CN102020995A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

该液晶配向剂可形成垂直配向用液晶配向膜。使用该液晶配向膜的液晶显示元件在加热试验中可长时间保持高的电压保持率，且具有减低残留DC的效果。This invention is a liquid crystal aligning agent containing the polyamic acid obtained by making tetracarboxylic dianhydride represented by formula (Q) react with specific side chain type diamine, or its derivative|guide_body.

The liquid crystal alignment agent can form a liquid crystal alignment film for vertical alignment. The liquid crystal display element using the liquid crystal alignment film can maintain a high voltage retention rate for a long time in a heating test, and has the effect of reducing residual DC.

Description

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

technical field

The present invention relates to a liquid crystal alignment agent containing polyamic acid or its derivatives obtained by reacting tetracarboxylic dianhydride with diamine, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal alignment film with the liquid crystal alignment film Liquid crystal display element, in particular to a liquid crystal alignment agent that can be suitably used in liquid crystal display elements without physical rubbing treatment, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display with the liquid crystal alignment film element.

Background technique

Liquid crystal display components are used in various liquid crystals such as viewfinders of video cameras and projection displays, including monitors of note personal computers and desktop computers. Among display devices, it has recently begun to be used as a television. In addition, it can also be used as an optoelectronic related element such as an optical printer head, an optical Fourier transform element, and a light valve. The mainstream of previous liquid crystal display elements is the display element using nematic liquid crystal, and 1) TN (Twisted Nematic, twisted nematic) type liquid crystal display element twisted by 90 degrees, 2) STN ( Super Twisted Nematic (Super Twisted Nematic) type liquid crystal display elements, 3) So-called TFT (Thin Film Transistor, thin film transistor) type liquid crystal display elements using thin film transistors have been put into practical use.

These liquid crystal display elements have disadvantages in that the viewing angle at which an image can be viewed appropriately is narrow, and when viewed from an oblique direction, a reduction in brightness or contrast and brightness inversion of halftones occur. In recent years, the problem of viewing angle has been improved by using the following technologies: 1) TN-TFT liquid crystal display element using optical compensation film, 2) VA (Vertical Alignment, vertical alignment) using vertical alignment and optical compensation film 3) MVA (Multi Domain Vertical Alignment, multi-quadrant vertical alignment) liquid crystal display element using vertical alignment and protrusion structure technology, or 4) IPS (In-Plane Switching, total Surface switching) type liquid crystal display element, 5) ECB (Electrically Controlled Birefringence, electronically controlled birefringence) type liquid crystal display element, 6) Optically Compensated Bend (Optically Compensated Bend or Optically self-Compensated Birefringence: OCB) type liquid crystal display element, etc., These display elements are being put into practical use, or are being studied for practical use.

The development of liquid crystal display element technology is not only the improvement of their driving method and element structure, but also can be achieved through the improvement of the components used in the display element. Among the components used in the display element, especially the liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element. With the high quality of the display element, the role of the liquid crystal alignment film becomes more and more important year by year. .

A liquid crystal alignment film can be prepared from a liquid crystal alignment agent. The liquid crystal alignment agent mainly used at present is a solution obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After coating such a solution on a substrate, a film is formed by means such as heating to form a polyimide-based alignment film. Although various liquid crystal alignment agents other than polyamic acid and soluble polyimide have been studied, self-heat resistance, chemical resistance (liquid crystal resistance), coatability, liquid crystal alignment, electrical characteristics, optical characteristics Considering aspects such as display characteristics, etc., it has not been practically used.

In order to improve the display quality of a liquid crystal display element, the important characteristic requested|required of a liquid crystal alignment film is a voltage retention rate and residual DC. If the voltage retention rate is low, the voltage applied to the liquid crystal during the frame time decreases, resulting in a decrease in luminance, which hinders normal harmonious display. On the other hand, if the residual DC is large, even if the voltage is turned OFF after the voltage is applied, a so-called "residual image" in which an erased image remains remains.

As an attempt to solve the problem, several methods have recently been proposed.

(1) Known polyamic acid compositions used in combination of two or more polyamic acids having different physical properties for forming a liquid crystal alignment film (refer to Japanese Patent Laid-Open Publication No. 11-193345, Japanese Patent Laid-Open Publication No. 11- 193347).

(2) A varnish composition using a polyamic acid and a polyamide as the polymer component and a solvent is known (see WO 00/061684 specification).

(3) A varnish composition using two or more types of polyamic acid and polyamide having different physical properties, and a solvent is known (see WO 01/000733 specification).

(4) A varnish composition using a polymer material using polyamic acid synthesized using an amine component having a specific structure is known (refer to Japanese Patent Application Laid-Open No. 2002-162630 ) .

However, since reduction of residual DC by tetracarboxylic dianhydride reacted with diamine has not been sufficiently studied, there is room for further improvement.

As an invention example of tetracarboxylic dianhydride, for example, a liquid crystal alignment film using dicyclohexanetetracarboxylic dianhydride is known, and it is disclosed that the alignment film is horizontally aligned and the sealant ( liquid crystal contamination caused by sealing agents) or encapsulant (refer to Japanese Patent Laid-Open No. 2000-214467).

It can be seen that the above-mentioned existing liquid crystal alignment agents obviously still have inconveniences and defects in structure and use, and need to be further improved. In order to solve the above-mentioned problems, the relevant manufacturers have tried their best to find a solution, but no suitable design has been developed for a long time, and the general products do not have a suitable structure to solve the above-mentioned problems. This is obviously the relevant industry. urgent problem to be solved. Therefore, how to create a new type of liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element is one of the current important research and development topics, and has also become a goal that the industry needs to improve.

Contents of the invention

The purpose of the present invention is to overcome the defects existing in the existing liquid crystal alignment agent, and provide a new type of liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element, the technical problem to be solved is to provide a kind of liquid crystal alignment agent, said The liquid crystal alignment agent can form a liquid crystal alignment film with excellent long-term thermal reliability of the liquid crystal display element, that is, it can maintain a high voltage retention rate for a long time in the heating test of the element, and reduce the residual DC of the liquid crystal display element. A liquid crystal alignment film formed by using the liquid crystal alignment agent and a liquid crystal display element using the liquid crystal alignment film are very suitable for practical use.

The purpose of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions. In order to achieve the above object, according to the present invention, a liquid crystal alignment agent is provided, which can form a liquid crystal display element with excellent long-term thermal reliability, that is, it can maintain a high voltage retention rate for a long time in the heating test of the element, and A liquid crystal alignment film for vertical alignment that reduces the residual DC of a liquid crystal display element; and a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

The inventors of the present invention found that the composition of polyamic acid or its derivatives containing specific tetracarboxylic dianhydride and diamine with vertical alignment side chains as raw materials is used in the liquid crystal alignment agent for vertical alignment, which has the following advantages: The long-term thermal reliability of the liquid crystal display element of the liquid crystal alignment film formed in this way is excellent, and residual DC is low, and this invention was completed.

In addition, in the detailed description of the invention, the left-right asymmetric base is defined as left-right orientation in any direction (for example, -COCH=CH- means any of "-COCH=CH-" or "-CH=CHCO-") By).

When -CH ₂ - in the alkyl or alkylene group is replaced by -O-, -O- is not continuous.

An alkyl group or an alkylene group may be either linear or branched.

The present invention includes the following configurations.

[1] A liquid crystal alignment agent for vertical alignment, which contains a tetracarboxylic dianhydride represented by formula (Q), a diamine with a side chain structure represented by formula (V-2) or a compound with formula (V- 2) the polyamic acid or derivative thereof obtained by reacting the diamine with side chain structure and other diamine mixtures,

In formula (V-2),

X ¹⁰ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, or -(CH ₂ ) _m -, m is an integer of 1 to 6;

^Y11 is a group having a steroid skeleton, a succinimide skeleton, a phthalimide skeleton or a cinnamate skeleton, or a group represented by the following formula (XXIII).

In formula (XXIII),

A ⁴ is independently a single bond, or an alkylene group with 1 to 12 carbons, the -CH ₂ - of the alkylene group can also be substituted by -O-, -NH- or -CO-, and -CH ₂ CH ₂ - can also be Can be substituted by -CH=CH-, -C≡C- or -N=N-, the -H of the alkylene group can also be substituted by -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H or -PO ₃ H ₂ substitution;

Y ¹² is independently -F or -CH ₃ ;

Ring S is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, piperidine-1,4-diyl, pyrimidine-2,5 -diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;

Y ¹³ is -H, -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ or an alkyl group with a carbon number of 1 to 30, and -CH ₂ of an alkyl group - can also be substituted by -O-, -NH- or -CO-, -CH ₂ CH ₂ - can also be substituted by -CH=CH-, -C≡C- or -N=N-, the -H of the alkyl may also be substituted by -F _, -Cl, -C≡N, -OH, -COOH, _-SO3H , or _-PO3H2 ; and,

b is independently an integer of 0-4, c, d, and e are independently integers of 0-3, f is independently an integer of 0-2, and c+d+e≥1.

[2] The liquid crystal alignment agent for vertical alignment according to item [1], wherein Y ¹¹ in formula (V-2) is selected from the following formula (Y ¹¹ -1) to formula (Y ¹¹ -8 ) is one of the groups of bases represented by .

In the formulas (Y ¹¹ -1) to (Y ¹¹ -8),

^Y2 is -H, -F, alkyl with 1 to 30 carbons, fluorine-substituted alkyl with 1 to 30 carbons, alkoxy with 1 to 30 carbons, 2 to 30 carbons Alkenyl, -C≡N, -OCH ₂ F, -OCHF ₂ or -OCF ₃ ;

A ¹ is -O- or an alkylene group with 1 to 6 carbons; and,

A ² is -OCO-, -COO-, -O- or an alkylene group having 1 to 6 carbon atoms.

[3] The liquid crystal alignment agent for vertical alignment according to item [1], wherein the diamine having a side chain group is selected from the following formula (V-2-1) to formula (V-2-8) and at least one of the group of compounds represented by formula (V-2-53).

In formula (V-2-2), Y ² is an alkyl group with 6 to 30 carbons;

In formula (V-2-3) ~ formula (V-2-6), Y ² is an alkyl group with a carbon number of 3 to 30;

In formula (V-2-7), Y ² is an alkyl group with 2 to 30 carbons;

In formula (V-2-8), Y ² is an alkyl group with 2 to 30 carbons; and

In formula (V-2-53), Y ¹⁸ is -F, -CF ₃ or -OCF ₃ .

[4] The liquid crystal alignment agent for vertical alignment according to item [1], wherein the diamine is at least one of the diamines represented by the formula (V-2) and selected from the following formula (V-1- 1)～Formula (V-1-5), Formula (V-1-14), Formula (V-1-15), Formula (VI-1-1)～Formula (VI-1-12), Formula ( VI-1-28) ~ formula (VI-1-30), formula (VI-1-35) ~ formula (VI-1-39), formula (VII-2-1), and formula (VII-2- 2) A mixture of at least one of the indicated diamine groups.

[5] The liquid crystal alignment agent for vertical alignment according to item [1], wherein tetracarboxylic dianhydride represented by formula (Q) and a compound selected from the following formula (1), formula (2), Polyamic acid obtained by reacting at least one of the group of aromatic tetracarboxylic acids represented by formula (5) to formula (7) and formula (12) with diamine, or a derivative thereof.

[6] The liquid crystal alignment agent for vertical alignment according to item [1], wherein the tetracarboxylic dianhydride represented by the formula (Q) and the group selected from the following formula (19), formula (23), At least one of the group of alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by formula (25), formula (35) to formula (39), formula (44) and formula (49) Polyamic acid or its derivatives obtained by reacting with diamine.

[7] The liquid crystal alignment agent for vertical alignment according to item [1], wherein the diamine is at least one of the diamines represented by the formula (V-2), and selected from the following formula (VI-11 -4) Diamine having a photosensitive structure represented by formula (VI-11-16), formula (V-11-2) and formula (V-11-17) to formula (V-11-19) A mixture of at least one of the group, and has photoalignment.

[8] The liquid crystal alignment agent for vertical alignment according to item [1], wherein the diamine is at least one of the diamines represented by the formula (V-2), and selected from the following formula (VI-11 -7), formula (VI-11-11), formula (V-11-2) and formula (V-11-17) ~ formula (V-11-19) represented by the diamine having a photosensitive structure A mixture of at least one of the group, and has photoalignment.

[9] The liquid crystal alignment agent for vertical alignment according to any one of items [1] to [8], which further contains alkenyl-substituted nadiimide compound), a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound.

[10] A liquid crystal alignment film for vertical alignment, which is formed by heating the coating film of the liquid crystal alignment agent for vertical alignment according to any one of items [1] to [9].

[11] A liquid crystal display element, which is a liquid crystal comprising a pair of substrates, a liquid crystal layer formed between the substrates, electrodes for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction In a display element, the liquid crystal alignment film is the liquid crystal alignment film for vertical alignment according to item [10].

Compared with the prior art, the present invention has obvious advantages and beneficial effects. By means of the above-mentioned technical solution, the present invention (liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element) has at least the following advantages and beneficial effects: According to the present invention, liquid crystals with excellent long-term thermal reliability of voltage retention and low residual DC can be provided. Display components.

The above description is only an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention, it can be implemented according to the contents of the description, and in order to make the above and other purposes, features and advantages of the present invention more obvious and understandable , the following special preferred embodiments are described in detail as follows.

Detailed ways

In order to further explain the technical means and effects of the present invention to achieve the intended purpose of the invention, the specific implementation methods, characteristics and characteristics of the liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element proposed according to the present invention will be described below in conjunction with preferred embodiments. Its effect is described in detail below.

The liquid crystal alignment agent of this invention contains the reaction product polyamic acid of tetracarboxylic dianhydride and diamine, or its derivative|guide_body. The so-called derivatives of polyamic acid are components that dissolve in solvents when making liquid crystal alignment agents containing solvents, and can form polyimide-based components when the liquid crystal alignment agents are made into liquid crystal alignment films. Components of liquid crystal alignment film. As for the derivative of such polyamic acid, a soluble polyimide, polyamic acid ester, polyamic acid amide, etc. are mentioned, for example. More specifically, 1) a polyimide in which all amine groups and carboxyl groups of a polyamic acid undergo a dehydration ring-closure reaction, 2) a partial polyimide in which a part of the amine groups and carboxyl groups undergo a dehydration ring-closure reaction, 3) a polyimide in which Polyamic acid ester in which the carboxyl group of polyamic acid is converted to ester, 4) Polyamic acid-polyamic acid obtained by replacing part of the acid dianhydride contained in tetracarboxylic dianhydride compound with organic dicarboxylic acid and reacting An amide copolymer, and 5) a polyamideimide obtained by subjecting part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyamic acid or its derivatives may be used alone in a liquid crystal alignment agent, or multiple compounds may be used in combination.

The tetracarboxylic dianhydride used by this invention contains the tetracarboxylic dianhydride represented by formula (Q).

From the viewpoint of exhibiting the desired voltage retention rate in the liquid crystal display element and realizing its long-term thermal reliability, it is preferable to contain 10 mol% to 100 mol% of It is more preferable that the tetracarboxylic dianhydride represented by the formula (Q) contains 20 mol% - 100 mol% of the tetracarboxylic dianhydride represented by the formula (Q).

The tetracarboxylic dianhydride which comprises the polyamic acid in the liquid crystal aligning agent of this invention may contain aromatic tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by formula (Q). The so-called aromatic tetracarboxylic dianhydride is a compound in which at least one of two -CO-O-CO- is bonded to an aromatic compound. As aromatic tetracarboxylic dianhydride, the compound represented by following formula (1) - a formula (13) can be illustrated.

The aromatic tetracarboxylic dianhydride used together with the tetracarboxylic dianhydride represented by formula (Q) is preferably formula (1), formula (2), formula (5) to formula (7) and formula (12) The compounds represented are more preferably compounds represented by formula (1) and formula (12). When an aromatic tetracarboxylic dianhydride is used together, it has the effect of improving the light resistance of a liquid crystal display element, and the effect of reducing residual DC. Among all the acid dianhydrides constituting the polyamic acid in the liquid crystal alignment agent of the present invention, it is preferred to contain 1 mol% to 90 mol% of aromatic tetracarboxylic dianhydride, more preferably 2 mol% to 60 mol% of aromatic tetracarboxylic acid Dianhydride.

The tetracarboxylic dianhydride constituting the polyamic acid in the liquid crystal alignment agent of the present invention may contain alicyclic tetracarboxylic dianhydride and/or aliphatic tetracarboxylic dianhydride in addition to the tetracarboxylic dianhydride represented by formula (Q). Carboxylic dianhydride. The alicyclic tetracarboxylic dianhydride is a compound in which at least one of two -CO-O-CO- is bonded to an alicyclic compound. The aliphatic tetracarboxylic dianhydride is a compound in which at least one of two -CO-O-CO- is bonded to an aliphatic compound. Alicyclic tetracarboxylic dianhydrides can be exemplified by the following formula (19) to formula (22), formula (24), formula (25), formula (27) to formula (44), formula (49) to formula (58) ), and compounds represented by formula (62) to formula (64).

As an aliphatic tetracarboxylic dianhydride, the compound represented by following formula (23), formula (45) - formula (48), formula (66), and formula (67) can be illustrated.

Alicyclic tetracarboxylic dianhydride and the preferred formula (19), formula (23), formula (25), formula (35) ~ formula (39), formula (44) and formula The compound represented by (49) is more preferably a compound represented by formula (19) and formula (23). When alicyclic tetracarboxylic dianhydride and/or aliphatic tetracarboxylic dianhydride are used in combination, there is an effect of improving the heat resistance of a liquid crystal display element and an effect of improving transparency. In all tetracarboxylic dianhydrides constituting the polyamic acid in the liquid crystal alignment agent of the present invention, it is preferable to contain 1 mol% to 90 mol% of alicyclic tetracarboxylic dianhydride and/or aliphatic tetracarboxylic dianhydride, more It is preferable to contain 10 mol% - 80 mol% of alicyclic tetracarboxylic dianhydrides and/or aliphatic tetracarboxylic dianhydrides.

The tetracarboxylic dianhydride used in the present invention preferably contains a silsesquioxane (silsesquioxane) dianhydride derivative. Since silsesquioxane is a highly cross-linked body and does not hydrolyze, the storage stability as a liquid crystal aligning agent can be made excellent by containing silsesquioxane. Moreover, since it does not hydrolyze even after film formation, the liquid crystal alignment film with high thermal reliability can be formed.

As the silsesquioxane dianhydride used in the present invention, for example, a compound described in International Publication No. 03/024870 can be used, and it is represented by the following formula.

In formula (S), R is independently selected from hydrogen, alkyl groups with 1 to 45 carbons, substituted or unsubstituted aryl groups and substituted or unsubstituted arylalkyl groups, and Y is represented by the following represented by formula (a) or (b).

X in formula (a) and formula (b) is independently hydrogen, halogen, hydroxyl or monovalent organic group with acid anhydride structure (-CO-O-CO-), at least two of X are with acid anhydride structure (- CO-O-CO-), a monovalent organic group, Z is -O-, -CH ₂ - or a single bond. Among them, in the alkyl group with a carbon number of 1 to 45, any hydrogen can also be replaced by fluorine, and any -CH ₂ - can also be replaced by -O-, -CH=CH-, cycloalkylene or cycloalkene base substitution. In the alkylene group in the substituted or unsubstituted arylalkyl group, any hydrogen can also be replaced by fluorine, and any -CH ₂ - can also be replaced by -O-, -CH=CH- or cycloalkylene base substitution.

Among the silsesquioxane dianhydrides represented by the formula (S), a compound represented by the following formula (S-1) is preferable.

In formula (S-1), R is the same as R in the above formula (S).

When silsesquioxane dianhydride is used together, it has the effect of improving the voltage retention of a liquid crystal display element, improving light resistance and heat resistance, and reducing an ion density. Among all the tetracarboxylic dianhydrides constituting the polyamic acid in the liquid crystal alignment agent of the present invention, it is preferable to contain 1 mol% to 60 mol% of silsesquioxane dianhydride, more preferably 10 mol% to 40 mol% of silsesquioxane Oxyalkylene dianhydride.

The tetracarboxylic dianhydride used together with the tetracarboxylic dianhydride represented by a formula (Q) can be used arbitrarily about the kind or compounding quantity as long as the effect of this invention is obtained. In the present invention, the use of tetracarboxylic dianhydrides represented by formula (Q) together with at least one other tetracarboxylic dianhydrides and copolymers formed by reacting with diamines can improve the storage stability of the alignment agent. preferred.

The tetracarboxylic dianhydride used together with the tetracarboxylic dianhydride represented by formula (Q) may replace a part with carboxylic anhydride. By such substitution, the termination (termination) of the polymerization reaction at the time of producing a polyamic acid can arise, and progress of a polymerization reaction can be suppressed. Therefore, the molecular weight of the obtained polymer (polyamic acid or its derivative) can be controlled easily, for example, the coating characteristic of a liquid crystal alignment agent can be improved without impairing the effect of this invention. The ratio of carboxylic acid anhydride to tetracarboxylic dianhydride should just be in the range which does not impair the effect of this invention, However, It is preferable that it is 10 mol% or less of the total tetracarboxylic dianhydride amount as a standard. As long as the effect of the present invention is not impaired, only one kind of compound may be used for the carboxylic anhydride, or two or more kinds may be used. Examples of the carboxylic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and cyclohexanedicarboxylic anhydride.

The tetracarboxylic dianhydride used together with the tetracarboxylic dianhydride represented by the formula (Q) may be partially replaced within the range where the ratio of the dicarboxylic acid to the tetracarboxylic dianhydride is 10 mol% or less. For dicarboxylic acids. As long as the effects of the present invention are not impaired, dicarboxylic acids may be used alone or in combination of two or more.

The diamine reacted with the tetracarboxylic dianhydride represented by the formula (Q) that constitutes the polyamic acid or its derivatives in the liquid crystal alignment agent of the present invention has a side chain represented by the following formula (V-2): Structured compounds.

In formula (V-2),

X ¹⁰ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _m -, m is an integer of 1 to 6,

^Y11 is a group having a steroid skeleton, a succinimide skeleton, a phthalimide skeleton, or a cinnamate skeleton or a group represented by the following formula (XXIII),

In formula (XXIII), A ⁴ is independently a single bond, or an alkylene group with 1 to 12 carbons, and -CH ₂ - of the alkylene group can also be substituted by -O-, -NH- or -CO-, -CH ₂ CH ₂ - can also be substituted by -CH=CH-, -C≡C- or -N=N-, and the -H of the alkylene group can also be substituted by -F, -Cl, -C≡N, -OH , -COOH, -SO ₃ H or -PO ₃ H ₂ substitution,

Y ¹² is independently -F or -CH ₃ ,

Ring S is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, piperidine-1,4-diyl, pyrimidine-2,5 -diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl,

Y ¹³ is -H, -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ or an alkyl group with a carbon number of 1 to 30, and -CH ₂ of an alkyl group - can also be substituted by -O-, -NH- or -CO-, -CH ₂ CH ₂ - can also be substituted by -CH=CH-, -C≡C- or -N=N-, the -H of the alkyl Can also be substituted by -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H or -PO ₃ H ₂ ,

b is independently an integer of 0-4, c, d, and e are independently integers of 0-3, f is independently an integer of 0-2, and c+d+e≥1.

The diamine represented by formula (V-2) is preferably a compound in which Y ¹¹ is one compound selected from the group represented by the following formula (Y ¹¹ -1) to formula (Y ¹¹ -8).

In formula (Y ¹¹ -1) ~ formula (Y ¹¹ -8),

^Y2 is -H, -F, alkyl with 1 to 30 carbons, fluorine-substituted alkyl with 1 to 30 carbons, alkoxy with 1 to 30 carbons, 2 to 30 carbons Alkenyl, -C≡N, -OCH ₂ F, -OCHF ₂ , or -OCF ₃ ,

A ¹ is -O- or an alkylene group having 1 to 6 carbon atoms, and,

A ² is -OCO-, -COO-, -O- or an alkylene group having 1 to 6 carbon atoms.

Examples of the diamine represented by formula (V-2) are compounds represented by the following formula (V-2-1) to formula (V-2-54).

In the formulas (V-2-1) to (V-2-54),

^Y2 is independently -H, -F, alkyl with 1 to 30 carbons, fluorine-substituted alkyl with 1 to 30 carbons, alkoxy with 1 to 30 carbons, and 2 to 30 carbons 30 alkenyl, -C≡N, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , preferably independently -H, alkyl with 1 to 20 carbons or alkenyl with 2 to 20 carbons,

^Y5 is independently an alkyl group with 1 to 30 carbons, or an alkenyl group with 2 to 30 carbons,

^Y16 is independently -H, an alkyl group with 1 to 30 carbons, an alkoxy group with 1 to 29 carbons, or an alkenyl group with 2 to 30 carbons, and,

Y ¹⁸ is -F, -CF ₃ or -OCF ₃ .

The diamine represented by formula (V-2) is preferably selected from the group of compounds represented by the above-mentioned formula (V-2-2) to formula (V-2-8) and formula (V-2-53). at least one.

In formula (V-2-2), Y ² is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 9 to 20 carbon atoms.

In formulas (V-2-3) to (V-2-6), Y ² is preferably an alkyl group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 20 carbon atoms.

In formula (V-2-7), Y ² is preferably an alkyl group having 2 to 30 carbon atoms, more preferably an alkyl group having 4 to 25 carbon atoms.

In the formula (V-2-8), Y ² is preferably an alkyl group having 2 to 30 carbon atoms, more preferably an alkyl group having 2 to 12 carbon atoms. and,

Y ¹⁸ in formula (V-2-53) is -F, -CF ₃ or -OCF ₃ .

The diamine represented by formula (V-2) can be used in combination, and other diamines reacted with tetracarboxylic dianhydride represented by formula (Q) can be used suitably according to the required characteristic. When using the liquid crystal aligning agent for vertical alignment of this invention, it is preferable to use the diamine which has an alignment side chain structure similarly to the diamine represented by formula (V-2). The so-called diamine having an alignment side chain structure refers to a substituent (side chain) branching from the main chain when the substituent linking two amine groups is used as the main chain, and has a vertical alignment or Pretilt properties of diamines. The side chain can be appropriately selected according to the required alignment. Among the diamines used in combination, a compound not having an aligning side chain structure may be selected within the range not impairing the effect of the present invention. The liquid crystal alignment agent of the present invention can be applied to a TN or IPS liquid crystal display element depending on the structure of the diamine used in combination.

Other diamines that can be used in the present invention can be appropriately selected according to the required properties, and examples include formula (II-1), formula (III-1), formula (IV-1), and formula (V-1) , formula (V-11), formula (VI-1), formula (VI-2), formula (VI-3), formula (VI-11), formula (VI-12), formula (VII-1), Formula (VII-2), Formula (VII-3), Formula (VII-11), Formula (VII-12), Formula (VIII-1), Formula (VIII-2), Formula (VIII-3), Formula (VIII-4), a compound represented by formula (VIII-11) or formula (IX-1).

Among these diamines, when two amine groups are bonded to the same carbon of the six-membered ring, they are preferably bonded to each other at the meta-position or para-position.

In formula (II-1), formula (III-1), formula (IV-1), formula (V-1), formula (V-11), formula (VI-1), formula (VI-2), Formula (VI-3), Formula (VI-11), Formula (VI-12), Formula (VII-1), Formula (VII-2), Formula (VII-12), Formula (VII-3), Formula In (VII-11), formula (VIII-1), formula (VIII-2), formula (VIII-3), formula (VIII-4), formula (VIII-11) and formula (IX-1),

X ¹¹ is independently an alkylene group with 1 to 12 carbons, and -H on the alkylene group can also be substituted by an alkyl group with 1 to 10 carbons,

X ^is independently -COCH=CH-, -N=N- or -C≡C-,

X ⁶ is independently a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -COO-, -NH-, -N(CH ₃ )-(CH ₂ ) _m -N(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S -(CH ₂ ) _m -S-, -COCH=CH-, -N=N- or -C≡C-, and,

m is an integer of 1 to 6,

^X7 is independently methylene or phenylene, and the -H of phenylene can also be substituted by an alkyl group with 1 to 30 carbons,

^X8 is independently a single bond or an alkylene group with 1 to 3 carbons,

^X is independently a single bond, 1,4-phenylene or 1,4-cyclohexylene,

X ¹⁰ is a single bond, -O-, -COO-, -CO-, -CONH-, -(CH ₂ ) _m -, -CHY ² -, -C(Y ² ) ₂ - or -NY ² -, and ,

m is an integer of 1 to 6,

a is an integer of 0 to 4 corresponding to the atoms or ring structures to which Y ² , Y ³ , Y ⁴ , Y ⁷ and Y ¹⁴ are bonded,

1 is an integer from 1 to 10,

^Y2 is independently -H, an alkyl group with a carbon number of 1 to 20, or an alkenyl group with a carbon number of 2 to 20,

^Y3 is independently -H, -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ or an alkyl group with 1 to 2 carbons,

When ^Y3 exists in plural, they may be bonded to each other to form a ring,

Y ⁴ is independently benzyl, -H, -F, -Cl, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , -NHY ⁵ , or -N(Y ⁵ ) ₂ ,

^Y5 is independently an alkyl group with 1 to 20 carbons, or an alkenyl group with 2 to 20 carbons,

^Y6 is independently an alkyl or phenyl group with 1 to 3 carbons,

Y ⁷ is independently an alkyl group with 1 to 30 carbons, cyclohexyl, or bicyclohexyl, and -H of the cyclohexyl or bicyclohexyl may be substituted with an alkyl group with 1 to 30 carbons.

^Y8 is -H or an alkyl group with 1 to 30 carbons,

The -CH ₂ - of the alkyl group can also be substituted by -O-, -NH- or -CO-,

The -CH ₂ CH ₂ - of the alkyl group may also be substituted by -CH=CH-, -C≡C- or -N=N-,

The -H of the alkyl group may also be substituted by -F, -Cl, -Br, -C≡N, -OH, -COOH, _{-SO3H or -PO3H2} .

^Y9 is an alkyl group with a carbon number of 6 to 30,

Y ¹⁰ is an alkyl group having 1 to 30 carbon atoms.

Y ¹⁷ is -H, -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ or an alkyl group with 1 to 20 carbons,

The -CH ₂ - of the alkyl group can also be substituted by -O-, -NH- or -CO-,

The -CH ₂ CH ₂ - of the alkyl group may also be substituted by -CH=CH-, -C≡C- or -N=N-,

The -H of the alkyl group may also be substituted by -F, -Cl, -Br, -C≡N, -OH, -COOH, _{-SO3H or -PO3H2} .

^Y11 is: a group having a steroid skeleton, a succinimide skeleton or a phthalimide skeleton or a group represented by the following formula (XXIII),

In formula (XXIII),

-H on the ring can also be substituted by -F, -Cl, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , alkyl with 1 to 30 carbons, or phenyl,

The -CH ₂ - of the alkyl group can also be substituted by -O-, -NH- or -CO-,

The -CH ₂ CH ₂ - of the alkyl group may also be substituted by -CH=CH-, -C≡C- or -N=N-,

The -H of the alkyl group may also be substituted by -F, -Cl, -Br, -C≡N, -OH, -COOH, _{-SO3H or -PO3H2} ,

The -H of phenyl can also be independently replaced by -F, -Cl, -Br, -C≡N, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , -OH, -COOH , -SO ₃ H or -PO ₃ H ₂ substitution.

^A4 is independently a single bond or an alkylene group with 1 to 12 carbons,

The -CH ₂ - of the alkylene group can also be substituted by -O-, -NH- or -CO-,

The -CH ₂ CH ₂ - of the alkylene group may also be substituted by -CH=CH-, -C≡C- or -N=N-,

-H of the alkylene group may also be substituted by -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO ₃ H or -PO ₃ H ₂ .

Y ¹² is independently -F or CH ₃ ,

Ring S is independently cyclohexane, 1,3-dioxane, piperidine, piperazine, pyrrolidine, phenylene, pyridine, pyrazine, pyridazine, pyrimidine, triazine, pyrrole, furan, thiophene, imidazole, Oxazole, thiazole, triazole, naphthalene, anthracene, indole, steroid, or hexahydrofuro[3.2-b]furan,

b is independently an integer of 0 to 1, c, d and e are independently an integer of 0 to 3, f is independently an integer of 0 to 4, c+d+e≥1 and 6≥b+c+d+e.

Y ¹³ is -H, -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ or an alkyl group with 1 to 30 carbons,

The -CH ₂ - of the alkyl group can also be substituted by -O-, -NH- or -CO-,

The -CH ₂ CH ₂ - of the alkyl group may also be substituted by -CH=CH-, -C≡C- or -N=N-,

The -H of the alkyl group may also be substituted by -F, -Cl, -Br, -C≡N, -OH, -COOH, _{-SO3H or -PO3H2} .

Y ¹⁴ independently represents the following general formula (XXI),

~A ¹ -A ¹ -A ¹ -A ¹ -A ¹ -A ¹ -A ² (XXI)

^A1 independently represents a single bond, an alkylene group having 1 to 12 carbons, or a ring in which the sum of the respective atomic numbers of carbon, nitrogen, and oxygen constituting the skeleton is 3 to 30,

-CH ₂ - in the alkylene group can also be substituted by -O-, -NH-, -CO-, -CHY ² -, -C(Y ² ) ₂ - or NY ² -,

^Y2 independently represents -H, an alkyl group with 1 to 30 carbons, an alkoxy group with 1 to 29 carbons, or an alkenyl group with 2 to 30 carbons,

-CH ₂ CH ₂ - may also be substituted by -CH=CH-, -C≡C- or N=N-,

The -H of the alkylene group can also be substituted by -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H or PO ₃ H ₂ ,

The -H of the ring can also be substituted by -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ or the following general formula (XXII),

~A ³ -A ³ -A ³ -A ² (XXI)

^A3 independently represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a ring in which the total number of atoms of carbon, nitrogen, and oxygen constituting the skeleton is 3 to 30,

The -CH ₂ - of the alkylene group can also be substituted by -O-, -NH-, -CO-, -CHY ² -, -C(Y ² ) ₂ - or NY ² -,

^Y2 independently represents -H, an alkyl group with 1 to 20 carbons, an alkoxy group with 1 to 19 carbons, or an alkenyl group with 2 to 20 carbons,

-CH ₂ CH ₂ - may also be substituted by -CH=CH-, -C≡C- or N=N-,

The -H of the alkylene group can also be substituted by -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H or PO ₃ H ₂ ,

_The -H of the ring may also be substituted by -F, -Cl, -C≡N, -OH, -COOH, _-SO3H or _PO3H2 ,

A ² independently represents -H, -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , or straight or branched carbon number of 1 to 40 alkyl,

-CH ₂ - in the alkyl group can also be substituted by -O-, -NH- or CO-,

-CH ₂ CH ₂ - may also be substituted by -CH=CH-, -C≡C- or N=N-,

The -H of the alkyl group can also be substituted by -F, -Cl, -OH, -COOH, -SO ₃ H or PO ₃ H ₂ ,

wherein at least one of Y ¹⁴ is a group comprising -COCH=CH-, -N=N- or C≡C-, and,

In formula (II-1), formula (III-1), formula (IV-1), formula (V-1), formula (V-11), formula (VI-1), formula (VI-2), Formula (VI-3), Formula (VI-11), Formula (VI-12), Formula (VII-1), Formula (VII-2), Formula (VII-12), Formula (VII-3), Formula In (VII-11), formula (VIII-1), formula (VIII-2), formula (VIII-3), formula (VIII-4), formula (VIII-11), and formula (IX-1), The benzene ring can also be replaced by a piperazine ring, piperidine ring, pyrrolidine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, triazole ring, pyridine ring, pyrazine ring, pyridazine ring , pyrimidine ring, triazine ring, indole ring, steroid ring, bicyclo[2.2.1]heptane ring, bicyclo[2.2.2]octane ring, or hexahydrofuro[3.2-b]furan ring.

As other diamine, the compound represented by the following formula is mentioned more specifically.

The diamine represented by a formula (II-1) can illustrate the compound represented by following formula (II-1-1) - a formula (II-1-4).

H ₂ N-(CH ₂ ) ₂ -NH ₂ H ₂ N-(CH ₂ ) ₄ -NH ₂ H ₂ N-(CH ₂ ) ₄ -NH ₂ H ₂ N-(CH ₂ ) ₁₂ -NH ₂

(II-1-1) (II-1-2) (II-1-3) (II-1-4)

Examples of the diamine represented by formula (III-1) include compounds represented by the following formula (III-1-1) and formula (III-1-2).

The diamine represented by formula (IV-1) can illustrate the compound represented by formula (IV-1-1) - a formula (IV-1-3).

The diamine represented by a formula (V-1) can illustrate the compound represented by following formula (V-1-1) - a formula (V-1-19).

The diamine represented by a formula (V-11) can illustrate the compound represented by following formula (V-11-1) - a formula (V-11-19).

The diamine represented by a formula (VI-1) can illustrate the compound represented by following formula (VI-1-1) - a formula (VI-1-39).

The diamine represented by a formula (VI-2) can illustrate the compound represented by following formula (VI-2-1) - (VI-2-8).

In formula (VI-2-1) ~ formula (VI-2-8),

Y ¹⁵ is independently an alkyl group having 3 to 30 carbons, an alkoxy group having 3 to 29 carbons, or an alkenyl group having 3 to 30 carbons.

Y ¹⁶ is independently -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

The diamine represented by a formula (VI-3) can illustrate the compound represented by following formula (VI-3-1) and a formula (VI-3-2).

In formula (VI-3-1)～(VI-3-2),

Y ¹⁵ is independently an alkyl group having 3 to 30 carbons, an alkoxy group having 3 to 29 carbons, or an alkenyl group having 3 to 30 carbons.

Y ¹⁶ is independently -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

The diamine represented by a formula (VI-11) can illustrate the compound represented by following formula (VI-11-1) - a formula (VI-11-16).

The diamine represented by formula (VI-12) can illustrate the compound represented by following formula (VI-12-1).

The diamine represented by a formula (VII-1) can illustrate the compound represented by following formula (VII-1-1) - a formula (VII-1-6).

The diamine represented by a formula (VII-2) can illustrate the compound represented by following formula (VII-2-1) - a formula (VII-2-15).

The diamine represented by a formula (VII-3) can illustrate the compound represented by following formula (VII-3-1) - a formula (VII-3-4).

The diamine represented by a formula (VII-11) can illustrate the compound represented by following formula (VII-11-1) - a formula (VII-11-6).

The diamine represented by formula (VII-12) can illustrate the compound represented by following formula (VII-12-1).

Examples of the diamine represented by the formula (VIII-1) include compounds represented by the following formula (VIII-1-1) to formula (VIII-1-16).

Examples of the diamine represented by the formula (VIII-2) include compounds represented by the following formula (VIII-2-1) to formula (VIII-2-8).

In formula (VIII-2-1) ~ formula (VIII-2-8),

Y ¹⁶ is independently -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

Examples of the diamine represented by the formula (VIII-3) include compounds represented by the following formula (VIII-3-1) to the formula (VIII-3-3).

In formula (VIII-3-1) ~ formula (VIII-3-3),

^Y16 is independently -H, alkyl with 1 to 30 carbons, alkoxy with 1 to 29 carbons, or alkenyl with 2 to 30 carbons,

Y ⁹ is an alkyl group having 6 to 30 carbon atoms.

Examples of the diamine represented by the formula (VIII-4) include compounds represented by the following formula (VIII-4-1) to formula (VIII-4-8).

As the diamine represented by the formula (VIII-11), a compound represented by the following formula (VIII-11-1) can be exemplified.

The diamine represented by formula (IX-1) can illustrate the compound represented by following formula (IX-1-1).

As diamines other than the compounds exemplified so far, naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, and the like are exemplified.

Among the diamines constituting the polyamic acid in the liquid crystal aligning agent of the present invention, other diamines that can be used in the present invention can be used within the range that does not impair the effects of the present invention.

The polyamic acid of this invention or its derivative(s) may contain a monoisocyanate compound further in the monomer. By containing a monoisocyanate compound in a monomer, the terminal of the obtained polyamic acid or its derivative can be modified and molecular weight can be adjusted. By using this terminal-modified polyamic acid or its derivative, the application|coating characteristic of a liquid crystal aligning agent can be improved, for example without impairing the effect of this invention. From such a viewpoint, it is preferable that content of the monoisocyanate compound in a monomer is 1 mol% - 10 mol% with respect to the total amount of the diamine and tetracarboxylic dianhydride in a monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid or its derivative molecular weight of this invention is polystyrene conversion weight average molecular weight (Mw), Preferably it is 10,000-500,000, More preferably, it is 20,000-200,000. The molecular weight of the said polyamic acid or its derivative can be measured and calculated|required by the gel permeation chromatography (GPC) method.

The presence of the polyamic acid of the present invention or its derivative can be confirmed by analyzing the solid matter obtained by precipitating with a large amount of poor solvent by IR or NMR. Furthermore, after decomposing the polyamic acid or derivatives thereof of the present invention with an aqueous solution of a strong base such as KOH or NaOH, the components extracted from the decomposed product with an organic solvent are analyzed by GC, HPLC or GC-MS , so that the monomer used can be confirmed.

The liquid crystal alignment agent of the present invention may also contain other components than the polyamic acid or its derivatives. The other components may be one kind or two or more kinds.

For example, from the viewpoint of stabilizing the electrical characteristics of a liquid crystal display element over a long period of time, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted terimide compound. The above-mentioned alkenyl-substituted nadilimide compound may be used alone or in combination of two or more compounds. The content of alkenyl-substituted nadiimide compound is preferably 0.01-1.00, more preferably 0.01-0.70, and further More preferably, it is 0.01-0.50.

The alkenyl-substituted nadilimide compound is preferably a compound that is soluble in the solvent for dissolving polyamic acid or its derivative used in the present invention. Examples of such an alkenyl-substituted nadilimide compound include compounds represented by the following formula (Ina).

In formula (Ina), L ¹ and L ² are independently hydrogen, alkyl with 1 to 12 carbons, alkenyl with 3 to 6 carbons, cycloalkyl with 5 to 8 carbons, aryl Or benzyl, n is 1 or 2.

When n=1,

W is an alkyl group with 1 to 12 carbons, an alkenyl group with 2 to 6 carbons, a cycloalkyl group with 5 to 8 carbons, an aryl group with 6 to 12 carbons, benzyl, -Z ¹ - (O) _q -(Z ² O) _r -Z ³ -H, -(Z ⁴ ) _s -BZ ⁵ -H, -BTBH, or 1 to 1 of these groups A group in which 3 hydrogens are replaced by hydroxyl groups.

Here, Z ¹ , Z ² and Z ³ are independently an alkylene group with 2 to 6 carbons, q is 0 or 1, and r is an integer of 1 to 30,

Z ⁴ and Z ⁵ are independently an alkylene group with 1 to 4 carbons or a cycloalkylene group with 5 to 8 carbons, B is phenylene, s is 0 or 1, and,

T is -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- or -SO ₂ -.

At this time, preferred W is an alkyl group with 1 to 8 carbons, alkenyl with 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly(ethyleneoxy) with 4 to 10 carbons ) ethyl group, phenyloxyphenyl group, phenylmethylphenyl group, phenylisopropylidenephenyl group, and groups in which one or two hydrogens of these groups are replaced by hydroxyl groups.

When n=2,

W is an alkylene group with 2 to 20 carbons, a cycloalkylene group with 5 to 8 carbons, an arylene group with 6 to 12 carbons, -Z ¹ -O-(Z ² O) _r -Z The group represented by ^3- , the group represented by -Z ⁴ -BZ ⁵ -, the group represented by -B-(OB) _s -T-(BO) _s -B-, or 1 to 3 hydrogens of these groups A group substituted by a hydroxyl group.

Here, the meanings of Z ¹ to Z ³ , r, Z ⁴ , Z ⁵ and B are as described above,

T is an alkylene group having 1 to 3 carbon atoms, -O- or -SO ₂ -, and s is 0 or 1.

In this case, W is preferably an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenylene group, a tolylene group, a xylylene group, or -C ₃ H ₆ -O -(Z ² -O) _r -OC ₃ H ₆ -(Z ² is an alkylene group having 2 to 6 carbon atoms, r represents 1 or 2), -BTB-(B is phenylene, And T is a group represented by -CH ₂ -, -O- or SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (B is a phenylene group), and one or two of these groups A group in which hydrogen is replaced by a hydroxyl group.

Such an alkenyl-substituted resilicate imide compound can be used, for example, as described in Japanese Patent No. 2729565, by making an alkenyl-substituted resilicate anhydride derivative and a diamine at a temperature of 80° C. to 220° C. The synthetic compound or the commercially available compound is kept at the lower temperature for 0.5 hours to 20 hours. Specific examples of the alkenyl-substituted nadilimide compound are the compounds shown below.

N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-methyl-allylmethylbicyclo[2.2.1]hept-5- ene-2,3-dicarboxyimide, N-methyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-methyl-methyl N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxyimide,

N-(2-ethylhexyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-allyl-allylbicyclo[ 2.2.1] Hept-5-ene-2,3-dicarboxyimide, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide imine, N-allyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-isopropenyl-allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxyimide, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide Amine, N-isopropenyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allylbicyclo[2.2.1]heptane -5-ene-2,3-dicarboxyimide, N-cyclohexyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N -Cyclohexyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-phenyl-allylbicyclo[2.2.1]hept-5-ene -2,3-Dicarboxyimide,

N-phenyl-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-benzyl-allylbicyclo[2.2.1]hept- 5-ene-2,3-dicarboxyimide, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-benzyl -Methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxyimide, N-(2-hydroxyethyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide Amine, N-(2-hydroxyethyl)-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,

N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2,2- Dimethyl-3-hydroxypropyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2,3-dihydroxypropyl Base)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2,3-dihydroxypropyl)-allyl(methyl)bicyclo[ 2.2.1] Hept-5-ene-2,3-dicarboxyimide, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-Dicarboxyimide, N-(4-hydroxycyclohexyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,

N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-hydroxyphenyl)-allyl(methyl base) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-hydroxyphenyl)-methallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxyimide, N-(4-hydroxyphenyl)-methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-hydroxyphenyl)-allyl(methyl Base) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-Dicarboxyimide, N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,

N-{2-(2-hydroxyethoxy)ethyl}-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-{2 -(2-hydroxyethoxy)ethyl}-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-{2-(2-hydroxyethyl Oxy)ethyl}-methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-[2-{2-(2-hydroxyethoxy Base) ethoxy} ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-[2-{2-(2-hydroxyethoxy )ethoxy}ethyl]-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-[2-{2-(2-hydroxy Ethoxy)ethoxy}ethyl]-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-{4-(4-hydroxyphenyl Isopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-{4-(4-hydroxyphenylisopropylidene) Phenyl}-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-{4-(4-hydroxyphenylisopropylidene)benzene Base}-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, and their oligomers,

N, N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept- 5-ene-2,3-dicarboxyimide), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide ), N, N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylene-bis(allylbicyclo[2.2. 1] Hept-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxyimide), N, N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N '-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),

1,2-bis{3′-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy}ethane, 1,2-bis{3′ -(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy}ethane, 1,2-bis{3′-(methallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]heptane -5-ene-2,3-dicarboxyimide)propoxy}ethyl]ether, bis[2′-{3′-(allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxyimide)propoxy}ethyl]ether, 1,4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimide)propoxy}butane, 1,4-bis{3′-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propane Oxygen}butane,

N, N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-p-phenylene-bis( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N′-m-phenylene-bis(allylbicyclo[2.2.1] Hept-5-ene-2,3-dicarboxyimide), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxyimide), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxyimide), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N '-P-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-m-xylylene-bis (Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxyimide),

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[ 4-{4-(Methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, bis{4-(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxyimide) phenyl} methane,

Bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(methallylmethylbicyclo [2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl} ether, bis{ 4-(Methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}ether, bis{4-(allylbicyclo[2.2.1]heptan -5-ene-2,3-dicarboxyimide)phenyl}pyridine, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide Amine) phenyl} phenyl,

Bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}sulfone, 1,6-bis(allylbicyclo[2.2. 1] Hept-5-ene-2,3-dicarboxyimide)-3-hydroxyl-hexane, 1,12-bis(methallylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxyimide)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide Amine)-5-hydroxy-cyclohexane, 1,5-bis{3′-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy} -3-Hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2-hydroxy-benzene,

1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2,5-dihydroxyl-benzene, N,N'-p-( 2-Hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-p-(2-hydroxy)benzenedi Methyl-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-(2-hydroxy)xylylene-bis (Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-(2-hydroxy)xylylene-bis(methallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-p-(2,3-dihydroxy)xylylene-bis(allylbicyclo[2.2 .1] hept-5-ene-2,3-dicarboxyimide),

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2-hydroxy-phenoxy}phenyl]propane , bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2-hydroxy-phenyl}methane, bis{3-(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-4-hydroxyl-phenyl}ether, bis{3-(methallylbicyclo[2.2.1]heptane -5-ene-2,3-dicarboxyimide)-5-hydroxy-phenyl}sulfone, 1,1,1-tri{4-(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxyimide)}phenoxymethylpropane, N,N′,N″-tris(ethylenemethylallylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxyimide) isocyanurate, and their oligomers, etc.

In addition, the alkenyl-substituted imide compound used in the present invention may be a compound represented by the following structural formula including an asymmetric alkylene/phenylene group.

As the alkenyl-substituted nadilimide compound, the following compounds are preferably used.

N, N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept- 5-ene-2,3-dicarboxyimide), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide ), N, N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylene-bis(allylbicyclo[2.2. 1] Hept-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxyimide), N, N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N '-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-p-phenylene-bis( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N′-m-phenylene-bis(allylbicyclo[2.2.1]heptane -5-ene-2,3-dicarboxyimide), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimide), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimide), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'- p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-xylylene-bis(ene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]heptane -5-ene-2,3-dicarboxyimide), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyacyl imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide )phenoxy}phenyl]propane, 2,2-bis[4-{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)benzene Oxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane,

Bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(methallylmethylbicyclo [2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl} ether, bis{ 4-(Methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}ether, bis{4-(allylbicyclo[2.2.1]heptan -5-ene-2,3-dicarboxyimide)phenyl}sulfone, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide amine)phenyl}sulfone, bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}sulfone.

More preferably used alkenyl-substituted nandiimide compounds are as follows.

N, N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept- 5-ene-2,3-dicarboxyimide), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide ), N, N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylene-bis(allylbicyclo[2.2. 1] Hept-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxyimide), N, N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N '-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-p-phenylene-bis( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N′-m-phenylene-bis(allylbicyclo[2.2.1]heptane -5-ene-2,3-dicarboxyimide), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimide), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimide), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'- p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-xylylene-bis(ene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]heptane -5-ene-2,3-dicarboxyimide),

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[ 4-{4-(Methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, bis{4-(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxyimide)phenyl}methane, bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane , bis{4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane.

Moreover, a particularly preferred alkenyl-substituted nadiimide compound is bis{4-(allylbicyclo[2.2.1]hept-5-ene-2 represented by the following formula (Ina-1), 3-Dicarboxyimide) phenyl} methane, N, N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene- represented by formula (Ina-2) 2,3-dicarboxyimide), and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2 represented by formula (Ina-3), 3-dicarboxyimide).

Moreover, the liquid crystal alignment agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond from a viewpoint of stabilizing the electric characteristic of a liquid crystal display element for a long period of time, for example. The compound having a radically polymerizable unsaturated double bond may be used alone or in combination of two or more compounds. In addition, the compound having a radically polymerizable unsaturated double bond does not include the above-mentioned alkenyl-substituted endimide compound. From this point of view, the content of the compound having a radically polymerizable unsaturated double bond is preferably 0.01 to 1.00, more preferably 0.01 to 0.70, by weight ratio relative to the total amount of polyamic acid or its derivatives, Still more preferably, it is 0.01 to 0.50.

In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted imide compound can reduce the ion density of the liquid crystal display device, suppress the increase of the ion density over time, and also suppress the afterimage. From a viewpoint, it is preferable that it is 0.1-10 by weight ratio, and it is more preferable that it is 0.5-5.

As a compound which has a radically polymerizable unsaturated double bond, (meth)acrylic acid derivatives, such as (meth)acrylate and (meth)acrylamide, and bismaleimide are illustrated. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of (meth)acrylates are cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, bicyclohexyl (meth)acrylate Amyloxyethyl ester, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid 2-Hydroxypropyl ester.

Specific examples of 2-functional (meth)acrylates are, for example, ethylene glycol diacrylate, ARONIX M-210, ARONIX M-240, and ARONIX M-6200 produced by Toagosei Chemical Industry Co., Ltd., and KAYARAD produced by Nippon Kayaku Co., Ltd. HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products V260, V312 and V335HP of Osaka Organic Chemical Industry Co., Ltd., and products of Kyoeisha Oleochemical Industry Co., Ltd. Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA.

Specific examples of trifunctional or more polyfunctional (meth)acrylates include 4,4'-methylene bis(N,N-dihydroxyethylene acrylate aniline), ARONIX M-400, ARONIX M- 405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Osaka Organic Chemical Industry Co., Ltd. product VGPT.

Specific examples of (meth)acrylamide derivatives are, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, N-n-propylacrylamide, N-n-propylmethacrylamide, N -Cyclopropylacrylamide, N-cyclopropylmethacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N- Tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methacrylamide, N,N-diethylacrylamide, N-methyl-N-n-propylacrylamide , N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidone, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide , N, N'-dihydroxyethylene bisacrylamide, N-(4-hydroxyphenyl) methacrylamide, N-phenyl methacrylamide, N-butyl methacrylamide, N-(isobutyl Oxymethyl)methacrylamide, N-[2-(N,N-dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3 -(Dimethylamino)propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)-2-methacrylamide, N-benzyl- 2-methacrylamide, and N,N'-methylenebismethacrylamide.

Particularly preferred compounds among the above-mentioned (meth)acrylic acid derivatives are N,N'-methylenebisacrylamide, N,N'-dihydroxyethylene-bisacrylamide, ethylene glycol diacrylate, and 4, 4'-methylene bis(N,N-dihydroxyethylene acrylate aniline).

Specific examples of bismaleimides are BMI-70 and BMI-80 manufactured by Japan KI Chemical Industry Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI manufactured by Daiwa Chemical Industry Co., Ltd. -5000 and BMI-7000.

Moreover, the liquid crystal alignment agent of this invention may further contain an oxazine compound from a viewpoint of the long-term stability of the electrical characteristic of a liquid crystal display element, for example. As the oxazine compound, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination. The content of the oxazine compound is preferably 0.1 wt % to 50 wt %, more preferably 1 wt % to 40 wt %, and even more preferably 1 wt % to 20 wt %, based on the total amount of the polyamic acid or its derivatives.

The oxazine compound is preferably an oxazine compound that is soluble in a solvent in which the polyamic acid or its derivative is dissolved and that has ring-opening polymerizability.

Furthermore, the number of oxazine structures in the oxazine compound is not particularly limited.

Oxazine compounds have various structures. The structure of the oxazine compound used in the present invention is not particularly limited, and examples thereof include oxazine compounds having an aromatic group including a condensed polycyclic aromatic group, such as benzoxazine or naphthoxazine.

Examples of oxazine compounds are compounds represented by the following formulas (a) to (f). In addition, in the following formulae, the bond shown toward the center of the ring means a bond to any carbon constituting the ring and to which a substituent may be bonded.

In formulas (a) to (c), R ¹ and R ² are organic groups having 1 to 30 carbon atoms.

In formula (a) to formula (f), R ³ to R ⁶ are hydrogen or a hydrocarbon group having 1 to 6 carbons.

In formula (c), formula (d) and formula (f), X is a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO- , -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH ₂ ) _m -S- . Here, m is an integer of 1-6.

Moreover, in formula (e) and formula (f), Y is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or An alkylene group having 1 to 3 carbon atoms.

Furthermore, the oxazine compound includes oligomers or polymers having an oxazine structure in the side chain, and oligomers or polymers having an oxazine structure in the main chain.

The following compounds can be illustrated as an oxazine compound represented by formula (a).

In the formula, R ¹ is preferably an alkyl group with 1 to 30 carbons, more preferably an alkyl group with 1 to 20 carbons.

The following compounds can be illustrated as an oxazine compound represented by formula (b).

In the formula, R ¹ is preferably an alkyl group with 1 to 30 carbons, more preferably an alkyl group with 1 to 20 carbons.

Examples of the oxazine compound represented by the formula (c) include oxazine compounds represented by the following formula (c').

In formula (c'), R ¹ and R ² are organic groups with 1 to 30 carbons, R ³ to R ⁶ are hydrogen or hydrocarbon groups with 1 to 6 carbons, X is a single bond, -CH ₂ - , -C(CH ₃ ) ₂ -, -CO-, -O-, -SO ₂ - or C(CF ₃ ) ₂ -. Specific examples of the oxazine compound represented by the formula (c') are the following compounds.

In the formula, R ¹ is preferably an alkyl group with 1 to 30 carbons, more preferably an alkyl group with 1 to 20 carbons.

Specific examples of the oxazine compound represented by formula (d) are the following compounds.

Specific examples of the oxazine compound represented by formula (e) are the following compounds.

Specific examples of the oxazine compound represented by formula (f) are the following compounds.

Preferred among these compounds are formula (b-1), formula (c-1), formula (c-3), formula (c-5), formula (c-7), formula (c-9), formula ( Oxazine compounds represented by d-1) to formula (d-6), formula (e-3), formula (e-4), and formula (f-2) to formula (f-4).

The oxazine compound can be produced by referring to the methods described in International Publication No. 2004/009708, Japanese Patent Laid-Open No. 11-12258, and Japanese Patent Laid-Open No. 2004-352670.

For example, an oxazine compound represented by formula (a) can be obtained by reacting a phenolic compound with a primary amine and an aldehyde (see International Publication No. 2004/009708).

Moreover, the oxazine compound represented by the formula (b) can be obtained by adding a compound having a naphthol-based hydroxyl group and reacting after the primary amine is slowly added to formaldehyde (refer to International Publication No. 2004 /009708 instructions).

Moreover, the oxazine compound represented by the formula (c) can be obtained by making the phenolic compound 1 Mole, at least 2-fold mole of aldehyde with respect to one phenolic hydroxyl group, and equimolar primary amine are reacted (see International Publication No. 2004/009708 specification and Japanese Patent Application Laid-Open No. 11-12258).

Moreover, the oxazine compounds represented by formulas (d) to (f) can be obtained by making 4,4'-diaminodiphenylmethane, etc. Diamine having a plurality of benzene rings and organic groups bonded to the benzene rings, aldehydes such as formalin, and phenol undergo dehydration condensation reaction (see JP-A-2004-352670).

Moreover, the liquid crystal alignment agent of this invention may further contain an oxazoline compound from a viewpoint of the long-term stability of the electrical characteristic of a liquid crystal display element, for example. The term "oxazoline compound" refers to a compound having an oxazoline structure. As the oxazoline compound, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination. The content of the oxazoline compound is preferably 0.1 wt % to 50 wt %, more preferably 1 wt % to 40 wt %, and even more preferably 1 wt % to 20 wt %, based on the total amount of the polyamic acid or its derivatives. Alternatively, when the oxazoline structure in the oxazoline compound is converted into oxazoline, the content of the oxazoline compound is preferably 0.1 wt% to 40 wt% relative to the polyamic acid or its derivative.

An oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. Furthermore, the oxazoline compound may be a homopolymer or a copolymer having an oxazoline ring structure in a side chain. The polymer that has oxazoline structure in side chain can be the homopolymer of the monomer that has oxazoline structure in side chain, also can be the monomer that has oxazoline structure in side chain and does not have oxazoline structure monomeric copolymers. The copolymer that has oxazoline structure in side chain can be the copolymer of two or more monomers that have oxazoline structure in side chain, also can be the monomer that has more than two kinds of oxazoline structures in side chain and A copolymer of monomers without an oxazoline structure.

The oxazoline structure is preferably a structure in which one or both of oxygen and nitrogen in the oxazoline structure exists in the oxazoline compound in a form that can react with the carbonyl group of the polyamic acid.

Specific examples of oxazoline compounds are 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, 4-furan-2-yl Methylene-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-bis Hydrogen-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxa Azoline, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylene bis(4-tert-butyl-2-oxazoline), and 2, 2'-methylenebis(4-phenyl-2-oxazoline). In addition to these compounds, polymers or oligomers having an oxazole group such as EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.) can also be exemplified.

Moreover, the liquid crystal alignment agent of this invention may further contain an epoxy compound from a viewpoint of the long-term stability of the electrical characteristic of a liquid crystal display element, for example. One kind of epoxy compound may be used alone, or two or more kinds of compounds may be used in combination. The content of the epoxy compound is preferably 0.1 wt % to 50 wt %, more preferably 1 wt % to 40 wt %, and even more preferably 1 wt % to 20 wt %, based on the total amount of the polyamic acid or its derivatives.

Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cycloaliphatic epoxy compounds. In addition, an epoxy compound means a compound which has an epoxy group, and an epoxy resin means a resin which has an epoxy group.

Specific examples of glycidyl ethers are bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol type epoxy compounds, hydrogenated bisphenol-A type epoxy compounds, hydrogenated bisphenol Phenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenolic Novolak-type epoxy compounds, cresol-type epoxy compounds, brominated phenol-based novolak-type epoxy compounds, brominated cresol-type epoxy compounds, bisphenol A novolak-type epoxy compounds, naphthalene skeleton-containing Epoxy compounds, aromatic polyglycidyl ether compounds, dicyclopentadiene phenol type epoxy compounds, alicyclic diglycidyl ether compounds, aliphatic polyglycidyl ether compounds, polysulfide type diglycidyl ether compounds, And biphenol type epoxy compounds.

Examples of glycidyl esters include diglycidyl ester compounds and glycidyl ester epoxy compounds.

As glycidylamine, polyglycidylamine compounds can be exemplified.

Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having an oxiranyl group.

Glycidyl amide type epoxy compound can be illustrated as a glycidyl amide group.

As a chain aliphatic epoxy compound, the compound containing an epoxy group obtained by oxidizing the carbon-carbon double bond of an alkene compound can be illustrated.

As a cycloaliphatic epoxy compound, the compound containing an epoxy group obtained by oxidizing the carbon-carbon double bond of a cycloalkene compound can be illustrated.

Specific examples of bisphenol A-type epoxy compounds are 828, 1001, 1002, 1003, 1004, 1007, and 1010 (all of which are Japan Epoxy Resins Co., Ltd (now: available as jER series products of Mitsubishi Chemical Corporation/ The same below), Epotohto YD-128 (manufactured by Dongdu Chemical Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (all manufactured by DIC Corporation), EPOMIK R-140, EPOMIK R-301, and EPOMIK R-304 (all manufactured by Mitsui Chemicals, Ltd.).

Specific examples of bisphenol F type epoxy compounds are 806, 807, 4004P (all manufactured by Japan Epoxy Resins Co., Ltd), Epotohto YDF-170, Epotohto YDF-175S, Epotohto YDF-2001 (all manufactured by Tohto Chemical Co., Ltd. company), DER-354 (manufactured by The Dow Chemical Company), Epiclon 830, and Epiclon 835 (all manufactured by DIC Corporation).

A specific example of the bisphenol type epoxy compound is the epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Specific examples of hydrogenated bisphenol-A type epoxy compounds are Sun Tohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Ricaresin HBE-100 (manufactured by New Japan Physical and Chemical Co., Ltd.), and DENACOL EX-252 (manufactured by Nagase ChemteX Corporation) ).

A specific example of the hydrogenated bisphenol type epoxy compound is the epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Specific examples of brominated bisphenol-A type epoxy compounds are 5050, 5051 (all manufactured by Japan Epoxy Resins Co., Ltd), Epotohto YDB-360, Epotohto YDB-400 (all manufactured by Tohto Chemical Co., Ltd.), DER-530, DER-538 (all manufactured by The Dow Chemical Company), Epiclon 152, and Epiclon 153 (all manufactured by DIC Corporation).

Specific examples of the phenolic novolak type epoxy compound are 152, 154 (all manufactured by Japan Epoxy Resins Co., Ltd), YDPN-638 (manufactured by Tohto Chemical Co., Ltd.), DEN431, DEN438 (all manufactured by The Dow Chemical Company manufactured), Epiclon N-770 (manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).

Specific examples of the cresol novolac type epoxy compound are 180S75 (manufactured by Japan Epoxy Resins Co., Ltd), YDCN-701, YDCN-702 (both manufactured by Tohto Kasei Co., Ltd.), Epiclon N-665, Epiclon N-695 (all manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

Specific examples of the bisphenol A novolak-type epoxy compound are 157S70 (manufactured by Japan Epoxy Resins Co., Ltd.), and Epiclon N-880 (manufactured by DIC Corporation).

Specific examples of epoxy compounds containing a naphthalene skeleton are Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (all manufactured by DIC Corporation), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.).

Specific examples of the aromatic polyglycidyl ether compound are hydroquinone diglycidyl ether (the following formula E101), catechol diglycidyl ether (the following formula E102) and resorcinol diglycidyl ether (the following formula E102) Formula E103), tris(4-glycidyloxyphenyl)methane (formula E105 below), 1031S, 1032H60 (both manufactured by Japan Epoxy Resins Co., Ltd), TACTIX-742 (manufactured by The Dow Chemical Company) , DENACOL EX-201 (manufactured by Nagase ChemteX Corporation), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals Corporation), the following formula E106 The compound represented by and the compound represented by the following formula E107.

Specific examples of dicyclopentadiene phenol type epoxy compounds are TACTIX-556 (manufactured by The Dow Chemical Company) and Epiclon HP-7200 (manufactured by DIC Corporation).

Specific examples of the alicyclic diglycidyl ether compound are cyclohexanedimethanol diglycidyl ether compound and Ricaresin DME-100 (manufactured by Shin Nippon Chemical Co., Ltd.).

Specific examples of aliphatic polyglycidyl ether compounds are ethylene glycol diglycidyl ether (the following formula E108), diethylene glycol diglycidyl ether (the following formula E109), polyethylene glycol diglycidyl ether, propylene glycol Diglycidyl ether (the following formula E110), tripropylene glycol diglycidyl ether (the following formula E111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following formula E112), 1,4- Butanediol diglycidyl ether (the following formula E113), 1,6-hexanediol diglycidyl ether (the following formula E114), dibromoneopentyl glycol diglycidyl ether (the following formula E115), DENACOL EX-810, DENACOL EX-851, DENACOL EX-8301, DENACOL EX-911, DENACOL EX-920, DENACOL EX-931, DENACOL EX-211, DENACOL EX-212, DENACOL EX-313 (all manufactured by Nagase chemteX Corporation ), DD-503 (manufactured by ADEKA Co., Ltd.), Ricaresin W-100 (manufactured by Nippon Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (the following formula E116 ), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, DENACOL EX-313, DENACOL EX-611, DENACOL EX-321, and DENACOL EX -411 (both manufactured by Nagase ChemteX Corporation).

Specific examples of polysulfide-type diglycidyl ether compounds are FLDP-50 and FLDP-60 (both manufactured by Toray Thiokol Co., Ltd.).

Specific examples of biphenol type epoxy compounds are YX-4000, YL-6121H (all manufactured by Japan Epoxy Resins Co., Ltd), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.) .

Specific examples of diglycidyl ester compounds are diglycidyl terephthalate (formula 117 below), diglycidyl phthalate (formula E118 below), bis(2-methyl phthalate), Oxiranylmethyl) ester (the following formula E119), a compound represented by the following formula E121, a compound represented by the following formula E122, and a compound represented by the following formula E123.

Specific examples of glycidyl ester epoxy compounds are 871, 872 (both manufactured by Japan Epoxy Resins Co., Ltd), Epiclon 200, Epiclon 400 (both manufactured by DIC Corporation), DENACOL EX-711, and DENACOL EX-721 (both manufactured by Nagase ChemteX Corporation).

Specific examples of polyglycidylamine compounds are N,N-diglycidylaniline (formula E124 below), N,N-diglycidyl-o-toluidine (formula E125 below), N,N-diglycidylaniline Base-m-toluidine (the following formula E126), N,N-diglycidyl-2,4,6-tribromoaniline (the following formula E127), 3-(N,N-diglycidyl)amine Propyltrimethoxysilane (formula E128 below), N,N,O-triglycidyl-p-aminophenol (formula E129 below), N,N,O-triglycidyl-m-amino Phenol (the following formula E130), N, N, N', N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (manufactured by Mitsubishi Gas Chemical Company), the following formula E132), 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (manufactured by Mitsubishi Gas Chemical Company), following formula E133), 1,4-bis(N,N-diglycidyl Aminomethyl)cyclohexane (formula E134 below), 1,3-bis(N,N-diglycidylamino)cyclohexane (formula E135 below), 1,4-bis(N, N-diglycidylamino)cyclohexane (following formula E136), 1,3-bis(N,N-diglycidylamino)benzene (following formula E137), 1,4-bis( N,N-diglycidylamino)benzene (following formula E138), 2,6-bis(N,N-diglycidylaminomethyl)bicyclo[2.2.1]heptane (following formula E139), N, N, N', N'-tetraglycidyl-4,4'-diaminodicyclohexyl methane (following formula E140), 2,2'-dimethyl-(N,N , N', N'-tetraglycidyl)-4,4'-diaminobiphenyl (the following formula E141), N,N,N',N'-tetraglycidyl-4,4'- Diaminodiphenyl ether (following formula E142), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (following formula E143), 2, 4,4'-tris(N,N-diglycidylamino)diphenyl ether (formula E144 below), tris(4-(N,N-diglycidyl)aminophenyl)methane (below Formula E145), 3,4,3',4'-tetra(N,N-diglycidylamino)biphenyl (formula E146 below), 3,4,3',4'-tetra(N , N-diglycidylamino) diphenyl ether (the following formula E147), a compound represented by the following formula E148, and a compound represented by the following formula E149.

A specific example of a homopolymer of a monomer having an oxirane group is poly(glycidyl methacrylate). Specific examples of copolymers of monomers having an oxirane group are N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate Ester copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate Copolymer, (3-ethyl-3-epoxypropyl)methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Specific examples of monomers having an oxiranyl group are glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methylglycidyl (meth)acrylate .

Examples of other monomers other than the monomer having an oxirane group in the copolymer of monomers having an oxirane group include: (meth)acrylic acid, methyl (meth)acrylate, (methyl) ) ethyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, Benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (methyl) (3-Ethyl-3-epoxypropyl)methyl acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

A specific example of glycidyl isocyanurate is 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ( The following formula E150), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (the following formula E151), and glycidyl isocyanurate epoxy resin.

Specific examples of chain aliphatic epoxy compounds are epoxidized polybutadiene and Epolead PB3600 (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.).

A specific example of cycloaliphatic epoxy compound is 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (hereinafter Formula E153), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (the following formula E154), ε-caprolactone modified 3,4-epoxycyclohexyl methyl -3',4'-epoxycyclohexane carboxylate, 1,2:8,9-diepoxylimonene (Celloxide 3000 (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), the following formula E155), the following Compound represented by formula E156, CY-175, CY-177, CY-179 (all manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan K.K.)), EHPD-3150 (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD. ), and cycloaliphatic epoxy resins.

Furthermore, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of various additives are high-molecular compounds and low-molecular compounds other than polyamic acid and its derivatives, which can be selected and used according to the respective purposes.

As a polymer compound, a polymer compound which is soluble in an organic solvent can be illustrated. By adding such a polymer compound to the liquid crystal alignment agent of the present invention, the voltage retention rate of the liquid crystal display element can be increased, the ion density can be reduced, and the light resistance and heat resistance can be improved to manufacture a highly reliable liquid crystal display element. Specific examples of the polymer compound include, for example, polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

As for the low-molecular compound, 1) when it is desired to improve the coatability, a surfactant for the purpose can be exemplified, 2) when it is necessary to improve antistatic, an antistatic agent can be exemplified, 3) when it is desired to improve the adhesion to the substrate Or a silane coupling agent or a titanium-based coupling agent can be exemplified for friction resistance, or 4) an imidization catalyst can be exemplified when imidization is performed at a low temperature.

Specific examples of silane coupling agents are vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropylmethyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltrimethoxysilane silane, m-aminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(1,3-dimethylbutylene)-3- (triethoxysilyl)-1-propylamine, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine.

Specific examples of imidization catalysts include: aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N, N-dimethylaniline, N, N-diethylaniline, methyl Aromatic amines such as base substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, iso Cyclic amines such as quinoline, methyl-substituted isoquinoline, hydroxyl-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxyl-substituted imidazole. The imidization catalyst is preferably selected from N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline or Two or more.

The amount of the silane coupling agent added is usually 0.1 wt % to 50 wt %, preferably 0.1 wt % to 30 wt %, based on the total weight of the polyamic acid or its derivatives.

The addition amount of an imidation catalyst is 0.01 equivalent - 5 equivalents normally with respect to the carbonyl group of a polyamic acid or its derivative|guide_body, Preferably it is 0.05 equivalent - 3 equivalents.

The addition amount of other additives varies according to the use thereof, and is usually 0.1 wt % to 50 wt %, preferably 0.1 wt % to 30 wt %, based on the total weight of the polyamic acid or its derivatives.

Moreover, for example, the liquid crystal alignment agent of the present invention may further contain acrylic polymer, acrylate polymer and other polymer components such as polyamideimide, which is a reaction product of tetracarboxylic dianhydride, dicarboxylic acid or its derivatives, and diamine.

Furthermore, the liquid crystal alignment agent of the present invention may further contain a solvent, for example, from the viewpoint of adjusting the coatability of the liquid crystal alignment agent or the concentration of the polyamic acid or its derivative. The solvent can be used without any particular limitation as long as it has the ability to dissolve the polymer component. The solvent is widely used in the production process or application of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected according to the purpose of use. One kind of solvent may be used, or two or more kinds may be used as a mixed solvent.

Solvents can be roughly classified into mother liquors of polyamic acid or derivatives thereof, and other solvents for the purpose of improving coatability.

Aprotic polar organic solvents are used in the mother liquor of polyamic acid or its derivatives, and its specific examples are N-methyl-2-pyrrolidone, dimethylimidazolinone, N-methylcaprolactam, N-methyl Nyl propionamide, N,N-dimethylacetamide, dimethylsulfoxide, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrol Esters and other lactones.

Examples of other solvents for the purpose of improving coatability, etc. include ethylene glycol such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and ethylene glycol monobutyl ether. Monoalkyl ether, diethylene glycol monoethyl ether and other diethylene glycol monoalkyl ether, ethylene glycol monoalkyl ester or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl Propylene glycol monoalkyl ethers such as ethers, dialkyl malonates such as diethyl malonate, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, and ester compounds such as acetates of these compounds.

Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, and propylene glycol monobutyl ether are particularly preferred. Methyl ether, and dipropylene glycol monomethyl ether.

The liquid crystal alignment agent in the present invention can be used in the form of a solution by diluting the polymer component containing the general polyamic acid or its derivatives with a solvent. At this time, the concentration of the polymer component is not particularly limited, but is preferably 0.1 wt% to 40 wt%. When coating this liquid crystal alignment agent on a board|substrate, in order to adjust a film thickness, the operation of diluting the polymer component contained beforehand with a solvent may be required. At this time, from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent, the concentration of the polymer component is preferably 40 wt % or less.

The density|concentration of the said polymer component in a liquid crystal alignment agent may be adjusted according to the coating method of a liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain a good film thickness, the concentration of the polymer component is usually 10 wt % or less in many cases. It is also possible to further reduce the concentration by other coating methods, such as dipping or inkjet methods. On the other hand, when the density|concentration of a polymer component is 0.1 wt% or more, the film thickness of the obtained liquid crystal alignment film becomes easy to become optimum. Therefore, the concentration of the polymer component is 0.1 wt % or more, preferably 0.5 wt % to 10 wt %, in a typical spin coating method, printing method, or the like. However, depending on the coating method of the liquid crystal alignment agent, it may be used at a lower concentration.

Moreover, when it is used for preparation of a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of this invention can be determined by the means or method of forming the film of this liquid crystal alignment agent. For example, when using a printing machine to form a film of a liquid crystal alignment agent, from the viewpoint of obtaining a sufficient film thickness, it is preferably 5 mPa s or more, and from the viewpoint of suppressing printing unevenness, it is preferably 100 mPa s or less. More preferably, it is 10 mPa□s to 80 mPa□s. When applying a liquid crystal alignment agent by spin coating to form a film of the liquid crystal alignment agent, from the same viewpoint, it is preferably 5 mPa□s to 200 mPa□s, more preferably 10 mPa□s to 100 mPa□s. The viscosity of the liquid crystal alignment agent can be reduced by diluting with a solvent or aging with stirring.

The liquid crystal alignment agent of the present invention may be in the form of a polyamic acid or its derivatives, or in the form of a so-called polymer blend in which two or more polyamic acids or its derivatives are mixed. When the liquid crystal alignment agent in the form of a polymer blend is made into a composition containing polyamic acid or its derivative A and polyamic acid or its derivative B, the source contained in any one of A and B or both can be exemplified. Aspects of a structural unit derived from a tetracarboxylic dianhydride represented by formula (Q) and a structural unit derived from a diamine having a side chain structure represented by formula (V-2). However, assuming that the polyamic acid or its derivative having such a side chain structure is segregated in the upper layer of the alignment film by the polymer blend method, the polyamic acid or its derivative segregated in the lower layer does not need to have side chain structure. Therefore, the polyamic acid or its derivatives which usually become any one of A and B and segregate in the upper layer include structural units derived from tetracarboxylic dianhydride represented by formula (Q) and atomic formula (V-2). The structural unit which has the diamine of a side chain structure is shown, and the aspect which uses the polyamic acid which consists of diamine which does not contain a side chain structure, or its derivative is used for the other. It does not matter if the structural unit derived from the tetracarboxylic dianhydride represented by formula (Q) is contained in the other polyamic acid or its derivative|guide_body.

In the case of blending three or more polyamic acids or derivatives thereof, the structural unit derived from the tetracarboxylic dianhydride represented by the formula (Q) and the compound having a side chain structure represented by the formula (V-2) The structural unit of the diamine can be contained in only one of the mixed polyamic acids or derivatives thereof, can also be contained in two kinds of polyamic acids or derivatives thereof, or can be contained in all polyamic acids or derivatives thereof. Contained in the derivative, however as mentioned above, usually only in the polyamic acid or its derivative that segregates in the uppermost part, contain the structural unit derived from the tetracarboxylic dianhydride represented by formula (Q) and the structural unit derived from the formula ( The aspect of the structural unit of the diamine which has a side chain structure represented by V-2). In this case, it does not matter if the structural unit derived from the tetracarboxylic dianhydride represented by formula (Q) is included in the remaining two polyamic acids or derivatives thereof.

The liquid crystal alignment film of the present invention is a film formed by heating the above-mentioned coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a common method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained through the steps of forming a coating film of the liquid crystal alignment agent of the present invention and heating and calcining it. Regarding the liquid crystal alignment film of the present invention, the film obtained through the calcination step may also be subjected to rubbing treatment if necessary.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention on a substrate of a liquid crystal display element in the same manner as preparation of a normal liquid crystal alignment film. The substrate may be a glass substrate on which electrodes such as ITO (Indium Tin Oxide) electrodes or color filters may be provided.

As a method of coating a liquid crystal alignment agent on a substrate, generally known methods include spin coating, printing, dipping, dropping, and inkjet. These methods can also be similarly applied to the present invention.

Calcination of the coating film can be carried out under conditions necessary for the polyamic acid or its derivatives to exhibit dehydration and ring-closure reactions. Calcination of the above coating film generally includes a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like. These methods can also be similarly applied to the present invention. Usually, it is preferable to carry out at a temperature of about 150°C to 300°C for 1 minute to 3 hours.

The rubbing treatment can be performed in the same manner as the rubbing treatment used for the alignment treatment of a general liquid crystal alignment film, as long as it is the condition for obtaining sufficient retardation in the liquid crystal alignment film of the present invention. Particularly preferable conditions are that the gross indentation is 0.2 mm to 0.8 mm, the table moving speed is 5 mm/sec to 250 mm/sec, and the roll rotation speed is 500 rpm to 2,000 rpm. As an alignment treatment method of a liquid crystal alignment film, a photo-alignment method, a transfer method, etc. are generally known besides a rubbing method. Within the scope of obtaining the effects of the present invention, these other alignment treatment methods may be replaced by the rubbing treatment, or may be used in combination with the rubbing treatment.

Regarding the photo-alignment method of performing alignment treatment by irradiating light, a large number of alignment mechanisms such as photo-decomposition method, photo-isomerization method, photo-dimerization method, and photo-crosslinking method have been proposed (for example, refer to Liquid Crystal, Vol. 3, No. 4 , p. 262, 1999; Japanese Patent Laid-Open No. 2005-275364 and Japanese Patent Laid-Open No. 11-15001). Among these photo-alignment methods, development of a photo-dimerization method and a photo-isomerization method that do not contaminate the liquid crystal composition with decomposition products or additives has been carried out.

Regarding the photodimerization reaction method, for example, the introduction of Jpn.J.Appl.Phys. by M.Schadt et al., 31, 2155 (1992) or Japanese Patent No. 2608661 uses polyvinyl cinnamate or its derivatives Documentation on the photo-alignment film of the photo-dimerization reaction caused by the irradiation of linearly polarized ultraviolet light. Moreover, in Japanese Patent Laying-Open No. 10-251513, a liquid crystal alignment film formed by a photoalignment composition comprising polyimide having a cinnamate group in a side chain is introduced, and in Japanese Patent Laid-Open 2002- Japanese Patent Publication No. 069180 proposes a liquid crystal alignment film comprising a polyamic acid having a substituted cinnamoyl group in a side chain.

On the other hand, a photoalignment method using a photoisomerization reaction of an azo group or the like is also disclosed. In Japanese Patent Application Laid-Open No. 2005-275364, etc., it is described that a polyamic acid film containing an azo group or the like on the main chain is irradiated with linearly polarized ultraviolet light and then imidized by heating to obtain a polyamic acid film having a large alignment index. liquid crystal alignment film.

As mentioned above, the liquid crystal alignment agent of the present invention contains tetracarboxylic dianhydride represented by formula (Q), diamine having a side chain structure represented by formula (V-2), or diamine represented by formula (V-2). Polyamic acid or its derivatives obtained by reacting a mixture of diamines with side chain structures and other diamines with tetracarboxylic dianhydride, are coated on a substrate and heated to cause dehydration and ring closure reactions, thereby becoming polyimide amine. When the polyimide film formed on the substrate is irradiated with linearly polarized ultraviolet light, and then the two substrates are bonded together to manufacture a cell (cell), a liquid crystal composition can be obtained by enclosing a side chain endowed by photoalignment. A liquid crystal display element in the desired alignment state of liquid crystal molecules, wherein the polyimide film is made of a diamine containing a suitable side chain containing a photosensitive group, such as formula (V-11-1) to formula (V-11 The compound represented by -19) is a polyimide film formed on a substrate as a liquid crystal alignment agent of a polyamic acid or a derivative thereof produced as a diamine represented by formula (V-2). At this time, diamines containing photosensitive groups represented by formulas (V-11-1) to (V-11-19) and formulas (V-2) having other side chain structures may be used in combination. Represented diamine. In addition, diamines containing photosensitive groups represented by formulas (V-11-1) to (V-11-19), diamines represented by formula (V-2) having other side chain structures Among them, other diamines not having a side chain structure can also be used in combination.

Furthermore, by irradiating the film of polyamic acid or its derivatives formed on the substrate with ultraviolet light, followed by imidization by heating, and then encapsulating the liquid crystal composition in a cell manufactured by laminating two substrates together, it is possible Obtain a liquid crystal display element that gives liquid crystal molecules a desired alignment state due to the influence of the main chain of photoalignment, wherein the film of polyamic acid or its derivatives is formed by using a liquid crystal alignment agent containing polyamic acid or its derivatives A film of polyamic acid or a derivative thereof formed on a substrate, wherein the polyamic acid or its derivative is obtained by combining a diamine represented by formula (V-2) with a diamine having a photosensitive group as other diamine , For example, obtained by reacting a mixture of compounds represented by formulas (VI-11-1) to (VI-11-16) with tetracarboxylic dianhydride.

In a liquid crystal display element having an alignment film manufactured by using a liquid crystal alignment agent containing a polymer containing a photosensitive group in the main chain as described above, when it is desired to exhibit a predetermined pretilt angle, the following can be appropriately selected The method: the method of irradiating the substrate with linearly polarized light from an arbitrary angle when irradiating ultraviolet light, or the method of combining the method of irradiating the substrate with linearly polarized light from a vertical direction and non-polarized light from an arbitrary angle. In a liquid crystal display element in which a liquid crystal alignment film is formed by using the liquid crystal alignment agent of the present invention, when it is desired to make the liquid crystal molecules exhibit a pretilt angle, the film of the polyamic acid or its derivatives can be irradiated with polarized light. Ultraviolet light may also be irradiated with non-polarized ultraviolet light.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further comprising other steps in addition to the above steps. Such other steps include a step of drying the coating film, a step of washing the film before and after rubbing treatment with a cleaning solution, and the like.

In the drying step, a method of heat-treating in an oven or an infrared furnace, a method of heat-treating on a hot plate, etc. are generally known, similarly to the above-mentioned calcination step. These methods can be applied equally well. The drying step is preferably performed at a temperature within a range in which the solvent can evaporate, more preferably at a lower temperature than that in the calcining step.

The method of cleaning the liquid crystal alignment film before and after the alignment treatment using a cleaning solution includes brushing, jet spray, steam cleaning, ultrasonic cleaning, and the like. These methods may be used alone or in combination. The cleaning solution can be pure water, or various alcohols such as methanol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as methylene chloride, and ketones such as acetone and butanone. It is not limited to these cleaning solutions. Of course, these cleaning solutions need to use fully purified cleaning solutions with less impurities. This cleaning method can also be applied to the cleaning step when forming the liquid crystal alignment film of the present invention.

The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm to 300 nm, more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of this invention can be measured using well-known film thickness measuring apparatuses, such as a profilometer (profilometer) and an ellipsometer (ellipsometer).

The liquid crystal display element of the present invention includes: a pair of substrates, a liquid crystal layer formed between the pair of substrates, electrodes for applying voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning liquid crystal molecules in a predetermined direction. As the liquid crystal alignment film, the above-mentioned liquid crystal alignment film of the present invention is used.

The glass substrate described in the liquid crystal alignment film of the present invention can be used for the substrate, and the ITO electrode formed on the glass substrate exemplified in the description of the liquid crystal alignment film can be used for the electrode.

The liquid crystal layer may be formed of a liquid crystal composition sealed between the pair of substrates in which surfaces on which the liquid crystal alignment film is formed are bonded to face each other. In a liquid crystal display element having a liquid crystal alignment film produced by using the liquid crystal alignment agent for vertical alignment of the present invention, it is preferable to use a liquid crystal composition having a negative dielectric anisotropy.

Preferred liquid crystal compositions with negative dielectric anisotropy include Japanese Patent Laid-Open No. 57-114532, Japanese Patent Laid-Open No. 2-4725, Japanese Patent Laid-Open No. 4-224885, and Japanese Patent Laid-Open No. 4-224885. Kokai No. 8-40953, Japanese Patent Kokai No. 8-104869, Japanese Patent Kokai No. 10-168076, Japanese Patent Kokai No. 10-168453, Japanese Patent Kokai No. 10-236989, Japanese Patent Kokai Unexamined Patent Publication No. 10-236990, Japanese Patent Laid-Open Publication No. 10-236992, Japanese Patent Laid-Open Publication No. 10-236993, Japanese Patent Laid-Open Publication No. 10-236994, Japanese Patent Laid-Open Publication No. 10-237000, Unexamined Patent Publication No. 10-237004, Japanese Patent Laid-Open Publication No. 10-237024, Japanese Patent Laid-Open Publication No. 10-237035, Japanese Patent Laid-Open Publication No. 10-237075, Japanese Patent Laid-Open Publication No. 10-237076, KOKAI Publication No. 10-237448 (EP967261A1 specification), Japanese Patent Application Publication No. 10-287874, Japanese Patent Application Publication No. 10-287875, Japanese Patent Application Publication No. 10-291945, Japanese Patent Application Publication No. 11-029581 , JP-A-11-080049, JP-2000-256307, JP-2001-019965, JP-2001-072626, JP-2001-192657, etc. liquid crystal composition.

When the liquid crystal display element having the liquid crystal alignment film produced by the liquid crystal alignment agent of the present invention is driven by TN mode or IPS mode, the liquid crystal display element can also use a liquid crystal composition with positive dielectric anisotropy. Preferred liquid crystal compositions with positive dielectric anisotropy include: Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, and Japanese Patent Laid-Open No. 8-157826 , Japanese Patent Laid-Open Publication No. 8-231960, Japanese Patent Laid-Open Publication No. 9-241644 (EP885272A1 specification), Japanese Patent Laid-Open Publication No. 9-302346 (EP806466A1 specification), Japanese Patent Laid-Open Publication No. 8-199168 (EP722998A1 Instructions), Japanese Patent Laid-Open No. 9-235552, Japanese Patent Laid-Open No. 9-255956, Japanese Patent Laid-Open No. 9-241643 (EP885271A1 specification), Japanese Patent Laid-Open No. 10-204016 (EP844229A1 specification) , Japanese Patent Laid-Open No. 10-204436, Japanese Patent Laid-Open No. 10-231482, Japanese Patent Laid-Open No. 2000-087040, and Japanese Patent Laid-Open No. 2001-48822.

One or more optically active compounds may be added to the liquid crystal composition having positive or negative dielectric anisotropy.

The liquid crystal display element of the present invention can be obtained by forming the liquid crystal alignment film of the present invention on at least one of a pair of substrates, making the resulting pair of substrates face each other with the liquid crystal alignment film facing inward and separating them with spacers. A liquid crystal composition is sealed in a gap formed between the substrates to form a liquid crystal layer. In the manufacture of the liquid crystal display element of the present invention, a step of sticking a polarizing film or the like on the substrate may be further included as necessary.

The liquid crystal display element of the present invention is a liquid crystal display element for a vertical electric field system in which a voltage is applied to a liquid crystal layer in a direction perpendicular to a substrate surface. The liquid crystal display element used in the vertical electric field mode needs to show a larger pretilt angle, so the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can be suitably used, and the liquid crystal alignment agent contains tetracarboxylic dianhydride, formula (V- 2) A polyamic acid obtained by reacting a diamine having a side chain structure or a mixture of diamines containing the same, or a derivative thereof.

The liquid crystal alignment film produced from the liquid crystal alignment agent of the present invention can also be used in liquid crystal display elements driven by the TN mode or IPS mode of the transverse electric field mode. In this case, there is no need for a larger pretilt angle in the TN mode or the IPS mode, so when the mixture of the diamine represented by the formula (V-2) and the diamine without a side chain structure is mixed with the diamine of the tetracarboxylic acid During the anhydride reaction, it is possible to set a mode suitable for the TN system or the IPS system by appropriately reducing the content of the diamine represented by the formula (V-2).

As mentioned above, the liquid crystal alignment film prepared by using the liquid crystal alignment agent of the present invention as a raw material can be applied to liquid crystal display elements of various display driving methods by appropriately selecting the polymer as the raw material.

The liquid crystal display element of the present invention may further have elements other than the above-mentioned constituent elements. As such other constituent elements, constituent elements commonly used in liquid crystal display elements, such as polarizing plates (polarizing films), wave plates, light scattering films, and drive circuits, may be incorporated in the liquid crystal display element of the present invention.

[example]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. Compounds used in Examples are shown below.

<Tetracarboxylic dianhydride>

BPDA-H: Dicyclohexanetetracarboxylic dianhydride, formula (Q), manufactured by Iwatani Gas Co., Ltd.

H-PMDA: cyclohexane tetracarboxylic dianhydride, formula (25)

CBDA: cyclobutane tetracarboxylic dianhydride, formula (19)

BTDA: butane tetracarboxylic dianhydride, formula (23)

PSQ1: 18,21-bis(3-(2,5-dioxotetrahydrofuran-3-yl)propyl)-18,21-dimethyl-1,3,5,7,9,11,13, 15-Octaphenyl-pentacyclo[10.5.1.25, 13.17, 11.19, 15] decasiloxane, formula (S-1)

<Diamine>

MBMA: 4,4'-methylenebis(3-methylaniline), formula (VI-1-5)

DDM: 4,4'-diaminodiphenylmethane, formula (VI-1-1)

5ChCh: 5-{4-[4-(4-n-pentylcyclohexyl)]cyclohexyl}phenylmethyl-1,3-diaminobenzene, in formula (V-2-7) Y ² is Alkyl diamines with chain length 5

16Ch:: In the formula (V-2-2), Y ² is the diamine of the alkyl group with a chain length of 16

DABC: 3,5-diaminobenzyl cinnamate, formula (V-11-2)

PDAB: 4,4'-diaminoazobenzene, formula (VI-11-11)

OPDA: 6-(2,5-dioxo-3-phenyl-2,5-dihydro-1H-pyrrol-1-yl)hexyl 3,5-diaminobenzoate, formula (V- 11-19)

<additive>

BANI-M: bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane

HEA: N,N'-dihydroxyethylenebisacrylamide

EHS: 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane

GPS: 3-Glycidoxypropyltrimethoxysilane

<solvent>

NMP: N-methyl-2-pyrrolidone

BC: Butyl cellosolve (ethylene glycol monobutyl ether)

<Synthesis of polyamic acid>

[Synthesis Example 1]

0.285g of 5ChCh, 1.341g of MBMA and 30.0g of dehydrated NMP were charged into a 100ml four-neck flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen inlet, and stirred under a dry nitrogen flow. Next, after adding 1.613g of BPDA-H and 0.2610g of BTDA to react for 30 hours, 16.5g of BC was added to synthesize a polyamic acid solution PA1 with a polymer solids concentration of 7wt%. When the temperature rises due to the reaction temperature during the reaction of the raw materials, the reaction is carried out while suppressing the reaction temperature to about 70° C. or lower.

The weight-average molecular weight of polyamic acid is obtained by the following method: the obtained polyamic acid is diluted with phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100, weight ratio) so that the polyamic acid concentration becomes about 1 wt% was measured by the GPC method using a 2695 separation module 2414 differential refractometer (manufactured by Waters) using the above-mentioned mixed solution as a developer, and it was calculated in terms of polystyrene. In addition, HSPgel RT MB-M (manufactured by Waters) was used as a column, and the measurement was performed under conditions of a column temperature of 40° C. and a flow rate of 0.35 mL/min.

[Comparative Synthesis Example 1, Comparative Synthesis Example 2]

In addition to changing the tetracarboxylic dianhydride in the manner shown in Table 1, based on Synthesis Example 1, polyamic acid solutions CP1 and CP1 having a polymer solid content concentration of 7 wt% without using BPDA-H in the monomer were prepared. CP2.

[Synthesis Example 2]

In addition to changing the tetracarboxylic dianhydride and diamine as shown in Table 1, based on Synthesis Example 1, the solid content concentration of the polymer in which an acid anhydride having a silsesquioxane skeleton was further used in the monomer was prepared as follows: 7wt% polyamic acid solution PA2. Table 1 summarizes the monomer compositions of the polyamic acid solutions of Synthesis Example 1, Synthesis Example 2, and Comparative Example 1 and Comparative Example 2, and the weight average molecular weight of the obtained polymer.

Table 1

[instance 1]

The polyamic acid solution that the polymer solids concentration synthesized in Synthesis Example 1 is 7wt% is diluted to the polymer solids concentration by adding a mixed solvent of NMP/BC=1/1 (weight ratio) and is 4wt%. into liquid crystal alignment agent AL1. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

<Production of VA-type liquid crystal display element>

On a pair of substrates with ITO transparent electrodes, the obtained liquid crystal alignment agent AL1 was coated by spin coating, and dried on a heating plate at 80° C. for 90 seconds. Next, heat and calcinate in an oven set at 200° C. for 60 minutes to obtain a substrate on which a liquid crystal alignment film is formed. With the surface on which the alignment film was formed as the inner side, an epoxy-based adhesive was applied in a strip shape on one of the substrates so that liquid crystal injection holes remained on the periphery, and a gap material of 4.25 μm was spread on the other substrate for bonding. combine. The liquid crystal composition shown below was vacuum injected into the obtained cell, and the injection hole was sealed with a UV curable sealant. Finally, heat processing (isotropy processing) was performed at 110 degreeC for 30 minutes, and the VA type liquid crystal display element was obtained.

[Example 2, Comparative Example 1, Comparative Example 2]

The polyamic acid solution PA2, CP1 and CP2 of 7wt% by the polyamic acid solution PA2, CP1 and CP2 that synthetic polymer solids concentration is synthesized in synthetic example 2 and comparative synthetic example 1, comparative synthetic example 2, by adding NMP/BC=1/1 (weight ratio) Mix solvents and dilute to a polymer solid concentration of 4 wt%, to prepare liquid crystal alignment agents AL2, CA1 and CA2. Based on Example 1, a liquid crystal display element was fabricated using the obtained liquid crystal alignment agent.

[Example 3-Example 6]

In the polyamic acid solutions PA1 and PA2, after adding the additives shown in Table 2 corresponding to 30 wt% of the weight of the polymer, add a mixed solvent of NMP/BC=1/1 (weight ratio) to dilute to polymerize The solids concentration was 4 wt%. A liquid crystal display element was fabricated based on Example 1 by using a diluted liquid crystal alignment agent.

<Measurement of VHR>

The VHR of the VA-type liquid crystal display element was measured using a liquid crystal physical property evaluation device Model 6254 manufactured by Toyo Corporation. The measurement conditions were a grid width of 60 µsec, a frequency of 0.3 Hz, a wave height of ±5 V, and a measurement temperature of 60°C.

<Measurement of ion density>

The ion density of the VA-type liquid crystal display element was measured using a liquid crystal physical property evaluation device Model 6254 manufactured by Toyo Corporation. The measurement conditions were a frequency of 0.01 Hz, a voltage of ±10 V, and a measurement temperature of 60°C.

Table 2

As shown in Table 2, when using a polyamide obtained by reacting a liquid crystal alignment agent (the liquid crystal alignment agent contains tetracarboxylic dianhydride represented by formula (Q) and diamine represented by formula (V-2) Acid) in the VA-type liquid crystal display element of the liquid crystal alignment film obtained, compared with the case of using other tetracarboxylic dianhydrides, it showed extremely high VHR value. In addition, it was found that by using together an acid anhydride having a silsesquioxane skeleton such as PSQ1, further improvement in voltage retention and reduction in ion density can be achieved.

<Evaluation of residual DC>

Using a signal generator FG110 manufactured by Yokogawa Electric Corporation, a 30 Hz, 3 V rectangular wave was applied to a VA-type liquid crystal display element mounted on a polarizing microscope manufactured by Nikon Corporation with polarizing plates arranged at 90 degrees using a jig. After superimposing a DC voltage of 3 V on it for 30 minutes, the superimposition of the DC voltage was terminated, and then a photomultiplier tube manufactured by Hamamatsu Photon Electronics Co., Ltd. connected to a DSO3062 oscilloscope manufactured by Agilent Technologies was used to detect the liquid crystal display element. The amount of light transmitted. The offset of the signal generator was adjusted so that the change in the waveform indicating the change in light quantity displayed on the voltage oscilloscope becomes the least, and the offset voltage was recorded as the flicker elimination voltage. The absolute value of this value was taken as residual DC. The smaller the residual DC is, the less afterimages remain and are favorable.

The residual DC was measured for the liquid crystal display elements produced in Examples 1 to 6, and Comparative Example 1 and Comparative Example 2, and the flicker after 1 minute and 30 minutes after the DC voltage superimposition was completed were compared between each element. Change the voltage. The results are shown in Table 3.

table 3

As shown in Table 3, it can be seen that: when using a liquid crystal alignment agent (the liquid crystal alignment agent contains tetracarboxylic dianhydride represented by formula (Q) and diamine represented by formula (V-2) Amic acid) in the VA-type liquid crystal display element of the obtained liquid crystal alignment film, the reduction of residual DC is remarkable.

<Synthesis of Polyamic Acid Forming Photoalignment Liquid Crystal Alignment Agent>

[Synthesis Example 3 to Synthesis Example 6, Comparative Synthesis Example 3 to Comparative Synthesis Example 5]

Except that the synthesis was carried out in a yellow room using fluorescent lamps that cut off ultraviolet rays, polyamic acid solutions PA3-PA6 and CP3-CP5 for photoalignment with a concentration of 7 wt% were prepared based on the method of Synthesis Example 1. In addition, the raw material of polyamic acid PA6 of Synthesis Example 6 does not contain the diamine having a side chain structure represented by formula (V-2), which is used to combine polyamic acid PA3 to PA5 and polyamic acid PA5 as described later. Polyamic acid solution for blending CP3-CP5. Table 4 summarizes the measurement results of the solution composition and weight average molecular weight of Synthesis Example 3 to Synthesis Example 6 and Comparative Synthesis Example 3 to Comparative Synthesis Example 5.

Table 4

[Example 7-Example 9]

The polyamic acid solution PA3 that is 7wt% the polyamic acid solution PA3 that is the polyamic acid solution PA3 of 7wt% the polymer solid content concentration that is synthesized in the synthetic example 3, the polyamic acid solution PA6 that the polymer solid content concentration that is synthesized in the synthetic example 6 is 7wt% with weight ratio 20/80 (the former /the latter) were mixed, followed by adding a mixed solvent of NMP/BC=1/1 (weight ratio) to dilute it so that the polymer solids concentration was 4wt%, thereby preparing liquid crystal alignment agent AL7. Based on this method, AL8, AL9, and CA3 to CA5 were modulated at the composition ratios shown in Table 5.

[Example 10-Example 13]

The polyamic acid solution was mixed at the composition ratio shown in Table 5, and additives corresponding to 30 wt% of the total polymer weight were added respectively. Next, a mixed solvent of NMP/BC=1/1 (weight ratio) was added to dilute it to a polymer solid concentration of 4 wt%, to prepare liquid crystal alignment agents AL10˜AL13.

table 5

  Liquid crystal alignment agent Polyamic acid solution blending ratio Additives Example 7 AL7 PA3/PA6 20/80 none Example 8 AL8 PA4/PA6 20/80 none Example 9 AL9 PA5/PA6 20/80 none Comparative example 3 CA3 CP3/PA6 20/80 none Comparative example 4 CA4 CP4/PA6 20/80 none Comparative Example 5 CA5 CP5/PA6 20/80 none Example 10 AL10 PA3/PA6 20/80 BANI-M Example 11 AL11 PA3/PA6 20/80 GPS Example 12 AL12 PA4/PA6 20/80 HEA Example 13 AL13 PA5/PA6 20/80 EHS

[Example 14]

<Production of photo-alignment VA-type liquid crystal display element>

On a pair of substrates with ITO transparent electrodes, the obtained liquid crystal alignment agent AL7 was coated by spin coating, and dried on a heating plate at 80° C. for 90 seconds. Next, heat processing was performed for 15 minutes in an oven set at 210° C. to form a polyimide film having a film thickness of about 100 nm. Next, in a direction inclined about 40° from the normal line of the substrate, using an ultraviolet irradiation device (ML-501C/B) (the ultraviolet irradiation device uses an ultra-high pressure mercury lamp (USH-500BY1) manufactured by Ushio Inc.), through polarized light The plate was irradiated with linearly polarized light (365 nm, energy about 200 mJ/cm ² ), to obtain a substrate on which a liquid crystal alignment film was formed. With the surface on which the alignment film was formed as the inner side, an epoxy-based adhesive was applied in a strip shape on one of the substrates so that liquid crystal injection holes remained on the periphery, and a 4.25 μm gap material was spread on the other substrate and pasted. combine. The liquid crystal composition shown below was vacuum injected into the obtained cell, and the injection hole was sealed with a UV curable sealant. Finally, heat treatment (isotropic treatment) was performed at 110° C. for 30 minutes to obtain a photoalignment VA-type liquid crystal display element.

[Examples 15-20 and Comparative Examples 6-8]

Using liquid crystal alignment agents AL8-AL13 and CA3-CA5, based on Example 14, a photo-aligned VA-type liquid crystal display element was produced.

<Evaluation of long-term thermal reliability of VHR>

For the photoalignment VA-type liquid crystal display elements produced in Examples 14 to 20 and Comparative Examples 6 to 8, the long-term thermal reliability of VHR was evaluated in the following manner.

<Measurement of VHR>

The VHR of the VA-type liquid crystal display device was measured with the same device as that used in Example 1. The measurement conditions were a grid width of 60 µsec, a frequency of 30 Hz, a wave height of ±1 V, and a measurement temperature of 60°C.

<Calculation of long-term thermal reliability of VHR>

About the liquid crystal display element produced in Example 14-Example 20 and Comparative Example 6-Comparative Example 8, the VHR value measured within 24 hours after element production was made VHR (initial). And the liquid crystal display element after VHR measurement was hold|maintained in the oven maintained at 100 degreeC for 100 hours, and the VHR value measured on the said conditions was made into VHR (100 hours). From the obtained two VHRs, the VHR decrease rate was calculated according to the following formula. It can be said that the smaller this value is, the better the long-term thermal reliability of the VHR is. The results are shown in Table 6.

VHR reduction rate = [{VHR(initial)-VHR(100 hours)}×100]/VHR(initial)

Table 6

As shown in Table 6, the liquid crystal display element using the liquid crystal alignment film obtained by the liquid crystal alignment agent (the liquid crystal alignment agent contains polyamic acid containing BPDA-H) can play the same role as the use of the liquid crystal alignment agent (the Compared with the liquid crystal display element of the obtained liquid crystal alignment film containing the liquid crystal alignment agent containing polyamic acid containing monocyclic H-PMDA, the initial characteristics of VHR and the effect of VHR long-term thermal reliability are higher.

<Evaluation of residual DC>

Based on Example 1, the evaluation of residual DC measurement was performed about the liquid crystal display element produced in Example 14-Example 20 and Comparative Example 6-Comparative Example 8. The results are shown in Table 7.

Table 7

As shown in Table 7, it can be seen that when using a liquid crystal alignment agent (the liquid crystal alignment agent contains tetracarboxylic dianhydride represented by formula (Q) and diamine represented by formula (V-2) Amic acid) and the obtained photo-alignment type liquid crystal alignment film in the photo-alignment VA-type liquid crystal display element, the residual DC is also significantly reduced.

The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this field Those skilled in the art, without departing from the scope of the technical solution of the present invention, may use the structure and technical content disclosed above to make some changes or modifications to equivalent embodiments with equivalent changes, but any content that does not depart from the technical solution of the present invention, Any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solutions of the present invention.

Claims (11)

1. A liquid crystal alignment agent for vertical alignment, characterized in that it contains polyamic acid or derivatives thereof, said polyamic acid is represented by formula (Q) tetracarboxylic dianhydride, and formula (V-2 ) represented by a diamine having a side chain structure or reacting with a mixture of a diamine having a side chain structure represented by formula (V-2) and other diamines,

In formula (V-2), X ¹⁰ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, or -(CH ₂ ) _m -, m is an integer of 1 to 6; ^Y11 is a group having a steroid skeleton, a succinimide skeleton, a phthalimide skeleton, or a cinnamate skeleton or a group represented by the following formula (XXIII),

In formula (XXIII), A ⁴ is independently a single bond, or an alkylene group with 1 to 12 carbons, the -CH ₂ - of the alkylene group can also be substituted by -O-, -NH- or -CO-, and -CH ₂ CH ₂ - can also be Can be substituted by -CH=CH-, -C≡C- or -N=N-, the -H of the alkylene group can also be substituted by -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H or -PO ₃ H ₂ substitution; Y ¹² is independently -F or -CH ₃ ; Ring S is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, piperidine-1,4-diyl, pyrimidine-2,5 -diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl; Y ¹³ is -H, -F, -Cl, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ or an alkyl group with a carbon number of 1 to 30, and -CH ₂ of an alkyl group - can also be substituted by -O-, -NH- or -CO-, -CH ₂ CH ₂ - can also be substituted by -CH=CH-, -C≡C- or -N=N-, the -H of the alkyl can also be substituted by -F, -Cl, -C≡N, _-OH , -COOH, _-SO3H , or _-PO3H2 ; and, b is independently an integer of 0-4, c, d, and e are independently integers of 0-3, f is independently an integer of 0-2, and c+d+e≥1. 2. The liquid crystal alignment agent for vertical alignment according to claim 1, wherein Y ¹¹ in the formula (V-2) is selected from the following formula (Y ¹¹ -1) to formula (Y ¹¹ -8) one of the groups of bases represented,

In formula (Y ¹¹ -1) ~ formula (Y ¹¹ -8), ^Y2 is -H, -F, alkyl with 1 to 30 carbons, fluorine-substituted alkyl with 1 to 30 carbons, alkoxy with 1 to 30 carbons, 2 to 30 carbons Alkenyl, -C≡N, -OCH ₂ F, -OCHF ₂ , or -OCF ₃ ; A ¹ is -O- or an alkylene group with 1 to 6 carbons; and, A ² is -OCO-, -COO-, -O- or an alkylene group having 1 to 6 carbon atoms. 3. The liquid crystal alignment agent for vertical alignment according to claim 1, wherein the diamine having a side chain group is selected from the following formula (V-2-2) to formula (V-2- 8) and at least one of the group of compounds represented by formula (V-2-53),

In formula (V-2-2), Y ² is an alkyl group with 6 to 30 carbons; In formula (V-2-3) ~ formula (V-2-6), Y ² is an alkyl group with a carbon number of 3 to 30; In formula (V-2-7), Y ² is an alkyl group with 2 to 30 carbons; In formula (V-2-8), Y ² is an alkyl group with 2 to 30 carbons; and In formula (V-2-53), Y ¹⁸ is -F, -CF ₃ or -OCF ₃ . 4. The liquid crystal alignment agent for vertical alignment according to claim 1, wherein said diamine is at least one of the diamines represented by formula (V-2) and selected from the following formula (V- 1-1)～Formula (V-1-5), Formula (V-1-14), Formula (V-1-15), Formula (VI-1-1)～Formula (VI-1-12), Formula (VI-1-28) ~ formula (VI-1-30), formula (VI-1-35) ~ formula (VI-1-39), formula (VII-2-1), and formula (VII- 2-2) a mixture of at least one of the group of diamines represented,

5. The liquid crystal alignment agent for vertical alignment according to claim 1, characterized in that the tetracarboxylic dianhydride represented by formula (Q) and the group selected from the following formula (1), formula (2) are used. ), polyamic acid or derivatives thereof obtained by reacting at least one of the group of aromatic tetracarboxylic acids represented by formula (5) to formula (7) and formula (12) with diamine, 6. The liquid crystal alignment agent for vertical alignment according to claim 1, characterized in that the tetracarboxylic dianhydride represented by formula (Q) and the group selected from the following formula (19), formula (23 ), formula (25), formula (35) ~ formula (39), formula (44) and the group of alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by formula (49) at least A polyamic acid or derivative thereof obtained by reacting with a diamine, 7. The liquid crystal alignment agent for vertical alignment according to claim 1, wherein said diamine is at least one of the diamines represented by formula (V-2), and selected from the following formula (VI -11-4)～Formula (VI-11-16), Formula (V-11-2) and Formula (V-11-17)～Formula (V-11-19) represented by two compounds having a photosensitive structure A mixture of at least one of the group of amines, and has photoalignment,

8. The liquid crystal alignment agent for vertical alignment according to claim 1, wherein said diamine is at least one of the diamines represented by formula (V-2), and selected from the following formula (VI -11-7), formula (VI-11-11), formula (V-11-2) and formula (V-11-17) ~ formula (V-11-19) represented by the two A mixture of at least one of the group of amines, and has photoalignment,

9. The liquid crystal alignment agent for vertical alignment according to any one of claims 1 to 8, characterized in that it also contains alkenyl-substituted imide compounds selected from the group consisting of free radical polymerizable unsaturated At least one of a double bond compound, an oxazine compound, an oxazoline compound, and an epoxy compound. 10. A liquid crystal alignment film for vertical alignment, characterized in that it is formed by heating the coating film of the liquid crystal alignment agent for vertical alignment according to any one of claims 1 to 9. 11. A liquid crystal display element, characterized in that it comprises: a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction In a liquid crystal display element, the liquid crystal alignment film is the liquid crystal alignment film for vertical alignment according to claim 10 .