ml eggplant type flask, 163.0 g of NMP was added, and a 6.0 wt% solution was prepared. To this solution, 15.12 g (148.10 mmol) of acetic anhydride and 11.72 g (148.10 mmol) of pyridine were added and stirred at room temperature for 30 minutes, then heated to 45 ° C. and reacted for 3 hours.

  After the reaction, this solution was slowly poured into 800 g of methanol cooled to 10 ° C. or lower to precipitate a solid. The solid was collected by suction filtration, repulped with 500 g of methanol twice, and then vacuum-dried at 60 ° C. to obtain the polyimide [SPI-2] of the present invention. The imidation ratio was 81%.

  Measure 2.00 g of SPI-2 in a 50 ml Erlenmeyer flask equipped with a stir bar, add 18.0 g of GBL, and stir at 50 ° C. for 24 hours to dissolve. Confirm that GBL is completely dissolved. 13.33 g was added and stirred at room temperature for 30 minutes to obtain 6.0% by mass of SPI-2 and 94% by mass n polyimide solution [SPI-2S] of GBL.

Synthesis example 3
A-1, A-4 (50) / B-2 Polymerization of polyamic acid and varnish adjustment In a 200 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, 9.91 g (50.00 mmol) of B-2 was measured. , 56.04 g of NMP and 56.04 g of GBL were added and dissolved, cooled to about 10 ° C., 4.41 g (22.50 mmol) of A-1 was measured and added little by little, and 5.45 g of A-4 ( 25.00 mmol) was added little by little, and the reaction was allowed to return to room temperature until the viscosity was stabilized, to obtain a 15% by mass polyamic acid solution [PAA-3]. The viscosity after stabilization was about 350 mPa · s. The reaction was performed in a nitrogen atmosphere.

  Weigh 100.0 g of the polyamic acid solution obtained above into a 500 ml Erlenmeyer flask equipped with a stir bar, add 23.33 g of γBL, 26.67 g of NMP and 50.00 g of BCS, and stir at room temperature for 30 minutes. Thus, a polyamic acid solution [PAA-1S] containing 6.0% by mass of PAA-3, 59% by mass of γBL, 20% by mass of NMP, and 15% by mass of BCS was obtained.

Synthesis example 4
Polymerization of A-1, A-3 (20) / B-2, B-3 (20) polyamic acid and varnish adjustment 1. 200 g of B-2 was added to a 200 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. (10.00 mmol), 8.40 g (40.00 mmol) of B-3 was measured, 152.10 g of NMP was added and dissolved, cooled to about 10 ° C., and A-1: 7.35 g (38.00 mmol) was added. A little by little, then A-3: 3.00 g (10.00 mmol) was added little by little, and the mixture was allowed to return to room temperature and reacted until the viscosity was stabilized, to obtain a 15% by mass polyamic acid solution [PAA-4]. The viscosity after stabilization was about 180 mPa · s. The reaction was performed in a nitrogen atmosphere.

  In a 500 ml Erlenmeyer flask equipped with a stirrer, 100.0 g of the polyamic acid solution obtained above was weighed, 40 g of NMP and 60.00 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes. A polyamic acid solution [PAA-2S] having 0% by mass, 64% by mass of NMP, and 30% by mass of BCS was obtained.

Synthesis example 5
A-1, A-2 (65) / B-6, B-8 (30) Synthesis and varnish adjustment of soluble polyimide In a 100 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, B- 6.84 g (28.00 mmol) of 6 and 6.68 g (12.00 mmol) of B-8 were weighed, 57.60 g of NMP was added, and it was confirmed that the diamine component was completely dissolved. While adding 5.15 g (26.00 mmol) of A-2, subsequently adding 2.26 g (11.50 mmol) of A-1, adding 25.8 g of NMP and stirring for 10 minutes, the temperature was raised to 40 ° C. It was made to react until a viscosity became stable and the 20 mass% polyamic acid solution [PAA-5] was obtained. The viscosity after stabilization was about 1200 mPa · s. The reaction was performed in a nitrogen atmosphere.

  40.0 g of the resulting polyamic acid solution was transferred to a 200 ml eggplant-shaped flask, 83.0 g of NMP was added, and a 6.5 wt% solution was prepared. To this solution, 3.90 g (3.79 mmol) of acetic anhydride and 1.81 g (2.28 mmol) of pyridine were added, and the temperature was raised to 50 ° C. and reacted for 2 hours.

  After the reaction, this solution was slowly poured into 450 g of methanol cooled to 10 ° C. or lower to precipitate a solid. The solid was collected by suction filtration, repulped with 200 g of methanol twice, and then vacuum-dried at 60 ° C. to obtain the polyimide [SPI-3] of the present invention. The imidization ratio was 65%.

  In a 100 ml Erlenmeyer flask equipped with a stirrer, weigh 5.3 g of SPI-3, add 19.4 g of NMP and 10.6 g of GBL, and stir at 50 ° C. for 20 hours to dissolve. Confirm that NMP. 12.4 g, 14.1 g of γBL, and 20.6 g of BCS were added and stirred at room temperature for 30 minutes, so that SPI-3 was 6.0% by mass, NMP was 39.0% by mass, and GBL was 30.0% by mass. %, BCS 25.0 mass% polyimide solution [SPI-3S] was obtained.

Synthesis Example 6
Polymerization of A-1, A-5 (45) / B-3, B-6 (50) polyamic acid and varnish adjustment In a 100 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, 3.98 g of B-3 (20.00 mmol), 4.88 g (20.00 mmol) of B-6 was measured, 32.50 g of NMP and 32.50 g of GBL were added and dissolved, cooled to about 10 ° C., and 3.68 g of A-1 (18.80 mmol) Weighed and added little by little, 13.50 g of NMP and 13.50 g of γBL were added and stirred for 2 hours, then 5.30 g (18.00 mmol) of A-5 was added little by little, and NMP was added. After adding 19.40g and 19.40g of (gamma) BL, it was made to react at 40 degreeC until a viscosity became stable, and 12 mass% polyamic acid solution [PAA-6] was obtained. The viscosity after stabilization was about 270 mPa · s. The reaction was performed in a nitrogen atmosphere.

  Weigh 40.0 g of the polyamic acid solution obtained above into a 100 ml Erlenmeyer flask equipped with a stir bar, add 23.33 g of γBL, 26.67 g of NMP and 20.00 g of BCS, and stir at room temperature for 30 minutes. As a result, a polyamic acid solution [PAA-3S] containing 6.0% by mass of PAA-3, 30.0% by mass of γBL, 39.0% by mass of NMP, and 25.0% by mass of BCS was obtained.

Synthesis example 7
A-5 / B-3, polymerization of B-5 (20) polyamic acid and varnish adjustment In a 200 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, 8.21 g (41.20 mmol) of B-3, B 15.5 g (10.30 mmol) of -5 was measured, 69.5 g of NMP and 69.5 g of GBL were added and dissolved, cooled to about 10 ° C., and 13.90 g (47.20 mmol) of A-5 was measured. , 17.4 g of NMP and 17.4 g of γBL were added, and after stirring for a while, the mixture was allowed to react at 40 ° C. until the viscosity was stabilized to obtain a 12% by mass polyamic acid solution [PAA-7]. . The viscosity after stabilization was about 300 mPa · s. The reaction was performed in a nitrogen atmosphere.

  Weigh 40.0 g of the polyamic acid solution obtained above into a 100 ml Erlenmeyer flask equipped with a stir bar, add 23.33 g of γBL, 26.67 g of NMP and 20.00 g of BCS, and stir at room temperature for 30 minutes. Thus, a polyamic acid solution [PAA-4S] having 6.0% by mass of PAA-3, 39.0% by mass of NMP, 30.0% by mass of γBL, and 25.0% by mass of BCS was obtained.

Synthesis example 8
A-3 / B-6 Synthesis of soluble polyimide and varnish adjustment In a 100 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, 5.00 g (20.47 mmol) of B-6 was measured as a diamine component, and NMP 44.6 g was added, and it was confirmed that the diamine component was completely dissolved. While cooling in an ice bath, 6.14 g (20.47 mmol) of A-3 was added, stirred for 10 minutes, and then heated to 50 ° C. The reaction was continued until the viscosity became stable, and a 20% by mass polyamic acid solution [PAA-4] was obtained. The viscosity after stabilization was about 1100 mPa · s. The reaction was performed in a nitrogen atmosphere.

  30.0 g of the obtained polyamic acid solution was transferred to a 200 ml eggplant type flask, 60.0 g of NMP was added, and a 6.0 wt% solution was prepared. To this solution was added 5.60 g (55.13 mmol) of acetic anhydride and 4.36 g (55.13 mmol) of pyridine, and the mixture was stirred at room temperature for 30 minutes, then heated to 40 ° C. and reacted for 3 hours.

  After the reaction, this solution was slowly poured into 350 g of methanol cooled to 10 ° C. or lower to precipitate a solid. The solid was collected by suction filtration, repulped with 200 g of methanol twice, and then vacuum dried at 60 ° C. to obtain a comparative polyimide [SPI-4]. The imidation ratio was 63%.

  Measure 2.00 g of SPI-4 in a 50 ml Erlenmeyer flask equipped with a stir bar, add 18.0 g of GBL, stir at 50 ° C. for 24 hours to dissolve, and confirm that GBL is completely dissolved. .33 g was added and stirred at room temperature for 30 minutes to obtain a polyimide solution [SPI-4S] with SPI-4 of 6.0% by mass and GBL of 94% by mass.

Synthesis Example 9
A-4 / B-7 Polymerization of polyamic acid and varnish adjustment In a 200 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, 5.00 g (17.46 mmol) of B-7 was measured, and 56.67 g of NMP was added. Dissolve, cool to about 10 ° C., measure 3.50 g (16.06 mmol) of A-4, add little by little, return to room temperature, react until the viscosity is stable, 15% polyamic acid solution [PAA- 5] was obtained. The viscosity after stabilization was about 420 mPa · s. The reaction was performed in a nitrogen atmosphere. The obtained PAA- had a number average molecular weight of 12,500 and a weight average molecular weight of 33800.

  Weigh 50.0 g of the polyamic acid solution obtained above into a 500 ml Erlenmeyer flask equipped with a stir bar, add 11.67 g of γBL, 13.34 g of NMP, and 25.00 g of BCS, and stir at room temperature for 30 minutes. Thus, a polyamic acid solution [PAA-5S] containing 6.0% by mass of PAA-4, 20% by mass of NMP, and 15% by mass of BCS was obtained.

Example 1
Adjustment of liquid crystal aligning agent-1 [SPI-1S / PAA-1S 30:70 (weight ratio)] and evaluation of liquid crystal aligning film SPI-1S obtained by the method of Synthesis Example 1 in a 100 ml Erlenmeyer flask equipped with a stirrer 30.0 g and 70.0 g of PAA-1S obtained by the method of Synthesis Example 3 were weighed and stirred for 20 hours under a nitrogen atmosphere. Then, the liquid crystal aligning agent-1 of this invention was obtained by carrying out pressure filtration with the membrane filter with a pore diameter of 1 micrometer.

Example 2
Preparation of liquid crystal aligning agent-2 [SPI-2S / PAA-2S 30:70 (weight ratio)] and evaluation of liquid crystal alignment film SPI-2S obtained by the method of Synthesis Example 2 in a 100 ml Erlenmeyer flask equipped with a stirrer 30.0 g and 70.0 g of PAA-2S obtained by the method of Synthesis Example 4 were weighed and stirred for 20 hours under a nitrogen atmosphere. Then, the liquid crystal aligning agent-2 of this invention was obtained by carrying out pressure filtration with the membrane filter with a pore diameter of 1 micrometer.

Example 3
Adjustment of liquid crystal aligning agent-3 [SPI-3s / PAA-3s 30:70 (weight ratio)] and evaluation of liquid crystal alignment film SPI-3S obtained by the method of Synthesis Example 5 in a 100 ml Erlenmeyer flask equipped with a stirrer 30.0 g and 70.0 g of PAA-3S obtained by the method of Synthesis Example 6 were weighed and stirred for 20 hours under a nitrogen atmosphere. Then, the liquid crystal aligning agent-3 of this invention was obtained by carrying out pressure filtration with the membrane filter with a pore diameter of 1 micrometer.

Example 4
Adjustment of liquid crystal aligning agent-4 [SPI-3s / PAA-4s 30:70 (weight ratio)] and evaluation of liquid crystal alignment film SPI-3S obtained by the method of Synthesis Example 5 in a 100 ml Erlenmeyer flask equipped with a stirrer 30.0 g and 70.0 g of PAA-4S obtained by the method of Synthesis Example 7 were weighed and stirred for 20 hours under a nitrogen atmosphere. Then, the liquid crystal aligning agent-4 of this invention was obtained by carrying out pressure filtration with the membrane filter with a pore diameter of 1 micrometer.

Comparative Example 1
Adjustment of liquid crystal aligning agent-5 [SPI-4s / PAA-3s 30:70 (weight ratio)] and evaluation of liquid crystal alignment film SPI-4S obtained by the method of Synthesis Example 8 in a 100 ml Erlenmeyer flask equipped with a stirrer 30.0 g and 70.0 g of PAA-3S obtained by the method of Synthesis Example 6 were weighed and stirred for 20 hours under a nitrogen atmosphere. Then, the liquid crystal aligning agent-5 used as a comparison object was obtained by carrying out pressure filtration with the membrane filter with a pore diameter of 1 micrometer.

Comparative Example 2
Adjustment of liquid crystal aligning agent-6 [PAA-5s / PAA-2s 20:80 (weight ratio)] and evaluation of liquid crystal alignment film PAA-5S obtained by the method of Synthesis Example 9 in a 100 ml Erlenmeyer flask equipped with a stirrer 20.0 g and 80.0 g of PAA-2S obtained by the method of Synthesis Example 4 were weighed and stirred for 20 hours under a nitrogen atmosphere. Then, the liquid crystal aligning agent-6 used as a comparison object was obtained by carrying out pressure filtration with the membrane filter with a pore diameter of 1 micrometer.

  Evaluation of the liquid crystal aligning film was implemented based on the following method using the liquid crystal aligning agent obtained in Examples 1-4 and Comparative Examples 1-2.

<Evaluation of film uniformity of alignment agent>
After filtering the liquid crystal aligning agent through a 1.0 μm filter, a substrate with an electrode (a glass substrate with a size of 30 mm wide × 40 mm long and 1.1 mm thick. The electrode is a rectangle 10 mm wide × 40 mm long, It was applied by spin coating to a 35 nm thick ITO electrode). After spin coating, let stand at room temperature 23 ° C, humidity 50% for 5 minutes, and bake in 220 ° C IR oven for 20 minutes. DFM (Direct Force Atomic Force Microscope: manufactured by Hitachi High-Tech) Was used for surface analysis, and the roughness per 10 μm was calculated and compared. The smaller the roughness, the better the film uniformity and film formability.

<Evaluation of backlight resistance of voltage holding ratio>
The backlight resistance of the voltage holding ratio was evaluated as follows.

[Creation of liquid crystal cell for measuring voltage holding ratio]
After filtering the liquid crystal aligning agent through a 1.0 μm filter, a substrate with an electrode (a glass substrate with a size of 30 mm wide × 40 mm long and 1.1 mm thick. The electrode is a rectangle 10 mm wide × 40 mm long, It was applied by spin coating to a 35 nm thick ITO electrode). After drying on a hot plate at 50 ° C. for 5 minutes, baking was performed in an IR oven at 230 ° C. for 20 minutes to form a coating film having a thickness of 100 nm to obtain a substrate with a liquid crystal alignment film. This liquid crystal alignment film is rubbed (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm) with a rayon cloth (YA-20R, manufactured by Yoshikawa Chemical), and then into pure water. The substrate was cleaned by irradiating with ultrasonic waves for 1 minute, and after removing water droplets by air blow, it was dried at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.

  Prepare two substrates with the above-mentioned liquid crystal alignment film, spray a 4 μm spacer on the surface of one liquid crystal alignment film, print a sealant on it, and reverse the rubbing direction of the other substrate. After laminating with the direction and the film surfaces facing each other, the sealing agent was cured to produce an empty cell. Negative liquid crystal MLC-7206 (manufactured by Merck & Co., Inc.) and MLC-2041 (manufactured by Merck & Co., Inc.) were injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C. for 1 hour and left at 23 ° C. overnight to obtain a liquid crystal cell for measuring voltage holding ratio.

[Evaluation of backlight resistance]
A voltage of 1 V was applied to the liquid crystal cell for measuring the voltage holding ratio at a temperature of 60 ° C. for 60 μsec, the voltage after 100 msec was measured, and the voltage holding ratio was calculated as the voltage holding ratio. This is the initial voltage holding ratio.

  Next, as a backlight resistance test, the liquid crystal cell was left for 72 hours under a temperature of 70 ° C. and an LED light source (1000 cd). The voltage holding ratio of this liquid crystal cell was measured in the same manner as described above. This is the voltage holding ratio after the durability test.

  The backlight resistance of the voltage holding ratio was evaluated based on the magnitude of the voltage holding ratio measured as described above. That is, if the amount of change in the voltage holding ratio after the durability test is small compared to the initial voltage holding ratio, it means that the backlight resistance is good.

[Relaxation characteristics of RDC]
The liquid crystal cell for measuring the voltage holding ratio is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the two electrodes are short-circuited between the pixel electrode and the counter electrode to have the same potential. The angle of the liquid crystal cell was adjusted so that the brightness of the LED backlight transmitted light measured on the two polarizing plates was minimized by irradiating the LED backlight from the bottom of the polarizing plate.

  Next, while applying a rectangular wave with a frequency of 30 Hz to this liquid crystal cell, the VT characteristics (voltage-transmittance characteristics) at a temperature of 23 ° C. are measured, and an AC voltage with a relative transmittance of 23% is measured. Calculated. Since this AC voltage corresponds to a region where the change in luminance with respect to the voltage is large, it is convenient for evaluating the RDC via the luminance.

  Next, while applying a rectangular wave having a relative transmittance of 23% and a rectangular wave with a frequency of 30 Hz, a DC voltage of +3.0 V was superimposed and driven for 1 hour. Thereafter, the DC voltage was turned off, and again a rectangular wave having a relative transmittance of 23% and a frequency of 30 Hz was applied for 30 minutes, and the recovery time of flicker (flickering) generated at this time was measured.

  The faster the relaxation of the accumulated charge, the shorter the time, the better the relaxation characteristics of the RDC.

  The flicker intensity can be calculated by converting the luminance into a DC voltage using a photodiode and an AC-DC converter, and reading this with an oscilloscope. When flicker occurs, it is monitored as an alternating voltage correlated with a rectangular wave of 30 Hz. Therefore, the time during which this alternating voltage becomes direct current can be regarded as the relaxation time of RDC.

  Since this could not be evaluated with MLC-7206, which is a negative type liquid crystal, due to driving of the liquid crystal, this measurement was performed using MLC-2041.

<Evaluation of liquid crystal alignment>
The liquid crystal alignment was evaluated as follows.

[Preparation of substrate with electrode for FFS system]
The board | substrate with the electrode for FFS systems was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An IZO electrode constituting the counter electrode is formed on the entire surface as a first layer on the substrate. A SiN (silicon nitride) film formed by a CVD method is formed as a second layer on the first IZO electrode. The second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film. On the second SiN film, a comb-like pixel electrode formed by patterning an IZO film as the third layer is arranged to form two pixels, a first pixel and a second pixel. ing. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.

  The pixel electrode of the third layer has a comb-like shape configured by arranging a plurality of “<”-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 3 μm, and the distance between the electrode elements is 6 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It is bent and has a shape similar to the bold “ku” character. Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.

  When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and the pixel in the second region of the pixel. The electrode element of the electrode is formed so as to form an angle of −10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.

<Creation of liquid crystal cell for evaluating liquid crystal orientation>
The liquid crystal aligning agent was filtered with a 1.0 μm filter, and then applied to the substrate with the FFS mode electrode by spin coating. After drying on a hot plate at 100 ° C. for 100 seconds, baking was performed in a hot air circulation oven at 230 ° C. for 20 minutes to obtain a polyimide film having a thickness of 60 nm. This polyimide film is rubbed with rayon cloth (YA-20R manufactured by Yoshikawa Chemical Industries) (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm / sec, indentation length: 0.3 mm, rubbing direction: third layer IZO comb (In a direction inclined by 80 ° with respect to the tooth electrode), followed by washing with ultrasonic irradiation for 1 minute in a 3/7 mixed solvent of isopropyl alcohol and pure water, removing water droplets by air blow, The substrate with a liquid crystal alignment film was obtained by drying at 15 ° C for 15 minutes.

  In addition, as a counter substrate, a polyimide film is formed in the same manner as described above on a glass substrate having a columnar spacer having a height of 4 μm and ITO on the back surface, and an alignment process is performed in the same manner as described above. The obtained substrate with a liquid crystal alignment film was obtained.

  The above two substrates with a liquid crystal alignment film are made into one set, and a sealing agent is printed in a form leaving a liquid crystal injection port on the substrate, and the liquid crystal alignment film surface faces the rubbing direction antiparallel with the other substrate. Then, the sealing agent was cured to produce an empty cell having a cell gap of 4 μm.

  By adjusting the negative liquid crystal MLC-7206 (manufactured by Merck & Co., Ltd.) and MLC-2041 (manufactured by Merck & Co., Ltd.) as a comparative object by adjusting the vacuum cell by vacuum injection, the inlet is sealed, An FFS liquid crystal cell was obtained. Thereafter, the obtained liquid crystal cell was heated at 110 ° C. for 30 minutes and left at 23 ° C. overnight to obtain a liquid crystal cell for evaluating liquid crystal alignment.

[Evaluation of liquid crystal alignment]
In the liquid crystal cell for evaluating liquid crystal orientation, an alternating voltage with a relative transmittance of 100% at a frequency of 30 Hz was applied in a constant temperature environment of 60 ° C. for 168 hours. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left as it was at room temperature for one day. After leaving, the liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal, and the backlight is turned on with no voltage applied so that the brightness of the transmitted light is minimized. The arrangement angle of the liquid crystal cell was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second area of the first pixel became darkest to the angle at which the first area became darkest was calculated as an angle Δ. Similarly, for the second pixel, the second region and the first region were compared, and a similar angle Δ was calculated. The average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell, and the liquid crystal orientation was evaluated based on the magnitude of the value. That is, if the value of the angle Δ is small, the liquid crystal alignment is good.

※Ｐ＝ＭＬＣ−２０４１、Ｎ＝ＭＬＣ−７２０６

* P = MLC-2041, N = MLC-7206

※１ Ｐ＝ＭＬＣ−２０４１、Ｎ＝ＭＬＣ−７２０６
※２ ＭＬＣ−２０４１を使用して測定。
※３ フリッカーが収まった後、再度フリッカーが発生。

* 1 P = MLC-2041, N = MLC-7206
* 2 Measured using MLC-2041.
* 3 Flicker occurs again after flicker is settled.

  The liquid crystal aligning agent of the present invention uses a liquid crystal that has good coating and film forming properties, is resistant to film peeling and scraping during rubbing, does not easily accumulate initial charge even when a DC voltage is applied, and has poor reliability. However, a good liquid crystal alignment film can be obtained, and the voltage holding ratio is hardly lowered even when exposed to a backlight for a long time. Therefore, the liquid crystal display element produced using the liquid crystal aligning agent of this invention can be made into a highly reliable liquid crystal display element, TN liquid crystal display element, STN liquid crystal display element, TFT liquid crystal display element, VA liquid crystal display element. And IPS liquid crystal display elements, OCB liquid crystal display elements, and the like.

Claims (8)

The liquid crystal aligning agent characterized by including the soluble polyimide obtained from the diamine component and tetracarboxylic dianhydride component which contain at least 1 sort (s) of diamine chosen from the diamine of following formula (i) and (ii).

In the formula, D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and D may have various substituents. E is a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, and F is a single bond or an ether bond (—O—). Represents an ester bond (—OCO—, —COO—). m is 1 or 0. The liquid crystal aligning agent according to claim 1, further comprising a polyamic acid obtained by using at least one compound represented by formulas (iii) to (vi).

In formula (vi), R represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. The liquid crystal alignment according to claim 2, wherein the soluble polyimide and the polyamic acid are contained in a total amount of 1 to 10% by mass, and the ratio of the weight of the polyimide to the weight of the polyamic acid is 95: 5 to 5:95. Agent. Said soluble polyimide of the formula (i), a soluble polyimide obtained from a diamine of at least one diamine from 10 to 90 mole% containing diamine ingredient and tetracarboxylic dianhydride selected from (ii), claim The liquid crystal aligning agent of any one of Claim 1 to 3 . The liquid crystal aligning agent of any one of Claims 1-4 whose imidation ratio of the said soluble polyimide is 20%-100%. The soluble polyimide is a soluble polyimide obtained from equation (vii) ~ formula (x) at least diamine component containing one or more diamines and tetracarboxylic acid dianhydride selected from claims 1 to 5 The liquid crystal aligning agent of any one of these.

n represents an integer of 1 to 6, R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ is a linear alkylene group having 1 to 5 carbon atoms.   The liquid crystal aligning film obtained using the liquid crystal aligning agent of any one of Claims 1-6. A liquid crystal display element comprising the liquid crystal alignment film according to claim 7.