KR20150118527A - Liquid crystal aligning agents, liquid crystal alignment films and liquid crystal display devices - Google Patents

Abstract

The subject of the present invention is a liquid crystal aligning agent for a light alignment film containing terminal encapsulated polyamic acid or derivatives thereof, obtained by reacting tetracarboxylic acid dianhydride, a diamine compound, and an amino silane compound. The liquid crystal display device having a liquid crystal alignment film formed by using a liquid crystal aligning agent for a light alignment film of the present invention is capable of controlling generation of foreign substance in a liquid crystal layer inside the device, and maintaining various properties such as alignment of the liquid crystal, alignment stability, contrast, an AC afterimage, etc.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent for a photo alignment film containing a polyamic acid or a derivative thereof encapsulating an end thereof, a liquid crystal alignment film obtained from the liquid crystal aligning agent for the photo alignment film, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal aligning agent for a photo alignment film, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element capable of controlling foreign substances generated in a liquid crystal display element of a transversal electric field driving system of IPS or FFS . The term " liquid crystal aligning agent " in the present invention means a polymer-containing composition used for forming a liquid crystal alignment film. The liquid crystal alignment agent for the photo alignment film may be referred to as a " photo alignment agent ", and the liquid crystal alignment film obtained from the liquid crystal alignment agent may be referred to as a " photo alignment film ".

Various display devices such as a PC monitor, a liquid crystal TV, a viewfinder of a video camera, and a projection type display, and optoelectronic devices such as an optical printer head, a light Fourier transform device, and a light valve, In general, liquid crystal display devices which are in circulation form display devices using nematic liquid crystals. As a display method of a nematic liquid crystal display device, TN (Twisted Nematic) mode and STN (Super Twisted Nematic) mode are well known. In recent years, in order to solve the problem of narrow viewing angle which is one of the problems of these modes, a TN type liquid crystal display device using an optical compensation film, an MVA (Multi-domain Vertical Alignment) mode in which a technique of vertical orientation and projection structure are used in combination, (In-Plane Switching) mode, an FFS (Fringe Field Switching) mode, and the like have been proposed and practically used (see Patent Documents 1 to 3). 2. Description of the Related Art [0002] In recent years, a panel having a transverse electric field system represented by IPS or FFS has been used as a display for a small-sized touch panel portable terminal such as a tablet or a mobile phone, A problem arises in that a foreign substance is generated due to the impact of the impact.

Up to now, many methods have been reported for improving the coatability of the liquid crystal aligning agent and improving the rubbing slurry by introducing an additive comprising an organic silicon material or a silane coupling agent into the liquid crystal alignment film for rubbing based on polyamic acid See Document 4). Furthermore, by using a silylated polymer prepared by using a silylated diamine compound or a silylating agent (see Patent Document 6) or by modifying the end of the polymer with a silane coupling agent (see Patent Document 5) Stability, adhesiveness to a substrate, liquid crystal orientation, and the like have been reported. In addition, a liquid crystal aligning agent containing a polyorganosiloxane having an epoxy group has been reported to have high heat resistance and light resistance, and other excellent electrical properties (see Patent Document 7).

In a polyamic acid ester-based liquid crystal alignment film for photo-alignment, a method has been reported in which the terminal of a polyamic acid ester is reacted with a chlorocarbonyl compound to change the terminal thereof (see Patent Document 8). Although improvement of the solubility of the liquid crystal aligning agent and improvement of the orientation property and electrical properties have been reported, there is a problem in that the method of producing the liquid crystal aligning agent generates a byproduct and requires purification after the reaction (see Patent Document 9 ).

On the other hand, in the liquid crystal alignment film of the polyamic acid type, as described above, a method of improving scratching by rubbing has been studied, but the generation of foreign matter at the time of touch panel operation has not been sufficiently studied. In addition, a method of maintaining various panel characteristics (especially orientation and residual image of liquid crystal) while controlling the generation of foreign matter is not yet known.

Japanese Patent Laid-Open No. 6-194646 Japanese Patent Laid-Open No. 2001-117083 Japanese Patent Application Laid-Open No. 6-160878 Japanese Patent Application Laid-Open No. 61-108627 Japanese Patent Application Laid-Open No. 63-14126 Japanese Patent Application Laid-Open No. 2002-20754 Japanese Patent Application Laid-Open No. 2009-282440 International publicity 2011/115076 International Disclosure 2011/115077

An object of the present invention is to provide a liquid crystal aligning agent capable of maintaining various properties required for a liquid crystal alignment film such as liquid crystal alignability, alignment stability, contrast and AC afterimage while controlling the generation of foreign substances.

The inventors of the present invention have found that a liquid crystal display element which can satisfy the above requirements can be obtained by using a liquid crystal alignment film formed from a liquid crystal aligning agent for optical alignment in which the terminal of the polyamic acid is encapsulated with a specific aminosilane compound, .

The present invention comprises the following items.

[1] A liquid crystal aligning agent for a photo alignment film, which comprises a terminal-blocked polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride, a diamine compound and an aminosilane compound.

[2] The liquid crystal aligning agent for a photo alignment film according to [1], wherein the aminosilane compound is a compound represented by the following formula (AS).

In formula (AS), n is 0 or 1;

R is alkylene having 1 to 10 carbon atoms or 1,4-phenylene, and when the alkylene has 2 or more carbon atoms, at least one -CH ₂ -CH ₂ - in alkylene is substituted with -CH ₂ -NH- ; And,

And X is -OCH ₃ or -OCH ₂ CH _3.

[3] The liquid crystal aligning agent for photo alignment layers described in [1] or [2], wherein the aminosilane compound is at least one selected from the group consisting of the following formulas (AS-1) to (AS- .

[4] The liquid crystal aligning agent for a photo alignment film according to any one of [1] to [3], further comprising a compound capable of crosslinking with a terminal endblock polyamic acid or a derivative thereof.

[5] The liquid crystal alignment for a photo alignment film according to the item [4], wherein the terminal-sealed polyamic acid or a derivative thereof is at least one compound selected from the group consisting of the following compounds (a) to (d) My.

(a) a silane coupling agent containing at least one epoxy ring in the molecule

(b) a compound containing two or more epoxy rings in the molecule

(c) a compound containing two or more benzoxazine structures in the molecule

(d) a compound containing two or more oxazoline structures in the molecule

[6] A process for producing a polyvinyl alcohol resin composition according to any one of [1] to [4], wherein the terminal endblock polyamic acid or a derivative thereof is crosslinkable with a compound represented by any one of the following formulas (EPX-1 to EPX-7, The liquid crystal aligning agent for a photo alignment layer according to the above item [4], which is at least one selected from the group consisting of formula (OX-1).

[7] The liquid crystal aligning agent for a photo alignment film according to any one of [1] to [6], wherein the diamine compound comprises at least one of photosensitive diamines.

[8] The liquid crystal aligning agent for a photo alignment film as described in the item [7], wherein the photosensitive diamine is at least one compound hinder selected from the group consisting of the following formulas (PDI-1) to (PDI-13)

In the formula (PDI-7), R ⁵¹ are each independently selected from _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, and;

s is independently an integer of 0 to 2,

In formula (PDI-8), R ⁵² is independently a single bond, a straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, or -CONH-,

At least one -CH ₂ of the straight-chain alkylene - may be substituted with -O-;

R ⁵³ is each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH;

q is, each independently, an integer of 0 to 4;

In formula (PDI-12), R ⁵⁴ is alkyl or alkoxy having 1 to 10 carbon atoms,

At least one hydrogen of alkyl or alkoxy may be substituted with fluorine; And,

In the formulas (PDI-1) to (PDI-8), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the ring is bonded at a bonding position in the ring.

[9] The liquid crystal aligning agent for a photo alignment film according to the item [7] or [8], wherein the photosensitive diamine is a compound represented by the following formula (PDI-7)

In the formula (7-PDI), ⁵¹ R are each independently selected from _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, s are each independently an integer of 0 to 2.

[10] The liquid crystal aligning agent for a photo alignment film as described in any one of [7] to [10], wherein the photosensitive diamine is a compound represented by the following formula (PDI-7-1) or .

[11] The photosensitive resin composition of [11], wherein the diamine compound is at least one compound selected from the group consisting of a photosensitive diamine represented by the following formula (DI-5-1), formula (DI-5-17), formula (DI- 5-30) (1) to (10), wherein the mixture is a mixture of diamines containing at least one compound selected from the group consisting of a compound represented by the formula (13-1), a compound represented by the formula (DI-34-4) Wherein the liquid crystal aligning agent is a liquid crystal aligning agent for a photo alignment layer.

In the formula (DI-5-1), m is an integer of 2 to 12;

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

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

In formula (DI-34-4) and formula (DI-34-7), R ⁴¹ is -H or alkyl of 1 to 12 carbon atoms.

[12] The composition according to any one of [1] to [6], wherein the tetracarboxylic acid dianhydride is at least one selected from the following formulas (AN-1-13), (AN-4-17), The liquid crystal aligning agent for a photo alignment film according to any one of [1] to [11] above, further comprising:

In the formulas (AN-4-17) and (PAN-9), m is an integer of 1 to 12.

[13] The resin composition according to any one of the above items [1] to [12], further comprising a polymer other than the terminal-blocked polyamic acid or its derivative obtained by reacting the tetracarboxylic acid dianhydride, the diamine compound and the aminosilane compound Liquid crystal aligning agent for photo alignment layer.

[14] The liquid crystal aligning agent for a photo alignment film according to the above item [13], wherein the other polymer is a polyamic acid or a derivative thereof.

[15] A liquid crystal alignment film using the liquid crystal aligning agent according to any one of [1] to [14].

[16] A liquid crystal display element using the liquid crystal alignment film according to the above-mentioned [15].

According to the present invention, it is possible to provide a liquid crystal display element comprising a liquid crystal alignment film for photo-alignment, which is capable of controlling the generation of foreign substances during operation of the touch panel while maintaining various characteristics such as liquid crystal alignability, alignment stability, contrast, A liquid crystal aligning agent is provided.

In the present invention, the mechanism by which the generation of foreign matter is suppressed and the orientation property and electric characteristics of the liquid crystal display element can be maintained by using a polyamic acid in which the terminal is sealed with a specific amino silane compound is not necessarily clear, It can be thought as follows.

The specific aminosilane compound represented by the formula (AS) reacts with the acid anhydride group at the terminal of the polyamic acid. After the reaction, a part of the polyamic acid molecule is connected to the alkoxysilyl at the terminal. It is considered that the alkoxysilyl condenses with other alkoxysilyl at the time of heating and firing of the alignment film, and forms a bond in the thickness direction of the alignment film. It is considered that the coupling in the thickness direction increases the film strength in the thickness direction and controls the generation of foreign matter during the operation of the touch panel.

The liquid crystal aligning agent of the present invention can also be used as a so-called blend type aligning agent in which the above-mentioned polyamic acid is mixed with another polymer and used as an aligning agent. In such a case, it is considered that not only the film strength in the thickness direction of the orientation film is increased, but also the effect that the amino siloxane compound used in the end sealing promotes phase separation between the above-mentioned polyamic acid and other polymer. That is, even when the blend system alignment agent is used, various other characteristics can be maintained while controlling the generation of foreign matter. Further, it is more effective to control the generation of foreign matter by using a compound capable of crosslinking to such an extent that the liquid crystal alignability of the liquid crystal display element is not disrupted.

The terms used in the present invention will be described. For example, the "diamine represented by formula (I)" may be described as "diamine (I)". The compound represented by the formula (I-1) may be described as the compound (I-1). Similarly, the compounds represented by other formulas may be abbreviated. The term " arbitrary " used to define the chemical structural formulas indicates arbitrary not only the position but also the number. In the chemical structural formula, a group in which a letter (for example, A) is surrounded by a circle or a hexagon is a ring group (ring A).

The polyamic acid and its derivatives of the present invention will be described.

The polyamic acid and derivatives thereof of the present invention are end-capped polyamic acids or derivatives thereof obtained by reacting a tetracarboxylic acid dianhydride, a diamine compound and an aminosilane compound. The derivative of the polyamic acid is a component dissolved in a solvent when it is a liquid crystal aligning agent to be described later and contains a solvent. When the liquid crystal aligning agent is used as a liquid crystal alignment film, a derivative capable of forming a liquid crystal alignment film containing polyimide as a main component to be. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides, and more specifically, 1) polyimides obtained by dehydrocondensation of carboxyl with all amino groups of polyamic acid, 2) 3) polyamic acid ester converted into carboxyl ester of polyamic acid, 4) polyamic acid ester obtained by reacting part of acid dianhydride contained in tetracarboxylic acid dianhydride with organic dicarboxylic acid A polyamic acid-polyamide copolymer, and 5) a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyamic acid and its derivatives may be one kind of compound or two or more kinds. The polyamic acid and its derivative may be any compound having a structure of the reaction product of tetracarboxylic dianhydride and diamine and may be obtained by using other raw materials and reacting by reaction other than the reaction of tetracarboxylic acid dianhydride and diamine Product. ≪ / RTI >

Aminosilane compounds used for producing the polyamic acid and derivatives thereof of the present invention will be described.

The aminosilane compound used in the present invention is used to encapsulate the terminals of polyamic acid and its derivatives. In the diamine constituting the polyamic acid and the derivative thereof, a part of the diamine is substituted with the aminosilane compound in the range of the proportion of the aminosilane compound relative to the diamine of 40 mol% or less. By such substitution, it is possible to cause termination of the polymerization reaction when the polyamic acid is produced, so that the terminal of the polyamic acid and the derivative thereof can be sealed.

The aminosilane compound may be selected from compounds represented by the following formula (AS).

In formula (AS), n is 0 or 1;

R is an alkyl group having 1 to 10 carbon atoms, and one or more -CH ₂ -CH ₂ - structures existing in the alkyl group may be substituted with a -CH ₂ -NH- structure; X is -OCH ₃ , or -OCH ₂ CH ₃ .

More specifically, the aminosilane compound represented by the formula (AS) is an aminosilane compound represented by the following formulas (AS-1) to (AS-5).

The substituted aminosilane compounds may be used singly or in combination of two or more, unless the effect of the present invention is impaired.

The compounds represented by the formulas (AS-3) to (AS-5) are preferable, and the compounds represented by the formula (AS-5) are preferred for improving the hardness and orientation of the orientation film simultaneously in the aminosilane compound Particularly preferred.

&Quot; Crosslinkable compound " used for producing the liquid crystal aligning agent for the photo alignment layer of the present invention will be described.

The liquid crystal aligning agent for a photo alignment layer of the present invention contains a terminal-blocked polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride, a diamine compound and an aminosilane compound, but also increases the strength in the thickness direction of the alignment layer, , One or more crosslinkable compounds selected from the group consisting of the crosslinkable compounds represented by the following (a) to (d) may be contained in order to obtain the effect of suppressing the occurrence of the crosslinking.

(a) a silane coupling agent containing at least one epoxy ring in the molecule

(b) a compound containing two or more epoxy rings in the molecule

(c) a compound containing two or more benzoxazine structures in the molecule

(d) a compound containing two or more oxazoline structures in the molecule

Examples of the silane coupling agent containing (a) at least one epoxy ring in the molecule include 3-glycidoxypropylmethyldimethoxysilane represented by the following formulas (EPX-1) to (EPX-6) , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, and can be preferably used. Among them, preferable silane coupling agents are 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (EPX-5) and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane (EPX- to be.

(b) compounds containing two or more epoxy rings in the molecule include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl Ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromonopentyl glycol Diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 2 - [4- (1,1-bis [4- (2,3-epoxypropoxy) phenyl]] ethyl] phenyl] propane Tetramethyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl methacrylate (manufactured by Mitsui Chemicals, Inc.) Xylenediamine, 1,3-bis (N, N- N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane represented by the following formula (EPX-7) . A preferred epoxy compound is N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

(c) compounds containing two or more benzoxazine structures in the molecule include, for example, compounds represented by the following formulas (BOX-1) to (BOX-5). In the following formulas, the bond indicated toward the center of the ring indicates that it forms a ring, and the substituent is bonded to any one bondable carbon.

In the formula (BOX-1) and formula (BOX-2), L ³ and L ⁴ is an organic group of 1 to 30 carbon atoms. In the formula (BOX-1) ~ expression (BOX-5) according to, L ⁵ ~ L ⁸ is in a hydrocarbon group of 1 to 6 carbon atoms or hydrogen. in the formula (BOX-2), formula (BOX-3) and formula (BOX-5), Q ¹ represents a single bond, -O-, -S- _{, -SS-, -SO 2 -, -CO-} , -CONH-, -NHCO-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) v -, -O - (CH ₂ ) _v -O-, -S- (CH ₂ ) _v -S-, wherein v is an integer of 1 to 6. Equation (BOX-4) and formula (BOX-5) in, Q ² are each independently a single bond, -O-, -S-, -CO-, -C (CH 3) 2 in -, -C (CF ₃ ) _2- or an alkylene of 1 to 3 carbon atoms. Then, the expression (BOX-1) ~ expression (BOX-5) in the hydrogen which is bonded to a benzene ring, a naphthalene ring, each _{independently, -F, -CH 3, -OH,} -COOH, -SO 3 H , -PO ₃ H ₂ . Among these, preferred compounds include compounds represented by the following formulas (BOX-2-1) and (BOX-2-2).

(d) Examples of the compound containing two or more oxazoline structures in the molecule include 2,2'-bis (2-oxazoline), 1,2,4-tris (2-oxazolinyl- Benzene, 4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-one, 1,4-bis (4,5- dihydro-2-oxazolyl) benzene, , 5-dihydro-2-oxazolyl) benzene (OX-1), 2,3-bis 4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazoline-2-yl) pyridine, 2,2'- 2-oxazoline), 2,2'-methylenebis (4-tert-butyl-2-oxazoline), and 2,2'-methylene Bis (4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also exemplified.

The tetracarboxylic dianhydride used for producing the polyamic acid and derivatives thereof of the present invention will be described.

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

Preferable examples of such tetracarboxylic dianhydrides include tetracarboxylic acid dianhydrides represented by the formulas (AN-I) to (AN-VII) from the viewpoints of ease of raw material availability, ease of polymer polymerization, .

In the formulas (AN-I), (AN-IV) and (AN-V), each X is independently a single bond or -CH ₂ -. In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number _{1~20 -, -C (CH 3)} 2 -, or - C (CF ₃ ) ₂ -, and -CH ₂ - of the alkylene may be substituted with -CH═CH- or -C≡-. In the formulas (AN-II) to (AN-IV), each Y is independently selected from the group consisting of the following trivalent groups, and the bonding hand is connected to any carbon, Hydrogen may be substituted with methyl, ethyl or phenyl.

In the formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to ¹⁰ carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, The hydrogen may be substituted with methyl, ethyl or phenyl, and the bonding hands connected to the ring may be connected to any carbon constituting the ring, and two bonding hands may be connected to the same carbon. In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl and Ph represents phenyl. In the formula (AN-VII), G ¹⁰ is each independently -O-, -COO- or -OCO-, and each r is independently 0 or 1.

More specifically, the tetracarboxylic acid dianhydride represented by the following formulas (AN-1) to (AN-16-14) is exemplified.

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

In formula (AN-1), G ¹¹ is a single bond, alkylene of 1 to 12 carbon atoms, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ each independently represents a single bond or -CH ₂ -. G ¹² each independently represents one of the following trivalent groups.

When G ¹² is > CH-, the hydrogen of > CH- may be substituted with -CH ₃ . When G ¹² is> N-, G ¹¹ is not a single bond and -CH ₂ -, and X ¹¹ is not a single bond. And R ¹¹ is hydrogen or -CH _3.

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

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

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

In the formula (AN-2), each R ¹² is independently hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formulas.

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

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring.

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

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

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

In the formula (G13-1), G G ^13a and ^13b is a divalent group represented by each independently, a single bond, -O-, or -NHCO-. Phenylene is preferably 1,4-phenylene and 1,3-phenylene. Ring A ¹¹ is each independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ¹¹ .

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

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

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

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

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

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

In the formula (AN-6), X ¹¹ is each independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH = CH-. n is 1 or 2;

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

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

In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -.

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

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

In formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl, and the ring A ¹² is a cyclohexane ring or a cyclohexene ring.

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

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

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

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

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

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

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

In the formula (AN-11), each of the rings A < ¹¹ > is independently a cyclohexane ring or a benzene ring.

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

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

In the formula (AN-12), each of the rings A < ¹¹ > is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-12) include the compounds represented by the following formulas.

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

In the formula (AN-13), X ¹³ is alkylene having 2 to 6 carbon atoms, and Ph represents phenyl.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-13) include the compounds represented by the following formulas.

In the formula (AN-13-1), Ph represents phenyl.

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

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

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

[Tetracarboxylic acid dianhydride represented by the formula (AN-15)] [

In the formula (AN-15), w is an integer of 1 to 10.

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

As the tetracarboxylic acid dianhydride other than the above, the following compounds are exemplified.

In addition to the above tetracarboxylic acid dianhydride, it can be selected from known photosensitive tetracarboxylic acid dianhydrides without limitation. Examples of such photosensitive tetracarboxylic acid dianhydrides include the following formulas (PAN-1) to (PAN-9).

In the formula (PAN-9), m is an integer of 1 to 12.

Preferred materials for improving the properties of the acid dianhydride are described below. (AN-4-17), (AN-4-30), and (PAN-9) are preferred when the orientation of the liquid crystal is emphasized, M = 4 or 8, and in the formula (AN-4-30), m = 2 or 4 is preferable, and m = 4 is particularly preferable.

When it is important to improve the transmittance of the liquid crystal display element, among the above acid anhydrides, the formulas (AN-1-13) and (AN-4-30) are preferable.

It is effective to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film as one of the methods for preventing burning. When this object is emphasized, a compound represented by the formula (AN-1-13) and the formula (AN-4-30) among the above acid anhydrides is preferable.

The diamines and dihydrazides used for producing the polyamic acid and derivatives thereof of the present invention will be described. The polyamic acid or derivative thereof of the present invention can be selected from known diamines and dihydrazides without limitation.

The diamine can be divided into two types according to its structure. That is, when a skeleton connecting two amino groups is regarded as a main chain, it is a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples thereof include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and a group having a steroid skeleton. The group having at least one ring has an effect as an airway side chain group having at least 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 following description, the diamine having such a side chain group is sometimes referred to as a side chain type diamine. The diamine having no side chain group may be referred to as a non-branched chain diamine.

By properly using the non-branched diamine and the branched-chain diamine separately, it is possible to cope with the pre-tilt angle required for each. The side chain type diamine is preferably used in combination so as not to impair the characteristics of the present invention. Further, it is preferable to select and use the side chain type diamine and the non-side chain type diamine for the purpose of improving the vertical alignment property, the voltage holding ratio, the burning property and the orientation property to the liquid crystal.

The non-branched diamine will be explained. Examples of the diamine having no known side chain include diamines of the following formulas (DI-1) to (DI-16).

In the above formula (DI-1), G ²⁰ is -CH ₂ -, and at least one -CH ₂ - may be substituted with -NH- or -O-, and m is an integer of 1 to 12 , And at least one hydrogen in the alkylene may be substituted with -OH. In the formulas (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, _{SS-, -SO 2 -, -CO-,} -COO-, -CONCH 3 -, -CONH-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m ' -, -O- (CH ₂ ) _{m '} -O-, -N (CH ₃ ) - (CH ₂ ) _k -N (CH ₃ ) -, - (OC ₂ H ₄ ) _{m' -CH 2 -C (CF 3) 2} -CH 2 -O-, -O-CO- (CH 2) m '-CO-O-, -CO-O- (CH 2) m' -O-CO- _{, - (CH 2) m '} -NH- (CH 2) m' -, -CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ') k - _{NH-, -CO-C 3 H 6} - (NH-C 3 H 6) n -CO-, or -S- (CH _{2) m 'is} -S-, m' are each independently an integer from 1 to 12 , K is an integer of 1 to 5, and n is 1 or 2. In the formula (DI-4), each s is independently an integer of 0 to 2. In the formulas (DI-6) and (DI-7), G ²² each independently represents a single bond, -S-, -CO-, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, or alkylene having 1 to 10 carbon atoms. Formula (DI-2) ~ (DI -7) of the cyclohexane ring and benzene, at least one hydrogen, -F, -Cl, alkylene, -OCH _3, -OH, -CF of 1 to 3 carbons of the ring ₃ (DI-4), at least one hydrogen in the benzene ring may be replaced by -O-, -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl. -a) to formula (DI-4-e). A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² .

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is each independently hydrogen or -CH ₃ .

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

In formula (DI-12), R ²¹ and R ²² are each independently alkyl having 1 to 3 carbon atoms or phenyl, and G ²³ is independently selected from alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms And w is an integer of 1 to 10. In formula (DI-13), R ²³ is independently an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, q is 0 to 4 Lt; / RTI > In formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, and R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy, vinyl or alkynyl, Lt; / RTI > In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In the formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) may be mentioned as the diamines having no side chain of the formulas (DI-1) to (DI-16).

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

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

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

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

Examples of the diamine 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 formula (DI- 5-39), m is an integer of 1 to 12, DI-5-39), k is an integer of 1 to 5, and in the formula (DI-5-40), n is an integer of 1 or 2.

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

Examples of the diamine 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.

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

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

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

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

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

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

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

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

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

The dihydrazide will be explained. Examples of the dihydrazide having no known side chain include compounds represented by the following formulas (DIH-1) to (DIH-3).

In formula (DIH-1), G ²⁵ represents a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ - - (CF ₃ ) ₂ -.

In the formula (DIH-2), the ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one of these groups may be substituted with methyl, ethyl, or phenyl. In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one of these groups may be substituted with methyl, ethyl, or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -. In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position.

Examples of compounds represented by formulas (DIH-1) to (DIH-3) are shown below.

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

Such non-branched chain diamines and hydrazides have the effect of improving the electrical characteristics such as lowering the ion density of the liquid crystal display element. When a non-branched-chain diamine and / or hydrazide is used as the diamine used for producing the polyamic acid or its derivative used in the liquid crystal aligning agent of the present invention, the proportion of the diamine and / or dihydrazide in the total amount of the diamine and / Is preferably 90 mol%, more preferably 0 to 50 mol%.

The side chain type diamine will be explained. As the side chain group of the side chain type diamine, the following groups are exemplified.

The side chain group is preferably a group selected from the group consisting of alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy , Alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, and the like. The alkyl, alkenyl and alkynyl in these groups are all three or more carbon atoms. However, in alkyloxyalkyl, the number of carbon atoms in the whole group may be 3 or more. These groups may be linear or branched.

Subsequently, the ring may be substituted with at least one substituent selected from the group consisting of phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy, and phenylcarbonyl, provided that the terminal ring thereof has 1 or more carbon atoms, Cyclohexyloxyphenyl, cyclohexylphenylalkyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, (Cyclohexyl) phenyloxy, bis (cyclohexyl) oxy carbonyl, bis (cyclohexyl) phenyloxycarbonyl, And cyclohexyl bis (phenyl) oxycarbonyl, and the like.

Further, a group having two or more benzene rings, a group having two or more cyclohexane rings, or two or more rings composed of a benzene ring and a cyclohexane ring, each of which is independently a single bond, -O-, COO-, -OCO-, -CONH- or alkylene having 1 to 3 carbon atoms, and the terminal ring is substituted with alkyl having 1 or more carbon atoms, fluorine-substituted alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms, or alkoxyalkyl having 2 or more carbon atoms For example, a ring condensing group. Is effective as an airway side chain group having a steroid skeleton.

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

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} -, and m' is an integer of 1 to 12. Preferred examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene having 1 to 3 carbon atoms, particularly preferred examples are a single bond, -O-, -COO -, -OCO-, -CH ₂ O-, -CH ₂ - and -CH ₂ CH ₂ -. R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen may be substituted with -F And at least one -CH ₂ - may be replaced by -O-, -CH═CH-, or -C≡C-. Hydrogen of the phenyl _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, may be substituted with alkyl or alkoxy having a carbon number of 3 to 30 carbon atoms of 3 to 30. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para. That is, when the coupling position of the group " R ²⁵ -G ²⁶ - " is set to the first position, it is preferable that the two coupling positions are the third position and the fifth position or the second position and the fifth position.

In formula (DI-31-a), G 27, G 28 and G ²⁹ is a coupler, which are respectively a single bond, or an alkylene group having 1 to 12 carbon atoms independently, at least one of the alkylene -CH ₂ - May be substituted with -O-, -COO-, -OCO-, -CONH-, -CH = CH-. Ring B ²¹ , ring B ²² , ring B ^23, and ring B ²⁴ are each independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, and ring B ²¹ , ring B ²² , ring B ²³ And ring B ²⁴ , at least one hydrogen may be substituted with -F or -CH ₃ , s, t and u are each independently an integer of 0 to 2, the sum thereof is 1 to 5, and s , when t or u is 2, the two couplers in each parenthesis may be the same or different and the two rings may be the same or different. R ²⁶ is hydrogen, -F, -OH, alkoxy, -CN of fluorine-substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF _2, or -OCF ₃ , And at least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

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

In formula (DI-32) and formula (DI-33), G ³⁰ are each independently a single bond, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, respectively, R ³⁰ Is hydrogen, alkyl of 1 to 20 carbon atoms, or alkenyl of 2 to 20 carbon atoms. At least one hydrogen in the benzene ring in the formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl. A group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. 2 groups of the formula (DI-32) "- phenylene -G ³⁰ -O-" is one of bonded to position 3 of the steroid nucleus, and in that the other end is coupled to the 6-position of the steroid nucleus desirable. Formula (DI-33) 2 group of from the "- phenylene -G ³⁰ -O-", binding position of the benzene ring of the, with respect to the bonding position of the steroid nucleus, preferably in the meta-position or para-position, respectively . In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

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

Specific examples of the side chain type diamine are illustrated below. Examples of the diamines having side chains of the formulas (DI-31) to (DI-35) include the compounds represented by the following formulas (DI-31-1) to (DI-35-3).

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

In the formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl of 1 to 30 carbon atoms or alkoxy of 1 to 30 carbon atoms, preferably alkyl of 5 to 25 carbon atoms or alkyl Lt; / RTI > R ³⁵ is alkyl of 1 to 30 carbon atoms or alkoxy of 1 to 30 carbon atoms, preferably alkyl of 3 to 25 carbon atoms or alkoxy of 3 to 25 carbon atoms.

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

In the formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl of 1 to 20 carbon atoms or alkoxy of 1 to 20 carbon atoms, preferably alkyl of 3 to 20 carbon atoms, Lt; / RTI > R ³⁹ is hydrogen, -F, alkyl of 1 to 30 carbon atoms, an alkoxy _{group, -CN, -OCH 2 F, -OCHF} 2 or -OCF ₃ group of 1 to 30 carbon atoms, and preferably having a carbon number of 3 to 25 alkyl, or Alkoxy of 3 to 25 carbon atoms. And G ³³ is alkylene having 1 to 20 carbon atoms.

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

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

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

Formula (DI-34-1) ~ expression in (DI-34-12), R ⁴⁰ is hydrogen or alkyl of 1 to 20 carbon atoms, preferably hydrogen or alkyl of 1 to 10 carbon atoms, and R ⁴¹ is hydrogen Or an alkyl having 1 to 12 carbon atoms.

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

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

(DI-1-1) to (DI-16-1), (DIH-1-1) to (DIH-3-6) Diamines other than the diamines represented by the formulas (1) to (DI-35-3) may also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13).

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

In formula (DI-36-9) to formula (DI-36-11), e is an integer of 2 to 10, and in formula (DI-36-12), R ⁴³ is each independently hydrogen, -NHBoc or an -N (Boc) _2, at least one of R ⁴³ is ₂ -NHBoc or -N (Boc), in the formula (DI-36-13), R ⁴⁴ is -NHBoc or -N (Boc) _2, and , And m is an integer of 1 to 12. Wherein Boc is a tert-butoxycarbonyl group.

(DI-5-1), the formula (DI-7-3), the formula (DI-34-4) and the dihydroxy compound It is preferable to use a diamine represented by the formula (DI-34-7). In the formula (DI-5-1), a compound wherein m = 2, 4 or 6 is preferable, and a compound wherein m = 4 is more preferable. In the formula (DI-7-3), m = 2 Or 3, and n = 1 or 2 is preferable, m = 3 and n = 1 are more preferable.

(DI-5-1), (DI-5-17), and (DI-7-3), among the diamines and dihydrazides described above, Is preferably used. In the formula (DI-5-1), a compound wherein m = 2, 4 or 6 is preferable, and a compound wherein m = 4 is more preferable. In the formula (DI-7-3), a compound wherein m = 2 or 3 and n = 1 or 2 is preferable, and m = 3 and n = 1 are more preferable.

(DI-5-17), the formula (DI-5-30), and the formula (DI-13-1) out of the diamines and dihydrazides described above in order to improve the VHR of the liquid crystal display element. Diamine represented by the formula (DI-2-1), the formula (DI-5-1) and the formula (DI-13-1) is particularly preferable. Among them, in formula (DI-5-30), k = 2 is particularly preferable.

It is effective as one of the methods for preventing the baking by decreasing the volume resistivity of the liquid crystal alignment film and improving the relaxation rate of the residual charge (residual DC) in the alignment film. In the case of placing importance on this object, it is preferable to use a diamine represented by the formula (DI-5-13) among the above diamines and dihydrazides.

The polyamic acid or derivative thereof of the present invention can be selected without limitation from known photosensitive diamines. For example, azobenzene derivatives, stilbene derivatives, acetylene derivatives, coumarin derivatives, cinnamic acid derivatives, and benzophenone derivatives. Examples of such photosensitive diamine compounds include the following formulas (PDI-1) to (PDI-13).

In the formula (7-PDI), ⁵¹ R are each independently selected from _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, s are each independently an integer of 0 to 2. In formula (PDI-8), R ⁵² is independently a single bond, a straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, or -CONH-, and at least one -CH ₂ - may be substituted with -O-. R ⁵³ is independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH, and q is, independently of each other, an integer of 0 to 4. In formula (PDI-12), R ⁵⁴ is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be substituted with fluorine. In the formulas (PDI-1) to (PDI-8), a group in which the bonding position is not fixed to any carbon atom constituting the ring means that the bonding position in the ring is arbitrary.

(PDI-1), the formula (PDI-6) and the formula (PDI-7) are preferable from the viewpoint of further improving the orientation property of the liquid crystal in the photosensitive diamine. , And a diamine represented by the formula (PDI-7-2) are particularly preferable. Further, two or more photosensitive diamines may be used in combination in order to improve various characteristics such as electrical characteristics, afterimage characteristics, and the like.

The polyamic acid or derivative thereof of the present invention may further comprise a monoisocyanate compound in its monomer. By incorporating the monoisocyanate compound into the monomer, the terminal of the resulting polyamic acid or derivative thereof is modified to control the molecular weight. By using this terminal modification type polyamic acid or its derivative, for example, the effect of the present invention is not impaired and the application properties of the liquid crystal aligning agent can be improved. The content of the monoisocyanate compound in the monomer is preferably from 1 to 10 mol% based on the total amount of the diamine and the tetracarboxylic acid dianhydride in the monomer from the viewpoint of the above. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid and derivatives thereof of the present invention are obtained by reacting the tetracarboxylic dianhydride, the diamine compound and the aminosilane compound described above in a solvent. In this synthesis reaction, special conditions other than the selection of the raw materials are not required, and the conditions for usual polyamic acid synthesis can be applied as they are. The solvent to be used will be described later.

The liquid crystal aligning agent of the present invention may further contain other components other than the terminal-blocked polyamic acid or derivative thereof obtained by reacting the tetracarboxylic acid dianhydride, the diamine compound and the aminosilane compound. Other components include, for example, other polymers and compounds described below.

Examples of the other polymer include polyamic acid or a derivative thereof (hereinafter referred to as "other polyamic acid or derivative thereof") obtained by reacting tetracarboxylic dianhydride with diamine, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, Polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates. These polymers may be used alone or in combination of two or more. Among them, other polyamic acid or derivatives thereof and polysiloxane are preferable, and other polyamic acid or derivatives thereof are more preferable.

In the alignment agent in which the polyamic acid or its derivative of the present invention is blended with other polyamic acid or a derivative thereof, the structure and the molecular weight of each polymer are controlled, and the preliminary drying is performed , The polyamic acid or its derivative component [A] of the present invention and the other polyamic acid or its derivative component [B]. This can be controlled by using a 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 in a mixed polymer. Confirmation of layer separation can be confirmed by that the surface energy of the formed alignment film is equal to or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the [A] component.

The diamine used for synthesizing the other polyamic acid or its derivative preferably contains 30 mol% or more, and more preferably 50% or more, of the aromatic diamine with respect to the total diamine.

The other polyamic acid or derivative thereof can be synthesized in accordance with the method described below as a method for synthesizing polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention.

The proportion of the [A] component relative to the total amount of the polyamic acid or derivative thereof (component [A]) and the other polyamic acid or derivative thereof (component [B]) of the present invention is preferably 10% by weight to 100% And more preferably 20% by weight to 100% by weight.

As the polysiloxane, there can be mentioned, for example, Japanese Patent Publication Nos. 2009-036966, 2010-185001, 2011-102963, Japanese Patent Laid-Open No. 2011-253175, Japanese Laid-Open Patent Application No. 2012-159825, International Publication 2009/148099, International Publication 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International Publication 2012/165354, and the like.

≪ Alkenyl-substituted 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 electrical characteristics of the liquid crystal display element for a long period of time. The alkenyl-substituted nadimide compound may be used singly or in combination of two or more. The content of the alkenyl-substituted nadimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight, based on the polyamic acid or its derivative, Is more preferable.

The nadimide compound will be described in detail below.

The alkenyl-substituted nadimide compound is preferably a compound capable of dissolving in the solvent for dissolving the polyamic acid or derivative thereof used in the present invention. An example of such an alkenyl-substituted nadimide compound is a compound represented by the following formula (NA).

In formula (NA), L ¹ and L ² each independently represent hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms or benzyl , and n is 1 or 2.

In the formula (NA), n = If = 1, W is alkyl, alkenyl, 2 to 6 carbon atoms having 1 to 12 carbon atoms, having a carbon number of 5-8 cycloalkyl, a 6 to 12 carbon atoms, aryl, benzyl, -Z ¹ - (O) _r - (Z ² O) _k -Z ³ -H wherein Z ¹ , Z ² and Z ³ are each independently an alkylene having 2 to 6 carbon atoms, r is 0 or 1, (Z ⁴ ) _r -BZ ⁵ -H wherein Z ⁴ and Z ⁵ are each independently an alkylene group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, is alkylene, B is phenylene, and, r is a group represented by 0 or 1), -BTBH (wherein, B is phenylene, and, T is _{-CH 2 -, -C (CH 3} ) ₂ -, -O-, -CO-, -S-, or -SO ₂ -), or a group in which one to three hydrogens of these groups are substituted with -OH.

In this case, preferable W is an alkyl group having 1 to 8 carbon atoms, alkenyl having 3 to 4 carbon atoms, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbon atoms, phenyloxyphenyl, phenylmethylphenyl, Propylidenephenyl, and groups in which one or two hydrogens of these groups are substituted with -OH.

In the formula (NA), when n = 2, W represents an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -Z ¹ -O- (Z ² O ) _k -Z ³ - (wherein, Z ¹ ~Z ^3, and k is the mean of the group represented by the same) as described above, -Z ⁴ -BZ ⁵ - (wherein, Z ^4, Z ^5, and B is the mean -B- (OB) _r -T- (BO) _r -B- wherein B is phenylene, T is alkylene having 1 to 3 carbon atoms, -O- or -SO ₂ -, the meaning of r is the same as defined above), or a group in which one to three hydrogens of these groups are substituted with -OH.

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

Such an alkenyl-substituted nadimide compound is a compound obtained by maintaining an alkenyl-substituted nadic anhydride derivative and a diamine at a temperature of 80 to 220 캜 for 0.5 to 20 hours, for example, as disclosed in Japanese Patent No. 2729565 Or commercially available compounds can be used.

<Compound Having Radically Polymerizable Unsaturated Double Bond>

For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The compound having a radically polymerizable unsaturated double bond may be a single compound or two or more compounds. The compound having a radically polymerizable unsaturated double bond does not contain an alkenyl-substituted nadimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, more preferably 1 to 70% by weight, based on the polyamic acid or a derivative thereof, More preferably 50% by weight.

The ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound is such that the ion density of the liquid crystal display element is reduced, the increase of the ion density over time is suppressed, The compound having a radically polymerizable unsaturated double bond / alkenyl-substituted nadimide compound in a weight ratio of preferably 0.1 to 10, more preferably 0.5 to 5.

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

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

Specific examples of the (meth) acrylic acid ester include (meth) acrylate such as cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the bifunctional (meth) acrylic acid ester include ethylenebisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200 (all trade names), products of Toagosei Chemical Industry Co., KAYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684 (all trade names), products of Nippon Yakusho Co., Ltd., V260, V312 and V335HP (all trade names), products of Osaka Organic Chemical Industry Co., Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA (both trade names) manufactured by Kugo Kogyo Co., Ltd. can be mentioned.

Specific examples of the trifunctional or more polyfunctional (meth) acrylic acid esters include 4,4'-methylene bis (N, N-dihydroxyethylene acrylate aniline), Aronix M manufactured by Doa Synthetic Chemical Industry Co., KAYARADTMPTA, KAYARADDPCA-20, and KAYARADDPCA-20, all of which are products of Nippon Yakuza Co., Ltd., Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M- KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120 (all trade names), and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylic acid amide derivative include N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propyl acrylamide, Nn-propylmethacrylamide, N-cyclopropyl acrylamide, N- Tetrahydrofurfuryl acrylamide, N-tetrahydrofuryl methacrylamide, N-ethylacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N- N-methylacrylamide, N, N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butyl methacrylamide, N- (iso- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethyl methacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, (Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N'-methylenebis methacrylamide .

Among the above (meth) acrylic acid derivatives, preferred are N, N'-methylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, ethylenebisacrylate and 4,4'- Dihydroxyethylene acrylate aniline) is particularly preferred.

Examples of the bismaleimide include BMI-70 and BMI-80 (all trade names) manufactured by K-I Hwaseong Co., Ltd. and BMI-1000, BMI-3000, BMI -4000, BMI-5000 and BMI-7000 (all trade names).

<Epoxy Compound>

For example, the liquid crystal aligning agent of the present invention is a liquid crystal aligning agent which, for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, comprises (a) a silane coupling agent containing at least one epoxy ring in the molecule, and (b) And may further contain an epoxy compound other than a compound containing two or more epoxy rings. The epoxy compound may be one kind of compound or two or more kinds of compounds. The content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight, based on the polyamic acid or the derivative thereof, Do.

Hereinafter, the epoxy compound will be specifically described.

Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide (Nonafluoro-n-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N, N- Diglycidyl aniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

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

Examples of other monomers copolymerizable with the monomer having an epoxy ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobutyl (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. Specific examples of preferred copolymers of monomers having an epoxy ring and other monomers include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl Methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl- 3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

Further, for example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include polymer compounds other than polyamic acid and derivatives thereof, and low-molecular compounds, and they can be selected depending on the purpose.

For example, the polymer compound may be a polymer compound soluble in an organic solvent. The addition of such a polymer compound to the liquid crystal aligning agent of the present invention is preferable from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone modified polyurethanes, and silicone modified polyesters.

Examples of the above-mentioned low-molecular compounds include: 1) a surfactant suited for this purpose when it is desired to improve the coating property, 2) an antistatic agent when it is necessary to improve the charge prevention, 3) A silane coupling agent or a titanium-based coupling agent, and (4) an imidation catalyst when imidization proceeds at a low temperature.

The silane coupling agent may further contain a silane coupling agent other than the aminosilane compounds described in the above formulas (AS-1) to (AS-5). For example, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

Examples of imidization catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline, and hydroxy substituted aniline; Substituted substituted isoquinoline, substituted isoquinoline, substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, and the like can be used. Examples of the substituted pyrrolidine derivative include pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, Of cyclic amines. Wherein the imidation catalyst is at least one selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline desirable.

The addition amount of the silane coupling agent is usually 0 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the polyamic acid or the derivative thereof.

The addition amount of the imidation catalyst is usually 0.01 to 5 equivalents (equivalent) to the carbonyl group of the polyamic acid or its derivative, preferably 0.05 to 3 equivalents.

The amount of other additives to be added varies depending on the application, but is usually 0 to 100 parts by weight, preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the total amount of the polyamic acid or its derivative.

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

The molecular weight of the polyamic acid or derivative thereof of the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000, in terms of weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or its derivative can be determined by measurement according to a gel permeation chromatography (GPC) method.

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

Further, for example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of the application of the liquid crystal aligning agent and the adjustment of the concentration of the polyamic acid or its derivative. The solvent can be applied without particular limitation as long as it is a solvent capable of dissolving a polymer component. The solvent widely includes a solvent commonly used in the production process or application of a polymer component such as polyamic acid and soluble polyimide, and can be appropriately selected depending on the purpose of use. The solvent may be one kind or two or more kinds of mixing agents.

Examples of the solvent include a solvent for the above-described polyamic acid or a derivative thereof and other solvents for the purpose of improving coatability.

Examples of the aprotic polar organic solvent that is a hydrophilic solvent for a polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, And lactones such as dimethylacetamide, dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide and? -Butyrolactone.

Examples of other solvents for improving the coating properties include ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone and ethylene glycol monobutyl ether, diethylene glycol mono Propylene glycol monoalkyl ether such as ethylene glycol monoalkyl ether or ethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenylacetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monobutyl ether, diethyl malonate or the like , Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, and ester compounds such as acetates thereof.

Among them, the solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, dimethylimidazolidinone,? -Butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, Monomethyl ether, and dipropylene glycol monomethyl ether are particularly preferred.

The concentration of the polyamic acid in the alignment agent of the present invention is preferably 0.1 to 40% by weight. When this alignment agent is applied to a substrate, it is sometimes necessary to dilute the contained polyamic acid 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, it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the varnish, in order to suppress unevenness in application and pinhole.

The viscosity of the liquid crystal aligning agent of the present invention differs depending on the method of application, the concentration of the polyamic acid or its derivative, the type of the polyamic acid or derivative thereof, and the type and ratio of the solvent. For example, it is 5 to 100 mPa · s (more preferably 10 to 80 mPa · s) in the case of application by a printing machine. If it is smaller than 5 mPa · s, it is difficult to obtain a sufficient film thickness. If it exceeds 100 mPa · s, printing unevenness may become large. In the case of applying by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measuring method and measured (measured temperature: 25 ° C) using, for example, a rotational viscometer (TVE-20L manufactured by Toki Industry Co., Ltd.).

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 above-mentioned liquid crystal aligning 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 aligning agent of the present invention, a step of heating and drying, and a step of heating and firing. In the liquid crystal alignment film of the present invention, anisotropy may be imparted by rubbing a film obtained through a heating and drying step and a heating and firing step, as described later, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating process, the heating and drying process, or by irradiating light after the heating and firing process. It is also possible to use a liquid crystal alignment film for VA which does not undergo rubbing treatment.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display element in the same manner as in the production of a normal liquid crystal alignment film. Substrate, a glass substrate with such as ITO (IndiumTinOxide), IZO (In2O 3 -ZnO), IGZO (In-Ga-ZnO 4) electrode and a color filter, such as electrodes may be provided.

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

The heating and drying process is generally known as a heating process in an oven or an infrared heating process, a heating process on a hot plate, or the like. The heat drying step is preferably performed at a temperature within a range in which evaporation of the solvent is possible, and more preferably at a relatively low temperature with respect to the temperature in the heat-firing step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C and more preferably in the range of 50 ° C to 120 ° C.

The heating and firing step may be carried out under the conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closing reaction. The baking of the coating film is generally known as a heating process in an oven or an out-room furnace, a heating process on a hot plate, and the like. These methods are also applicable to the present invention. In general, the temperature is preferably about 100 to 300 캜 for 1 minute to 3 hours, more preferably 120 to 280 캜, and even more preferably 150 to 250 캜.

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 can be formed by applying anisotropy to a coated film by irradiating linearly polarized light or unpolarized light of radiation after heating and drying the coated film and heating and firing the film. Alternatively, the coating film can be formed by heating and drying, heating and baking, and then irradiating linearly polarized light or unpolarized light of radiation. From the standpoint of the orientation property, it is preferable that the irradiation step of the radiation is performed before the heating and firing step.

In addition, in order to enhance the liquid crystal alignment capability of the liquid crystal alignment film, it is also possible to irradiate linearly polarized light or unpolarized light of radiation while heating the coating film. The irradiation of the radiation may be performed in a step of heating and drying the coating film or a step of heating and firing, or may be carried out between the heating and drying step and the heating and firing step. The heating and drying temperature in the above step is preferably in the range of 30 ° C to 150 ° C and more preferably in the range of 50 ° C to 120 ° C. The heating and firing temperature in the above step is preferably in the range of 30 ° C to 300 ° C and more preferably in the range of 50 ° C to 250 ° C.

As the radiation, for example, ultraviolet rays or visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light of 300 to 400 nm are preferable. In addition, linearly polarized light or unpolarized light can be used. The light is not particularly limited as long as it is a light capable of imparting liquid crystal aligning ability to the coating film, but linear polarization is preferable when it is intended to exhibit a strong alignment regulating force with respect to the liquid crystal.

The liquid crystal alignment film of the present invention can exhibit a high liquid crystal aligning ability even with light irradiation with low energy. Dose of the linearly polarized light in the irradiation step is preferably 0.05~20 J / cm ^2, and more preferably 0.5~10 J / cm ^2. The wavelength of linearly polarized light is preferably 200 to 400 nm, more preferably 300 to 400 nm. The irradiation angle with respect to the film surface of the linearly polarized light is not particularly limited, but when it is intended to exhibit a strong alignment regulating force against the liquid crystal, it is preferable that the film is perpendicular to the film surface from the viewpoint of shortening the orientation treatment time. Further, the liquid crystal alignment film of the present invention can orient the liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

In the case where the pretilt angle is intended to be expressed, light to be irradiated to the film may be linearly polarized light or non-lighted light as described above. When the pretilt angle is to be developed, the amount of light irradiated to the film is preferably 0.05 to 20 J / cm ² , more preferably 0.5 to 10 J / cm ² , and the wavelength is preferably 250 to 400 nm , And particularly preferably from 300 to 380 nm. When the pretilt angle is intended to be developed, the irradiation angle of the light irradiated to the film on the film surface is not particularly limited, but it is preferable that the irradiation angle is 30 ° to 60 ° from the viewpoint of shortening the orientation treatment time.

Examples of the light source used in the step of irradiating linearly polarized light or unpolarized light of radiation include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a Deep UV lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, and a microwave excitation non-electrode lamp.

The liquid crystal alignment film of the present invention is preferably obtained by a method including the steps other than the above-described steps. For example, the liquid crystal alignment film of the present invention requires a step of cleaning the film after baking or irradiation with a cleaning liquid, However, the cleaning process can be provided for other processes.

Examples of the cleaning method using a cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning, and the like. Examples of the cleaning liquid include pure water or various alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, aromatic hydrocarbons such as methylene chloride, and the like. Halogenated solvents, ketones such as acetone, methyl ethyl ketone, etc., but are not limited thereto. Needless to say, these cleaning liquids are sufficiently purified so that a small amount of impurities are used. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention.

Annealing treatment by heat or light can be used before or after the heat firing step, before or after the rubbing step, or before or after irradiation with polarized or unpolarized light, in order to enhance the liquid crystal alignment capability of the liquid crystal alignment film of the present invention have. In the annealing treatment, the annealing temperature is 30 to 180 캜, preferably 50 to 150 캜, and the time is preferably 1 to 2 hours. Examples of the annealing light used in the annealing process include a UV lamp, a fluorescent lamp, and an LED lamp. The amount of light to be irradiated is preferably 0.3 to 10 J / cm ² .

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, 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 stepped system or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having anisotropy particularly in a large orientation. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in Japanese Laid-Open Patent Publication No. 2005-275364. It can also be evaluated by a method using ellipsometry as shown in the following examples. Specifically, the birefringence phase difference value of the liquid crystal alignment film can be measured by the spectroscopic ellipsometer. The birefringence phase difference value of the film becomes larger in proportion to the degree of orientation of the polymer main chain. That is, having a large birefringence phase difference value has a large degree of orientation, and when used as a liquid crystal alignment film, it is considered that an alignment film having a larger anisotropy has a large alignment restricting force for the liquid crystal composition.

The liquid crystal alignment film of the present invention is characterized by being less colored and having a high transmittance. The transmittance can be evaluated using an ultraviolet visible spectrophotometer. In order to exhibit good display characteristics, the transmittance calculated from the average value of the absorbance at 380 nm to 780 nm is preferably 85% or more, more preferably 87% or more.

The liquid crystal alignment film of the present invention can be preferably used for a liquid crystal display device of a transverse electric field system. When used in a liquid crystal display device of a transverse electric field system, the lower the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark (dark) state and the contrast is improved. The Pt angle is preferably 0.1 DEG or less.

The alignment film of the present invention can be used for alignment control of optical compensation materials and all other liquid crystal materials in addition to alignment of liquid crystal compositions for liquid crystal displays. Further, since the alignment film of the present invention has a large anisotropy, it can be used solely for optical compensation materials.

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

The present invention provides a liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one or both sides of opposing surfaces of the pair of substrates; a liquid crystal alignment film formed on the opposing surfaces of the pair of substrates; And a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is an alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Such electrodes include, for example, a vapor-deposited film of ITO or metal. The electrode may be formed on the entire surface of one side of the substrate, or may be formed into a desired shape that is patterned, for example. The desired shape of the electrode is, for example, a comb-shaped or zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. For example, in the case of an IPS type liquid crystal display device, electrodes are disposed on one side of the pair of substrates, and in the case of other liquid crystal display devices, the pair of electrodes Electrodes are disposed on both sides of the substrate. And the liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed in a form in which the liquid crystal composition is sandwiched by the pair of substrates on which the liquid crystal alignment film is formed and the surfaces thereof face each other. In the formation of the liquid crystal layer, a spacer, such as fine particles or a resin sheet, which is interposed between the pair of substrates and forms an appropriate gap can be used as needed.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy may be used. A preferred liquid crystal composition having a positive dielectric anisotropy is disclosed in JP 3086228, JP 2635435, JP 5-501735, JP 08-157826, JP 8-231960, JP 8825272A1 Japanese Patent Application Laid-Open No. 9-302346 (EP806466A1), Japanese Patent Application Laid-Open No. 8-199168 (EP722998A1), Japanese Patent Application Laid-Open Nos. 9-235552, 9-255956, 9-241643 (EP885271A1) , JP-A 10-204016 (EP844229A1), JP-A 10-204436, JP-A 10-231482, JP-A 2000-087040, JP-A 2001-48822, etc. For example.

As a preferable example of the liquid crystal composition having negative dielectric anisotropy described above, JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A- 8-104869, 10-168076, 10-168453, 10-236989, 10-236990, 10-236992, 10- Japanese Patent Application Laid-Open No. Hei 10-237704, Japanese Patent Application Laid-open No. Hei 10-237035, Japanese Patent Application Laid-open No. Hei 10-237075, Japanese Patent Application Laid-Open Nos. 10-237076 and 10-237448 (EP967261A1), Japanese Patent Laid-Open Nos. 10-287874, 10-287875, 10-291945, 11-029581 Japanese Patent Application Laid-Open No. 11-080049, Japanese Patent Application Laid-Open No. 2000-256307, Japanese Laid-Open Patent Application No. 2001-019965, Japanese Laid-Open Patent Application No. 2001-072626 , Japanese Laid-Open Patent Publication No. 2001-192657, Japanese Laid-Open Patent Application No. 2010-037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Laid-Open Patent Application No. 2010-537010, Japanese Laid-Open Patent Application No. 2012-077201, 084362 and the like.

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

[Example]

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

The solvent and liquid crystal composition used in the examples are as follows.

<Solvent>

NMP: N-methyl-2-pyrrolidone

DMI: 1,3-dimethyl-2-imidazolidinone

GBL:? -Butyrolactone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

&Lt; Liquid crystal composition &

Positive liquid crystal composition:

Property: NI 100.1 ℃; Δε 5.1; ? N 0.093; η 25.6 mPa · s.

Negative Liquid Crystal Composition:

Property Value: NI 75.7 ℃; Δε -4.1; [Delta] n 0.101; η 14.5 mPa · s.

<Evaluation method>

1. Weight average molecular weight (Mw)

The weight average molecular weight of the polyamic acid was determined by the GPC method using a 2695 separation module · 2414 differential refractometer (manufactured by Waters) and calculating 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 became about 2% by weight. The column was a HSPgel RT MB-M (manufactured by Waters), and the mixed solution was measured as a developing agent under the conditions of a column temperature of 50 ° C and a flow rate of 0.40 mL / min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

2. Measurement of film thickness of orientation film

And spectral Ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.).

3. Pencil hardness measurement

The hardness of the orientation film was measured using a pencil scratch tester C221 (manufactured by Yoshimitsu Precision Machinery Co., Ltd.), and the pencil hardness was determined according to JIS K 5600-5-4 standard. The pencil hardness is preferably H or more.

4. Foreign matter test

The foreign substance test of the liquid crystal display element described later was performed using FORCE MEASUREMENT, DS2-50N (manufactured by Imada Co., Ltd.). A force of 9.8 N was applied to the produced liquid crystal display element at 60 times / minute for 1 minute. The liquid crystal display element was observed by a microscope, and the presence or absence of a foreign substance was confirmed after pressing.

5. Contrast

The contrast of a liquid crystal device to be described later was evaluated using a luminance meter (YOKOGAWA 3298F). A liquid crystal display element was placed under a polarization microscope under a crossed Nicol state, and the minimum luminance was measured as black luminance. Next, an arbitrary rectangular wave voltage was applied to the device, and the maximum luminance was measured as white luminance. The value of white luminance / black luminance was defined as a contrast. If the contrast is less than 2500, it is defective. If the contrast is 2500 or more, it is good. If the contrast is 3000 or more, the contrast is the best.

6. AC afterimage measurement

The luminance-voltage characteristic (B-V characteristic) of the liquid crystal display element described later was measured. This is regarded as a luminance-voltage characteristic before the stress application: B (before). Next, an AC voltage of 4.5 V and 60 Hz was applied to the device for 20 minutes, followed by a short circuit for 1 second, and the luminance-voltage characteristic (B-V characteristic) was measured again. This is regarded as a luminance-voltage characteristic after the application of the stress: B (after). Based on these values, the luminance change rate? B (%

B (%) = [B (after) - B (before)] / B (before) (Equation 1)

Using the following formula. These measurements were made by referring to the pamphlet of International Publication No. 2000/43833. It can be seen that the smaller the value of? B (%) at the voltage of 0.75 V is, the more the AC afterimage can be prevented. It is preferable that the value is 3.0% or less.

<Synthesis of polyamic acid>

[Synthesis Example A-1]

(PDI-7-1) and 0.992 g of a diamine represented by formula (PDI-7-1) in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a feed inlet and a nitrogen gas inlet, 1.011 g of diamine, 0.199 g of aminosilane of formula (AS-5), and 24.0 g of dehydrated NMP were placed and dissolved under stirring in a dry nitrogen stream. Then 3.798 g of tetracarboxylic dianhydride having an m of 8 in the formula (AN-4-17) and 20.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. 30.0 g of dehydrated NMP and 20.0 g of BC were added to this reaction solution to obtain a polyamic acid solution having a polymer solid content concentration of 6% by weight. This polyamic acid solution was designated as PA-1. The weight average molecular weight of the polyamic acid contained in PA-1 was 26,300.

[Synthesis Examples A-2 to A-30 and Synthesis Examples B-1 to B-14]

(PA-2) to (PA-2) having a polymer solid content concentration of 6% by weight in accordance with Synthesis Example 1, except that the tetracarboxylic dianhydride, diamine, and solvent composition were changed as shown in Tables 1 and 2, 30) and (PB-1) to (PB-14) were prepared.

[Table 1]

From the table, and the AN-4-17 m is 8, and the DI-5-1 m is 4, R ⁴¹ in the DI-34-4 is a C ₅ H _11, R ⁴¹ is the DI-34-7 C ₇ is the H _15.

The molar percentage of the diamine converted to the aminosilane is 1/2 of the numerical value in the table.

[Table 1 (continued)]

From the table, and a PAN-9 and m is 4, and the AN-4-17 and m is 8, the DI-5-1 and m is 4, R ⁴¹ in the DI-34-4 is a C ₇ H _15.

The molar percentage of the diamine converted to the aminosilane is 1/2 of the numerical value in the table.

[Table 2]

The molar percentage of the diamine converted to the aminosilane is 1/2 of the numerical value in the table.

<Polymer blending>

A polyamic acid solution (PB-1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example A-1 and a polyamic acid solution (PB-1) having a polymer solid concentration of 6% by weight prepared in Synthesis Example B- 1) were mixed at a mixing ratio by weight ratio [A] / [B] = 3.0 / 7.0. The obtained polyamic acid solution is referred to as PC-1.

(PC-2) to (PC-36) having a polymer solid concentration of 6 wt% based on PC-1 were prepared except that the kinds of the polyamic acid [A] and [B] . PC-1, &lt; / RTI &gt;

[Table 3]

Additive (EPX-1) was added to a polyamic acid solution (PA-1) having a polymer solid content concentration of 6% by weight at a ratio of 20 parts by weight per 100 parts by weight of the polymer. The obtained polyamic acid solution is referred to as PD-1.

Polyamic acid solutions (PD-2) to (PD-39) having a polymer solid content concentration of 6% by weight were prepared in accordance with PD-1 except that the polyamic acid to be mixed and the kind and amount of additives were changed. PD-1, &lt; / RTI &gt;

[Table 4]

&Lt; Measurement method of substrate for measurement and pencil hardness measurement >

[Example 1]

A mixed solvent of NMP / BC = 77/20 (weight ratio) was added to a polyamic acid solution (PA-1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 1 and diluted to a polymer solid concentration of 4% made. The liquid crystal aligning agent was applied to a glass substrate by a spinner (spin coater (1H-DX2), manufactured by Mikasa Chemical Co., Ltd.). Incidentally, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including the following examples and comparative examples, so that the orientation film had the following film thickness. After the coating, the coating was heated and dried at 70 DEG C for 80 seconds on a hot plate (EC hot plate (EC-1200N) manufactured by As One Corporation). Then, using Multilight ML-501C / B manufactured by Ushio Electric Co., linearly polarized light of ultraviolet rays was irradiated from the perpendicular direction to the substrate through a polarizing plate. The exposure energy at this time was measured using UV ultraviolet light intensity meter UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., and the light quantity was measured to be 1.0 ± 0.1 J / cm ² at a wavelength of 365 nm , And the exposure time was adjusted. Subsequently, the substrate was heat-treated at 230 占 폚 for 15 minutes in a clean oven (Clean oven (PVHC-231) manufactured by Espace Kabushiki Kaisha) to form an alignment film having a thickness of 100 ± 10 nm. The pencil hardness of the obtained substrate was measured and found to be H.

&Lt; Fabrication method of FFS cell, confirmation of flow orientation, confirmation of foreign matter generation, and measurement of residual image after AC &

The surfaces on which the alignment films of the two substrates having the alignment films formed on the substrate are formed face each other so that the rubbing direction is parallel to each alignment film and a gap for injecting the liquid crystal composition is formed between the alignment films facing each other , And an empty FFS cell having a cell thickness of 4 탆 was assembled. The positive type liquid crystal composition was vacuum-injected into the fabricated blank FFS cell to produce an FFS liquid crystal display device. When the orientation of the liquid crystal in the obtained liquid crystal display element was confirmed, the flow orientation could not be observed. Subsequently, when the liquid crystal display element after the foreign matter test was observed with a microscope, the generation of foreign matter could not be observed. Further, the contrast value was measured to be 2750, and the AC residual image was measured, and the ΔB was 2.6%.

[Examples 2 to 35]

Except that the polyamic acid solution shown in Table 5-1 was used, the substrate for measurement was prepared by the method according to Example 1, and the pencil hardness was measured. Further, FFS cells were fabricated by the method according to Example 1, and flow orientation confirmation, foreign matter test, contrast measurement and AC afterimage measurement were performed. The measurement results are shown in Table 5-1.

[Comparative Examples 1 to 4]

Except that the polyamic acid solution shown in Table 5-1 was used, the substrate for measurement was prepared by the method according to Example 1, and the pencil hardness was measured. Further, FFS cells were fabricated by the method according to Example 1, and flow orientation confirmation, foreign matter test, contrast measurement and AC afterimage measurement were performed. The measurement results are shown in Table 5-1 together with Examples 1 to 32.

[Table 5-1]

As shown in Table 5-1, when Examples 1 to 35 and Comparative Examples 1 to 4 are compared, when the present invention is applied to an FFS liquid crystal display device, it is possible to control the generation of foreign substances, It is possible to maintain the AC afterimage characteristic.

[Examples 36 to 53]

A substrate for measurement was prepared in the same manner as in Example 1 except that the polyamic acid solution shown in Table 5-2 was used and the pencil hardness was measured. The results of the obtained pencil hardness are shown in Table 5-2.

An FFS liquid crystal display device was produced in the same manner as in Example 1 except that the above negative type liquid crystal composition was vacuum-injected instead of the positive type liquid crystal composition. The results of the flow orientation confirmation, the foreign matter test, the contrast measurement and the AC afterimage measurement are shown in Table 5-2.

[Table 5-2]

As shown in Table 5-2, when the present invention is applied to an FFS liquid crystal display element even when a negative type liquid crystal composition is used, it is possible to maintain the liquid crystal alignment property, the alignment stability, the contrast, and the after- .

[Example 54]

A mixed solvent of DMI / BC = 74/20 (weight ratio) was added to a polyamic acid solution (PC-5) having a blended polymer solid content concentration of 6% by weight and diluted to a polymer solid content concentration of 4% by weight to prepare a liquid crystal aligning agent. The liquid crystal aligning agent was applied to a glass substrate by a spinner (spin coater (1H-DX2), manufactured by Mikasa Chemical Co., Ltd.). Incidentally, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including the following examples and comparative examples, so that the orientation film had the following film thickness. After the coating, the coating was heated and dried at 70 DEG C for 80 seconds on a hot plate (EC hot plate (EC-1200N) manufactured by As One Corporation). Then, using Multilight ML-501C / B manufactured by Ushio Electric Co., linearly polarized light of ultraviolet rays was irradiated from the perpendicular direction to the substrate through a polarizing plate. The exposure energy at this time was measured by using UV ultraviolet spectrometer UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., and the light quantity was measured to be 0.5 ± 0.1 J / cm ² at a wavelength of 365 nm , And the exposure time was adjusted. During ultraviolet exposure, the substrate temperature was heated to 50 占 폚. Subsequently, the substrate was heated and fired at 230 占 폚 for 15 minutes in a clean oven (Clean oven (PVHC-231) manufactured by Espace Kabushiki Kaisha) to form an alignment film having a thickness of 100 nm ± 10 nm. The pencil hardness of the resulting substrate was measured and found to be 2H.

The surfaces on which the alignment films of the two substrates on which the alignment films were formed were formed so as to face each other so that the polarizing directions of the ultraviolet rays irradiated to the respective alignment films were parallel to each other and also the spaces for injecting the liquid crystal composition between the facing alignment films were formed To prepare a blank FFS cell having a cell thickness of 4 탆. The above-mentioned positive type liquid crystal composition was vacuum-injected into the fabricated blank FFS cell to produce an FFS liquid crystal display device. When the orientation of the liquid crystal in the obtained liquid crystal display element was confirmed, the flow orientation could not be observed. Subsequently, when the liquid crystal display element after the foreign matter test was observed with a microscope, the generation of foreign matter could not be observed. The contrast value was measured to be 3270, and the AC residual image was measured, and the ΔB was 1.9%.

[Examples 55 to 69]

A measurement substrate was prepared in the same manner as in Example 54 except that the polyamic acid solution shown in Table 5-3 was used, and the pencil hardness was measured. Further, an FFS cell was fabricated by the method according to Example 54, and flow orientation confirmation, foreign matter test, contrast measurement and AC afterimage measurement were performed. The measurement results are shown in Table 5-3 including Example 54. [

[Table 5-3]

As shown in Table 5-3, when the present invention is applied to a liquid crystal display element even when the temperature of the substrate is heated to 50 占 폚 during ultraviolet exposure, in the FFS liquid crystal display element, the liquid crystal orientation , Orientation stability, contrast, and AC afterimage characteristics can be maintained.

[Example 70]

A mixed solvent of NMP / BC = 74/20 (weight ratio) was added to a polyamic acid solution (PC-6) having a polymer solid content concentration of 6 wt% prepared by blending and diluted to a polymer solid concentration of 4 wt% to prepare a liquid crystal aligning agent. The liquid crystal aligning agent was applied to a glass substrate by a spinner (spin coater (1H-DX2), manufactured by Mikasa Chemical Co., Ltd.). Incidentally, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including the following examples and comparative examples, so that the orientation film had the following film thickness. After the coating, the coating was heated and dried at 70 DEG C for 80 seconds on a hot plate (EC hot plate (EC-1200N) manufactured by As One Corporation). Subsequently, linearly polarized ultraviolet light was irradiated from a perpendicular direction to the substrate through a polarizing plate by using a UV lamp (UVL-1500M2-N1) manufactured by Ushio Electric Co., Ltd. The exposure energy at this time was measured using UV ultraviolet spectrometer UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., and the light quantity was measured to be 1.0 ± 0.1 J / cm ² at a wavelength of 365 nm , And the exposure time was adjusted. Subsequently, the substrate was heated and fired at 230 占 폚 for 15 minutes in a clean oven (Clean oven (PVHC-231) manufactured by Espace Kabushiki Kaisha) to form an alignment film having a thickness of 100 nm ± 10 nm. Finally, the heated substrate was subjected to heating annealing at 120 占 폚 for 30 minutes in a clean oven. The pencil hardness of the resulting substrate was measured and found to be 2H.

The surfaces on which the alignment films of the two substrates on which the alignment films were formed were formed so as to face each other so that the polarizing directions of the ultraviolet rays irradiated to the respective alignment films were parallel to each other and also the spaces for injecting the liquid crystal composition between the facing alignment films were formed To prepare a blank FFS cell having a cell thickness of 4 탆. The positive type liquid crystal composition was vacuum-injected into the fabricated blank FFS cell to produce an FFS liquid crystal display device. When the orientation of the liquid crystal in the obtained liquid crystal display element was confirmed, the flow orientation could not be observed. Subsequently, when the liquid crystal display element after the foreign matter test was observed with a microscope, the generation of foreign matter could not be observed. Further, the value of contrast was measured to be 3230, and the after-image of the AC was measured and found to be 1.7%.

[Examples 71 to 81]

A substrate for measurement was prepared in the same manner as in Example 70 except that the polyamic acid solution shown in Table 5-4 was used, and the pencil hardness was measured. Further, an FFS cell was fabricated by the method according to Example 70, and flow orientation confirmation, foreign matter test, contrast measurement and AC afterimage measurement were performed. The measurement results are shown in Table 5-4 including Example 70. [

[Table 5-4]

As shown in Table 5-4, when the present invention is applied to a liquid crystal display element even when a UV lamp (UVL-1500M2-N1) manufactured by Ushio Electric Co., Ltd. is used at the time of ultraviolet irradiation, , It is possible to maintain the liquid crystal alignment property, the alignment stability, the contrast and the after-image characteristic while controlling the generation of foreign substances.

[Example 82]

A mixed solvent of NMP / BC = 77/20 (weight ratio) was added to a polyamic acid solution (PC-1) having a polymer solid content concentration of 6 wt% prepared by blending and diluted to a polymer solid content concentration of 3.5 wt% to prepare a liquid crystal aligning agent. The liquid crystal aligning agent was applied to a glass substrate by an ink-jet applying apparatus (DMP-2831, manufactured by Fuji Film Co., Ltd.). Then, the droplet gap and the cartridge application voltage were adjusted so that the alignment film had the following film thicknesses. After coating, the coating was heated and dried at 60 占 폚 for 80 seconds on a hot plate (EC hot plate (EC-1200N) manufactured by As One Corporation). Then, using Multilight ML-501C / B manufactured by Ushio Electric Co., linearly polarized light of ultraviolet rays was irradiated from the perpendicular direction to the substrate through a polarizing plate. The exposure energy at this time was measured using UV ultraviolet spectrometer UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., and the light quantity was measured to be 1.0 ± 0.1 J / cm ² at a wavelength of 365 nm , And the exposure time was adjusted. Subsequently, the substrate was heat-treated at 230 占 폚 for 15 minutes in a clean oven (Clean oven (PVHC-231), manufactured by Espace Kabushiki Kaisha) to form an alignment film having a thickness of 80 ± 10 nm. The pencil hardness of the resulting substrate was measured and found to be 3H.

The surfaces on which the alignment films of the two substrates on which the alignment films were formed were formed so as to face each other so that the polarizing directions of the ultraviolet rays irradiated to the respective alignment films were parallel to each other and also the spaces for injecting the liquid crystal composition between the facing alignment films were formed To prepare a blank FFS cell having a cell thickness of 4 탆. The positive type liquid crystal composition was vacuum-injected into the fabricated blank FFS cell to produce an FFS liquid crystal display device. When the orientation of the liquid crystal in the obtained liquid crystal display element was confirmed, the flow orientation could not be observed. Subsequently, when the liquid crystal display element after the foreign matter test was observed with a microscope, the generation of foreign matter could not be observed. Further, the value of the contrast was measured to be 3100, and the AC residual image was measured and found to be 1.9%.

[Examples 83 to 88]

A substrate for measurement was prepared in the same manner as in Example 82 except that the polyamic acid solution shown in Table 5-5 was used, and the pencil hardness was measured. Further, an FFS cell was fabricated by the method according to Example 82, and flow orientation confirmation, foreign matter test, contrast measurement and AC afterimage measurement were performed. The measurement results are shown in Table 5-5 including Example 82. [

[Table 5-5]

As shown in Table 5-5, when the present invention is applied to a liquid crystal display element even if a light distributing agent is printed by an ink-jet method, the FFS liquid crystal display element exhibits excellent liquid crystal alignment properties, , It is possible to maintain the AC afterimage characteristic.

When the present invention is applied to a liquid crystal display element, in a transverse electric field type liquid crystal display element, light that maintains various characteristics such as liquid crystal alignment property, alignment stability, contrast, A liquid crystal aligning agent for an alignment film is provided.

Claims (16)

A liquid crystal aligning agent for a photo alignment layer containing a terminal polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride, a diamine compound and an aminosilane compound. The method according to claim 1,
Wherein the aminosilane compound is a compound represented by the following formula (AS): Liquid crystal aligning agent for photo alignment layer:

In the above formula (AS), n is 0 or 1;
R is alkylene having 1 to 10 carbon atoms or 1,4-phenylene, and when the alkylene has 2 or more carbon atoms, at least one -CH ₂ -CH ₂ - in alkylene is substituted with -CH ₂ -NH- ; And,
X is -OCH ₃ or -OCH ₂ CH _3. 3. The method according to claim 1 or 2,
Wherein the aminosilane compound is at least one selected from the group consisting of the following formulas (AS-1) to (AS-5): liquid crystal aligning agent for photo alignment layer:

. 4. The method according to any one of claims 1 to 3,
A liquid crystal aligning agent for a photo alignment film, further comprising a compound capable of crosslinking with a terminal endblock polyamic acid or a derivative thereof. 5. The method of claim 4,
Wherein the end-capping polyamic acid or its derivative and the crosslinkable compound are at least one selected from the group consisting of the following compounds (a) to (d): a liquid crystal aligning agent for photo-
(a) a silane coupling agent containing at least one epoxy ring in the molecule
(b) a compound containing two or more epoxy rings in the molecule
(c) a compound containing two or more benzoxazine structures in the molecule
(d) a compound containing two or more oxazoline structures in the molecule. 5. The method of claim 4,
(EPX-1) to (EPX-7), (BOX-2-1), (BOX-2-2), and the formula (OX- 1), a liquid crystal aligning agent for a photo alignment layer, at least one selected from the group consisting of

. 7. The method according to any one of claims 1 to 6,
Wherein the diamine compound comprises at least one of photosensitive diamines. 8. The method of claim 7,
Wherein the photosensitive diamine is at least one compound selected from the group consisting of the following formulas (PDI-1) to (PDI-13): Liquid crystal aligning agent for photo alignment layer:

In the formula (PDI-7), R ⁵¹ are each independently selected from _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, and;
s is independently an integer of 0 to 2,
In formula (PDI-8), R ⁵² is independently a single bond, straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, or -CONH-,
At least one -CH ₂ of the straight-chain alkylene - may be substituted with -O-;
R ⁵³ is each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH;
q is, each independently, an integer of 0 to 4;
In formula (PDI-12), R ⁵⁴ is alkyl or alkoxy having 1 to 10 carbon atoms,
At least one hydrogen of alkyl or alkoxy may be substituted with fluorine; And,
In the formulas (PDI-1) to (PDI-8), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the ring is bonded at a position capable of bonding in the ring. 9. The method according to claim 7 or 8,
Wherein the photosensitive diamine is a compound represented by the following formula (PDI-7):

In the formula (PDI-7), R ⁵¹ are each independently selected from -CH _3, -OCH _3, and -CF _3, or -COOCH _3, s is an integer of 0 to 2, each independently. 10. The method according to any one of claims 7 to 9,
Wherein the photosensitive diamine is a compound represented by the following formula (PDI-7-1) or (PDI-7-2): Liquid crystal aligning agent for photo alignment layer:

. 11. The method according to any one of claims 1 to 10,
(DI-5-17), formula (DI-5-30), formula (DI-7-3), formula (DI- (DI-34-4), and the formula (DI-34-7). The liquid crystal aligning agent for a photo alignment layer,

In the formula (DI-5-1), m is an integer of 2 to 12;
In the formula (DI-5-30), k is an integer of 1 to 5;
In the formula (DI-7-3), m is an integer of 1 to 12, n is independently 1 or 2;

In the formulas (DI-34-4) and (DI-34-7), R ⁴¹ is -H or alkyl having 1 to 12 carbon atoms. 12. The method according to any one of claims 1 to 11,
Wherein the tetracarboxylic dianhydride comprises at least one selected from the following formulas (AN-1-13), (AN-4-17), (AN-4-30), and , Liquid crystal aligning agent for photo alignment layer:

In the formulas (AN-4-17) and (PAN-9), m is an integer of 1 to 12. 13. The method according to any one of claims 1 to 12,
Further comprising a polymer other than the terminal-blocked polyamic acid or its derivative obtained by reacting a tetracarboxylic acid dianhydride, a diamine compound and an aminosilane compound. 14. The method of claim 13,
Wherein the other polymer is a polyamic acid or a derivative thereof. A liquid crystal alignment film using the liquid crystal aligning agent according to any one of claims 1 to 14. A liquid crystal display element using the liquid crystal alignment film according to claim 15.