TW201632587A - Liquid crystal aligning agent for forming liquid crystal aligning layer, liquid crystal aligning layer and liquid crystal display device using the same - Google Patents

Abstract

The invention relates to a liquid crystal aligning agent containing at least one polymer selected from a polyamic acid obtained by allowing tetracarboxylic acid dianhydride to react with a diamine compound, and a derivative thereof, and at least one compound represented by formula (1) below. A liquid crystal alignment layer that is high in layer hardness, hard to be scratched and excellent in liquid crystal alignment properties can be obtained by using the liquid crystal aligning agent according to the invention. A liquid crystal display device in which the liquid crystal alignment layer is used has no defect due to bright spots derived from foreign matters, and is excellent in display characteristics. In formula (1), R1 is a single bond, straight-chain alkylene having 1 to 8 carbons, branched-chain alkylene having 2 to 8 carbons or a divalent organic group having 3 to 8 carbons and having an alicyclic structure.

Description

Liquid crystal alignment agent for forming liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element using the same

The present invention relates to a liquid crystal alignment agent containing polyglycine or a derivative thereof and a specific compound, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film.

Various personal display devices such as monitors for personal computers, LCD TVs, viewfinders for cameras, projection displays, optical optics, optical Fourier transform components, optical valves, and other optoelectronics related components The mainstream of liquid crystal display elements that have been commercialized and generally circulated today are display elements using nematic liquid crystals. The display mode of the nematic liquid crystal display element is widely known as a twisted nematic (TN) mode or a super twisted nematic (STN) mode. In recent years, in order to improve the problem of one of these modes, that is, the viewing angle is narrow, a multi-domain vertical alignment (MVA) using a TN type liquid crystal display element using an optical compensation film and using a technique of vertical alignment and protrusion structures has been proposed. In-Plane Switching (IPS) mode or Fringe Field Switching (FFS) mode, such as mode or transverse electric field mode, has been put into practical use.

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. At present, a liquid crystal alignment agent which is mainly used is a solution (varnish) obtained by dissolving polyacrylic acid, polyamidomate or polyimine in an organic solvent. After the solution is applied onto a substrate, film formation is carried out by heating or the like to form a polyimide film. After film formation, an alignment process suitable for the display mode is performed as needed.

A rubbing method which can easily perform large-area high-speed processing in an industrial manner is widely used as an alignment treatment method. 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 there are problems such as dusting and static electricity generated by the friction method. At present, the alignment treatment method using friction is still used in the manufacturing steps of the liquid crystal display element, but in recent years, the alignment treatment method instead of this has been actively developed.

As an alignment treatment method instead of the rubbing method, attention has been paid to an optical alignment treatment method in which light is irradiated and an alignment treatment is performed. In the photo-alignment processing method, a large number of alignment mechanisms such as a photo-decomposition method, a photo-isomerization method, a photodimerization method, and a photo-crosslinking method are proposed (for example, refer to Non-Patent Document 1, Patent Document 1 and Patent Document 2). Since the alignment of the photo-alignment method is higher than that of the rubbing method, and it is a non-contact alignment treatment method, there is an advantage that the liquid crystal display element can be reduced in display or the like without causing damage to the film.

In the past, a photo-alignment film having a photoreactive group such as photoisomerization or photodimerization has been studied in the polyamic acid structure (see, for example, Patent Documents 1 to 6). By applying the technique of photoisomerization described in Patent Documents 4 to 6, it is possible to obtain a liquid crystal alignment film having high anchoring energy, good alignment, and excellent electrical characteristics such as voltage holding ratio. However, when such a light alignment film is applied to an actual liquid crystal display element, since the film hardness is lower than that of the liquid crystal alignment film widely used in the rubbing method, there is a problem in that the liquid crystal display element is in the manufacturing step of the liquid crystal. Fine flaws are generated on the alignment film, and the foreign matter generated thereby lowers the display quality of the liquid crystal display element.

In order to improve the film, the method of improving the film hardness of the liquid crystal alignment film by adding a crosslinking agent to the liquid crystal alignment agent is known (for example, refer to Patent Document 7 to Patent Document 9). However, it has been found that when such a crosslinking agent is added, the film hardness is improved, but the alignment of the liquid crystal is greatly lowered. In the case of the liquid crystal display element of the FFS mode, after a long time of driving, an afterimage is generated. Further, there is also a crosslinking agent which does not lower the alignment property of the liquid crystal. However, the film hardness is insufficient for such a crosslinking agent, and when it is used as a liquid crystal display element, it is impossible to prevent the flaw due to the liquid crystal alignment film. Display bad results. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9- 297 313 [Patent Document 2] Japanese Patent Laid-Open No. Hei 10-251646 [Patent Document 3] Japanese Patent Laid-Open No. 2005-275364 [Patent Document 4] Japanese Patent Laid-Open No. 2010-049230 [Patent Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei 9-146100 [Patent Document No. 7] Japanese Patent Laid-Open No. Hei 9-146100 [Patent Document 8] Japanese Patent Laid-Open No. Hei 10-333153 [Patent Document 9] Japan Patent Special Open 2007-121991 Non-Patent Literature

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

[Problems to be Solved by the Invention] An object of the present invention is to provide a liquid crystal alignment agent which has high film hardness, is difficult to be scratched, and has good liquid crystal alignment properties, and a liquid crystal alignment film comprising the liquid crystal alignment agent. Liquid crystal display element. [Technical means to solve the problem]

As a result of intensive studies, it has been found that by using the liquid crystal alignment agent containing the compound represented by the formula (1) of the present invention, a liquid crystal alignment film having high film hardness, difficulty in scratching, and good liquid crystal alignment property can be obtained. this invention.

The present invention includes the following constitutions. [1] A liquid crystal alignment agent comprising at least one of a polymer selected from the group consisting of a compound represented by the following formula (1), wherein the polymer is selected from the group consisting of reacting a tetracarboxylic dianhydride with a diamine compound. At least one of polyamine and its derivatives, In the formula (1), R ¹ is a single bond, a linear alkylene group having 1 to 8 carbon atoms, a branched alkyl group having 2 to 8 carbon atoms, or a divalent organic compound having an alicyclic structure having 3 to 8 carbon atoms. base.

[2] The liquid crystal alignment agent according to [1], wherein the compound of the formula (1) is at least one of the compounds represented by the formula (1-1) to the formula (1-7); .

[3] The liquid crystal alignment agent according to [1], wherein the tetracarboxylic dianhydride contains a group selected from the group consisting of compounds represented by the following formulas (AN-I) to (AN-VII) At least one of the diamines includes a diamine having no side chain represented by the following formula (DI-1) to formula (DI-16), and a formula (DIH-1) to (DIH-3) And at least one of a group of diterpenes having no side chain and a group of diamines having a side chain represented by the following formula (DI-31) to formula (DI-35); 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, and the carbon number is 1 to 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; (AN-II)~ In (AN-IV), Y is independently one selected from the group consisting of trivalent groups in which a bond is bonded to an arbitrary carbon, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group. ; 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, and at least the group of the group One hydrogen may be substituted by a methyl group, an ethyl group or a phenyl group, and the bond bond attached 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 a C 2 to 6 alkylene group, Me represents a methyl group, Ph represents a phenyl group; in the formula (AN-VII), G ^{10 is} independently -O-, -COO- or -OCO-, and r is independently 0 or 1; In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH-, -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group is extended. It can be substituted by -OH; in formula (DI-3) and formula (DI-5) to 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 an integer from 1 to 5 , n is 1 or 2; in the formula (DI-4), s is independently an integer of 0 to 2; in the formula (DI-6) and the formula (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -NH-, or an alkylene group having 1 to 10 carbon atoms; formula (DI-2) to formula ( At least one hydrogen of the cyclohexane ring and the benzene ring in DI-7) may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , a phenyl group, or a benzyl group, and In (DI-4), at least one hydrogen of the benzene ring may be substituted with one selected from the group consisting of a group represented by the following formula (DI-4-a) to formula (DI-4-e); bonding position The group which is not fixed to the carbon atom constituting the ring in the formula means that the bonding position on the ring is arbitrary; the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is G ²¹ or G Any position other than the bonding position of ²² ; In formula (DI-4-a) and formula (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ ; In formula (DI-11), r is 0 or 1; of formula (DI-8) ~ of formula (DI-11) in bonded on the ring -NH ₂ bonding positions to an arbitrary position; 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 1 to 6 carbon atoms, a phenyl group or an alkyl group. a phenyl group, w is an integer of 1 to 10; in the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, and p is independently 0. An integer of ～3, q is an integer of 0 to 4; in the formula (DI-14), ring B is a monocyclic heteroaromatic group, and R ²⁴ is hydrogen, -F, -Cl, an alkyl group having 1 to 6 carbon atoms. , alkoxy group, vinyl group, alkynyl group, q is an integer of 0 to 4, in the formula (DI-15), ring C is a monocyclic ring containing a hetero atom; in the formula (DI-16), G ²⁴ is a single bond a C 2 to 6 alkylene group or a 1,4-phenylene group, r is 0 or 1; a bond site which is not fixed to a carbon atom constituting the ring in the formula is represented on the ring The bonding position is arbitrary; in the formula (DI-13) to the formula (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position; In the formula (DIH-1), G ²⁵ 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 -; wherein, in the formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the ring 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 ring 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 -; (DIH-2) and formula ( In DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position; 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 of 1 to 12; 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 formula (DI-31-a) in which at least one hydrogen may be substituted by -F, and at least one -CH ₂ - may be -O-, -CH=CH- or -C≡C Substituting, the hydrogen of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. a substituent, the bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and more than one -CH of the alkylene group ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and 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, acridine-1,4-di At least one hydrogen of the group, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ -F or -CH ₃ substitution, s, t and u are independently an integer of 0 to 2, and their total is 0 to 5. When s, t or u is 2, the two bonding groups in each parenthesis may be the same , may also be different, and the two rings may be the same or different, R ²⁶ is hydrogen, -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, and a carbon number. 1 to 30 alkoxy group, -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 represented by the following formula (DI-31- b) the divalent base substitution indicated, In the formula (DI-31-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6; In the formula (DI-32) and the 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 carbon number is 1 - An alkyl group of 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 be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the bonding position is not fixed in the constitution. The group on any one of the carbon atoms of the ring in the formula represents any bonding position on the ring; in the formula (DI-32) and formula (DI-33), -NH bonded to the benzene ring ₂ indicates that the bonding position on the ring is arbitrary; In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O-, -NH- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or a carbon number of 1 to 3 An alkyl group, 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-, and R ³² is a carbon number. An alkyl group of 6 to 22, R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms, and ring B ²⁵ is a 1,4-phenylene group or a 1,4-cyclohexylene group, and r is 0 or 1, and a bond The -NH ₂ attached to the benzene ring indicates that the bonding position on the ring is arbitrary.

The liquid crystal alignment agent according to [3], wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (AN-1-1), the formula (AN-1-2), the formula (AN-1-13), and the formula (PA-1), Formula (AN-3-1), Formula (AN-3-2), Formula (AN-4-5), Formula (AN-4-17), Formula (AN-4-21) , formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN- 11-3), at least one of the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4); the diamine is selected from the following formula (DI-1- 3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula ( DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17 ), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI -13-1), at least one of the group consisting of formula (DI-16-1), formula (DI-31-56), and formula (DIH-2-1); In the formula (AN-1-2) and the formula (AN-4-17), m is an integer of 1 to 12; In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), and the formula (DI-7-3), m is an integer of 1 to 12; In 5-30), k is an integer of 1 to 5; and in the formula (DI-7-3), n is independently 1 or 2.

[5] The liquid crystal alignment agent according to any one of [1], wherein the polyphthalic acid and the derivative thereof are at least one of a tetracarboxylic dianhydride and a diamine and a photoreactive structure. The polymer (a) obtained by the reaction of the compound.

[6] The liquid crystal alignment agent according to [5], wherein the photoreactive structure is selected from the group consisting of structures represented by the following formulas (P-1) to (P-7) At least one In the formula (P-1), R ^{61 is} independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

[7] The liquid crystal alignment agent according to [6], wherein the compound having the photoreactive structure is selected from the group consisting of the following formula (II-1), formula (II-2), and formula (III-1). Formula (III-2), Formula (IV-1), Formula (IV-2), Formula (V-1) to Formula (V-3), and Formula (VI-1) and Formula (VI-2) At least one tetracarboxylic dianhydride or diamine compound in the group consisting; In the above formula, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R ^{6 is} independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH ₃ , a are each independently an integer of 0 to 2; in the formula (V-3), ring A and ring B are each independently selected from a monocyclic hydrocarbon, a condensed polycyclic ring. At least one of a hydrocarbon and a heterocyclic ring, R ¹¹ is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N(CH ₃ )CO-, and R ¹² is a carbon number of 1 ～20 of a linear alkyl group, -COO-, -OCO-, -NHCO- or -N(CH ₃ )CO-, R ¹¹ and R ¹² , a linear alkyl group of -CH ₂ - or Two may be substituted by -O-, and R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ or -OH, and b to e are each independently an integer of 0 to 4.

[8] The liquid crystal alignment agent according to [7], wherein the diamine compound having the photoreactive structure is represented by the following formula (PDI-7); In the formula (PDI-7), R ^{51 is} independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , and s is independently an integer of 0 to 2, respectively.

[9] The liquid crystal alignment agent according to any one of [5] to [8] which contains a polymer (a) and further contains a polymer (b) selected from the group consisting of At least one of polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic dianhydride having no photoreactive structure and a diamine having no photoreactive structure.

[10] The liquid crystal alignment agent according to [9], wherein the tetracarboxylic dianhydride used in the synthesis of the polymer (b) is selected from the following formula (AN-1-1), formula (AN-1) -2), Formula (AN-1-13), Formula (PA-1), Formula (AN-3-1), Formula (AN-3-2), Formula (AN-4-5), Formula (AN) -4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2) At least one of the formula (AN-10-1), the formula (AN-11-3), the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4) The diamine is selected from the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4- 10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula ( DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3 ), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DI-31-56), and formula (DIH-2-1) At least one of the groups; In the formula (AN-1-2) and the formula (AN-4-17), m is an integer of 1 to 12; In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), and the formula (DI-7-3), m is an integer of 1 to 12; In 5-30), k is an integer of 1 to 5; and in the formula (DI-7-3), n is independently 1 or 2.

[11] The liquid crystal alignment agent according to any one of [1] to [10] further comprising an epoxy group selected from the group consisting of an oxazine compound, an oxazoline compound, and a compound represented by the formula (1). At least one of the group consisting of a compound and a compound of a decane coupling agent.

A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of [1] to [11].

A liquid crystal alignment film for a transverse electric field, which is formed by the liquid crystal alignment agent according to any one of [1] to [11].

A liquid crystal display element comprising the liquid crystal alignment film according to [12] or [13]. [Effects of the Invention]

When the liquid crystal alignment agent containing the compound represented by the formula (1) of the present invention is used, a liquid crystal alignment film having high film hardness and good liquid crystal alignment property can be obtained. Further, by using the liquid crystal alignment film, it is possible to obtain a liquid crystal display element which does not cause a bright spot defect due to foreign matter and which is excellent in display characteristics.

<Compound represented by the formula (1)> The present invention is a liquid crystal alignment agent containing at least one of the following polymers and a compound represented by the following formula (1), which is selected from the group consisting of tetracarboxylic acids At least one of polyphthalic acid and a derivative thereof obtained by reacting a dianhydride with a diamine. R ¹ in the formula (1) is a single bond, a linear alkylene group having 1 to 8 carbon atoms, a branched alkyl group having 2 to 8 carbon atoms, or a divalent organic compound having an alicyclic structure having 3 to 8 carbon atoms. base.

Specifically, the compound represented by the formula (1) can be represented by the following formula (1-1) to formula (1-7).

The compound represented by the formula (1) can also be used as a liquid crystal alignment agent for rubbing, and can also be used as a liquid crystal alignment agent for photoalignment. When the amount of the compound represented by the formula (1) is used for a liquid crystal alignment agent for rubbing, in order to obtain an effect of preventing thinning at the time of friction due to a decrease in film hardness, the amount of addition is preferably polyamine or The total weight of the derivative is 0.1 wt% or more. On the other hand, in order to prevent misalignment due to a decrease in the alignment property of the liquid crystal alignment film, the amount of addition is preferably 10 wt% or less. The amount of addition for use in the liquid crystal alignment agent for rubbing is more preferably 0.3% by weight to 3% by weight. Further, in the case of use for a liquid alignment alignment agent for photoalignment, in order to obtain an effect of preventing damage due to a decrease in film hardness, 0.1 wt% or more of the total weight of the polyaminic acid or its derivative is preferable. On the other hand, in order to prevent misalignment due to a decrease in the alignment property of the liquid crystal alignment film, the amount of addition is preferably 30% by weight or less. The amount of addition for use in the liquid alignment alignment agent for photoalignment is more preferably 5 wt% to 20 wt%.

In the compound represented by the formula (1), a compound represented by the formula (1-1) to the formula (1-5) is preferably used, and more preferably used, in order to obtain a liquid crystal alignment film having high liquid crystal alignment and high film hardness. A compound of the formula (1-1).

<Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is a reaction product of at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof and a diamine, and is characterized by containing the following polymer and the formula (1) At least one of the compounds represented, the polymer being at least one selected from the group consisting of polylysine and derivatives thereof. The term "poly-proline derivative" refers to a component which is dissolved in a solvent when it is prepared as a liquid crystal alignment agent to be described later, and means that 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 the derivative of the polyproline are, for example, soluble polyimine, polyphthalamide, and polyamine amide, and more specifically, 1) polylysine Polyimine which is obtained by dehydration ring-closing reaction of all amino groups and carboxyl groups, 2) partial polyimine which is partially subjected to dehydration ring-closure reaction, and 3) polyfluorene obtained by converting a carboxyl group of poly-proline to an ester. An amine ester, 4) a polyphthalic acid-polyimine copolymer obtained by substituting a part of an acid dianhydride contained in a tetracarboxylic dianhydride compound with an organic dicarboxylic acid, and 5) A polyamidoquinone imine obtained by subjecting a part or all of the polyaminic acid-polyimine copolymer to a dehydration ring-closure reaction. The polyamic acid and its derivative may be one type of polymer or two or more types. Further, the polyamic acid and a derivative thereof may be a polymer having a structure of a reaction product of a tetracarboxylic dianhydride and a diamine, and may also contain the following reaction product: using other raw materials, passing through a tetracarboxylic acid It is obtained by a reaction other than the reaction of an anhydride with a diamine.

Polyammonium esters can be synthesized by a method of synthesizing the polylysine with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or by subjecting an acid dianhydride to A method of synthesizing a derivatized tetracarboxylic acid diester or tetracarboxylic acid diester dichloride with a diamine. The tetracarboxylic acid diester derived from an acid dianhydride can be obtained, for example, by reacting an acid dianhydride with 2 equivalents of an alcohol and ring-opening, and the tetracarboxylic acid diester dichloride can be obtained by making a tetracarboxylic acid diester and 2 equivalents of chlorine. It is obtained by reacting a chemical (for example, sulfoxide, etc.). Further, the polyglycolate may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

The tetracarboxylic dianhydride used for producing the polyphthalic acid and its derivative contained in the liquid crystal alignment agent of the present invention will be described. The tetracarboxylic dianhydride used in the present invention can be selected from known tetracarboxylic dianhydrides without limitation. The 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 in which a dicarboxylic acid anhydride is not directly bonded to an aromatic ring (including Tetracarboxylic dianhydride in the group of any of the heterocyclic groups. As the tetracarboxylic dianhydride, one compound may be reacted with a diamine, or two or more kinds of compounds may be mixed and reacted with a diamine. In the present specification, the term "tetracarboxylic dianhydride" means not only one compound but also a mixture of two or more kinds of compounds.

The tetracarboxylic dianhydride can be roughly classified into a tetracarboxylic dianhydride having a photoreactive structure and a tetracarboxylic dianhydride having no photoreactive structure.

A suitable example of the tetracarboxylic dianhydride which does not have the photoreactive structure is a formula (for the viewpoint of easiness of obtaining a raw material, easiness in polymerization of a polymer, and electrical properties of a film) AN-I) to a tetracarboxylic dianhydride represented by the formula (AN-VII).

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 of trivalent groups described below, and the bond is bonded to any carbon, and at least one hydrogen of the group may be Substituted by ethyl, ethyl or phenyl.

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, and at least the group of the group One hydrogen may be substituted by a methyl group, an ethyl group or a phenyl group, and the bond bond attached 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 is} independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

More specifically, tetracarboxylic dianhydride represented by the following formula (AN-1) and formula (AN-3) to formula (AN-16-15) can be mentioned.

[Tetracarboxylic dianhydride represented by the formula (AN-1)] 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 any of the following trivalent groups. When G ¹² is >CH-, the hydrogen of >CH- can be substituted by -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.

[Tetracarboxylic dianhydride represented by the formula (AN-3)] Of formula (AN-3), ring A ¹¹ is a benzene ring or a cyclohexane ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas.

[Tetracarboxylic dianhydride represented by the formula (AN-4)] 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. Ring A ^{11 is} independently a cyclohexane ring or a benzene ring. G ¹³ can be bonded to any position of the ring A ¹¹ . In the formula (G13-1), G ^13a and G ^13b are each independently a single bond, -O- or a divalent group represented by -NHCO-. The phenyl group is preferably a 1,4-phenylene group and a 1,3-phenylene group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas. In the formula (AN-4-17), m is an integer of 1 to 12.

[Tetracarboxylic dianhydride represented by the formula (AN-5)] In the formula (AN-5), R ¹¹ is hydrogen or -CH ₃ . R ¹¹ in which the bonding position is not fixed to the carbon atom constituting the benzene ring indicates that the bonding position in the benzene ring is arbitrary.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formulas.

[Tetracarboxylic dianhydride represented by the formula (AN-6)] 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.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulas.

[Tetracarboxylic dianhydride represented by the formula (AN-7)] 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.

[Tetracarboxylic dianhydride represented by the formula (AN-8)] 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 a phenyl group, 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.

[Tetracarboxylic dianhydride represented by the formula (AN-9)] In the formula (AN-9), r is independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-10-1) and the formula (AN-10-2)]

[Tetracarboxylic dianhydride represented by the formula (AN-11)] 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.

[Tetracarboxylic dianhydride represented by the formula (AN-12)] 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.

[Tetracarboxylic dianhydride represented by formula (AN-13)] 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.

[Tetracarboxylic dianhydride represented by the formula (AN-14)] In the formula (AN-14), G ^{14 is} independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formulas.

[Tetracarboxylic dianhydride represented by the formula (AN-15)] In the formula (AN-15), w is an integer of 1 to 10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulas.

Examples of the tetracarboxylic dianhydride other than the above include the following compounds.

A suitable material for improving various properties in a tetracarboxylic dianhydride having no such photoreactive structure will be described.

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-4-5), the formula (AN-4-17), and the formula (AN-4-29), Among them, in the formula (AN-1-2), m=4 or 8 is preferable, and 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 tetracarboxylic dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), and the formula (AN-3-1). , formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN- 16-3), and a compound represented by the formula (AN-16-4), wherein, in the formula (AN-1-2), m=4 or 8 is preferable, and in the formula (AN-4-17), Preferably m = 4, or 8, particularly preferably m = 8.

When it is important to increase the voltage holding ratio (VHR) of the liquid crystal display element, the tetracarboxylic dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), Formula (AN-3-1), Formula (AN-4-17), Formula (AN-4-30), Formula (AN-7-2), Formula (AN-10-1), Formula (AN-16) -1), a compound represented by the formula (AN-16-3), and the formula (AN-16-4), wherein, in the formula (AN-1-2), m = 4 or 8 is preferred, In AN-4-17), m = 4 or 8, preferably m = 8.

As one of methods for preventing burn marks, it is effective to increase the relaxation speed of residual electric charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. In the case where the object is important, the tetracarboxylic 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).

The diamine and dioxime used to produce the poly-proline and its derivative contained in the liquid crystal alignment agent of the present invention will be described. The diamine and dioxime used in the present invention can be selected from known diamines and dioxins without limitation. As the diamine, one compound may be reacted with a tetracarboxylic dianhydride, or two or more kinds of compounds may be mixed and reacted with a tetracarboxylic dianhydride. In the present specification, the term "diamine" means not only one compound but also a mixture of two or more compounds in its meaning. Further, in the present specification, the diterpene may also be treated as a "diamine".

Similarly to the tetracarboxylic dianhydride, the diamine compound can be roughly classified into a diamine compound having a photoreactive structure and a diamine compound having no photoreactive structure. Diamines which do not have a photoreactive structure can be classified into two according to their structures. That is, a diamine having a side chain group and a diamine having no side chain group, the side chain group being a group branched from the main chain when the skeleton linking the two amino groups is regarded as a main chain. The side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect is required to have a carbon number of 3 or more. Specific examples thereof include an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, and an alkoxyalkyl group having 3 or more carbon atoms. a base, and a group having a steroid skeleton. A group having one or more rings and having a ring having a carbon number of 1 or more, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as a substituent As an effect of the side chain. 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 having no such a side chain group is sometimes referred to as a non-side chain type diamine.

By suitably separating the non-side chain type diamine from the side chain type diamine, it is possible to correspond to the respective pretilt angles required. The side chain type diamine is preferably used in combination to the extent that the characteristics of the present invention are not impaired. In addition, it is preferable to use a side chain type diamine and a non-side chain type diamine 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 non-side chain type diamine is described. Examples of the known diamine having no side chain include the following diamines of the formula (DI-1) to the formula (DI-16).

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH-, -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group is extended. Can be replaced by -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 of 1 to 12, k is an integer of 1 to 5, and n is 1 or 2. In the formula (DI-4), s is independently an integer of 0 to 2. In the formula (DI-6) and the formula (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -NH-, or an alkylene group having 1 to 10 carbon atoms. At least one hydrogen of the cyclohexane ring and the benzene ring in the formula (DI-2) to the formula (DI-7) may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH, - CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl substitution, further, in formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring may be selected from One of the groups of the groups represented by the following formulas (DI-4-a) to (DI-4-e) is substituted. The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary. Further, the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² .

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

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

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 1 to 6 carbon atoms, a phenyl group or a substituted alkyl group. Phenyl is extended, and w is an integer of from 1 to 10. In the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 . In the formula (DI-14), ring B is a monocyclic heteroaromatic group, R ²⁴ is hydrogen, -F, -Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a vinyl group, an alkynyl group, and q is independently It is an integer from 0 to 4. In the formula (DI-15), the ring C is a single ring containing a hetero atom. In the formula (DI-16), G ²⁴ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1. Further, the group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary. In the formula (DI-13) to the formula (DI-16), the bonding position of -NH ₂ bonded to the ring 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 formula (DI-1-1) to formula (DI-16-1).

An example of the diamine represented by the formula (DI-1) is shown below. In the formula (DI-1-7) and the formula (DI-1-8), k is independently an integer of 1 to 3.

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

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

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-5-1), 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. In the formula (DI-5-30), k is an integer of 1 to 5. In the formula (DI-5-35) to the formula (DI-5-37) and the formula (DI-5-39), m is independently an integer of 1 to 12, and the formula (DI-5-38) and the formula (DI) In -5-39), k is independently an integer of 1 to 5, and in the formula (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.

An example of the diamine represented by the formula (DI-7) is shown below. In the formula (DI-7-3) and the formula (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2. In the formula (DI-7-12), m is an integer of 1 to 12.

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

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.

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

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

In the formula (DIH-1), G ²⁵ 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 (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 by 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 has a carbon number of 1 to 20 carbon atoms. 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 -CONHNH ₂ bonded to the ring is an arbitrary position.

Examples of the formula (DIH-1) to the formula (DIH-3) are shown below. In the formula (DIH-1-2), m is an integer of 1 to 12.

Such a non-side chain type diamine and diterpene have an effect of improving electrical characteristics such as a decrease in ion density of a liquid crystal display element. The use of a non-side chain type diamine and/or dioxime as a liquid crystal alignment agent for producing a polyglycolic acid, a polyamidomate or a polyimine used in the liquid crystal alignment agent of the present invention In the case of an amine, the proportion of the total amount of the diamine and the dioxane is preferably 0 mol% (% by mole) to 90 mol%, more preferably 0 mol% to 50 mol%.

The side chain type diamine is described. Examples of the side chain group of the side chain type diamine include the following groups.

As the side chain group, first, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, an alkene group can be mentioned. Alkylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, 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 3 or more carbon atoms. 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, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, and examples thereof include a phenyl group and a phenylalkyl group. , phenyl alkoxy group, phenoxy group, phenylcarbonyl group, phenylcarbonyloxy group, phenoxycarbonyl group, phenylaminocarbonyl group, phenylcyclohexyloxy group, cycloalkyl group having 3 or more carbon atoms, cyclohexyl alkane , cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclo) a cyclyl group such as a phenyl group, a bis(cyclohexyl)phenylalkyl group, a bis(cyclohexyl)oxycarbonyl group, a bis(cyclohexyl)phenoxycarbonyl group, and a cyclohexyl bis(phenyl)oxycarbonyl group; .

Further, examples thereof include a ring group having two or more benzene rings, a group having two or more cyclohexane rings, or two or more rings including a benzene ring and a cyclohexane ring. And the bonding group is independently a single bond, -O-, -COO-, -OCO-, -CONH- or an alkylene group having 1 to 3 carbon atoms, and the terminal ring has an alkyl group having 1 or more carbon atoms and a carbon number A fluorine-substituted alkyl group having 1 or more, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms is used as a substituent. A group having a steroid skeleton is also effective as a side chain group.

The diamine having a side chain includes 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 1 to 3 carbon atoms, 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 be substituted by -F, and at least one -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-. The hydrogen of the phenyl group may be substituted by -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, and 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 1 position, 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 which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and more than one -CH of the alkylene group ₂ - may 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, acridine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or oxime-9,10- In the diradical, ring B ²¹ , ring B ²² , 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 0. ～5, when s, t or u is 2, the two bonding 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, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted 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 , 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).

In the formula (DI-31-b), R ²⁷ and R ^{28 are each} independently an alkyl group having 1 to 3 carbon atoms, and 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 the formula (DI-32) and the 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 carbon number is 1 - An alkyl group of 20 or an alkenyl group having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in the formula (DI-32) and the formula (DI-33) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group. Further, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position in the ring is arbitrary. Preferably, one of the two base "-phenyl-G ³⁰ -O-" in 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 position or a para position relative to the steroid nucleus, respectively. 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-, -NH-, or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or a carbon number of 1 to 3. Alkyl. 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. Moreover, -NH ₂ bonded to the benzene ring means that the bonding position on the ring is arbitrary, but is preferably independent and the bonding position with respect to G ³¹ is meta or para.

Specific examples of the side chain type diamine are exemplified below. The diamine having a side chain of the formula (DI-31) to the formula (DI-35) is represented by the following formula (DI-31-1) to formula (DI-35-3). Compound.

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 an alkyl group having 5 to 25 carbon atoms. Or an alkoxy group 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.

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 an alkyl group having 3 to 20 carbon atoms. Or an alkoxy group 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 3 to 25. An alkyl group or an alkoxy group having 3 to 25 carbon atoms. Further, G ³³ is an alkylene group having 1 to 20 carbon atoms.

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

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. In the formula (DI-34-1) to the formula (DI-34-14), 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, a formula (DI-1-1) to a formula (DI-16-1), a formula (DIH-1-1) to a formula (DIH-3-6), and a formula ( DI-31-1) to a diamine other than the diamine represented by the formula (DI-35-3). 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.

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

Suitable materials for enhancing the properties of the diamines and dioximes are described.

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-4-1), and the formula (DI-5-1) among the diamine and the dioxime. ), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI -6-7), a compound represented by the formula (DI-7-3) and the formula (DI-11-2). More preferably, it is represented by the formula (DI-4-1), the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), and the formula (DI-7-3). Diamine. In the formula (DI-5-1), m = 2, 4 or 6, preferably m = 4. In the formula (DI-5-12), m = 2 to 6, preferably m = 5. In the formula (DI-5-13), m = 1, or 2 is preferable, and m = 1 is more preferable. In the formula (DI-7-3), m = 2, or 3, and n = 1, or 2, more preferably m = 1 is 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 compound represented by the formula (DI-5-5), the formula (DI-5-17), and the formula (DI-7-3) is more preferably a diamine represented by the formula (DI-2-1). In the formula (DI-5-1), m = 2, 4 or 6, preferably m = 4. In the formula (DI-7-3), m = 2, or 3, and n = 1, or 2, more preferably m = 1 is preferable.

In the case where the VHR of the liquid crystal display element is emphasized, in the diamine and the dioxime, it is preferred to use the formula (DI-2-1), the formula (DI-4-1), and the formula (DI-4-2). ), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), and formula ( The compound represented by DI-13-1) and the formula (DI-31-56) is more preferably of the formula (DI-2-1), the formula (DI-5-1), and the formula (DI-13-1). And a compound represented by the formula (DI-31-56). In the formula (DI-5-1), m = 1 is preferred. In the formula (DI-5-30), k = 2 is preferred.

As one of methods for preventing burn marks, it is effective to increase the relaxation speed of residual electric charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. In the case where the object is emphasized, it is preferable to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (II). DI-4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), and formula (DI-16- 1) The compound represented by the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-5-13) are more preferable. In the formula (DI-5-1), m = 2, 4 or 6, preferably m = 4. In the formula (DI-5-12), m = 2 to 6, preferably m = 5. In the formula (DI-5-13), m = 1, or 2 is preferable, and m = 1 is more preferable.

In each of the diamines, a part of the diamine may be substituted with a monoamine in a ratio of 40 mol% or less to the monoamine of the diamine. Such substitution can cause termination of the polymerization reaction when polyamic acid is formed, and further progress of the polymerization reaction can be suppressed. Therefore, by such substitution, the molecular weight of the obtained polymer (polyglycine, polyphthalate or polyimide) can be easily controlled, for example, the coating of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. characteristic. The diamine substituted with a monoamine may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and positive ten Monoamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-dodecylamine.

The poly-proline and the derivative thereof of the present invention may further contain a monoisocyanate compound in the monomer. By containing a monoisocyanate compound in the monomer, the terminal of the obtained polyaminic acid or its derivative 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 this point of view, 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.

In the present invention, polylysine having a photoreactive structure and a derivative thereof can be suitably used. The photoreactive structure may, for example, be a photoisomerization structure which is isomerized by ultraviolet irradiation, a photodecomposition structure which causes decomposition, a photodimerization structure which causes dimerization, and the like.

Polylysine having a photoreactive structure and a derivative thereof are referred to as polymer (a). In the polymer (a), a diamine having a photoreactive structure or a photoreactive structure tetracarboxylic dianhydride and a derivative thereof may be used in a raw material, or a diamine having a photoreactive structure may be used in combination with Photoreactive structure of tetracarboxylic dianhydride and its derivatives. The photoreactive structure is a structure represented by the following formula (P-1) to formula (P-7). In the formula (P-1), R ^{61 is} independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

The compound represented by the following formula (PA-1) to formula (PA-6) is exemplified as the compound having a photoreactive structure which causes photodecomposition represented by the formula (P-1). In the formulae (PA-3) to (PA-6), R ^{62 is} independently an alkyl group having 1 to 5 carbon atoms.

Among the compounds represented by the formula (P-1), the formula (PA-1), the formula (PA-2) and the formula (PA-5) can be suitably used.

When the compound represented by the formula (PA-1) to the formula (PA-6) is used as a material of the following liquid crystal alignment agent, it can be used as the tetracarboxylic dianhydride having no photoreactive structure. The liquid crystal alignment agent is a liquid crystal alignment agent using a liquid crystal alignment energy based on a photoisomerization reaction, a liquid crystal alignment agent using a liquid crystal alignment energy based on photodimerization, or a liquid crystal alignment agent for rubbing.

Examples of the compound having a photoreactive structure represented by the formula (P-2) to the formula (P-4) include a tetracarboxylic acid represented by the following formula (II-1) to formula (VI-2). Di-anhydride and diamine compounds. In the above formula, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R ^{6 is} independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , a is an integer of 0 to 2; in the formula (V-3), ring A and ring B are each independently selected from a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, and At least one of the heterocyclic rings, R ¹¹ is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N(CH ₃ )CO-, and R ¹² is a carbon number of 1 to 20 One or two of linear alkyl, -COO-, -OCO-, -NHCO- or -N(CH ₃ )CO-, R ¹¹ and R ¹² , linear alkyl-CH ₂ - It may be substituted by -O-, and R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ or -OH, and b to e are each independently an integer of 0 to 4.

From the viewpoint of the photosensitivity, the compounds represented by the above formula (V-1), formula (V-2) and formula (VI-2) can be used particularly suitably. From the viewpoint of the alignment property, a compound in which the bonding position of the amino group in the formula (V-2) and the formula (VI-2) is para-position, and a = in the formula (V-2) can be more suitably used. Compound of 0.

The acid dianhydride or diamine having a structure capable of photoisomerization by ultraviolet irradiation represented by the formula (II-1) to the formula (VI-2) can be represented by the following formula (II-1-1) to formula (VI-). 2-3) Specifically indicated.

By using the compound of the formula (VI-1-1) to the formula (V-3-8) having a structure capable of isomerization by ultraviolet irradiation, it is possible to obtain a liquid alignment liquid crystal having higher sensitivity to ultraviolet light irradiation. An aligning agent. By formula (V-1-1), formula (V-2-1), formula (V-2-4) to formula (V-2-11), and formula (V-3-1) to formula (V) -3-8) A compound having a structure capable of isomerization by irradiation with ultraviolet rays, and a liquid crystal alignment agent for photoalignment which can align liquid crystal molecules more uniformly can be obtained. By setting the formula (V-2-4) to the formula (V-3-8) as a compound having a structure capable of isomerization by ultraviolet irradiation, it is possible to obtain a color reduction which can further reduce the coloration of the formed alignment film. A liquid crystal alignment agent for light alignment.

Among them, the compound represented by the formula (V-2-1) can be more suitably used from the viewpoint of exhibiting greater anisotropy when the liquid crystal alignment film is formed.

Examples of the compound having a photoreactive structure represented by the formula (P-5) to the formula (P-7) include a diamine compound represented by the following formula (PDI-9) to formula (PDI-13). In the formula (PDI-12), R ⁵⁴ is an alkyl group or alkoxy group having 1 to 10 carbon atoms, and at least one hydrogen of the alkyl group or alkoxy group may be substituted with fluorine.

The above formula (PDI-9) to formula (PDI-11) can be suitably used.

In the case of using a tetracarboxylic dianhydride having no photoreactive structure (non-photosensitive) and a tetracarboxylic dianhydride having a photoreactive structure (photosensitive property), in order to prevent the sensitivity of the liquid crystal alignment film to light The total amount of the tetracarboxylic dianhydride used as a raw material in the production of the poly-proline and the derivative of the present invention is preferably 0 mol% to 70 mol%, particularly preferably 0 mol% to 70 mol%. 0 mol% to 50 mol%. Further, in order to improve various characteristics such as sensitivity to light, electrical characteristics, and afterimage characteristics, two or more kinds of photosensitive tetracarboxylic dianhydrides may be used in combination.

In the case where a diamine having no photoreactive structure (non-photosensitive) and a diamine having a photoreactive structure (photosensitive) are used in combination, in order to prevent a decrease in sensitivity of the alignment film to light, as a manufacturing cost The total amount of the diamine used in the raw material of the polyglycine or the derivative thereof is preferably 20 mol% to 100 mol%, particularly preferably 50 mol% to 100 mol%. Further, in order to improve various characteristics such as sensitivity to light and afterimage characteristics, two or more kinds of photosensitive diamines may be used in combination. As described above, in the aspect of the present invention, the case where the non-photosensitive tetracarboxylic dianhydride occupies the total amount of the tetracarboxylic dianhydride is contained, and even in the case, the minimum amount of the diamine is required to be 20 mol. % is a photosensitive diamine.

In order to improve various characteristics such as sensitivity to light and afterimage characteristics, a photosensitive tetracarboxylic dianhydride and a photosensitive diamine may be used in combination, or two or more kinds may be used in combination.

The polyproline and its derivative of the present invention can be obtained by reacting a mixture of the above tetracarboxylic dianhydride with a diamine in a solvent. In the synthesis reaction, conditions other than the usual polyamine synthesis can be directly applied, except for the selection of the raw materials, without special conditions. The solvent to be used will be described later.

The polymer contained in the liquid crystal alignment agent of the present invention may be one type or two or more types of doping. In the aspect of doping two or more kinds of polymers, the case where at least one of the polymers is obtained by reacting at least one of a tetracarboxylic dianhydride and a diamine with a raw material monomer having a photoreactive structure At least one of the polymer (a) and the other polymer is selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride having no photoreactive structure and a diamine having no photoreactive structure, and a polymer (b) of at least one of its derivatives. The polymer (a) can be isomerized, decomposed, or dimerized by irradiation with an energy ray such as ultraviolet rays, and the structure thereof is changed, and the polymer film is brought into contact with the polymer film. The property of liquid crystal molecules to align (light alignment) in a specific direction. Such polymers are sometimes doped with other polymers that do not have a photoreactive structure.

The liquid crystal alignment agent of the present invention may further contain other components than polyglycine or a derivative thereof. The other components may be one type or two or more types. As another component, other polymers, compounds, etc. which are mentioned later are mentioned, for example.

In the liquid crystal alignment agent of the present invention, when a plurality of polymers are used by doping, the structure or molecular weight of each polymer is controlled, and as described later, it is applied onto a substrate and pre-dried, whereby, for example, it may have The photo-aligned polymer (a) is separated into the upper layer of the coating film, and the other polymer (b) is separated into the lower layer of the coating film. In the mixed polymer, it can be controlled by separating a polymer having a small surface energy into an upper layer and a polymer having a large surface energy as a lower layer. The confirmation of the layer separation was confirmed by the fact that the surface energy of the formed alignment film was the same as or close to the surface energy of the alignment film formed using the liquid crystal alignment agent containing only the polymer (a).

As the tetracarboxylic dianhydride for synthesizing the polymer (b), it can be used without limitation from the tetracarboxylic acid II which is an essential component for synthesizing the liquid crystal alignment agent of the present invention, that is, polyglycine or a derivative thereof The tetracarboxylic dianhydride which is known as an anhydride is selected, and the same as the above-mentioned tetracarboxylic dianhydride is mentioned.

Among them, in the case where the separation property of the layer is emphasized, the tetracarboxylic dianhydride is preferably a formula (AN-3-2), a formula (AN-1-13), and a formula (AN-4-30).

When it is important to increase the transmittance of the liquid crystal display device, the acid dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), the formula (PA-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-10-1) A compound represented by the formula (AN-10-2), the formula (AN-16-3), and the formula (AN-16-4). In the formula (AN-1-2), m = 4 or 8 is preferred. In the formula (AN-4-17), m = 4 or 8, more preferably m = 8.

In the case where the VHR of the liquid crystal display element is emphasized, the acid dianhydride preferably has the formula (PA-1), the formula (AN-4-17), the formula (AN-7-2), and the formula (AN-). 10-1), a compound represented by the formula (AN-10-2), the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4). In the formula (AN-1-2) and the formula (AN-4-17), m = 4 or 8 is preferred.

As one of methods for preventing burn marks, it is effective to increase the relaxation speed of residual electric charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. In the case where the object is important, the tetracarboxylic 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).

The tetracarboxylic dianhydride used for the synthesis of the polymer (b) preferably contains 10 mol% or more of an aromatic tetracarboxylic dianhydride with respect to all tetracarboxylic dianhydrides, and more preferably contains 30 mol% or more of aromatics. Tetracarboxylic dianhydride.

Examples of the diamine and the dioxime used for the synthesis of the polymer (b) include the other diamines which are polyamines or derivatives thereof which are essential components for synthesizing the liquid crystal alignment agent of the present invention. The exemplified diamines are the same.

In the case where the layer separation property is emphasized, that is, the alignment property of the liquid crystal is further improved, it is preferable to use the formula (DI-4-1), the formula (DI-4-2), and the formula in the diamine and the dioxime. (DI-4-10), a compound represented by the formula (DI-5-1), the formula (DI-5-9), the formula (DI-5-28), and the formula (DIH-2-1). In the formula (DI-5-1), m = 1, 2, or 4 is preferable, and m = 1, or 2 is more preferable.

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

In the case where the VHR of the liquid crystal display element is emphasized, in the diamine and the dioxime, it is preferred to use the formula (DI-2-1), the formula (DI-4-1), and the formula (DI-4-2). ), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), formula (DI-13-1) and formula (DI -13-56) The diamine represented. More preferably, the diamine represented by the formula (DI-2-1), the formula (DI-5-1), the formula (DI-13-1), and the formula (DI-36-14). In the formula (DI-5-1), m=1 or 2 is preferable. In the formula (DI-5-30), k = 2 is preferred.

As one of methods for preventing burn marks, it is effective to increase the relaxation speed of residual electric charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. In the case where the object is emphasized, it is preferable to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (II). DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28 a compound represented by the formula (DI-5-30) and the formula (DI-16-1), more preferably a formula (DI-4-1), a formula (DI-5-1), and a formula (DI) -5-12) The diamine represented. In the formula (DI-5-1), m=1 or 2 is preferable. In the formula (DI-5-12), m = 2 to 6, preferably m = 5. In the formula (DI-5-13), m=1 or 2 is preferable, and m=1 is more preferable. In the formula (DI-5-30), k = 2 is preferred.

The diamine used for the synthesis of the polymer (b) preferably contains 30 mol% or more of an aromatic diamine with respect to all diamines, and more preferably contains 50 mol% or more of an aromatic diamine.

In the liquid crystal alignment agent of the present invention, the ratio of the polymer (a) to the total amount of the polymer (a) and the polymer (b) is preferably 10% by weight to 100% by weight, and more preferably 20% by weight. %~100 wt%.

The liquid crystal alignment agent of the present invention may further contain other components than the polyaminic acid of the present invention or a derivative thereof. The other components may be one type or two or more types. As another component, other polymers, compounds, etc. which are mentioned later are mentioned, for example.

Examples of the other polymer include polyester, polyamine, polyoxyalkylene, cellulose derivative, polyacetal, polystyrene derivative, and poly(styrene-phenylmethylenebuteneimide). Derivatives, poly(meth)acrylates, and the like. It may be one type or two or more types. Among these polymers, other polyaminic acid or a derivative thereof and polyoxyalkylene oxide are preferable, and other polylysine or a derivative thereof is more preferable.

The polyoxane may further include Japanese Patent Laid-Open No. 2009-036966, Japanese Patent Laid-Open No. 2010-18500, Japanese Patent Laid-Open No. 2011-102963, Japanese Patent Laid-Open No. 2011-253175, and Japanese Patent Laid-Open No. 2012-159825 , International Publications 2008/044644, International Publications 2009/148099, International Publications 2010/074261, International Publications 2010/074264, International Publications 2010/126108, International Publications 2011/068123, International Publications 2011/068127, International Publications 2011/068128, International The polyoxyalkylene disclosed in 2012/115157, International Publication No. 2012/165354, and the like.

Further, the liquid crystal alignment agent of the present invention may further contain an additive other than the compound represented by the formula (1). Examples of the additives other than the compound represented by the formula (1) include an alkenyl-substituted nadic ylidene imine compound, an oxazine compound, an oxazoline compound, and an epoxy compound other than the compound represented by the formula (1). Polymer compounds other than polyamine and its derivatives, and other low molecular compounds can be selected and used according to their respective purposes.

<Alkenyl Substituted Nadickimide Compound> The liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted nadic ylidene imide compound for the purpose of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The alkenyl-substituted nadicylimine compound may be used singly or in combination of two or more. For the purpose described, the content of the alkenyl-substituted nadic ylidene compound is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, and furthermore, relative to the poly-proline or its derivative. It is preferably from 1 wt% to 50 wt%.

The Nadik imine compound is specifically described below. The alkenyl-substituted nadicylimine compound is preferably a compound which is soluble in a solvent which dissolves the poly-proline or a derivative thereof used in the present invention. Examples of such an alkenyl-substituted nadicylimine compound include compounds represented by the following formula (NA). 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 an aromatic group having 6 to 12 carbon atoms. Base 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 an aryl group having 6 to 12 carbon atoms. , benzyl, from -Z ¹ -(O) _r -(Z ² O) _k -Z ³ -H (here, Z ¹ , Z ² and Z ^{3 are} independently an alkylene group having 2 to 6 carbon atoms, r A group represented by 0 or 1 and k is an integer of 1 to 30, and -(Z ⁴ ) _r -BZ ⁵ -H (wherein Z ⁴ and Z ^{5 are} independently a carbon number of 1 to 4) An alkyl group or a cycloalkylene group having 5 to 8 carbon atoms, B is a phenyl group, and r is a group represented by 0 or 1), and is represented by -BTBH (wherein B is a stretching phenyl group, and T is a group represented by -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, or -SO ₂ -), or a hydrogen to three hydrogen groups of these groups -OH Substituted base.

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, or a poly(ethyleneoxy)ethyl group having 4 to 10 carbon atoms. A phenoxyphenyl group, a phenylmethylphenyl group, a phenylisopropylidenephenyl group, and a group in which one hydrogen or two hydrogens of these groups are substituted with -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 arylene group having 6 to 12 carbon atoms, and -Z ¹ - a group represented by O-(Z ² O) _k -Z ³ - (here, Z ¹ - Z ³ and k are as defined above), and -Z ⁴ -BZ ⁵ - (here, Z ⁴ , Z ⁵ and B are as defined above), represented by -B-(OB) _r -T-(BO) _r -B- (where B is a phenyl group and T is a carbon number of 1-3). The alkyl group, -O- or -SO ₂ -, r is as defined above, the group represented by the group, or the group of one hydrogen to three hydrogens of these groups substituted by -OH.

In this case, preferred W is an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenylene group, a benzylidene group, a benzene dimethyl group, and a -C ₃ H ₆ -O-(Z ² -O) group. _{a group represented by n} -OC ₃ H ₆ - (here, Z ² is an alkylene group having 2 to 6 carbon atoms, and n is 1 or 2), and is represented by -BTB- (wherein B is a stretching phenyl group, and , T is a group represented by -CH ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (here, B is a stretching phenyl group), and a group of these groups One hydrogen or two hydrogen-substituted groups.

Such an alkenyl-substituted nadicylimine compound can be maintained by heating an alkenyl-substituted nadic anhydride anhydride and a diamine at a temperature of from 80 ° C to 220 ° C for 0.5 hour, as described in Japanese Patent No. 2,729,565. A compound obtained by the synthesis in ～20 hours or a commercially available compound. Specific examples of the alkenyl-substituted nadicylimine compound 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-dicarboxy quinone imine, N-allyl-allyl bicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindole Imine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-allyl bicyclo [2.2.1 Gh-5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-isopropenyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-cyclohexyl-allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-phenyl-allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine,

N-phenyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-benzyl-allylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-benzyl -Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-(2-hydroxyethyl)-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine,

N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[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-dihydroxypropane -Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2,3-dihydroxypropyl)-allyl(methyl)bicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine, 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-dicarboxyindenine, N-(4-hydroxyphenyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxyphenyl)-methylallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, 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-dicarboxyindolimine, N-(3-hydroxyphenyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-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}-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-{2-(2-hydroxyethyl) Oxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-[2-{2-(2-hydroxyethoxy) Ethyloxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-[2-{2-(2-hydroxyethoxy) Ethoxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-[2-{2-(2-hydroxyl) Ethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-{4-(4-hydroxyphenyl) Isopropyl)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-{4-(4-hydroxyphenylisopropylidene) Phenyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene)benzene 5-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, and oligomers thereof,

N,N'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-ethylidene-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-ene-2,3-dicarboxy quinone imine), N,N '-Extended cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine),

1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, 1,2-double {3' -(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, 1,2-bis{3'-(methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, bis[2'-{3'-(allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) propoxy}ethyl]ether, 1,4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine]propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) Oxy}butane,

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,

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}anthracene,

Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}indole, 1,6-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine)-3-hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinoid imine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy} 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-dicarboxyindolimine)-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 Methyl-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-(2-hydroxy)benzylidene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-(2-hydroxy)benzyl-bis(methallyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-(2,3-dihydroxy)benzenedimethyl-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxynonimine),

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)}phenoxymethylpropane, N,N',N''-tris(ethylene methallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine) isomeric cyanurate, and oligomers thereof.

Further, the alkenyl-substituted nadicylimine compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene group.

Preferred compounds among the alkenyl substituted nadic quinone imine compounds are shown below. N,N'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-ethylidene-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-ene-2,3-dicarboxy quinone imine), N,N '-Extended cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine),

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-dicarboxyfluorene Imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine Phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallyl double [2.2.1]hept-5-ene-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-dicarboxy quinazoline)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'-Ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-ethylene-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-ethylidene-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-ene-2,3-dicarboxy quinone imine), N,N '-Extended cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinylimine).

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.

Further, as a particularly preferred alkenyl-substituted nadicylimine compound, a bis{4-(allylbicyclo[2.2.1]hept-5-ene represented by the following formula (NA-1) is exemplified. -2,3-dicarboxy quinhomine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]heptane represented by formula (NA-2) 5-ene-2,3-dicarboxy quinimine), and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5 represented by formula (NA-3) -ene-2,3-dicarboxy quinone imine).

<Compound having a radically polymerizable unsaturated double bond> 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 device 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, an alkenyl-substituted nadic quinone imine compound is not contained in the compound having a radical polymerizable unsaturated double bond. For the purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, based on the polyphthalic acid or a derivative thereof. More preferably, it is 1 wt% - 50 wt%.

In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl substituted imidide compound is reduced in order to reduce the ion density of the liquid crystal display element, suppress the increase in the ion density over time, and further suppress The generation of the afterimage, the compound having a radical polymerizable unsaturated double bond/alkenyl-substituted nadic ylidene compound is preferably 0.1 to 10, more preferably 0.5 to 5 by weight.

The compound having a radical polymerizable unsaturated double bond will be specifically described below. Examples of the compound having a radically polymerizable unsaturated double bond include a (meth)acrylic acid ester, a (meth)acrylic acid derivative such as (meth)acrylamide, and a bis-synylene diimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl methacrylate.

Specific examples of the difunctional (meth) acrylate include, for example, ethylene diacrylate, and Aronix M-210 (Aronix M-210), which is a product of the East Asian synthetic chemical industry. Ronex M-240 and Aronix M-6200, KAYARAD HDDA, Kayad HX-220, Kayad R-604 and Kaya as products of Nippon Chemical Co., Ltd. R-684, V260, V312 and V335HP, which are products of the Osaka Organic Chemical Industry Co., Ltd., and Light Acrylate BA-4EA, which is a product of the Kyoei Oil & Fat Chemical Industry Co., Ltd. Light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4′-methylenebis(N,N-dihydroxyethylene acrylate aniline), which is a synthetic chemical industry in East Asia. (Shares) products of the Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, as a product of Nippon Kayaku (share), Kayad TPTA, Kayad DPCA-20, Kayad DPCA-30, Kayad DPCA-60, Kayad DPCA-120, and as Osaka VGPT for products of the organic chemical industry (shares).

Specific examples of the (meth) acrylamide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, and N-positive Propyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylate Amine, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-di Ethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-propenyl acridine, N-propenylpyrrolidine, N,N'-methylenebis propylene amide, N,N'-ethylenebis propylene amide, N,N'-dihydroxyethylene bis acrylamide, N-(4-hydroxyphenyl) Methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl)methacrylamide, N-[2-(N,N- Dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-(methoxy Methyl methacrylamide, N-(hydroxyl Yl) -2-methyl-acrylamide, N- benzyl-2-methyl acrylamide, and N, N'- methylene bis methyl acrylamide.

Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylene-bisacrylamide, ethylene diacrylate, and the like are particularly preferable. And 4,4'-methylenebis(N,N-dihydroxyethylene acrylate aniline).

Examples of the bis-s-butylene diimide include BMI-70 and BMI-80 manufactured by KI Chemical Co., Ltd., and BMI-1000, BMI-3000, and BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. BMI-5000 and BMI-7000.

<Oxazine compound> The liquid crystal alignment agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The oxazine compound may be one compound or two or more compounds. For the purpose described, the content of the oxazine 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 1% by weight to 20%, based on the poly phthalic acid or a derivative thereof. Wt%.

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

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

The structure of the oxazine is known in various structures. In the present invention, the structure of the oxazine is not particularly limited, and examples of the oxazine structure in the oxazine compound include an aldehyde having a condensed polycyclic aromatic group such as benzoxazine or naphthoxazine. The structure of the azine.

Examples of the oxazine compound include compounds represented by the following formula (OX-1) to formula (OX-6). Further, in the following formula, a bond represented toward the center of the ring means that the bond is bonded to any one of the carbons constituting the ring and the bondable substituent. In the formula (OX-1) to the formula (OX-3), L ³ and L ⁴ are an organic group having 1 to 30 carbon atoms, and in the formula (OX-1) to the formula (OX-6), L ⁵ to L ⁸ It 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, and in the formula (OX-5) and 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 1 to 3 carbon atoms, a benzene ring or a naphthalene ring in Q ² The hydrogen bonded thereto is independently and may be substituted by -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ .

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

Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds. 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.

Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds. In the formula, L ³ is preferably an alkyl group having 1 to 30 carbon atoms, and still more preferably an alkyl group having 1 to 20 carbon atoms.

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

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

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

Among these, more preferably, it is exemplified by the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the formula (OX-3). -7), formula (OX-3-9), formula (OX-4-1) to formula (OX-4-6), formula (OX-5-3), formula (OX-5-4), and An oxazine compound represented by the formula (OX-6-2) to the formula (OX-6-4).

The oxazine compound can be produced by the same method as the method described in International Publication No. 2004/009708, Japanese Patent Laid-Open No. Hei 11-12258, and Japanese Patent Laid-Open No. 2004-352670.

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

The oxazine compound represented by the formula (OX-2) can be obtained by reacting a compound having a naphthol-based hydroxyl group by a method in which a primary amine is slowly added to formaldehyde, and reacting (refer to International Publication 2004/ 009708).

The oxazine compound represented by the formula (OX-3) can be obtained by subjecting the phenol compound to 1 mol in the presence of a secondary aliphatic amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound. The aldehyde having at least 2 mols of a phenolic hydroxyl group of the phenol compound and the 1 mol of the primary amine are reacted in an organic solvent (refer to International Publication No. 2004/009708 and Japanese Patent Laid-Open No. Hei 11-12258).

The oxazine compound represented by the formula (OX-4) to the formula (OX-6) can be obtained by having a plurality of 4,4'-diaminodiphenylmethane or the like at a temperature of 90 ° C or higher. A benzene ring and an organic group-containing diamine bonded to these benzene rings, an aldehyde such as formalin, and a phenol are subjected to a dehydration condensation reaction in n-butanol (refer to Japanese Patent Laid-Open No. 2004-352670).

<Oxazoline Compound> The liquid crystal alignment agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. For the purpose, 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 1% by weight to the polylysine or a derivative thereof. 20 wt%. Alternatively, when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the content of the oxazoline compound is preferably 0.1 wt% with respect to the polyamine or its derivative. 40 wt%.

The oxazoline compound will be specifically described below. 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 structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure on the 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. Copolymer with a monomer having no oxazoline structure.

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

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, and 4-furan-2. - benzylidene-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis (4,5 -dihydro-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2 -oxazoline, 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'-methylenebis(4-phenyl-2-oxazoline). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group, such as Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.), may be mentioned. Among these oxazoline compounds, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is more preferable.

<Epoxy compound> The liquid crystal alignment agent of the present invention may further contain an epoxy compound other than the compound represented by the formula (1) for the purpose of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The epoxy compound may be one compound or two or more compounds. For the purpose, 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 from 1% by weight to 20%, relative to the polyaminic acid or a derivative thereof. Wt%.

The epoxy compound other than the compound represented by the formula (1) will be specifically described below. 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, and hexafluoropropylene oxide. , cyclohexane oxide, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-glycidyl phthalic acid Dimethyl imine, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N,N-diglycidylaniline, and 3-[2 -(Perfluorohexyl)ethoxy]-1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol dihydrate. Glycerol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-ring Oxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane.

As a compound having three epoxy rings in the molecule, for example, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4] -([2,3-Epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Tieke Moya VG3101L (Techmore VG3101L)", (manufactured by Mitsui Chemicals, Inc.)).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl. Base-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'- Diaminodiphenylmethane, and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

In addition to the above, an oligomer having an epoxy ring or a polymer may be exemplified as a compound having an epoxy ring in the molecule. Examples of the monomer having an epoxy ring include glycidyl (meth)acrylate, 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) (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, styrene, methyl styrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) (meth)acrylate Ester, N-cyclohexylmethyleneimine 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 another monomer include N-phenyl maleimide-glycidyl methacrylate copolymer and N-ring. Hexyl maleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, methyl 2-hydroxyethyl acrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and styrene-A Glycidyl acrylate 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 "Tieke Moya VG3101L", 3,4-epoxycyclohexenylmethyl -3',4'-epoxycyclohexene carboxylate, N-phenyl maleimide-glycidyl methacrylate copolymer, and 2-(3,4-epoxy ring Hexyl) ethyltrimethoxydecane.

More specifically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, and isocyanuric glycidyl glycol. 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 glycol, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, glycidyl isocyanurate, and chain aliphatic. An epoxy compound and a cyclic aliphatic epoxy compound.

Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, and a hydrogenated bisphenol-A epoxy compound. Hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, Phenolic novolak type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolac type epoxy compound, brominated cresol novolak type epoxy compound, bisphenol A novolac type epoxy compound, containing naphthalene Skeleton epoxy compound, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidyl ether compound, polysulfide type diglycidyl ether A compound and a biphenol type epoxy compound.

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

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

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

Examples of the glycidyl decylamine include a glycidyl guanamine type epoxy compound.

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

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

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, and jER1010 (all manufactured by Mitsubishi Chemical Corporation), and Eptoto YD-128 (Epotohto YD) -128) (Manufactured by Tohto Kasei Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Ai Piklon 840 (Epiclon 840), Ai Piklon 850, Ai Piklon 1050 (all manufactured under the trade name, Di Ai Sheng (DIC) (share)), Apollo R-140 (Epomik R-140), Apollo R-301, and Apollok R-304 (all manufactured by Mitsui Chemicals Co., Ltd.).

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

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

Examples of the hydrogenated bisphenol-A type epoxy compound include: TOPTO ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), and Rikaresin HBE-100 (Rikaresin HBE- 100) (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.), and Danacol EX-252 (trade name, manufactured by Nagase ChemteX (share)).

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 manufactured by Mitsubishi Chemical Corporation), Aptuoto YDB-360, and Aptuoto YDB-400 (both For the trade name, manufactured by Tohto Kasei (share), DER-530, DER-538 (all trade names, manufactured by Dow Chemical Company), Ai Piklon 152, and Ai Piklon 153 (all are trade names, Di Aisheng (shares) manufacturing).

Examples of the phenol novolak-type epoxy compound include jER152 and jER154 (all manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade name, manufactured by Tohto Kasei Co., Ltd.), and DEN431 and DEN438 (all products). Name, manufactured by Dow Chemical Co., Ltd., Ai Piklon N-770 (trade name, manufactured by Di Ai Sheng (share)), EPPN-201, and EPPN-202 (all manufactured by Nippon Chemical Co., Ltd.).

Examples of the cresol novolac type epoxy compound include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all manufactured by Dongdu Chemical Co., Ltd.), and Ai Piklon N. -665, Ai Piklon N-695 (all manufactured under the trade name, Di Ai Sheng (share)), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (both Product name, manufactured by Nippon Kay (Pharmaceuticals).

Examples of the bisphenol A novolak-type epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), and Ai Piklon N-880 (trade name, manufactured by Di Ai Sheng (share)).

Examples of the epoxy compound containing a naphthalene skeleton include eppylon HP-4032, eppylon HP-4700, and ipexlon HP-4770 (all manufactured under the trade name, Di Ai Sheng (share)), and NC- 7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (formula: EP-1), catechol diglycidyl ether (formula: EP-2), and resorcinol. Diglycidyl ether (formula EP-3), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([ 2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (formula EP-4), tris(4-glycidoxyphenyl)methane (formula EP-5 below) ), jER1031S, jER1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by Dow Chemical Co., Ltd.), Dana Kerr EX-201 (product) Name, Changsong Huacheng (share) manufacturing), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Chemical Co., Ltd.), Temmoiya VG3101L (trade name, Mitsui Chemicals) (manufactured by the company), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7.

Examples of the dicyclopentadiene phenol type epoxy compound include Tekexix-556 (trade name, manufactured by The Dow Chemical Company), and Ai Piklon HP-7200 (trade name, Di Ai Sheng (share) Manufacturing).

Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and Ricardo new 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 (formula EP-10), tripropylene glycol diglycidyl ether (formula EP-11 below), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether ( Formula EP-12), 1,4-butanediol diglycidyl ether (formula EP-13 below), 1,6-hexanediol diglycidyl ether (formula EP-14 below), dibromo Neopentyl glycol diglycidyl ether (EP-15 below), Dana Kerr EX-810, Dana Kerr EX-851, Dana Kerr EX-8301, Dana Kerr EX-911, Dana Kerr EX- 920, Dana Kerr EX-931, Dana Kerr EX-211, Dana Kerr EX-212, Dana Kerr EX-313 (all manufactured by Changchun Huacheng (share)), DD-503 (trade name) , ADEKA (manufactured by ADEKA), Rikari New W-100 (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4- Hexanediol (Equation EP-16), Gan Polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Dana Kerr EX-313, Dana Kerr EX-611, Dana Kerr EX-321, and Dana Kerr EX-411 (all manufactured under the trade name, Changchun Huacheng (share)).

Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both of which are trade names, manufactured by Toray Thiokol Co., Ltd.).

Examples of the biphenol-based epoxy compound include YX-4000 and YL-6121H (all manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all are trade names, Japanese chemical drugs). (shares) manufacturing).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (formula: EP-17), diglycidyl phthalate (formula: EP-18), and phthalic acid (2-Methoxy-oxiranylmethyl) ester (Equation EP-19), hexahydrophthalic acid diglycidyl ester (Equation EP-20), and the following formula EP-21 The compound represented by the formula, the compound represented by the following formula EP-22, and the compound represented by the following formula EP-23.

Examples of the glycidyl ester epoxy compound include jER871 and jER872 (all of which are trade names, manufactured by Mitsubishi Chemical Corporation), Ai Piklon 200, and Ai Piklon 400 (all manufactured under the trade name, Di Ai Sheng (share)). ), Dana Kerr EX-711, and Dana Kerr EX-721 (all manufactured by Changchun Huacheng (share)).

Examples of the polyglycidylamine compound include N,N-diglycidylaniline (Equation EP-24), N,N-diglycidyl-o-toluidine (Equation EP-25), N,N-diglycidyl-m-toluidine (formula EP-26), N,N-diglycidyl-2,4,6-tribromoaniline (formula EP-27), 3- (N,N-diglycidyl)aminopropyltrimethoxydecane (formula EP-28), N,N,O-triglycidyl-p-aminophenol (formula EP-29), N , N, O-triglycidyl-m-aminophenol (formula EP-30), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (under 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-bis(N,N-diglycidylaminomethyl)cyclohexane (iron-trad-C (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) , the following formula EP-33), 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane (formula: EP-34), 1,3-bis(N,N-di Glycidylamino)cyclohexane (described below) EP-35), 1,4-bis(N,N-diglycidylamino)cyclohexane (formula EP-36 below), 1,3-bis(N,N-diglycidylamino)benzene (Formula EP-37), 1,4-bis(N,N-diglycidylamino)benzene (formula: EP-38), 2,6-bis(N,N-diglycidylamino) Methyl)bicyclo[2.2.1]heptane (formula EP-39), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (the following formula EP-40), 2,2'-dimethyl-(N,N,N',N'-tetraglycidyl)-4,4'-diaminobiphenyl (formula EP-41), N ,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether (formula EP-42), 1,3,5-tris(4-(N,N-bi-shrink) Glyceryl)aminophenoxy)benzene (formula EP-43), 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether (formula EP-44 below), three (4-(N,N-diglycidyl)aminophenyl)methane (formula EP-45), 3,4,3',4'-tetrakis (N,N-diglycidylamino) Benzene (formula EP-46 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl ether (formula: EP-47), from the following formula EP- The compound represented by 48 and the compound represented by the following formula EP-49.

Examples of the homopolymer of the monomer having an oxiranyl group include polyglycidyl methacrylate. Examples of the copolymer of the oxiranyl group-containing monomer include N-phenyl maleimide-glycidyl methacrylate copolymer and N-cyclohexylmethylene iodide. - Glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-A A glycidyl acrylate copolymer, a (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

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

Examples of the monomer other than the monomer having an oxiranyl group in the copolymer of the oxopropyl group-containing monomer include (meth)acrylic acid, methyl (meth)acrylate, and (a) Ethyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, Benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (meth)acrylic acid ( 3-ethyl-3-oxetanyl)methyl ester, N-cyclohexylmethyleneimine, and N-phenylmaleimide.

As the glycidyl iso-glycidyl cyanide, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (EP-50 of the following formula), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ( The following formula EP-51) and an isomeric isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Eprod PB3600 (Epolead PB3600) (trade name, manufactured by Daicel).

As the cyclic aliphatic epoxy compound, for example, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (矽罗基赛2021) (Celloxide 2021) (manufactured by Daicel (product), the following formula EP-52), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3', 4'-ring Oxycyclohexyl carboxylate (formula EP-53 below), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (formula EP-54 below), ε - caprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2:8,9-dicyclooxy limonene (Celloxide 3000 ( The product name, Daicel (manufactured by the company), 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 Manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan (shares)), EHPD-3150 (trade name, manufactured by Daicel (share)), and ring An aliphatic epoxy resin.

The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolak type epoxy compound, and a cyclic aliphatic type epoxy compound, and more 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 "Tieke Moya VG3101L", 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene Carboxylic acid ester, N-phenyl maleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac type epoxy compound, And one or more kinds of cresol novolac type epoxy compounds.

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than polyglycine and a derivative thereof, and a low molecular compound, and can be selected and used according to each purpose.

The polymer compound is a polymer compound 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, fluorenone modified polyurethane, and fluorenone. Polyester.

As the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant suitable for the purpose may be mentioned, 2) an antistatic agent may be mentioned when it is required to enhance the antistatic property, and 3) when it is desired to improve the adhesion to the substrate. In the case of a decane coupling agent or a titanium-based coupling agent, 4) a ruthenium imidization catalyst may be mentioned when hydrazine imidization is carried out at a low temperature.

Examples of the decane coupling agent include vinyltrimethoxydecane, vinyltriethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, and N-( 2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-aminobenzene Triethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl A Dimethoxy decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyl Trimethoxydecane, N-(1,3-dimethylbutylene)-3-(triethoxydecyl)-1-propylamine, and N,N'-bis[3-(trimethoxydecyl) ) propyl] ethylene diamine. A preferred decane coupling agent is 3-aminopropyltriethoxydecane.

Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-diethylaniline, and methyl group. Aromatic amines such as aniline and hydroxy-substituted aniline; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy substitution Cyclic amines such as isoquinoline, imidazole, methyl substituted imidazole, and hydroxy substituted imidazole. The ruthenium amide catalyst is preferably 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 to be added is usually from 0 wt% to 20 wt%, preferably from 0.1 wt% to 10 wt%, based on the total weight of the polyamic acid or a derivative thereof.

The amount of the ruthenium imidization catalyst added is usually from 0.01 equivalents to 5 equivalents, preferably from 0.05 equivalents to 3 equivalents, based on the carbonyl group of the polyamic acid or a derivative thereof.

The amount of the other additives to be added varies depending on the use thereof, but is usually from 0 wt% to 100 wt%, preferably from 0.1 wt% to 50 wt%, based on the total weight of the polyamic acid or its derivative.

The polyaminic acid or a derivative thereof of the present invention can be produced in the same manner as the known polyaminic acid or a derivative thereof for forming a film of polyimine. The total addition amount of the tetracarboxylic dianhydride is preferably set to be 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 the derivative thereof of the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyaminic acid or its derivative can be determined by measurement by a gel permeation chromatography (GPC) method.

The poly-proline or a derivative thereof of the present invention can be confirmed by the following means: using poly Infrared (IR), Nuclear Magnetic Resonance (NMR) to make the polylysine of the present invention or its derivative The solid component obtained by precipitation in a large amount of poor solvent was analyzed. In addition, the monomer to be used can be confirmed by gas chromatography (GC), high performance liquid chromatography (HPLC) or gas chromatography mass spectrometry (Gas Chromatography-Mass). Spectrometry, GC-MS) The extract obtained by decomposing the polyamic acid or its derivative using an aqueous solution of a strong base such as KOH or NaOH, and extracting the extract from the decomposition product using an organic solvent.

Further, for example, from the viewpoint of the coatability of the liquid crystal alignment agent or the adjustment of the concentration of the polyaminic acid or its 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 generally used for a production step or a use of a polymer component such as polyacrylic acid or a 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 lyophilic solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability.

Examples of the aprotic polar organic solvent which is a solvophilic solvent with respect to polyglycine or a derivative thereof include N-methyl-2-pyrrolidone, dimethylimidazolidinone, 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.

It is particularly preferable to use at least one solvent selected from the group consisting of alcohols, ethers, and ketones for other solvents for the purpose of improving coatability and the like.

Examples of the alcohol include butyl cellosolve (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and propylene glycol monopropyl acetate. Ether, 1-butoxy-2-propanol, 2-(2-methoxypropoxy)propanol, ethyl lactate, methyl lactate, propyl lactate, butyl lactate, and the like.

Examples of the ether include an alkylene glycol dialkyl ether such as ethylene glycol dimethyl ether or ethylene glycol diethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol. Dialkylene glycol dialkyl ether such as methyl ethyl ether or diethylene glycol butyl methyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Ethylene glycol monoalkyl ether; ethylene glycol mono-n-butyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate , diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol single Alkyl glycol alkyl ether acetate such as butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and other propylene glycol A monoalkyl ether propionate; a cyclic ether such as tetrahydrofuran or the like.

Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and diisobutyl butyl. Ketone, methyl-3-methoxypropionate, and the like.

Among these solvents, 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, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether and 1-butoxy-2-propanol.

The concentration of the polyaminic acid or its derivative in the alignment agent of the present invention is preferably from 0.1% by weight to 40% by weight. When the alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the contained polyamic acid with a solvent in advance.

The solid content concentration in the alignment agent of the present invention is not particularly limited, and may be selected in accordance with various coating methods described below. In general, in order to suppress unevenness at the time of coating, pinholes, and the like, it is preferably 0.1 wt% to 30 wt%, more preferably 1 wt% to 10 wt%, 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, when coating is performed by a printing machine, it is 5 mPa·s to 100 mPa·s (more preferably 10 mPa·s to 80 mPa·s). If it is less than 5 mPa·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 preferably 5 mPa·s to 200 mPa·s (more preferably 10 mPa·s to 100 mPa·s). In the case of coating using an inkjet coating device, it is preferably 5 mPa·s to 50 mPa·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. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a 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 a step 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, if necessary, the film obtained by the heating and drying step and the heating and calcining step may be subjected to a rubbing treatment to impart anisotropy. Alternatively, if necessary, the light may be irradiated after the coating step, the heat drying step, or the light may be irradiated after the heating calcination step 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 to a substrate in a liquid crystal display element, similarly to the production of a normal liquid crystal alignment film. The substrate may be an electrode or color in which an indium tin oxide (ITO), an indium zinc oxide (In ₂ O ₃ -ZnO, IZO), an indium gallium zinc oxide (In-Ga-ZnO ₄ , IGZO) electrode, or the like may be provided. A glass substrate such as a filter.

As a method of applying a liquid crystal alignment agent onto a substrate, a rotator method, a printing method, a dipping method, a dropping method, an inkjet method, and the like are generally known. These methods can also be equally applied to the present invention.

The heating and drying step is generally known as a method of performing heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. The heat drying step is preferably carried out at a temperature within a range in which the solvent can be evaporated, more preferably at a relatively low temperature with respect to the temperature in the heating calcination step. Specifically, the heating and 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 can be carried out under the conditions required for the polyglycine or its derivative to exhibit a dehydration/ring closure reaction. 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. It is usually 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 to 250 ° C.

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

The liquid crystal alignment film of the present invention using a rubbing method can be formed by the steps of applying the liquid crystal alignment agent of the present invention onto a substrate, heating and drying the substrate coated with the alignment agent, and heating the film. The step of simmering and the step of rubbing the film.

The rubbing treatment can be carried out in the same manner as the rubbing treatment for the alignment treatment of the liquid crystal alignment film, as long as it is a condition that a sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. The preferred conditions are a hair intrusion of 0.2 mm to 0.8 mm, a platform moving speed of 5 mm/sec to 250 mm/sec, and a roll rotation speed of 500 rpm to 2,000 rpm.

A method of forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described 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, imparting anisotropy to the coating film by linearly polarizing or non-polarizing light irradiated with radiation, and then heating the film. Simmered. In addition, it can be formed by heating and drying the coating film, heating and sintering, and irradiating the linearly polarized light or the non-polarized light of the radiation. From the viewpoint of the alignment property, it is preferred to carry out the irradiation step of the radiation before the heating calcination step.

Further, in order to improve the liquid crystal alignment ability of the liquid crystal alignment film, it is also possible to face the linearly polarized light or the non-polarized light which irradiates the radiation while the coating film is heated. The irradiation of the radiation may be carried out in the step of heating and drying the coating film or the step of heating and calcining the coating film, or between the heating drying step and the heating calcining 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.

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

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even under low-energy light irradiation. The irradiation amount of the linearly polarized light in the radiation irradiation step is preferably 0.05 J/cm ² to 20 J/cm ² , and more preferably 0.5 J/cm ² to 10 J/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 on the surface of the film is not particularly limited. When the liquid crystal exhibits a strong alignment regulating force, it is preferable that the alignment treatment time is shortened as far as possible 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 or unpolarized as described above. In the case where the pretilt angle is to be expressed, the irradiation amount of the light irradiated to the film is preferably 0.05 J/cm ² to 20 J/cm ² , particularly preferably 0.5 J/cm ² to 10 J/cm ² , and the wavelength is preferably 250 nm to 400 nm, 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 from the viewpoint of shortening the alignment treatment time, it is preferably 30 to 60 degrees.

In the light source used in the step of irradiating the linearly polarized or non-polarized light of the radiation, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a deep ultraviolet lamp, a halogen lamp, a metal halide lamp, and a high power can be used without limitation. Metal halide lamps, xenon lamps, mercury xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, light emitting diode (LED) lamps, sodium lamps, microwave discharged electrodeless lamps, and the like.

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

Examples of the cleaning method using the cleaning liquid include brushing, spraying, steam cleaning, and ultrasonic cleaning. These methods can be performed separately or in combination. As the cleaning liquid, pure alcohol or various alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as dichloromethane, acetone, and methyl ethyl ketone can be used. Ketones are not limited to these cleaning solutions. Of course, these cleaning liquids can use a cleaning liquid which is sufficiently refined and has less impurities. Such a cleaning method can also be applied to the cleaning step in forming 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 applied 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 for the annealing treatment include a UV lamp, a fluorescent lamp, an LED lamp, and the like. The amount of light irradiation is preferably from 0.3 J/cm ² to 10 J/cm ² .

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

The liquid crystal alignment film of the present invention is characterized by an anisotropy having a particularly large alignment. The size of such anisotropy can be evaluated by a method using polarized light described in JP-A-2005-275364 or the like. Further, as shown in the following examples, it can also be evaluated by a method using ellipsometry. In detail, the retardation value of the liquid crystal alignment film can be measured using a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of alignment of the polymer backbone. That is, a film having a large retardation value has a large degree of alignment, and when the alignment film of the present invention is used as a liquid crystal alignment film, an alignment film having greater anisotropy can be considered to have a large alignment limit for a liquid crystal composition. force.

The liquid crystal alignment film of the present invention can be suitably used in a liquid crystal display device of a transverse electric field type. 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.

In addition to the alignment use of the liquid crystal composition for liquid crystal displays, the liquid crystal alignment film of the present invention can be used for alignment control of optical compensation materials or all other liquid crystal materials. Further, since the alignment film of the present invention has a large anisotropy, it can be used alone for 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 element including a pair of substrates disposed oppositely, electrodes formed on one or both of opposite surfaces of the pair of substrates, and pairs formed on the pair of substrates a liquid crystal alignment film on the surface and a liquid crystal layer formed between the pair of substrates, and the liquid crystal alignment film is an alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include a vapor deposited film of ITO or metal. Further, the electrode may be formed on the entire surface of one face of the substrate, or may be formed, for example, in a patterned desired shape. The desired shape of the electrode may, for example, be a comb type or a sawtooth structure or the like. 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, the electrode is disposed on one of the pair of substrates, and in the case of another liquid crystal display element, the electrode is 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 formed in a form of sandwiching a liquid crystal composition by the pair of substrates facing each other in which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as a fine particle or a resin sheet interposed between the pair of substrates and forming an appropriate interval may be used as needed.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. 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, Japanese Patent Laid-Open No. Hei 8-157826, and Japanese Patent Laid-Open No. Hei 8-231960. Japanese Patent Laid-Open No. Hei 9-241644 (EP 885272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1), Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japan Patent Publication No. Hei 9-241643 (EP885271A1), Japanese Patent Laid-Open No. Hei 10-204016 (EP844229A1), Japanese Patent Laid-Open No. Hei 10-204436, Japanese Patent Laid-Open No. Hei 10-231482, Japanese Patent Laid-Open No. 2000-087040, Japanese Patent Laid-Open No. 2001 The liquid crystal composition disclosed in -48822 or the like.

Even if one or more optically active compounds are added to a liquid crystal composition having a positive or negative dielectric anisotropy, it has no effect.

A liquid crystal composition having a negative dielectric anisotropy will be described. The liquid crystal composition having a negative 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 number of at least one hydrogen substituted by fluorine 2 to 2 The alkenyl group of 12, ring A ² and ring B ^{2 are} independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-di Base, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-benzene Base, 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-diyl, Z ¹ Independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -COO-, or -CF ₂ O-, j is 1, 2, or 3, and when j is 2 or 3, any two rings A ² may be the same or different, and any two Z ¹ may be the same or different.

In order to increase the dielectric anisotropy, it is preferred that ring A ² and ring B ² are 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl, respectively. The viscosity is lowered, and preferred ring A ² and ring B ² are each a 1,4-cyclohexylene group.

In order to improve the dielectric anisotropy, Z ¹ is preferably -CH ₂ O-, and in order to lower the viscosity, Z ¹ is preferably a single bond.

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.

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). 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 number of at least one hydrogen substituted by fluorine 2 to 2 The alkenyl group of 12, 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, and Z ¹¹ and Z ^{12 are} independently Single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, or -COO-.

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 1 to 12 carbon atoms.

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. In order to lower the viscosity, a more preferred alkenyl group is a vinyl group, a 1-propenyl group, a 3-butenyl group or a 3-pentenyl group. The preferred steric configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. Alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl are considered for reasons such as lowering the viscosity and the like. It is preferably 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. Further preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.

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.

In order to improve the dielectric anisotropy, Z ¹¹ and Z ¹² are preferably -CH ₂ O-, and in order to lower the viscosity, Z ¹¹ and Z ¹² are preferably a single bond.

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).

Preferable examples of the liquid crystal composition having a negative dielectric anisotropy are exemplified in Japanese Patent Laid-Open No. Hei 57-114532, Japanese Patent Laid-Open No. Hei 2-4725, Japanese Patent Laid-Open No. Hei-4-224885, and Japanese Patent No. Kaiping 8-40953, Japanese Patent Laid-Open No. Hei 8-104869, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Laid-Open 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. 10 -236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Laid-Open No. Hei 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, 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. 10- 291945, Japanese Patent Laid-Open No. Hei 11-029581, Japanese Patent Laid-Open No. Hei 11-080049, Japanese Patent Laid-Open No. 2000-256307, Japanese Patent Laid-Open No. 2001-019965, Japanese Patent Laid-Open No. 2001-072626, Japanese Patent JP 2001-192657, Japanese Patent Laid-Open 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. 2009-084362, and the like The disclosed liquid crystal composition.

Further, for example, from the viewpoint of improving the alignment property, for example, the liquid crystal composition used in the element of the present invention may further contain an additive. 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 the liquid crystal, the most preferable structure of the photopolymerizable monomer or oligomer is a structure of the formula (PM-1-1) to the formula (PM-1-6).

In order to exhibit the effect of determining the tilt direction of the liquid crystal after polymerization, the photopolymerizable monomer or oligomer is preferably 0.01 wt% or more. Further, in order to make the alignment effect of the polymer after polymerization suitable, or to prevent the unreacted monomer or oligomer from eluting into the liquid crystal after ultraviolet irradiation, it is preferably 30% by weight or less.

The optically active compound is mixed in the composition in order to cause a twist angle of the liquid crystal to impart a twist angle. 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 still more preferred ratio is in the range of 0.01 wt% to 2 wt%.

In order to prevent a decrease in specific resistance due to heating in the atmosphere, or 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 time, in liquid crystal The composition is mixed with an antioxidant.

Preferable examples of the antioxidant are compounds (AO-1) and the like in which w is an integer of 1 to 10. In the compound (AO-1), preferred w is 1, 3, 5, 7, or 9. Still 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 still more preferred ratio is in the range of 100 ppm to 300 ppm.

Preferable examples of the ultraviolet absorber are a benzophenone derivative, a benzoate derivative, a triazole derivative, and the like. Further, a light stabilizer such as an amine having a steric hindrance is also preferable. 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 still more preferred ratio is in the range of 100 ppm to 10,000 ppm.

In order to be suitable for the element of the guest host (GH) mode, a dichroic dye such as an azo dye or an anthraquinone dye is mixed in the composition. A preferred ratio of the pigment is in the range of 0.01 wt% to 10 wt%.

In order to prevent foaming, an antifoaming agent such as dimethyl hydrazine oil or methyl phenyl hydrazine oil is mixed in the composition. 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 still more preferred ratio is in the range of 1 ppm to 500 ppm.

In order to be suitable for the elements of the polymer sustained alignment (PSA) mode, a polymerizable compound may 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 thereof, 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 still more preferred ratio is in the range of from about 0.1 wt% to about 2 wt%.

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 is independently 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), Yanjiagu 184 (registered trademark), or Darocure 1173 (registered trademark) as a photopolymerization initiator (Ciba, Japan) Japan KK)) is suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1 wt% to 5 wt%. It is particularly preferred to include a photopolymerization initiator in the range of 1 wt% to 3 wt%.

In the radical polymerization system, the polymerization inhibitor can be mixed by 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, polymerization is achieved. The reaction stopped. 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 still 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> 1. Weight average molecular weight (Mw) The weight average molecular weight of polyglycine was determined by using a 2695 separation module·2414 differential refractometer (manufactured by Waters) and using the GPC method. The measurement was carried out and then converted to polystyrene. The obtained polylysine was obtained by using a mixed solution of phosphoric acid-dimethylformamide (DMF) (phosphoric acid/DMF=0.6/100: weight ratio) to a polyglycine concentration of about 2 wt%. Dilute. 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 uses TSK standard polystyrene manufactured by Tosoh.

2. Pencil hardness The method according to JIS standard "JIS-K-5400, 8.4, pencil scratch test". The result is expressed by the hardness of the pencil lead. When the pencil hardness is low, peeling or thinning is likely to occur, and if the value is more than 2H, an alignment film which is less likely to be thinned or the like can be obtained.

3. Friction resistance test The abrasion resistance test was carried out using a friction treatment device (manufactured by Iinuma Gauge Co., Ltd.). Polyimide coated on a glass substrate with a rubbing cloth (hair length of 1.9 mm: rayon) of 0.40 mm, a platform moving speed of 60 mm/sec, and a roll rotation speed of 1000 rpm The film was subjected to rubbing treatment and subjected to surface observation using a microscope to confirm whether or not the polyimide film was thinned. The case where the film was not thinned was ○, and the case where the film was thinned was set to ×.

4. Foreign matter test The foreign matter test of the liquid crystal display element described later was carried out using a force measuring device (FORCE MEASUREMENT) and DS2-50N (manufactured by Ida (IMADA) Co., Ltd.). A force of 9.8 N was applied to the produced liquid crystal display element at 60 times/min for 1 minute. The liquid crystal display element was observed with a microscope to confirm whether or not foreign matter was present after pressurization.

5. Contrast The contrast of the liquid crystal display element described later was evaluated using a luminance meter (Yokogawa 3298F). The liquid crystal display element was placed under a polarizing microscope in a crossed Nicols state, and the minimum brightness was measured as black brightness. Next, an arbitrary rectangular wave voltage was applied to the element, and the maximum brightness was measured as white brightness. The value of the white luminance/black luminance is set as the contrast. Regarding the contrast, the case of less than 2500 was judged to be defective, the case of 2500 or more was judged to be good, and the case of 3000 or more was judged to be optimal.

6. Alternating Current (AC) afterimage measurement The luminance-voltage characteristic (B-V characteristic) of the liquid crystal display element described later was measured. This is set as the luminance-voltage characteristic before stress is applied: B (front). Next, after applying an alternating current of 4.5 V and 60 Hz for 20 minutes to the device, the short circuit was performed for 1 second, and then the luminance-voltage characteristic (B-V characteristic) was measured again. This was set as the luminance-voltage characteristic after stress application: B (post). Based on these values, the luminance change rate ΔB (%) is estimated using the following formula. ΔB (%) = [B (post) - B (pre)] / B (pre) (formula AC1) These measurements were carried out in accordance with International Publication No. 2000/43833. It can be said that the smaller the value of ΔB (%) in the voltage of 0.75 V, the more the generation of the AC afterimage can be suppressed, and it is preferably 3.0% or less.

<tetracarboxylic dianhydride>

<Diamine>

<Solvent> NMP: N-methyl-2-pyrrolidone BC: butyl cellosolve (ethylene glycol monobutyl ether) GBL: γ-butyrolactone BP: 1-butoxy-2-propanol EDM: diethylene Alcohol ethyl methyl ether BDM: diethylene glycol butyl methyl ether EDE: diethylene glycol diethyl ether DIBK: diisobutyl ketone

<additive> Ad1: N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane Ad2: 3,4-epoxycyclohexenylmethyl-3', 4'- Epoxycyclohexene carboxylate (Celloxide 2021 (manufactured by Daicel)) Ad3: 1,4-butanediol diglycidyl ether Ad4: 1,3,5-triglycidyl-1,3, 5-triazine-2,4,6-(1H,3H,5H)-trione Ad5: 1,3-bis(4,5-dihydro-2-oxazolyl)benzene

[Synthesis Example 1] Synthesis of a compound represented by the formula (1-4) <Phase 1> Construction of cyclohexene ring To a 1000 mL three-necked flask equipped with a thermometer and a reflux tube, 1,7-octadiene (50.0 g, 453.7 mmol) and 1,3-butadiene (73.6 g, 1360 mmol) were added, and xylene was added. 500 mL. The solution was stirred under reflux for 48 hours. The solvent was distilled off under reduced pressure to give a crude product. The obtained original body was purified by silica gel column chromatography to obtain the following compound. The yield was 52.1 g and the yield was 53%.

<Phase 2> Epoxylation To the 1000 mL three-necked flask equipped with a thermometer and a reflux tube, the compound obtained in the first stage (50.0 g, 229.0 mmol) was added, and 100 mL of dichloromethane was added. While the solution was ice-cooled, a dichloromethane solution (200 mL) of m-chloroperoxybenzoic acid (158.0 g, 915.8 mmol) was added dropwise, and the mixture was stirred at 0 ° C to 5 ° C for 12 hours. 2-Methyl-2-butene (200.0 g, 916.0 mmol) was added and the reaction solution was stirred at room temperature to consume excess m-chloroperoxybenzoic acid. A saturated aqueous solution of sodium hydrogencarbonate was added to the reaction mixture, and extracted with dichloromethane. The organic phase was washed with saturated sodium sulfite·5% aqueous sodium hydroxide and water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained original material was purified by silica gel column chromatography to obtain the following compound. The yield was 48.0 g and the yield was 84%.

[Synthesis Example 2] Synthesis of a compound represented by the formula (1-5) <Phase 1> Construction of cyclohexene ring To a 300 mL three-necked flask equipped with a thermometer and a reflux tube, 1,11-dodecanediene (10.0 g, 60.1 mmol) and 1,3-butadiene (9.76 g, 180.4 mmol) were added and added. Xylene 100 mL. The solution was stirred under reflux for 48 hours, and then the solvent was distilled off under reduced pressure to give a crude product. The obtained original body was purified by silica gel column chromatography to obtain the following compound. The yield was 5.3 g and the yield was 32%.

<Phase 2> Epoxylation To a 300 mL three-necked flask equipped with a thermometer and a reflux tube, the compound obtained in the first stage (5.0 g, 18.2 mmol) was added, and 20 mL of dichloromethane was added. While the solution was ice-cooled, a dichloromethane solution (40 mL) of m-chloroperoxybenzoic acid (12.6 g, 72.9 mmol) was added dropwise, and the mixture was stirred at 0 ° C to 5 ° C for 12 hours. 2-Methyl-2-butene (4.1 g, 73.0 mmol) was added and the reaction solution was stirred at room temperature to consume excess m-chloroperoxybenzoic acid. A saturated aqueous solution of sodium hydrogencarbonate was added to the reaction mixture, and extracted with dichloromethane. The organic phase was washed with saturated sodium sulfite·5% aqueous sodium hydroxide and water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained original material was purified by silica gel column chromatography to obtain the following compound. The yield was 4.8 g and the yield was 86%.

[Example 1] Synthesis of varnish To a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, 0.9004 g of a compound represented by the formula (DI-4-1) and a formula (DI-5-1) were added ( m = 1) 1.6507 g of the compound represented, and N-methyl-2-pyrrolidone (NMP) 34.0 g was added. The solution was ice-cooled, and the liquid temperature was set to 5 ° C. Then, 1.6328 g of the compound represented by the formula (PA-1) and 1.8161 g of the compound represented by the formula (AN-3-2) were added, and the mixture was stirred at room temperature. hour. 40.0 g of NMP and 20.0 g of butyl cellosolve (BC) were added thereto, and the solution was heated and stirred at 60 ° C until the weight average molecular weight of the polymer of the solute became the desired weight average molecular weight, thereby obtaining a weight average of the solute. Varnish 1 having a molecular weight of about 63,000 and a resin component concentration of 6 wt%.

[Examples 2 to 31] A varnish 2 to varnish 31 having a polymer solid content concentration of 6 wt% was prepared in the same manner as in Example 1 except that the tetracarboxylic dianhydride and the diamine were changed. The weight average molecular weight of the tetracarboxylic dianhydride and the diamine used and the obtained polymer are shown in Table 1-1 to Table 1-3. Example 1 is again disclosed in Table 1-1.

Table 1-1

Table 1-2

Table 1-3

[Example 32] <Preparation of liquid crystal alignment agent, rubbing resistance test> 1 10 g of varnish was weighed into a 50 mL eggplant type flask, and 0.5 kg part by weight of 100 parts by weight of the polymer was added thereto (1) -1) The compound represented, 7 g of N-methyl-2-pyrrolidone, and 3 g of butyl cellosolve were shaken for 2 hours to obtain a liquid crystal alignment agent RA-1 having a solid content of 3 wt%.

The obtained liquid crystal alignment agent RA-1 was coated on a substrate with a SiNx/ITO comb electrode by a spinner, and on the opposite side, a liquid crystal alignment agent RA-1 was coated on a glass substrate with a spacer (spacer) Height: 4 μm). The coating conditions were 2,300 rpm and 15 seconds. After coating, pre-baked at 80 ° C for about 5 minutes, and then calcined at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. Using a rubbing treatment device, the rubbing cloth (hair length 1.9 mm: rayon) has a hair pressing amount of 0.40 mm, the table moving speed is 60 mm/sec, and the roll rotating speed is 1000 rpm. The amine film was subjected to rubbing treatment, and observation of the surface of the film was carried out, and as a result, no thinning of the film was observed.

<Preparation of FFS unit, confirmation of flow alignment, contrast, and measurement of AC afterimage> After the rubbed substrate was ultrasonically cleaned in ethanol for 5 minutes, the surface was washed with ultrapure water, and then in an oven. Dry at 120 ° C for 30 minutes. Two sheets of the substrate on which the alignment film is formed on the substrate are faced with the alignment film formed so that the rubbing directions are parallel in the respective alignment films, and the liquid crystal combination is formed between the opposing alignment films. After the voids of the objects were attached, they were assembled into an empty FFS unit having a cell thickness of 4 μm. The following positive type liquid crystal composition A was vacuum-injected into the produced empty FFS unit, and the injection port was sealed with a light hardener. Then, heat treatment was performed at 110 ° C for 30 minutes to prepare an FFS liquid crystal display element (FFS unit) 1-1.

<Positive liquid crystal composition A> Physical property values: NI 100.1 ° C; Δ ε 5.1; Δn 0.093; η 25.6 mPa·s.

The alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, and as a result, no flow alignment was observed. Further, when the value of the contrast was measured, it was 2700, and the AC afterimage was measured, and as a result, ΔB was 2.5%.

[Examples 33 to 66] In addition to the varnish and the additive used, the abrasion resistance, the contrast, and the AC afterimage were measured in accordance with Example 32. The measurement results are shown together with Example 32 in Table 2-1.

table 2-1

[Comparative Example 1 to Comparative Example 4] The abrasion resistance, the contrast, and the AC afterimage were measured in accordance with Example 32 except that the additive was changed. The measurement results are shown in Table 2-2.

Table 2-2

Comparing Example 32 to Example 66 with Comparative Example 1 to Comparative Example 4, it was revealed that the FFS liquid crystal display having good abrasion resistance, contrast, and AC afterimage characteristics can be obtained by applying the present invention to an FFS liquid crystal display device. element.

[Example 67] The varnish 12 2.0 g synthesized in Example 12 and the varnish 23 8.0 g synthesized in Example 23 were weighed into a 50 mL eggplant type flask equipped with a stirring blade and a nitrogen introduction tube, and added thereto in relation to 100 parts by weight of the polymer, 7.5 parts by weight of the compound represented by the formula (1-1), 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve, and stirred at room temperature for 1 hour to obtain a resin component. The concentration agent is 3 wt% of the alignment agent RB-1.

The obtained alignment agent RB-1 was coated on a glass substrate by a spinner. After coating, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then Multi-Light ML-501C/B manufactured by Ushio Electric Co., Ltd. was used to be perpendicular to the substrate. The direction is linearly polarized by ultraviolet rays through a polarizing plate. The exposure energy at this time was measured by using an ultraviolet ray cumulative photometer UIT-150 (photoreceptor: UVD-S365) manufactured by Oxtail Motor Co., Ltd. to become 1.3 J/cm ² ±0.1 J/ at a wavelength of 365 nm. The exposure time is adjusted in cm ² way. The film was calcined at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The pencil hardness of the obtained substrate was measured and found to be 5H.

<Method for Producing FFS Unit, Confirmation of Flow Orientation, Confirmation of Foreign Matter Generation, and Measurement of AC Afterimage> The obtained alignment agent RB-1 was applied onto a substrate with a SiNx/ITO comb electrode by a spinner. On the side, the alignment agent RB-1 was coated on a glass substrate with a spacer (height of the spacer: 4 μm). After the application, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then a line of ultraviolet rays was irradiated through the polarizing plate in a direction perpendicular to the substrate using Mchlet ML-501C/B manufactured by Oxtail Motor Co., Ltd. Polarized light. The exposure energy at this time was measured by using an ultraviolet ray cumulative photometer UIT-150 (photoreceptor: UVD-S365) manufactured by Oxtail Motor Co., Ltd. to become 1.3 J/cm ² ±0.1 J/ at a wavelength of 365 nm. The exposure time is adjusted in cm ² way. The film was calcined at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The alignment direction of the alignment film formed on the two alignment film forming substrates is such that the polarization directions of the linear polarizations irradiated to the respective alignment films are parallel, and the liquid crystal is injected between the opposing alignment films. The voids of the composition were then laminated to assemble an empty FFS unit having a cell thickness of 4 μm. The positive liquid crystal composition was vacuum-injected into the produced empty FFS unit to fabricate an FFS liquid crystal display element. The alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, and as a result, no flow alignment was observed. Then, the liquid crystal display element after the foreign matter test was observed with a microscope, and as a result, no foreign matter was observed. Further, when the value of the contrast was measured, it was 3100, and the AC afterimage was measured. As a result, ΔB was 2.6%.

[Examples 68 to 96] Pencil hardness, foreign matter test, contrast, and AC afterimage were measured in accordance with Example 67 except that the varnish and the additive used were changed. The measurement results are shown together with Example 67 in Table 3-1.

Table 3-1

[Comparative Example 5 to Comparative Example 8] Pencil hardness, foreign matter test, contrast, and AC afterimage were measured in accordance with Example 67 except that the varnish and the additive used were changed. The measurement results are shown in Table 3-2.

Table 3-2

Comparative Examples 67 to 96 and Comparative Examples 5 to 8 show that FFS liquid crystals having excellent contrast and AC afterimage characteristics can be obtained by applying the present invention to an FFS liquid crystal display device. Display component.

[Liquid crystal alignment agent for inkjet coating method] The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent suitable for coating by an inkjet method by appropriately selecting a solvent to be used.

[Example 97] The varnish synthesized in Example 12 was poured into a large amount of excess methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure, whereby 3 g of polylysine (PAA-12) was obtained. To the polyamic acid (PAA-12), NMP 48.0 g, γ-butyrolactone (GBL) 12.0 g, 1-butoxy-2-propanol (BP) 16.0 g, diethylene glycol ethyl group were added. Methyl ether (EDM) 15.0 g, diethylene glycol butyl methyl ether (BDM) 3.0 g, diisobutyl ketone (DIBK) 3.0 g, the solid content concentration was 3.0 wt% and the solvent composition became NMP/GBL/BP. /EDM/BDM/DIBK=48/12/16/15/3/3 varnish (12-a).

[Example 98] In the same manner as in the varnish synthesized in Example 23, the solid content concentration was 3.0 wt% and the solvent composition became NMP/GBL/BP/EDM/BDM/DIBK=48/12/16. /15/3/3 varnish (23-a).

[Example 99] 2.0 g of the varnish (12-a) prepared in Example 97 and 8.0 g of the varnish (23-a) prepared in Example 98 were weighed and added thereto in an amount of 15 parts by weight based on 100 parts by weight of the polymer. The compound represented by the formula (1-1) was prepared in a weight ratio of 3.0 wt% and the solvent composition became NMP/GBL/BP/EDM/BDM/DIBK=48/12/16/15/3/3. Liquid crystal alignment agent (RB-35) for inkjet coating.

[Example 100] 15 2.0 g of the varnish synthesized in Example 15 and 25 8.0 g of the varnish synthesized in Example 25 were weighed, and 15 parts by weight of the formula (1-1) based on 100 parts by weight of the polymer was added thereto. The compound represented, NMP 2.2 g, GBL 2.6 g, BC 1.4 g, BDM 1.0 g, and EDE 2.8 g, the solid content concentration was 3.0 wt% and the solvent composition became NMP: GBL:BC:BDM:EDE=48 : 13:17:5:14 liquid crystal alignment agent (RB-36) for inkjet coating.

[Example 101] 12 g of the varnish synthesized in Example 12 and 8.0 g of the varnish 23 synthesized in Example 23 were weighed, and 15 parts by weight of the formula (1-1) based on 100 parts by weight of the polymer was added thereto. The compound represented, NMP 2.2 g, GBL 5.2 g, BC 2.0 g, and DIBK 0.6 g, the solid content concentration was 3.0 wt% and the solvent composition became NMP: GBL: BC: DIBK = 48:26:20:3 A liquid crystal alignment agent (RB-37) for inkjet coating.

[Example 102] A liquid crystal alignment agent (RB-35) for inkjet coating was applied onto a glass substrate by an inkjet coating apparatus (manufactured by Fujifilm Co., Ltd., DMP-2831), and In Example 67, pencil hardness, foreign matter test, contrast, and AC afterimage measurement were performed. Further, the droplet interval and the applied voltage of the cartridge were adjusted so that the film thickness of the liquid crystal alignment film was 100 nm.

[Examples 103 to 104] Pencil hardness, foreign matter test, contrast, and AC afterimage were measured according to Example 102 except that the varnish used was changed. The measurement results are shown together with Example 102 in Table 3-3.

Table 3-3

When the liquid crystal alignment agent of the present invention is applied to an FFS liquid crystal display device, it is possible to obtain an FFS liquid crystal display which is capable of suppressing generation of foreign matter and having good contrast and AC afterimage characteristics. element.

[Example 105] The varnish 15 2.0 g synthesized in Example 15 and the varnish 25 8.0 g synthesized in Example 25 were weighed into a 50 mL eggplant type flask equipped with a stirring blade and a nitrogen introduction tube, and added thereto in relation to The compound represented by the formula (1-1) and the compound of the additive (Ad5) in an amount of 5 parts by weight based on 100 parts by weight of the polymer, N-methyl-2-pyrrolidone, in an amount of 2.5 parts by weight based on 100 parts by weight of the polymer. 5.0 g and 5.0 g of butyl cellosolve were stirred at room temperature for 1 hour to obtain an alignment agent RB-38 having a resin component concentration of 3 wt%.

The obtained alignment agent RB-38 was coated on a glass substrate by a spinner. After the application, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then Mchlet ML-501C/B manufactured by Oxtail Electric Co., Ltd. was used to irradiate ultraviolet rays through a polarizing plate in a direction perpendicular to the substrate. Straight line polarization. The exposure energy at this time was measured by using an ultraviolet ray cumulative photometer UIT-150 (photoreceptor: UVD-S365) manufactured by Oxtail Motor Co., Ltd. to become 1.3 J/cm ² ±0.1 J/ at a wavelength of 365 nm. The exposure time is adjusted in cm ² way. The film was calcined at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The pencil hardness of the obtained substrate was measured and found to be 4H.

<Manufacturing method of FFS unit, confirmation of flow alignment, confirmation of generation of foreign matter, and measurement of AC afterimage> The obtained alignment agent RB-38 was applied onto a substrate with a SiNx/ITO comb electrode by a rotator, in the pair On the side, the alignment agent RB-38 was coated on a glass substrate with a spacer (height of the spacer: 4 μm). After the application, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then Mchlet ML-501C/B manufactured by Oxtail Electric Co., Ltd. was used to irradiate ultraviolet rays through a polarizing plate in a direction perpendicular to the substrate. Straight line polarization. The exposure energy at this time was measured by using an ultraviolet ray cumulative photometer UIT-150 (photoreceptor: UVD-S365) manufactured by Oxtail Motor Co., Ltd. to become 1.3 J/cm ² ±0.1 J/ at a wavelength of 365 nm. The exposure time is adjusted in cm ² way. The film was calcined at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The alignment direction of the alignment film formed on the two alignment film forming substrates is such that the polarization directions of the linear polarizations irradiated to the respective alignment films are parallel, and the liquid crystal is injected between the opposing alignment films. The voids of the composition were then laminated to assemble an empty FFS unit having a cell thickness of 4 μm. The positive liquid crystal composition was vacuum-injected into the produced empty FFS unit to fabricate an FFS liquid crystal display element. The alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, and as a result, no flow alignment was observed. Then, the liquid crystal display element after the foreign matter test was observed with a microscope, and as a result, no foreign matter was observed. Further, when the value of the contrast was measured, it was 3300, and the AC afterimage was measured. As a result, ΔB was 2.3%.

[Example 106] Pencil hardness, foreign matter test, contrast, and AC afterimage measurement were performed according to Example 105 except that the varnish, the additive, and the amount thereof used were changed. The measurement results are shown together with Example 105 in Table 4-1.

Table 4-1

Comparing Example 105 to Example 106 with Comparative Example 5 to Comparative Example 8, it was revealed that FFS liquid crystal which can suppress generation of foreign matter and has good contrast and AC afterimage characteristics can be obtained by applying the present invention to an FFS liquid crystal display element. Display component.

[Liquid crystal alignment agent for inkjet coating method] The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent suitable for coating by an inkjet method by appropriately selecting a solvent to be used.

[Example 107] 16 2.0 g of the varnish synthesized in Example 16 and 8.0 g of the varnish 26 synthesized in Example 26 were weighed, and the formula (1-1) was added thereto in an amount of 5 parts by weight based on 100 parts by weight of the polymer. The compound represented by the formula (Ad5) is 3 parts by weight based on 100 parts by weight of the polymer, and the solid content concentration is 3.0 wt%, and the solvent composition becomes NMP/GBL/BP/EDM/BDM/ DIBK=48/12/16/15/3/3 liquid crystal alignment agent (RB-40) for inkjet coating.

[Example 108] The varnish 17 2.0 g synthesized in Example 17 and the varnish 28 8.0 g synthesized in Example 28 were weighed, and the formula (1-1) was added thereto in an amount of 8 parts by weight based on 100 parts by weight of the polymer. The compound represented by the formula (Ad1) is added in an amount of 2 parts by weight based on 100 parts by weight of the polymer, and NMP 2.2 g, GBL 2.6 g, BC 1.4 g, BDM 1.0 g, and EDE 2.8 g are added. A liquid crystal alignment agent (RB-41) for inkjet coating was prepared having a solid content concentration of 3.0 wt% and a solvent composition of NMP:GBL:BC:BDM:EDE=48:13:17:5:14.

[Example 109] Example 105 was applied to a glass substrate by using an inkjet coating device (manufactured by Fujifilm Co., Ltd., DMP-2831) to apply a liquid crystal alignment agent (RB-40) for inkjet coating. Pencil hardness, foreign matter test, contrast, and measurement of AC afterimage were performed. In addition, the droplet interval and the voltage application were adjusted so that the film thickness of the liquid crystal alignment film was 100 nm.

[Example 110] A pencil hardness, a foreign matter test, a contrast, and an AC afterimage were measured in accordance with Example 109 except that the alignment agent used was changed. The measurement results are shown together with Example 109 in Table 4-2.

Table 4-2

When the liquid crystal alignment agent of the present invention is applied to an FFS liquid crystal display device, it is also possible to obtain an FFS liquid crystal which can suppress generation of foreign matter and has good contrast and AC afterimage characteristics. Display component. [Industrial availability]

It was confirmed that the liquid crystal alignment agent of the present invention can form a liquid crystal alignment film having a high film hardness and exhibiting excellent liquid crystal alignment properties. It has been confirmed that the liquid crystal display element including the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention has excellent characteristics such that it is hard to cause foreign matter to be generated during the operation of the touch panel, exhibits high contrast, and is hard to cause an AC afterimage. The liquid crystal alignment agent of the present invention is particularly suitably applied to a lateral electric field type liquid crystal display element.

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Claims (14)

A liquid crystal alignment agent comprising at least one of a polymer selected from the group consisting of a compound represented by the following formula (1), wherein the polymer is selected from the group consisting of reacting a tetracarboxylic dianhydride with a diamine compound. At least one of polyamine and its derivatives, In the formula (1), R ¹ is a single bond, a linear alkylene group having 1 to 8 carbon atoms, a branched alkyl group having 2 to 8 carbon atoms, or a divalent organic compound having an alicyclic structure having 3 to 8 carbon atoms. base. The liquid crystal alignment agent according to claim 1, wherein the compound of the formula (1) is at least one of the compounds represented by the formula (1-1) to the formula (1-7); . The liquid crystal alignment agent according to the above aspect, wherein the tetracarboxylic dianhydride contains a group selected from the compounds represented by the following formulas (AN-I) to (AN-VII). At least one of the diamines includes a diamine having no side chain represented by the following formula (DI-1) to formula (DI-16), and a formula (DIH-1) to (DIH-) 3) at least one of a group of diterpenes having no side chain and a group of diamines having a side chain represented by the following formula (DI-31) to formula (DI-35); 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, and the carbon number is 1 to 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; (AN-II)~ In (AN-IV), Y is independently one selected from the group consisting of trivalent groups, the bonding bond is bonded to any carbon, and at least one hydrogen of the group may be methyl, ethyl or phenyl. Replace 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 group of a condensed polycyclic hydrocarbon having 6 to 30 carbon atoms. At least one hydrogen may be substituted by a methyl group, an ethyl group or a phenyl group, and a bond bonded 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 is} independently -O-, -COO- or -OCO-, and r is independently 0. Or 1; In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH-, -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group is extended. It can be substituted by -OH; in formula (DI-3) and formula (DI-5) to 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 an integer from 1 to 5 , n is 1 or 2; in the formula (DI-4), s is independently an integer of 0 to 2; in the formula (DI-6) and the formula (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -NH-, or an alkylene group having 1 to 10 carbon atoms; formula (DI-2) to formula ( At least one hydrogen of the cyclohexane ring and the benzene ring in DI-7) may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , a phenyl group, or a benzyl group, and In (DI-4), at least one hydrogen of the benzene ring may be substituted with one selected from the group consisting of a group represented by the following formula (DI-4-a) to formula (DI-4-e); bonding position The group which is not fixed to the carbon atom constituting the ring in the formula means that the bonding position on the ring is arbitrary; the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is G ²¹ or Any position other than the bonding position of G ²² ; In formula (DI-4-a) and formula (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ ; In formula (DI-11), r is 0 or 1; of formula (DI-8) ~ of formula (DI-11) in bonded on the ring -NH ₂ bonding positions to an arbitrary position; 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 1 to 6 carbon atoms, a phenyl group or an alkyl group. a phenyl group, w is an integer of 1 to 10; in the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, and p is independently 0. An integer of ～3, q is an integer of 0 to 4; in the formula (DI-14), ring B is a monocyclic heteroaromatic group, and R ²⁴ is hydrogen, -F, -Cl, an alkyl group having 1 to 6 carbon atoms. , alkoxy group, vinyl group, alkynyl group, q is an integer of 0 to 4; in the formula (DI-15), ring C is a monocyclic ring containing a hetero atom; in the formula (DI-16), G ²⁴ is a single bond a C 2 to 6 alkylene group or a 1,4-phenylene group, r is 0 or 1; a bond site which is not fixed to a carbon atom constituting the ring in the formula is represented on the ring The bonding position is arbitrary; in the formula (DI-13) to the formula (DI-16), the bonding position of the -NH ₂ bonded to the ring is an arbitrary position; In the formula (DIH-1), G ²⁵ 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 (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the ring may be substituted by 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 ring may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond, a carbon number of 1 ～20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; formula (DIH-2) and In the formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position; 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 of 1 to 12; 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 formula (DI-31-a) in which at least one hydrogen may be substituted by -F, and at least one -CH ₂ - may be -O-, -CH=CH- or -C≡ C-substituted, the hydrogen of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or a carbon number of 3 to 30 The alkoxy group is substituted, and the bonding position of -NH ₂ bonded to the benzene ring means an arbitrary position in the ring. In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more of the alkyl groups are - CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ^{24 are} independently 1,4-phenylene Base, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, acridine-1,4- At least one hydrogen of diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ It can be substituted by -F or -CH ₃ , and s, t and u are independently an integer of 0 to 2, and their total is 0 to 5. When s, t or u is 2, the two bonding groups in each parenthesis can be The same or different, and the two rings may be the same or different, and R ²⁶ is hydrogen, -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, or carbon. The alkoxy group having 1 to 30, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , and at least one -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be represented by the following formula (DI- The divalent base substitution represented by 31-b), In the formula (DI-31-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6; In the formula (DI-32) and the 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 carbon number is 1 - An alkyl group of 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 be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group; the bonding position is not fixed in the constitution The group on the carbon atom of the ring in the formula represents any bonding position on the ring; in the formula (DI-32) and formula (DI-33), -NH ₂ bonded to the benzene ring Indicates that the bonding position on the ring is arbitrary; In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O-, -NH- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or a carbon number of 1 to 3 An alkyl group, 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-, and R ³² is carbon An alkyl group of 6 to 22, R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms, and ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1, and The -NH ₂ bonded to the benzene ring indicates that the bonding position on the ring is arbitrary. The liquid crystal alignment agent according to claim 3, wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (AN-1-1), the formula (AN-1-2), and the formula (AN-1- 13), formula (PA-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN- 4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), At least one of the formula (AN-11-3), the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4); the diamine is selected from the following formula ( DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15 ), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI -5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2) At least one of the group consisting of: (DI-13-1), (DI-16-1), (DI-31-56), and (DIH-2-1); In the formula (AN-1-2) and the formula (AN-4-17), m is an integer of 1 to 12; In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), and the formula (DI-7-3), m is an integer of 1 to 12; In 5-30), k is an integer of 1 to 5; and in the formula (DI-7-3), n is independently 1 or 2. The liquid crystal alignment agent according to claim 1 or 2, wherein the poly-proline and the derivative thereof are at least one of a tetracarboxylic dianhydride and a diamine reacted with a compound having a photoreactive structure. And the obtained polymer (a). The liquid crystal alignment agent according to claim 5, wherein the photoreactive structure is selected from the group consisting of structures represented by the following formulas (P-1) to (P-7); At least one type; In the formula (P-1), R ^{61 is} independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. The liquid crystal alignment agent according to claim 6, wherein the compound having the photoreactive structure is selected from the group consisting of the following formula (II-1), formula (II-2), and formula (III-1). , formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), and formula (VI-1), formula (VI-2) At least one tetracarboxylic dianhydride or diamine compound in the group formed; In the above formula, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R ^{6 is} independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH ₃ , a are each independently an integer of 0 to 2; in the formula (V-3), ring A and ring B are each independently selected from a monocyclic hydrocarbon, a condensed polycyclic ring. At least one of a hydrocarbon and a heterocyclic ring, R ¹¹ is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N(CH ₃ )CO-, and R ¹² is a carbon number 1 to 20 of a linear alkyl group, -COO-, -OCO-, -NHCO- or -N(CH ₃ )CO-, R ¹¹ and R ¹² , a linear alkyl group of -CH ₂ - Or two may be substituted by -O-, and R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ or -OH, and b to e are each independently an integer of 0 to 4. The liquid crystal alignment agent according to claim 7, wherein the diamine compound having the photoreactive structure is represented by the following formula (PDI-7); In the formula (PDI-7), R ^{51 is} independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , and s is independently an integer of 0 to 2, respectively. The liquid crystal alignment agent according to claim 5, wherein the polymer (a) is further contained, and further the polymer (b) is selected from the group consisting of a photoreactive structure. At least one of polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic dianhydride with a diamine having no photoreactive structure. The liquid crystal alignment agent according to claim 9, wherein: the tetracarboxylic dianhydride used in the synthesis of the polymer (b) is selected from the group consisting of the following formula (AN-1-1), and the formula (AN- 1-2), formula (AN-1-13), formula (PA-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula ( AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2 At least one of (AN-10-1), (AN-11-3), (AN-16-1), (AN-16-3), and (AN-16-4) One; the diamine is selected from the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4) -10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7- 3), the formula (DI-11-2), the formula (DI-13-1), the formula (DI-16-1), the formula (DI-31-56), and the formula (DIH-2-1) At least one of the groups; In the formula (AN-1-2) and the formula (AN-4-17), m is an integer of 1 to 12; In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), and the formula (DI-7-3), m is an integer of 1 to 12; In 5-30), k is an integer of 1 to 5; and in the formula (DI-7-3), n is independently 1 or 2. The liquid crystal alignment agent according to claim 1 or 2, further comprising an epoxy compound selected from the group consisting of an oxazine compound, an oxazoline compound, and a compound represented by the formula (1), and At least one of the group consisting of compounds of a decane coupling agent. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 11. A liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, which is formed by the liquid crystal alignment agent according to any one of claims 1 to 11. A liquid crystal display element comprising the liquid crystal alignment film according to claim 12 or claim 13.