CN106916307B

CN106916307B - Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

Info

Publication number: CN106916307B
Application number: CN201611008166.3A
Authority: CN
Inventors: 塚田裕以智; 藤马大亮; 瓜生阳一; 伊泽启介
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: Changsha Dao'anjie New Materials Co ltd
Priority date: 2015-11-16
Filing date: 2016-11-16
Publication date: 2021-03-12
Anticipated expiration: 2036-11-16
Also published as: CN106916307A; JP6520657B2; JP2017088801A

Abstract

The present invention relates to a diamine, a polyamic acid or a derivative thereof, a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. The present invention relates to a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride with a diamine containing at least 1 kind of diamine represented by formula (1). The liquid crystal display element having a liquid crystal alignment film formed using a liquid crystal aligning agent containing the polymer has the following features: has excellent viewing angle characteristics, and the display quality is not reduced even when exposed to intense light for a long time.

In the formula (1), R is hydrogen, -OH, alkyl with 1-6 carbon atoms or alkoxy with 1-6 carbon atoms, and X¹And X²Each independently is a 2-valent organic group having an alkylene group and/or a phenylene group having 1 to 8 carbon atoms.

Description

Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

Technical Field

The present invention relates to a polyamic acid and a derivative thereof using a diamine represented by formula (1) as a raw material, a liquid crystal aligning agent containing the polyamic acid and the derivative thereof, and a liquid crystal display element.

Background

Among liquid crystal display devices that are currently widely distributed as products, display devices using nematic liquid crystals are the mainstream. As display modes of a Nematic liquid crystal display device, a TN (Twisted Nematic) mode and an STN (Super Twisted Nematic) mode are well known. In recent years, In order to improve the narrow viewing angle, which is one of the problems of these modes, a TN type liquid crystal display element using an optical compensation film, an MVA (Multi-domain Vertical Alignment) mode using a combination of Vertical Alignment and a technology of a protrusion structure, an IPS (In-Plane Switching) mode of a lateral electric Field method, an FFS (Fringe Field Switching) mode, and the like have been proposed and put into practical use (see patent documents 1 to 3).

The development of liquid crystal display elements has been achieved not only by improving the driving method and the element structure, but also by improving the constituent members used in the elements. Among the constituent members used in liquid crystal display elements, in particular, liquid crystal alignment films are one of important materials for display quality, and it is becoming important to improve the performance of alignment films as the quality of liquid crystal display elements increases.

A liquid crystal alignment film mainly used at present is a polyimide-based liquid crystal alignment film formed by applying a solution (varnish) obtained by dissolving polyamic acid or soluble polyimide in an organic solvent to a substrate and then heating the solution or the varnish.

In industrial fields, a brushing method capable of easily realizing a high-speed treatment over a large area is widely used as an alignment treatment method. The brushing method is a method in which a surface of a liquid crystal alignment film is rubbed in one direction using a cloth in which fibers such as nylon, rayon, and polyester are raised and burred, thereby obtaining uniform alignment of liquid crystal molecules.

As an alignment treatment method instead of the brushing method, a photo-alignment treatment method in which alignment treatment is performed by irradiating light may be used. As for the photo-alignment treatment method, various alignment mechanisms such as a photo-decomposition method, a photo-isomerization method, a photo-dimerization method, a photo-crosslinking method, and the like have been proposed (for example, see non-patent documents 1,4, and 5). The photo-alignment method has the following advantages: the alignment uniformity is high as compared with the brush-rubbing method, and the film is not damaged due to the non-contact alignment treatment method, and causes of display defects of the liquid crystal display element, such as dust generation and static electricity, can be reduced.

The liquid crystal display element is used in various fields such as a display for a personal computer, a display unit of a liquid crystal television, a mobile phone, a smart phone, and a liquid crystal projector. In recent years, in view of improvement in display quality and outdoor use, there is a demand for a liquid crystal display element in which the luminance of a backlight serving as a light source is higher than that of a conventional use, and the display quality does not deteriorate even when exposed to strong light for a long time.

In response to such a demand, various investigations have been made on liquid crystal alignment films, and for example, the following methods are known: a method in which a diamine having a hindered amine structure and a hindered phenol structure is included as a raw material, and the same structure is introduced into a polyimide chain (see patent document 6); a method in which an antioxidant having a hindered amine structure or a hindered phenol structure is added to a liquid crystal aligning agent (see patent document 7); a method of introducing a hindered amine structure into a side chain site of a side chain type diamine (see patent document 8.). However, the influence of the above method on the viewing angle characteristics and the afterimage characteristics has not been studied in detail.

Documents of the prior art

Patent document

Patent document 1: japanese unexamined patent publication No. 6-194646

Patent document 2: japanese patent application laid-open No. 2001 + 117083

Patent document 3: japanese unexamined patent publication No. 6-160878

Patent document 4: japanese patent laid-open No. 9-297313

Patent document 5: japanese unexamined patent publication Hei 10-251646

Patent document 6: japanese patent laid-open No. 2010-244015

Patent document 7: japanese patent laid-open publication No. 2013-127597

Patent document 8: international publication No. 2008/078629

Non-patent document

Non-patent document 1: liquid crystal, volume 3, No. 4, page 262, 1999

Disclosure of Invention

Problems to be solved by the invention

The invention provides a liquid crystal display element which does not reduce the display quality even if exposed to strong light for a long time, and provides a liquid crystal display element which has excellent viewing angle characteristics and image retention characteristics. Also provided are a liquid crystal aligning agent and a liquid crystal alignment film which can provide such a display element.

Means for solving the problems

As a result of intensive studies, the present inventors have completed a liquid crystal aligning agent and a liquid crystal alignment film which can provide a liquid crystal display element excellent in viewing angle characteristics and/or after-image characteristics and free from deterioration in display quality even when exposed to intense light for a long period of time by using a diamine represented by the following formula (1). The liquid crystal display device can be suitably used for a liquid crystal display device of a transverse electric field system such as an IPS mode or an FFS mode.

The invention comprises the following technical scheme.

[1] A polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride with a diamine containing at least 1 kind of diamine represented by the formula (1).

In the formula (1), R is hydrogen, -OH, alkyl with 1-6 carbon atoms or alkoxy with 1-6 carbon atoms; and the number of the first and second electrodes,

X¹and X²Each independently is a 2-valent organic group having an alkylene group and/or a phenylene group having 1 to 8 carbon atoms.

[2] The polyamic acid or derivative thereof according to [1], wherein the diamine represented by the formula (1) is a diamine represented by the formula (1').

In the formula (1'), R is hydrogen, -OH, alkyl with 1-6 carbon atoms or alkoxy with 1-6 carbon atoms;

A¹and A²Each independently a single bond or a C1-6 subunitAn alkyl group; and the number of the first and second electrodes,

bonded to the ring by-NH₂The bonding position of (a) is an arbitrary position.

[3] The polyamic acid or derivative thereof according to item [1] or item [2], wherein R in the diamine represented by formula (1) is hydrogen or-OH.

[4] The polyamic acid or derivative thereof according to item [1] or item [2], wherein the diamine represented by formula (1) is a compound represented by formula (1-15) or formula (1-29).

[5] The polyamic acid or the derivative thereof according to any one of [1] to [4], wherein the tetracarboxylic dianhydride is at least 1 selected from the group consisting of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII);

the other diamines used together with the diamine represented by the formula (1) are at least 1 selected from the group consisting of the following formulae (DI-1) to (DI-16), formulae (DIH-1) to (DIH-3), and formulae (DI-31) to (DI-35).

In the formulae (AN-I), (AN-IV) and (AN-V), X is independently a single bond or-CH₂-；

In the formula (AN-II), G is a single bond, alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-；

In the formulas (AN-II) to (AN-IV), Y is independently 1 selected from the following group of 3-valent groups,

at least 1 hydrogen on these groups is optionally substituted by methyl, ethyl or phenyl;

formula (AN-III) to formula (III)In (AN-V), ring A¹⁰Is monocyclic hydrocarbon group of 3-10 carbon atoms or condensed polycyclic hydrocarbon group of 6-30 carbon atoms, at least 1 hydrogen on the group is optionally substituted by methyl, ethyl or phenyl, the bond connected with the ring is connected with any carbon forming the ring, and 2 bonds are optionally connected with the same carbon;

in the formula (AN-VI), X¹⁰An alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, Ph represents a phenyl group,

in the formula (AN-VII), G¹⁰independently-O-, -COO-or-OCO-; and, r is independently 0 or 1;

in the formula (DI-1), G²⁰is-CH₂-, at least 1-CH₂-optionally substituted by-NH-, -O-, m is an integer from 1 to 12, and at least 1 hydrogen on the alkylene group is optionally substituted by-OH;

in the formulae (DI-3) and (DI-5) to (DI-7), G²¹Independently a single bond, -NH-, -NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONH-、-CONCH₃-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m’-、-O-(CH₂)_m’-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m’-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m’-CO-O-、-CO-O-(CH₂)_m’-O-CO-、-(CH₂)_m’-NH-(CH₂)_m’-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m’)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-or-S- (CH)₂)_m’-S-, m' is independently an integer from 1 to 12, 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 formulae (DI-6) and (DI-7), G²²Independently a single bond, -O-, -S-, -CO-, -C (CH)₃)₂-、-C(CF₃)₂-, -NH-or an alkylene group having 1 to 10 carbon atoms;

in the formulas (DI-2) to (DI-7), at least 1 hydrogen on the cyclohexane ring and the benzene ring is optionally substituted by-F, -Cl, alkyl with 1-3 carbon atoms, -OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅Phenyl or benzyl, and, in formula (DI-4), at least 1 hydrogen on the benzene ring is optionally substituted by 1 selected from the group of groups represented by the following formulae (DI-4-a) to (DI-4-e);

in the formulae (DI-4-a) and (DI-4-b), R²⁰Independently is hydrogen or-CH₃；

The group whose bonding position on the carbon atom constituting the ring is not fixed means that the bonding position on the ring is arbitrary, -NH₂The bonding position on the cyclohexane or benzene ring being other than G²¹Or G²²Any position other than the bonding position of (a);

in the formula (DI-11), r is 0 or 1;

in the formulae (DI-8) to (DI-11), -NH bonded to the ring₂The bonding position of (a) is an arbitrary position;

in the formula (DI-12), R²¹And R²²Independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, G²³Independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a phenylene group substituted with an alkyl group,w is an integer of 1-10;

in the formula (DI-13), R²³Independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or-Cl, p independently is an integer of 0 to 3, q is an integer of 0 to 4;

in the formula (DI-14), the ring B is a monocyclic heteroaromatic ring, R²⁴Hydrogen, -F, -Cl, alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms and alkynyl with 2-6 carbon atoms, and q is an integer of 0-4 independently;

in formula (DI-15), ring C is a monocyclic ring containing a heteroatom;

in the formula (DI-16), G²⁴Is a single bond, an alkylene group having 2 to 6 carbon atoms or a1, 4-phenylene group, r is 0 or 1;

in the formulae (DI-13) to (DI-16), the group whose bonding position on the carbon atom constituting the ring is not fixed means that the bonding position on the ring is arbitrary;

in the formula (DIH-1), G²⁵A single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)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 1 hydrogen on the ring is optionally substituted by methyl, ethyl or phenyl;

in the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least 1 hydrogen on the ring is optionally substituted by methyl, ethyl or phenyl, Y is a single bond, alkylene with 1-20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-；

In the formulae (DIH-2) and (DIH-3), -CONHNH bonded to the ring₂The bonding position of (a) is an arbitrary position;

in the formula (DI-31), G²⁶Is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-or- (CH)₂)_m’-, m' is an integer of 1 to 12, R²⁵Is 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), wherein at least 1 hydrogen in the alkyl group is optionally substituted by-F and at least 1-CH₂-optionally substituted by-O-, -CH ═ CH-or-C ≡ C-, the hydrogen on the phenyl group optionally being-F, -CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃A C3-30 alkyl group or a C3-30 alkoxy group, and-NH bonded to the benzene ring₂Represents an arbitrary position on the ring,

in the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are linking groups, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, wherein 1 or more-CH groups in the alkylene group₂Optionally substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-, ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴In which at least 1 hydrogen is optionally replaced by-F or-CH₃And (b) a substituent, s, t and u are independently an integer of 0 to 2, and the total of s, t and u is 1 to 5, and when s, t or u is 2,2 linking groups in each bracket may be the same or different, 2 rings may be the same or different,

R²⁶hydrogen, -F, -OH, alkyl with 1-30 carbon atoms, fluorine substituted alkyl with 1-30 carbon atoms, C1-30Alkoxy, -CN, -OCH₂F、-OCHF₂or-OCF₃At least 1-CH in the alkyl group having 1 to 30 carbon atoms₂Optionally substituted with a 2-valent group of the formula (DI-31-b),

in the formula (DI-31-b), R²⁷And R²⁸Independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

in formulae (DI-32) and (DI-33), G³⁰Independently a single bond, -CO-or-CH₂-，R²⁹Independently is hydrogen or-CH₃，R³⁰Hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms;

1 hydrogen on the benzene ring in the formula (DI-33) is optionally substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group, and,

in the formulae (DI-32) and (DI-33), a group whose bonding position on any carbon atom constituting the ring is not fixed means that the bonding position on the ring is arbitrary;

in formulae (DI-34) and (DI-35), G³¹Independently represents-O-, -NH-or an alkylene group having 1 to 6 carbon atoms, G³²A single bond or an alkylene group having 1 to 3 carbon atoms,

R³¹is hydrogen or alkyl with 1-20 carbon atoms, at least 1-CH in the alkyl₂-optionally substituted by-O-, -CH ═ CH-or-C ≡ C-, R³²Is alkyl of 6 to 22 carbon atoms, R³³Is hydrogen or alkyl of 1 to 22 carbon atoms, ring B²⁵Is 1, 4-phenylene or 1, 4-cyclohexylene, r is 0 or 1, and is bonded to the benzene ring-NH₂Indicating that the bonding position on the ring is arbitrary.

[6] The polyamic acid or derivative thereof according to [5], wherein, the tetracarboxylic dianhydride is at least 1 selected from the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-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), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4);

the other diamine used together with the diamine represented by the formula (1) is selected from the group consisting of the following formula (DI-1-3), formula (DI-2-1), 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 1 of the group consisting of formula (DI-16-1), formula (DIH-2-1) and formula (DI-31-56).

In the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1-12;

in the formulas (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is an integer of 1-12;

in the formula (DI-5-30), k is an integer of 1 to 5; and the number of the first and second electrodes,

in the formula (DI-7-3), n is 1 or 2.

[7] The polyamic acid or the derivative thereof according to any one of [1] to [6], wherein at least 1 of the tetracarboxylic dianhydride and the diamine contains a compound having a photoreactive structure.

[8] The polyamic acid or derivative thereof according to [7], wherein the photoreactive structure is at least 1 selected from the group consisting of structures represented by the following formulae (P-1) to (P-7).

In the formula (P-1), R⁶¹Independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

[9] The polyamic acid or derivative thereof according to [7], wherein the compound having a photoreactive structure is at least 1 selected from the group consisting of the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), formula (VI-1), and formula (VI-2).

In the above formulae, the group having an unfixed bonding position on any carbon atom constituting the ring means that the bonding position on the ring is arbitrary, and in the formula (V-2), R⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is an integer of 0 to 2, in the formula (V-3), the ring A and the ring B are at least 1 selected from monocyclic hydrocarbon, condensed polycyclic hydrocarbon and heterocyclic ring, and R¹¹Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹²Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²In (1) or 2-CH groups on the linear alkylene group₂Optionally substituted by-O-, R⁷～R¹⁰Each independently is-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

[10] The polyamic acid or derivative thereof according to [7], wherein the compound having a photoreactive structure is a diamine represented by the following formula (PDI-7).

In the formula (PDI-7), R⁵¹Each independently is-CH₃、-OCH₃、-CF₃or-COOCH₃And s is an integer of 0 to 2.

[11] A liquid crystal aligning agent comprising the polyamic acid or derivative thereof according to any one of [1] to [10 ].

[12] A liquid crystal aligning agent for photo-alignment, comprising a polymer [ A ] and a polymer [ B ], the polymer [ A ] and the polymer [ B ] being polyamic acid or a derivative thereof;

at least 1 of the raw material monomers of the polymer has a photoreactive structure, and the raw material monomers of the polymer include at least 1 of the compounds represented by the following formula (1).

[13] The liquid crystal aligning agent for photoalignment according to [12], which comprises at least 1 polymer [ A ] and at least 1 polymer [ B ],

the polymer [ A ] is obtained by reacting raw material monomers comprising a tetracarboxylic dianhydride and a diamine, wherein at least 1 of the tetracarboxylic dianhydride and the diamine comprises a compound having a photoreactive structure,

the polymer [ B ] is obtained by reacting a raw material monomer which does not have a photoreactive structure in both a tetracarboxylic dianhydride and a diamine and contains at least 1 of the compounds represented by the formula (1).

[14] The liquid crystal aligning agent for photoalignment according to [12], which comprises at least 1 polymer [ A ] and at least 1 polymer [ B ],

the polymer [ A ] is obtained by reacting raw material monomers containing tetracarboxylic dianhydride and diamine, wherein at least 1 of the tetracarboxylic dianhydride and the diamine contains a compound with a photoreactive structure, and the diamine contains at least 1 of the compounds shown in a formula (1),

the polymer [ B ] is obtained by reacting a raw material monomer containing a tetracarboxylic dianhydride and a diamine, both of which have no photoreactive structure.

[15] The liquid crystal aligning agent for photoalignment according to [12], which comprises at least 1 polymer [ A ] and at least 1 polymer [ B ],

the polymer [ B ] is obtained by reacting raw material monomers containing tetracarboxylic dianhydride and diamine, wherein the tetracarboxylic dianhydride and the diamine do not have a photoreactive structure, and the diamine contains at least 1 of the compounds represented by the formula (1).

[16] The liquid crystal aligning agent for photoalignment according to [12], which comprises at least 1 polymer [ A ] and at least 1 polymer [ B ],

the polymer [ B ] is obtained by reacting raw material monomers comprising a tetracarboxylic dianhydride and a diamine, wherein at least 1 of the tetracarboxylic dianhydride and the diamine comprises a compound having a photoreactive structure, and the diamine comprises at least 1 of the compounds represented by the formula (1).

[17] The liquid crystal aligning agent for photoalignment according to any one of [12] to [16], wherein the diamine represented by the formula (1) is a diamine represented by the formula (1').

A¹and A²Each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms; and the number of the first and second electrodes,

[18] The liquid crystal aligning agent for photoalignment according to any one of [12] to [17], wherein R in the diamine represented by the formula (1) is hydrogen or-OH.

[19] The liquid crystal aligning agent for photoalignment according to any one of [12] to [18], wherein the diamine represented by the formula (1) is a compound represented by the following formula (1-15) or formula (1-29).

[20] The liquid crystal aligning agent for photoalignment according to any one of [12] to [19], wherein the compound having a photoreactive structure has at least 1 structure selected from the group consisting of the following formulae (P-1) to (P-7).

[21] The liquid crystal aligning agent for photoalignment according to any one of [12] to [19], wherein the compound having a photoreactive structure is at least 1 selected from the group consisting of the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), formula (VI-1), and formula (VI-2).

In the above formulae, the group having an unfixed bonding position on any carbon atom constituting the ringThe bonding position on the ring is arbitrary, and in the formula (V-2), R is⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is an integer of 0 to 2, in the formula (V-3), the ring A and the ring B are at least 1 selected from monocyclic hydrocarbon, condensed polycyclic hydrocarbon and heterocyclic ring, and R¹¹Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹²Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²In (1) or 2-CH groups on the linear alkylene group₂Optionally substituted by-O-, R⁷～R¹⁰Each independently is-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

[22] The liquid crystal aligning agent for photoreaction according to any one of [12] to [19], wherein the compound having a photoreactive structure is a diamine represented by the following formula (PDI-7).

[23] The liquid crystal aligning agent for photoalignment according to any one of [12] to [22], wherein the tetracarboxylic dianhydride not having a photoreactive structure is at least 1 selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII);

the diamine having no photoreactive structure is at least 1 selected from the group consisting of the following formulae (DI-1) to (DI-16), formulae (DIH-1) to (DIH-3), and formulae (DI-31) to (DI-35).

Formula (AN-I),In the formulae (AN-IV) and (AN-V), X is independently a single bond or-CH₂-；

in the formulae (AN-III) to (AN-V), the ring A¹⁰Is monocyclic hydrocarbon group of 3-10 carbon atoms or condensed polycyclic hydrocarbon group of 6-30 carbon atoms, at least 1 hydrogen on the group is optionally substituted by methyl, ethyl or phenyl, the bond connected with the ring is connected with any carbon forming the ring, and 2 bonds are optionally connected with the same carbon;

in the formula (AN-VII), G¹⁰Independently is-O-, -COO-or-OCO-, and r independently is 0 or 1;

in the formula (DI-4), s is independently an integer of 0 to 2;

The group whose bonding position on the carbon atom constituting the ring is not fixed means that the bonding position on the ring is arbitrary, -NH₂The bonding position on the cyclohexane or benzene ring being other than G²¹Or G²²The bonding position of (a) is at an arbitrary position outside;

in the formula (DI-11), r is 0 or 1;

in the formula (DI-12), R²¹And R²²Independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, G²³Independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a phenylene group substituted with an alkyl group, and w is an integer of 1 to 10;

in formula (DI-15), ring C is a monocyclic ring containing a heteroatom;

in the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are linking groups, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, wherein 1 or more-CH groups in the alkylene group₂Optionally substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-, ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴In which at least 1 hydrogen is optionally replaced by-F or-CH₃And (b) a substituent, s, t and u are independently an integer of 0 to 2, and the total of s, t and u is 1 to 5, and when s, t or u is 2,2 linking groups in each bracket may be the same or different, and 2 rings may be the same or different,

R²⁶hydrogen, -F, -OH, alkyl with 1-30 carbon atoms, fluorine substituted alkyl with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms, -CN, -OCH₂F、-OCHF₂or-OCF₃At least 1-CH in the alkyl group having 1 to 30 carbon atoms₂Optionally substituted with a 2-valent group of the formula (DI-31-b),

in the formulae (DI-32) and (DI-33), the group in which the bonding position on any carbon atom constituting the ring is not fixed means that the bonding position on the ring is arbitrary;

R³¹is hydrogen or alkyl with 1-20 carbon atoms, at least 1-CH in the alkyl₂-optionally substituted by-O-, -CH ═ CH-or-C ≡ C-, R³²Is alkyl of 6 to 22 carbon atoms, R³³Is hydrogen or alkyl of 1 to 22 carbon atoms, ring B²⁵Is 1, 4-phenylene or 1, 4-cyclohexylene, r is 0 or 1, and-NH is bonded to the benzene ring₂Indicating that the bonding position on the ring is arbitrary.

[24] The liquid crystal aligning agent for photo-alignment according to [23], wherein, the tetracarboxylic dianhydride not having a photoreactive structure is at least 1 selected from the group consisting of the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-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), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4);

the diamine having no photoreactive structure is selected from the group consisting of formula (DI-1-3), formula (DI-2-1), 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), At least 1 of the group consisting of formula (DIH-2-1) and formula (DI-31-56).

In the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1-12.

in the formula (DI-7-3), n is each independently 1 or 2.

[25] The liquid crystal aligning agent according to any one of [11] to [24], further comprising at least 1 selected from the group of compounds consisting of an oxazine compound, an oxazoline compound, an epoxy compound, and a silane coupling agent.

[26] A liquid crystal alignment film comprising the liquid crystal aligning agent according to any one of [11] to [25 ].

[27] A liquid crystal alignment film for a transverse electric field, which is formed from the liquid crystal aligning agent according to any one of [11] to [25 ].

[28] A liquid crystal display element having the liquid crystal alignment film according to item [26] or item [27 ].

[29] A diamine represented by the formula (1').

[30] The diamine according to [29], which is represented by the following formula (1-15) or formula (1-29).

The phrase "at least 1 of the tetracarboxylic dianhydrides and diamines contains a compound having a photoreactive structure" as described above means that "at least one compound has a photoreactive structure among the tetracarboxylic dianhydrides and diamines", specifically, 1 or 2 or more kinds of the tetracarboxylic dianhydrides and 1 or 2 or more kinds of the diamines can be used, and among all the compounds, at least one compound has a photoreactive structure, and includes the following forms: at least one of the tetracarboxylic dianhydrides alone has a photoreactive structure, at least one of the diamines alone has a photoreactive structure, and at least one of the tetracarboxylic dianhydrides has a photoreactive structure and at least one of the diamines has a photoreactive structure.

ADVANTAGEOUS EFFECTS OF INVENTION

The liquid crystal alignment film of the present invention, which is formed from a liquid crystal alignment agent containing a polyamic acid or derivative thereof obtained by using a diamine represented by formula (1) as a raw material, has excellent long-term reliability. In addition, the liquid crystal display element of the transverse electric field type including the liquid crystal alignment film formed by the brush rubbing method is excellent in viewing angle characteristics because the pretilt angle can be kept low. The liquid crystal display element of the transverse electric field type having the liquid crystal alignment film formed by the photo-alignment method is excellent in image sticking characteristics. When it is desired to impart other characteristics such as improvement in printability for printing on a substrate, a liquid crystal alignment film having desired characteristics can be provided by blending with other polymers or by using in combination with additives.

Detailed Description

In the diamine shown in the formula (1), R is hydrogen, -OH, alkyl with 1-6 carbon atoms or alkoxy with 1-6 carbon atoms; x¹And X²Each independently is a 2-valent organic group having an alkylene group having 1 to 8 carbon atoms, a 2-valent organic group having a phenylene group, or a 2-valent organic group having an alkylene group having 1 to 8 carbon atoms and a phenylene group.

When a liquid crystal aligning agent having higher solubility in a solvent is desired, a diamine in which R is an alkoxy group in the formula (1) is preferably used. When a more reliable liquid crystal alignment film is desired, a compound in which R is hydrogen or — OH is preferably used in formula (1).

Specific examples of the diamine represented by the formula (1) are compounds represented by the following formulae (1-1) to (1-84).

By using the diamines represented by the formulae (1-1) to (1-84) as one of the raw materials of the polymer constituting the liquid crystal aligning agent of the present invention, a liquid crystal alignment film having high liquid crystal alignment properties can be obtained without lowering the display quality even when used for a long period of time.

When a liquid crystal aligning agent having higher solubility in a solvent is desired, diamines of the formulae (1-23) and (1-37) are preferably used. Further, when a liquid crystal alignment film having higher reliability is desired, diamines of the formulae (1-1), (1-15), (1-29) and (1-43) are preferably used, and diamines of the formulae (1-15) and (1-29) are more preferably used.

The polyamic acid and the derivative thereof of the present invention will be explained. The polyamic acid and the derivative thereof of the present invention are a reaction product between tetracarboxylic dianhydride and diamine including diamine represented by formula (1). The "diamine containing a diamine represented by the formula (1)" specifically means a mixture of 1 kind of diamine represented by the formula (1), 2 or more kinds of diamines represented by the formula (1), and a mixture of at least 1 kind of diamine represented by the formula (1) and at least 1 kind of diamine other than the diamine represented by the formula (1). Further, the "other diamine" described later also includes dihydrazides that function as the diamine in the polyamic acid and the derivative thereof of the invention. In this specification, there is a description that dihydrazide is regarded as diamine. That is, in the present specification, the term "diamine" may be used in a sense including dihydrazide.

The derivative of the foregoing polyamic acid means: the component dissolved in a solvent when a liquid crystal aligning agent described later containing a solvent is prepared is a component capable of forming a liquid crystal alignment film containing polyimide as a main component when the liquid crystal aligning agent is prepared as a liquid crystal alignment film. Examples of derivatives of such polyamic acids include soluble polyimides, polyamic acid esters, and polyamic acid amides, and more specifically, include 1) polyimides obtained by subjecting all amino groups of polyamic acid and carboxyl groups to a dehydration ring-closure reaction; 2) partially dehydrating and ring-closing to obtain a partial polyimide; 3) polyamic acid ester obtained by converting carboxyl group of polyamic acid into ester; 4) a polyamic acid-polyamide copolymer obtained by replacing a part of acid dianhydride contained in a tetracarboxylic dianhydride compound with an organic dicarboxylic acid and reacting the same; and 5) a polyamide-imide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyamic acid and the derivative thereof may be 1 kind of compound or 2 or more kinds. The polyamic acid and the derivative thereof may be a compound having a structure of a reaction product of a tetracarboxylic dianhydride and a diamine, or may contain a reaction product obtained by a reaction other than a reaction of a tetracarboxylic dianhydride and a diamine using another raw material.

The tetracarboxylic dianhydride used for producing the polyamic acid and the derivative thereof of the present invention will be described. The tetracarboxylic dianhydride used in the present invention can be selected from known tetracarboxylic dianhydrides without limitation. Such tetracarboxylic dianhydride may belong to any group of aromatic systems (including heteroaromatic ring systems) in which a dicarboxylic anhydride is directly bonded to an aromatic ring, and aliphatic systems (including heteroaromatic ring systems) in which a dicarboxylic anhydride is not directly bonded to an aromatic ring.

As a suitable example of such a tetracarboxylic dianhydride, from the viewpoints of easiness of obtaining raw materials, easiness in producing a polymer, and electrical characteristics of a film, tetracarboxylic dianhydrides represented by formulae (AN-I) to (AN-VII) can be cited.

In the formulae (AN-I), (AN-IV) and (AN-V), X is independently a single bond or-CH₂-. In the formula (AN-II), G is a single bond, alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-. In the formulae (AN-II) to (AN-IV), Y is independently 1 selected from the group consisting of the following 3-valent groups, bonded to any carbon atomAt least 1 hydrogen on the group is optionally substituted with methyl, ethyl or phenyl.

In the formulae (AN-III) to (AN-V), the ring A¹⁰The hydrocarbon group is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, wherein at least 1 hydrogen in the group is optionally substituted by a methyl group, an ethyl group or a phenyl group, the bond to the ring is bonded to any carbon constituting the ring, and 2 bonds are optionally bonded to the same carbon. In the formula (AN-VI), X¹⁰An alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group. In the formula (AN-VII), G¹⁰independently-O-, -COO-or-OCO-, and r independently is 0 or 1.

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

[ tetracarboxylic dianhydride represented by the formula (AN-1) ]

In the formula (AN-1), G¹¹A single bond, an alkylene group having 1 to 12 carbon atoms, a1, 4-phenylene group or a1, 4-cyclohexylene group. X¹¹Independently is a single bond or-CH₂-。G¹²Independently any of the following 3-valent groups.

G¹²Is composed of>When the molecular weight is CH-, the molecular weight is,>hydrogen on CH-is optionally replaced by-CH₃And (4) substitution. G¹²Is composed of>N-time, G¹¹Not a single bond and-CH₂-、X¹¹Not a single bond. And R is¹¹Is hydrogen or-CH₃。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulae.

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

[ tetracarboxylic dianhydride represented by the formula (AN-3) ]

In the formula (AN-3), ring A¹¹Is a cyclohexane ring or a benzene ring.

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

[ tetracarboxylic dianhydride represented by the formula (AN-4) ]

In the formula (AN-4), G¹³Is a single bond, - (CH)₂)_m-、-O-、-S-、-C(CH₃)₂-、-SO₂-、-CO-、-C(CF₃)₂-, or a 2-valent group represented by the following formula (G13-1), and m is an integer of 1 to 12. Ring A¹¹Each independently a cyclohexane ring or a benzene ring. G¹³Optionally bound to ring A¹¹At any position of (a).

In the formula (G13-1), G^13aAnd G^13bEach independently is a single bond, -O-, or-NHCO-represented 2-valent group. The phenylene group is preferably a1, 4-phenylene group and a1, 3-phenylene group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulae.

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

[ tetracarboxylic dianhydride represented by the formula (AN-5) ]

In the formula (AN-5), R¹¹Is hydrogen or-CH₃. R having unfixed bonding position on carbon atom constituting benzene ring¹¹The bonding position on the benzene ring is arbitrary.

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

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

In the formula (AN-6), X¹¹Independently is a single bond or-CH₂-。X¹²is-CH₂-、-CH₂CH₂-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 formulae.

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

In the formula (AN-7), X¹¹Is a single bond or-CH₂-。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-8) ]

In the formula (AN-8), X¹¹Is a single bond or-CH₂-。R¹²Is hydrogen, -CH₃、-CH₂CH₃Or phenyl, ring A¹²Is a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-9) ]

In the formula (AN-9), r is each independently 0 or 1.

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

[ tetracarboxylic dianhydrides represented by the formulae (AN-10-1) and (AN-10-2) ]

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

In the formula (AN-11), ring A¹¹Independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulae.

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

In the formula (AN-12), ring A¹¹Each 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 formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-13) ]

In the formula (AN-13), X¹³Is 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 formulae.

In the formula (AN-13), Ph represents a phenyl group.

[ tetracarboxylic dianhydride represented by the formula (AN-14) ]

In the formula (AN-14), G¹⁴independently-O-, -COO-or-OCO-, and r independently is 0 or 1.

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

[ 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 formulae.

Examples of the tetracarboxylic dianhydrides other than those mentioned above include the following compounds.

Among the tetracarboxylic dianhydrides, materials suitable for improving various characteristics are described. When importance is attached to improving the alignment properties of liquid crystals, compounds represented by formula (AN-1), formula (AN-3), and formula (AN-4) are preferable, and compounds represented by formula (AN-1-2), formula (AN-1-13), formula (AN-3-2), formula (AN-4-17), and formula (AN-4-29) are particularly preferable, wherein m is preferably 4 or 8 in formula (AN-1-2), and m is preferably 4 or 8 in formula (AN-4-17), and more preferably m is 8.

When importance is attached to improve the transmittance of the liquid crystal display element, preferred are compounds represented by formula (AN-1-1), formula (AN-1-2), 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 formula (AN-16-4), wherein m is preferably 4 or 8 in formula (AN-1-2), and m is preferably 4 or 8 in formula (AN-4-17), and more preferably m is 8.

When emphasis is placed on increasing the VHR of the liquid crystal display element, compounds represented by formula (AN-1-1), 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-16-3), and formula (AN-16-4) are preferred, wherein m is preferably 4 or 8 in formula (AN-1-2), and m is preferably 4 or 8, and particularly preferably 8 in formula (AN-4-17).

Increasing the relaxation speed of residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one method of preventing the afterimage. When importance is attached to this purpose, preferred are compounds represented by the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29) and the formula (AN-11-3).

The diamine and dihydrazide used for producing the polyamic acid and the derivative thereof of the present invention will be described. When the polyamic acid or the derivative thereof of the present invention is produced, it can be selected from known diamines and dihydrazides without limitation.

Diamines are classified into 2 types according to their structures. Namely, the method comprises the following steps: when the skeleton to which 2 amino groups are bonded is regarded as the main chain, a diamine having a side chain group which is a group branched from the main chain, and a diamine having no side chain group are used. The side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms, and specific examples thereof include an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, an alkoxyalkyl group having 3 or more carbon atoms, and a group having a steroid skeleton. The group having 1 or more rings and having any one of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms and an alkoxyalkyl group having 2 or more carbon atoms as a substituent in the ring at the end thereof also has an effect as a side chain group. In the following description, a diamine having such a side chain group is sometimes referred to as a side chain type diamine. Also, diamines not having such side chain groups are sometimes referred to as non-side chain diamines.

By appropriately using the non-side chain type diamine and the side chain type diamine flexibly, it is possible to cope with the respective required pretilt angles. The side chain type diamines are preferably used in combination to such an extent that the characteristics of the present invention are not impaired. In addition, the side chain type diamine and the non-side chain type diamine are preferably selected and used for the purpose of improving the vertical alignment property, the voltage holding ratio, the sticking property, and the alignment property with respect to the liquid crystal.

The non-side chain type diamine is explained. The known diamines having no side chain include diamines of the following formulae (DI-1) to (DI-16).

In the above formula (DI-1), G²⁰is-CH₂-, at least 1-CH₂Optionally substituted by-NH-, -O-, m being an integer from 1 to 12 on the alkylene radicalAt least 1 hydrogen of (a) is optionally substituted with-OH. In the formulae (DI-3) and (DI-5) to (DI-7), G²¹Independently a single bond, -NH-, -NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_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 formulae (DI-6) and (DI-7), G²²Independently a single bond, -O-, -S-, -CO-, -C (CH)₃)₂-、-C(CF₃)₂-, -NH-or an alkylene group having 1 to 10 carbon atoms. At least 1 hydrogen of the cyclohexane ring and the benzene ring in the formulas (DI-2) to (DI-7) is optionally replaced by-F, -Cl, alkyl with 1-3 carbon atoms, -OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅And a phenyl group or a benzyl group, and, in formula (DI-4), at least 1 hydrogen on the cyclohexane ring and the benzene ring is optionally substituted with 1 selected from the group of the groups represented by the following formulae (DI-4-a) to (DI-4-e). The group having an unfixed bonding position on the carbon atom constituting the ring means that the bonding position on the ring is arbitrary. and-NH₂The bonding position on the cyclohexane or benzene ring being other than G²¹Or G²²At any position other than the bonding position of (a).

In the formulae (DI-4-a) and (DI-4-b), R²⁰Independently is hydrogen or-CH₃。

In the formula (DI-11), r is 0 or 1. In the formulae (DI-8) to (DI-11), -NH bonded to the ring₂The bonding position of (a) is an arbitrary position.

In the formula (DI-12), R²¹And R²²Independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, G²³Independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a phenylene group substituted with an alkyl group, and w is an integer of 1 to 10. In the formula (DI-13), R²³Independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or-Cl, p independently is 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 heterocyclic aromatic group, R²⁴Hydrogen, -F, -Cl, alkyl with 1-6 carbon atoms, alkoxy, alkenyl and alkynyl, and q is an integer of 0-4 independently. In the formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the formula (DI-16), G²⁴Is a single bond, an alkylene group having 2 to 6 carbon atoms or a1, 4-phenylene group, and r is 0 or 1. The term "group whose bonding position on the carbon atom constituting the ring is not fixed" means that the bonding position on the ring is arbitrary. Formula (DI-13) to formula (DI-16) wherein-NH is bonded to the ring₂The bonding position of (a) is an arbitrary position.

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

Examples of the diamines represented by the formula (DI-1) are shown below.

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

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

Examples of diamines represented by the formula (DI-4) are shown below.

Examples of the diamines represented by the formula (DI-5) are shown below.

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

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

Examples of diamines represented by the formula (DI-6) are shown below.

Examples of diamines represented by the formula (DI-7) are shown below.

In the formulas (DI-7-3) and (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.

Examples of diamines represented by the formula (DI-8) are shown below.

Examples of diamines represented by the formula (DI-9) are shown below.

Examples of diamines represented by the formula (DI-10) are shown below.

Examples of the diamines represented by the formula (DI-11) are shown below.

Examples of diamines represented by the formula (DI-12) are shown below.

Examples of diamines represented by the formula (DI-13) are shown below.

Examples of diamines represented by the formula (DI-14) are shown below.

Examples of diamines represented by the formula (DI-15) are shown below.

Examples of diamines represented by the formula (DI-16) are shown below.

The dihydrazide is explained. The known dihydrazides having no side chain include the following formulae (DIH-1) to (DIH-3).

In the formula (DIH-1), G²⁵A single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)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 1 hydrogen of the group is optionally substituted by a methyl group, an ethyl group or a phenyl group. In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least 1 hydrogen of the group is optionally substituted by methyl, ethyl or phenyl, Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-. In the formulae (DIH-2) and (DIH-3), -CONHNH bonded to the ring₂The bonding position of (a) is an arbitrary position.

Examples of the formulae (DIH-1) to (DIH-3) are shown below.

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

Such non-side chain type diamines and dihydrazides have an effect of improving electrical characteristics such as lowering ion density of a liquid crystal display element. When a non-side-chain diamine and/or dihydrazide is used as the diamine used for producing the polyamic acid or derivative thereof used in the liquid crystal aligning agent of the present invention, the ratio of the diamine to the dihydrazide is preferably 0 to 90 mol%, more preferably 0 to 50 mol% based on the total amount of the diamine and the dihydrazide.

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

Examples of the side chain group include alkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, and alkynylaminocarbonyl. The alkyl group, alkenyl group and alkynyl group in these groups are each a group having 3 or more carbon atoms. Among them, the alkoxyalkyl group may have 3 or more carbon atoms in the whole group. These groups may be linear or branched.

Next, under the condition that 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, there may be mentioned a group having a ring structure such as a phenyl group, a phenylalkyl group, a phenylalkoxy group, a phenoxy group, a phenylcarbonyl group, a phenylaminocarbonyl group, a phenylcyclohexyloxy group, a cycloalkyl group having 3 or more carbon atoms, a cyclohexylalkyl group, a cyclohexyloxy group, a cyclohexyloxycarbonyl group, a cyclohexylphenyl group, a cyclohexylphenylalkyl group, a cyclohexylphenoxy group, a bis (cyclohexyl) oxy group, a bis (cyclohexyl) alkyl group, a bis (cyclohexyl) phenyl group, a bis (cyclohexyl) phenylalkyl group, a bis (cyclohexyl) oxycarbonyl group, a bis (cyclohexyl) phenoxycarbonyl group, or a cyclohexylbis (phenyl) oxycarbonyl group.

Further, there may be mentioned polycyclic groups having 2 or more benzene rings, 2 or more cyclohexane rings, or 2 or more rings composed of a benzene ring and a cyclohexane ring, wherein the linking groups are 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, a fluorine-substituted 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. Groups having a steroid skeleton are also effective as side chain groups.

Examples of the diamine having a side chain include compounds represented by the following formulae (DI-31) to (DI-35).

In the formula (DI-31), G²⁶Is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-or- (CH)₂)_m’-, m' is an integer of 1 to 12. G²⁶Preferred examples of (B) are a single bond, -O-, -COO-, -OCO-, -CH₂O-and C1-3 alkylene, particularly preferred examples being a single bond, -O-, -COO-, -OCO-, -CH₂O-、-CH₂-and-CH₂CH₂-。R²⁵Is 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 1 hydrogen is optionally substituted by-F, and, at least 1-CH₂-is optionally substituted by-O-, -CH ═ CH-, or-C ≡ C-. The hydrogen on the phenyl group being optionally substituted by-F, -CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃An alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. -NH bound to the benzene ring₂The bonding position of (b) represents an arbitrary position on the ring, and the bonding position is preferably a meta-position or a para-position. I.e. coupling the radical "R²⁵-G²⁶When the bonding position of-is 1-position, the 2-bonding positions are preferably 3-and 5-positions or 2-and 5-positions.

In the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are linking groups, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, wherein 1 or more-CH groups in the alkylene group₂-is optionally substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-. Ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴In which at least 1 hydrogen is optionally replaced by-F or-CH₃And (c) substitution, s, t and u are independently integers of 0 to 2, and the total of s, t and u is 1 to 5, and when s, t or u is 2,2 linking groups in each bracket may be the same or different, and 2 rings may be the same or different. R²⁶Hydrogen, -F, -OH, alkyl with 1-30 carbon atoms, fluorine substituted alkyl with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms, -CN, -OCH₂F、-OCHF₂or-OCF₃At least 1-CH in the alkyl group having 1 to 30 carbon atoms₂-optionally substituted with a 2-valent group represented by the following formula (DI-31-b).

In the formula (DI-31-b), R²⁷And R²⁸Independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6. R²⁶Preferred examples thereof include an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

In formulae (DI-32) and (DI-33), G³⁰Independently a single bond, -CO-or-CH₂-，R²⁹Independently is hydrogen or-CH₃，R³⁰Is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. At least 1 hydrogen on the benzene ring in the formula (DI-33) is optionally substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group. The term "group whose bonding position on any carbon atom constituting the ring is not fixed" means that the bonding position on the ring is arbitrary. Preferably, 2 groups' -phenylene in formula (DI-32)-G³⁰One of the-O- "groups is bonded to the 3-position of the steroid nucleus and the other group is bonded to the 6-position of the steroid nucleus. 2 groups' -phenylene-G in formula (DI-33)³⁰The bonding position of-O- "on the benzene ring is preferably meta or para, respectively, with respect to the bonding position of the steroid nucleus. In the formulae (DI-32) and (DI-33), -NH bonded to the benzene ring₂Indicating that the bonding position on the ring is arbitrary.

In formulae (DI-34) and (DI-35), G³¹Independently represents-O-, -NH-or an alkylene group having 1 to 6 carbon atoms, G³²Is a single bond or an alkylene group having 1 to 3 carbon atoms. R³¹Is hydrogen or alkyl with 1-20 carbon atoms, at least 1-CH in the alkyl₂-is optionally substituted by-O-, -CH ═ CH-, or-C ≡ C-. R³²Is alkyl of 6 to 22 carbon atoms, R³³Is hydrogen or an alkyl group having 1 to 22 carbon atoms. Ring B²⁵Is 1, 4-phenylene or 1, 4-cyclohexylene, r is 0 or 1. and-NH bound to the benzene ring₂The bonding position on the ring is arbitrary, preferably with respect to G³¹The bonding position of (A) is meta or para, respectively.

Specific examples of the side chain type diamine are shown below. Examples of the diamine having a side chain of the above-mentioned formulae (DI-31) to (DI-35) include compounds of the following formulae (DI-31-1) to (DI-35-3).

Examples of the compounds represented by the formula (DI-31) are shown below.

In the formulae (DI-31-1) to (DI-31-11), R³⁴Is 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. R³⁵Is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 25 carbon atomsOr an alkoxy group having 3 to 25 carbon atoms.

In the formulae (DI-31-12) to (DI-31-17), R³⁶Is an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R³⁷Is an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms.

In the formulae (DI-31-18) to (DI-31-43), R³⁸Is 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. R³⁹Hydrogen, -F, alkyl with 1-30 carbon atoms, alkoxy with 1-30 carbon atoms, -CN, -OCH₂F、-OCHF₂or-OCF₃Preferably, the alkyl group has 3 to 25 carbon atoms or the alkoxy group has 3 to 25 carbon atoms. And, G³³Is an alkylene group having 1 to 20 carbon atoms.

Examples of the compounds represented by the formula (DI-32) are shown below.

Examples of the compounds represented by the formula (DI-33) are shown below.

Examples of the compounds represented by the formula (DI-34) are shown below.

In the formulae (DI-34-1) to (DI-34-14), R⁴⁰Is hydrogen or alkyl having 1 to 20 carbon atoms, preferably hydrogen or alkyl having 1 to 10 carbon atoms, and R⁴¹Is hydrogen or an alkyl group having 1 to 12 carbon atoms.

Examples of the compounds represented by the formula (DI-35) are shown below.

In the formulae (DI-35-1) to (DI-35-3), R³⁷Is alkyl of 6 to 30 carbon atoms, R⁴¹Is hydrogen or an alkyl group having 1 to 12 carbon atoms.

As the diamine in the present invention, diamines other than those represented by the formulae (DI-1-1) to (DI-16-1), the formulae (DIH-1-1) to (DIH-3-6), and the formulae (DI-31-1) to (DI-35-3) may be used. Examples of such diamines include compounds represented by the following formulae (DI-36-1) to (DI-36-13).

In the formulae (DI-36-1) to (DI-36-8), R⁴²Each independently represents an alkyl group having 3 to 30 carbon atoms.

In the formulae (DI-36-9) to (DI-36-11), e is an integer of 2 to 10, and in the formula (DI-36-12), R⁴³Each independently hydrogen, -NHBoc or-N (Boc)₂At least 1R⁴³is-NHBoc or-N (Boc)₂In the formula (DI-36-13), R⁴⁴is-NHBoc or-N (Boc)₂And m is an integer of 1 to 12. Herein, Boc is tert-butoxycarbonyl.

Among the diamines and dihydrazides, materials suitable for improving the respective properties are described. When importance is attached to further improving the alignment properties of liquid crystals, it is preferable to use compounds represented by formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3) and formula (DI-11-2). In formula (DI-5-1), m is preferably 2,4 or 6, and more preferably m is 4. In the formula (DI-5-12), m is preferably 2 to 6, and more preferably 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1.

When importance is placed on the improvement of transmittance, diamines represented by the formulae (DI-1-3), (DI-2-1), (DI-5-5), (DI-5-24) and (DI-7-3) are preferably used, and compounds represented by the formula (DI-2-1) are more preferred. In formula (DI-5-1), m is preferably 2,4 or 6, and more preferably m is 4. In the formula (DI-7-3), m is preferably 2 or 3, and n is preferably 1 or 2, and more preferably m is 3 and n is 1.

In the case where emphasis is placed on improving the VHR of a liquid crystal display element, compounds represented by the formulae (DI-2-1), (DI-4-2), (DI-4-10), (DI-4-15), (DI-5-28), (DI-5-30) and (DI-13-1) are preferably used, and diamines represented by the formulae (DI-2-1), (DI-5-1) and (DI-13-1) are more preferably used. In formula (DI-5-1), m is preferably 1. In the formula (DI-5-30), k is preferably 2.

Increasing the relaxation rate of residual charge (residual DC) of the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one method for preventing the afterimage. In the case where this object is important, it is preferable to use compounds represented by the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15), the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), the formula (DI-5-28), the formula (DI-7-12) and the formula (DI-16-1), and more preferably the formula (DI-4-1), the formula (DI-5-1) and the formula (DI-5-13). In formula (DI-5-1), m is preferably 2,4 or 6, and more preferably m is 4. In the formula (DI-5-12), m is preferably 2 to 6, and more preferably 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1. In the formula (DI-7-12), m is preferably 3 or 4, and more preferably 4.

In each diamine, a part of the diamine is optionally replaced with a monoamine in a range where the ratio of the monoamine to the diamine is 40 mol% or less. This substitution can cause termination of the polymerization reaction when the polyamic acid is produced, and can inhibit the polymerization reaction from progressing again. Therefore, by such substitution, the molecular weight of the resulting polymer (polyamic acid or derivative thereof) can be easily controlled, and for example, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. The diamine substituted with a monoamine may be 1 or 2 or more, as long as the effect of the present invention is not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine and n-eicosylamine.

The polyamic acid or derivative thereof of the present invention may further include a monoisocyanate compound in its monomer. By including a monoisocyanate compound in the monomer, the end of the resulting polyamic acid or a derivative thereof is modified, and the molecular weight is adjusted. By using the end-modified polyamic acid or a derivative thereof, for example, the coating characteristics of a liquid crystal aligning agent can be improved without impairing the effects of the present invention. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 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.

When the polyamic acid or the derivative thereof of the present invention is used as a photo-alignment film to which a liquid crystal alignment ability is imparted by light irradiation, for example, ultraviolet irradiation, a monomer having a photoreactive structure can be suitably used as a raw material of the polyamic acid or the derivative thereof. By using the monomer having a photoreactive structure, polyamic acid and its derivative having a photoreactive structure can be synthesized. The photoreactive structure refers to, for example, a photolytic structure represented by the following formula (P-1) which is decomposed by ultraviolet irradiation, a photoisomerization structure represented by the formulae (P-2) to (P-4) which is isomerized, a photodimerization structure represented by the formulae (P-5) to (P-7) which is dimerized, and the like.

Examples of the compound having a photolytic structure represented by the formula (P-1) include compounds represented by the following formulae (PA-1) to (PA-3).

Among these compounds, the compounds represented by the above-mentioned formulae (PA-1) and (PA-2) can be suitably used.

When the compounds represented by the formulae (PA-1) to (PA-3) are used as raw material monomers of a polymer used in a liquid crystal aligning agent utilizing the liquid crystal aligning ability by photoisomerization reaction, a liquid crystal aligning agent utilizing the liquid crystal aligning ability by photodimerization, or a liquid crystal aligning agent for brushing, they are regarded as tetracarboxylic dianhydrides having no photoreactive structure.

The compound having the photoisomerization structure represented by formula (P-2) to formula (P-4) is preferably at least 1 selected from the group consisting of compounds represented by formula (II) to formula (VI) having good photosensitivity, and more preferably a compound represented by formula (V).

R²-C≡C-R³ (II)

R²-C≡C-C≡C-R³ (III)

R²-C≡C-R⁴-C≡C-R³ (IV)

R²-N＝N-R³ (V)

R⁵-CH＝CH-R⁵ (VI)

In the formulae (II) to (V), R²And R³To have-NH₂Or a 1-valent organic group having-CO-O-CO-, in the formula (IV), R⁴Is a 2-valent organic radical of the formula (VI)⁵To have-NH₂Or an aromatic ring of-CO-O-CO-.

The photoisomerization structure may be incorporated into any one of the main chain or the side chain of the polyamic acid or the derivative thereof of the present invention, and by incorporating into the main chain, it can be suitably used for a liquid crystal display element of a lateral electric field system.

As the material having the aforementioned photoisomerization structure, at least 1 selected from the group of compounds represented by the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), formula (VI-1), and formula (VI-2) can be suitably used.

In the above formulae, the group whose bonding position on any carbon atom constituting the ring is not fixed means that the bonding position on the ring is arbitrary, and in the formula (V-2), R⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is an integer of 0 to 2, in the formula (V-3), ring A and ring B are each independently at least 1 selected from monocyclic hydrocarbon, condensed polycyclic hydrocarbon and heterocyclic ring, R¹¹Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹²Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²In (1), or 2-CH's in the straight chain alkylene group₂-optionally substituted by-O-, R⁷～R¹⁰Each independently is-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

The compounds represented by the above formulae (V-1), (V-2) and (VI-2) are particularly suitably used from the viewpoint of photosensitivity. In the formula (V-2) and the formula (VI-2), a compound in which the bonding position of the amino group is para, and further a compound in which a is 0 in the formula (V-2) can be more suitably used from the viewpoint of orientation.

The acid dianhydride or diamine having a structure capable of being isomerized by ultraviolet irradiation, represented by the formulae (II-1) to (VI-2), can be specifically represented by the formulae (II-1-1) to (VI-2-3).

Among these, by using the compounds represented by the formulae (VI-1-1) to (V-3-8) as compounds having a structure which can be isomerized by ultraviolet irradiation, a liquid crystal aligning agent for photo-alignment having higher sensitivity to ultraviolet irradiation can be obtained. By using the compounds represented by the formulae (V-1-1), (V-2-4) to (V-2-11) and (V-3-1) to (V-3-8) as compounds having a structure which can be isomerized by ultraviolet irradiation, a liquid crystal aligning agent for photoalignment which can align liquid crystal molecules more uniformly can be obtained. By using the compounds represented by the formulae (V-2-4) to (V-3-8) as compounds having a structure which can be isomerized by ultraviolet irradiation, a liquid crystal aligning agent for photo-alignment can be obtained which is less colored in the alignment film to be formed.

In synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, tetracarboxylic dianhydride having a photoreactive structure (hereinafter, may be referred to as photosensitive tetracarboxylic dianhydride) or the diamine having a photoreactive structure (hereinafter, may be referred to as photosensitive diamine) may be used as a raw material. The diamine having a photoreactive structure and the tetracarboxylic dianhydride having a photoreactive structure may be used in combination.

When a photosensitive tetracarboxylic dianhydride is used as a raw material in synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, a tetracarboxylic dianhydride not having a photoreactive structure (hereinafter, may be referred to as a non-photosensitive tetracarboxylic dianhydride) may be used in combination. In this case, in order to prevent the sensitivity of the alignment film to light from decreasing, the proportion of the photosensitive tetracarboxylic dianhydride in the total amount of the tetracarboxylic dianhydrides used as the raw material is preferably 20 mol% or more, and more preferably 50 mol% or more. In addition, in order to improve the sensitivity to light, the residual image characteristics and other various characteristics, can also be used in combination with more than 2 kinds of photosensitive tetracarboxylic acid dianhydride.

When a photosensitive diamine is used as a raw material in synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, the diamine represented by formula (1) of the present invention is used in combination with the photosensitive diamine. The diamine represented by the formula (1) does not have a photoreactive structure. A diamine having no photoreactive structure other than the diamine represented by formula (1) (hereinafter, may be referred to as a non-photosensitive diamine) may be used in combination. In this case, in order to prevent the sensitivity of the alignment film to light from decreasing, the proportion of the photosensitive diamine in the total amount of diamines used as raw materials is preferably 20 mol% or more, and more preferably 50 mol% or more. In addition, in order to improve the various characteristics such as sensitivity to light and image retention characteristics, 2 or more kinds of photosensitive diamines may be used in combination.

When a photosensitive tetracarboxylic dianhydride and a photosensitive diamine are used in combination as a raw material in synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, a non-photosensitive tetracarboxylic dianhydride and a non-photosensitive diamine other than the diamine represented by formula (1) may be used in combination. In this case, in order to prevent the sensitivity of the alignment film to light from decreasing, the total ratio of the photosensitive tetracarboxylic dianhydride and the photosensitive diamine in the total amount of the tetracarboxylic dianhydride and the diamine used as the raw materials is preferably 20 mol% or more, and more preferably 50 mol% or more. In addition, in order to improve the sensitivity to light, residual image characteristics and other various characteristics, can also use a photosensitive tetracarboxylic dianhydride and/or photosensitive diamine combination use 2 or more.

The liquid crystal aligning agent of the present invention will be explained. The liquid crystal aligning agent of the present invention may further contain other components than the polyamic acid or the derivative thereof using at least 1 kind of diamine represented by the formula (1) as a raw material. The other components may be 1 or more than 2. Examples of the other component include other polymers and compounds described later.

The other polymer is a polymer other than polyamic acid or a derivative thereof obtained by reacting tetracarboxylic dianhydride with a diamine containing a diamine of formula (1). Specifically, the polyamic acid or a derivative thereof (hereinafter, sometimes referred to as another polyamic acid or a derivative thereof) obtained by reacting a diamine not containing the diamine of the formula (1) with a tetracarboxylic dianhydride is represented by a polyester, a polyamide, a polysiloxane, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly (styrene-phenylmaleimide) derivative, a poly (meth) acrylate, and the like. Among these, other polyamic acids or derivatives thereof and polysiloxanes are preferable, and other polyamic acids or derivatives thereof are more preferable.

The tetracarboxylic acid dianhydride and the diamine used for synthesizing another polyamic acid or a derivative thereof may be selected from known tetracarboxylic acid dianhydrides and diamines shown in the above examples without limitation.

In the present invention, polyamic acid or a derivative thereof synthesized using diamine including diamine of formula (1) may be used as an alignment agent after being blended with other polyamic acid or a derivative thereof. When such a two-component polymer is used, for example, the following means may be used: one of them is a polymer having excellent liquid crystal alignment ability, and the other is a polymer having excellent properties for improving the electrical characteristics of the liquid crystal display element. In this case, by controlling the structure and molecular weight of each polymer, in the process of forming a thin film by applying a liquid crystal aligning agent obtained by dissolving these polymers in a solvent to a substrate and predrying the applied liquid crystal aligning agent as described later, a polymer having excellent performance in liquid crystal aligning ability can be segregated to an upper layer of the thin film, and a polymer having excellent performance in improving electrical characteristics of a liquid crystal display element can be segregated to a lower layer of the thin film. In contrast, the phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer among polymers mixed together can be applied. The confirmation of such layer separation can be confirmed by that the surface energy of the formed alignment film is the same value or a similar value to that of a film formed of a liquid crystal aligning agent containing only a polymer intended to segregate to the upper layer.

In the embodiment where the liquid crystal aligning agent of the present invention is a liquid crystal aligning agent for photo-alignment, the polyamic acid or derivative thereof having a photoreactive structure of the present invention can be used without considering layer separation in a film. Further, a liquid crystal aligning agent having a photoreactive structure may be used as the polymer segregated to the upper layer of the film. In this case, the polyamic acid or a derivative thereof having no photoreactive structure may be used as the polymer segregated to the lower layer of the film, but the polyamic acid or a derivative thereof having a photoreactive structure may be used as the polymer segregated to the lower layer of the film.

The diamine represented by the formula (1) of the present invention may be used as a raw material monomer for a polymer segregated to the upper layer of the thin film or may be used as a raw material monomer for a polymer segregated to the lower layer of the thin film. The diamine represented by the formula (1) may be used as a raw material monomer for either of the two polymers, or may be used as a raw material monomer for both polymers.

The non-photosensitive tetracarboxylic dianhydride used for synthesizing the polyamic acid or derivative thereof segregated to the upper layer of the thin film can be selected from the known tetracarboxylic dianhydrides shown in the above examples without limitation.

Among them, compounds represented by the formulae (AN-1-1), (AN-4-17) and (PA-1) are preferable in order to improve the layer separation property. In formula (AN-4-17), m is preferably 4 or 8, and more preferably m is 8.

When importance is attached to improving the transmittance of the liquid crystal display element, preferred are compounds represented by formula (AN-1-1), formula (AN-1-2), formula (PA-1), 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-10-2), formula (AN-16-3), and formula (AN-16-4), wherein m is preferably 4 or 8 in formula (AN-1-2), m is preferably 4 or 8 in formula (AN-4-17), and m is more preferably 8.

When emphasis is placed on improving VHR of a liquid crystal display element, compounds represented by formula (PA-1), formula (AN-7-2), formula (AN-10-1), formula (AN-10-2), formula (AN-16-3), and formula (AN-16-4) are preferred, and m is 4 or 8 in formula (AN-1-2).

Increasing the relaxation rate of residual charge (residual DC) of the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one method for preventing the afterimage. When importance is attached to this purpose, preferred are compounds represented by the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29) and the formula (AN-11-3).

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or derivative thereof segregated to the upper layer of the film preferably contains 10 mol% or more, more preferably 30 mol% or more, of the aromatic tetracarboxylic dianhydride in the total amount of the tetracarboxylic dianhydride.

The non-photosensitive diamine and dihydrazide used for synthesizing the polyamic acid or derivative thereof segregated to the upper layer of the thin film can be selected from the known diamines shown in the above examples without limitation.

Among them, when importance is attached to further improving the layer separation property, in other words, the alignment property of liquid crystal, it is preferable to use compounds represented by the formulae (DI-4-1), (DI-5-1) and (DI-7-3). Among them, m is preferably 1,2 or 4, and more preferably 4 in formula (DI-5-1). In the formula (DI-7-3), m is preferably 3 and n is preferably 1.

When importance is attached to the improvement of transmittance, diamines represented by the formulae (PA-1), (DI-5-1) and (DI-7-3) are preferably used, and compounds represented by the formula (PA-1) are particularly preferred. In formula (DI-5-1), m is preferably 1,2 or 4, and more preferably m is 1 or 2.

In the case where emphasis is placed on improving VHR of a liquid crystal display element, compounds represented by the formulae (DI-4-1), (DI-4-2), (DI-4-15), (DI-5-1), (DI-5-17), (DI-5-28), (DI-5-30) and (DI-13-1) are preferably used, and more preferably compounds represented by the formulae (DI-5-1) and (DI-13-1). Among them, a compound of formula (DI-5-1) in which m is 1 or 2, and a compound of formula (DI-5-30) in which k is 2 are more preferable.

Increasing the relaxation rate of residual charge (residual DC) of the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one method for preventing the afterimage. In the case where this object is important, it is preferable to use compounds represented by the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15), the formula (DI-5-1), the formula (DI-5-9), the formula (DI-5-12), the formula (DI-5-13), the formula (DI-5-28), the formula (DI-5-30) and the formula (DI-16-1), more preferably the formula (DI-4-1), the formula (DI-5-1) and the formula (DI-5-12). In formula (DI-5-1), m is preferably 1 or 2. In the formula (DI-5-12), m is preferably 2 to 6, and more preferably m is 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1. In the formula (DI-5-30), k is preferably 2.

The non-photosensitive diamine used for synthesizing the polyamic acid or derivative thereof segregated to the upper layer of the film preferably contains 30 mol% or more, more preferably 50 mol% or more of the aromatic diamine in the total amount of the diamine.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid or the derivative thereof segregated to the lower layer of the thin film can be selected from the known tetracarboxylic acid dianhydrides shown in the above examples without limitation.

Among them, compounds represented by the formula (AN-3-2), the formula (AN-1-13), the formula (AN-1-1) and the formula (AN-4-21) are preferable in the case where importance is attached to the improvement of layer separation.

When importance is attached to the improvement of the transmittance of the liquid crystal display element, preferred are compounds represented by the formulae (AN-1-1), (AN-1-2), (PA-1), (AN-3-1), (AN-4-17), (AN-4-30), (AN-5-1), (AN-7-2), (AN-10-1), (AN-10-2), (AN-16-3) and (AN-16-4). Preferably, m is 4 or 8 in formula (AN-1-2), and m is 4 or 8 in formula (AN-4-17), more preferably, m is 8.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or derivative thereof segregated to the lower layer of the film preferably contains 10 mol% or more, more preferably 30 mol% or more, of the aromatic tetracarboxylic dianhydride in the total amount of the tetracarboxylic dianhydride.

The non-photosensitive diamine and dihydrazide used for synthesizing the polyamic acid or derivative thereof segregated to the lower layer of the thin film can be selected from the known diamines shown in the above examples without limitation.

Among them, compounds represented by the formulae (DI-4-1), (DI-4-2), (DI-4-10), (DI-5-9), (DI-5-28), (DI-5-30) and (DIH-2-1) are preferable in order to further improve the layer separation property, that is, the alignment property of liquid crystal. Among them, diamines of formula (DI-5-30) in which k is 2 are preferred.

When importance is attached to the improvement of transmittance, the compounds represented by the formulae (PA-1), (DI-5-1) and (DI-7-3) are preferred, and the compound represented by the formula (PA-1) is more preferred. In formula (DI-5-1), m is preferably 1,2 or 4, and more preferably m is 1 or 2.

In the case where emphasis is placed on improving the VHR of a liquid crystal display element, preferred are compounds represented by the formulae (DI-4-1), (DI-4-2), (DI-4-15), (DI-5-1), (DI-5-17), (DI-5-28), (DI-5-30) and (DI-13-1), and more preferred are compounds represented by the formulae (DI-5-1) and (DI-13-1). Among them, m is particularly preferably 1 or 2 in formula (DI-5-1), and k is particularly preferably 2 in formula (DI-5-30).

Increasing the relaxation rate of residual charge (residual DC) of the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one method for preventing the afterimage. When this object is considered important, preferred are compounds represented by the formulae (DI-4-1), (DI-4-2), (DI-4-10), (DI-4-15), (DI-5-1), (DI-5-9), (DI-5-12), (DI-5-13), (DI-5-28), (DI-5-30) and (DI-16-1), and more preferred are compounds represented by the formulae (DI-4-1), (DI-5-1) and (DI-5-12). Among them, m is preferably 1 or 2 in formula (DI-5-1). In the formula (DI-5-12), m is preferably 2 to 6, and more preferably m is 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1. In the formula (DI-5-30), k is preferably 2.

The non-photosensitive diamine used for synthesizing the polyamic acid or derivative thereof segregated to the lower layer of the film preferably contains 30 mol% or more, more preferably 50 mol% or more of the aromatic diamine with respect to the total diamines.

The polyamic acid or derivative thereof segregated to the upper layer of the film and the polyamic acid or derivative thereof segregated to the lower layer of the film can be synthesized as described below according to the method for synthesizing the polyamic acid or derivative thereof, which is an essential component of the liquid crystal aligning agent of the present invention.

The ratio of the polyamic acid or the derivative thereof segregated to the upper layer of the film is preferably 5 to 50 wt%, more preferably 10 to 40 wt%, relative to the total amount of the polyamic acid or the derivative thereof segregated to the upper layer of the film and the polyamic acid or the derivative thereof segregated to the lower layer of the film.

< polysiloxanes >

The polysiloxane may further contain polysiloxanes disclosed in Japanese patent laid-open publication No. 2009-03696, Japanese patent laid-open publication No. 2010-185001, Japanese patent laid-open publication No. 2011-102963, Japanese patent laid-open publication No. 2011-253175, Japanese patent laid-open publication No. 2012-159825, International publication No. 2008/044644, International publication No. 2009/148099, International publication No. 2010/074261, International publication No. 2010/074264, International publication No. 2010/126108, International publication No. 2011/068123, International publication No. 2011/068127, International publication No. 2011/068128, International publication No. 2012/115157, International publication No. 2012/165354, and the like.

< alkenyl-substituted nadimide (nadimide) compound >

For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long period of time. The alkenyl-substituted nadimide compound may be used in 1 kind, or 2 or more kinds may be used in combination. The content of the alkenyl-substituted nadimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and still more preferably 1 to 50% by weight, based on the polyamic acid or derivative thereof, for the above purpose.

Hereinafter, the nadimide compound will be specifically described.

The alkenyl-substituted nadimide compound is preferably a compound soluble in a solvent in which the polyamic acid or the derivative thereof used in the present invention is dissolved. Examples of such an alkenyl-substituted nadimide compound include compounds represented by the following formula (NA).

In the formula (NA), L¹And L²Independently hydrogen, alkyl with 1-12 carbon atoms, alkenyl with 3-6 carbon atoms, naphthenic base with 5-8 carbon atoms, aryl with 6-12 carbon atoms or benzyl, and n is 1 or 2.

In the formula (NA), when n is 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, a C6 to E12 aryl, benzyl, -Z¹-(O)_r-(Z²O)_k-Z³H (here, Z)¹、Z²And Z³Independently an alkylene group having 2 to 6 carbon atoms, r is 0 or 1, and k is an integer of 1 to 30. ) A group represented by the formula, - (Z)⁴)_r-B-Z⁵H (here, Z)⁴And Z⁵Independently an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms, B is a phenylene group, and r is 0 or 1. ) A group represented by the formula, -B-T-B-H (here, B is phenylene and T is-CH)₂-、-C(CH₃)₂-, -O-, -CO-, -S-or-SO₂-. ) The group represented by the formula (I) or a group obtained by substituting 1 to 3 hydrogens of the group with-OH.

In this case, W is preferably 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, a poly (oxyethylene) ethyl group having 4 to 10 carbon atoms, a phenoxyphenyl group, a phenylmethylphenyl group, a phenylisopropylidenylphenyl group, or a group obtained by substituting 1 or 2 hydrogens of these groups with-OH.

In the formula (NA), when n is 2, W is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -Z¹-O-(Z²O)_k-Z³- (Here, Z)¹～Z³And k is as defined above for n ═ 1. ) A group shown as, -Z⁴-B-Z⁵- (Here, Z)⁴、Z⁵And B is as defined above for n ═ 1. ) The group shown, -B- (O-B)_r-T-(B-O)_r-B- (here, B is phenylene, T is alkylene having 1 to 3 carbon atoms, -O-, or-SO-₂The definition of r is as defined above for n ═ 1. ) The group represented by the formula (I) or a group obtained by substituting 1 to 3 hydrogens of the group with-OH.

In this case, W is preferably an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenylene group, a tolylene group, a xylylene group or a-C group₃H₆-O-(Z²-O)_n-O-C₃H₆- (Here, Z)²Is an alkylene group having 2 to 6 carbon atoms, and n is 1 or2. ) A group represented by, -B-T-B- (where B is phenylene and T is-CH)₂-, -O-or-SO₂-. ) A group shown as, -B-O-B-C₃H₆A group represented by-B-O-B- (wherein B is phenylene.), and a group in which 1 or 2 hydrogens of these groups are substituted with-OH.

As such an alkenyl-substituted nadimide compound, for example, a compound synthesized by maintaining an alkenyl-substituted nadimide derivative and a diamine at a temperature of 80 to 220 ℃ for 0.5 to 20 hours as described in Japanese patent No. 2729565, or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadimide compound include the compounds shown below.

N-methylallyl bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N-methylallyl methylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N-methylallyl bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N-methyl-methylallyl methylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (2-ethylhexyl) allyl bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N-methylallyl bicyclo [2.2,

N- (2-ethylhexyl) allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N-allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N-allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N-isopropenylallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N-isopropenylallyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide, N-cyclohexylallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide, N-cyclohexylallyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide, N-phenylallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide, N-cyclohexylallylbicyclo [2.2.1] hept-5-ene-,

N-phenylallyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-imide, N-benzylallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-imide, N-benzylallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (2-hydroxyethyl) allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-imide, N- (2-hydroxyethyl) allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (2-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide,

N- (2, 2-dimethyl-3-hydroxypropyl) allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (2, 2-dimethyl-3-hydroxypropyl) allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (2, 3-dihydroxypropyl) allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (2, 3-dihydroxypropyl) allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (3-hydroxy-1-propenyl) allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N- (4-hydroxycyclohexyl) allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide,

N- (4-hydroxyphenyl) allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (4-hydroxyphenyl) allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (4-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (3-hydroxyphenyl) allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- (3-hydroxyphenyl) allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N- (p-hydroxybenzyl) allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N- {2- (2-hydroxyethoxy) ethyl } allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, and a salt thereof,

N- {2- (2-hydroxyethoxy) ethyl } -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- {2- (2-hydroxyethoxy) ethyl } -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- {2- (2-hydroxyethoxy) ethyl } -methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide, N- [2- {2- (2-hydroxyethoxy) ethoxy } ethyl ] -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-mide (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide, N- [2- {2- (2-hydroxyethoxy) ethoxy } ethyl ] methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl } allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl } allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl } methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimides and their oligomers,

N, N ' -ethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -ethylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -ethylenebis (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -trimethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -hexamethylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N '-dodecamethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N' -dodecamethylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N '-cyclohexylidenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N' -cyclohexylidenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide),

1, 2-bis {3 ' - (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } ethane, 1, 2-bis {3 ' - (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } ethane, 1, 2-bis {3 ' - (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } ethane, bis [2 ' - {3 ' - (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } ethyl ] ether, bis [2 ' - {3 ' - (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide) propoxy } ethyl ] ether, 1, 4-bis {3 '- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } butane, 1, 4-bis { 3' - (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } butane, and mixtures thereof,

N, N ' -p-phenylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -p-phenylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -m-phenylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -m-phenylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' - { (1-methyl) -2, 4-phenylene } -bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N, n '-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide), N' -p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide), N '-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide), N' -m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide),

2, 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenoxy } phenyl ] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } methane,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } ether, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimido) phenyl } sulfone, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimido) phenyl } sulfone, a salt thereof, a hydrate thereof,

bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } sulfone, 1, 6-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -3-hydroxyhexane, 1, 12-bis (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -3, 6-dihydroxydodecane, 1, 3-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -5-hydroxycyclohexane, 1, 5-bis { 3' - (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) propoxy } -3-hydroxypentane, 1, 4-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -2-hydroxybenzene,

1, 4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) -2, 5-dihydroxybenzene, N '-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N' -p- (2-hydroxy) xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N '-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N' -m- (2-hydroxy) xylylene-bis (methylallylby [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N' -p- (2, 3-dihydroxy) benzenedimethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide),

2, 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -2-hydroxyphenoxy } phenyl ] propane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -2-hydroxyphenyl } methane, bis {3- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -4-hydroxyphenyl } ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) -5-hydroxyphenyl } sulfone, 1, 1-tris {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) } phenoxymethylpropane, N', N "-tris (ethylenemethallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) isocyanurate, and oligomers thereof and the like.

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

Among the alkenyl-substituted nadimide compounds, preferred compounds are shown below.

N, N ' -p-phenylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -p-phenylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -m-phenylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -m-phenylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' - { (1-methyl) -2, 4-phenylene } -bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N, n '-p-xylylene bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide), N' -p-xylylene bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide), N '-m-xylylene bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide), N' -m-xylylene bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide), 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (methylbicyclo [2.2.1] hept-5-one- Alkene-2, 3-dicarbodiimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenoxy } phenyl ] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } methane.

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } ether, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } sulfone, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } sulfone.

More preferred alkenyl-substituted nadimide compounds are shown below.

N, N ' -ethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -ethylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -ethylenebis (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -trimethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -hexamethylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N '-dodecamethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N' -dodecamethylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N '-cyclohexylidenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N' -cyclohexylidenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide).

N, N ' -p-phenylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -p-phenylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -m-phenylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' -m-phenylenebis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N ' - { (1-methyl) -2, 4-phenylene } -bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide), N, n '-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-imide), N' -p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-imide), N '-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-imide), N' -m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-imide).

2, 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenoxy } phenyl ] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbo-diimide) phenyl } methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } methane, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimide) phenyl } methane.

Further, examples of particularly preferred alkenyl-substituted nadiimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimido) phenyl } methane represented by the following formula (NA-1), N '-m-xylylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimine) represented by the following formula (NA-2), and N, N' -hexamethylenebis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarbodiimine) represented by the following formula (NA-3).

< Compound having a radically polymerizable unsaturated double bond >

For example, the liquid crystal aligning agent of the present invention may contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be 1 type of compound, or may be 2 or more types of compounds. The compound having a radical polymerizable unsaturated double bond does not include an alkenyl-substituted nadimide compound. For the above purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and still more preferably 1 to 50% by weight based on the polyamic acid or the derivative thereof.

The ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound is preferably 0.1 to 10, more preferably 0.5 to 5 in terms of the weight ratio of the compound having a radical polymerizable unsaturated double bond/the alkenyl-substituted nadimide compound in order to reduce the ion density of the liquid crystal display element, suppress an increase in the ion density with time, and further suppress the occurrence of an afterimage.

Hereinafter, a compound having a radical polymerizable unsaturated double bond will be specifically described.

Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylamide, and bismaleimides. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having 2 or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylic ester include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the 2-functional (meth) Acrylate include ethylene bisacrylate, ARONIX M-210, ARONIX M-240 and ARONIX M-6200, products KAYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684, products V260, V312 and V335HP, available from Kagaku K.K., and products Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA, available from Kyowa Kagaku K.K.

Specific examples of the 3-or more-functional polyfunctional (meth) acrylate include, for example, 4' -methylenebis (N, N-dihydroxyethylene acrylate aniline), ARONIX M-400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, products KAYARADTMPTA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120 of Nippon Kagaku K.K., and VGPT of Osaka organic chemical Co.

Specific examples of the (meth) acrylamide derivative include, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, N-N-propylacrylamide, N-N-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethylacrylamide, N-ethyl acrylamide, N-ethyl-N-methylacrylamide, N-diethylacrylamide, N-methyl-N-N-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-isopropylacrylamide, N-acryloylpyrrolidine, N ' -methylenebisacrylamide, N ' -ethylenebisacrylamide, N ' -dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethylacrylamide, N-butylmethacrylamide, N- (isobutoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl ] methacrylamide, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl ] methacrylamide, N- (methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, N-hydroxysuccinimide, N-methyl-2-methacrylamide, N-hydroxysuccinimide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (isobutoxymethyl) methacrylamide, N- (2-methacrylamide, N- (4-hydroxyphenyl), And N, N' -methylenebismethacrylamide.

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

Examples of bismaleimides include K.I Chemical Industry Co., LTD. BMI-70 and BMI-80, and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000, which are manufactured by Kazakhstan Chemical industries, Ltd.

< oxazine Compound >

For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be 1 type of compound, or 2 or more types of compounds. For the above purpose, the content of the oxazine compound is preferably 0.1 to 50 wt%, more preferably 1 to 40 wt%, and still more preferably 1 to 20 wt% with respect to the polyamic acid or derivative thereof.

The following is a specific description of the oxazine compound.

The oxazine compound is preferably a solvent that dissolves the polyamic acid or derivative thereof and has ring-opening polymerizability.

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

Various structures are known for oxazine 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 oxazine structure having an aromatic group containing a fused polycyclic aromatic group, such as benzoxazine and naphthoxazine.

Examples of the oxazine compound include compounds represented by the following formulae (OX-1) to (OX-6). In the following formula, the bond shown toward the center of the ring represents any carbon that is bonded to the ring and to which a substituent can be bonded.

In the formulae (OX-1) to (OX-3), L³And L⁴Is an organic group having 1 to 30 carbon atoms, wherein L is represented by the formulae (OX-1) to (OX-6)⁵～L⁸Is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, formula (OX-3),In the formulae (OX-4) and (OX-6), Q¹Is a single bond, -O-, -S-S-, -SO₂-、-CO-、-CONH-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_v-、-O-(CH₂)_v-O-、-S-(CH₂)_v-S-, where v is an integer of 1 to 6, and in the formulae (OX-5) and (OX-6), Q²Independently a single bond, -O-, -S-, -CO-, -C (CH)₃)₂-、-C(CF₃)₂Or alkylene having 1 to 3 carbon atoms, wherein hydrogen bonded to the benzene ring or the naphthalene ring in the formulae (OX-1) to (OX-6) is optionally independently represented by-F, -CH₃、-OH、-COOH、-SO₃H、-PO₃H₂And (4) substitution.

Further, oxazine compounds include: oligomers and polymers having an oxazine structure in a side chain; oligomers and polymers having an oxazine structure in the main chain.

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

In the formula (OX-1-2), L³Preferably 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 formula (OX-2) include the following oxazine compounds.

In the formula, L³Preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

As the oxazine compound represented by formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) can be cited.

In the formula (OX-3-I), L³And L⁴Is an organic group having 1 to 30 carbon atoms, L⁵～L⁸Is hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, Q¹Is a single bond, -CH₂-、-C(CH₃)₂-、-CO-、-O-、-SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-. Examples of the oxazine compound represented by formula (OX-3-I) include the following oxazine compounds.

In the formula, L³And L⁴Preferably 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 formula (OX-4) include the following oxazine compounds.

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

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

Of these, oxazine compounds represented by formula (OX-2-1), formula (OX-3-3), formula (OX-3-5), 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 formula (OX-6-2) to formula (OX-6-4) are more preferable.

The oxazine compound can be produced by the same method as described in International publication No. 2004/009708, Japanese patent application laid-open No. 11-12258, and Japanese patent application laid-open No. 2004-352670.

The oxazine compound represented by formula (OX-1) can be obtained by reacting a phenol compound with a primary amine and an aldehyde (see international publication No. 2004/009708).

The oxazine compound represented by formula (OX-2) can be obtained as follows: after the reaction by gradually adding primary amine to formaldehyde, a compound having a naphthol-based hydroxyl group is added and reacted (see international publication No. 2004/009708).

The oxazine compound represented by formula (OX-3) can be obtained by reacting 1 mole of a phenol compound, 1 aldehyde at least 2 moles or more relative to the phenolic hydroxyl group thereof, and 1 mole of a primary amine in an organic solvent in the presence of an aliphatic secondary amine, an aliphatic tertiary amine, or a basic nitrogen-containing heterocyclic compound (see international publication No. 2004/009708 and japanese patent application laid-open No. 11-12258).

The oxazine compounds represented by the formulae (OX-4) to (OX-6) can be obtained by subjecting a diamine having a plurality of benzene rings and organic groups bonded thereto, such as 4, 4' -diaminodiphenylmethane, an aldehyde such as formaldehyde, and a phenol to a dehydration condensation reaction in n-butanol at a temperature of 90 ℃ or higher (see Japanese patent laid-open publication No. 2004-352670).

< oxazoline Compound >

For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be 1 kind of compound or 2 or more kinds of compounds. For the above purpose, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and preferably 1 to 20% by weight based on the polyamic acid or a derivative thereof. In addition, the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the polyamic acid or a derivative thereof for the above purpose when the oxazoline structure in the oxazoline compound is converted into oxazoline.

Hereinafter, the oxazoline compound will be specifically described.

The oxazoline compound may have only 1 oxazoline structure in 1 compound, or may have 2 or more oxazoline structures. The oxazoline compound may have 1 oxazoline structure out of 1 compound, and preferably has 2 or more oxazoline structures. The oxazoline compound may be a polymer having an oxazoline structure in a side chain or a copolymer. The polymer having an oxazoline structure in a side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or may be a copolymer of a monomer having an oxazoline structure in a side chain and a monomer having no oxazoline structure. The copolymer having an oxazoline structure in a side chain may be a copolymer of 2 or more monomers having an oxazoline structure in a side chain, or a copolymer of 2 or more monomers having an oxazoline structure in a side chain and a monomer having no oxazoline structure.

The oxazoline structure is preferably present in the oxazoline compound in such a manner that one or both of oxygen and nitrogen in the oxazoline structure are capable of reacting with the carbonyl group of the polyamic acid.

Examples of oxazoline compounds include 2,2 '-bis (2-oxazoline), 1,2, 4-tris (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H-oxazolin-5-one, 1, 4-bis (4, 5-dihydro-2-oxazolinyl) benzene, 1, 3-bis (4, 5-dihydro-2-oxazolinyl) benzene, 2, 3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2' -bis-4-benzyl-2-oxazoline, 2, 6-bis (isopropyl-2-oxazolin-2-yl) pyridine, and, 2,2 '-isopropylidenebis (4-tert-butyl-2-oxazoline), 2' -isopropylidenebis (4-phenyl-2-oxazoline), 2 '-methylenebis (4-tert-butyl-2-oxazoline), and 2, 2' -methylenebis (4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having an oxazoline group such as EPOCROS (trade name, manufactured by Nippon catalyst Co., Ltd.) are also included. Among these, 1, 3-bis (4, 5-dihydro-2-oxazolinyl) benzene can be more preferably exemplified.

< epoxy Compound >

For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be 1 kind of compound, or 2 or more kinds of compounds. For the above purpose, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 1 to 20% by weight based on the polyamic acid or a derivative thereof.

The epoxy compound will be specifically described below.

Examples of the epoxy compound include various compounds having 1 or 2 or more epoxy rings in the molecule. Examples of the compound having 1 epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3, 3-trifluoromethylepoxypropane, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N-diglycidylaniline and 3- [2- (perfluorohexyl) ethoxy ] -1, 2-epoxypropane.

Examples of the compound having 2 epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 3, 4-epoxycyclohexenylmethyl-3 ', 4' -epoxycyclohexene carboxylate, and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

Examples of the compound having 3 epoxy rings in the molecule include 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- ([2, 3-epoxypropoxy ] phenyl) ] ethyl ] phenyl ] propane (trade name "Techmore VG 3101L" (manufactured by Mitsui chemical Co., Ltd.).

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

In addition to the above, as examples of the compound having an epoxy ring in the molecule, oligomers and polymers having an epoxy ring can be cited. Examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.

Examples of the other monomer copolymerizable with the monomer having an epoxy ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

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

Among these examples, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4 ' -diaminodiphenylmethane, a product name "Techmore VG310 3101L", 3, 4-epoxycyclohexenylmethyl-3 ', 4 ' -epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferable.

More specifically, examples of the epoxy compound include glycidyl ethers, glycidyl esters, glycidyl amines, epoxy group-containing acrylic resins, glycidyl amides, glycidyl isocyanurates, chain aliphatic epoxy compounds, and cyclic aliphatic epoxy compounds. The epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic type epoxy compound and cyclic aliphatic type epoxy compound.

Examples of the glycidyl ether include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol type epoxy compounds, brominated bisphenol A type epoxy compounds, brominated bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, brominated phenol novolac type epoxy compounds, brominated cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, epoxy compounds having a naphthalene skeleton, aromatic polyglycidyl ether compounds, dicyclopentadiene phenol oxide compounds, diglycidyl ether compounds of the formula, aliphatic polyglycidyl ether compounds, alicyclic polyglycidyl ether compounds, bisphenol A novolac type epoxy compounds, brominated bisphenol A novolac type epoxy compounds, and the like, A polythioether type diglycidyl ether compound, and a biphenyl type epoxy compound.

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

Examples of the glycidyl amine include polyglycidyl amine compounds and glycidyl amine type epoxy resins.

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

Examples of the glycidyl amide include glycidyl amide type epoxy compounds.

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

Examples of the cyclic aliphatic epoxy compound include epoxy group-containing compounds 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, jER1010 (both trade names, manufactured by Mitsubishi Chemical corporation), Epotohto YD-128 (manufactured by Tokyo Kasei Co., Ltd.), DER-331, DER-332, DER-324 (both manufactured by The Dow Chemical Company), EPICLON 840, EPICLON 850, EPICLON 1050 (both trade names, manufactured by DIC Co., Ltd.), MIC R-140, EPOMIC EPOMER-301, and EPOMIC R-304 (both trade names, manufactured by Mitsui Chemical Co., Ltd.).

Examples of The bisphenol F type epoxy compound include jER806, jER807, jER4004P (both trade names, manufactured by Mitsubishi Chemical corporation), Epotohto YDf-170, epohto YDf-175S, epohto YDf-2001 (both trade names, manufactured by Tokyo Chemical Co., Ltd.), DER-354 (trade name, manufactured by The Dow Chemical Company), EPICLON 830, and EPICLON 835 (both trade names, manufactured by DIC Co., Ltd.).

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 Santohto ST-3000 (trade name, manufactured by Tokyo chemical Co., Ltd.), RIKARESIN HBE-100 (trade name, manufactured by Nippon chemical Co., Ltd.), and DENACOL EX-252 (trade name, manufactured by Nagase ChemteX Corporation).

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

Examples of The brominated bisphenol A type epoxy compound include jER5050, jER5051 (trade name, manufactured by Mitsubishi Chemical corporation), Epotohto YDB-360, Epotohto YDB-400 (trade name, manufactured by Tokyo Kaisha), DER-530, DER-538 (trade name, manufactured by The Dow Chemical Company), EPICLON 152 and EPICLON 153 (trade name, manufactured by DIC corporation).

Examples of The phenol novolak-type epoxy compound include jER152, jER154 (both trade names, manufactured by Mitsubishi Chemical corporation), YDPN-638 (trade name, manufactured by Tokyo Chemical corporation), DEN431, DEN438 (both trade names, manufactured by The Dow Chemical Company), EPICLON-770 (both trade names, manufactured by DIC corporation), EPPN-201, and EPPN-202 (both trade names, manufactured by Nippon Chemical Co., Ltd.).

Examples of the cresol novolak-type epoxy compound include JeR180S75 (trade name, manufactured by Mitsubishi chemical corporation), YDCN-701, YDCN-702 (trade name, manufactured by Tokyo chemical Co., Ltd.), EPICLON-665, EPICLON-695 (trade name, manufactured by DIC Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (trade name, manufactured by Nippon chemical Co., Ltd.).

Examples of the bisphenol A novolak type epoxy compound include JeR157S70 (trade name, manufactured by Mitsubishi chemical corporation) and EPICLON-880 (trade name, manufactured by DIC corporation).

Examples of the epoxy compound having a naphthalene skeleton include EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 (trade name, available from DIC corporation), and NC-7000 (trade name, available from Nippon Kabushiki Kaisha).

Examples of The aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (represented by The following formula EP-1), catechol diglycidyl ether (represented by The following formula EP-2), resorcinol diglycidyl ether (represented by The following formula EP-3), 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- ([2, 3-epoxypropoxy ] phenyl) ] ethyl ] phenyl ] propane (represented by The following formula EP-4), tris (4-glycidyloxyphenyl) methane (represented by The following formula EP-5), jER1031S, jER1032H60 (all trade names, product name of Mitsubishi Chemical Corporation), TACTIX-742 (trade name, product name of The Dow Chemical Company), DENACOL EX-201 (trade name, product of Nagase ChemteX Corporation), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (both trade name, manufactured by Nippon Kagaku K.K.), Techmore VG3101L (trade name, manufactured by Mitsui chemical Co., Ltd.), 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 TACTIX-556 (trade name, manufactured by The Dow Chemical Company) and EPICLON HP-7200 (trade name, manufactured by DIC corporation).

Examples of the alicyclic diglycidyl ether compound include cyclohexanedimethanol diglycidyl ether compound and RIKARESIN DME-100 (trade name, available from Nissan chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (represented by the following formula EP-8), diethylene glycol diglycidyl ether (represented by the following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (represented by the following formula EP-10), tripropylene glycol diglycidyl ether (represented by the following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (represented by the following formula EP-12), 1, 4-butanediol diglycidyl ether (represented by the following formula EP-13), 1, 6-hexanediol diglycidyl ether (represented by the following formula EP-14), dibromoneopentyl glycol diglycidyl ether (represented by the following formula EP-15), DENACOL EX-810, DENACOL EX-851, DENACOL EX-8301, DENACOL EX-911, DENACOL EX-920, and DENACOL, DENACOL EX-931, DENACOL EX-211, DENACOL EX-212, DENACOL EX-313 (both trade names, manufactured by Nagase ChemteX Corporation), DD-503 (trade name, manufactured by ADEKA CORPORATION), RIKARESIN W-100 (trade name, manufactured by Nippon Kabushiki Kaisha), 1,3,5, 6-tetraglycidyl-2, 4-hexanediol (hereinafter referred to as formula EP-16), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, DENACOL EX-313, DENACOL EX-611, DENACOL EX-321, and DENACOL EX-411 (both trade names, manufactured by Nagase ChemteX Corporation).

As the polythioether type diglycidyl ether compound, for example, FLDP-50 and FLDP-60 (both trade names, Toray Thiokol Co., Ltd., manufactured by Ltd.) can be cited.

Examples of the bisphenol epoxy compound include YX-4000, YL-6121H (trade name, manufactured by Mitsubishi chemical corporation), NC-3000P and NC-3000S (trade name, manufactured by Nippon chemical Co., Ltd.).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (represented by the following formula EP-17), diglycidyl phthalate (represented by the following formula EP-18), bis (2-methyloxirane methyl) phthalate (represented by the following formula EP-19), diglycidyl hexahydrophthalate (represented by the following formula EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.

Examples of the glycidyl ester epoxy compound include jER871, jER872 (both trade names, manufactured by Mitsubishi chemical Corporation), EPICLON 200, EPICLON 400 (both trade names, manufactured by DIC Corporation), DENACOL EX-711, and DENACOL EX-721 (both trade names, manufactured by Nagase ChemteX Corporation).

Examples of the polyglycidyl amine compounds include N, N-diglycidylaniline (the formula EP-24), N, N-diglycidylotolidine (the formula EP-25), N, N-diglycidylmethyltoluidine (the formula EP-26), N, N-diglycidyl2, 4, 6-tribromoaniline (the formula EP-27), 3- (N, N-diglycidylaminopropyltrimethoxysilane (the formula EP-28), N, N, O-triglycidylpp-aminophenol (the formula EP-29), N, N, O-triglycidym-aminophenol (the formula EP-30), N, N, N ', N' -tetraglycidyl-4, 4 ' -diaminodiphenylmethane (the following formula EP-31), N, N, N ', N ' -tetraglycidyl m-xylylenediamine (TETRAD-X (trade name, product of Mitsubishi gas chemical Co., Ltd.), the following formula EP-32), 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (trade name, product of Mitsubishi gas chemical Co., Ltd.), the following formula EP-33), 1, 4-bis (N, N-diglycidylaminomethyl) cyclohexane (the following formula EP-34), 1, 3-bis (N, N-diglycidylamino) cyclohexane (the following formula EP-35), 1, 4-bis (N, N-diglycidylamino) cyclohexane (the following formula EP-36), 1, 3-bis (N, N-diglycidylamino) benzene (the following formula EP-37), 1, 4-bis (N, N-diglycidylamino) benzene (the following formula EP-38), 2, 6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (the following formula EP-39), N, N, N ', N' -tetraglycidyl-4, 4 '-diaminodicyclohexylmethane (the following formula EP-40), 2' -dimethyl- (N, N, N ', N' -tetraglycidyl) -4,4 '-diaminobiphenyl (the following formula EP-41), N, N, N', N '-tetraglycidyl-4, 4' -diaminodiphenyl ether (the following formula EP-42), 1,3, 5-tris (4- (N, N-diglycidylamino) aminophenoxy) benzene (the following formula EP-43), 2,4,4 ' -tris (N, N-diglycidylamino) diphenyl ether (the following formula EP-44), tris (4- (N, N-diglycidylamino) aminophenyl) methane (the following formula EP-45), 3,4,3 ', 4 ' -tetrakis (N, N-diglycidylamino) biphenyl (the following formula EP-46), 3,4,3 ', 4 ' -tetrakis (N, N-diglycidylamino) diphenyl ether (the following formula EP-47), a compound represented by the following formula EP-48 and a compound represented by the following formula EP-49.

Examples of the homopolymer of the monomer having an oxirane group include polyglycidyl methacrylate. Examples of the copolymer of the monomer having an oxirane group include an N-phenylmaleimide-glycidyl methacrylate copolymer, an N-cyclohexylmaleimide-glycidyl methacrylate copolymer, a benzyl methacrylate-glycidyl methacrylate copolymer, a butyl methacrylate-glycidyl methacrylate copolymer, a 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, a (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

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

Examples of the other monomer other than the monomer having an oxirane group in the copolymer of monomers having an oxirane group include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, N-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, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

As the glycidyl isocyanurate, for example, 1,3, 5-triglycidyl-1, 3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (the following formula EP-50), 1, 3-diglycidyl-5-allyl-1, 3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (the following formula EP-51) and a glycidyl isocyanurate type epoxy resin can be cited.

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

Examples of the cycloaliphatic epoxy compound include 3, 4-epoxycyclohexenylmethyl-3 ', 4' -epoxycyclohexenylcarboxylate (CELLOXIDE 2021 (manufactured by Daicel corporation), the following formula EP-52), 2-methyl-3, 4-epoxycyclohexylmethyl-2 '-methyl-3', 4 '-epoxycyclohexylcarboxylate (the following formula EP-53), 2, 3-epoxycyclopentane-2', 3 '-epoxycyclopentane ether (the following formula EP-54), epsilon-caprolactone-modified 3, 4-epoxycyclohexylmethyl-3', 4 '-epoxycyclohexane carboxylate, 1,2:8, 9-diepoxy-limonene (CELLOXIDE 3000 (manufactured by Daicel corporation), the following formula EP-55, 4' -epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexane carboxylate, 1,2:8, 9-diepoxy-limonene, A compound represented by The following formula EP-56, CY-175, CY-177, CY-179 (all of which are trade names, manufactured by The Ciba-Geigy Chemical Corp (available from Huntsman Japan KK)), EHPD-3150 (trade name, manufactured by Daicel corporation), and a cyclic aliphatic type epoxy resin.

The epoxy compound is preferably at least one of a polyglycidyl amine compound, a bisphenol A novolac-type epoxy compound, a cresol novolac-type epoxy compound, and a cyclic aliphatic-type epoxy compound, preferably, the epoxy resin is at least 1 selected from the group consisting of N, N, N ', N' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N ', N' -tetraglycidyl-4, 4 '-diaminodiphenylmethane, Techmore VG 3101L' as a trade name, 3, 4-epoxycyclohexenylmethyl-3 ', 4' -epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type epoxy compounds and cresol novolak type epoxy compounds.

For example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include a high molecular compound and a low molecular compound other than polyamic acid and its derivative, and these additives can be selected and used according to the purpose.

For example, the polymer compound may be a polymer compound soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics and alignment properties of the liquid crystal alignment film to be formed, it is preferable to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

Further, examples of the low-molecular-weight compound include: 1) a surfactant which is desired to improve coatability and which meets the purpose; 2) antistatic agents when antistatic needs to be improved; 3) silane coupling agents and titanium coupling agents for improving adhesion to substrates; further, 4) an imidization catalyst in imidization at a low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyl, 3-mercaptopropyltrimethoxysilane, N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine and N, N' -bis [3- (trimethoxysilyl) propyl ] ethylenediamine. The silane coupling agent is preferably 3-aminopropyltriethoxysilane.

Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline; and cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. The imidization catalyst is preferably 1 or 2 or more selected from the group consisting of N, N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine and isoquinoline.

The silane coupling agent is added in an amount of usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or derivative thereof.

The amount of the imidization catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or its derivative.

The amount of the other additive added varies depending on the use, and is usually 0 to 100% by weight, preferably 0.1 to 50% by weight based on the total weight of the polyamic acid or derivative thereof.

The polyamic acid or the derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or a derivative thereof for forming a polyimide film. The total amount of the tetracarboxylic dianhydride is preferably set to a molar number (about 0.9 to 1.1) substantially equal to the total molar number of the diamine.

The molecular weight of the polyamic acid or derivative thereof of the present invention is preferably 7000 to 500000, more preferably 10000 to 200000 in terms of a weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or the derivative thereof can be determined by measurement by a Gel Permeation Chromatography (GPC) method.

The polyamic acid or derivative thereof of the present invention can be confirmed by analyzing a solid component obtained by precipitating the polyamic acid or derivative thereof with a large amount of a poor solvent by IR or NMR. Further, the used monomer can be confirmed by analyzing an extract obtained from the decomposition product of the polyamic acid or the derivative thereof obtained from an aqueous solution of a strong base such as KOH or NaOH with an organic solvent by GC, HPLC, or GC-MS.

For example, the liquid crystal aligning agent of the present invention may further contain a solvent in order to adjust the coatability of the liquid crystal aligning agent and the concentration of the polyamic acid or the derivative thereof. The solvent is not particularly limited, and any solvent can be used as long as it has an ability to dissolve the polymer component. The solvent widely includes solvents generally used in the production steps and applications of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected depending on the purpose of use. The solvent may be a mixed solvent of 1 kind or 2 or more kinds.

Examples of the solvent include a good solvent for the polyamic acid or the derivative thereof and other solvents for improving coatability.

Examples of the aprotic polar organic solvent which is a good solvent for the polyamic acid or a derivative thereof include lactones such as N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylhexanolactone, N-methylpropionamide, N-dimethylacetamide, dimethyl sulfoxide, N-dimethylformamide, N-diethylacetamide, and γ -butyrolactone.

Examples of other solvents for improving coatability and the like include ester compounds such as alkyl lactate, ethylene glycol monoalkyl ethers such as 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether and the like, diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether and the like, ethylene glycol monoalkyl acetates or ethylene glycol phenyl acetates, triethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monobutyl ether and the like, dialkyl malonates such as diethyl malonate and the like, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether and the like, and acetic acid esters thereof.

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

The concentration of the polyamic acid in the alignment agent of the present invention is preferably 0.1 to 40% by weight. When the alignment agent is applied to a substrate, the polyamic acid to be contained may be diluted with a solvent in advance in order to adjust the film thickness.

The concentration of the solid content in the alignment agent of the present invention is not particularly limited, and an optimum value may be selected in accordance with the following various coating methods. In general, the amount of the varnish is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, in order to suppress unevenness, pinholes and the like during coating.

The preferable range of the viscosity of the liquid crystal aligning agent of the present invention varies depending on the coating method, the concentration of the polyamic acid or its derivative, the kind of the polyamic acid or its derivative used, and the kind and proportion of the solvent. For example, when the coating is applied by a printer, the viscosity is 5 to 100 mPas (more preferably 10 to 80 mPas). When the viscosity is less than 5 mPas, it is difficult to obtain a sufficient film thickness, and when the viscosity exceeds 100 mPas, the unevenness in printing may be large. When the coating is carried out by spin coating, the viscosity is preferably 5 to 200 mPas (more preferably 10 to 100 mPas). When the coating is carried out by using an ink jet coating apparatus, it is preferably 5 to 50 mPas (more preferably 5 to 20 mPas). The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measuring method, for example, by using a rotational viscometer (TVE-20L manufactured by Toyobo industries Co., Ltd.) (measurement temperature: 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 aligning 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 performing heat baking. As described later, the liquid crystal alignment film of the present invention may be subjected to a brushing treatment to give anisotropy to the film obtained through a heat drying step and a heat baking step, as necessary. Further, if necessary, anisotropy may be imparted by irradiating light after the coating step, the heat drying step, or after the heat baking step. Further, the liquid crystal alignment film for VA may be used without being subjected to a brushing treatment.

The coating film is formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display device, in the same manner as in the production of a general liquid crystal alignment film. The substrate may be optionally provided with ITO (Indium Tin Oxide), IZO (In)₂O₃-ZnO)、IGZO(In-Ga-ZnO₄) Electrodes such as electrodes, and glass substrates such as color filters.

As a method for applying the liquid crystal aligning agent to the substrate, a spin coater method, a printing method, a dipping method, a dropping method, an ink jet method, and the like are generally known. These methods are equally applicable to the present invention.

The aforementioned heat drying step is generally known as: a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like. The heat drying step is preferably performed at a temperature within a range in which the solvent can be evaporated, and more preferably at a relatively low temperature compared to the temperature of the heat firing step. Specifically, the heating and drying temperature is preferably in the range of 30 to 150 ℃, and more preferably in the range of 50 to 120 ℃.

The heating and firing step may be performed under conditions necessary for the dehydration/ring-closure reaction of the polyamic acid or derivative thereof. The baking of the coating film is generally known as follows: a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like. These methods can be applied equally well in the present invention. The reaction is usually carried out at a temperature of about 100 to 300 ℃ for 1 minute to 3 hours, preferably 120 to 280 ℃, and more preferably 150 to 250 ℃. Further, the heating and firing may be performed a plurality of times at different temperatures. A plurality of heating apparatuses set to different temperatures may be used, or the heating may be performed while sequentially changing to different temperatures using 1 heating apparatus. When the firing is carried out at different temperatures for 2 times, the firing is preferably carried out at 90 to 140 ℃ for the 1 st time and at 180 ℃ or higher for the 2 nd time.

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

The liquid crystal alignment film of the present invention using the rubbing process can be formed through a step of applying the liquid crystal alignment agent of the present invention to a substrate, a step of heat-drying the substrate applied with the alignment agent, a step of heat-baking the film, and a step of rubbing the film.

The rubbing treatment may be performed in the same manner as a general rubbing treatment for the purpose of alignment treatment of a liquid crystal alignment film, and may be performed under conditions that a sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. Preferred conditions are: the bristle length press-in amount is 0.2 to 0.8mm, the base moving speed is 5 to 250mm/sec, and the roller rotating speed is 500 to 2000 rpm.

The 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 is formed as follows: the coating film is formed by heating and drying the coating film, irradiating the coating film with linearly polarized light or unpolarized light of a radiation ray to impart anisotropy to the coating film, and heating and baking the coating film. The coating film may be formed by heating, drying, and baking the coating film, followed by irradiation with linearly polarized light or unpolarized light of radiation. From the viewpoint of directionality, the radiation irradiation step is preferably performed before the heat firing step.

Further, in order to improve the liquid crystal alignment ability of the liquid crystal alignment film, the coating film may be heated and irradiated with linearly polarized light or unpolarized light of a radiation ray. The irradiation with radiation may be performed in a step of heat-drying the coating film or in a step of heat-baking the coating film, or may be performed between the heat-drying step and the heat-baking step. The heating and drying temperature in this step is preferably in the range of 30 to 150 ℃, and more preferably in the range of 50 to 120 ℃. The heating and firing temperature in this step is preferably in the range of 30 to 300 ℃, and more preferably in the range of 50 to 250 ℃.

As the radiation ray, for example, ultraviolet rays or visible rays including light having a wavelength of 150 to 800nm, preferably ultraviolet rays including light having a wavelength of 300 to 400nm, can be used. Further, linearly polarized light or unpolarized light may be used. These lights are not particularly limited as long as they can impart liquid crystal alignment ability to the coating film, and when it is desired to exhibit strong alignment regulating force for liquid crystal, they are preferably linearly polarized lights.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even under light irradiation of low energy. The irradiation amount of the linearly polarized light in the irradiation step is preferably 0.05 to 20J/cm²More preferably 0.5 to 10J/cm². The wavelength of the linearly polarized light is preferably 200 to 400nm, more preferably 300 to 400 nm. The irradiation angle of the linearly polarized light to the film surface is not particularly limited, and when it is desired to exhibit a strong alignment regulating force to the liquid crystal, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. In addition, the liquid crystal alignment film of the present invention can align liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating the linearly polarized light.

The light source used in the irradiation step of the linearly polarized light or unpolarized light of the radiation ray may use, without limitation, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a Deep ultraviolet (Deep UV) lamp, a halogen lamp, a metal halide lamp, a high-power metal halide lamp, a xenon lamp, a mercury-xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave-excited electrodeless lamp, or the like.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further comprising other steps than the aforementioned steps. For example, in the liquid crystal alignment film of the present invention, a step of cleaning the film after firing or irradiation with a cleaning liquid is not essential, and a cleaning step may be provided depending on the case of other steps.

Examples of the method of cleaning with the cleaning liquid include brushing, spraying, steam cleaning, and ultrasonic cleaning. These methods may be carried out alone or in combination. Examples of the cleaning liquid include pure water, various alcohols such as methanol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone, but are not limited thereto. Of course, these cleaning solutions may be sufficiently purified and contain few impurities. This cleaning method can also be applied to the aforementioned 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 used before and after the heat baking step, before and after the brushing step, or before and after irradiation with polarized or unpolarized radiation. In the annealing treatment, the annealing temperature is 30 to 180 ℃, preferably 50 to 150 ℃, and the time is preferably 1 minute to 2 hours. Examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp. The irradiation amount of light is preferably 0.3 to 10J/cm²。

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300nm, and more preferably 30 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 apparatus such as a level difference meter or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having particularly large alignment anisotropy. The magnitude of such anisotropy can be evaluated by the method using polarized light IR described in Japanese patent laid-open No. 2005-275364 and the like. As shown in the following examples, the evaluation can also be performed by a method using an ellipsometer. In detail, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. Namely, it can be considered that: having a large retardation value means having a large degree of orientation, and when used as a liquid crystal alignment film, the alignment film having a larger anisotropy has a large orientation regulating force with respect to the liquid crystal composition.

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

The liquid crystal alignment film of the present invention can be used for alignment of a liquid crystal composition for a liquid crystal display, and can also be used for controlling alignment of an optical compensation material and other liquid crystal materials. In addition, the alignment film of the present invention has large anisotropy, and thus can be used alone for optical compensation material applications.

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

The present invention provides a liquid crystal display element, which comprises: the liquid crystal display device includes a pair of substrates disposed to face each other, an electrode formed on one or both of facing surfaces of the pair of substrates, a liquid crystal alignment film formed on the facing surface of the pair of substrates, and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film in the liquid crystal display device is the alignment film of the present invention.

The electrode is not particularly limited as long as it is formed on one surface of the substrate. Examples of such an electrode include ITO and a metal deposition film. The electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape by patterning, for example. Examples of the desired shape of the electrode include a comb-like shape and a zigzag structure. The electrode may be formed on one of the pair of substrates or may be formed on both of the substrates. The form of the electrode varies depending on the type of the liquid crystal display element, and for example, in the case of an IPS 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 state in which the liquid crystal composition is sandwiched between the pair of substrates facing each other on the surface on which the liquid crystal alignment film is formed. For the formation of the liquid crystal layer, spacers may be formed with an appropriate interval by sandwiching particles, resin sheets, or the like between the pair of substrates as necessary.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having positive dielectric anisotropy include liquid crystal compositions disclosed in Japanese patent No. 3086228, Japanese patent No. 2635435, Japanese Kohyo publication No. Hei 5-501735, Japanese patent No. Hei 8-157826, Japanese patent No. Hei 8-231960, Japanese patent No. Hei 9-241644(EP885272A1), Japanese patent No. Hei 9-302346(EP806466A1), Japanese patent No. Hei 8-199168(EP722998A1), Japanese patent No. Hei 9-235552, Japanese patent No. Hei 9-255956, Japanese patent No. Hei 9-241643(EP885271A1), Japanese patent No. Hei 10-204016(EP844229A1), Japanese patent No. Hei 10-204436, Japanese patent No. Hei 10-231482, Japanese patent No. 2000-087040, Japanese patent No. 2001-48822.

The liquid crystal composition having positive or negative dielectric anisotropy may be used by adding 1 or more kinds of optically active compounds.

The liquid crystal composition having negative dielectric anisotropy will be described. Examples of the liquid crystal composition having negative dielectric anisotropy include a composition containing, as component 1, at least 1 liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1).

Here, R^1aAnd R^2aIndependently 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 an alkenyl group having 2 to 12 carbon atoms in which at least 1 hydrogen is substituted by fluorine, ring A²And ring B²Independently 1, 4-cyclohexylidene, tetrahydrofuran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2-fluoro-3-chloro-1, 4-phenylene, 2, 3-difluoro-6-methyl-1, 4-phenylene, 2, 6-naphthalenediyl or 7, 8-difluorochroman-2, 6-diyl, where ring A is²And ring B²At least 1 of which 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, Z¹Independently a single bond, - (CH)₂)₂-、-CH₂O-, -COO-or-CF₂O-, j is 1,2 or 3, and when j is 2 or 3, any 2 rings A²May be the same or different, and any 2Z¹May be the same or different.

To improve the dielectric anisotropy, the ring A²And ring B²Preferably 2, 3-difluoro-1, 4-phenylene or tetrahydrofuran-2, 5-diyl, respectively, ring A in order to reduce the viscosity²And ring B²1, 4-cyclohexylidene is preferred.

To improve the dielectric anisotropy, Z¹Is preferably-CH₂O-to reduce the viscosity, Z¹Preferably a single bond.

J is preferably 1 in order to lower the lower limit temperature, and j is preferably 2 in order to raise the upper limit temperature.

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

Here, R^1aAnd R^2aIndependently 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 an alkenyl group having 2 to 12 carbon atoms in which at least 1 hydrogen is substituted by fluorine, ring A²¹Ring A²²Ring A²³Ring B²¹And ring B²²Independently of one another is 1, 4-cyclohexylidene or 1, 4-phenylene, Z¹¹And Z¹²Independently a single bond, - (CH)₂)₂-、-CH₂O-or-COO-.

For the purpose of improving stability to ultraviolet light or heat, etc., R^1aAnd R^2aPreferably an alkyl group having 1 to 12 carbon atoms, and R is a group having a high dielectric anisotropy in order to increase the absolute value^1aAnd R^2aPreferably an alkoxy group having 1 to 12 carbon atoms.

The alkyl group is preferably a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group. To reduce the viscosity, the alkyl group is further preferably an ethyl group, a propyl group, a butyl group, a pentyl group or a heptyl group.

The alkoxy group is preferably methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy. To reduce the viscosity, the alkoxy group is further preferably a methoxy group or an ethoxy group.

The alkenyl group is preferably vinyl, 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. To reduce the viscosity, the alkenyl group is further preferably an ethenyl group, a 1-propenyl group, a 3-butenyl group or a 3-pentenyl group. The preferred stereoconfiguration of-CH ═ CH-in these alkenyl groups depends on the position of the double bond. For the purpose of reducing viscosity and the like, the trans form is preferable for an alkenyl group such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl. Cis-forms are preferred for alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl. Among these alkenyl groups, a linear alkenyl group is preferable to a branched alkenyl group.

Preferable examples of the alkenyl group in which at least 1 hydrogen is substituted with fluorine are 2, 2-difluorovinyl, 3-difluoro-2-propenyl, 4-difluoro-3-butenyl, 5-difluoro-4-pentenyl and 6, 6-difluoro-5-hexenyl. Further preferred examples for reducing the viscosity are 2, 2-difluorovinyl and 4, 4-difluoro-3-butenyl.

To reduce viscosity, ring A²¹Ring A²²Ring A²³Ring B²¹And ring B²²1, 4-cyclohexylidene is preferred.

To improve the dielectric anisotropy, Z¹¹And Z¹²Is preferably-CH₂O-to reduce the viscosity, Z¹¹And Z¹²Preferably a single bond.

Among the aforementioned liquid crystal compositions having negative dielectric anisotropy, the compounds represented by the formula (NL-1) which are preferred as the component 1 are compounds represented by the formulae (NL-1-1), (NL-1-4), (NL-1-7) and (NL-1-32).

Preferred examples of the liquid crystal composition having negative dielectric anisotropy include Japanese patent application laid-open No. Sho 57-114532, Japanese patent application laid-open No. Hei 2-4725, Japanese patent application laid-open No. Hei 4-224885, Japanese patent application laid-open No. Hei 8-40953, Japanese patent application laid-open No. Hei 8-104869, Japanese patent application laid-open No. Hei 10-168076, Japanese patent application laid-open No. Hei 10-168453, Japanese patent application laid-open No. Hei 10-236989, Japanese patent application laid-open No. Hei 10-236990, Japanese patent application laid-open No. Hei 10-236992, Japanese patent application laid-open No. Hei 10-236993, Japanese patent application laid-open No. Hei 10-236994, Japanese patent application laid-open No. Hei 10-237000, Japanese patent application laid-open No. Hei 10-237024, Japanese patent application, Liquid crystal compositions disclosed in Japanese patent application laid-open Nos. H10-291945, H11-029581, H11-080049, H2000-256307, H2001-019965, H2001-072626, H2001-192657, H2010-037428, International publication No. 2011/024666, International publication No. 2010/072370, JP 2010-705310, H2012-077201, H2009-084362 and the like.

In addition, for example, in the liquid crystal composition used in the element of the present invention, an additive may be further added, for example, from the viewpoint of improving the alignment property. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

The most preferable structure of the photopolymerizable monomer or oligomer for improving the alignment of the liquid crystal is represented by the formulae (PM-1-1) to (PM-1-6).

The photopolymerizable monomer or oligomer is desirably 0.01 wt% or more in order to exhibit an effect of determining the tilt direction of the liquid crystal after polymerization. Further, it is desirable that the amount of the polymer is 30% by weight or less in order to obtain an appropriate orientation effect of the polymer after polymerization thereof or to prevent unreacted monomers or oligomers from being eluted into the liquid crystal after ultraviolet irradiation.

An optically active compound is mixed into the composition in order to induce a helical structure of the liquid crystal and impart a twist angle. Examples of such compounds are those represented by the formulae (PAC-1-1) to (PAC-1-4).

The preferable proportion of the optically active compound is 5% by weight or less. The more preferable ratio is in the range of 0.01 to 2 wt%.

An antioxidant is mixed with the liquid crystal composition in order to prevent a decrease in resistivity due to heating in the atmosphere, or in order to maintain a large voltage holding ratio at room temperature and at high temperature after long-term use of the device.

Preferred examples of the antioxidant include compounds represented by the formula (AO-1) wherein w is an integer of 1 to 10. In formula (AO-1), w is preferably 1,3,5, 7 or 9. w is more preferably 1 or 7. Since the compound represented by the formula (AO-1) wherein w is 1 has high volatility, it is effective in preventing a decrease in resistivity due to heating in the atmosphere. The compound represented by the formula (AO-1) wherein w is 7 has low volatility and is therefore effective for maintaining a large voltage holding ratio at room temperature and at high temperature after long-term use of the device. The preferable proportion of the antioxidant is 50ppm or more in order to obtain the effect thereof, and 600ppm or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. Further preferably, the proportion is in the range of 100ppm to 300 ppm.

Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable ratio of these absorbents and stabilizers is 50ppm or more in order to obtain the effect thereof, and 10000ppm or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. Further preferably, the ratio is in the range of 100ppm to 10000 ppm.

In order to satisfy an element of GH (Guest host) mode, a dichroic dye (dichromatic dye) such as an azo dye or an anthraquinone dye is mixed in the composition. The preferable ratio of the coloring matter is in the range of 0.01 to 10% by weight.

In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed in the composition. The preferable ratio of the defoaming agent is 1ppm or more for obtaining the effect thereof, and 1000ppm or less for preventing the display failure. The more preferable ratio is in the range of 1ppm to 500 ppm.

In order to conform to the elements of the PSA (polymer stabilized alignment) mode, a compound capable of polymerization may be mixed in the composition. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as an acrylate, a methacrylate, a vinyl compound, an ethyleneoxy compound, a propylene ether, an epoxy compound (ethylene oxide, oxetane) and a vinyl ketone. Particularly preferred examples are derivatives of acrylic or methacrylic esters. Examples of such compounds are those represented by the formulae (PM-2-1) to (PM-2-9). The preferable proportion of the polymerizable compound is about 0.05 wt% or more for obtaining the effect thereof, and about 10 wt% or less for preventing the display failure. A further preferred ratio is in the range of about 0.1 wt% to about 2 wt%.

Here, R^3a、R^4a、R^5aAnd R^6aIndependently is acryloyl or methacryloyl, R^7aAnd R^8aIndependently hydrogen, halogen or alkyl with 1-10 carbon atoms, Z¹³、Z¹⁴、Z¹⁵And Z¹⁶Independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least 1-CH₂-is optionally substituted by-O-or-CH ═ CH-, s, t and u are each independently 0, 1 or 2.

As a substance necessary for easily generating a radical or ion to initiate the chain polymerization reaction, a polymerization initiator may be mixed. For example, Irgacure651 (registered trademark), Irgacure184 (registered trademark), or Darocure1173 (registered trademark) (Ciba Japan K.K.) as a photopolymerization initiator is suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in a range of 0.1 to 5 wt%. Particularly, the photopolymerization initiator is preferably contained in a range of 1 to 3% by weight.

In the radical polymerization system, a polymerization inhibitor may be mixed in order to rapidly react with a radical generated from a polymerization initiator or a monomer and convert it into a stable radical or a neutral compound to terminate the polymerization reaction. Polymerization inhibitors are structurally classified into several types. One of them is a stable free radical of itself such as tris-p-nitrophenylmethyl, di-p-fluorophenyl amine, etc., and the other is a substance which is easily converted into a stable free radical by reacting with a free radical existing in a polymer system, and is represented by nitro, nitroso, amino, polyhydroxy compound, etc. Representative examples of the latter include hydroquinone, dimethoxybenzene and the like. The preferable ratio of the polymerization inhibitor is 5ppm or more for obtaining the effect thereof and 1000ppm or less for preventing the display failure. The more preferable ratio is in the range of 5ppm to 500 ppm.

The liquid crystal display element of the present invention can provide a liquid crystal display element having excellent afterimage characteristics and good alignment stability by using a liquid crystal composition having negative dielectric anisotropy.

Examples

The present invention will be described below with reference to examples. 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 the polyamic acid was measured by a GPC method using a 2695Separations Module 2414 differential refractometer (manufactured by Waters corporation), and determined by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF 0.6/100: weight ratio) so that the polyamic acid concentration reached about 2 wt%. The column was measured using HSPgel RT MB-M (manufactured by Waters) at a column temperature of 50 ℃ and a flow rate of 0.40mL/min using the above-mentioned mixed solution as an eluent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh corporation was used.

2. Measurement of pretilt Angle

The measurement was carried out according to the crystal rotation (crystal rotation) method. The pretilt angle is a physical value which is an index for predicting viewing angle characteristics, and when the pretilt angle is 2.0 or less, a liquid crystal display element having good viewing angle characteristics in the IPS mode and the FFS mode is obtained.

3. Voltage holding ratio

The method was carried out according to the method described in "Water island and others, and liquid Crystal conference on 14 th order, P78 (1988)". The measurement was performed by applying a rectangular wave with a wave height of ± 5V to the cell. The measurement was carried out at 60 ℃. This value is an index indicating how much the applied voltage can be held after the frame period, and if the value is 100%, it indicates that all the charges are held. If 99.5% or more of the cells carrying positive liquid crystal and 97.5% or more of the cells carrying negative liquid crystal are used, a liquid crystal display element with good display quality is obtained.

4. Measurement of ion amount in liquid Crystal (ion Density)

The measurement was carried out by the method described in applied Physics 65, No. 10, page 1065 (1996) using model 6254 liquid crystal physical property measurement System manufactured by TOYO Corporation. The measurement was carried out at a voltage of. + -. 10V and a temperature of 60 ℃ using a triangular wave having a frequency of 0.01Hz (the area of the electrode was 1 cm)²). If the ion density is high, defects such as image sticking due to ionic impurities are likely to occur. That is, the ion density is a physical property value which is an index for predicting the occurrence of afterimage. If this value is 40pC or less, a liquid crystal display element with good display quality is obtained.

5. Orientation of flow

The phenomenon that the liquid crystal cell is sandwiched between 2 polarizing plates arranged as crossed prisms and the liquid crystal is aligned in the direction of flow from the inlet when observed by visual observation is called flow alignment. The flow alignment is an index of the alignment property of the alignment film, and the alignment film in which the flow alignment does not occur has a good alignment property.

< diamine >

< tetracarboxylic dianhydride >

< monomer having photoisomerization Structure >

< solvent >

N, N-dimethylformamide: DMF (dimethyl formamide)

Tetrahydrofuran: THF (tetrahydrofuran)

N-methyl-2-pyrrolidone: NMP

Gamma-butyrolactone: GBL

Butyl cellosolve (ethylene glycol monobutyl ether): BC

[ example 1]

Synthesis of the diamine represented by the formula (1-15).

< stage 1 > Synthesis of Nitro substrates

A500 mL three-necked flask equipped with a thermometer and a reflux tube was charged with 4-amino-2, 2,6, 6-tetramethylpiperidine (20.0g, 128.0mmol) and potassium carbonate (44.2g, 320.0mmol), and 200mL of DMF was added thereto. The solution was kept below 5 ℃ and 4-fluoronitrobenzene (39.7g, 281.6mmol) was added slowly. The reaction solution was stopped from cooling and further stirred at room temperature for 24 hours. The reaction solution was poured into 500mL of pure water, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solvent was removed by distillation under the reduced pressure to obtain a crude product. The crude product obtained was recrystallized from ethanol (50mL) to obtain the following compound. The yield was 26.3g, 52%.

< stage 2 > reduction of Nitro

Into a 1L autoclave reactor were charged the compound obtained in the 1 st stage (26.3g, 66.0mmol) and 5 wt% palladium on carbon powder (2.6g), and 250mL of THF was added. Stirring was carried out at 50 ℃ under a hydrogen atmosphere of 0.5mPa until the absorption of hydrogen was stopped. After cooling, the palladium-carbon powder was removed by filtration, and the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was recrystallized from 40mL of ethanol to give a compound represented by the formula (1-15). The yield was 19.3g, 86%.

[ example 2]

Synthesis of diamine represented by the formula (1-29)

< stage 1 > Synthesis of Nitro substrates

A500 mL three-necked flask equipped with a thermometer and a reflux tube was charged with 4-amino-2, 2,6, 6-tetramethylpiperidine (20.0g, 128.0mmol) and potassium carbonate (44.2g, 320.0mmol), and 200mL of DMF was added thereto. The solution was kept below 5 ℃ and a solution of 4-nitrobenzyl bromide (60.8g, 281.6mmol) in DMF (50mL) was slowly added. The reaction solution was stopped from cooling and further stirred at room temperature for 5 hours. The reaction solution was poured into 500mL of pure water, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solvent was removed by distillation under the reduced pressure to obtain a crude product. The crude product obtained was recrystallized from ethanol (50mL) to obtain the following compound. The yield was 46.2g, 85%.

< stage 2 > reduction of Nitro

A1000 mL three-necked flask equipped with a thermometer and a reflux tube was charged with the compound obtained in the 1 st stage (46.2g, 108.3mmol), and 300mL of ethanol and 50mL of water were added. The solution was kept below 25 ℃ and sodium sulfide nonahydrate (295.4g, 649.9mmol) was added slowly. The reaction mixture was poured into purified water (500mL) and extracted with ethyl acetate (500mL) after cooling, and the organic layer was washed 3 times with purified water (500 mL). The organic layer was dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solvent was removed by distillation under the reduced pressure to obtain a crude product. The obtained crude product was recrystallized from ethanol (50mL), thereby obtaining a compound represented by the formula (1-29). The yield was 27.3g, and 69%.

[ example 3]

Synthesis of diamine represented by the formula (1-1)

< stage 1 > Methanesulphonation

A2000 mL three-necked flask equipped with a thermometer and a reflux tube was charged with 2-nitroethanol (30.0g, 329.4mmol) and triethylamine (50.0g, 494.2mmol), and 600mL of THF was added. The solution was kept below 5 ℃ and methanesulfonyl chloride (45.3g, 395.3mmol) was added slowly thereto. The reaction solution was stopped from cooling and further stirred at room temperature for 24 hours. The reaction solution was poured into 500mL of pure water, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solvent was removed by distillation under the reduced pressure to obtain the following compound. The yield was 53.2g, 95%.

< stage 2 > Synthesis of Nitro substrates

A2000 mL three-necked flask equipped with a thermometer and a reflux tube was charged with 4-amino-2, 2,6, 6-tetramethylpiperidine (13.5g, 86.5mmol) and potassium carbonate (27.5g, 199.0mmol), and 200mL of DMF was added thereto. The solution was kept at 5 ℃ or lower, and a solution obtained by dissolving the compound obtained in the 1 st stage (30.0g, 177.4mmol) in DMF (50mL) was slowly added thereto. The reaction solution was stopped from cooling and further stirred at room temperature for 5 hours. The reaction solution was poured into 500mL of pure water, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solvent was removed by distillation under the reduced pressure to obtain a crude product. The crude product obtained was recrystallized from ethanol (50mL) to obtain the following compound. The yield was 19.2g, 73%.

< stage 3 > reduction of Nitro

To a 1000mL three-necked flask equipped with a thermometer and a reflux tube were added the compound obtained in the 2 nd stage (15.0g, 49.6mmol) and 50mL of methanol. The solution was kept at-10 ℃ and 10% Pd/C (1.5g) and ammonium formate (30.8g, 496.1mmol) were added slowly and stirred at the same temperature for 8 h. The catalyst was filtered off. Then, the solvent was distilled off under reduced pressure, and ethyl acetate and a saturated aqueous sodium carbonate solution were added to adjust the pH to 7 or more. The organic layer was dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solvent was removed by distillation under the reduced pressure to obtain a crude product. The obtained crude product was recrystallized from ethanol (50mL), thereby obtaining a compound represented by the formula (1-1). The yield was 9.6g, 80%.

EXAMPLE 4 preparation of the varnish

In a 200mL eggplant type flask equipped with a thermometer, a nitrogen purge port, and a stirring rod, 2.5874g of compound DI-7-3(m ═ 3, n ═ 1) and 0.610g of the compound represented by formula (1-1-1) were charged, and 59.0g of NMP and 15.0g of GBL were added. The solution was cooled to 5 ℃ or lower, 0.5553g of the compound represented by the formula (AN-3-1), 0.9152g of the compound represented by the formula (PA-1) and 0.3261g of the compound represented by the formula (AN-1-13) were added thereto, and the mixture was further stirred at room temperature for 6 hours. 20.0g of Butyl Cellosolve (BC) was added thereto, and the mixture was heated and stirred at 70 ℃ until the viscosity of the solution reached about 35.0cP, thereby obtaining varnish 1 having a solid content of 6 wt%. The weight average molecular weight (Mw) of the varnish was 68000.

Examples 5 to 35 and comparative examples 1 to 3

According to the method described in example 4, a varnish having the following solid content of 6 wt% was obtained. The compositions and weight-average molecular weights (Mw) of the varnishes thus obtained are shown in tables 1 to 1 and 1 to 2. Example 4 is described again. [] The molar ratios of the tetracarboxylic acid compound group and the diamine compound group are shown in the inner table.

[ tables 1-1]

[ tables 1-2]

[ example 36]

< preparation of liquid Crystal alignment agent, method for producing FFS Unit, measurement of Voltage holding ratio/ion Density and Pre-Tilt Angle >

10g of varnish 1 was weighed into a 50mL eggplant type flask, 10g of N-methyl-2-pyrrolidone and 10g of butyl cellosolve were added thereto, and the mixture was shaken for 2 hours to obtain a liquid crystal aligning agent 1 having a solid content of 3 wt%. The alignment agent 1 was applied to the FFS electrode-attached glass substrate and the glass spacer-attached glass substrate by spin coating (2000rpm, 15 seconds). After the coating film was baked at 80 ℃ for about 5 minutes, the film was baked at 200 ℃ for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The obtained polyimide film was subjected to brushing treatment under conditions of a brush cloth (brush length 1.9 mm: rayon) having a brush length pressing amount of 0.40mm, a base moving speed of 60mm/sec and a roll rotating speed of 1000rpm, using a brushing treatment apparatus manufactured by Iinuma Gauge Manufacturing Co., Ltd. The resulting substrate was ultrasonically cleaned in ethanol for 5 minutes, and then the surface was cleaned with ultrapure water, followed by drying in an oven at 120 ℃ for 30 minutes. With respect to 2 substrates on which alignment films were formed, the surfaces on which the alignment films were formed were opposed to each other, and a gap for injecting a liquid crystal composition between the opposed alignment films was further provided so that the brushing directions of the respective alignment films were parallel to each other, and the substrates were bonded to each other, thereby assembling an empty FFS cell having a cell thickness of 4 μm. The following positive liquid crystal composition a was vacuum-injected into the prepared empty FFS cell, and the injection port was sealed with a photo-curing agent. Subsequently, the liquid crystal cell for measurement was prepared by performing heat treatment at 110 ℃ for 30 minutes.

< Positive liquid Crystal composition A >

Physical property values: NI is 100.1 ℃; Δ ε 5.1; Δ n 0.093; eta.25.6 mPas.

The voltage holding ratio of the obtained cell for measurement was 99.8% at 5V and 30Hz, the ion density was 10pC, and the pretilt angle was 1.3 °. Backlight tester (Fuji thin) for lighting the cellFujiCOLOR LED Viewer Pro HR-2, available from Membrane corporation; luminance of 2700cd/m²) The test piece was placed on the tray for 1000 hours to conduct a reliability test. The cell for measurement after the reliability test had a voltage holding ratio of 99.7%, an ion density of 10pC and a pretilt angle of 1.3 deg.

Examples 37 to 67 and comparative examples 4 to 6

Preparation of liquid crystal aligning agent, preparation of FFS cell, and measurement of voltage holding ratio, ion density, and pretilt angle were also performed for varnishes 2 to 32 and varnishes C1 to C3 by the method described in example 36. The results are shown in Table 2. The results of example 36 are again reported.

[ Table 2]

In all the results of the liquid crystal display elements using the liquid crystal aligning agents 1 to 32, good results were obtained both initially and after the reliability test. The liquid crystal display devices using the liquid crystal aligning agents C1 to C2 exhibited good results in terms of voltage holding ratio and ion density, but exhibited large pretilt angles and poor viewing angle characteristics. The liquid crystal display element using the liquid crystal aligning agent C3 exhibited good results in pretilt angle, but large ion density and poor reliability.

Examples 68 to 110 and comparative examples 7 to 9

Varnishes 33 to 75 and varnishes C4 to 6 each having a polymer solid content of 6% by weight were prepared in accordance with example 4, except that the tetracarboxylic dianhydrides and the diamines were changed. The weight average molecular weight is adjusted to about 12000 to 13000 using a base material having a photoisomerization structure, and is adjusted to 40000 to 50000 without using a base material having a photoisomerization structure. The weight average molecular weights of the tetracarboxylic dianhydride and diamine used and the resulting polymer are shown in tables 3-1 to 3-4.

[ Table 3-1]

[ tables 3-2]

[ tables 3 to 3]

[ tables 3 to 4]

EXAMPLE 111 preparation of Single-layer type alignment agent, production of cell for measuring Electrical characteristics, and measurement of Electrical characteristics

10.0g of varnish 33 synthesized in example 68 was weighed into a 50mL round bottom flask equipped with a stirring blade and a nitrogen inlet tube, and 5.0g of N-methyl-2-pyrrolidone and 5.0g of butyl cellosolve were added thereto and stirred at room temperature for 1 hour to obtain an aligning agent 33 having a resin component concentration of 3 wt%. The alignment agent was applied to the FFS electrode-attached glass substrate and the glass spacer-attached glass substrate by spin coating (2000rpm, 15 seconds). After coating, the substrate was heated at 80 ℃ for 3 minutes to evaporate the solvent, and then irradiated with linearly polarized ultraviolet Light from a direction perpendicular to the substrate through a polarizing plate using Multi-Light ML-501C/B manufactured by USHIO inc. The exposure energy at this time was measured by using an ultraviolet ray cumulative light quantity meter UIT-150 (light receiver: UVD-S365) manufactured by USHIO INC. to obtain a light quantity at 1.3. + -. 0.1J/cm at an energy of 365nm in wavelength²The exposure time is adjusted. Subsequently, the resultant was subjected to heat treatment at 230 ℃ for 15 minutes in a dust-free oven (ESPEC co., ltd., PVHC-231), thereby forming an alignment film having a film thickness of 100 ± 10 nm. The 2 substrates on which the alignment films were formed were attached so that the surfaces on which the alignment films were formed were opposed to each other and a gap for injecting the liquid crystal composition between the opposed alignment films was provided. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films are made parallel. Inject into these unitsA liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm was prepared by incorporating the positive type liquid crystal composition A.

The liquid crystal cell prepared as described above was sandwiched between 2 polarizing plates arranged as cross prisms, and observed by visual observation. As a result, so-called flow alignment in which liquid crystals are aligned in the direction of flow from the inlet was not observed at all. In addition, the voltage holding ratio of the liquid crystal unit is 99.8% under 5V-30Hz, and the ion density is 10 pC. The cell was placed in a backlight tester (FujiCOLOR LED Viewer Pro HR-2, manufactured by Fuji film Co., Ltd.; luminance: 2700 cd/m)²) The test piece was placed on the tray for 1000 hours to conduct a reliability test. The cell for measurement after the reliability test had a voltage holding ratio of 99.7% and an ion density of 10 pC.

Examples 112 to 123 and comparative examples 10 to 12

Liquid crystal cells were produced in accordance with example 111 except that the varnish used was changed, and the flow alignment was observed and the voltage holding ratio and the ion density before and after the reliability test were measured. The measurement results are shown in table 4 together with example 111.

[ Table 4]

The initial values and the values after the reliability test were good for all the units of examples 111 to 123. Here, the initial value is a result measured without being placed on the backlight tester after the cell is created. In the cells of comparative examples 10 to 11, good results were obtained in the initial values and the values after the reliability test, but the cells were observed to be flow-aligned and exhibited poor alignment of the liquid crystal. In comparative example 12, no flow alignment was observed, and good liquid crystal alignment properties were obtained, but the ion density value was large, and the reliability was poor.

EXAMPLE 124 preparation of blend-type orientation agent, production of cell for measuring Electrical characteristics, and measurement of Electrical characteristics

2.0g of the varnish 38 synthesized in example 73 and 8.0g of the varnish 67 synthesized in example 102 were weighed into a 50mL eggplant type flask equipped with a stirring blade and a nitrogen gas inlet tube, 5.0g of N-methyl-2-pyrrolidone and 5.0g of butyl cellosolve were added thereto, and the mixture was stirred at room temperature for 1 hour to obtain an alignment agent 46 having a resin component concentration of 3 wt%. A liquid crystal cell was produced by the method described in example 111. As a result of observation by visual observation of the liquid crystal cell sandwiched by 2 polarizing plates arranged as crossed prisms, no so-called flow alignment in which liquid crystals were aligned in the direction in which the liquid crystals flowed from the inlet port was observed at all. In addition, the voltage holding ratio of the liquid crystal unit is 99.8% under 5V-30Hz, and the ion density is 10 pC. The cell for measurement after the reliability test had a voltage holding ratio of 99.7% and an ion density of 10 pC.

Examples 125 to 172 and comparative examples 13 to 15

Liquid crystal cells were produced in accordance with example 124 except that the varnish used was changed, and the flow alignment was observed and the voltage holding ratio and the ion density before and after the reliability test were measured. The varnishes used and the measurement results are shown in tables 5-1 and 5-2 together with example 124. In the table, varnish a represents varnish containing a polymer using a raw material having a photoisomerization structure, and varnish B represents varnish containing a polymer not using a raw material having a photoisomerization structure.

[ Table 5-1]

[ tables 5-2]

In all the units of examples 124 to 172, good results were obtained for the initial values and the values after the reliability test. Here, the initial value is a result measured without being placed on the backlight tester after the cell is created. In the cells of comparative examples 13 to 14, good results were obtained in the initial values and the values after the reliability test, but the cells were observed to have flow alignment and poor liquid crystal alignment. In comparative example 15, no flow alignment was observed, and good liquid crystal alignment properties were obtained, but the ion density value was large, and the reliability was poor.

According to the above embodiments: a liquid crystal display element including a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention has excellent viewing angle characteristics, and maintains good display quality even after a long period of time.

Industrial applicability

By using the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention, an excellent liquid crystal display element which is excellent in viewing angle characteristics and image sticking characteristics and whose display quality does not deteriorate even when used for a long time can be obtained. The present invention is particularly suitable for IPS mode and FFS mode liquid crystal display devices of the lateral electric field type.

Claims

1. A polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride with a diamine containing at least 1 kind of diamine represented by the formula (1),

2. The polyamic acid or derivative thereof according to claim 1, wherein the diamine represented by the formula (1) is a diamine represented by the formula (1'),

3. The polyamic acid or derivative thereof according to claim 1, wherein R in the diamine represented by formula (1) is hydrogen or-OH.

4. The polyamic acid or derivative thereof according to claim 1, wherein the diamine represented by the formula (1) is a compound represented by the following formula (1-15) or formula (1-29),

5. the polyamic acid or derivative thereof according to claim 1, wherein the tetracarboxylic dianhydride is at least 1 selected from the group consisting of tetracarboxylic dianhydrides represented by the following formulae (AN-I) to (AN-VII),

the other diamines used together with the diamine represented by the formula (1) are at least 1 selected from the group consisting of the following formulae (DI-1) to (DI-16), formulae (DIH-1) to (DIH-3), and formulae (DI-31) to (DI-35),

in the formula (DI-4), s is independently an integer of 0 to 2;

in the formula (DI-11), r is 0 or 1;

formula (DI-8) to formula (DI-11)In which-NH is bonded to the ring₂The bonding position of (a) is an arbitrary position;

in formula (DI-15), ring C is a monocyclic ring containing a heteroatom;

in the formula (DIH-3), the rings E are each independently a cyclohexane ring orA benzene ring, wherein at least 1 hydrogen atom on the ring is optionally substituted by methyl, ethyl or phenyl, Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-；

in the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are linking groups, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, wherein 1 or more-CH groups in the alkylene group₂Optionally substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-, ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diylNaphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴In which at least 1 hydrogen is optionally replaced by-F or-CH₃And (b) a substituent, s, t and u are independently integers of 0 to 2, and the total of them is 1 to 5, and when s, t or u is 2,2 linking groups in each bracket are the same or different, and 2 rings are the same or different,

in the formulae (DI-32) and (DI-33), a group whose bonding position on any one of carbon atoms constituting the ring is not fixed means that the bonding position on the ring is arbitrary;

6. The polyamic acid or the derivative thereof according to claim 5, wherein, the tetracarboxylic dianhydride is at least 1 selected from the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4);

the other diamine used together with the diamine represented by the formula (1) is selected from the group consisting of the following formula (DI-1-3), formula (DI-2-1), 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 1 of the group consisting of formula (DI-16-1), formula (DIH-2-1) and formula (DI-31-56),

in the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1-12;

in the formula (DI-7-3), n is 1 or 2.

7. The polyamic acid or derivative thereof according to claim 1, wherein at least 1 of the tetracarboxylic dianhydride and the diamine comprises a compound having a photoreactive structure.

8. The polyamic acid or derivative thereof according to claim 7, wherein the photoreactive structure is at least 1 selected from the group consisting of the structures represented by the following formulae (P-1) to (P-7),

9. The polyamic acid or derivative thereof according to claim 7, wherein the compound having a photoreactive structure is at least 1 selected from the group consisting of the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), formula (VI-1), and formula (VI-2),

in the above formulae, the group whose bonding position on any one of the carbon atoms constituting the ring is not fixed means that the bonding position on the ring is arbitrary, and in the formula (V-2), R⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is an integer of 0 to 2, in the formula (V-3), the ring A and the ring B are at least 1 selected from monocyclic hydrocarbon, condensed polycyclic hydrocarbon and heterocyclic ring, and R¹¹Is carbonA linear alkylene group having 1 to 20 atoms, -COO-, -OCO-, -NHCO-, or-N (CH)₃)CO-，R¹²Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²In (1) or 2-CH groups on the linear alkylene group₂Optionally substituted by-O-, R⁷～R¹⁰Each independently is-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

10. The polyamic acid or the derivative thereof according to claim 7, wherein the compound having a photoreactive structure is a diamine represented by the following formula (PDI-7),

11. A liquid crystal aligning agent comprising the polyamic acid or the derivative thereof according to any one of claims 1 to 10.

12. A liquid crystal aligning agent for photo-alignment comprising a polymer [ A ] and a polymer [ B ], the polymer [ A ] and the polymer [ B ] being polyamic acid or a derivative thereof,

at least 1 of the raw material monomers of the polymer has a photoreactive structure, and the raw material monomers of the polymer include at least 1 of the compounds represented by the following formula (1), wherein the polymer [ A ] is different from the polymer [ B ],

13. The liquid crystal aligning agent for photoalignment of claim 12, comprising at least 1 polymer [ A ] and at least 1 polymer [ B ],

14. The liquid crystal aligning agent for photoalignment of claim 12, comprising at least 1 polymer [ A ] and at least 1 polymer [ B ],

15. The liquid crystal aligning agent for photoalignment of claim 12, comprising at least 1 polymer [ A ] and at least 1 polymer [ B ],

16. The liquid crystal aligning agent according to claim 12, wherein the diamine represented by the formula (1) is a diamine represented by the formula (1'),

17. The liquid crystal aligning agent for photoalignment according to claim 12, wherein R in the diamine represented by formula (1) is hydrogen or-OH.

18. The liquid crystal aligning agent for photoalignment according to claim 12, wherein the diamine represented by formula (1) is a compound represented by formula (1-15) or formula (1-29),

19. the liquid crystal aligning agent for photoalignment according to claim 12, wherein the compound having a photoreactive structure has at least 1 of the structures represented by the following formulae (P-1) to (P-7),

20. The liquid crystal aligning agent for photoalignment according to claim 12, wherein the compound having a photoreactive structure is at least 1 selected from the group consisting of the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), formula (VI-1), and formula (VI-2),

in the above formulae, the group whose bonding position on any one of the carbon atoms constituting the ring is not fixed means that the bonding position on the ring is arbitrary, and in the formula (V-2), R⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is an integer of 0 to 2, in the formula (V-3), the ring A and the ring B are at least 1 selected from monocyclic hydrocarbon, condensed polycyclic hydrocarbon and heterocyclic ring, and R¹¹Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹²Is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²In (1) or 2-CH groups on the linear alkylene group₂Optionally substituted by-O-, R⁷～R¹⁰Each independently is-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

21. The liquid crystal aligning agent according to claim 12, wherein the compound having a photoreactive structure is a diamine represented by the following formula (PDI-7),

22. The liquid crystal aligning agent for photoalignment according to claim 12, wherein the tetracarboxylic dianhydride not having a photoreactive structure is at least 1 selected from the group consisting of tetracarboxylic dianhydrides represented by the following formulae (AN-I) to (AN-VII),

the diamine having no photoreactive structure is at least 1 selected from the group consisting of the following formulae (DI-1) to (DI-16), formulae (DIH-1) to (DIH-3), and formulae (DI-31) to (DI-35),

in the formula (AN-VI), X¹⁰Is 2 c6, Me represents a methyl group, Ph represents a phenyl group,

in the formula (DI-4), s is independently an integer of 0 to 2;

in the formulae (DI-2) to (DI-7), at least 1 hydrogen on the cyclohexane ring and the benzene ring is optionally substituted by-F, -Cl, or the number of carbon atoms1 to 3 alkyl groups, -OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅Phenyl or benzyl, and, in formula (DI-4), at least 1 hydrogen on the benzene ring is optionally substituted by 1 selected from the group of groups represented by the following formulae (DI-4-a) to (DI-4-e);

in the formula (DI-11), r is 0 or 1;

in the formula (DI-14), the ring B is a monocyclic heteroaromatic ring, R²⁴Is hydrogen,-F, -Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, q is independently an integer of 0 to 4;

in formula (DI-15), ring C is a monocyclic ring containing a heteroatom;

in the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are linking groups, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, wherein 1 or more-CH groups in the alkylene group₂Optionally substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-, ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴In which at least 1 hydrogen is optionally replaced by-F or-CH₃And (b) a substituent, s, t and u are independently integers of 0 to 2, and the total of them is 1 to 5, and when s, t or u is 2,2 linking groups in each bracket are the same or different, and 2 rings are the same or different,

23. The liquid crystal aligning agent according to claim 22, the tetracarboxylic dianhydride not having a photoreactive structure is at least 1 selected from the group consisting of the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4);

the diamine having no photoreactive structure is selected from the group consisting of formula (DI-1-3), formula (DI-2-1), 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), At least 1 of the group consisting of formula (DIH-2-1) and formula (DI-31-56),

in the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1 to 12,

in the formula (DI-7-3), n is each independently 1 or 2.

24. The liquid crystal aligning agent for photoalignment according to claim 12, further comprising at least 1 selected from the group of compounds consisting of an oxazine compound, an oxazoline compound, an epoxy compound, and a silane coupling agent.

25. A liquid crystal alignment film comprising the liquid crystal aligning agent according to claim 11 or the liquid crystal aligning agent for photoalignment according to any one of claims 12 to 24.

26. A liquid crystal alignment film for transverse electric field, which is formed from the liquid crystal aligning agent according to claim 11 or the liquid crystal aligning agent for photoalignment according to any one of claims 12 to 24.

27. A liquid crystal display element having the liquid crystal alignment film according to claim 25.

28. A diamine represented by the formula (1'),

29. The diamine of claim 28, which is represented by the following formula (1-15) or formula (1-29),