KR20080114628A - Allyl-substituted nadimide compound, liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device - Google Patents

Abstract

An allyl-substituted nadimide compound, a liquid crystal aligning agent, a liquid crystal alignment layer and a liquid crystal display device are provided to solve the problems of long period reliability and voltage holding rate. An allyl-substituted nadimide compound is represented by the formula (A). In the formula (A), Q is a divalent group containing a side chain having the carbon number 3 or more. A liquid crystal alignment layer is produced by using a liquid crystal aligning agent containing an allyl-substituted nadimide compound.

Description

Allyl substituted nadiimide compound, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element TECHNICAL FIELD

The present invention relates to novel allyl substituted nadiimide compounds and their use in the field of liquid crystals.

Liquid crystal display elements have been used in various liquid crystal display devices such as notebooks and monitors of desktop computers, viewfinders of video cameras, projection displays, and the like, and have recently been used as televisions. Moreover, it is used also as optoelectronics related elements, such as an optical printer head, a high Fourier conversion element, a light valve.

The liquid crystal display device is typically 1) a pair of substrates that are arranged to face each other, 2) an electrode formed on one or both of the opposing surfaces of each of the pair of substrates, and 3) each of the pair of substrates. And a liquid crystal layer formed between the pair of substrates.

Conventional liquid crystal display devices are mainly display devices using nematic liquid crystals, 1) twisted nematic (TN) type liquid crystal display elements twisted 90 degrees, and 2) super twisted nematic (STN) type liquid crystal displays twisted more than 180 degrees. Element, 3) A so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor has been put into practical use. These liquid crystal display elements have a drawback in that the viewing angle at which an image can be properly viewed is narrow, and when viewed in an inclined direction, a decrease in luminance and contrast and inversion of luminance in an intermediate color tone occur.

Recently, this viewing angle problem includes: 1) a TN-TFT type liquid crystal display element using an optical compensation film, 2) a vertical alignment and a VA (Vertical Alignment) type liquid crystal display element using an optical compensation film, and 3) a vertical alignment and a projection structure. MVA (Multi Domain Vertical Alignment) type liquid crystal display device using technology, or 4) In-Plane Switching (IPS) type liquid crystal display device of transverse electric field method, 5) Electrically Controlled Birefringence (ECB) type liquid crystal display device, 6) The optical compensation bend (Optically Compensated Bend or Optically Self-Compensated Birefringence (OCB)) type, such as a liquid crystal display device has been improved, and the improved technology has been put into practice or examined.

The development of the technology of the liquid crystal display element is achieved not only by the improvement of these drive systems and element structures, but also by the improvement of the structural member used for a liquid crystal display element. Among the constituent members used in the liquid crystal display device, in particular, the liquid crystal alignment film is one of important factors affecting the display quality of the liquid crystal display device, and the role of the liquid crystal alignment film is increasingly important as the quality of the liquid crystal display device is improved.

A liquid crystal aligning film is prepared from a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is the solution which melt | dissolved polyamic acid or soluble polyimide in the organic solvent. After apply | coating this solution to a board | substrate, it forms into a film by means, such as a heating, and forms a polyimide oriented film. Various liquid crystal aligning agents other than polyamic acid are also examined, but most of them have not been put to practical use in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical characteristics, optical characteristics, display characteristics, and the like.

The voltage retention is mentioned as an important characteristic calculated | required by the liquid crystal aligning film in order to improve the display quality of a liquid crystal display element. When the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may cause trouble in normal gray scale display. Moreover, even if an initial orientation state is good, for example, when the orientation state after a high temperature acceleration test worsens and it is difficult to maintain a normal display quality, there exists a problem.

As an attempt to solve these problems, various methods have recently been proposed.

1) The polyamic-acid composition containing two or more polyamic acids from which a physical property differs for forming a liquid crystal aligning film is known (for example, refer patent document 1 and 2).

2) The varnish composition containing the polymer component containing a polyamic acid and polyamide, and a solvent is known (for example, refer patent document 3).

3) Varnish compositions containing two or more polyamic acids and polyamides having different physical properties and a solvent are known (see Patent Document 4, for example).

4) A varnish composition containing a polymer mixture containing, as a main component, a polyamic acid synthesized using a diamine having a specific structure is known (see Patent Document 5, for example).

However, these prior arts have not sufficiently solved the problem of the voltage retention and the orientation state after the high temperature acceleration test.

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-193345

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-193347

[Patent Document 3] International Publication No. 2000/61684

[Patent Document 4] International Publication 2001/00733 Pamphlet

[Patent Document 5] Japanese Patent Application Laid-Open No. 2002-162630

In view of the above situation, development of a liquid crystal aligning agent for a liquid crystal display device having improved voltage retention and long-term reliability problems, a liquid crystal alignment film formed using the same, and a liquid crystal display device having the same are desired.

The present inventors conducted research in order to solve the said subject. As a result, it was found that by using the liquid crystal aligning agent containing a novel allyl substituted nadiimide compound as a liquid crystal aligning film, good voltage retention and long-term reliability can be imparted to the liquid crystal display element having this alignment film. It was completed.

The allyl substituted nadiimide compound of the present invention is represented by the following [1] term.

[1] A nadiimide compound represented by formula (A).

(Wherein Q is a divalent group having 3 or more side chain groups)

Industrial Applicability According to the present invention, it is possible to provide liquid crystal display elements of various drive systems with high voltage retention and good long-term reliability.

First, the term used by this invention is demonstrated.

"Nadiimide compound" means the compound which has the following nadiimide group. And the bonding position of the substituent in this nadiimide group is 1, 5, or 7 positions.

"Epoxy compound" means a compound having at least one oxirane ring.

Symbols such as B and C surrounded by hexagons mean ring B and ring C, respectively.

The substituent or free group in which the bond is not fixed to the position of the carbon atom of the group of the ring structure means that the group of the ring structure and their bonding position are arbitrary.

"Arbitrary" used when defining a chemical formula means that it is arbitrary about the number as well as a position. Moreover, the expression that any A may be substituted with B, C or D is not only when any A is replaced by B, when any A is substituted by C and when any A is substituted by D, as well as It means that it also includes the case where some A can be substituted by at least two of B-D.

The compound represented by formula (A) may be called a compound (A). This abbreviation also applies to compounds represented by other formulas. Me in the formula represents methyl and Ph represents phenyl.

This invention consists of said item [1] and [2]-[35] which are shown next.

[2] The nadiimide compound according to [1], wherein Q is a group represented by any one of formulas (A-1) to (A-5).

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with —O—, —CH═CH— or C≡C—, and any hydrogen of this phenyl is replaced with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon numbers of R ² is 3 or more;

Where R ¹³ , R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or al cheyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2;

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30)

Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl of 1 to 30 carbon atoms, or alkenyl of 2 to 30 carbon atoms; and R ⁵ is independently a single bond, -CO- or -CH _2-

Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl of 1 to 30 carbon atoms, or alkenyl of 2 to 30 carbon atoms; R ⁵ is independently a single bond, -CO- or -CH ₂ -and R ⁶ and R ⁷ are independently hydrogen, alkyl having 1 to 30 carbon atoms, or phenyl)

Wherein R ⁸ is hydrogen or alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl may be substituted with -O-, -CH = CH- or -C≡C-; ⁹ is independently -O- or alkylene having 1 to 6 carbon atoms; Ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 or 2 And c is independently 0 or 1)

(Wherein, R ¹⁰ is alkyl having a carbon number of 3 to 30 or 3 to 30 carbon atoms, fluorinated alkyl of; R ¹¹ is hydrogen, alkyl of 1 to 30 carbon atoms or from 1 to 30 carbon atoms, fluorinated alkyl of; R ¹² is independently And -O- or alkylene having 1 to 6 carbon atoms, and d is independently 0 or 1)

[3] The nadiimide compound according to [2], wherein Q is a group represented by formula (A-1).

[4] Q is a group represented by the formula (A-1), and R ¹ is a single bond, -O-, -COO-, -CONH-, -CH ₂ O-, or methylene; The nadiimide compound as described in [2] which is group represented by group which R <^2> has a steroid skeleton, C1-C30 alkyl, or Formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and one of —CH ₂ — in alkyl and alkoxy may be substituted with a group represented by formula (D-2-1). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, the sum thereof is 1 to 3)

[5] Q is a group represented by the formula (A-1), and R ¹ is a single bond, -O-, -COO-, -CONH-, -CH ₂ O-, or methylene; The nadiimide compound as described in [2] whose R <^2> is group represented by C1-C30 alkyl or a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3).

[6] The nadiimide compound according to [5], wherein Q is any of the groups shown below.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms

[7] The nadiimide compound represented by formula (A-1-2-1).

[8] The nadiimide compound represented by formula (A-1-5-1).

[9] A liquid crystal aligning agent containing at least one of the nadiimide compounds according to any one of [1] to [8].

[10] A polymer, a radically polymerizable monomer, and an epoxy containing at least one of the nadiimide compounds represented by formula (A) and being a compound represented by the formula (B), a polyamic acid or a derivative of this polyamic acid, as other components. A liquid crystal aligning agent containing at least one compound and / or polymer selected from the group consisting of compounds.

(Wherein Q is a divalent group having 3 or more side chain groups)

Wherein R ^b1 and R ^b2 are independently hydrogen, alkyl of 1 to 12 carbon atoms, alkenyl of 3 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, aryl or benzyl; n is 1 or 2;

When n is 1, R ^b3 is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, -L ^1- (O) _q − (L ² O) a group represented by _r -R ^b4 , a group represented by-(L ³ ) _s -B ² -R ^b5 , or a group represented by -B ² -TB ¹ ;

In these formulas, L ¹ is alkylene having 2 to 6 carbon atoms; q is 0 or 1; L ² is alkylene having 2 to 6 carbon atoms, and r is an integer of 1 to 30; R ^b4 is alkyl having 2 to 6 carbon atoms; L ³ is alkylene having 1 to 4 carbon atoms, and s is 0 or 1; R ^b5 is alkyl having 1 to 4 carbons; B ² is phenylene, wherein any hydrogen may be substituted with —OH; T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- ; And B ¹ is phenyl in which any hydrogen may be substituted with —OH;

And optionally hydrogen of alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, aryl of 6 to 12 carbon atoms, and benzyl may be substituted with -OH;

when n is 2, R ^b3 is a 2 to 20 carbon atoms in the straight-chain alkylene, arylene, cycloalkylene of -L, 6 to 12 carbon atoms, having a carbon number of _{^{5~8 1 - (O) q -}} (L 2 O) r A group represented by -L ^4- , a group represented by-(L ³ ) _s -B ² -L ^5- , a group represented by -B ² -TB ^2- , or -B ² -OB ² -C (CH ₃ ) a group represented by ₂ -B ² -OB ^2- ;

In these formulae, L ¹ , L ² And L ⁴ is independently straight chain alkylene having 2 to 6 carbon atoms, q is 0 or 1, and r is an integer of 1 to 30; L ³ And L ⁵ is independently straight chain alkylene having 1 to 4 carbon atoms, s is 0 or 1, and B ² is independently phenylene in which any hydrogen may be substituted with -OH; And T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- ;

And any hydrogen of cycloalkylene having 5 to 8 carbon atoms and arylene having 6 to 12 carbon atoms may be substituted with -OH, and any hydrogen of arylene having 6 to 12 carbon atoms may be substituted with methyl)

[11] the other component is at least one of the compounds represented by formula (B); And the liquid crystal aligning agent as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.01-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B).

[12] the other component is at least one of the compounds represented by formula (B); Q in Formula (A) is a group represented by Formula (A-1); And the liquid crystal aligning agent as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.1-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B).

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with -O-, -CH = CH- or C≡C-, and any hydrogen of this phenyl is substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon number of R ² is 3 or more).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or alkyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2)

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30)

[13] The other component is at least one of the compounds represented by the formula (B), and Q in the formula (A) is a group represented by the formula (A-1), and a nadiimide represented by the formula (A) The ratio of a compound is 0.1-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and a compound represented by Formula (B); In formula (A-1), R ¹ is a single bond, —O—, —COO—, —CONH—, —CH ₂ O— or methylene; The liquid crystal aligning agent as described in [12] which is group represented by group which R <^2> has a steroid skeleton, C1-C30 alkyl, or Formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and one -CH ₂ -in these alkyl and alkoxy may be substituted with a group represented by the formula (D-2-1) ; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3).

[14] The other component is at least one of the compounds represented by the formula (B), Q in the formula (A) is a group represented by the formula (A-1), and a nadiimide represented by the formula (A) The ratio of a compound is 0.1-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and a compound represented by Formula (B); In formula (A-1), R ¹ is a single bond, —O—, —COO—, —CONH—, —CH ₂ O— or methylene; The liquid crystal aligning agent as described in [12] whose R <^2> is group represented by C1-C30 alkyl or a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3).

[15] the other component is a compound represented by any one of formulas (B-1) to (B-3); Q in Formula (A) is either of the groups shown below; And the liquid crystal aligning agent as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B).

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms

[16] the other component is a compound represented by any one of formulas (B-1) to (B-3); The nadiimide compound represented by Formula (A) is a compound represented by Formula (A-1-2-1) or Formula (A-1-5-1); And the ratio of the nadiimide compound represented by Formula (A-1-2-1) or Formula (A-1-5-1) is with respect to the total amount of this nadiimide compound and the compound represented by Formula (B) The liquid crystal aligning agent as described in [10] which is 0.2-0.99 by weight ratio.

[17] the other component is at least one polymer selected from polyamic acid and derivatives of the polyamic acid; And the liquid crystal aligning agent as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.01-0.99 by weight ratio with respect to the total amount of this nadiimide compound and this polymer.

[18] the other component is at least one polymer selected from polyamic acid and derivatives of the polyamic acid; The polyamic acid is at least one of aromatic tetracarboxylic dianhydrides of formulas (1) to (6), or at least one of aromatic tetracarboxylic dianhydrides of formulas (1) to (6) and formulas (7) to ( A polyamic acid obtained by reacting a mixture with at least one of tetracarboxylic dianhydrides other than aromatics of 14) with at least one diamine selected from the group of compounds represented by formulas (I) to (VII); Q in Formula (A) is a group represented by Formula (A-1); And the liquid crystal aligning agent as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.1-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and this polymer.

Wherein A ¹ is alkylene having ² to 12 carbon atoms; A ² is alkylene having 1 to 12 carbon atoms; and A ³ is independently a single bond, -O-, -CO-, -CONH-, -NHCO -, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _m -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _m- S- or alkylene having 1 to 12 carbon atoms, m is an integer of 1 to 12; and any hydrogen of the cyclohexane ring or the benzene ring is -F, -CH ₃ , -OH, -COOH,- May be substituted with SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl)

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with -O-, -CH = CH- or C≡C-, and any hydrogen of this phenyl is substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon number of R ² is 3 or more).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or alkyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2)

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30)

[19] In the formula (A-1), R ¹ is a single bond, -O-, -COO-, -CONH-, -CH ₂ O- or methylene, and R ² is a group having a steroid skeleton and 1 carbon atom. The liquid crystal aligning agent as described in [18] of the group represented by -30 alkyl or a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and one -CH ₂ -in these alkyl and alkoxy may be substituted with a group represented by the formula (D-2-1) ; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3).

[20] In the formula (A-1), R ¹ is a single bond, -O-, -COO-, -CONH-, -CH ₂ O- or methylene, and R ² is alkyl having 1 to 30 carbon atoms, or The liquid crystal aligning agent of description of [18] which is group represented by a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3).

[21] Q in Formula (A) is any of the groups shown below; And the liquid crystal aligning agent as described in [18] whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by weight ratio with respect to the total amount of this nadiimide compound and the polymer which is another component.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms

[22] The liquid crystal aligning agent according to [21], wherein Q in Formula (A) is any of the groups shown below.

[23] The polyamic acid is at least one of tetracarboxylic dianhydrides of formulas (1) to (6) and formulas (IV-1), (IV-2), (IV-15) and (IV-16). ), A polymer obtained by reacting at least one of formula (V-1) to formula (V-12), formula (V-33), and formula (VII-2) with any one of [18] to [22]. The liquid crystal aligning agent of one.

[24] The polyamic acid is tetracarboxylic dianhydride of formula (1), formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) The liquid crystal aligning agent in any one of [18]-[22] which is a polymer obtained by making at least one of-the formula (V-12), a formula (V-33), and the formula (VII-2) react.

[25] A mixture of polyamic acid with at least one of tetracarboxylic dianhydrides of formulas (1) to (6) and at least one of tetracarboxylic dianhydrides of formulas (7) to (14) and formula (IV-1) ), Formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), formula (V-33) and formula (VII-2) The liquid crystal aligning agent in any one of [18]-[22] which is a polymer obtained by making at least 1 of diamine of reaction react.

[26] A mixture of polyamic acid with at least one of tetracarboxylic dianhydride of formula (1) and tetracarboxylic dianhydride of formulas (7) to (14), and formulas (IV-1) and (IV-2) , By reacting at least one of the diamines of formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), formula (V-33) and formula (VII-2) The liquid crystal aligning agent in any one of [18]-[22] which is a polymer obtained.

[27] A mixture of polyamic acid with tetracarboxylic dianhydride of formula (1) and tetracarboxylic dianhydride of formula (7), formula (IV-1), formula (IV-2), formula (IV-15), [18] A polymer obtained by reacting at least one of the diamines of formulas (IV-16), (V-1) to (V-12), (V-33) and (VII-2). The liquid crystal aligning agent in any one of-[22] term | claim.

[28] A composition containing at least one of the nadiimide compounds represented by formula (A), at least one of the compounds represented by formula (B), and at least one polymer selected from polyamic acid and derivatives of this polyamic acid. ; The polyamic acid is at least one of the aromatic tetracarboxylic dianhydrides of the formulas (1) to (6), or at least one of the aromatic tetracarboxylic dianhydrides of the formulas (1) to (6) and formulas (7) to Polyamic acid obtained by reacting a mixture with at least one of tetracarboxylic dianhydrides other than the aromatics of (14) and at least one diamine selected from the group of compounds represented by formulas (I) to (VII), respectively. ; And the liquid crystal orientation as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.01-0.99 by weight ratio with respect to the total amount of this nadiimide compound, the compound represented by Formula (B), and this polymer. My.

Wherein A ¹ is alkylene having ² to 12 carbon atoms; A ² is alkylene having 1 to 12 carbon atoms; and A ³ is independently a single bond, -O-, -CO-, -CONH-, -NHCO -, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _m -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _m- S- or alkylene having 1 to 12 carbon atoms, m is an integer of 1 to 12; and any hydrogen of the cyclohexane ring or the benzene ring is -F, -CH ₃ , -OH, -COOH,- May be substituted with SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl)

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with -O-, -CH = CH- or C≡C-, and any hydrogen of this phenyl is substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon number of R ² is 3 or more).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or alkyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2)

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30)

[29] the other component is at least one of radically polymerizable monomers; Q in Formula (A) is either of the groups shown below; And the liquid crystal aligning agent as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by weight ratio with respect to the total amount of this nadiimide compound and the radically polymerizable monomer which is another component.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms

[30] The liquid crystal aligning agent according to [29], wherein Q in Formula (A) is any of the groups shown below.

[31] the other component is at least one of the epoxy compounds; Q in Formula (A) is either of the groups shown below; And the liquid crystal aligning agent as described in [10] whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by weight ratio with respect to the total amount of this nadiimide compound and the epoxy compound which is another component.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms

[32] The liquid crystal aligning agent according to [31], wherein Q in Formula (A) is any of the groups shown below.

[33] A liquid crystal aligning film formed by applying the liquid crystal aligning agent according to [9] or [10] on a substrate and baking in the state of the film.

A pair of substrates arranged opposite to each other, an electrode formed on one or both of the opposing surfaces of each of the pair of substrates, a liquid crystal alignment film formed on the opposing surfaces of the pair of substrates, A liquid crystal display device having a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is a liquid crystal alignment film according to [33].

The allyl substituted nadiimide compound of this invention is represented by Formula (A).

(Wherein Q is a divalent group having 3 or more branched groups).

That is, the allyl substituted nadiimide compound of this invention has the structure which couple | bonded the two nadiimide groups which have an allyl group by the bivalent group which has a C3 or more side chain group. It is preferable that carbon number of this side chain group is 6 or more.

Preferred examples of the divalent group having such a side chain group are groups represented by formulas (A-1) to (A-5).

Among these groups, the group represented by the formula (A-1) is most preferred. Formula (A-1) is demonstrated.

In formula (A-1), R ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O- or 1 to 6 is alkylene. Preferred examples of R ¹ are a single bond, -O-, -COO-, -CONH-, -CH ₂ O- or -CH _2- , and the most preferred example is -CH _2- .

R ² in formula (A-1) is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1), and the sum of the carbon numbers of R ¹ and R ² . Is 3 or more. In the alkyl having 1 to 30 carbon atoms, when the carbon number is 2 to 6, any of -CH ₂ -may be substituted with -O-, -CH = CH-, or -C≡C-, Any hydrogen of this phenyl may be substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy.

In formula (D-1), R ¹³ , R ¹⁴ and R ¹⁵ are each independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, and having 1 to C carbon atoms. Oxyalkylene of 3 or alkyleneoxy of 1 to 3 carbon atoms, R ¹⁶ and R ¹⁷ are independently fluorine or methyl, R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, Trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, or alkoxyalkyl of 2 to 30 carbon atoms, such alkyl, alkoxy and alkoxy Any -CH ₂ -in alkyl may be substituted by the group represented by difluoromethylene or a formula (D-2). Ring B and Ring C are independently 1,4-phenylene or 1,4-cyclohexylene. e, f, and g are the integers of 0-3 independently, and the sum total is one or more. And m1 and m2 are 0, 1 or 2 independently.

(Wherein R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently C 1-10 alkyl or phenyl, n is an integer of 1-30)

Preferred examples of R ² are a group having a steroid skeleton, an alkyl having 1 to 30 carbon atoms, or a group represented by formula (D-1-1).

In formula (D-1-1), R ¹³ , R ¹⁴ and R ¹⁵ are independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and one -CH ₂ -in such alkyl and alkoxy may be substituted with a group represented by formula (D-2-1). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f, and g are the integers of 0-3 independently, and the sum total is 1-3.

More preferable examples of R ² are alkyl having 1 to 30 carbons and a group represented by the above formula (D-1-1), and in this formula (D-1-1), R ¹³ , R ¹⁴ and R ^15. Are independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f, and g are the integers of 0-3 independently, and the sum total is 1-3.

Particularly preferred examples of R ² are groups represented by the above formula (D-1-1), and in this formula (D-1-1), R ¹³ , R ¹⁴ and R ¹⁵ are each independently a single bond or- CH ₂ CH _2- ; R ¹⁸ is alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f, and g are the integers of 0-3 independently, and the sum total is 1-3.

Next, the example of the nadiimide compound of this invention whose Q is a formula (A-1) is shown.

In these formulas, R ²³ is alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, preferably alkyl having 5 to 25 carbon atoms or alkoxy having 5 to 25 carbon atoms.

In these formulas, R ²⁴ is alkyl having 4 to 30 carbon atoms, preferably alkyl having 6 to ²⁵ carbon atoms.

In formulas (A-1-13) to (A-1-31), R ²⁵ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 3 to 25 carbon atoms or 3 carbon atoms. -25 is alkoxy. In compound (A-1-1)-a compound (A-1-35), a compound (A-1-1)-a compound (A-1-6) are preferable, and a compound (A-1-2) and Compound (A-1-4)-a compound (A-1-6) are especially preferable.

Next, Formula (A-2) will be described.

In formula (A-2), R <^3> is hydrogen or methyl independently, and methyl is preferable. R ⁴ is hydrogen, alkyl having 1 to 30 carbon atoms, or alkenyl having 2 to 30 carbon atoms, and alkyl having 3 to 25 carbon atoms or alkenyl having 3 to 25 carbon atoms is preferable. And R ⁵ is independently a single bond, -CO- or -CH _2- , and -CO- is preferred. It is preferable that -OR ^5- , which has an arbitrary binding position to the steroid nucleus, is bound to the 6 position of the steroid nucleus. It is preferable that the bonding position of the free group (that is, N of an allyl substituted nadiimide group) to a benzene ring is a meta position or para position with respect to R <^5> .

The preferable example of the nadiimide compound of this invention whose Q is Formula (A-2) is shown next.

Next, Formula (A-3) will be described.

In formula (A-3), R <^3> is hydrogen or methyl independently, and methyl is preferable. R ⁴ is hydrogen, alkyl having 1 to 30 carbon atoms, or alkenyl having 2 to 30 carbon atoms, and alkyl having 3 to 25 carbon atoms or alkenyl having 3 to 25 carbon atoms is preferable. R ⁵ is independently a single bond, -CO- or -CH _2- , with a single bond or -CO- being preferred. And R ⁶ and R ⁷ are independently hydrogen, alkyl having 1 to 30 carbon atoms, or phenyl. It is preferable that R <^6> is hydrogen or methyl, and it is preferable that R <^7> is hydrogen. On the other hand, it is preferable that the bonding position of the free group to a benzene ring is a meta position or a para position with respect to R <^5> .

The preferable example of the nadiimide compound of this invention whose Q is Formula (A-3) is shown next.

Next, Formula (A-4) will be described.

In the formula (A-4), R ⁸ is hydrogen or alkyl of 1 to 30 carbon atoms, and any -CH ₂ in the alkyl - is replaced by -O-, -CH = CH- or -C≡C- It may be. R ⁸ is preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 6 to 20 carbon atoms. R ⁹ is independently —O— or alkylene having 1 to 6 carbon atoms, and c is independently 0 or 1. It is preferred that c is 1, in which two R ⁹ are together —O—, —CH ₂ — or —CH ₂ CH ₂ —. Ring A is 1,4-phenylene or 1,4-cyclohexylene, preferably 1,4-cyclohexylene. b is 0, 1 or 2, Preferably it is 0. And a is 0 or 1. On the other hand, the bonding position of the free group to a benzene ring is preferably a meta position or a para position with respect to R ⁹ , and more preferably a para position.

The preferable example of the nadiimide compound of this invention whose Q is Formula (A-4) is shown next.

R <^26> in these formula is C1-C30 alkyl, Preferably it is C6-C20 alkyl.

Next, Formula (A-5) will be described.

In formula (A-5), R <^10> is C3-C30 alkyl or C3-C30 fluorinated alkyl, Preferably it is C6-C20 alkyl. R ¹¹ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms, preferably hydrogen or alkyl having 1 to 10 carbon atoms. R ¹² is independently —O— or alkylene having 1 to 6 carbon atoms; And d is independently 0 or 1. On the other hand, the bonding position of the free group to a benzene ring is preferably a meta position or a para position with respect to R ¹² , and more preferably a para position.

The preferable example of the nadiimide compound of this invention whose Q is Formula (A-5) is shown next.

In these formulae, R ²⁷ is alkyl having 6 to ²⁰ carbon atoms, and R ²⁸ is hydrogen or alkyl having 1 to 10 carbon atoms.

Compound (A) reacts a compound having two maleimide groups with an arylcyclopentadiene as described in the examples, or a diamino compound and allylbicyclo [2,2,1] hepto-5- It is obtained by reacting ene-2,3-dicarboxylic anhydride. And allyl bicyclo [2,2,1] hepto-5-ene-2,3-dicarboxylic anhydride is obtained by making arylcyclopentadiene react with maleic anhydride. That is, arylcyclopentadiene is an essential intermediate for preparing compound (A). This arylcyclopentadiene obtained by reacting allyl chloride and cyclopentadiene is more likely to be a mixture of a plurality of compounds having different bonding positions of allyl groups than a single compound. And it is difficult to separate this mixture into a single compound. Moreover, there is no reason to say that using this single compound is essential in order to achieve the objective of this invention. That is, in this invention, since the same effect is acquired even if a compound (A) is a mixture, this arylcyclopentadiene can be used in the state which left possibility of being a mixture. Therefore, there is a strong possibility that compound (A) is also a mixture of compounds having different bonding positions of allyl groups. This is the reason why the substitution position of an allyl group is not fixed to any carbon which comprises a ring in Formula (A).

Next, the liquid crystal aligning agent of this invention is demonstrated.

The liquid crystal aligning agent of this invention is a composition containing said compound (A). Preferable examples of the liquid crystal aligning agent of the present invention include a compound (A), and are an essential component other than the compound (A), a compound represented by the formula (B), a polyamic acid or a derivative of this polyamic acid. It is a composition containing at least 1 compound and / or a polymer chosen from the group which consists of a polymer, a radically polymerizable monomer, and an epoxy compound. The compound (A) and the other components may be used alone, or two or more may be mixed and used. Such a composition contains at least 1 solvent other than the said essential component, and may contain the additive which can be normally used for a liquid crystal aligning agent. Even if a liquid crystal aligning agent containing a compound (A) as an essential component does not contain a polymerization catalyst, another polymerizable compound, a polymer, etc., it can crosslink-polymerize easily by heating, and can form a liquid crystal aligning film.

In the preferable example of the liquid crystal aligning agent of this invention, the composition whose other components are at least one of a compound (B) is demonstrated first. Compound (B) is an alkenyl substituted nadiimide compound represented by formula (B).

In formula (B), R ^b1 and R ^b2 are independently hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl or benzyl. R ^b1 is preferably hydrogen or alkyl having 1 to 12 carbon atoms. R ^b2 is preferably hydrogen or alkyl having 1 to 12 carbon atoms, and more preferably hydrogen. And n is 1 or 2.

When n is 1, R ^b3 is alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, -L ^1- (O) _q − (L ² O) is a group represented by _r -R ^b4 , a group represented by-(L ³ ) _s -B ² -R ^b5 , or a group represented by -B ² -TB ¹ .

In these formulas, L ¹ is alkylene having 2 to 6 carbon atoms; q is 0 or 1; L ² is alkylene having 2 to 6 carbon atoms, and r is an integer of 1 to 30; R ^b4 is alkyl having 2 to 6 carbon atoms; L ³ is alkylene having 1 to 4 carbon atoms, and s is 0 or 1; R ^b5 is alkyl having 1 to 4 carbons; B ² is phenylene in which any hydrogen may be substituted at —OH; T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- ; And B ¹ is phenyl in which any hydrogen may be substituted in —OH. And optionally hydrogen of alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, and benzyl may be substituted with -OH.

when n is 2, R ^b3 is a 2 to 20 carbon atoms in the straight-chain alkylene, arylene, cycloalkylene of -L, 6 to 12 carbon atoms, having a carbon number of _{^{5~8 1 - (O) q -}} (L 2 O) r A group represented by -L ^4- , a group represented by-(L ³ ) _s -B ² -L ^5- , a group represented by -B ² -TB ^2- , or -B ² -OB ² -C (CH ₃ ) A group represented by ₂ -B ² -OB ^2- . In these formulas, L ¹ , L ^2, and L ⁴ are independently straight chain alkylene having 2 to 6 carbon atoms, q is 0 or 1, and r is an integer of 1 to 30; L ³ and L ⁵ are independently straight chain alkylene having 1 to 4 carbon atoms, s is 0 or 1, and B ² is independently phenylene in which any hydrogen may be substituted with -OH; And T is —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ —. And arbitrary hydrogen of C5-C8 cycloalkylene and C6-C12 arylene may be substituted by -OH, and arbitrary hydrogen of C6-C12 arylene may be substituted by methyl have.

That is, compound (B) is an alkenyl substituted nadiimide compound which does not have a C3 or more side chain group. In Formula (B), it is preferable that n is two. At this time, R ^b3 is a C2-C12 linear alkylene, cyclohexylene, phenylene in which arbitrary hydrogen may be substituted by methyl, a group represented by -B ² -TB ^2- , or -B ² -OB A group represented by ² -C (CH ₃ ) ₂ -B ² -OB ^2- . In these formulas, B ² is phenylene and T is —CH ₂ —, —O— or —SO ₂ —.

Specific examples of compound (B) are shown below.

N-methyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-methyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-methyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-methyl-metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-allyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-allyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-allyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-isopropenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-isopropenyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-cyclohexyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-cyclohexyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-cyclohexyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-phenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-phenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-benzyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-benzyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N-benzyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2'-hydroxyethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2'-hydroxyethyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2'-hydroxyethyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 ', 3'-dihydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 ', 3'-dihydroxypropyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (3'-hydroxy-1'-propenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (4'-hydroxycyclohexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (4'-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (4'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (4'-hydroxyphenyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (4'-hydroxyphenyl) -methylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (3'-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (3'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 '-(2'-hydroxyethoxy) ethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 '-(2'-hydroxyethoxy) ethyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 '-(2'-hydroxyethoxy) ethyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 '-(2'-hydroxyethoxy) ethyl) -metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 '-(2'-(2 "-hydroxyethoxy) ethoxy) ethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 '-(2'-(2 "-hydroxyethoxy) ethoxy) ethyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (2 '-(2'-(2 "-hydroxyethoxy) ethoxy) ethyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (4 '-(4'-hydroxyphenylisopropylidene) phenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N- (4 '-(4'-hydroxyphenylisopropylidene) phenyl) -allylmethylbicyclo [2.2.1] hepto-5-en-2,3-dicarboxyimide

N- (4 '-(4'-hydroxyphenylisopropylidene) phenyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

1,2-bis (3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) ethane

1,2-bis (3 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) ethane

1,2-bis (3 '-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) ethane

Bis (2 '-(3'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) ethyl) ether

Bis (2 '-(3'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) ethyl) ether

1,4-bis (3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) butane

1,4-bis (3 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) butane

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N '-((1-methyl) -2,4-phenylene) -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

2,2-bis (4 '-(4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

2,2-bis (4 '-(4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

2,2-bis (4 '-(4'-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

Bis (4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) ether

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) ether

Bis (4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) ether

Bis (4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) sulfone

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) sulfone

Bis (4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) sulfone

1,6-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3-hydroxy-hexane

1,12-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3,6-dihydroxy-dodecane

1,3-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxycyclohexane

1,5-bis (3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy) -3-hydroxy-pentane

1,4-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene

1,4-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2,5-dihydroxy-benzene

N, N'-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m- (2-hydroxy) xylylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

2,2-bis (4 '-(4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2'-hydroxy-phenoxy) phenyl) propane

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenyl) methane

Bis (3- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -4-hydroxy-phenyl) ether

Bis (3- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxy-phenyl) sulfone

1,1,1-tri (4 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)) phenoxymethylpropane

N, N ', N "-tri (ethylenemetallylcyclocyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) isocyanurate

In addition, in the liquid crystal aligning agent of this invention, the oligomer of said compound can also be used.

Examples of the preferable compound (B) among the above are shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N '-((1-methyl) -2,4-phenylene) -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

2,2-bis (4 '-(4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

2,2-bis (4 '-(4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

2,2-bis (4 '-(4'-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

Bis (4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) ether

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) ether

Bis (4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) ether

Bis (4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) sulfone

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) sulfone

Bis (4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) sulfone

Examples of more preferred compounds (B) are given below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N '-((1-methyl) -2,4-phenylene) -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-p-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

N, N'-m-xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)

2,2-bis (4 '-(4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

2,2-bis (4 '-(4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

2,2-bis (4 '-(4'-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy) phenyl) propane

Bis (4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

Bis (4- (metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl) methane

The ratio of the compound (A) in the liquid crystal aligning agent whose other component is a compound (B) is 0.01-0.99 by weight ratio with respect to the total amount of a compound (A) and a compound (B). This weight ratio becomes like this. Preferably it is 0.1-0.99, More preferably, it is 0.2-0.99, More preferably, it is 0.5-0.99. By carrying out the ratio of a compound (A) in such a range, it can be made into the liquid crystal aligning agent in which the balance between voltage retention, liquid crystal alignability, and display quality was maintained. In addition, said [11]-[16] is an example which combined the preferable ratio of such a compound (A) with the preferable range of each definition of a compound (A) and a compound (B).

Next, a composition is described in which the other component is at least one polymer selected from polyamic acid and derivatives of the polyamic acid.

Polyamic acid is a polymer obtained by making tetracarboxylic dianhydride and diamine react. Preferred examples of the polyamic acid derivatives are polyimide, partially imidized polyamic acid, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide. The polyimide is a polymer obtained by completely dehydrating and closing the polyamic acid, and the partially imidized polyamic acid is obtained by partially stopping the dehydration ring. The polyamic acid ester is a derivative in which the carboxyl group of the polyamic acid is esterified with alcohol. Polyamic acid-polyamide polypolymers are polymers obtained by substituting part of tetracarboxylic dianhydride with dicarboxylic acids or derivatives of dicarboxylic acids (dihalides and anhydrides), and polyamideimide partially or partially replaces this polyamic acid-polyamide copolymer. It is obtained by complete dehydration ring closing. On the other hand, this polyamic acid-polyamide copolymer may actually be a mixture of a polyamic acid-polyamide copolymer and a polyamic acid and / or polyamide. However, in the present invention, the polyamic acid- It is called polyamide copolymer. The same applies to polyamideimide.

Preferred examples of tetracarboxylic dianhydride are shown below.

It is preferable to use at least one of such tetracarboxylic dianhydrides. Of these compounds, aromatic tetracarboxylic dianhydrides of formulas (1) to (6) are more preferred, and compounds of formula (1) are most preferred. On the other hand, in this invention, in order to make molecular weight control of the polyamic acid obtained easy by a termination reaction, you may replace a part of tetracarboxylic dianhydride with dicarboxylic anhydride. At this time, it is preferable to make ratio of dicarboxylic anhydride into the range which does not impair the effect of this invention, and it is preferable to set it as 0.1 or less by the carboxylic acid equivalent ratio with respect to tetracarboxylic dianhydride as a reference.

In this invention, at least one of the said aromatic tetracarboxylic dianhydride and tetracarboxylic dianhydride other than aromatic can be used in combination. Preferable examples of tetracarboxylic dianhydride other than aromatic are the compounds (7) to (14), and the most preferred example is compound (7).

Preferable examples of the diamine used in the present invention are diamines represented by formulas (I) to (VII), respectively.

In these formulas, A ¹ is alkylene having 2 to 12 carbon atoms. A <^2> is C1-C12 alkylene. A ³ is independently a single bond, -O-, -CO-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _{m -O-, -S-, -SS-, -SO 2} -, -S- (CH 2) m -S- , or an alkylene of 1 to 12 carbon atoms, m is an integer from 1 to 12. Then, a cyclohexane ring or a benzene ring any hydrogen may be substituted with _{-F, -CH 3, -OH, -COOH} , -SO 3 H, -PO 3 H 2, benzyl or 4-hydroxybenzyl.

Preferable examples of the diamine represented by the formula (I) are compound (I-1) to compound (I-4).

Preferable examples of the diamine represented by the formula (II) are compound (II-1) and compound (II-2).

Preferable examples of the diamine represented by the formula (III) are compounds (III-1) to (III-3).

Preferable examples of the diamine represented by the formula (IV) are compounds (IV-1) to (IV-16).

Preferable examples of the diamine represented by the formula (V) are compounds (V-1) to (V-34).

Preferable examples of the diamine represented by the formula (VI) are compounds (VI-1) to (VI-6).

Preferable examples of the diamine represented by the formula (VII) are compounds (VII-1) to (VII-16).

Among them, compound (IV-1) to compound (IV-5), compound (IV-15), compound (IV-16), compound (V-1) to compound (V-12), and compound (V-26). ), Compound (V-27), Compound (V-31), Compound (V-33), Compound (VI-1), Compound (VI-2), Compound (VI-6), and Compound (VII-1) ) -Compound (VII-5) is more preferable, and compound (IV-1), compound (IV-2), compound (IV-15), compound (IV-16), compound (V-1) to compound (V-12), compound (V-33) and compound (VII-2) are more preferable.

In the present invention, at least one diamine selected from the group of the above compounds (I) to (VII) may be used alone, or two or more diamines may be used in combination. At least one diamine selected from the group of compounds (I) to (VII) may be used in combination with diamines other than compounds (I) to (VII). In the following description, diamines other than compound (I)-compound (VII) are called other diamine.

Other diamines can be selected without limitation as long as the object of the present invention can be achieved, but for example, naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, siloxane-based diamines represented by formula (VIII), And diamines represented by formulas (1 ') to (8').

In formula (VIII), R ³³ and R ³⁴ independently represent alkyl or phenyl having 1 to 3 carbon atoms, A ³ is independently alkylene, phenylene or phenylene having 1 to 6 carbon atoms, m Is an integer of 1 to 10.

Here, R ³⁵ and R ³⁶ are independently alkyl having 3 to 30 carbons.

In the present invention, only other diamines may be used. However, it is preferable to make the ratio of the compound (I)-the compound (VII) into 5-100 mol% in the diamine used. It is most preferable to use only compounds (I) to (VII).

In addition, a part of diamine may be substituted by monoamine. By substituting a part of diamine with monoamine, advancing of a polymerization reaction can be suppressed and the molecular weight of the polymer (polyamic acid) obtained by adjustment of the usage-amount of monoamine can be controlled easily. The ratio of the monoamine to the diamine can be in a range that does not impair the effects of the present invention, and it is preferable to be 10 mol% or less of the total amine amount on the basis.

In the present invention, the polyamic acid and its derivatives may have any weight average molecular weight. Although a weight average molecular weight is not specifically limited, When used as a component of a liquid crystal aligning agent, it is preferable that it is 5 * 10 <^3> or more, and it is more preferable that it is 1 * 10 <^4> or more. The polyamic acid and its derivative having a weight average molecular weight of 5 × 10 ³ or more do not evaporate at the firing step of the liquid crystal aligning film, and have preferable physical properties as a component of the liquid crystal aligning agent.

The weight average molecular weight of polyamic acid and its derivatives is measured by gel permeation chromatography (GPC) method. For example, a solution of the obtained polyamic acid or derivative thereof is diluted in dimethylformamide (DMF) such that the polyamic acid concentration is about 1% by weight, and DMF is developed using chromatography pack C-R7A (manufactured by Shimadzu Corporation). After measuring by gel permeation chromatography analysis (GPC) method used as a solvent, it can obtain | require by polystyrene conversion. In addition, in order to perform GPC measurement such as polyamic acid or polyacrylic acid with good accuracy, a developing solvent in which inorganic acids such as phosphoric acid, hydrochloric acid, acetic acid and sulfuric acid, and inorganic salts such as lithium bromide and lithium chloride are dissolved in DM solvent may be prepared. It may be.

The polyamic acid and its derivatives of the present invention can be produced using a known method. For example, in the reaction vessel provided with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer and a condenser, at least one diamine selected from at least one of compounds (I) to (VII), and optionally other diamines, In addition, desired amount of monoamine is injected as necessary.

Next, at least one of a solvent (for example, N-methyl-2-pyrrolidone, dimethylformamide, etc.) which is an amide polar solvent, and the above-mentioned tetracarboxylic dianhydride, and carboxylic anhydride are added as needed. At this time, it is preferable that the total amount of tetracarboxylic acid dianhydride is set to a molar amount (molar ratio of about 0.9 to 1.1) which is almost equal to the total moles of diamine.

It is made to react for 1 to 48 hours at the temperature of 0-70 degreeC under stirring, and the solution of polyamic acid can be obtained. Moreover, heating can raise reaction temperature (for example, 50-80 degreeC), and the polyamic acid with a small molecular weight can also be obtained.

The polyamic acid of the present invention is identified by precipitating with a large amount of cosolvent, separating the solids and the solvent completely by filtration and the like and analyzing by IR and NMR. In addition, the monomer used can be identified by decomposing a solid polyamic acid with a strong alkaline aqueous solution such as KOH or NaOH, extracting with an organic solvent, and analyzing with GC, HPLC or GC-MS.

The solution of the obtained polyamic acid can be used diluted with a solvent in order to adjust to a desired viscosity.

When the polyamic acid of the present invention is a soluble polyimide which is a polyamic acid derivative, the polyamic acid solution is anhydrides such as acetic anhydride, pyrophytic anhydride, and trifluoroacetic anhydride, which is a dehydrating agent, and triethylamine, which is a dehydration ring closure catalyst. It can be obtained by imidization reaction at a temperature of 20 to 150 ° C with a tertiary amine such as pyridine and collidine.

Soluble polyimide is a polyamic acid solution using a large amount of cosolvent (alcohol solvents such as methanol, ethanol, isopropanol or glycol solvents) to precipitate polyamic acid, and the precipitated polyamic acid is dissolved in a solvent such as toluene or xylene. It can also be obtained by carrying out an imidation reaction at the temperature of 20-150 degreeC with the above dehydrating agent and dehydration ring-closure catalyst.

In the said imidation reaction, it is preferable that the ratio of a dehydrating agent and a dehydration ring-closure catalyst is 0.1-10 (molar ratio). It is preferable that the total usage-amount of all these is 1.5-10 times mole with respect to the total molar amount of the acid dianhydride contained in tetracarboxylic dianhydride to be used. By adjusting the dehydrating agent, catalyst amount, reaction temperature, and reaction time of such chemical imidation, the degree of imidation can be controlled and a partial polyimide can be obtained.

The obtained polyimide can be separated from the solvent, re-dissolved together with a compound having an oxadine structure in a solvent described later, and used as a liquid crystal aligning agent, or by adding a compound having an oxadine structure without separating from a solvent to align the liquid crystal. It can also be used as a zero.

In the liquid crystal aligning agent in which the other component is at least one polymer selected from polyamic acid and a derivative of the polyamic acid, the ratio of the compound (A) is 0.01 to 0.99 by weight ratio with respect to the total amount of the compound (A) and this polymer. . This weight ratio becomes like this. Preferably it is 0.1-0.99, More preferably, it is 0.2-0.99, More preferably, it is 0.5-0.99. By carrying out the ratio of a compound (A) in such a range, it can be set as the liquid crystal aligning agent in which the balance between voltage retention, liquid crystal alignability, and display quality was maintained. On the other hand, the above [17] to [29] are examples in which a preferable ratio of such a compound (A) is combined with a preferred range of definition of each polymer selected from a compound (A), a polyamic acid and a derivative of a polyamic acid. .

As a preferable example of the liquid crystal aligning agent of this invention, the composition containing the polymer selected from a compound (A), a compound (B), a polyamic acid, and a derivative of this polyamic acid as an essential component is contained as mentioned above. The definition range of these components and its preferable range are the same as the above-mentioned, and the preferable ratio of the compound (A) in a liquid crystal aligning agent is also the same as the case of the other liquid crystal aligning agent demonstrated previously.

 Next, the liquid crystal aligning agent whose other component is at least one of a radically polymerizable monomer is demonstrated. Examples of preferred radically polymerizable monomers are acrylic esters and methacrylic esters. Specific examples of acrylic esters include cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl acrylate, isoboroyl acrylate, phenyl acrylate, and benzyl acrylate. Specific examples of methacrylic acid esters include cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, and methacrylate methacrylate. , Methacrylic acid benzyl, methacrylic acid 2-hydroxyethyl, and methacrylic acid 2-hydroxy propyl.

Specific examples of the difunctional acrylic acid ester and the bifunctional methacrylic acid ester include ethylene bisacrylate, Alonics M-210, Alonics M-240 and Alonics M-6200 manufactured by Dong-A Synthetic Chemical Co., Ltd. KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, KAYARAD R-684, V260, V312 and V335HP, manufactured by Osaka Organic Chemical Industry Co., Ltd., and Kyoara Oil Chemical Co., Ltd. Acrylate BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of the trifunctional or higher trifunctional acrylic acid ester and the trifunctional or higher polyfunctional methacrylic acid ester include 4,4'-methylene bis (N, N-dihydroxyethylene acrylate aniline), manufactured by Dong-A Synthetic Chemical Co., Ltd. Alonics M-400, Alonics M-405, Alonics M-450, Alonics M-7100, Alonics M-8030 and Alonics M-8060, KAYARAD TMPTA, KAYARAD DPCA- 20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT by Osaka Organic Chemical Industry Co., Ltd. are mentioned.

Specific examples of the acrylic acid amide derivative and the methacrylic acid amide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, Nn-propyl acrylamide, Nn-propyl methacrylamide, N-cyclopropyl acrylamide, N -Cyclopropyl methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethyl methacrylamide, N-tetrahydroperfuryl acrylamide, N-tetrahydroperfuryl methacrylamide, N-ethyl acrylamide, N -Ethyl-N-methyl acrylamide, N, N-diethyl acrylamide, N-methyl-Nn-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloylpiperidine, N-acryl Loylpyrrolidine, N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide , N-phenyl methacrylamide, N-butyl methacrylamide Mead, N- (iso-butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethyl Amino) propyl] methacryl amide, N- (methoxymethyl) methacryl amide, N- (hydroxymethyl) -2-methacryl amide, N-benzyl-2-methacryl amide, N, N'-methylenebis Methacrylamide is mentioned. More preferably, N, N'methylenebisacrylamide, N, N'dihydroxy ethylene-bisacrylamide, ethylenebisacrylate, and 4,4'-methylene bis (N, N-dihydroxyethyleneacryl Late aniline).

In the liquid crystal aligning agent whose other component is a radically polymerizable monomer, the ratio of a compound (A) is 0.01-0.99 by weight ratio with respect to the total of a compound (A) and this monomer. This weight ratio becomes like this. Preferably it is 0.1-0.99, More preferably, it is 0.2-0.99, More preferably, it is 0.5-0.99. Said [30] and [31] are the examples which combined the preferable ratio of such a compound (A) with the preferable range of the definition of a compound (A).

Next, the liquid crystal aligning agent whose other component is at least any one of an epoxy compound is demonstrated. Epoxy compounds are compounds having at least one oxirane ring in the molecule. Examples of the compound having one oxysilane ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoro propylene oxide, cyclohexene oxide, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline And 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxy propane.

Examples of the compound having two oxysilane rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol digly Cydyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 3, 4-ethoxycyclohexenylmethyl-3 ', 4'-ethoxycyclohexenecarboxylate, and 3- (N, N- diglycidyl) aminopropyl trimethoxysilane.

Examples of compounds having three oxirane rings in the molecule include 2- [4- (2,3-epoxy propoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxy Propoxy] phenyl)] ethyl] phenyl] propane (trade name "Tekmore VG3101L", manufactured by Mitsui Chemicals, Inc.).

Examples of compounds having four oxirane rings in the molecule include 1,3,5,6-tetra glycidyl-2,4-hexanediol, N, N, N ', N'-tetra glycidyl-m-xylene Diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diamino diphenylmethane, and 3 -(N-allyl-N-glycidyl) aminopropyl trimethoxysilane.

In addition to the above, oligomers and polymers which may be obtained by polymerizing a monomer having an oxirane ring are also exemplified by the epoxy compound. Examples of the monomer having an oxysilane ring are glycidyl (meth) acrylate, 3,4-epoxy cyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate. An oligomer or polymer having an oxirane ring polymerizes a monomer having an oxirane ring alone, copolymerizes two or more of monomers having an oxirane ring, or at least one of monomers having an oxirane ring does not have an oxirane ring. Obtained by copolymerizing at least one of the other monomers.

Examples of the other monomer copolymerized with the monomer having an oxirane ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and iso-. Butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy propyl (meth) Acrylate, styrene, methyl styrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

In the liquid crystal aligning agent whose other component is at least one of an epoxy compound, the ratio of a compound (A) is 0.01-0.99 by weight ratio with respect to the sum total of a compound (A) and this monomer. The said weight ratio becomes like this. Preferably it is 0.1-0.99, More preferably, it is 0.2-0.99, More preferably, it is 0.5-0.99. Said [32] and [33] are the examples which combined the preferable ratio of such a compound (A) with the preferable range of the definition of a compound (A).

Next, a solvent and other additives are demonstrated.

The solvent which can be used for this invention includes the compound normally used for manufacturing processes, such as a compound (A), a compound (B), a polyamic acid, a soluble polyimide, a polyamideimide, and these uses, However, a polyamic acid and It is preferable that it is a mixed solvent containing the aprotic polar organic solvent which is a good solvent of soluble polyimide, and the solvent for the purpose of improving applicability | paintability by changing surface tension.

Preferable examples of the aprotic polar organic solvent (hereinafter referred to as the aprotic polar organic solvent) as a good solvent for polyamic acid and soluble polyimide include N-methyl-2-pyrrolidone, dimethyl imidazolidinone, and N-. Methyl caprolactam, N-methylpropion amide, N, N-dimethyl acetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethyl acetamide, γ-butyrolactone And γ-valerolactone. Among these, N-methyl-2-pyrrolidone, dimethyl imidazolidinone, (gamma) -butyrolactone, and (gamma) -valerolactone are more preferable.

Preferable examples of the solvent (hereinafter, other solvents) for the purpose of improving the coating property by changing the surface tension include alkyl lactate, 3-methyl-3-methoxy butanol, tetralin, isopron, ethylene glycol monoalkyl ether ( Examples: monobutyl ether), diethylene glycol monoalkyl ether (e.g. monoethyl ether), ethylene glycol monoalkyl ether acetate, ethylene glycol monophenyl ether acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (e.g. Monobutyl ether), dialkyl malonic acid (eg diethyl ester), dipropylene glycol monoalkyl ether (eg monomethyl ether), and ester compounds (eg acetate) of the above glycol monoalkyl ethers. Among these, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether are more preferable.

The kind and ratio of an aprotic polar solvent and other solvent can be suitably set in consideration of the printability, applicability | paintability, solubility, storage stability, etc. of a liquid crystal aligning agent. Aprotic polar solvents are superior in solubility and storage stability relative to other solvents, and other solvents tend to be excellent in printability and applicability.

As mentioned above, the liquid crystal aligning agent of this invention may contain various additives. As various additives, a high molecular compound or a low molecular compound other than polyamic acid and its derivatives can be selected and used according to each purpose.

For example, you may add a soluble high molecular compound to an organic solvent, and the electrical property and orientation of the liquid crystal aligning film formed by adding them can be controlled. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone modified polyurethane, silicone modified polyester and the like.

Moreover, as an additive of a low molecular weight compound, 1) surfactant according to the objective regarding the expectation of the improvement of applicability, 2) an antistatic agent, when an antistatic improvement is needed, 3) adhesiveness with a board | substrate In addition, when the improvement of rubbing resistance is anticipated, an imidation catalyst can be used when imidation of a silane coupling agent, a titanium-type coupling agent, an epoxy group containing compound, or 4) low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propylmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-glycidoxyoxytrimethylsilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethyl butylidene) -3 -(Triethoxysilyl) -1-propylamine, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, etc. The can.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo neopentylglycol diglycidyl ether, 1,3,5,6- Tetra glycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclo Hexane and N, N, N ', N'-tetra glycidyl-4,4'-diamino diphenylmethane.

Examples of the imidation catalyst 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; Pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, and hydroxy substituted imidazole Cyclic amines, such as these, are mentioned. Among these, N, N-dimethyl aniline, o-hydroxy aniline, m-hydroxy aniline, p-hydroxy aniline, o-hydroxy pyridine, m-hydroxy pyridine, p-hydroxy pyridine, and isoquinoline are desirable.

The addition amount of a silane coupling agent is 0 to 10 weight% of the total weight of a polymer normally, and it is preferable that it is 0.1 to 3 weight%. The addition amount of an epoxy compound is 0.1-30% of the total weight of a polymer normally, and 1-20% is preferable. The amount of the imidization catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid and its derivatives. Although the addition amount of another additive changes with the use, it is usually 0-30 weight% of the total weight of a polyamic acid and its derivative, and it is preferable that it is 0.1-10 weight%.

The viscosity of the liquid crystal aligning agent of this invention varies in various ways according to the method of apply | coating, the density | concentration of polyamic acid and its derivatives, the kind of polyamic acid and its derivatives used, and the kind and ratio of a solvent. For example, in the case of application | coating by the printing machine (including offset printing machine and inkjet printing machine) which can be used at the manufacturing process of a normal liquid crystal display element, it is 3-100 mPa * s (more preferably 5-80 mPa * s). It is preferable. If it is less than 3 mPa · s, it is difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa · s, printing unevenness may increase. In the case of coating by spin coating, 3 to 200 mPa · s (more preferably 5 to 100 mPa · s) is suitable.

The viscosity of a liquid crystal aligning agent is measured by the rotational viscometry method, for example, it is measured (measurement temperature: 25 degreeC) using a rotational viscometer (the TVE-20L type made by Tokyo Co., Ltd.).

The liquid crystal aligning film of this invention is formed by baking the liquid crystal aligning agent of this invention in the state of a film | membrane. This liquid crystal aligning film apply | coats the liquid crystal aligning agent of this invention to the board | substrate for liquid crystal display elements, or the measurement board | substrates, such as calcium fluoride and silicon, for example, and makes the film of this liquid crystal aligning agent 150-400 degreeC, Preferably, it can form by heating at 180-280 degreeC. It is preferable that it is 10-300 nm, and, as for the film thickness of a liquid crystal aligning film here, it is more preferable that it is 30-150 nm. Moreover, it is preferable that the liquid crystal aligning film is rubbing process as needed.

The film thickness of this liquid crystal aligning film can be adjusted with the viscosity of a liquid crystal aligning agent, and the coating method of a liquid crystal aligning agent. Moreover, the film thickness of a liquid crystal aligning film can be measured by well-known film thickness measuring devices, such as a stepmeter and an ellipsometer. In addition, the component in a liquid crystal aligning film can process hydrolysis etc. as needed, and can analyze using ordinary analysis means, such as IR and MS.

The liquid crystal display device of the present invention comprises: 1) a pair of substrates arranged oppositely; 2) a liquid crystal alignment film of the present invention formed on opposing surfaces of each of the pair of substrates; and 3) interposed between the pair of substrates. It includes a liquid crystal layer. It is preferable that the pair of electrode-attached substrates arranged opposite to each other is a transparent substrate (for example, a glass substrate).

Electrodes are provided on at least one direction of the pair of substrates or on the surfaces of both substrates corresponding to the shape of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one side of the substrate. As such an electrode, ITO, the vapor deposition film of a metal, etc. are mentioned, for example. The electrode may be formed entirely on the surface of the substrate, or may be formed in a predetermined shape that is patterned, for example. The liquid crystal aligning film of this invention is formed in the board | substrate with which an electrode is not provided, and the liquid crystal aligning film of this invention is formed on an electrode in the board | substrate with which an electrode is provided. Formation of the liquid crystal aligning film of this invention is as above-mentioned.

The liquid crystal layer interposed between the pair of substrates includes a liquid crystal composition. There is no restriction | limiting in particular here, A liquid crystal composition can respond also to a drive mode, The composition of either of the liquid crystal composition whose dielectric anisotropy is positive and the liquid crystal composition whose dielectric anisotropy is negative can be used. These liquid crystal compositions may contain one or more optically active compounds.

Examples of preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, Japanese Patent Application Laid-Open No. 8-157826, and Japanese Patent Application Laid-Open No. 8-231960. Japanese Patent Application Laid-Open No. 9-241644 (EP885272A1), Japanese Patent Application Laid-Open No. 9-302346 (EP806466A1), Japanese Patent Application Laid-Open No. 8-199168 (EP722998A1), Japanese Patent Application Laid-open No. 9-235552, Japanese Patent Application Laid-Open No. 9 -255956, Japanese Patent Laid-Open No. 9-241643 (EP885271A1), Japanese Patent Application Laid-Open No. 10-204016, Japanese Patent Application Laid-Open No. 10-204436, Japanese Patent Laid-Open No. 10-231482, Japanese Patent Laid-Open No. 2000- Published in Japanese Unexamined Patent Publication No. 087040 and Japanese Patent Laid-Open No. 2001-48822.

The liquid crystal composition which can be used in VA type liquid crystal display element can be set as the various liquid crystal composition whose dielectric anisotropy is negative. Examples of preferred liquid crystal compositions include Japanese Patent Application Laid-Open No. 57-114532, Japanese Patent Application Laid-Open No. 2-4725, Japanese Patent Application Laid-Open No. 4-224885, Japanese Patent Application Laid-Open No. 8-40953, and Japanese Patent Application Laid-Open No. 8-104869. JP-A-10-168076, JP-A-10-168453, JP-A 10-236989, JP-A 10-236990, JP-A 10-236992, JP-A Japanese Patent Application Laid-Open No. 10-236993, Japanese Patent Application Laid-Open No. 10-236994, Japanese Patent Application Laid-Open No. 10-237000, Japanese Patent Application Laid-open No. 10-237004, Japanese Patent Application Laid-Open No. 10-237024 Japanese Patent Laid-Open Publication No. 10-237075, Japanese Patent Laid-Open Publication No. 10-237076, Japanese Patent Laid-Open Publication No. 10-237448 (EP967261A1), Japanese Patent Laid-Open Publication No. 10-287874, Japanese Patent Laid-Open Publication No. 10-287875, Japan Japanese Patent Laid-Open No. 10-291945, Japanese Patent Laid-Open No. 11-029581, Japanese Patent Laid-Open No. 11-080049, Japanese Patent Laid-Open No. 2000-256307, Japanese Patent Laid-Open 2001 -019965, Japanese Patent Application Laid-Open No. 2001-072626, Japanese Patent Application Laid-Open No. 2001-192657, and the like.

Of course, the liquid crystal display element of this invention may have another member. For example, in a TFT type liquid crystal device of color display using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like are formed on a first transparent substrate, and a pixel is formed on a second transparent substrate. It may have a black matrix, a color filter, a planarization film, a pixel electrode, etc. that block light other than the region. In the VA type liquid crystal display element, especially the MVA type liquid crystal display element, a minute projection called a domain is formed on the first transparent substrate, but a spacer may be formed for adjusting the cell gap between the substrates.

Although the liquid crystal display device of the present invention can be produced by any method, for example, 1) a step of applying a liquid crystal aligning agent on the two transparent substrates, 2) a step of drying the applied liquid crystal aligning agent, 3 A) a step of performing heat treatment necessary for dehydrating and ring-closing the dried liquid crystal aligning agent, 4) a step of aligning the obtained alignment film, 5) a step of bonding two substrates together, and then sealing the liquid crystal between the substrates, Or after dripping liquid crystal on one board | substrate, it is produced by the method of including the process of sticking with the other board | substrate.

As a coating method in the process of apply | coating the said liquid crystal aligning agent, the spinner method, the printing method, the dipping method, the dripping method, the inkjet method, etc. which are generally known are applicable also in this invention.

As a method for performing the heat treatment necessary for the drying step and the dehydration reaction, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, or the like is applicable. It is preferable to perform a drying process at comparatively low temperature (50-140 degreeC) in the range which can evaporate a solvent. It is preferable to perform the process of heat processing at the temperature of about 150-300 degreeC generally.

Orientation processing to a liquid crystal aligning film is performed by a rubbing process normally in an IPS type liquid crystal display element, an OCB type liquid crystal display element, a TN type liquid crystal display element, and an STN type liquid crystal display element. VA type liquid crystal display elements do not perform rubbing in many cases, but can also be done.

Subsequently, an adhesive agent is applied on one substrate, and is bonded to the other substrate, and a liquid crystal is injected between these substrates in a vacuum. In the dropping injection method, the liquid crystals are dropped onto the substrate before being glued to each other, and then bonded together as the other substrate. The liquid crystal display element of this invention is produced by hardening the adhesive agent used for adhering to each other by heat or an ultraviolet-ray.

A polarizing plate (polarizing film), a wave plate, a light scattering film, a drive circuit, etc. may be mounted in the liquid crystal display element of this invention.

(Example)

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compound (B), tetracarboxylic dianhydride, diamine, and a solvent which are used in an Example are shown next. About the compound and solvent which are not represented by a formula in the past description, it may be represented by the following symbols. On the other hand, the unit liter of the capacity is indicated by L. Thus, mL is milliliters.

<Compound (B)>

Compound (B-1): "BANI-M" made by Maruzen Petrochemical Co., Ltd.

Compound (B-2): Maruzen Petrochemical Co., Ltd. "BANI-X"

Compound (B-3): "BANI-H" made by Maruzen Petrochemical Co., Ltd.

<Tetracarboxylic acid dianhydride>

Compound (1): pyromellitic dianhydride

Compound (7): 1,2,3,4-cyclobutane tetracarboxylic dianhydride

<Diamine>

Compound (V-1): 4,4'-diamino diphenylmethane

Compound (VII-2): 1,3-bis (p-aminobenzylphenyl) propane

12PDA: 1- (n-dodecyl) benzyl-3,5-phenylenediamine

<Other compound>

4,4'-methylenebis (N, N-diglycidylaniline)

3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (product name: ceoxide 2021P / Daicel Chemical Co., Ltd.)

4,4'-methylenebis (N, N-dihydroxyethylene acrylate aniline)

N, N '-(1,2-dihydroxyethylene) bisacrylamide

N, N'-methylenebisacrylamide

Ethylenediacrylate

<Solvent>

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

Example 1

<Synthesis of Compound (A-1-2-1) (1)>

(First process)

<Synthesis of 4- (n-hexadecyl) -3 ', 5'-dinitrobenzophenone>

A commercially available n-hexadecylbenzene (50 g: 165 mmol) was placed in a 1 L-3 neck flask equipped with a dropping funnel and a thermometer, and dissolved in dichloromethane (250 mL). The solution was cooled to 5 ° C. and aluminum chloride (33 g: 248 mmol) was added thereto. The solution which melt | dissolved 3, 5- dinitro benzoyl chloride (46 g: 198 mmol) in dichloromethane (250 mL) was dripped keeping the solution at 5 degreeC, and it stirred at room temperature for 12 hours. The reaction solution was poured into 3M hydrochloric acid (500 mL), and the obtained organic layer was washed twice with saturated aqueous sodium hydrogen carbonate solution (500 mL), followed by washing with pure water (500 mL). Anhydrous magnesium sulfate was added to the organic layer, and after drying, the solvent was distilled off under reduced pressure to obtain a crude crystal. The obtained crude crystal was separated and purified by column chromatography (eluant: toluene), and recrystallized from toluene to obtain 4- (n-hexadecyl) -3 ', 5'-dinitrobenzophenone (yield 69 g, yield 84). %).

(Second process)

<Synthesis of 1- (n-hexadecyl) benzyl-3,5-dinitrobenzene>

To a 1 L-3 neck flask equipped with a dropping funnel and a thermometer, 4- (n-hexadecyl) -3 ', 5'-dinitrobenzophenone (69 g: 138 mmol) obtained in the previous step was placed, and dichloromethane (300 mL) was added. )). Titanium (IV) tetrachloride (39 g: 207 mmol) and triethylsilane (48 g: 414 mmol) were then added dropwise while maintaining the solution at 5 ° C, followed by stirring at room temperature for 3 hours. The reaction solution was poured into 3M hydrochloric acid (500 mL), and the obtained organic layer was washed twice with saturated aqueous sodium hydrogen carbonate solution (500 mL), followed by washing with pure water (500 mL). After adding anhydrous magnesium sulfate to the organic layer and drying, the solvent was distilled off under reduced pressure to obtain a crude crystal. The obtained crude crystal was separated and purified by column chromatography (eluant: toluene), and recrystallized from heptane to obtain 1- (n-hexadecyl) benzyl-3,5-dinitrobenzene (yield 49 g, yield 73%). .

(Third process)

<Synthesis of 1- (n-hexadecyl) benzyl-3,5-phenylenediamine>

Into the autoclave reaction tube, 1- (n-hexadecyl) benzyl-3,5-dinitrobenzene (49 g: 102 mmol) and palladium carbon powder (5.0 g) obtained in the previous step were added, toluene (250 mL) and ethanol. (250 mL) was added. After stirring at 490 kPa hydrogen pressure and room temperature, the palladium carbon powder was filtered and the solvent was distilled off under reduced pressure. The obtained crude crystal was separated and purified by column chromatography (eluant: dichloromethane / methanol mixed solvent (volume ratio 10/1)), recrystallized from toluene, and then 1- (n-hexadecyl) benzyl-3,5-phenylenediamine Was obtained (yield 38g, yield 88%).

¹ H-NMR (ppm); 0.88 (t, -CH ₃ , 3H, J = 6.8 Hz), 1.25-1.59 (m, -CH _2- , 28H), 2.55 (t, -CH _2- , 2H, J = 7.8 Hz), 3.50 (br .s, -NH ₂ , 4H), 3.75 (s, -CH _2- , 2H), 5.89 (t, arm.H, 1H, J = 1.9 Hz), 5.97 (d, arm.H, 2H, J = 1.0 Hz), 7.07-7.11 (m, arm.H, 4H)

Melting point; 78.7-80.8 ℃

(Fourth process)

<Synthesis of 1- (n-hexadecyl) benzyl-3,5-bismaleimide>

Maleic anhydride (18 g: 185 mmol) was placed in a 500 mL-3 neck flask equipped with a dropping funnel and a thermometer, and dissolved in acetone (100 mL). A solution in which 1- (n-hexadecyl) benzyl-3,5-phenylenediamine (35 g: 83 mmol) obtained in the previous step was dissolved in acetone (100 mL) was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours, and acetic anhydride (51 g: 498 mmol) and sodium acetate (1.4 g: 17 mmol) were added thereto, followed by heating to reflux for 3 hours. After cooling, the reaction mixture solution was poured into dichloromethane (500 mL) and washed three times with pure water (500 mL). Anhydrous magnesium sulfate was added to the organic layer, and the solvent was distilled off under reduced pressure. The obtained crude crystal was separated and purified by column chromatography (eluent: toluene / ethyl acetate mixed solvent (volume ratio 5/1)) to obtain 1- (n-hexadecyl) benzyl-3,5-bismaleimide (water Yield 37 g, yield 76%).

¹ H-NMR (ppm); 0.88 (t, -CH ₃ , 3H, J = 6.9 Hz), 1.25-1.57 (m, -CH _2- , 28H), 2.56 (t, -CH _2- , 2H, J = 7.8 Hz), 4.02 (s , -CH _2- , 2H), 6.84 (s, -CH =, 4H), 7.11 (s, arm.H, 4H), 7.22 (d, arm.H, 2H, J = 1.5 Hz), 7.30 (t , arm.H, -1H, J = 2.0Hz)

(The fifth process)

<Synthesis of allylcyclopentadiene>

Commercially available cyclohexadiene was pyrolyzed according to the method described in Organic Synthesis Handbook, page 501, Maruzen (1990), to obtain cyclopentadiene. Sodium hydride (4.5 g: 189 mmol) was placed in a three-necked flask equipped with a thermometer, a dropping funnel and a nitrogen introduction tube, dehydrated tetrahydrofuran (25 mL) was added, and the solution was cooled to -20 ° C. The cyclopentadiene (11 g: 172 mmol) obtained was dripped keeping the liquid temperature at -20 degreeC. After completion of dropping, the mixture was stirred for 1 hour under a nitrogen atmosphere while maintaining the liquid temperature at -20 ° C. A solution in which allyl chloride (14 g) was dissolved in dehydrated tetrahydrofuran (25 mL) was added dropwise while maintaining the reaction mixture solution at -20 ° C. After completion of the dropwise addition, the reaction mixture solution was raised to room temperature, and then stirred at room temperature under nitrogen atmosphere for 1 hour. The reaction mixture solution was poured into toluene (100 mL) and washed three times with pure water (100 mL). After adding anhydrous magnesium sulfate to the organic layer and drying, the drying agent was filtered and the toluene solution of allylcyclopentadiene was obtained.

(The sixth process)

<Synthesis of Compound (A-1-2-1)>

To the obtained toluene solution, 1- (n-hexadecyl) benzyl-3,5-bismaleimide (20 g: 34 mmol) synthesize | combined previously was added, and it heated and refluxed for 8 hours in nitrogen atmosphere. After cooling, the reaction mixture solution was poured into toluene (100 mL) and washed three times with pure water (100 mL). Anhydrous magnesium sulfate was added to the organic layer, and the solvent was distilled off under reduced pressure after drying. The obtained viscous liquid was separated and purified by column chromatography (eluant: toluene) to obtain the desired compound (A-1-2-1) (yield 17g, yield 63%).

Example 2

<Synthesis of Compound (A-1-2-1) (2)>

Using a 200 mL three-necked flask equipped with a dropping funnel and a thermometer, 10 g (23.7 mmol) of 1- (n-hexadecyl) benzyl-3,5-phenylenediamine obtained in the third step of Example 1 was added to 50 mL of DMF. Dissolved. There, 10.6 g (52.1 mmol) of allylbicyclo [2,2,1] hepto-5-ene-2,3-dicarboxylic acid anhydride synthesized by the method described in Japanese Patent Application Laid-Open No. 08-277265, 30 mL of DMF The solution dissolved in was dripped. The solution was stirred at 50 ° C. under nitrogen atmosphere for 6 hours. Acetic anhydride 14.5g (142 mmol) was added there, and it stirred at 100 degreeC under nitrogen atmosphere for 2 hours. The obtained reaction solution was thrown in the mixed solution of 200 mL of pure waters-200 mL of ethyl acetate, and the obtained organic layer was wash | cleaned 3 times with 200 mL of pure waters. After adding anhydrous magnesium sulfate to the organic layer and drying, the solvent was distilled off under reduced pressure to obtain a crude crystal. The obtained crude crystal was separated and purified by column chromatography (toluene: ethyl acetate = 2: 1) to obtain a compound (A-1-2-1) in the form of yellow syrup.

Example 3

<Synthesis of Compound (A-1-5-1)>

5-((4- (4- (4-pentylcyclohexyl) cyclohexyl) phenyl) -methyl synthesized by the method described in Japanese Patent Application Laid-Open No. 2002-162630 using a 200 mL old flask equipped with a dropping funnel and a thermometer. 10 g (23.1 mmol) of -1,3-diaminobenzene was dissolved in 50 mL of DMF, and allyl bicyclo [2,2,1] hepto- synthesized by the method described in JP-A 08-277265. A solution in which 10.6 g (52.1 mmol) of 5-ene-2,3-dicarboxylic anhydride was dissolved in 30 mL of DMF was added dropwise, while the solution was stirred at 50 ° C. under a nitrogen atmosphere for 6 hours. 139 mmol) was added, and the mixture was stirred for 2 hours at 100 ° C. under a nitrogen atmosphere, and the obtained reaction solution was placed in a mixed solution of 200 mL of pure water / 200 mL of ethyl acetate, and the resulting organic layer was washed three times with 200 mL of pure water. After drying, the solvent was distilled off under reduced pressure to obtain a crude crystal. The crude crystal was purified by column chromatography (toluene: ethyl acetate = 2: 1) separated and purified by to obtain a yellow syrup form of the compound (A-1-5-1).

[Polymerization Example 1]

Synthesis of Polyamic Acid

Compound (V-1) (2.983 g) and dehydrated NMP (58.3 g) were placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, followed by stirring and dissolving under dry nitrogen stream. Then, compound (7) (2.361g) and compound (1) (0.6563g) were added, and it was made to react for 30 hours in room temperature environment. When reaction temperature rose during reaction, reaction temperature was suppressed to about 70 degreeC or less, and it was made to react. BC (37.7g) was added to the obtained reaction liquid, and the solution (PA1) whose polyamic-acid concentration was 6 weight% was prepared. The weight average molecular weight of the obtained polyamic acid was 54,000.

Here, the weight average molecular weight of a polyamic acid is diluted with the obtained polyamic acid so that a polyamic acid concentration may be about 1 weight% with diluent (phosphate /DMF=0.6/100:weight ratio), and chromatopack C-R7A (Shimadzu Corporation) ) Was measured by GPC method using the diluent as a developing agent and determined by polystyrene conversion. In addition, the column used GF-7HQ (made by Showa Denko Co., Ltd.), and measured on the conditions of a column temperature of 50 degreeC, and a flow rate of 0.6 mL / min.

[Polymerization Examples 2 and 3]

As shown in Table 1, the polyamic-acid solutions PA2 and PA3 were prepared according to the polymerization example 1 except having changed the composition of tetracarboxylic dianhydride, diamine, and a solvent. Including the polymerization example 1, the result was put together in Table 1.

TABLE 1

Polymerization example number Polyamic Acid Solution (Symbol) Tetracarboxylic acid dianhydride (mole fraction) Diamine (mole fraction) Polyamic Acid Weight Average Molecular Weight One PA1 Compound (1) Compound (7) 0.1 0.4 Compound (V-1) 0.5 54,000 2 PA2 Compound (1) Compound (7) 0.1 0.4 Compound (VII-2) 0.5 83,000 3 PA3 Compound (7) 0.5 12PDA 0.5 36,000

Example 4

<Preparation of liquid crystal aligning agent>

Compound (A-1-2-1) (6 g) was dissolved in NMP (6 g) to give a solution having a concentration of 50% by weight. Then, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the liquid crystal aligning agent of 17 weight% of the density | concentration of compound (A-1-2-1) was prepared.

<Production of Liquid Crystal Display Device>

The obtained liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes with the spinner, and the film | membrane with a film thickness of 70 nm was formed. After coating and heating at 80 degreeC for about 5 minutes after coating, it heat-processed at 220 degreeC for 40 minutes, and formed the liquid crystal aligning film. And these glass substrates which formed the liquid crystal aligning film on the surface were ultrasonic-cleaned for 5 minutes in ultrapure water, and were dried at 120 degreeC in oven for 30 minutes.

4 micrometers of gap materials were spread | spreaded on one glass substrate, two glass substrates were arrange | positioned inside the surface which formed the liquid crystal aligning film inside, and it sealed with the epoxy hardening | curing agent, and produced the parallel cell of gap 4 micrometers. . The following liquid crystal composition was injected into this cell, and the injection hole was sealed with the photocuring agent. Subsequently, heat processing were performed for 30 minutes at 110 degreeC, and the liquid crystal display element was produced.

Liquid crystal composition

<Evaluation of Electrical Characteristics>

About the obtained liquid crystal display element, the measurement of voltage retention and the orientation of liquid crystal were evaluated by the following method.

(1) Measurement of voltage retention

The voltage retention was measured using the liquid crystal physical property evaluation apparatus 6254 type | mold by Dongyang Technica. Measurement conditions were gate width of 60 microseconds, frequency 0.3 Hz, wavelength height ± 5V, and measurement temperature was 60 degreeC. The larger this value is, the better the electrical characteristics can be. The results are shown in Table 2.

(2) orientation of liquid crystal

After leaving a liquid crystal display element for 100 hours in the atmosphere of the temperature of 100 degreeC, the liquid crystal display element was observed with the polarization microscope, and the case where there was no abnormal domain was judged as "good". The results are shown in Table 2.

Example 5

Compound (A-1-2-1) (1.2 g) and compound (B-1) (4.8 g) were dissolved in 6 g of NMP to prepare a solution having a concentration of 50% by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the liquid crystal aligning agent whose solid content concentration was 17 weight% was prepared. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 6

Compound (A-1-2-1) (1.2 g) and compound (B-2) (4.8 g) were dissolved in NMP (6 g) to obtain a solution having a concentration of 50% by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the liquid crystal aligning agent whose solid content concentration was 17 weight% was prepared. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 7

Compound (A-1-2-1) (1.2 g) and compound (B-3) (4.8 g) were dissolved in NMP (6 g) to obtain a solution having a concentration of 50% by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the solid content concentration prepared the liquid crystal aligning agent of 17 weight%. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 8

A 6% by weight polyamic acid solution (PA1) synthesized in Polymerization Example 1 and a 6% by weight NMP solution of compound (A-1-2-1) were mixed at a weight ratio of 8/2. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the solid content concentration prepared the liquid crystal aligning agent of 4 weight%. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 9

A 6% by weight polyamic acid solution (PA2) synthesized in Polymerization Example 2 and an NMP solution of 6% by weight compound (A-1-2-1) were mixed at a weight ratio of 8/2. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the solid content concentration prepared the liquid crystal aligning agent of 4 weight%. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 10

4,4'-methylenebis (N, N- diglycidylaniline) to the compound (A-1-2-1) of the weight ratio 0.2 to the solution of the density | concentration adjusted in Example 4 with 17 weight% Was added to prepare a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 3, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 11

3,4-Epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate was added to the compound (A-1-2-1) in a solution having a concentration adjusted in Example 4 of 17% by weight. It added in the ratio of 0.2 by weight ratio, and prepared the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 12

4,4'-methylenebis (N, N-dihydroxyethylene acrylate aniline) was added to the solution of 17 weight% of density | concentration adjusted in Example 4, and weight ratio 0.3 with respect to compound (A-1-2-1) It added in the ratio of and prepared the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 13

N, N '-(1,2-dihydroxyethylene) bisacrylamide in the weight ratio 0.2 with respect to compound (A-1-2-1) in the solution of the density | concentration adjusted in Example 4 with 17 weight% Was added to prepare a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 14

N, N'-methylenebisacrylamide was added to the solution of the density | concentration adjusted in Example 4 in the ratio of the weight ratio 0.2 with respect to a compound (A-1-2-1), and the liquid crystal aligning agent was prepared. . Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 15

Ethylenediacrylate was added to the solution of 17 weight% of density | concentration adjusted in Example 4 in the ratio of 0.2 by weight ratio with respect to a compound (A-1-2-1), and the liquid crystal aligning agent was prepared. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the same method as Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 16

Compound (A-1-5-1) (6 g) was dissolved in NMP (6 g) to obtain a solution having a concentration of 50% by weight. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the solution which the density | concentration of compound (A-1-2-1) is 17 weight% was prepared. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Example 17

N, N '-(1,2-dihydroxyethylene) bisacrylamide in the ratio of the weight ratio 0.2 with respect to compound (A-1-5-1) in the solution of the density | concentration prepared in Example 16 at 17 weight%. Was added to prepare a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 4, and the electrical characteristic was evaluated. The results are shown in Table 2.

Comparative Example 1

A 6% by weight polyamic acid solution (PA1) synthesized in Polymerization Example 1 and a 6% by weight polyamic acid solution (PA3) synthesized in Polymerization Example 3 were mixed at a weight ratio of 8/2. Next, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the liquid crystal aligning agent whose solid content concentration was 4 weight% was prepared. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced by the method similar to Example 2, and the electrical characteristic was evaluated. The results are shown in Table 2.

TABLE 2

Example No. Voltage retention rate (%) Orientation of liquid crystal 4 95.8 Good 5 96.0 Good 6 96.1 Good 7 96.0 Good 8 95.9 Good 9 96.0 Good 10 95.4 Good 11 95.6 Good 12 95.6 Good 13 95.5 Good 14 95.5 Good 15 96.0 Good 16 95.2 Good 17 95.0 Good Comparative Example 1 94.8 Bad

Thus, when a liquid crystal aligning film is formed using the liquid crystal aligning agent containing the allyl-substituted nadiimide compound of this invention, the liquid crystal display which has a high voltage retention and can remarkably suppress deterioration of liquid crystal alignability with time progresses. A device can be obtained.

Claims (34)

Nadiimide compound represented by a formula (A).

(Wherein Q is a divalent group having a side chain group having 3 or more carbon atoms) The method of claim 1, The nadiimide compound which Q is group represented by either of formula (A-1)-formula (A-5).

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with -O-, -CH = CH- or C≡C-, and any hydrogen of this phenyl is substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon numbers of R ² is 3 or more;

Where R ¹³ , R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or alkyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2;

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30;

Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl of 1 to 30 carbon atoms, or alkenyl of 2 to 30 carbon atoms; and R ⁵ is independently a single bond, -CO- or -CH _2-

Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl of 1 to 30 carbon atoms, or alkenyl of 2 to 30 carbon atoms; R ⁵ is independently a single bond, -CO- or -CH ₂ -and R ⁶ and R ⁷ are independently hydrogen, alkyl having 1 to 30 carbon atoms, or phenyl)

Wherein R ⁸ is hydrogen or alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl may be substituted with -O-, -CH = CH- or -C≡C-; ⁹ is independently -O- or alkylene having 1 to 6 carbon atoms; Ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 or 2 And c is independently 0 or 1)

(Wherein, R ¹⁰ is alkyl having a carbon number of 3 to 30 or 3 to 30 carbon atoms, fluorinated alkyl of; R ¹¹ is hydrogen, alkyl of 1 to 30 carbon atoms or from 1 to 30 carbon atoms, fluorinated alkyl of; R ¹² is independently And -O- or alkylene having 1 to 6 carbon atoms, and d is independently 0 or 1) The method of claim 2, The nadiimide compound which Q is group represented by Formula (A-1). The method of claim 2, Q is a group represented by formula (A-1) and R ¹ is a single bond, -O-, -COO-, -CONH-, -CH ₂ O- or methylene; A nadiimide compound in which R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, or a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and one of —CH ₂ — in alkyl and alkoxy may be substituted with a group represented by the formula (D-2-1). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, the sum thereof is 1 to 3) The method of claim 2, Q is a group represented by formula (A-1) and R ¹ is a single bond, -O-, -COO-, -CONH-, -CH ₂ O- or methylene; The nadiimide compound which R <^2> is group represented by C1-C30 alkyl or a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3). The method of claim 5, The nadiimide compound whose Q is either of the following groups.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms Nadiimide compound represented by a formula (A-1-2-1).

Nadiimide compound represented by a formula (A-1-5-1).

The liquid crystal aligning agent containing at least 1 of the nadiimide compound of any one of Claims 1-8. Containing at least one of the nadiimide compounds represented by the formula (A) and consisting of a compound represented by the formula (B), a polyamic acid or a derivative of the polyamic acid, a polymer, a radical polymerizable monomer and an epoxy compound as other components. A liquid crystal aligning agent containing at least one compound and / or polymer selected from the group.

(Wherein Q is a divalent group having 3 or more side chain groups)

Wherein R ^b1 and R ^b2 are independently hydrogen, alkyl of 1 to 12 carbon atoms, alkenyl of 3 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, aryl or benzyl; n is 1 or 2; When n is 1, R ^b3 is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, -L ^1- (O) _q − (L ² O) a group represented by _r -R ^b4 , a group represented by-(L ³ ) _s -B ² -R ^b5 , or a group represented by -B ² -TB ¹ ; In these formulas, L ¹ is alkylene having 2 to 6 carbon atoms; q is 0 or 1; L ² is alkylene having 2 to 6 carbon atoms, and r is an integer of 1 to 30; R ^b4 is alkyl having 2 to 6 carbon atoms; L ³ is alkylene having 1 to 4 carbon atoms, and s is 0 or 1; R ^b5 is alkyl having 1 to 4 carbons; B ² is phenylene, wherein any hydrogen may be substituted with —OH; T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- ; And B ¹ is phenyl in which any hydrogen may be substituted with —OH; And optionally hydrogen of alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, aryl of 6 to 12 carbon atoms, and benzyl may be substituted with -OH; when n is 2, R ^b3 is a 2 to 20 carbon atoms in the straight-chain alkylene, arylene, cycloalkylene of -L, 6 to 12 carbon atoms, having a carbon number of _{^{5~8 1 - (O) q -}} (L 2 O) r A group represented by -L ^4- , a group represented by-(L ³ ) _s -B ² -L ^5- , a group represented by -B ² -TB ^2- , or -B ² -OB ² -C (CH ₃ ) a group represented by ₂ -B ² -OB ^2- ; In these formulae, L ¹ , L ² And L ⁴ is independently straight chain alkylene having 2 to 6 carbon atoms, q is 0 or 1, and r is an integer of 1 to 30; L ³ And L ⁵ is independently straight chain alkylene having 1 to 4 carbon atoms, s is 0 or 1, and B ² is independently phenylene in which any hydrogen may be substituted with -OH; And T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- ; And any hydrogen of cycloalkylene having 5 to 8 carbon atoms and arylene having 6 to 12 carbon atoms may be substituted with -OH, and any hydrogen of arylene having 6 to 12 carbon atoms may be substituted with methyl) The method of claim 10, The other component is at least one of the compounds represented by formula (B); And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.01-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B). The method of claim 10, The other component is at least one of the compounds represented by formula (B); Q in Formula (A) is a group represented by Formula (A-1); And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.1-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B).

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with -O-, -CH = CH- or C≡C-, and any hydrogen of this phenyl is substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon number of R ² is 3 or more).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or alkyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2)

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30) The method of claim 12, The other component is at least one of the compounds represented by formula (B), Q in formula (A) is a group represented by formula (A-1), and the ratio of the nadiimide compound represented by formula (A) It is 0.1-0.99 by weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B); In formula (A-1), R ¹ is a single bond, —O—, —COO—, —CONH—, —CH ₂ O— or methylene; The liquid crystal aligning agent which is group represented by group which R <^2> has a steroid skeleton, C1-C30 alkyl, or Formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and one -CH ₂ -in these alkyl and alkoxy may be substituted with a group represented by the formula (D-2-1) ; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3). The method of claim 12, The other component is at least one of the compounds represented by formula (B), Q in formula (A) is a group represented by formula (A-1), and the ratio of the nadiimide compound represented by formula (A) It is 0.1-0.99 by weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B); In formula (A-1), R ¹ is a single bond, —O—, —COO—, —CONH—, —CH ₂ O— or methylene; Liquid crystal aligning agent in which R <^2> is group represented by C1-C30 alkyl or a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3). The method of claim 10, The other component is a compound represented by any one of formulas (B-1) to (B-3); Q in Formula (A) is either of the groups shown below; And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the compound represented by Formula (B).

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms

The method of claim 10, The other component is a compound represented by any one of formulas (B-1) to (B-3); The nadiimide compound represented by Formula (A) is a compound represented by Formula (A-1-2-1) or Formula (A-1-5-1); And the ratio of the nadiimide compound represented by Formula (A-1-2-1) or Formula (A-1-5-1) is with respect to the total amount of this nadiimide compound and the compound represented by Formula (B). The liquid crystal aligning agent which is 0.2-0.99 by weight ratio.

The method of claim 10, The other component is at least one polymer selected from polyamic acid and derivatives of this polyamic acid; And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.01-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and this polymer. The method of claim 10, The other component is at least one polymer selected from polyamic acid and derivatives of this polyamic acid; The polyamic acid is at least one of aromatic tetracarboxylic dianhydrides of formulas (1) to (6), or at least one of aromatic tetracarboxylic dianhydrides of formulas (1) to (6) and formulas (7) to ( A polyamic acid obtained by reacting a mixture with at least one of tetracarboxylic dianhydrides other than aromatics of 14) with at least one diamine selected from the group of compounds represented by formulas (I) to (VII); Q in Formula (A) is a group represented by Formula (A-1); And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.1-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and this polymer.

Wherein A ¹ is alkylene having ² to 12 carbon atoms; A ² is alkylene having 1 to 12 carbon atoms; and A ³ is independently a single bond, -O-, -CO-, -CONH-, -NHCO -, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _m -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _m- S- or alkylene having 1 to 12 carbon atoms, m is an integer of 1 to 12; and any hydrogen of the cyclohexane ring or the benzene ring is -F, -CH ₃ , -OH, -COOH,- May be substituted with SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl)

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with -O-, -CH = CH- or C≡C-, and any hydrogen of this phenyl is substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon number of R ² is 3 or more).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or alkyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2)

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30) The method of claim 18, In the formula ^(A-1), R 1 is a single bond, -O-, -COO-, -CONH-, -CH 2 O- or is methylene, R ² is the group, 1 to 30 carbon atoms having a steroid skeleton The liquid crystal aligning agent which is group represented by alkyl or a formula (D-1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and one -CH ₂ -in these alkyl and alkoxy may be substituted with a group represented by the formula (D-2-1) ; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3). The method of claim 18, In the formula ^(A-1), R 1 is a single bond, -O-, -COO-, -CONH-, -CH 2 O- or is methylene, R ² is alkyl of 1 to 30 carbon atoms, or a group represented by the formula (D The liquid crystal aligning agent which is group represented by -1-1).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond or alkylene having 1 to 4 carbon atoms; R ¹⁸ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; And e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 to 3). The method of claim 18, Q in Formula (A) is either of the groups shown below; And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the polymer which is another component.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms The method of claim 21, The liquid crystal aligning agent whose Q in Formula (A) is any of the group shown next.

The method according to any one of claims 18 to 22, The polyamic acid is at least one of the tetracarboxylic dianhydrides of the formulas (1) to (6) and formulas (IV-1), (IV-2), (IV-15), (IV-16), and The liquid crystal aligning agent which is a polymer obtained by making (V-1)-the formula (V-12), the formula (V-33), and the diamine of formula (VII-2) react.

The method according to any one of claims 18 to 22, The polyamic acid is tetracarboxylic dianhydride of formula (1), formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula ( The liquid crystal aligning agent which is a polymer obtained by making at least one of V-12), the diamine of Formula (V-33), and Formula (VII-2) react.

The method according to any one of claims 18 to 22, The polyamic acid is a mixture of at least one of tetracarboxylic dianhydrides of formulas (1) to (6) with at least one of tetracarboxylic dianhydrides of formulas (7) to (14), and formulas (IV-1) In the diamines of (IV-2), (IV-15), (IV-16), (V-1) to (V-12), (V-33) and (VII-2) The liquid crystal aligning agent which is a polymer obtained by making at least 1 react.

The method according to any one of claims 18 to 22, The polyamic acid is a mixture of tetracarboxylic dianhydride of formula (1) and at least one of tetracarboxylic dianhydride of formulas (7) to (14), and formulas (IV-1), (IV-2), and formula ( IV-15), a polymer obtained by reacting at least one of the diamines of formula (IV-16), formula (V-1) to formula (V-12), formula (V-33) and formula (VII-2). Liquid crystal aligning agent.

The method according to any one of claims 18 to 22, The polyamic acid is a mixture of tetracarboxylic dianhydride of formula (1) and tetracarboxylic dianhydride of formula (7) and formula (IV-1), formula (IV-2), formula (IV-15), formula (IV) -16), a liquid crystal aligning agent which is a polymer obtained by making at least one of formula (V-1)-a formula (V-12), a formula (V-33), and a formula (VII-2) react.

The method of claim 10, A composition containing at least one of the nadiimide compounds represented by formula (A), at least one of the compounds represented by formula (B), and at least one polymer selected from polyamic acid and derivatives of this polyamic acid; The polyamic acid is at least one of aromatic tetracarboxylic dianhydrides of formulas (1) to (6), or at least one of aromatic tetracarboxylic dianhydrides of formulas (1) to (6) and formulas (7) to formula Polyamic acid obtained by reacting a mixture with at least one of tetracarboxylic dianhydrides other than the aromatics of (14) and at least one diamine selected from the group of compounds represented by formulas (I) to (VII), respectively. ; And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.01-0.99 by the weight ratio with respect to the total amount of this nadiimide compound, the compound represented by Formula (B), and this polymer.

Wherein A ¹ is alkylene having ² to 12 carbon atoms; A ² is alkylene having 1 to 12 carbon atoms; and A ³ is independently a single bond, -O-, -CO-, -CONH-, -NHCO -, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _m -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _m- S- or alkylene having 1 to 12 carbon atoms, m is an integer of 1 to 12; and any hydrogen of the cyclohexane ring or the benzene ring is -F, -CH ₃ , -OH, -COOH,- May be substituted with SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl)

Wherein R ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —CF ₂ O— or alkylene having 1 to 6 carbons R ² is a group having a steroid skeleton, alkyl having 1 to 30 carbon atoms, phenyl or a group represented by formula (D-1); when the alkyl has 2 to 6 carbon atoms, any of -CH ₂ -is May be substituted with -O-, -CH = CH- or C≡C-, and any hydrogen of this phenyl is substituted with fluorine, methyl, methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy And R ¹ And the sum of the carbon number of R ² is 3 or more).

Where R ¹³ and R ¹⁴ And R ¹⁵ is independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms or alkyleneoxy having 1 to 3 carbon atoms Is; R ¹⁶ And R ¹⁷ is independently fluorine or methyl; R ¹⁸ is hydrogen, fluorine, chlorine, cyano, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, alkyl having 1 to 30 carbons, alkyl having 1 to 30 carbon atoms Alkoxy of 30 or alkoxyalkyl having 2 to 30 carbon atoms, and any of -CH ₂ -in these alkyl, alkoxy and alkoxyalkyl may be substituted with difluoromethylene or a group represented by formula (D-2). There is; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; e, f and g are each independently an integer of 0 to 3, and the sum thereof is 1 or more; m1 and m2 are independently 0, 1 or 2)

Where R ¹⁹ , R ²⁰ , R ²¹ And R ²² is independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 30) The method of claim 10, The other component is at least one of the radically polymerizable monomers; Q in Formula (A) is either of the groups shown below; And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the radically polymerizable monomer which is another component.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms The method of claim 29, The liquid crystal aligning agent whose Q in Formula (A) is any of the group shown next.

The method of claim 10, The other component is at least one of the epoxy compounds; Q in Formula (A) is either of the groups shown below; And the liquid crystal aligning agent whose ratio of the nadiimide compound represented by Formula (A) is 0.2-0.99 by the weight ratio with respect to the total amount of this nadiimide compound and the epoxy compound which is another component.

Wherein R is alkyl of 3 to 30 carbon atoms or alkoxy of 3 to 30 carbon atoms The method of claim 31, wherein The liquid crystal aligning agent whose Q in Formula (A) is any of the group shown next.

The liquid crystal aligning film formed by apply | coating the liquid crystal aligning agent of Claim 9 or 10 on a board | substrate, and baking in the state of a film. A pair of substrates which are arranged to face each other, an electrode formed on one or both sides of the opposing surfaces of each of the pair of substrates, a liquid crystal alignment film formed on the opposing surfaces of each of the pair of substrates, and the pair The liquid crystal display element which has the liquid crystal layer formed between board | substrates of the said WHEREIN. The said liquid crystal aligning film is a liquid crystal aligning film of Claim 33, The liquid crystal display element characterized by the above-mentioned.