TW201605844A - Triazole-containing tetracaboxylic acid dianhydrides, polymer, liquid crystal aligning agents, liquid crystal alignment layers, and liquid crystal display devices using the same - Google Patents

Abstract

The invention provides a liquid crystal aligning agent for forming a liquid crystal alignment layer that suppresses peeling or scraping. A tetracarboxylic acid dianhydride is represented by formula (1). In formula (1), X is a divalent organic group that includes at least one triazole ring; each of R1 and R2 is independent and is one selected from the group of the trivalent groups below; and at least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl.

Description

a tetracarboxylic dianhydride containing a triazole, a polymer, a liquid crystal alignment agent, Liquid crystal alignment film, and liquid crystal display element

The present invention relates to a novel tetracarboxylic dianhydride, polylysine or a derivative thereof obtained using the same, and uses thereof. Further, the term "liquid crystal alignment agent" in the present invention means a polymer-containing composition for forming a liquid crystal alignment film.

Various display devices such as a monitor of a personal computer, a liquid crystal television, a view finder of a video camera, a projection display, and an optical printer head In optical electronic components such as optical Fourier transform elements and light valves, the mainstream of liquid crystal display elements that are currently commercialized and generally circulated is nematic liquid (nematic liquid). Crystal) display element. A twisted nematic (TN) mode and a Super Twisted Nematic (STN) mode are known as a display mode of a nematic liquid crystal display device. In recent years, In order to improve the narrow viewing angle of one of the problems of these modes, a TN-type liquid crystal display element using an optical compensation film and a multi-domain vertical alignment (MVA) mode using vertical alignment and protrusion structure technology are proposed. Or the transverse electric field mode of In-Plane Switching (IPS) mode, Fringe Field Switching (FFS) mode, and practical.

The development of the technology of the liquid crystal display element is realized not only by the improvement of these driving methods or the structure of the elements, but also by the improvement of the constituent members used in the elements. Among the constituent members used in the liquid crystal display device, in particular, the liquid crystal alignment film is one of important materials related to display quality, and as the liquid crystal display element is made higher in quality, it is important to improve the performance of the alignment film.

The liquid crystal alignment film is formed of a liquid crystal alignment agent. The liquid currently used The crystal alignment agent is a solution (varnish) obtained by dissolving polyacrylic acid or soluble polyimine in an organic solvent. After the solution is applied onto a substrate, the film is formed by heating or the like to form a polyimide film of the polyimide film.

A friction method that can easily perform large-area high-speed processing in an industrial manner is made It is widely used for the alignment treatment. In the rubbing method, a cloth to which a fiber such as nylon, rayon, or polyester is grafted is used, and the surface of the liquid crystal alignment film is rubbed in one direction, whereby uniform alignment of liquid crystal molecules can be obtained. However, it is pointed out that in the rubbing treatment, the dust generated by the reduction of the liquid crystal alignment film or the damage on the liquid crystal alignment film causes a problem of deterioration in display quality, and points out that electrostatic generation is caused, and the alignment is actively performed instead of the rubbing method. Development of the treatment method.

As an alignment treatment method instead of the rubbing method, attention is paid to illuminating light. A photo alignment processing method that performs alignment processing. In the photo-alignment processing method, a plurality of alignment mechanisms such as a photo-decomposition method, a photo-isomerization method, a photodimerization method, and a photo-crosslinking method have been proposed (for example, refer to Non-Patent Document 1, Patent Document 1 and Patent Document 2). The photo-alignment method has the advantages of high uniformity of alignment in comparison with the rubbing method, and non-contact alignment treatment, so that the film is not scratched, and the liquid crystal display element can be reduced by dust or static electricity. The cause of the defect is displayed. However, the anchoring energy is small and the alignment is low with respect to the rubbing method, and this phenomenon causes a decrease in the response speed of the liquid crystal molecules or causes burn marks, and therefore it is required to be improved.

In order to overcome the shortcomings of this optical alignment processing method, the following materials are proposed. By using a polyimine having liquid crystallinity, the material is heat-treated at the time of film formation, and the anisotropy of the film can be increased (for example, refer to Patent Document 3 to Patent Document 7). However, the photo-alignment film to which such a technique is applied has a problem in that peeling or reduction of the film is likely to occur when the panel is formed, and the generated foreign matter lowers the display quality of the panel.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-297313

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-251646

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-275364

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-248637

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-069493

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-049230

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2010-197999

[Non-patent literature]

[Non-Patent Document 1] "Liquid Crystal", Vol. 3, No. 4, Page 262, 1999

A first object of the present invention is to provide a liquid crystal alignment agent which uses a polymer of a specific tetracarboxylic dianhydride in a raw material, so that a liquid crystal alignment film which is less likely to be peeled off or reduced can be formed.

. A second object of the invention is to provide a liquid crystal display element comprising a liquid crystal alignment film having a high liquid crystal alignment ability by coating a liquid crystal alignment agent, and having excellent afterimage characteristics.

The inventors of the present invention have developed a tetracarboxylic dianhydride represented by the formula (1). It has been found that by using a liquid crystal alignment agent containing polyamic acid or a derivative thereof using the tetracarboxylic dianhydride as a raw material, a liquid crystal alignment film having high film hardness and not causing the foreign matter is obtained, and the present invention has been completed.

The present invention includes the following constitutions.

[1] A tetracarboxylic dianhydride characterized by being represented by the formula (1);

In the formula (1), X is a divalent organic group containing at least one triazole ring; and R ¹ and R ² are each independently one selected from the group consisting of the following trivalent groups;

At least one hydrogen of these groups may also be substituted by a methyl group, an ethyl group or a phenyl group.

[2] The tetracarboxylic dianhydride according to the above [1], which is represented by the formula (2);

In the formula (2), X is a divalent organic group containing at least one triazole ring.

[3] The tetracarboxylic dianhydride according to the above [1], which is represented by the formula (3);

In the formula (3), X ¹ is a triazole ring; A ¹ and A ² are each independently a single bond or an alkylene group having 1 to 12 carbon atoms; at least one hydrogen in the alkylene group may also be substituted by fluorine. Moreover, at least one -CH ₂ - may also be substituted by -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or -C≡C-.

[4] The tetracarboxylic dianhydride according to the above [1], which is represented by the formula (4);

In the formula (4), X ¹ and X ² are triazole rings; A ¹ to A ³ are each independently a single bond or an alkylene group having 1 to 12 carbon atoms; at least one hydrogen in the alkylene group may also be used. Substituted by fluorine; moreover, at least one -CH ₂ - in the alkylene group may also be -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or -C≡ C-substituted.

[5] A poly-proline or a derivative thereof, which is a tetracarboxylic dianhydride comprising at least one tetracarboxylic dianhydride according to any one of the above [1] to [4] Obtained by reaction with a diamine.

[6] A liquid crystal alignment agent comprising the polyacrylic acid or a derivative thereof according to the above [5].

[7] The liquid crystal alignment agent according to the above [6], which comprises the polyaminic acid or a derivative thereof according to the above [5], and other polymers.

[8] A liquid crystal alignment agent for photoalignment according to the above [6] or [7].

[9] A liquid crystal alignment agent for rubbing according to the above [6] or [7].

[10] A liquid crystal alignment agent for a liquid crystal display device according to any one of the above [6] to [9], wherein the liquid crystal alignment agent according to any one of the above [6] to [9].

[11] A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of the above [6] to [10].

[12] A liquid crystal display device comprising the liquid crystal alignment film according to [11] above.

The liquid crystal alignment film formed by coating a liquid crystal alignment agent containing a polymer obtained by using the tetracarboxylic dianhydride of the present invention as a raw material has high film hardness and good liquid crystal alignment property. Further, the liquid crystal display element including the liquid crystal alignment film of the present invention has good display performance and good electrical characteristics. Moreover, the same effect is also exhibited in the liquid crystal alignment agent prepared by blending the polymer with other polymers.

1‧‧‧ glass substrate

2‧‧‧ Column spacers

3‧‧‧ITO substrate

4‧‧‧LCD

5‧‧‧ Sealing material

6‧‧‧Alignment film

Figure 1 is a cross-sectional view of a test panel.

The terms used in the present invention will be described. The compound represented by the formula (I-1) is sometimes referred to as the compound (I-1). The compounds represented by the other formulas may be similarly enumerated in the same manner. The "arbitrary" used in defining the chemical structural formula means that the position is arbitrary and the number is arbitrary. In the chemical structural formula, a group enclosing a character (for example, A) with a circle or a hexagon is a group representing a ring structure (ring A).

The tetracarboxylic dianhydride of the present invention will be described. Further, in the specification, "tetracarboxylic dianhydride" may be simply referred to as "anhydride" or "acid dianhydride".

The tetracarboxylic dianhydride of the present invention is represented by the following formula (1).

In the formula (1), X is a divalent organic group containing at least one triazole ring, and R ¹ and R ² are each independently one selected from the group consisting of the following trivalent groups.

At least one hydrogen of these groups may also be substituted by a methyl group, an ethyl group or a phenyl group.

The tetracarboxylic dianhydride of the present invention has two anhydride portions as described above. In the position, there is a tetracarboxylic dianhydride containing a spacer of a triazole ring between the acid anhydride sites. The liquid crystal alignment film formed by coating a liquid crystal alignment agent containing a poly-proline or a derivative thereof is not sufficiently rigid, and there is a case where a foreign matter due to reduction is generated, and the polyamine or its derivative It is obtained by reacting a tetracarboxylic dianhydride having a spacer having an alkyl chain such as 5,5'-(octane-1,8-diyl)bis(phthalic anhydride) with a diamine. On the other hand, by using the tetracarboxylic dianhydride of the present invention in place of the tetracarboxylic dianhydride, the interaction between the polymer chains is strengthened by the interaction of the triazole rings, thereby allowing the liquid crystal alignment film to be The film hardness is increased.

Ease of obtaining from a raw material in the tetracarboxylic dianhydride represented by the formula (1) It is preferable that the tetracarboxylic dianhydride represented by the formula (3) or the formula (4) is preferable.

In the formula (3), X ¹ is a triazole ring, and A ¹ and A ² are each independently a single bond or an alkylene group having 1 to 12 carbon atoms, and any hydrogen in the alkylene group may be substituted by fluorine. Any -CH ₂ - may also be substituted by -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or -C≡C-.

In the formula (4), X ¹ and X ² are a triazole ring, and A ¹ to A ³ are each independently a single bond or an alkylene group having a carbon number of 1 to 12, and any hydrogen in the alkyl group may also be used. Substituted by fluorine, any -CH ₂ - may also be substituted by -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or -C≡C-.

The tetracarboxylic dianhydride of the formula (3) can be synthesized, for example, by the following route (Synthesis Example 1).

In the formula, A is a single bond or an alkylene group having a carbon number of 1 to 12, and any hydrogen in the alkylene group may be substituted by fluorine, and any -CH ₂ - may also be -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or -C≡C-substitution.

Azide phthalic acid derivative (a), in the presence of (b) The copper sulfate pentahydrate and sodium ascorbate are allowed to act, whereby the compound represented by (c) is obtained. Next, sodium hydroxide is allowed to act to hydrolyze the ester group, and acetic anhydride is allowed to act to acidify, and the tetracarboxylic dianhydride represented by the item (3) of the present invention is obtained.

The tetracarboxylic dianhydride of the formula (4) can be synthesized, for example, by the following route (synthesis) Example 2).

The alkyl bromide (d) is azide, and copper sulfate pentahydrate and sodium ascorbate are allowed to act in the presence of (c), whereby the compound represented by (e) is obtained. Then, sodium hydroxide is allowed to act to hydrolyze the ester group, and acetic anhydride is used to effect acidification, and the tetracarboxylic dianhydride represented by the invention (4) is obtained.

The tetracarboxylic dianhydride of the present invention may also be a tetracarboxylic dianhydride which has been purified by various purification methods such as recrystallization or column chromatography. Further, the poly-proline or the derivative thereof of the present invention can be used in various polyimine coating agents, polyimine resin molded articles, films, fibers, and the like, in addition to the liquid crystal alignment agent.

Examples of the tetracarboxylic dianhydride represented by the formula (1) include compounds represented by the following formulas.

[化12]

[Chemistry 13]

[化15]

[化18]

[Chemistry 20]

In the tetracarboxylic dianhydride, when the anchoring energy is high and the alignment property of the liquid crystal is further improved, the formula (1-1), the formula (1-5), and the formula (1-15) are preferable. And the tetracarboxylic dianhydride represented by the formula (1-26) to the formula (1-34), paying attention to the transmittance In the case of improvement, it is possible to obtain desired by using the tetracarboxylic dianhydride of the present invention of the formula (1-2) to the formula (1-4) and the formula (1-6) to the formula (1-8). In order to obtain an alignment agent having a higher solubility in a solvent, an alignment film having a characteristic can be obtained by using the tetracarboxylic dianhydride of the invention of the formula (1-9) to the formula (1-11). Characteristic alignment film.

From the viewpoints of easiness of synthesis and coloring inhibition, it is preferably Formula (1-1), Formula (1-5), and Formula (1-22) to Formula (1-28), and particularly preferably Formula (1-1). ) and formula (1-5).

The polyaminic acid of the present invention and derivatives thereof will be described.

The polyaminic acid of the present invention and a derivative thereof are reaction products of a diamine and a tetracarboxylic dianhydride compound containing a tetracarboxylic dianhydride compound represented by the formula (1). The "derivative of the polyaminic acid" is a component which is dissolved in a solvent when a liquid crystal alignment agent to be described later containing a solvent is prepared, and when the liquid crystal alignment agent is formed into a liquid crystal alignment film, it can be formed into a polyfluorene. A component of a liquid crystal alignment film containing an imine as a main component. Examples of such a derivative of polyamic acid include soluble polyimine, polyphthalamide, and polyamine amide, and more specifically, 1) all amine groups of polyglycine Polyimine which is obtained by dehydration ring-closure reaction with a carboxyl group, 2) partial polyimine which is subjected to partial dehydration ring-closing reaction, and 3) polylysine which is obtained by converting a carboxyl group of poly-proline to an ester. The ester, 4) a part of the acid dianhydride contained in the tetracarboxylic dianhydride compound, the polydiamine copolymer obtained by the reaction of the organic dicarboxylic acid, and 5) A polyamidoquinone imine obtained by subjecting a part or all of a proline-polyamine copolymer to a dehydration ring closure reaction. The polyaminic acid and its derivative may be a compound, also It can be two or more. Further, the poly-proline and its derivative may be a compound having a structure of a reaction product of a tetracarboxylic dianhydride and a diamine, and other raw materials may be used, and a reaction of a tetracarboxylic dianhydride with a diamine may be used. The reaction product of other reactions than others.

The tetracarboxylic dianhydride used for producing the poly-proline and its derivative of the present invention will be described.

The tetracarboxylic dianhydride used in the present invention can be selected from known tetracarboxylic dianhydrides without limitation. Such a tetracarboxylic dianhydride may be an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and an aliphatic system which does not directly bond a dicarboxylic acid anhydride to an aromatic ring. Any group of tetracarboxylic dianhydrides (including heterocyclic systems).

From the viewpoints of easiness of obtaining a raw material, easiness in polymerization of a polymer, and electrical properties of a film, a suitable example of such a tetracarboxylic dianhydride is represented by the formula (AN-I) to (AN-VII). Tetracarboxylic dianhydride.

[化22]

In the formula (AN-I), the formula (AN-IV), and the formula (AN-V), X is independently a single bond or -CH ₂ -. In the formula (AN-II), G is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -. In the formula (AN-II) to the formula (AN-IV), Y is independently one selected from the group consisting of a trivalent group, and a bond is bonded to any carbon, and at least one hydrogen of the group may also be Substituted by methyl, ethyl or phenyl.

[化23]

In the formula (AN-III) to the formula (AN-V), the ring A ¹⁰ is a group of a monocyclic hydrocarbon having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon having 6 to 30 carbon atoms. At least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and the bond to the ring may be bonded to any carbon constituting the ring, and the two bond bonds may be bonded to the same carbon. In the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group. In the formula (AN-VII), G ¹⁰ independently -O -, - COO- or -OCO-, r are independently 0 or 1.

More specifically, the tetracarboxylic dianhydride represented by the following formula (AN-1) to formula (AN-16-14) can be mentioned.

In the formula (AN-1), G ¹¹ is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group or a 1,4-cyclohexylene group. X ¹¹ is independently a single bond or -CH ₂ -. G ^{12 is} independently an arbitrary group of the following trivalent group.

[化25]

When G ¹² is >CH-, the hydrogen of >CH- may also be substituted with -CH ₃ . When G ¹² is >N-, G ¹¹ is not a single bond and -CH ₂ -, and X ¹¹ is not a single bond. Moreover, R ¹¹ is hydrogen or -CH ₃ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulas.

In the formula (AN-1-2) and the formula (AN-1-14), m is an integer of 1 to 12.

[化27]

In the formula (AN-2), R ^{12 is} independently hydrogen, -CH ₃ , -CH ₂ CH ₃ or a phenyl group. Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formulas.

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas.

[化30]

In the formula (AN-4), G ¹³ is a single bond, -(CH ₂ ) _m -, -O-, -S-, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO-, -C (CF ₃ ) ₂ - or a divalent group represented by the following formula (G13-1), and m is an integer of 1 to 12.

In the formula (G13-1), G ^13a and G ^13b are each independently a divalent group represented by a single bond, -O- or -NHCO-. The phenylene group is preferably a 1,4-phenylene group and a 1,3-phenylene group.

Ring A ^{11 is} independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded at any position of the ring A ^11. An example of the tetracarboxylic dianhydride represented by the formula (AN-4) is a compound represented by the following formula.

[化33]

[化34]

In the formula (AN-4-17), m is an integer of 1 to 12.

In the formula (AN-5), R ¹¹ is hydrogen or -CH ₃ . R ¹¹ in which the bonding position is not fixed at the carbon atom constituting the benzene ring means that the bonding position in the benzene ring is arbitrary. An example of the tetracarboxylic dianhydride represented by the formula (AN-5) is a compound represented by the following formula.

[化38]

In the formula (AN-6), X ^{11 is} independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH=CH-. n is 1 or 2. An example of the tetracarboxylic dianhydride represented by the formula (AN-6) is a compound represented by the following formula.

[化40]

In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -. Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulas.

[化42]

In the formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulas.

[化45]

In the formula (AN-9), r is independently 0 or 1. An example of the tetracarboxylic dianhydride represented by the formula (AN-9) is a compound represented by the following formula.

The formula (AN-10) is the following tetracarboxylic dianhydride.

[48]

In the formula (AN-11), the ring A ^{11 is} independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulas.

In the formula (AN-12), the ring A ^{11 is} independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formulas.

[化51]

In the formula (AN-13), X ¹³ is an alkylene group having 2 to 6 carbon atoms, and Ph represents a phenyl group. Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formulas.

In the formula ^(AN-14), G 14 independently -O -, - COO- or -OCO-, r are independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formulas.

[化55]

In the formula (AN-15), w is an integer of 1 to 10. An example of the tetracarboxylic dianhydride represented by the formula (AN-15) is a compound represented by the following formula.

[化57]

The tetracarboxylic dianhydride other than the above may be exemplified by the following compounds.

In the acid dianhydride, a suitable material for improving each property is added. To narrate. When it is important to improve the alignment of the liquid crystal, a compound represented by the formula (AN-1), the formula (AN-3), and the formula (AN-4) is preferable, and the formula (AN-1-2) is particularly preferable. , a compound represented by the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-17), and the formula (AN-4-29), wherein, in the formula (AN-1-2) In the case of m=4 or 8, m=4 or 8, in the formula (AN-4-17), m=4 or 8 is preferable, and m=8 is particularly preferable.

When it is important to increase the transmittance of the liquid crystal display element, the acid dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-1), and the formula. (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10) a compound represented by the formula (AN-16-3) and the formula (AN-16-4), wherein, in the formula (AN-1-2), preferably m=4 or 8, in the formula (AN- In 4-17), m=4 or 8 is preferable, and m=8 is particularly preferable.

In the case where the VHR of the liquid crystal display element is emphasized to be increased, the acid II Among the anhydrides, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-1), the formula (AN-3-1), the formula (AN-4-17), and the formula are preferable. a compound represented by (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-3), and formula (AN-16-4), wherein In the formula (AN-1-2), preferably m=4 or 8, in the formula (AN-4-17), m=4 or 8 is preferable, and m=8 is particularly preferable.

As one of the methods for preventing burn marks, it is effective to make the liquid crystal alignment film The volume resistance value is lowered to increase the relaxation rate of residual charge (residual DC) in the alignment film. When the purpose is emphasized, the acid dianhydride preferably has the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), and the formula (AN-4-29). And a compound represented by the formula (AN-11-3).

In the present invention, the tetracarboxylic dianhydride of the formula (1) can be used in combination with a photosensitive material. The photosensitive tetracarboxylic dianhydride which can be known can be selected without limitation. Such photosensitive four Examples of the carboxylic acid dianhydride include the following formula (PAN-1) to formula (PAN-8).

Two used in order to manufacture the poly-proline and its derivatives of the present invention Amines and diterpenes are described. In the manufacture of the poly-proline or its derivative of the present invention, There are no restrictions on the choice of diamines and dioximes.

Diamines can be classified into two types depending on their structures. That is, 2 amino groups will be attached When the skeleton is regarded as a main chain, a diamine having a branch of an autonomous chain, that is, a side chain group, and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect must be a group having 3 or more carbon atoms, and specific examples thereof include an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, and an alkoxy group having 3 or more carbon atoms. An alkyl group, and a group having a steroid skeleton. a group having one or more rings and having a terminal having a ring number of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as a substituent It also has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. Further, a diamine which does not have such a side chain group is sometimes referred to as a non-side chain type diamine.

It can be used by being suitably classified into a non-side chain type diamine and a side chain type diamine. Corresponding to the necessary pretilt angles respectively. It is preferred to use a side chain type diamine in such a manner as not to impair the characteristics of the present invention. Further, the side chain type diamine and the non-side chain type diamine are preferably selected and used for the purpose of improving the vertical alignment property, the voltage holding ratio, the burn-in property, and the alignment property of the liquid crystal.

The description will be made regarding a non-side chain type diamine. Known without side chains The diamine may be a diamine of the following formula (DI-1) to formula (DI-16).

[60]

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be replaced by -NH -, - O-, m is an integer from 1 to 12 alkylene group of At least one hydrogen may also be substituted with -OH. In the formula (DI-3) and the formula (DI-5) to the formula (DI-7), G ^{21 is} independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, -SS-, -SO ₂ -, -CO-, -COO-, -CONCH ₃ -, -CONH-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m' -, - O-(CH ₂ ) _m' -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, -(OC ₂ H ₄ ) _m' -O-, -O-CH _{2 -C (CF 3) 2 -CH 2} -O -, - O-CO- (CH 2) m '-CO-O -, - CO-O- (CH 2) m' -O-CO -, - ( CH ₂ ) _m' -NH-(CH ₂ ) _m' -, -CO-(CH ₂ ) _k -NH-(CH ₂ ) _k -, -(NH-(CH ₂ ) _m' ) _k -NH-, -CO-C ₃ H ₆ -(NH-C ₃ H ₆ ) _n -CO- or -S-(CH ₂ ) _m' -S-, m' is independently an integer from 1 to 12, and k is from 1 to 5. An integer, n is 1 or 2. In the formula (DI-4), s is independently an integer of 0 to 2. In formula (DI-6) and formula (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having a carbon number of 1 to 10. At least one hydrogen of the cyclohexane ring and the benzene ring in the formula (DI-2) to the formula (DI-7) may also be -F, -Cl, an alkylene group having a carbon number of 1 to 3, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl substitution, in addition, in formula (DI-4), at least one hydrogen of the benzene ring may also be selected from One base substitution of the group of the groups represented by the following formula (DI-4-a) to formula (DI-4-e). The group in which the bonding position is not fixed at the carbon atom constituting the ring means that the bonding position in the ring is arbitrary. Further, -NH ₂ bonding position on the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² is.

In the formulae (DI-4-a) and (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ .

[化62]

In the formula (DI-11), r is 0 or 1. In the formula (DI-8) to the formula (DI-11), the bonding position of -NH ₂ bonded to the ring is an arbitrary position.

[化63]

In the formula (DI-12), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. A phenyl group substituted by a group, and w is an integer of 1 to 10. In formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 -CI, p is independently an integer of 0 to 3, q is 0 to 4, The integer. In the formula (DI-14), the ring B is a monocyclic heterocyclic aromatic group, and R ²⁴ is hydrogen, -F, -Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a vinyl group, or an alkyne group. Base, q is an integer of 0~4. In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the formula (DI-16), G ²⁴ is a single bond, an alkylene group having a carbon number of 2 to 6 or a 1,4-phenylene group, and r is 0 or 1. Further, the group at which the bonding position is not fixed on the carbon atom constituting the ring means that the bonding position in the ring is arbitrary. In the formula (DI-13) to the formula (DI-16), the bonding position of the ring-bonded -NH ₂ is an arbitrary position.

Specific examples of the diamine having no side chain of the formula (DI-1) to the formula (DI-16) include the following examples (DI-1-1) to (DI-16-1).

An example of the diamine represented by the formula (DI-1) is shown below.

In the formulas (DI-1-7) and (DI-1-8), k is independently an integer of 1 to 3.

Examples of the diamine represented by the formula (DI-2) to the formula (DI-3) are shown below.

An example of the diamine represented by the formula (DI-4) is shown below.

[化68]

An example of the diamine represented by the formula (DI-5) is shown below.

In the formula (DI-5-1), m is an integer of 1 to 12.

In the formula (DI-5-12) and the formula (DI-5-13), m is an integer of 1 to 12.

In the formula (DI-5-16), v is an integer of 1 to 6.

[化73]

In the formula (DI-5-30), k is an integer of 1 to 5.

[化74]

In the formula (DI-5-35)~(DI-5-37) and (DI-5-39), m is an integer from 1 to 12, and the formula (DI-5-38) and formula (DI- In 5-39), k is an integer of 1 to 5, and in (DI-5-40), n is an integer of 1 or 2.

An example of the diamine represented by the formula (DI-6) is shown below.

[化75]

An example of the diamine represented by the formula (DI-7) is shown below.

In the formulae (DI-7-3) and (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2.

[化77]

An example of the diamine represented by the formula (DI-8) is shown below.

[化79]

An example of the diamine represented by the formula (DI-9) is shown below.

An example of the diamine represented by the formula (DI-10) is shown below.

An example of the diamine represented by the formula (DI-11) is shown below.

An example of the diamine represented by the formula (DI-12) is shown below.

An example of the diamine represented by the formula (DI-13) is shown below.

An example of the diamine represented by the formula (DI-14) is shown below.

An example of the diamine represented by the formula (DI-15) is shown below.

[化88]

An example of the diamine represented by the formula (DI-16) is shown below.

Explain about the second. The known diterpenes having no side chain include the following formula (DIH-1) to formula (DIH-3).

[化91]

In the formula (DIH-1) in, G ²⁵ is a single bond, an alkylene group having a carbon number of 1 to 20, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -or-C(CF ₃ ) ₂ -.

In the formula (DIH-2), the ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the group may be substituted with a methyl group, an ethyl group or a phenyl group. In the formula (DIH-3), the ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -. In the formula (DIH-2) and the formula (DIH-3), the bonding position of the ring-bonded -CONHNH ₂ is an arbitrary position.

The following shows an example of the formula (DIH-1) to the formula (DIH-3).

In the formula (DIH-1-2), m is an integer of 1 to 12.

Such non-side chain type diamines and diterpenes have ions for liquid crystal display elements The effect of improving electrical characteristics such as density reduction. In the case of using a non-side chain type diamine and/or dioxime as a diamine for producing a polyaminic acid or a derivative thereof used in the liquid crystal alignment agent of the present invention, it is preferably a diamine and The proportion of the total amount of dioxins is set to 0 mol% (% by mole) to 90 mol%, and more preferably set to 0 mol% to 50 mol%.

The side chain type diamine will be described. The side chain group of the side chain type diamine can be enumerated The following base.

As the side chain group, first, an alkyl group, an alkoxy group, an alkoxyalkyl group, Alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenoxycarbonyl, alkenylaminocarbonyl, alkynyl, Alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, and the like. The alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having a carbon number of 3 or more. However, in the alkoxyalkyl group, the carbon number of the entire group may be 3 or more. These groups may be linear or branched.

Next, the terminal ring has an alkyl group having 1 or more carbon atoms and a carbon number of 1 The alkoxy group or the alkoxyalkyl group having 2 or more carbon atoms as a substituent may, for example, be a phenyl group, a phenylalkyl group, a phenyl alkoxy group, a phenoxy group, a phenylcarbonyl group or a phenylcarbonyl group. An oxy group, a phenoxycarbonyl group, a phenylaminocarbonyl group, a phenylcyclohexyloxy group, a cycloalkyl group having 3 or more carbon atoms, a cyclohexylalkyl group, a cyclohexyloxy group, a cyclohexyloxycarbonyl group, a cyclohexylphenyl group , cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis( a ring structure of a cyclohexyloxycarbonyl group, a bis(cyclohexyl)phenoxycarbonyl group, and a cyclohexyl bis(phenyl)oxycarbonyl group.

Further, a collection ring group having two or more a group of a benzene ring, a group having two or more cyclohexane rings, or a ring containing two or more rings of a benzene ring and a cyclohexane ring, and the bond group is independently a single bond, -O-, -COO-, -OCO -, -CONH- or an alkylene group having a carbon number of 1 to 3, the terminal ring having an alkyl group having 1 or more carbon atoms, a fluorine-substituted alkyl group having 1 or more carbon atoms, and an alkyl group having 1 or more carbon atoms. Oxyl, Or an alkoxyalkyl group having 2 or more carbon atoms as a substituent. A group having a steroid skeleton is also effective as a side chain group.

The diamine having a side chain may, for example, be a compound represented by the following formula (DI-31) to formula (DI-35).

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ - or -(CH ₂ ) _m' -, m' is an integer from 1 to 12. Preferable examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and an alkylene group having a carbon number of 1 to 3, and a particularly preferred example is a single bond, -O -, - COO -, - OCO -, - CH 2 O -, - CH 2 - and -CH ₂ CH ₂ -. R ²⁵ is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl group, at least one hydrogen may also be substituted by -F, and at least one -CH ₂ - may also be substituted by -O-, -CH=CH- or -C≡C-. The hydrogen of the phenyl group may also be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or an alkane having 3 to 30 carbon atoms. Oxygen substitution. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably a meta or para position. That is, when the bonding position of the radical "R ²⁵ -G ²⁶ -" is set to one bit, the two bonding positions are preferably 3 bits and 5 bits, or 2 bits and 5 bits.

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, and these groups are independently a single bond, or an alkylene group having a carbon number of 1 to 12, and more than one alkyl group of the alkyl group - CH ₂ - may also be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-. Ring B ²¹ , ring B ²² , ring B ²³ and ring B ^{24 are} independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl, in ring B ²¹ , ring B ²² , in ring B ²³ and ring B ²⁴ , at least one hydrogen may be substituted by -F or -CH ₃ , and s, t and u are independently an integer of 0 to 2, and their total is 1 to 5, in s, t When u is 2, the two binding groups in each parenthesis may be the same or different, and the two rings may be the same or different. R ²⁶ is hydrogen, -F, -OH, alkyl having 1 to 30 carbon atoms having 1 to 30 fluoro-substituted alkyl group, an alkoxy group having a carbon number of 1 to 30, -CN, - OCH ₂ F, -OCHF ₂ or -OCF ₃ , at least one -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

[化97]

In formula (DI-31-b), R 27 and R ²⁸ are independently alkyl having 1 to 3, v is an integer of 1 to 6. Preferable examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

In formula (DI-32) and formula (DI-33), G ^{30 is} independently a single bond, -CO- or -CH ₂ -, R ^{29 is} independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, and the carbon number is An alkyl group of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in the formula (DI-33) may also be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group. Further, the group at which the bonding position is not fixed on any carbon atom constituting the ring means that the bonding position in the ring is arbitrary. Preferably, one of the two "-phenyl-G ³⁰ -O-" groups of the formula (DI-32) is bonded to the 3-position of the steroid core and the other is bonded to the 6-position of the steroid core. The bonding position of the two groups "-phenyl-G ³⁰ -O-" in the formula (DI-33) on the benzene ring is preferably a meta or para position with respect to the bonding position of the steroid nucleus. . In the formula (DI-32) and the formula (DI-33), -NH ₂ bonded to the benzene ring means that the bonding position in the ring is arbitrary.

In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms. . R ³¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-. R ³² is an alkyl group having 6 to 22 carbon atoms, and R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. Further, -NH ₂ bonded to the benzene ring means that the bonding position in the ring is arbitrary, and is preferably a meta or para position independently with respect to the bonding position of G ³¹ .

Specific examples of the side chain type diamine are exemplified below. The formula (DI-31)~ The diamine having a side chain of (DI-35) may, for example, be a compound represented by the following formula (DI-31-1) to formula (DI-35-3).

An example of the compound represented by the formula (DI-31) is shown below.

In the formula (DI-31-1) to the formula (DI-31-11), R ³⁴ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably having a carbon number of 5 ~25 alkyl or alkoxy having 5 to 25 carbon atoms. R ³⁵ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In the formula (DI-31-12) to the formula (DI-31-17), R ³⁶ is an alkyl group having 4 to 30 carbon atoms, and preferably an alkyl group having 6 to 25 carbon atoms. R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and preferably an alkyl group having 8 to 25 carbon atoms.

[化102]

[化104]

[化106]

In the formula (DI-31-18) to the formula (DI-31-43), R ³⁸ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably having a carbon number of 3 ~20 alkyl or alkoxy having 3 to 20 carbon atoms. R ³⁹ is hydrogen, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , preferably having a carbon number of An alkyl group of 3 to 25 or an alkoxy group having a carbon number of 3 to 25. Further, G ³³ is an alkylene group having a carbon number of 1 to 20.

[107]

[化109]

An example of the compound represented by the formula (DI-32) is shown below.

[111]

An example of the compound represented by the formula (DI-33) is shown below.

An example of the compound represented by the formula (DI-34) is shown below.

[化117]

In the formula (DI-34-1) to the formula (DI-34-12), R ⁴⁰ is hydrogen or an alkyl group having 1 to 20 carbon atoms, preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ⁴¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

An example of the compound represented by the formula (DI-35) is shown below.

In the formula (DI-35-1) to the formula (DI-35-3), R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and R ⁴¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

As the diamine in the present invention, the formula (DI-1-1) can also be used. (DI-16-1), formula (DIH-1-1)~ formula (DIH-3-6) and formula (DI-31-1)~ formula (DI-35-3) other than diamine Diamine. Examples of such a diamine include compounds represented by the following formula (DI-36-1) to formula (DI-36-13).

In the formula (DI-36-1) to the formula (DI-36-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

[化120]

In the formula (DI-36-9)~ (DI-36-11), e is an integer from 2 to 10. In the formula (DI-36-12), R ^{43 is} independently hydrogen, -NHBoc or - At least one of N(Boc) ₂ , R ⁴³ is -NHBoc or -N(Boc) ₂ , in the formula (DI-36-13), R ⁴⁴ is -NHBoc or -N(Boc) ₂ , and m is 1 An integer of ~12. Here, Boc is a tert-butoxycarbonyl group.

When it is important to further improve the alignment of the liquid crystal, it is preferable to use the formula (DI-1-3), the formula (DI-5-1), and the formula (DI-5-5) among the diamine and the dioxime. ), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI -7-3), and a diamine represented by the formula (DI-11-2), wherein in the formula (DI-5-1), preferably m = 2, 4 or 6, particularly preferably m = 4, at ( In DI-5-12), m=2~6 is preferable, m=5 is especially preferable, and in (DI-5-13), m=1 or 2 is preferable, and m=1 is especially preferable.

When it is important to increase the transmittance, it is preferable to use the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), and the diamine and the dioxime. The diamine represented by (DI-5-5), the formula (DI-5-24), and the formula (DI-7-3) is particularly preferably a diamine represented by (DI-2-1). In the formula (DI-5-1), preferably m=2, 4 or 6, especially excellent m = 4 is selected, and in the formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 1 is particularly preferable.

The diamine is emphasized in the case where the VHR of the liquid crystal display element is increased. It is preferable to use the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (DI-4-15). a diamine represented by the formula (DI-5-1), the formula (DI-5-28), the formula (DI-5-30), and the formula (DI-13-1), particularly preferably a formula (DI-) 2-1), a diamine represented by the formula (DI-5-1) and the formula (DI-13-1). Among them, in (DI-5-1), m=1 is particularly preferable, and in (DI-5-30), k=2 is particularly preferable.

As one of the methods for preventing burn marks, it is effective to make the liquid crystal alignment film The volume resistance value is lowered to increase the relaxation rate of residual charge (residual DC) in the alignment film. In the case of paying attention to this object, it is preferred to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (DI-) in the diamine and the dioxime. 4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), and formula (DI-16-1) The diamine represented by the formula (DI-4-1), the formula (DI-5-1), the formula (DI-5-12), and the diamine represented by the formula (DI-5-13) are particularly preferable. Among them, in the formula (DI-5-1), m = 2, 4 or 6, preferably m = 4, and in (DI-5-12), preferably m = 2 to 6, particularly preferably m = 5 In (DI-5-13), m = 1 or 2 is preferable, and m = 1 is particularly preferable.

In the present invention, a photosensitive material can be used in combination, and a known photosensitive film can be used. There is no limit to choice in the diamine. For example, it may be selected from the group consisting of an azobenzene derivative, an anthracene derivative, an acetylene derivative, a coumarin derivative, a cinnamic acid derivative, and a benzophenone derivative. Examples of such a photosensitive diamine compound include the following formula (PDI-1) to formula (PDI-12).

[化121]

[化124]

In the formula (PDI-7), R ^{51 is} independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , s is an integer of 0 to 2, and in the formula (PDI-12), R ⁵² is The alkyl group or alkoxy group having a carbon number of 1 to 10, at least one hydrogen may be substituted with fluorine.

Among the photosensitive diamines, (PDI-7) is preferred as it is important to improve the alignment of the liquid crystal. In the form in which the tetracarboxylic dianhydride of the present invention is reacted with a photosensitive diamine, in consideration of an improvement in the alignment property and a transmittance, the ratio of the photosensitive diamine/diamine which does not exhibit photosensitivity is preferably 100/0 (mol%) ~ 50/50 (mol%). Further, in order to improve various characteristics such as electrical characteristics and afterimage characteristics, two or more other photosensitive diamines may be used in combination.

In each diamine, a part of the diamine may be substituted with a monoamine in a range of a ratio of the monoamine to the diamine of 40 mol% or less. Such substitution can cause termination of the polymerization reaction when polyamic acid is formed, and can inhibit the progress of further polymerization. Therefore, by such substitution, the molecular weight of the obtained polymer (polylysine or its derivative) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The diamine substituted with a monoamine may be one type or two or more types, without impairing the effects of the present invention. The single Examples of the amine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and Decaalkylamine.

The polyaminic acid of the present invention or a derivative thereof can further be further in the monomer thereof Contains a monoisocyanate compound. By including a monoisocyanate compound in the monomer, the end of the obtained poly-proline or a derivative thereof is modified, and the molecular weight is adjusted. By using the terminal-modified polyglycine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From the above viewpoints, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The poly-proline and its derivatives of the present invention can be obtained by making the tetracarboxylic dianhydride It is obtained by reacting with a diamine in a solvent. In the synthesis reaction, no special conditions are required except for the selection of the raw materials, and the conditions for the synthesis of the usual polyaminic acid can be directly applied. The solvent to be used will be described later.

The liquid crystal alignment agent of the present invention may further contain polylysine or its derivative Other ingredients than living things. The other components may be one type or two or more types. Examples of other components include other polymers or compounds described later.

The liquid crystal alignment agent of the present invention may further contain the polyamine of the present invention. Other polymers than acids or derivatives thereof. The other polymer is a polymer other than the polyamic acid or a derivative thereof obtained by reacting the tetracarboxylic dianhydride of the present invention with a diamine, A polyglycine or a derivative thereof obtained by reacting a tetracarboxylic dianhydride containing no tetracarboxylic dianhydride of the formula (1) with a diamine (hereinafter referred to as "other polyamic acid or a derivative thereof" "), polyester, polyamine, polyoxyalkylene, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, Poly(meth)acrylate and the like. It may be one type or two or more types. Among these compounds, other polyaminic acid or a derivative thereof and a polyoxyalkylene are preferable, and other polylysine or a derivative thereof is more preferable.

Blending the polyaminic acid of the present invention or its derivative with other polylysine In the alignment agent of the derivative or the derivative thereof, the structure or molecular weight of each polymer is controlled, and it is applied to a substrate as described later, and pre-dried, whereby the poly-proline or its derivative component of the present invention can be obtained. Separated into the upper surface layer, the other polylysine or its derivative component [B] was separated into the lower layer. It can be controlled by utilizing a phenomenon in which a polymer having a small surface energy is separated into an upper surface layer and a polymer having a large surface energy is separated into a lower surface layer. As for the confirmation of the layer separation, it was confirmed that the surface energy of the formed alignment film was the same as or close to the surface energy of the film formed of the liquid crystal alignment agent containing only the [A] component.

Blending the polyaminic acid of the present invention or its derivative with other polylysine In the alignment agent of the derivative thereof, by controlling the structure or molecular weight of each polymer, an alignment film separated into an upper surface layer and a lower surface layer can be formed as will be described later. For example, an alignment film in which the poly-proline or the derivative component [A] of the present invention is separated into an upper surface layer and the other polyamine or its derivative component [B] is separated into the lower layer can be formed. It can be controlled by utilizing the phenomenon that the blended alignment agent is coated on a substrate, When heated and dried, a polymer having a small surface energy is separated into an upper surface layer, and a polymer having a large surface energy is separated into a lower surface layer. As for the confirmation of the layer separation, it was confirmed that the surface energy of the formed alignment film was the same as or close to the surface energy of the film formed of the liquid crystal alignment agent containing only the [A] component.

As a tetracarboxylic dianhydride for synthesizing other polyaminic acid or a derivative thereof, it can be used as a tetracarboxylic dianhydride of polylysine or a derivative thereof as an essential component for synthesizing the liquid crystal alignment agent of the present invention. The known tetracarboxylic dianhydride is selected without limitation, and the same tetracarboxylic dianhydride as the above-mentioned example is mentioned.

Among them, in the acid dianhydride, emphasis is placed on improving the layer separation property. Hereinafter, the formula (AN-3-2), the formula (AN-1-13), and the formula (AN-4-30) are preferred.

In the case where attention is paid to increasing the transmittance of the liquid crystal display element, the acid Among the dianhydrides, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-1), the formula (AN-3-1), the formula (AN-4-17), and the formula are preferred. (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10), Formula (AN-16-3), and Formula (AN-16-4) The compound represented by the formula (AN-1-2), preferably m = 4 or 8, in the formula (AN-4-17), preferably m = 4 or 8, particularly preferably m = 8.

In the case where the VHR of the liquid crystal display element is emphasized to be increased, the acid II Among the anhydrides, the formula (AN-1-2), the formula (AN-2-1), the formula (AN-7-2), the formula (AN-10), the formula (AN-16-3), and the formula (AN) are preferable. -16-4) The compound represented, wherein in the formula (AN-1-2), m = 4 or 8 is preferred.

As one of the methods for preventing burn marks, it is effective to make the liquid crystal alignment film The volume resistance value is lowered to cause a relaxation rate of residual charge (residual DC) in the alignment film Increased. When the purpose is emphasized, the acid dianhydride preferably has the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), and the formula (AN-4-29). And a compound represented by the formula (AN-11-3).

As a diamine and diterpene used to synthesize other polylysine or its derivatives The oxime may be the same as the above-exemplified other diamine which is a polyamine or a derivative thereof which can be used as an essential component of the liquid crystal alignment agent of the present invention.

Among them, attention is paid to further improving the layer separation property, that is, the alignment of the liquid crystal. In the case of high concentration, it is preferred to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (DI-5-1) among the diamine and the dioxime. a diamine and a diterpene represented by the formula (DI-5-9), the formula (DI-5-28), and the formula (DIH-2-1), wherein in the formula (DI-5-1) Preferably, m = 1, 2 or 4, particularly preferably m = 1 or 2.

In the case where the transmittance is increased, the diamine and the diterpene are excellent. The diamine represented by the formula (DI-1-2), the formula (DI-2-1), the formula (DI-5-1), and the formula (DI-7-3) is preferably selected (DI-2). -1) The diamine represented. In the formula (DI-5-1), m = 1, 2 or 4 is preferred, m = 1 or 2 is particularly preferred, and in the formula (DI-7-3), preferably m = 2 or 3, n = 1 or 2, particularly preferably m=1.

The diamine is emphasized in the case where the VHR of the liquid crystal display element is increased. It is preferable to use the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-15), and the formula (DI-5-1) , a diamine represented by the formula (DI-5-28), the formula (DI-5-30), and the formula (DI-13-1), particularly preferably the formula (DI-2-1), the formula (DI- 5-1), and a diamine represented by the formula (DI-13-1). Among them, in (DI-5-1), m=1 or 2 is particularly preferable, in (DI-5-30) Among them, k=2 is particularly preferable.

As one of the methods for preventing burn marks, it is effective to lower the volume resistance value of the liquid crystal alignment film to increase the relaxation rate of residual electric charge (residual DC) in the alignment film. In the case of paying attention to this object, it is preferred to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (DI-) in the diamine and the dioxime. 4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), The diamine represented by the formula (DI-5-30) and the formula (DI-16-1), particularly preferably the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-5-) 12) A diamine represented by the formula (DI-5-13) and the formula (DI-5-30). Wherein in the formula (DI-5-1), m = 1 or 2 is preferred, and in (DI-5-12), preferably m = 2 to 6, particularly preferably m = 5, in (DI-5-13) Among them, m = 1 or 2 is preferable, m = 1 is particularly preferable, and in (DI-5-30), k = 2 is particularly preferable.

Other polyaminic acid or its derivative may be respectively used as the liquid crystal of the present invention The method for synthesizing polyaminic acid or a derivative thereof, which is an essential component of the alignment agent, is synthesized as described below.

Relative to the polyaminic acid of the present invention or a derivative thereof (the [A] component) The ratio of the other polyamine or a derivative thereof (the component [B]) is preferably 10% by weight to 100% by weight, and more preferably 20% by weight to 100% by weight based on the total amount of the component [A].

The polypyroxane may further include Japanese Patent Laid-Open No. 2009-036966, Japanese Patent Laid-Open No. 2010-185001, Japanese Patent Laid-Open No. 2011-102963, and Japanese Patent Laid-Open No. 2011-253175 Japanese Patent Laid-Open Publication No. 2012-159825, International Publication No. 2008/044644 Book, International Publication No. 2009/148099, International Publication No. 2010/074261, International Publication No. 2010/074264, International Publication No. 2010/126108, International Publication No. 2011/068123, International Publication No. 2011/068127, The polyoxyalkylene described in the specification of International Publication No. 2011/068128, International Publication No. 2012/115157, and International Publication No. 2012/165354.

<Alkenyl substituted imine compound substituted by alkenyl group>

For example, the liquid crystal alignment agent of the present invention can further contain an alkenyl substituted nadicilimine compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The alkenyl imino compound substituted with an alkenyl group may be used alone or in combination of two or more. The content of the alkenyl imino compound substituted by the alkenyl group is preferably from 1% by weight to 100% by weight, more preferably 1% by weight, based on the above, with respect to the polyaminic acid or its derivative. ~70% by weight, further preferably from 1% by weight to 50% by weight.

Hereinafter, the Nadickylimine compound will be specifically described.

The alkenyl imino compound substituted with an alkenyl group is preferably a compound which is soluble in a solvent in which the poly-proline or a derivative thereof used in the present invention is dissolved. Examples of such an alkenyl-substituted nadic ylidene compound include compounds represented by the following formula (NA).

[化125]

In the formula (NA), L ¹ and L ^{2 are} independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 ~12 aryl or benzyl, n is 1 or 2.

In the formula (NA), when n=1, W is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 ~12 aryl, benzyl, -Z ¹ -(O) _r -(Z ² O) _k -Z ³ -H (here, Z ¹ , Z ² and Z ^{3 are} independently 2 to 6 carbon atoms a group represented by an alkyl group, wherein r is 0 or 1, and k is an integer of 1 to 30, -(Z ⁴ ) _r -BZ ⁵ -H (here, Z ⁴ and Z ⁵ independently have a carbon number of 1 to 4 alkylene or a cycloalkyl group having a carbon number of 5 to 8, B is a phenyl group, and r is a group represented by 0 or 1), -BTBH (here, B is a phenyl group) And T is a group represented by -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, or -SO ₂ -), or 1 to 3 of these groups A group in which hydrogen is replaced by -OH.

In this case, preferred W is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, and a poly(ethyleneoxy group) having a carbon number of 4 to 10. Ethyl, phenoxyphenyl, phenylmethylphenyl, phenylisopropylidenephenyl, and a group in which one or two hydrogens of these groups are substituted by -OH.

In the formula (NA), when n=2, W is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, Z ¹ -O-(Z ² O) _k -Z ³ - (here, Z ¹ -Z ³ , and the meaning of k are as described above), -Z ⁴ -BZ ⁵ - (here, Z ⁴ , Z ⁵ and B have the meanings indicated above, -B-(OB) _r -T-(BO) _r -B- (where B is a phenyl group and T is a carbon number of 1) The alkyl group of ~3, -O- or -SO ₂ -, r has the above-mentioned meaning, or a group in which one to three hydrogens of these groups are substituted by -OH.

In this case, preferred W is an alkylene group having a carbon number of 2 to 12, a cyclohexylene group, a phenylene group, a tolylene group, a xylylene group, and a -C ₃ H ₆ -O group. -(Z ² -O) _n -OC ₃ H ₆ - (wherein Z ² is an alkylene group having 2 to 6 carbon atoms, and n is 1 or 2), -BTB- (here, B is phenylene, and, T is -CH ₂ -, - O-, or -SO ₂ -) represented by the group, -BOBC ₃ H ₆ -BOB- (here, B is phenylene) represented a group and a group in which one or two hydrogens of these groups are substituted by -OH.

Such an alkenyl-substituted nadicilide compound can be, for example, an alkenyl-substituted nadic tetracarboxylic dianhydride derivative and a diamine at 80 ° C to 220 ° C as described in Japanese Patent No. 2,729,565. The compound obtained by the synthesis or the commercially available compound is maintained at a temperature of 0.5 hour to 20 hours. Specific examples of the alkenylimine compound substituted with an alkenyl group include the compounds shown below.

N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-methyl-allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-methyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-A Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(2-ethylhexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide, N-allyl-allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, N-allyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-isopropenyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-allyl (methyl) bicyclo [2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine , N-cyclohexyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] g -5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-benzene -Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-phenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-benzyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-benzyl-methylallylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindenine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl -Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2,2-dimethyl-3-hydroxypropyl)-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2,2-dimethyl-3-hydroxypropyl)-allyl (methyl)bicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(2,3-dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine, N-(2,3-dihydroxypropyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-hydroxy-1-propenyl)-ene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxycyclohexyl)-allyl(methyl)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- (4-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxyphenyl)-methylene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(4-hydroxyphenyl)-methylallylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- (3-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(p-hydroxybenzyl)-allyl bicyclo [2.2.1] H--5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine, N-{2-(2-hydroxyl Ethyl ethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-[2-{2-(2-hydroxyl Ethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-[2-{2-(2-hydroxyethyl) Oxy)ethoxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-[2-{2-(2 -hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-{4-(4-hydroxyl Phenyl isopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene Phenyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene Phenyl}-A Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, and oligomers thereof, N,N'-extended ethyl-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N, N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-hexamethylene-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), N,N'-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N, N'-dodecyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extension ring Hexyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine), 1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine) propoxy}ethane, 1,2 -Bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, 1,2-double {3'- (Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, bis[2'-{3'-(allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, bis[2'-{3'-(allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, 1,4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxyindolimine)propoxy}butane, 1,4-double {3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imino)propoxy}butane, N,N'-p-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl 醯imino), N,N'-p-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'- Inter-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-meta-phenyl-bis(allylmethyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-m-phenylene Methyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2,2-bis[4-{4-(allylbicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, Double {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imino)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)phenyl}methane, double { 4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine) phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine) phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}indole, double {4-(allyl Methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinazoline) Phenyl}indole, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}indole, 1,6-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-3-hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinimine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxy quinone imine)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine Propyloxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-2-hydroxy-benzene , 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-2,5-dihydroxy-benzene, N,N'-pair (2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-(2-hydroxy)benzene Dimethyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-(2-hydroxy)benzenedimethyl- Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine), N,N'-p-(2,3-dihydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenoxy}phenyl]propane , double {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenyl}methane, double {3-(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo[2.2.1]g -5-ene-2,3-dicarboxyindolimine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine)}phenoxymethyl Propane, N, N', N"-tris (extended ethyl methallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) iso-cyanate, and Their oligomers and the like.

Further, the alkenyl-substituted nadicizine imidization used in the present invention The compound may also be a compound comprising an asymmetric alkylene group, a phenylene group, and represented by the following formula.

Among the alkenyl substituted imine compounds substituted by alkenyl groups, preferred compounds such as Shown below.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindole Imine), N, N'-extended ethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-trimethylene Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxyindolimine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine), N,N'-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N '-Dodecylmethyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-cyclohexylene-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine), N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N, N'-p-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-meta-strand Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyfluorene Amine, N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine, N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Methyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allyl bicyclol) [2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) Phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenoxy Phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine Phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}methane.

Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}methane, bis{4-(methylallylmethylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyinimide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} ether, bis {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) phenyl} ether, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, bis{4-(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine) phenyl} hydrazine, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}indole.

More preferred alkenyl substituted nadic quinone imine compounds are shown below.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ).

N,N'-p-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene-bis( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-meta-phenyl-bis(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'- P-Benzyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-xylylene-bis(ene) Propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine).

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-dual [ 4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, double {4-(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane , bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane.

Moreover, a particularly preferred alkenyl substituted nadic ylidene compound can be A bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)phenyl}methane represented by the following formula (NA-1), formula (NA) -2) represents N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine), and formula (NA- 3) N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) represented.

<Compound having a radical polymerizable unsaturated double bond>

For example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one kind of compound or two or more types of compounds. Further, the compound having a radical polymerizable unsaturated double bond does not contain an alkenyl substituted imidide compound substituted with an alkenyl group. As a content of a compound having a radical polymerizable unsaturated double bond, The object of the present invention is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, even more preferably from 1% by weight to 50% by weight, based on the polyaminic acid or its derivative.

In addition, as for the compound having a radical polymerizable unsaturated double bond, The ratio of the alkenyl imine compound substituted by the alkenyl group is increased by the ion density of the liquid crystal display element, the ion density is suppressed to increase over time, and the generation of afterimage is further suppressed, and the radically polymerizable unsaturated double bond is provided. The compound/alkenyl substituted nadic ylidene compound is preferably from 0.1 to 10, more preferably from 0.5 to 5, by weight.

Hereinafter, a compound having a radical polymerizable unsaturated double bond is provided Body description.

Examples of the compound having a radical polymerizable unsaturated double bond include a (meth) acrylate, a (meth)acrylic acid derivative such as (meth) acrylamide, and a bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radical polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylate include (meth)acrylic acid. Cyclohexyl ester, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate Benzyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.

Specific examples of the bifunctional (meth) acrylate include dipropylene. Products of ethylene bisacrylate and East Asia Synthetic Chemical Industry Co., Ltd. ARONIX M-210, ARONIX M-240 and ARONIX M-6200, Nippon Chemical Co., Ltd. products KAYARAD HDDA, Karayade ( KAYARAD) HX-220, KAYARAD R-604 and KAYARAD R-684, Osaka Organic Chemical Industry Co., Ltd. products V260, V312 and V335HP, and Kyoeisha Oil Chemical Industry Co., Ltd. The product is Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylate are, for example, Examples include 4,4'-methylenebis(N,N-dihydroxyethylidene anilide), and products of the East Asian synthetic chemical industry (ARONIX) M-400, Aronix (ARONIX) ) M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, Nippon Kayaku ) KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 And the VGPT of the Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylamide derivative include, for example, N-iso Propyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, N-n-propyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl Methyl acrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylamide, N-tetrahydrofurfuryl propylene amide, N-tetrahydrofuran methyl methyl Acrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N,N-diethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropylacrylamide, N-propenyl acridine, N-propenylpyrrolidine, N,N'-methylenebis propylene amide, N,N'- Ethyl bis acrylamide, N, N'-dihydroxyethylidene bis decylamine, N-(4-hydroxyphenyl)methacrylamide, N-phenylmethacrylamide, N- Butyl methacrylamide, N-(isobutoxymethyl)methacrylamide, N-[2-(N,N-dimethylamino)ethyl]methacrylamide, N,N-di Methyl methacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl) 2-methylpropenylamine, N-benzyl-2-methylpropenylamine, and N,N'-methylenebismethacrylamide.

Among the (meth)acrylic acid derivatives, N,N'-methylenebispropene is particularly preferred. Indoleamine, N,N'-dihydroxyethylidene-bisacrylamide, ethylene diacrylate, and 4,4'-methylenebis(N,N-dihydroxyethyl phenyl aniline).

Bismaleimide can be exemplified by KI Chemical Co., Ltd. (KI Chemical) BMI-70 and BMI-80 manufactured by Industry Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000 manufactured by Daiwa Kasei Kogyo Co., Ltd.

<oxazine compound>

For example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound for the purpose of stabilizing electrical properties in the liquid crystal display element for a long period of time. The oxazine compound may be one compound or two or more compounds. For the purposes described, the content of the oxazine compound is preferably relative to the polyamic acid or a derivative thereof. 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, still more preferably 1% by weight to 20% by weight.

Hereinafter, the oxazine compound will be specifically described.

The oxazine compound is preferably an oxazine compound which is soluble in a solvent which dissolves poly-proline or a derivative thereof, and which has ring-opening polymerizability.

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

Various structures are known for the oxazine structure. In the present invention, the structure of the oxazine is The oxazine structure in the oxazine compound is exemplified by an oxazine structure having an aromatic group including a condensed polycyclic aromatic group such as benzoxazine or naphthoazine.

Examples of the oxazine compound include the following formula (OX-1) to formula (OX-6). The compound represented. Further, in the following formula, the bond represented as the center of the steering ring indicates that the bond is bonded to any carbon constituting the ring and bonding the substituent.

In the formula (OX-1)~(OX-3), L ³ and L ⁴ are an organic group having a carbon number of 1 to 30, and in the formula (OX-1) to (OX-6), L ⁵ ~L ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ is a single bond, -O-, -S -, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _v -, - O-(CH ₂ ) _v -O-, -S-(CH ₂ ) _v -S-, where v is an integer of 1 to 6, in the formula (OX-5) and the formula (OX-6), Q ^{2 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having a carbon number of 1 to 3, Q ² benzene ring, naphthalene ring bonded hydrogen may be independently _{-F, -CH 3, -OH, -COOH} , -SO 3 H, -PO 3 H 2 group.

Further, the oxazine compound includes an oligomer or a polymer having an oxazine structure in a side chain, an oligomer or a polymer having an oxazine structure in the main chain.

The oxazine compound represented by the formula (OX-1) is exemplified by the following oxazine compound.

In the formula (OX-1-2), L ³ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the formula (OX-2) is exemplified by the following oxazines. Compound.

[化131]

In the formula, L ³ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the following formula (OX-3-I) is exemplified by the oxazine compound represented by the formula (OX-3).

In the formula (OX-3-I), L ³ and L ⁴ are an organic group having a carbon number of 1 to 30, and L ⁵ to L ⁸ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is a single bond. -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -. The oxazine compound represented by the formula (OX-3-I) is exemplified by the following oxazine compound.

[化135]

In the formula, L ³ and L ^{4 are} preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the formula (OX-4) is exemplified by the following oxazine compound.

[化137]

The oxazine compound represented by the formula (OX-5) is exemplified by the following oxazines. Compound.

[化139]

The oxazine compound represented by the formula (OX-6) is exemplified by the following oxazines. Compound.

[化141]

More preferably, among these compounds, the formula (OX-2-1), the formula (OX-3-1), Formula (OX-3-3), formula (OX-3-5), formula (OX-3-7), formula (OX-3-9), formula (OX-4-1)~ formula (OX-4 -6), an oxazine compound represented by the formula (OX-5-3), the formula (OX-5-4), and the formula (OX-6-2) to (OX-6-4).

Oxazine compounds can be used in conjunction with International Publication No. 2004/009708, date It is produced by the same method as the method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2004-352670.

The oxazine compound represented by the formula (OX-1) can be obtained by reacting a phenol compound with a primary amine or an aldehyde (refer to International Publication No. 2004/009708).

The oxazine compound represented by the formula (OX-2) can be obtained by a method in which a primary amine is gradually added to formaldehyde, and then a compound having a naphthol-based hydroxyl group is added to cause a reaction ( Refer to International Publication No. 2004/009708).

The oxazine compound represented by the formula (OX-3) can be obtained by: In an organic solvent, 1 mole of a phenolic compound is present in the presence of an aliphatic secondary amine, a tertiary amine or a basic nitrogen-containing heterocyclic compound, relative to one of the phenolic hydroxyl groups. The aldehyde is at least 2 mol or more and the 1 mol of the primary amine is reacted (refer to the specification of International Publication No. 2004/009708 and Japanese Patent Laid-Open No. Hei 11-12258).

The oxazine compound represented by the formula (OX-4)~(OX-6) can be passed, for example Obtained in the following manner: a diamine having a plurality of benzene rings and an organic group bonded to the benzene ring such as 4,4'-diaminodiphenylmethane in n-butanol at a temperature of 90 ° C or higher. An aldehyde such as ermline or a phenol is subjected to a dehydration condensation reaction (refer to Japanese Laid-Open Patent Publication No. 2004-352670).

<oxazoline compound>

For example, for the purpose of making the electrical characteristics of the liquid crystal display element stable for a long period of time, The liquid crystal alignment agent of the present invention may further contain an oxazoline compound. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. The content of the oxazoline compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from about the polypyridic acid or a derivative thereof. 1% by weight to 20% by weight. Alternatively, for the purpose of the above, when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the content of the oxazoline compound is preferably 0.1% by weight relative to the polyaminic acid or its derivative. %~40% by weight.

Hereinafter, the oxazoline compound will be specifically described.

The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. Further, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure in a side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a monomer having an oxazoline structure in a side chain and having no oxazoline structure. Copolymer of monomer. The copolymer having an oxazoline structure in a side chain may be a copolymer of two or more monomers having an oxazoline structure in a side chain, or may be a monomer having two or more monomers having an oxazoline structure in a side chain. A copolymer of a monomer having an oxazoline structure.

The oxazoline structure is preferably one of oxygen and nitrogen in the oxazoline structure or The structure in which both can be present in the oxazoline compound in a form reactive with the carbonyl group of poly-proline.

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, and 4-furan-2-yl. Methyl-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydrogen) -2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxazole Porphyrin, 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'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'- Methylene bis(4-phenyl-2-oxazoline). In addition to these compounds, a polymer or oligomer having an oxazolyl group such as EPOCROS (trade name, manufactured by Nippon Catalyst) can also be mentioned. More preferably, among these compounds, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is mentioned.

<epoxy compound>

For example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The epoxy compound may be one compound or two or more compounds. The content of the epoxy compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably 1%, with respect to the polyamine or its derivative. Weight%~20% by weight.

Hereinafter, the epoxy compound will be specifically described.

Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having an epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, and a ring. Oxycyclohexane, 3-glycidoxypropyltrimethoxy Decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-glycidylphthalimide, (nonafluoro-n-butyl)epoxide, perfluoroethyl shrinkage Glycerol ether, epichlorohydrin, epibromohydrin, N,N-diglycidylaniline, and 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane.

The compound having two epoxy rings in the molecule may, for example, be ethylene glycol. Glycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol Glycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate Acid ester and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane.

Examples of the compound having three epoxy rings in the molecule include 2-[4-(2,3- Epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name) "Tecmoa VG3101L" (manufactured by Mitsui Chemicals Co., Ltd.).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetra. Glycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and 3-(N-allyl-N-glycidyl)aminopropyl Trimethoxy decane.

In addition to the above, examples of compounds having an epoxy ring in the molecule may also To cite an oligomer or polymer having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate. And methyl glycidyl (meth)acrylate.

Examples of the other monomer copolymerized with the monomer having an epoxy ring include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, styrene, methyl styrene, chloromethylstyrene, (meth)acrylic acid-(3-ethyl-3-oxetanyl) Ester, N-cyclohexylmaleimide and N-phenylmaleimide.

Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and other monomers include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexylmaleimide. - glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate - A glycidyl methacrylate copolymer, a (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

Among these, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Tecmoa VG3101L", 3,4-epoxycyclohexenylmethyl -3',4'-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2-(3,4-epoxy) Cyclohexyl)ethyltrimethoxydecane.

More systematically, examples of the epoxy compound include glycidyl ether and shrinkage. A glyceride, a glycidylamine, an epoxy group-containing acrylic resin, glycidylamine, glycidyl isocyanurate, a chain aliphatic epoxy compound, and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl ester, and shrinkage. A glycerolamine, an epoxy group-containing acrylic resin, glycidylamine, glycidyl isocyanurate, a chain aliphatic epoxy compound, and a cyclic aliphatic epoxy compound.

Examples of the glycidyl ether include a bisphenol A type epoxy compound and a bisphenol F type. Epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenation Bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolac Varnish type epoxy compound, brominated cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, epoxy compound containing naphthalene skeleton, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type An epoxy compound, an alicyclic diglycidyl ether compound, an aliphatic polyglycidyl ether compound, a polysulfide type diglycidyl ether compound, and a biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and glycidol. Ester epoxy compound.

Examples of the glycidylamine include a polyglycidylamine compound and a glycidylamine type epoxy resin.

The epoxy group-containing acrylic compound may, for example, be a homopolymer or a copolymer of a monomer having an oxiranyl group.

Examples of the glycidylamines include glycidylamine-type epoxy compounds.

Examples of the chain aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an alkene compound.

Examples of the cyclic aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cyclic olefin compound.

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, and jER1010 (all trade names; manufactured by Mitsubishi Chemical Corporation) and Epotohto YD-128 (trade name; Dongdu Chemical Co., Ltd., DER-331, DER-332, DER-324 (both trade names; manufactured by The Dow Chemical Company), Epiclon 840, Abby clone Epiclon) 850, Epiclon 1050 (both trade names; DIC), EPMIK R-140, EPOMIK R-301, And EPMIK (EPOMIK) R-304 (both trade names; manufactured by Mitsui Chemicals Co., Ltd.).

Examples of the bisphenol F-type epoxy compound include jER806, jER807, and jER4004P (all trade names; manufactured by Mitsubishi Chemical Corporation), Epotohto YDF-170, Epotohto YDF-175S, and Ai Epotohto YDF-2001 (both trade names; manufactured by Tohto Kasei Co., Ltd.), DER-354 (trade name; manufactured by Dow Chemical Co., Ltd.), Epiclon 830, and Epiclon 835 (both Commodity name; Di Aisheng (share) manufacturing).

Examples of the bisphenol type epoxy compound include epoxides of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the hydrogenated bisphenol-A type epoxy compound include Santoohto ST-3000 (trade name; manufactured by Tohto Kasei Co., Ltd.), and Rika Resin HBE-100 (trade name; New Japan Physical and Chemical ( () Manufacturing), and DENACOL EX-252 (trade name; manufactured by Changchun Chemicals Co., Ltd.).

Examples of the hydrogenated bisphenol type epoxy compound include an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the brominated bisphenol-A type epoxy compound include jER5050 and jER5051 (all trade names; manufactured by Mitsubishi Chemical Corporation), Epotohto YDB-360, and Epotohto YDB-400 ( All are trade names; manufactured by Dongdu Chemical Co., Ltd., DER-530, DER-538 (all trade names; manufactured by Dow Chemical Company), Epiclon 152, and Epiclon 153 ( All are trade names; Di Aisheng (shares) manufacturing).

Examples of the phenol novolak-type epoxy compound include jER152 and jER154 (both trade names; manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade name; manufactured by Tohto Chemical Co., Ltd.), DEN431, and DEN438 (all are trade names; Produced by Chemical Company, Epiclon N-770 (trade name; manufactured by Di Aisheng (share)), EPPN-201, and EPPN-202 (both trade names; Nippon Chemical Co., Ltd.) Made).

Examples of the cresol novolac type epoxy compound include jER180S75 (trade name; manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all trade names; manufactured by Tohto Kasei Co., Ltd.), and Epiclon N. -665, Epiclon N-695 (both trade names; manufactured by Di Aisheng Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all are trade names; manufactured by Nippon Chemical Co., Ltd.).

Examples of the bisphenol A novolac type epoxy compound include jER157S70 (trade name; manufactured by Mitsubishi Chemical Corporation) and Epiclon N-880 (trade name; manufactured by Di Aisheng Co., Ltd.).

Examples of the epoxy compound containing a naphthalene skeleton include Epiclon HP-4032, Epiclon HP-4700, and Epiclon HP-4770 (all are trade names; Di Aisheng (share) Manufactured, and NC-7000 (trade name; manufactured by Nippon Kayaku Co., Ltd.).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (hereinafter, EP-1), catechol diglycidyl ether (formula: EP-2), and resorcinol condensed water. Glycerol ether (formula EP-3 below), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3) -glycidoxy]phenyl)]ethyl]phenyl]propane (formula: EP-4), tris(4-glycidoxyphenyl)methane (formula: EP-5), jER1031S, jER1032H60 (all trade names; manufactured by Mitsubishi Chemical Co., Ltd.), TACTIX-742 (trade name; manufactured by Dow Chemical Co., Ltd.), DENACOL EX-201 (trade name; Stock) manufacturing), De Puen (DPPN)-503, DPPN-502H, DPPN-501H, NC6000 (all are trade names; manufactured by Nippon Kayaku Co., Ltd.), Tecmoa VG3101L (trade name; manufactured by Mitsui Chemicals Co., Ltd.), A compound represented by the formula EP-6 and a compound represented by the following formula EP-7.

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Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (trade name; manufactured by The Dow Chemical Company) and Epiclon HP-7200 (trade name; Di Aisheng (share)). Manufacturing).

Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and a physicochemical resin (Rika Resin) DME-100 (trade name; manufactured by Nippon Chemical and Chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (hereinafter, EP-8), diethylene glycol diglycidyl ether (hereinafter, EP-9), and polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether (Equation EP-10), tripropylene glycol diglycidyl ether (EP-11 below), polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether (formula EP-12), 1,4-butanediol diglycidyl ether (formula EP-13), 1,6-hexanediol diglycidyl ether (EP-14), dibromo neopentyl glycol diglycidyl ether (formula EP-15), DENACOL EX-810, DENACOL EX-851, Dion DENACOL) EX-8301, DENACOL EX-911, DENACOL EX-920, DENACOL EX-931, DENACOL EX-211, DAI 焅 ( DENACOL) EX-212, DENACOL EX-313 (all trade names; manufactured by Changchun Huacheng Co., Ltd.), DD-503 (trade name; manufactured by ADEKA), physical and chemical Resin (Rika Resin) W-100 (trade name; manufactured by Nippon Chemical and Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (Equation EP-16), 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 trade names; manufactured by Nagase Kasei Co., Ltd.).

Examples of the polysulfide type diglycidyl ether compound include FLDP-50. And FLDP-60 (all trade names; Toray Thiokol (manufactured by Toray Thiokol)).

Examples of the biphenol-based epoxy compound include YX-4000 and YL-6121H (all trade names; manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all trade names; Nippon Chemical Co., Ltd.) Manufacturing).

Examples of the diglycidyl ester compound include diglycidyl terephthalate. Base ester (formula EP-17 below), diglycidyl phthalate (formula: EP-18), bis(2-methyloxapropylpropyl) phthalate (under a compound represented by the following formula: EP-19), hexahydrophthalic acid diglycidyl ester (Equation EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and under The compound represented by the formula EP-23.

Examples of the glycidyl ester epoxy compound include jER871 and jER872 (both For the trade name; manufactured by Mitsubishi Chemical Co., Ltd., Epiclon 200, Epiclon 400 (both trade names; manufactured by Di Aisheng (share)), DENACOL EX-711 And DENACOL EX-721 (both trade names; manufactured by Changsong Chemicals Co., Ltd.).

Examples of the polyglycidylamine compound include N,N-diglycidylaniline. (Formula EP-24), N,N-diglycidyl-o-toluidine (Ethyl-25) N,N-diglycidyl-m-toluidine (formula EP-26), N,N-diglycidyl-2,4,6-tribromoaniline (formula EP-27), 3- (N,N-diglycidyl)aminopropyl Trimethoxy decane (formula EP-28), N,N,O-triglycidyl-p-aminophenol (formula EP-29), N,N,O-triglycidyl-m-aminophenol (Formula EP-30 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (Formula EP-31), N,N,N' , N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (trade name; manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-32), 1,3-double ( N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (trade name; manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-33), 1,4-double (N,N-diglycidylaminomethyl)cyclohexane (formula: EP-34), 1,3-bis(N,N-diglycidylamino)cyclohexane (formula EP- 35), 1,4-bis(N,N-diglycidylamino)cyclohexane (formula EP-36 below), 1,3-bis(N,N-diglycidylamino)benzene (under Formula EP-37), 1,4-bis(N,N-diglycidylamino)benzene (formula EP-38 below), 2,6-bis(N,N-diglycidylaminomethyl) Bicyclo[2.2.1]heptane (formula EP-39 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (formula EP- 40), 2,2'-dimethyl-(N,N,N' , N'-tetraglycidyl)-4,4'-diaminobiphenyl (formula EP-41), N,N,N',N'-tetraglycidyl-4,4'-diamino Diphenyl ether (formula: EP-42), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (formula: EP-43), 2, 4,4'-tris(N,N-diglycidylamino)diphenyl ether (formula EP-44 below), tris(4-(N,N-diglycidyl)aminophenyl)methane ( Formula EP-45), 3,4,3',4'-tetrakis(N,N-diglycidylamino)biphenyl (formula EP-46), 3,4,3',4' - tetrakis(N,N-diglycidylamino)diphenyl ether (formula: EP-47), a compound represented by the following formula EP-48, and a compound represented by the following formula EP-49.

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The homopolymer of the monomer having an oxiranyl group can be exemplified by polymethacryl Acid glycidyl ester. Examples of the copolymer of the oxopropyl group-containing monomer include N-phenylmaleimide-glycidyl methacrylate copolymer, and N-cyclohexylmaleimide-glycidyl methacrylate. Copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymerization , (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having an oxiranyl group include glycidyl (meth)acrylate. Oleate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

As for the copolymer of the monomer having an oxoheteropropyl group, Examples of the monomer other than the monomer of the group include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, N- Cyclohexylmaleimine, and N-phenylmaleimide.

Examples of glycidyl isocyanurate include 1,3,5-triglycidyl Base-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (formula EP-50), 1,3-diglycidyl-5-allyl -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (formula EP-51), and a glycidyl isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene. And Epolead PB3600 (trade name; (share) big game made).

The cyclic aliphatic epoxy compound may, for example, be a 3,4-epoxycyclohexenyl group. Methyl-3',4'-epoxycyclohexenecarboxylate (Celloxide 2021 (trade name; manufactured by Daicel), the following formula EP-52), 2-methyl -3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (formula EP-53 below), 2,3-epoxycyclopentane- 2',3'-epoxycyclopentane ether (formula EP-54 below), ε-caprolactone modified 3,4-ring Oxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2:8,9-diepoxylimene (Celloxide 3000 (trade name; (share) contest)璐 manufactured), the following formula EP-55), the compound represented by the following formula EP-56, CY-175, CY-177, CY-179 (all are trade names; Ciba-Jacky Chemical Company (The Ciba) -Geigy Chemical Corp.) (available from Huntsman Japan KK), EHPD-3150 (trade name; manufactured by Daicel), and cyclic aliphatic epoxy resin .

The epoxy compound is preferably a polyglycidylamine compound, bisphenol A novolac One or more of a lacquer type epoxy compound, a cresol novolac type epoxy compound, and a cyclic aliphatic type epoxy compound, preferably N, N, N', N'-tetraglycidyl-m-xylylenediamine , 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, Trade name "Tecmoa VG3101L", 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate, N-phenylmaleimide-A Glycidyl acrylate copolymer, One or more of N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac type epoxy compound, and cresol novolac type epoxy compound.

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include polymer compounds and low molecular compounds other than polyglycine and derivatives thereof, and can be selected and used depending on the respective purposes.

For example, the polymer compound may be a polymer compound which is soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics or the alignment property of the liquid crystal alignment film formed, it is preferred to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, anthrone modified polyurethane, and anthrone modified polyester.

Further, as the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant for achieving the object can be cited, 2) an antistatic agent can be cited when it is desired to improve the antistatic property, and 3) when it is desired to improve In the case of the adhesion of the substrate, a decane coupling agent or a titanium coupling agent may be mentioned, and 4) when the oxime imidization is carried out at a low temperature, a ruthenium amide catalyst may be mentioned.

Examples of the decane coupling agent include vinyl trimethoxy decane and vinyl three. Ethoxy decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-Aminophenyltrimethoxydecane, p-Aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3- Aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl Methyldimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercapto Propyltrimethoxydecane, N-(1,3-dimethylbutylene)-3-(triethoxydecyl)-1-propylamine, and N,N'-bis[3-(trimethyl) Oxonium alkyl) propyl] ethylene diamine. A preferred decane coupling agent is 3-aminopropyltriethoxydecane.

Examples of the ruthenium imidization catalyst include trimethylamine, triethylamine, and tripropylamine. An aliphatic amine such as tributylamine; an aromatic amine such as N,N-dimethylaniline, N,N-diethylaniline, methyl substituted aniline or hydroxy substituted aniline; pyridine, methyl group Substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole a cyclic amine such as a methyl-substituted imidazole or a hydroxy-substituted imidazole. The ruthenium amide catalyst is preferably one selected from the group consisting of 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 decane coupling agent added is usually the total weight of the polyamic acid or its derivative. The amount is from 0% by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight.

Generally, oxime imidization relative to the carbonyl group of poly-proline or its derivative The amount of the catalyst added is from 0.01 equivalents to 5 equivalents, preferably from 0.05 equivalents to 3 equivalents.

The amount of other additives added varies depending on the application, usually polylysine or The total weight of the derivative is from 0% by weight to 100% by weight, preferably from 0.1% by weight to 50% by weight.

The polyaminic acid or derivative thereof of the present invention can be formed with a polyimide film The known polyaminic acid or a derivative thereof used is produced in the same manner. The total amount of the tetracarboxylic dianhydride to be charged is preferably approximately equal to the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

The molecular weight of the poly-proline or its derivative of the present invention is in terms of polystyrene The weight average molecular weight (M.W.) is preferably from 7,000 to 500,000, more preferably from 10,000 to 200,000. The molecular weight of the polyaminic acid or its derivative can be determined by measurement by a gel permeation chromatography (GPC) method.

The polyaminic acid of the present invention or a derivative thereof can be confirmed by the following There is a case where a solid component obtained by precipitating with a large amount of poor solvent is analyzed by infrared rays (IR) or nuclear magnetic resonance (NMR). Further, an aqueous solution of a strong base such as KOH or NaOH is used to form a decomposition product of the polyamic acid or a derivative thereof by gas chromatography (GC), high pressure liquid chromatography (HPLC) or gas chromatography- Mass spectrometry (GC-MS) analyzes the extract extracted from the decomposition product using an organic solvent, whereby the monomer used can be determined.

Moreover, for example, coating properties from a liquid crystal alignment agent or the polyamic acid or From the viewpoint of adjusting the concentration of the derivative, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve a polymer component. The solvent widely includes a solvent which is usually used in the production step or use of a polymer component such as polyglycolic acid or soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be one type or a mixture of two or more types.

The solvent may, for example, be a mother liquor of the polyamic acid or a derivative thereof or another solvent for the purpose of improving coatability.

Examples of the aprotic polar organic solvent which is a mother liquid with respect to polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, imidazolidinone, and N-methylene. Indoleamine, N-methylpropionamide, N,N-dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, Lactone such as diethyl acetamide or γ-butyrolactone.

Examples of other solvents for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and ethylene glycol monobutyl ether. Diethylene glycol monoalkyl ether such as alcohol monoalkyl ether, diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol An ester compound such as a propylene glycol monoalkyl ether such as monobutyl ether or a dialkyl malonate such as diethyl malonate or a dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether or an acetate thereof.

Among these compounds, the solvent is particularly preferably N-methyl-2-pyrrolidone, Dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

The concentration of the polylysine in the alignment agent of the present invention is preferably 0.1% by weight~ 40% by weight. When the alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to previously dilute the contained polyamine acid with a solvent.

The concentration of the solid component in the alignment agent of the present invention is not particularly limited. The most suitable value can be selected according to the various coating methods described below. Usually, in order to suppress The unevenness at the time of coating or the pinhole or the like is preferably 0.1% by weight to 30% by weight, and more preferably 1% by weight to 10% by weight based on the weight of the varnish.

The viscosity of the liquid crystal alignment agent of the present invention differs depending on the method of coating, the concentration of polyglycine or a derivative thereof, the type of polyglycine or a derivative thereof used, and the kind and ratio of the solvent. For example, in the case of coating with a printing machine, it is 5 mPa. s~100mPa. s (more preferably 10 mPa.s to 80 mPa.s). If it is less than 5mPa. s, it becomes difficult to obtain a sufficient film thickness; if it exceeds 100 mPa. s, there is a phenomenon that printing unevenness becomes large. In the case of coating by spin coating, it is suitable to be 5 mPa. s~200mPa. s (more preferably 10 mPa.s to 100 mPa.s). In the case of coating using an inkjet coating device, it is suitable to be 5 mPa. s~50mPa. s (more preferably 5 mPa.s to 20 mPa.s). The viscosity of the liquid crystal alignment agent can be measured by a rotational viscosity measurement method, for example, using a rotary viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature is 25 ° C).

The liquid crystal alignment film of the present invention will be described in detail. Liquid crystal of the invention The alignment film is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention described above. The liquid crystal alignment film of the present invention can be obtained by a usual 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 by the steps of forming a coating film of the liquid crystal alignment agent of the present invention, a step of performing heat drying, and a step of heating and calcining. In the liquid crystal alignment film of the present invention, the film obtained by the heating and drying step and the heating and calcining step may be subjected to a rubbing treatment as needed to impart anisotropy. Alternatively, it may be irradiated with light after the coating step, the heating and drying step, or after the heating and calcining step. The light is irradiated to impart anisotropy. Further, it can also be used as a liquid crystal alignment film for vertical alignment (VA) which is not subjected to rubbing treatment.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention onto the substrate of the liquid crystal display element in the same manner as in the production of a normal liquid crystal alignment film. The substrate may be provided with electrodes such as Indium Tin Oxide (ITO), Indium Oxide (In ₂ O ₃ -ZnO, IZO), Indium Ga-Gal Oxide (In-Ga-ZnO ₄ , IGZO) electrodes, or A glass substrate such as a color filter.

A method of applying a liquid crystal alignment agent to a substrate is generally known as a rotator. (spinner) method, printing method, dipping method, dropping method, ink jet method, and the like. These methods can also be equally applied to the present invention.

The heat drying step is generally known to be carried out in an oven or an infrared oven. A method of heat treatment, a method of heat treatment on a hot plate, and the like. The heat drying step is preferably carried out at a temperature within the range in which the solvent can be evaporated, more preferably at a relatively low temperature relative to the temperature of the heating calcination step. Specifically, the heat drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

The heating calcination step may be carried out in the poly-proline or its derivative Perform under the conditions required for water and ring closure reactions. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. These methods can also be equally applied to the present invention. In general, it is preferably carried out at a temperature of from about 100 ° C to about 300 ° C for from 1 minute to 3 hours, more preferably from 120 ° C to 280 ° C, still more preferably from 150 ° C to 250 ° C.

In the method of forming a liquid crystal alignment film of the present invention, in order to make the liquid crystal relatively A well-known formation method such as a rubbing method or a photo-alignment method can be suitably used for the method of imparting anisotropy in one direction in the horizontal and/or vertical direction and imparting anisotropy to the alignment film. In particular, a photo-alignment method can be suitably used.

The liquid crystal alignment film of the present invention using a rubbing method can be shaped as follows The step of applying the liquid crystal alignment agent of the present invention to a substrate, the step of heating and drying the substrate coated with the alignment agent, the step of heating and calcining the film, and the step of subjecting the film to a rubbing treatment.

If the rubbing treatment is compatible with the conventional liquid crystal alignment film The rubbing treatment can be carried out in the same manner, and a sufficient retardation condition can be obtained in the liquid crystal alignment film of the present invention. Preferred conditions are a hair injection amount of 0.2 mm to 0.8 mm, a stage moving speed of 5 mm/sec to 250 mm/sec, and a roll rotation speed of 500 rpm to 2,000 rpm.

Regarding a method of forming a liquid crystal alignment film of the present invention by a photo-alignment method Explain in detail. The liquid crystal alignment film of the present invention using the photo-alignment method can be formed by heating and drying the coating film, irradiating the linearly polarized light or the non-polarized light of the radiation, thereby imparting anisotropy to the coating film, and heating the film. Simmered. Alternatively, it may be formed by heating and drying the coating film, and heating or simmering, and then irradiating the linearly polarized light or the non-polarized light of the radiation. From the viewpoint of self-alignment, the irradiation step of the radiation is preferably performed before the heating calcination step.

In addition, in order to improve the liquid crystal alignment ability of the liquid crystal alignment film, it is also possible to Straight or non-polarized light that radiates radiation while the coating film is heated. The irradiation of the radiation may be a step of heating and drying the coating film or a step of heating and calcining. This can also be carried out between the heat drying step and the heating calcination step. The heating and drying temperature in this step is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. Further, the heating calcination temperature in this step is preferably in the range of 30 ° C to 300 ° C, and more preferably in the range of 50 ° C to 250 ° C.

For the radiation, for example, ultraviolet light or visible light containing light having a wavelength of 150 nm to 800 nm, and ultraviolet light containing light having a wavelength of 300 nm to 400 nm can be used. Moreover, linear or unpolarized light can be used. The light is not particularly limited as long as it imparts a liquid crystal alignment ability to the coating film, and is preferably linearly polarized when it is desired to exhibit a strong alignment regulating force to the liquid crystal.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even with low-energy light irradiation. The irradiation amount in the irradiation step is preferably linearly polarized ^{0.05J / cm 2 ~ 20J / cm} 2, more preferably at ^{0.5J / cm 2 ~ 10J / cm} 2. Further, the wavelength of the linearly polarized light is preferably 200 nm to 400 nm, and more preferably 300 nm to 400 nm. The irradiation angle of the linearly polarized light with respect to the film surface is not particularly limited, and when it is desired to exhibit a strong alignment regulating force to the liquid crystal, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. Further, the liquid crystal alignment film of the present invention can align the liquid crystal in a direction perpendicular to the polarization direction of the linearly polarized light by irradiating the linearly polarized light.

In the case where the pretilt angle is to be expressed, the light irradiated to the film may be linearly polarized as described above, or may be unpolarized. To show the case where the pretilt angle of the light irradiation amount of the irradiated film is preferably ^{0.05J / cm 2 ~ 20J / cm} 2, particularly preferably of ^{0.5J / cm 2 ~ 10J / cm} 2, wavelength It is preferably 250 nm to 400 nm, and particularly preferably 300 nm to 380 nm. When the pretilt angle is to be expressed, the irradiation angle of the light irradiated to the film with respect to the film surface is not particularly limited, and is preferably 30 to 60 degrees from the viewpoint of shortening the alignment treatment time.

The light source used in the step of linearly polarizing or non-polarizing radiation to irradiate radiation can be used without limitation: ultra high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, deep ultraviolet (Heep UV) lamp, halogen lamp, metal halide lamp (metal halide) Lamp), high-power metal halide lamp, xenon lamp, mercury xenon lamp, excimer lamp, KrF excimer laser, fluorescent lamp, light emitting diode (LED) lamp, sodium lamp, microwave excitation without electrode Lights, etc.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further including other steps than the above steps. For example, the liquid crystal alignment film of the present invention does not require a step of washing the film after the smoldering or radiation irradiation with the cleaning liquid, but a cleaning step may be provided in the case of other steps.

The cleaning method using the cleaning liquid may be, for example, brushing, jet spray, steam cleaning or ultrasonic cleaning. These methods can be performed separately or in combination. The cleaning liquid may be pure water, various alcohols such as methanol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as dichloromethane, and ketones such as acetone and methyl ethyl ketone. However, it is not limited to these cleaning solutions. Of course, these cleaning solutions require the use of a thoroughly purified cleaning fluid with less impurities. This cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to improve the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment by heat or light may be used before and after the heating calcination step, before and after the rubbing step, or before or after the polarized or unpolarized radiation irradiation. In the annealing treatment, the annealing temperature is from 30 ° C to 180 ° C, preferably from 50 ° C to 150 ° C, and the time is preferably from 1 minute to 2 hours. Further, examples of the annealing light used in the annealing treatment include a UV lamp, a fluorescent lamp, an LED lamp, and the like. Light irradiation amount is preferably ^{0.3J / cm 2 ~ 10J / cm} 2.

The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm. ~300 nm, more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by using a known film thickness measuring device such as a step meter or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having a particularly large alignment direction opposite sex. The size of the anisotropy can be evaluated by a method using polarized light described in JP-A-2005-275364 or the like. Further, evaluation can be carried out by a method using ellipsometry as shown in the following examples. In detail, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film becomes larger in proportion to the degree of alignment of the polymer main chain. That is, those having a large retardation value have a large degree of alignment, and in the case of using a liquid crystal alignment film, it is considered that the alignment film having greater anisotropy has a large alignment restriction force with respect to the liquid crystal composition. .

The liquid crystal alignment film of the present invention is characterized in that it has less coloration and high transmittance. The transmittance can be evaluated using an ultraviolet-visible spectrophotometer. In order to exhibit good display characteristics, the transmittance calculated from the average value of the absorbances of 380 nm to 780 nm is preferably 85% or more, and more preferably 87% or more.

The liquid crystal alignment film of the present invention can be suitably used for a liquid crystal in a transverse electric field mode In the display component. In the case of a liquid crystal display element used in a lateral electric field mode, the smaller the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state, and the higher the contrast. The Pt angle is preferably 0.1 or less.

The alignment film of the present invention is used for the alignment of the liquid crystal composition for liquid crystal displays. In addition to the way, it can also be used in the alignment control of optical compensation materials or all other liquid crystal materials. Moreover, the alignment film of the present invention has a large anisotropy and thus can be used alone in optical compensation materials.

The liquid crystal display element of the present invention will be described in detail.

The present invention provides a liquid crystal display device comprising a pair of substrates disposed oppositely, and electrodes formed on one or both surfaces of the surfaces facing the pair of substrates, respectively, formed on each of the pair of substrates A liquid crystal alignment film of a facing surface, a liquid crystal display element formed of a liquid crystal layer between the pair of substrates, wherein the liquid crystal alignment film is an alignment film of the present invention.

If the electrode is an electrode that can be formed on one side of the substrate, there is no special limited. Examples of such an electrode include a vapor deposited film of ITO or metal. Moreover, the electrodes may be formed on the entire surface of one of the faces of the substrate, for example, may also be formed into a desired shape that is patterned. The desired shape of the electrode may, for example, be a comb type or a zigzag structure. The electrodes may be formed on one of the pair of substrates or may be formed on the two substrates. The form of formation of the electrode differs depending on the type of the liquid crystal display element. For example, in the case of an IPS type liquid crystal display element, an electrode is disposed on one of the pair of substrates; in other liquid crystal display elements In the case, electrodes are disposed on both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is the one facing the surface on which the liquid crystal alignment film is formed The substrate is formed by sandwiching a form of a liquid crystal composition. In the formation of the liquid crystal layer, spacers which are appropriately spaced apart may be formed by using fine particles or a resin thin plate or the like between the pair of substrates.

The liquid crystal composition is not particularly limited, and dielectric anisotropy can be used. (dielectric anisotropy) is a positive or negative liquid crystal composition. A preferred liquid crystal composition having a positive dielectric anisotropy is exemplified by Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent Laid-Open No. Hei 8-157826. Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Laid-Open No. Hei 9-241644 (EP 885 272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1), Japan Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP885271A1), Japanese Patent Laid-Open No. Hei 10-204016 (EP844229A1), Japanese Patent Laid-Open No. Hei 10 The liquid crystal composition described in Japanese Laid-Open Patent Publication No. Hei. No. 2001-48822, and the like.

It is also possible to add a liquid crystal composition having positive or negative dielectric anisotropy. More than one kind of optically active compound is used.

The liquid crystal composition in which the dielectric anisotropy is negative will be described. negative The liquid crystal composition of the dielectric anisotropy is, for example, a composition containing at least one liquid crystal compound selected from the group consisting of liquid crystal compounds represented by the following formula (NL-1) as the first component.

Here, R ^1a and R ^{2a are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon having at least one hydrogen replaced by fluorine. The number is 2 to 12 alkenyl groups; ring A ² and ring B ^{2 are} independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2 , 5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1, 4-phenylene, 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl, Or 7,8-difluorochroman-2,6-diyl, wherein at least one of ring A ² and ring B ² is 2,3-difluoro-1,4-phenylene, 2 -fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, or 7,8-difluorochroman-2,6-di Z ^{1 is} independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -COO-, or -CF ₂ O-; j is 1, 2, or 3.

Specific examples of the liquid crystal compound of the formula (NL-1) include compounds represented by the following formula (NL-1-1) to formula (NL-1-32).

[化155]

[化156]

[化157]

Here, R ^1a and R ^{2a are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon having at least one hydrogen replaced by fluorine. The number is 2 to 12 alkenyl groups. In order to improve the stability against ultraviolet rays or heat, R ^1a and R ^2a are preferably an alkyl group having 1 to 12 carbon atoms, or R ^1a and R ^{2a are} preferred in order to increase the absolute value of dielectric anisotropy. It is an alkoxy group having a carbon number of 1 to 12.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to lower the viscosity, a more preferred alkyl group is an ethyl group, a propyl group, a butyl group, a pentyl group or a heptyl group.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. In order to lower the viscosity, a more preferred alkoxy group is a methoxy group or an ethoxy group.

Preferred alkenyl groups are ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3- Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl for decreasing the viscosity. The preferred steric configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. It is preferred to use an alkenyl group such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl or 3-hexenyl for the purpose of lowering the viscosity and the like. It is trans. Among the alkenyl groups such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis is preferred. Among these alkenyl groups, a linear alkenyl group is preferred from the branch.

Preferred examples of the alkenyl group in which at least one hydrogen is substituted by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5, 5-difluoro-4-pentenyl, and 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, a more preferable example is 2,2-two. Fluorovinyl, and 4,4-difluoro-3-butenyl.

Ring A ² and Ring B ^{2 are} independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene Base, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3- Chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl, 7,8-difluorochroman-2,6 a diyl group, wherein at least one of ring A ² and ring B ² is 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4-phenylene, 2 , 3-difluoro-6-methyl-1,4-phenylene, 7,8-difluorochroman-2,6-diyl, when j is 2 or 3, any two rings A ² may The same can be different. In order to increase the dielectric anisotropy, preferred ring A ² and ring B ² are 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl, respectively, in order to achieve viscosity. reduction, preferably a cycloalkyl ring a ² and B ² are 1,4-cyclohexylene.

Ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ^{22 are} independently 1,4-cyclohexylene or 1,4-phenylene. In order to lower the viscosity, preferred ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each a 1,4-cyclohexylene group.

Z ¹ and Z ^{2 are} independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -COO-, -CF ₂ O-, and when j is 2 or 3, any two Z ¹ may be the same Alternatively, when k is 2 or 3, any two Z ² may be the same or different, and in order to improve dielectric anisotropy, preferred Z ¹ and Z ² are -CH ₂ O-, in order to lower the viscosity, Preferred Z ¹ and Z ² are single bonds.

Z ¹¹ and Z ^{12 are} independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, or -COO-. In order to improve dielectric anisotropy, preferred Z ¹¹ and Z ¹² are -CH ₂ O-, and in order to lower the viscosity, preferred Z ¹¹ and Z ¹² are single bonds.

j is 1, 2, or 3. In order to lower the lower limit temperature, it is preferable that j is 1, and in order to increase the upper limit temperature, it is preferable that j is 2.

In the liquid crystal composition having negative dielectric anisotropy, the compound (NL-1) which is preferable as the first component is a compound (NL-1-1), a compound (NL-1-4), and a compound ( NL-1-7) or compound (NL-1-32).

The preferred example of the liquid crystal composition having a negative dielectric anisotropy is exemplified in Japanese Patent Laid-Open No. Hei 57-114532, Japanese Patent Laid-Open No. Hei 2-4725, and Japanese Patent Laid-Open No. Hei-4-224885. Japanese Patent Laid-Open No. Hei 8-40953, Japanese Patent Laid-Open No. Hei 8-104869, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Laid-Open No. Hei No. Hei 10-168453, Japanese Patent Laid-Open No. Hei 10-236989 Japanese Patent Laid-Open No. Hei 10-236990, Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, No. 10-237000 Japanese Patent Laid-Open No. Hei 10-237004, Japanese Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, and Japanese Patent Laid-Open No. Hei 10-237076 Japanese Patent Laid-Open No. Hei 10-237448 (EP967261A1), Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. Hei 10-29194 Japanese Patent Laid-Open No. Hei 11-029581, Japanese Patent Laid-Open No. Hei 11-080049, Japanese Patent Laid-Open No. Hei No. 2000-256307, Japanese Patent Laid-Open No. 2001-019965, and Japanese Patent Laid-Open No. 2001- Bulletin No. 072626, Japanese Patent Laid-Open No. 2001-192657, Japan Japanese Patent Laid-Open Publication No. 2010-037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Patent Publication No. 2010-537010, Japanese Patent Laid-Open No. 2012-077201, Japanese Patent Laid-Open No. 2009 A liquid crystal composition disclosed in Japanese Laid-Open Patent Publication No. 084362.

Moreover, for example, from the viewpoint of improving the alignment, for example, the present invention Additives may be further added to the liquid crystal composition used in the element. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

In order to improve the alignment of liquid crystals, the photopolymerizable monomer or oligomer is optimal. The structure selected is a structure of (PM-1-1) to (PM-1-6).

In order to express the effect of determining the tilt direction of the liquid crystal after polymerization, the light is concentrated. The conjugated monomer or oligomer is desirably 0.01% by weight or more. Moreover, in order to make the alignment effect of the polymer after polymerization suitable, or to avoid ultraviolet irradiation, The reacted monomer or oligomer is eluted into the liquid crystal, preferably 30% by weight or less.

To impart a twist angle in order to cause the spiral structure of the liquid crystal, to be mixed in the composition An optically active compound. Examples of such compounds are the compound (PAC-1-1) to the compound (PAC-1-4). A preferred ratio of the optically active compound is 5% by weight or less. A more preferred ratio is in the range of 0.01% by weight to 2% by weight.

To prevent specific resistance due to heating in the atmosphere (specific The resistance is lowered, or in order to maintain a large voltage holding ratio not only at room temperature but also at a high temperature after using the element for a long period of time, the antioxidant is mixed in the liquid crystal composition.

[化160]

A preferred example of the antioxidant is a compound having an integer of w of 1 to 10. (AO-1) and so on. In the compound (AO-1), preferred w is 1, 3, 5, 7, or 9. More preferably w is 1 or 7. The compound (AO-1) having a w of 1 has a large volatility, and therefore is effective in preventing a decrease in specific resistance due to heating in the atmosphere. The compound (w-1) having a w of 7 has a small volatility, so that after a component is used for a long period of time, a large voltage holding ratio can be effectively maintained not only at room temperature but also at a high temperature. In order to obtain the effect, the preferable ratio of the antioxidant is 50 ppm or more, and in order not to lower the upper limit temperature or to increase the lower limit temperature, the preferable ratio of the antioxidant is 600 ppm or less. A more preferred ratio is in the range of 100 ppm to 300 ppm.

A preferred example of the ultraviolet absorber is a benzophenone derivative, benzoic acid An ester derivative, a triazole derivative or the like. Light stabilizers such as amines having steric hindrance are also preferred. In order to obtain the effect, a preferable ratio of these absorbents or stabilizers is 50 ppm or more, and a preferable ratio of these absorbents or stabilizers is 10000 ppm or less in order not to lower the upper limit temperature or to increase the lower limit temperature. A more preferred ratio is in the range of 100 ppm to 10,000 ppm.

In order to fit the components of the guest host (GH) mode, in the composition A dichroic dye such as an azo dye or an anthraquinone dye is mixed. A preferred ratio of the pigment is in the range of 0.01% by weight to 10% by weight.

In order to prevent bubbling, dimethyl oxime oil, methyl phenyl group is mixed in the composition. Defoamer such as oyster sauce. In order to obtain the effect, the preferable ratio of the antifoaming agent is 1 ppm or more, and a preferable ratio of the antifoaming agent is 1000 ppm or less in order to prevent display failure. A more preferred ratio is in the range of 1 ppm to 500 ppm.

In order to be suitable for polymer sustained alignment, A component of the PSA) mode in which a polymerizable compound can be mixed in the composition. Preferable examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone, etc. A compound having a polymerizable group. A particularly preferred example is a derivative of acrylate or methacrylate. Examples of such compounds are the compound (PM-2-1) to the compound (PM-2-9). In order to obtain the effect, a preferable ratio of the polymerizable compound is about 0.05% by weight or more, and a preferable ratio of the polymerizable compound is about 10% by weight or less in order to prevent display defects. A more preferred ratio is in the range of from about 0.1% by weight to about 2% by weight.

[化161]

Here, R ^3a , R ^4a , R ^5a , and R ^{6a are} independently propylene fluorenyl or methacryl fluorenyl groups, and R ^7a and R ^{8a are} independently hydrogen, halogen, or an alkyl group having 1 to 10 carbon atoms, Z. ¹³ , Z ¹⁴ , Z ¹⁵ , and Z ^{16 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one -CH ₂ - may also be substituted by -O- or -CH=CH-, s, t And u are independent of 0, 1, or 2.

As a substance which is required to generate radicals or ions and initiate chain polymerization, a polymerization initiator may be mixed. For example, Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) as a photopolymerization initiator (Japan Ciba Limited) The company (Ciba Japan KK) is suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1% by weight to 5% by weight. It is particularly preferable to include a photopolymerization initiator in the range of 1% by weight to 3% by weight.

In the radical polymerization system, the polymerization inhibitor may be mixed for the purpose of rapidly reacting with a radical generated by a polymerization initiator or a monomer to change to a stable radical or a neutral compound, and as a result, the polymerization reaction is carried out. stop. The polymerization inhibitors can be classified into several kinds in structure. One of them is a self-stabilizing radical such as tri-p-nitrophenylmethyl or di-p-fluorophenylamine, and the other is easily reacted with a radical existing in the polymerization system to become The stable free radicals are represented by nitro, nitroso, amino, polyhydroxy compounds and the like. Representative examples of the latter include hydroquinone, dimethoxybenzene, and the like. In order to obtain the effect, a preferable ratio of the polymerization inhibitor is 5 ppm or more, and a preferable ratio of the polymerization inhibitor is 1000 ppm or less in order to prevent display defects. A more preferred ratio is in the range of 5 ppm to 500 ppm.

In the liquid crystal display device of the present invention, a liquid crystal composition having negative dielectric anisotropy is used, whereby a liquid crystal display element having excellent afterimage characteristics and excellent alignment stability can be provided.

[Examples]

Hereinafter, the present invention will be described by way of examples. In addition, the evaluation methods and compounds used in the examples are as follows.

<evaluation method> Viscosity

The measurement was performed at 25 ° C using a viscometer (manufactured by Toki Sangyo Co., Ltd., TV-22).

2. Weight average molecular weight (M.W.)

The weight average molecular weight of polylysine was determined by a GPC method using a 2695 separation module-2414 differential refractometer (manufactured by Waters), and was obtained by polystyrene conversion. The obtained polylysine was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100:weight ratio) to a polyamid acid concentration of about 2% by weight. The column was measured using HSPgel RT MB-M (manufactured by Waters), and the mixed solution was used as a developing solvent under the conditions of a column temperature of 50 ° C and a flow rate of 0.40 mL/min. Standard polystyrene is TSK standard polystyrene manufactured by Tosoh Corporation.

3. Pencil hardness

According to the JIS standard "JIS-K-5400, 8.4, pencil erasing test" method. The result is expressed by the hardness of the pencil lead. If the pencil hardness is low, peeling or reduction is likely to occur, and if the value is more than 2H, an alignment film which is less likely to be cut or the like is obtained.

4. Determination of retardation and film thickness of alignment film

Using Spectroscopic Ellipsometer M-2000U (J.A. Worland Co., Ltd. (J.A. Woollam Co. Inc.) manufactured). In the case of the photo-alignment film of the present embodiment, the retardation value of the film becomes larger in proportion to the degree of alignment of the polymer main chain. That is, those having a large retardation value have a large alignment degree, and the liquid crystal alignment ability is high. If the value is more than 15, an alignment film having good display characteristics is obtained.

5. Resistance to reduction

In the liquid crystal cell, the test was performed using a test bar at a load of 1000 g once/second for 1 minute, and the presence or absence of film reduction was observed using a microscope.

6. Pretilt angle measurement

It was measured according to the crystal rotation method.

7. Voltage retention rate

This was carried out by the method described in "Water Margin, Proceedings of the 14th Liquid Crystal Symposium, p. 78 (1988)". A rectangular wave having a wave height of ±5 V was applied to the cell to measure. The measurement was carried out at 60 °C. This value is an index indicating how much the applied voltage remains after the frame period. If the value is 100%, it means that all charges are held.

8. Determination of ion amount in liquid crystal (ion density)

The liquid crystal physical property measurement system 6254 type manufactured by Dongyang Technology Co., Ltd. was used for measurement according to the method described in "Applied Physics", Vol. 65, No. 10, and 1065 (1996). The triangular wave having a frequency of 0.01 Hz was used for measurement at a voltage range of ±10 V and a temperature of 60 ° C (the area of the electrode was 1 cm ² ). If the ion density is large, problems such as burn marks due to ionic impurities are likely to occur. That is, the ion density is a physical property value which is an index for predicting the occurrence of burn marks.

<tetracarboxylic dianhydride>

Acid dianhydride (1-1): tetracarboxylic dianhydride obtained by the synthesis route of Synthesis Example 1.

Acid dianhydride (1-5): tetracarboxylic dianhydride obtained by the synthesis route of Synthesis Example 2

Acid dianhydride (1-6): tetracarboxylic dianhydride obtained according to the synthesis route of Synthesis Example 2

Acid dianhydride (1-28): tetracarboxylic dianhydride obtained according to the synthetic route of Synthesis Example 2.

Acid dianhydride (AN-2-1): 1,2,3,4,-cyclobutane tetracarboxylic dianhydride

Acid dianhydride (AN-3-2): pyromellitic dianhydride

Acid dianhydride (AN-4-1): 3,3',4,4'-bicyclohexane tetracarboxylic dianhydride

Acid dianhydride (AN-4-17, m=8): 1,8-bis(3,4-dicarboxylic acid phenyl) octane dianhydride

Acid dianhydride (AN-4-30): N,N'-(1,4-phenylene) bis(1,3-dioxo octahydroisobenzofuran-5-carboxamide)

Acid dianhydride (AN-7-2): 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

<Diamine>

Diamine (DI-1-3): 1,6-diaminohexane

Diamine (DI-2-1): 1,4-cyclohexanediamine

Diamine (DI-3-1): 4,4'-diaminodicyclohexylmethane

Diamine (DI-4-1): 1,4-phenylenediamine

Diamine (DI-5-1, m=4): 4,4'-diaminodiphenylbutane

Diamine (DI-5-9): 4,4'-diaminodiphenyl ether

Diamine (DI-5-29): biphenyl-4,4'-diamine

Diamine (DI-5-30, k=2): N,N'-bis(4-aminophenyl)-N,N'-dimethylethylenediamine

Diamine (DI-6-7): 4,4'-p-phenylene diphenylamine

Diamine (DI-7-3, m=3, n=1): 1,3-bis(4-((4-aminophenyl)methyl)phenyl)propane

Diamine (DI-8-1): 2,6-diaminonaphthalene

Diamine (DI-12-1): 1,3-bis(3-aminopropyl)tetramethyldioxane

Diamine (DI-13-1): 4,4'-N,N'-bis(4-aminophenyl)pyridazine

Diamine (DI-16-1): 1-(4-Aminophenyl)-1H-indole-5-amine

Diamine (PDI-7-a): 4,4'-diaminoazobenzene

Diamine (PDI-8-a): 4,4'-bis[(4-aminophenyl)methyl]azobenzene

Diamine (PDI-9): 4-Aminophenyl-4-aminocinnamate

Diamine (PDI-11): 4,4'-diaminochalcone

<solvent>

N-methyl-2-pyrrolidone: NMP

Butyl cellosolve (ethylene glycol monobutyl ether): BC

<additive>

Additive (Ad1): 1,3-bis(4,5-dihydro-oxazolyl)benzene

Additive (Ad2): N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Additive (Ad3): 3-aminopropyltriethoxydecane

[Example 1] Synthesis of Compound (1-1)

<Phase 1; Azide>

In a three-necked flask equipped with a thermometer and a nitrogen introduction tube, diethyl 4-(4-bromobutyl) phthalate (12.1 g, 34.0 mol) was placed, and 70 mL of DMF was added. Sodium azide (2.4 g, 37.4 mmol) was added thereto. Thereafter, the solution was warmed to 60 ° C, and stirred at the same temperature for 3 hours under a nitrogen atmosphere. The reaction solution was added to 400 mL of water, and extraction was performed twice with 300 mL of heptane. After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure to give diethyl 4-(4-azidobutyl)-phthalate (yield: 10.0 g, yield: 92%).

<Phase 2; formation of triazole ring>

Put in the first stage in a three-necked flask equipped with a thermometer and a nitrogen inlet tube. Diethyl 4-(4-azidobutyl)phthalate (10.0 g, 31.3 mmol), dimethyl 4-ethynyl-phthalate (7.5 g, 34.4 mmol), 50 mL Dichloromethane with 50 mL of water. After stirring at room temperature to dissolve the compound, copper sulfate pentahydrate (0.78 g, 3.1 mmol) and sodium L-ascorbate (1.2 g, 6.3 mmol) were added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 50 mL of water, and extracted twice with 100 mL of toluene. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to give a crude material. The crude was purified by column chromatography to give the compound (yield: 15.7 g, yield: 93%).

<stage 3; hydrolysis>

The compound (15.7 g, 29.2 mmol) obtained in the second stage was placed in a three-necked flask equipped with a thermometer and a reflux tube, and 30 mL of tetrahydrofuran was added. To the solution was added 30 mL of a 20% aqueous solution of sodium hydroxide, and the mixture was stirred under reflux for 2 hours. The reaction solution was allowed to stand to room temperature, and the tetrahydrofuran was distilled off with an evaporator, and then 6N HCl was added until the pH became 1.0. The precipitated crystals were taken out by suction filtration, and washed with purified water to give the compound (yield: 14.6 g, yield: 110%).

[Chem. 165]

<4th stage; acidification>

The compound (13.6 g, 30.0 mmol) obtained in the third stage and 68 mL of acetic anhydride were placed in a three-necked flask equipped with a thermometer and a reflux tube, and stirred under reflux for 6 hours. After the reaction solution was allowed to stand to room temperature, the precipitated crystals were removed by suction filtration, and washed with toluene to give Compound (1-1) (yield: 9.6 g, yield: 77%).

¹ H-NMR (500MHz, CDCl ₃ ): δ 8.99 (s, 1H), 8.49-8.45 (m, 2H), 8.17 (d, J = 7.5 Hz, 1 H), 8.00 (d, J = 7.8 Hz, 1H), 7.97 (s, 1H), 7.87-7.84 (m, 1H), 4.52 (t, J = 7 Hz, 2H), 2.90 (t, J = 7.6 Hz, 2H), 1.97-1.90 (m, 2H) , 1.73-1.65 (m, 2H); Melting point: 200.2 ° C ~ 201.9 ° C.

[Example 2] Synthesis of Compound (1-5)

<Phase 1; Azide>

In a 100 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 1,6- Dibromohexane (5.0 g, 20.5 mmol) was added to 25 mL of DMF. Sodium azide (2.9 g, 45.6 mmol) was added thereto. Thereafter, the solution was heated to 60 ° C, and stirred at the same temperature for 3 hours under a nitrogen atmosphere. The reaction solution was added to 200 mL of water, and extraction was performed twice with 100 mL of heptane. After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure to give 1,6-diazidehexane (yield: 3.2 g, yield: 93%).

<Phase 2; formation of triazole ring>

Put 1,6-diazidylhexane (2.2 g, 13.1 mmol) obtained in the first stage, dimethyl 4-ethynyl-phthalate (5.7 g, 26.2 mmol), and add 5 mL of two Methyl chloride with 5 mL of water. After stirring at room temperature to dissolve the compound, copper sulfate pentahydrate (0.16 g, 0.65 mmol) and sodium L-ascorbate (0.26 g, 1.3 mmol) were added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 50 mL of water, and extracted twice with 50 mL of toluene. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to give a crude material. The crude was purified by column chromatography to give the compound (yield: 3.2 g, yield 93%).

<stage 3; hydrolysis>

Add the second stage of the three-necked flask equipped with a thermometer and a return tube. Compound (6.8 g, 11.3 mmol) was added to 10 mL of tetrahydrofuran. 10 mL of a 20% aqueous solution of sodium hydroxide was added to the solution, and the mixture was stirred under reflux for 2 hours. The reaction solution was allowed to stand to room temperature, and the tetrahydrofuran was distilled off with an evaporator, and then 6N HCl was added until the pH became 1.0. The precipitated crystals were taken out by suction filtration, and washed with purified water and methanol to give the following compound (yield: 5.8 g, yield: 94%).

<4th stage; acidification>

The compound (5.8 g, 10.6 mmol) obtained in the third stage and 29 mL of acetic anhydride were placed in a three-necked flask equipped with a thermometer and a reflux tube, and stirred under reflux for 6 hours. The reaction solution was allowed to stand to room temperature, and the precipitated crystals were taken by suction filtration, and washed with toluene to give Compound (1-5) (yield: 4.9 g, yield: 91%).

¹ H-NMR (500MHz, CDCl ₃ ): δ 9.01 (s, 2H), 8.50 - 8.46 (m, 4H), 8.17 (d, J = 8.4 Hz, 2H), 4.46 (t, J = 7 Hz, 4H) , 1.95-1.87 (m, 4H), 1.39-1.32 (m, 4H); melting point: 254.3 ° C ~ 256.5 ° C.

[Example 3] Synthesis of Compound (1-6)

<First stage; formation of triazole ring>

Put 1,6-diazidehexane (2.2 g, 13.1 mmol), dimethyl 4-ethynyl-1,2-cyclohexanedicarboxylate (6.2 g, 27.5 mmol), add 20 ml of dichloro Methane with 20 ml of water. After stirring at room temperature to dissolve the compound, copper sulfate pentahydrate (0.16 g, 0.65 mmol) and sodium L-ascorbate (0.26 g, 1.3 mmol) were added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 50 ml of water, and extracted twice with 50 ml of toluene. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to give a crude material. The crude was purified by column chromatography to give the compound (yield: 7.8 g, yield 97%).

<stage 2; hydrolysis>

The compound (7.0 g, 11.3 mmol) obtained in the first stage was placed in a three-necked flask equipped with a thermometer and a reflux tube, and 10 mL of tetrahydrofuran was added. In the dissolution 10 mL of a 20% aqueous solution of sodium hydroxide was added to the solution, and the mixture was stirred under reflux for 2 hours. The reaction solution was allowed to stand to room temperature, and the tetrahydrofuran was distilled off with an evaporator, and then 6N HCl was added until the pH became 1.0. The precipitated crystals were taken out by suction filtration, and washed with purified water and methanol to give the following compound (yield: 6.0 g, yield: 94%).

<3rd stage; acidification>

The compound (5.9 g, 10.6 mmol) obtained in the second stage was placed in a three-necked flask equipped with a thermometer and a reflux tube, and 30 ml of acetic anhydride was added thereto, and the mixture was stirred under reflux for 6 hours. The reaction solution was allowed to stand to room temperature, and the precipitated crystals were taken by suction filtration, and washed with toluene to give Compound (1-6) (yield: 4.7 g, yield: 84%).

[Example 4] Synthesis of Compound (1-28)

<Phase 1; Azide>

1,4-Dibromobutane (6.5 g, 30.0 mmol) was placed in a 100 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, and 100 ml of DMF was added. Sodium azide (4.2 g, 65.0 mmol) was added thereto. Thereafter, the solution was warmed to 60 ° C, and stirred at the same temperature for 3 hours under a nitrogen atmosphere. The reaction solution was added to 500 ml of water, and extraction was carried out twice with 300 ml of heptane. After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure to give 1,4-diazide-butane (yield: 4.0 g, yield: 95%).

<Phase 2; formation of triazole ring>

In a three-necked flask equipped with a thermometer and a nitrogen introduction tube, 1,4-diazidobutane (2.8 g, 20.0 mmol) obtained in the first stage, and 4-(5-hexynyl)-o-benzene were placed. Dimethyl diformate (11.1 g, 40.4 mol) was added to 40 ml of dichloromethane and 40 ml of water. After stirring at room temperature to dissolve the compound, copper sulfate pentahydrate (0.5 g, 2.0 mol) and sodium L-ascorbate (0.8 g, 4.0 mol) were added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 100 ml of water, and extracted twice with 100 ml of toluene. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to give a crude material. The crude was purified by column chromatography to give the compound (yield: 13.2 g, yield: 96%).

<stage 3; hydrolysis>

The compound obtained in the second stage (11.9 g, 17.3 mol) was placed in a three-necked flask equipped with a thermometer and a reflux tube, and 50 ml of tetrahydrofuran was added. To the solution was added 16 ml of a 20% aqueous solution of sodium hydroxide, and the mixture was stirred under reflux for 2 hours. The reaction solution was allowed to stand to room temperature, and the tetrahydrofuran was distilled off with an evaporator, and then 6N HCl was added until the pH became 1.0. The precipitated crystals were taken out by suction filtration, and washed with purified water to obtain the compound (yield: 10.1 g, yield: 92%).

<4th stage; acidification>

The compound (9.6 g, 15.2 mol) obtained in the third stage and 100 ml of acetic anhydride were placed in a three-necked flask equipped with a thermometer and a reflux tube, and stirred under reflux for 6 hours. After the reaction solution was allowed to stand to room temperature, the precipitated crystals were removed by suction filtration, and washed with toluene to give compound (1-28) (yield: 8.9 g, yield 98%).

[Example 5] <Synthesis of polylysine>

3.3144 g of Example 1 was weighed in a three-necked flask equipped with a stirring blade and a thermometer. The compound (1-1) synthesized in the above and 1.6856 g of the compound (PDI-7-a) were charged with 65 g of N-methyl-2-pyrrolidone (NMP). The mixture was stirred at room temperature for 12 hours, and 30 g of ethylene glycol monobutyl ether (BC) was added thereto, and stirring was continued at room temperature for 24 hours to obtain a solution having a polyglycine concentration of 5% by weight. This solution was used as varnish A-1. The polyamine acid in the varnish had a weight average molecular weight (M.W.) of 74,000.

[Examples 6 to 34]

As shown in the following Table 1, a varnish having a polyamine concentration of 5% by weight of the polymer for forming a photo-alignment film was obtained by the method described in Example 5. ( ) indicates the percentage of moles in the case where the total amount of raw materials is set to 100 mol% (mol%). In Examples 32 to 34, after the varnish was prepared in the same manner as described above, The preparation was carried out by adding an additive (Ad1) to an additive (Ad3) in a proportion of 10 parts by weight per 100 parts by weight of the polymer. Example 5 is also disclosed again in Table 1.

*) 10 parts by weight per 100 parts by weight of polymer

[Comparative Example 1 to Comparative Example 3]

As shown in the following Table 2, a varnish having a polyglycine concentration of 5% by weight of the polymer for forming a photo-alignment film was obtained by the method described in Example 5. ( ) indicates the percentage of mol (mol%) in the case where the total amount of the raw materials is 100 mol%.

[Table 2]

[Example 35]

1.0 g of varnish A-1 was weighed in a sample bottle, and NMP/BC = 1/1 (weight ratio) was added to make it 1.67 g. The 3% by weight polylysine solution was dropped on a transparent glass substrate and applied by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then a multi-light source (Multi Light) ML-501C/B manufactured by Oxtail Motor was used, and the substrate was vertically oriented. Linear polarized light that is irradiated with ultraviolet rays by a polarizing plate. At this time, the exposure energy used Shelter motor (shares) for producing an ultraviolet integrated light amount meter UIT-150 (light receiver: UVD-S365) and the determination of the amount of light to be 1.3J / cm at a wavelength of 365nm ² ± 0.1J / cm ² The way to adjust the exposure time. The substrate after the light irradiation was subjected to heat treatment at 210 ° C for 15 minutes in an oven to obtain an alignment film A-1 having a film thickness of about 100 nm. The retardation of the alignment film A-1 was measured and found to be 19.8 nm. Further, the pencil hardness of the obtained alignment film A-1 was measured and found to be 3H.

[Examples 36 to 64] and [Comparative Examples 4 to 6]

As for varnish A-2~ varnish A-30 and varnish B-1~ varnish B-3, According to the operation of Example 35, the alignment film A-2 to the alignment film A-30 and the alignment film B-1 to the alignment film B-3 were formed, and the retardation and the pencil hardness were measured in accordance with the method of Example 35. These results are shown in Tables 3 and 4. The results of Example 35 are also disclosed again in Table 3.

It can be seen that the alignment film A-1~ obtained from varnish A-1 to varnish A-30 In Film A-30, there was a large retardation and a high pencil hardness in all of the alignment films. In the alignment film B-1 obtained from the varnish B-1, although the film has a large retardation, the pencil hardness is low. Further, it can be seen that in the alignment film obtained from the varnish B-2 and the varnish B-3, it cannot be said that the pencil hardness is sufficiently high and the retardation is small.

[Example 65]

An alignment film A-1 having a film thickness of about 100 nm was obtained by the method according to Example 35 except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one surface. Two sheets of the alignment film formed on the ITO electrode were formed with the alignment film facing each other, and a gap for injecting the liquid crystal composition was placed between the opposing alignment films to bond them. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films are made parallel. A positive liquid crystal composition A shown below was injected into the cell to prepare a liquid crystal cell A-1 (liquid crystal display element) having a cell thickness of 3.5 μm (Fig. 1).

<Positive liquid crystal composition A>

Physical property values: NI is 100.1 ° C; Δ ε is 5.1; Δ n is 0.093; η is 25.6 mPa. s.

The liquid crystal cell A-1 was visually observed, and as a result, no liquid crystal was observed at all. The injection inlets are arranged in a radial so-called flow alignment. When the polarizing microscope is in the state of a crossed Nicol prism, when the liquid crystal cell A-1 is rotated, a clear state and a dark state are observed. The pretilt angle of the liquid crystal cell A-1 (hereinafter sometimes abbreviated as Pt angle) was 0.1°. Further, VHR (voltage holding ratio) and ion density were 99.0% (30 Hz), 87.0% (0.3 Hz), and 80 pC. The reduction resistance of the liquid crystal cell was measured, and as a result, no reduction or peeling of the alignment film was observed at all after the button treatment.

[Examples 66 to 94] and [Comparative Examples 7 to 9]

According to the method described in Example 65, liquid crystal cell A-2 to liquid crystal cell A-30, and liquid crystal cell B were also produced for varnish A-2 to varnish A-30 and varnish B-1 to varnish B-3. -1 to liquid crystal cell B-3, and the alignment state, pretilt angle, VHR, ion density, and reduction resistance were measured. The measurement results are shown in Tables 5 and 6. Example 65 is also disclosed again in Table 5.

. Resistance reduction

○: After the button was pressed, no reduction or peeling of the alignment film was observed with a microscope.

×: After the button is pressed, the cut or peeling of the alignment film is observed with a microscope.

Good alignment in liquid crystal cell A-1~liquid crystal cell A-30 State, showing good resistance to cuts. Moreover, the electrical characteristics represented by VHR and ion density are also good results. In the liquid crystal cell B-1, a good alignment state was exhibited, and electrical characteristics were also good, but the alignment film was reduced. In the liquid crystal cell B-2 and the liquid crystal cell B-3, no reduction in the alignment film was observed, but the liquid crystal alignment was confirmed, and the liquid crystal cell was defective in display.

[Examples 95 to 109] and [Comparative Examples 10 to 12]

As shown in the following Tables 7 and 8, a varnish having a polyglycine concentration of 5% by weight was obtained according to the method described in Example 5. ( ) indicates the percentage of mol (mol%) in the case where the total amount of the raw materials is 100 mol%.

[Example 110]

1.0 g of varnish C-1 was weighed in a sample bottle, and NMP/BC = 1/1 (weight ratio) was added to make it 1.67 g. The 3% by weight polylysine solution was dropped on a transparent glass substrate and applied by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then dried in a clean oven (manufactured by Aspen Co., Ltd., clean oven (PVHC-231)) at 210 ° C for 15 minutes. Heat treatment to obtain an alignment with a film thickness of about 100 nm Film C-1. Next, using a friction treatment device manufactured by Gauge Co., Ltd., the frictional cloth (hair length 1.8 mm: rayon) has a hair injection amount of 0.20 mm, a table moving speed of 60 mm/sec, and a roller rotation. The obtained liquid crystal alignment film was subjected to a rubbing treatment at a speed of 1,000 rpm. The retardation of the obtained substrate was measured and found to be 0.26 nm. Further, the pencil hardness of the obtained alignment film C-1 was measured and found to be 5H.

[Examples 111 to 124] and [Comparative Examples 13 to 15]

As for the varnish C-2~varnish C-15 and the varnish D-1~varnish D-3, the alignment film C-2~ alignment film C-15 and the alignment film D-1~ alignment were also formed according to the operation of Example 110. Film D-3, retardation and pencil hardness were measured in accordance with the method of Example 110. These results are shown in Tables 9 and 10. The results of Example 110 are also disclosed again in Table 9.

According to the comparison of Examples 110 to 124 and Comparative Example 13 to Comparative Example 15, it was found that the alignment film of the present invention can greatly improve the pencil hardness without impairing the retardation.

[Example 125]

An alignment film C-1 having a film thickness of about 100 nm was obtained by the method according to Example 110 except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one side. Two sheets of the alignment film formed on the ITO electrode were formed with the alignment film facing each other, and a gap for injecting the liquid crystal composition was placed between the opposing alignment films to bond them. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films are made parallel. A positive liquid crystal composition A shown below was injected into the cell to prepare a liquid crystal cell C-1 (liquid crystal display element) having a cell thickness of 3.5 μm (Fig. 1).

<Positive liquid crystal composition A>

Physical property values: NI is 100.1 ° C; Δ ε is 5.1; Δ n is 0.093; η is 25.6 mPa. s.

The liquid crystal cell C-1 was visually observed, and as a result, no liquid crystal was observed at all. The injection inlets are arranged in a radial so-called flow alignment. The polarizing microscope is in the state of a crossed Nicol prism, and when the liquid crystal cell C-1 is rotated, a clear state is observed and Dark state. The pretilt angle of the liquid crystal cell C-1 (hereinafter sometimes abbreviated as Pt angle) was 0.1°. Further, VHR (voltage holding ratio) and ion density were 99.1% (30 Hz), 87.6% (0.3 Hz), and 75 pC. The liquid crystal cell was observed with a microscope, and as a result, no scratch or cut chips were confirmed.

[Examples 126 to 139] and [Comparative Examples 16 to 18]

According to the method described in Example 125, liquid crystal cell C-2 to liquid crystal cell C-15 and liquid crystal cell D-1 were also produced for varnish C-2 to varnish C-15 and varnish D-1 to varnish D-3. ~ Liquid crystal cell D-3, measuring the alignment state, pretilt angle, VHR, ion density, and reduction resistance. The measurement results are shown in Table 11 and Table 12. Example 125 is again disclosed in Table 11.

. Friction resistance

○: no frictional injury or slag was observed

×: frictional damage or slag was observed

A good alignment state is exhibited in the liquid crystal cell C-1 to the liquid crystal cell C-15, and good rubbing resistance is exhibited. Moreover, the electrical characteristics represented by VHR and ion density are also good results. In the liquid crystal cell D-1 to the liquid crystal cell D-3, although a good alignment state is exhibited, electrical characteristics are also good, but frictional damage or slag is generated.

[Examples 140 to 148]

As shown in the following Table 13, a varnish having a polyglycine concentration of 5 wt% as a polymer for blending was obtained according to the method described in Example 5. ( ) indicates the percentage of mol (mol%) in the case where the total amount of the raw materials is 100 mol%.

[Table 13]

[Example 149]

In a 50 mL eggplant-shaped flask equipped with a stirring blade and a nitrogen introduction tube, 2.0 g of the varnish A-1 synthesized in Example 5 and 8.0 g of the varnish E-1 synthesized in Example 140 were weighed, and 5.0 was added thereto. g N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were stirred at room temperature for 1 hour to obtain an alignment agent (varnish A-1 / varnish E-1) having a resin component concentration of 2.5% by weight. Using the obtained alignment agent, the alignment film F-1 was produced in accordance with the method described in Example 35. The retardation of the alignment film F-1 was measured and found to be 19.6 nm. Further, the pencil hardness of the obtained alignment film F-1 was measured and found to be 4H.

[Example 150 to Example 157 and Comparative Example 19 to Comparative Example 21]

The alignment film F-2 to the alignment film F-9 and the alignment film G-1 to the alignment film G-3 were produced in accordance with Example 149 except that the varnish used was changed, and the retardation and the pencil hardness were measured. The varnish used and the measurement results are shown in Tables 14 and 15 together with Example 149. Further, in Tables 14 and 15, varnish A is a varnish containing a polymer using a raw material having a photoisomerization structure, and varnish B is a varnish containing a polymer for blending.

It is understood that in the alignment film F-1 to the alignment film F-9, a large retardation and a high pencil hardness are obtained in all of the alignment films. In the alignment film G-1, although the film has a large retardation, the pencil hardness is low. In the alignment film G-2 and the alignment film G-3, it cannot be said that the pencil hardness is sufficiently high and the retardation is small.

[Example 158]

An alignment film F-1 having a film thickness of about 100 nm was obtained by the method according to Example 149 except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one side. Two sheets of the alignment film formed on the ITO electrode were formed with the alignment film facing each other, and a gap for injecting the liquid crystal composition was placed between the opposing alignment films to bond them. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films are made parallel. A positive liquid crystal composition A shown below was injected into the cell to prepare a liquid crystal cell F-1 (liquid crystal display element) having a cell thickness of 3.5 μm.

When the liquid crystal cell F-1 was visually observed, the so-called flow alignment in which the liquid crystals were arranged radially from the injection port was not observed at all. When the polarizing microscope is in the state of a crossed Nicol prism, when the liquid crystal cell F-1 is rotated, a clear state and a dark state are observed. The liquid crystal cell F-1 has a pretilt angle of 0.1°. Further, VHR (voltage holding ratio) and ion density were 99.0% (30 Hz), 87.2% (0.3 Hz), and 80 pC. The reduction resistance of the liquid crystal cell was measured, and as a result, no reduction or peeling of the alignment film was observed at all after the button treatment.

[Example 159 to Example 166 and Comparative Example 22 to Comparative Example 24]

The varnish used was changed, and a liquid crystal single was produced according to Example 158. Element, the alignment state, pretilt angle, VHR, ion density, and reduction resistance were measured. The varnish used and the measurement results are shown together with Example 158 in Tables 16 and 17.

. Resistance reduction

○: After the button was pressed, no reduction or peeling of the alignment film was observed with a microscope.

×: After the button is pressed, the cut or peeling of the alignment film is observed with a microscope.

Good alignment in liquid crystal cell F-1~liquid crystal cell F-9 State, showing good resistance to cuts. Moreover, the electrical characteristics represented by VHR and ion density are also good results. In the liquid crystal cell G-1, although a good alignment state was exhibited, electrical characteristics were also good, but the alignment film was reduced. In the liquid crystal cell G-2 and the liquid crystal cell G-3, no reduction in the alignment film was observed, but the liquid crystal alignment was confirmed to be a liquid crystal cell having poor display.

[Industrial availability]

By using an alignment agent, an alignment film having high alignment property and no reduction can be obtained in any of the photo-alignment method and the rubbing method, and the tetrazole-containing tetracarboxylic dianhydride of the present invention is used as the alignment agent. A polylysine or a derivative thereof. By using this alignment film, a liquid crystal display element excellent in display characteristics and electrical characteristics can be obtained.

1‧‧‧ glass substrate

2‧‧‧ Column spacers

3‧‧‧ITO substrate

4‧‧‧LCD

5‧‧‧ Sealing material

6‧‧‧Alignment film

Claims (12)

a tetracarboxylic dianhydride represented by the formula (1); In the formula (1), X is a divalent organic group containing at least one triazole ring; and R ¹ and R ² are each independently one selected from the group consisting of the following trivalent groups; At least one hydrogen of these groups may also be substituted by a methyl group, an ethyl group or a phenyl group. The tetracarboxylic dianhydride according to claim 1, which is represented by the formula (2); In the formula (2), X is a divalent organic group containing at least one triazole ring. The tetracarboxylic dianhydride according to claim 1, which is represented by the formula (3); In the formula (3), X ¹ is a triazole ring; A ¹ and A ² are each independently a single bond or an alkylene group having 1 to 12 carbon atoms; at least one hydrogen in the alkylene group may also be fluorine Further, at least one -CH ₂ - may also be substituted by -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or -C≡C-. The tetracarboxylic dianhydride according to claim 1, which is represented by the formula (4); In the formula (4), X ¹ and X ² are a triazole ring; and A ¹ to A ³ are each independently a single bond or an alkylene group having 1 to 12 carbon atoms; at least one hydrogen in the alkylene group is also It may be substituted by fluorine; moreover, at least one -CH ₂ - in the alkylene group may also be -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH=CH- or - C≡C-substituted. A poly-proline or a derivative thereof, which is a reaction of a tetracarboxylic dianhydride comprising at least one tetracarboxylic dianhydride according to any one of claims 1 to 4 with a diamine. obtain. A liquid crystal alignment agent containing the polyaminic acid or a derivative thereof as described in claim 5 of the patent application. The liquid crystal alignment agent according to claim 6, which comprises the poly-proline or the derivative thereof as described in claim 5, and other polymers. A liquid crystal alignment agent for photoalignment, which is a liquid crystal alignment agent according to claim 6 or 7. A liquid crystal alignment agent for rubbing, which is a liquid crystal alignment agent according to claim 6 or 7. A liquid crystal alignment agent for a liquid crystal display device of a transverse electric field type, which is a liquid crystal alignment agent according to any one of claims 6 to 9. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 6 to 10. A liquid crystal display device comprising the liquid crystal alignment film according to claim 11 of the patent application.