KR100958515B1 - Polyamic Acid, Polyimide, Liquid Crystal Aligning Agent and Liquid Crystal Display Element - Google Patents

Abstract

The present invention provides novel polyamic acid and imidized polymers useful as liquid crystal aligning agents. Moreover, this invention provides the liquid crystal aligning agent which can express favorable orientation characteristic, and can form a liquid crystal aligning film with a short time from the release of voltage application to the afterimage erasing in a liquid crystal display element.

That is, this invention provides the polyamic acid using the novel tetracarboxylic dianhydride, the imidation polymer, and the liquid crystal aligning agent using the same.

Polyamic acid, imidation polymer, liquid crystal aligning agent, liquid crystal display element

Description

Polyamic acid, imidized polymer, liquid crystal aligning agent and liquid crystal display element {Polyamic Acid, Polyimide, Liquid Crystal Aligning Agent and Liquid Crystal Display Element}

This invention relates to the liquid crystal display element which has a novel polyamic acid, a novel imidation polymer, the liquid crystal aligning agent containing at least one of these, and the liquid crystal aligning film formed using such a liquid crystal aligning agent.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy has a sandwich structure in a substrate with a transparent electrode having a liquid crystal alignment film made of polyimide and the like, and the long axis of the liquid crystal molecules is continuously twisted at least 90 degrees between the substrates. BACKGROUND ART Liquid crystal display devices having a twisted nematic (STN) type and super twisted nematic (STN) type liquid crystal cell are known. The liquid crystal orientation in these liquid crystal display elements is normally formed on the board | substrate, and is performed by the liquid crystal aligning film in which the rubbing process was performed.

Moreover, as a liquid crystal display element separate from the above, the liquid crystal display element which has the vertical alignment liquid crystal cell formed by orienting the liquid crystal molecule which has negative dielectric anisotropy perpendicular to a board | substrate is known. Liquid crystal alignment in such a liquid crystal display element is also usually performed by a liquid crystal alignment film formed on a substrate.

However, in the conventional liquid crystal display element, since the ionic charge generated when the voltage is applied is adsorbed to the liquid crystal alignment film, an afterimage occurs on the display screen after the voltage application is released, and the liquid crystal display element at the time of voltage application and release. There was a problem that sufficient contrast could not be obtained because the contrast difference was small. The present invention has been made to solve this problem.

It is a first object of the present invention to provide a novel polyamic acid useful as a liquid crystal aligning agent. A second object of the present invention is to provide a novel imidized polymer useful as a liquid crystal aligning agent. The third object of the present invention is that the liquid crystal can exhibit good alignment characteristics and has a short time (hereinafter referred to as "afterimage erasing time") from when the voltage is released in the liquid crystal display element until the afterimage is erased. It is providing the liquid crystal aligning agent which can form an alignment film. Still other objects and advantages of the present invention will become apparent from the following description.

The polyamic acid of the present invention is characterized by having a structure obtained by reacting a tetracarboxylic dianhydride containing at least one compound represented by the following formula (1) with a diamine compound represented by the following formula (2).                     

In formula, R <^1> and R <^3> is a monovalent organic group each independently, R <^2> is a hydrogen atom or a monovalent organic group, and a is an integer of 0-4.

In the formula, A is a divalent organic group.

In addition, the imidized polymer of the present invention is characterized by having a repeating unit represented by the following formula (3).

In formula, the definition of R <^1> , R <^2> , R <^3> , a, and A is based on said Formula (1) and Formula (2).

Moreover, the liquid crystal aligning agent of this invention contains the said polyamic acid and / or the imidation polymer, It is characterized by the above-mentioned.

Moreover, the liquid crystal display element of this invention has a liquid crystal aligning film formed using said liquid crystal aligning agent, It is characterized by the above-mentioned.

<Embodiment of the invention>

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Tetracarboxylic dianhydride

The polyamic acid of the present invention is characterized in that a compound represented by the formula (1) (hereinafter referred to as "specific tetracarboxylic dianhydride") is used as the tetracarboxylic dianhydride used in the synthesis reaction thereof. .

In General formula (1) which shows specific tetracarboxylic dianhydride, R <^1> is a halogen atom or a monovalent organic group, Preferably it is a C1-C20 organic group. R <^2> and R <^3> is respectively independently a hydrogen atom, a halogen atom, or a monovalent organic group, and a is an integer of 1-4.

Here, as a halogen atom represented by R <^1> , fluorine, chlorine, bromine, iodine is mentioned, for example. Of these, fluorine is preferable.

Moreover, as a monovalent organic group represented by R <^1> , Specifically, Alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group; Alicyclic groups such as cyclopentyl group, cyclohexyl group, decahydronaphthyl group and bicyclohexyl group; Aromatic groups such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenethyl group and trityl group; Furyl group, tetrahydrofuryl group, thienyl group, tetrahydrothienyl group, pyrrolyl group, pyridyl group, piperidyl group, piperidino group, morpholino group, quinolyl group, isoquinolyl group, piperidinomethyl group, morpholinol Heterocyclic containing organic groups such as nomethyl group; Methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, phenoxy group; An acetyl group, propionyl group, benzoyl group and cyclohexylcarbonyl group; Acetoxy group, propionyloxy group, benzoyloxy group, cyclohexylcarbonyloxy group; Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, decahydronaphthyloxycarbonyl group, bicyclohexyloxycarbonyl group, phenoxycarbonyl group; Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, hexyloxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, decahydronaphthyloxymethyl group, phenoxymethyl group; Acetoxymethyl group, propionyloxymethyl group, cyclohexylcarbonyloxymethyl group, benzoyloxymethyl group; Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, butoxycarbonylmethyl group, hexyloxycarbonylmethyl group, cyclopentyloxycarbonylmethyl group, cyclohexyloxycarbonylmethyl group, decahydronaphthyl Oxygen-containing organic groups such as oxycarbonylmethyl group, bicyclohexyloxycarbonylmethyl group, and phenoxycarbonylmethyl group; Carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, acetamidemethyl group, propionylaminomethyl group, benzoylaminomethyl group, cyclohexylcarbonylaminomethyl group, N-methylacetamidemethyl group, N-methyl -N-propionylaminomethyl group, N-methyl-N-benzoylaminomethyl group, N-methyl-N-cyclohexylcarbonylaminomethyl group, N-ethylacetamidemethyl group, N-ethyl-N-propionylaminomethyl group, N -Ethyl-N-benzoylaminomethyl group, N-ethyl-N-cyclohexylcarbonylaminomethyl group, N-propylacetamidemethyl group, N-propyl-N-propionylaminomethyl group, N-propyl-N-benzoylaminomethyl group Nitrogen-containing organic groups such as N-propyl-N-cyclohexylcarbonylaminomethyl group, cyano group and cyanomethyl group; The group obtained by substituting one or two or more hydrogen atoms of the said organic group by halogen, the group represented by following formula (1aa), etc. are mentioned. The polyamic acid and imidation polymer of this invention obtained using the tetracarboxylic dianhydride which has group represented by following General formula (1aa) are preferable at the point which can obtain a stable pretilt angle when used for a liquid crystal aligning agent.

<Formula 1aa>

In formula, E is a single bond or a divalent bond group, R 'is a monovalent group which has a C5-C30 alkyl group, a halogen atom, a C1-C30 haloalkyl group, or a C10-C30 polycyclic structure.

Herein, the alkyl group having 5 to 30 carbon atoms represented by R ′ in Formula 1aa may be any one of linear and branched chains, specifically, a pentyl group, hexyl group, octyl group, nonyl group, decyl group, and undecyl group , Dodecyl group, hexadecyl group, stearyl group, eicosyl group, docosyl group, hexacosyl group and triacyl group. Of these, long-chain alkyl groups having 14 to 20 carbon atoms in the main chain are preferred.

Moreover, as a halogen atom, fluorine, chlorine, bromine, iodine is mentioned, for example. Of these, fluorine is preferable.

As the haloalkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, t-butyl group, and The group in which one part or all of the hydrogen atoms in the same C5-C30 alkyl group was substituted by the above-mentioned halogen atom is mentioned. Of these, haloalkyl groups having 1 to 6 carbon atoms are preferable, and fluoroalkyl groups are particularly preferable.

Moreover, as a monovalent organic group which has a C10-C30 polycyclic structure, the monovalent organic group which has a steroid skeleton is mentioned, for example, the organic group etc. which are represented by following formula (1a)-1d are mentioned specifically ,. .

In addition, as the divalent bond group represented by E, specifically, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a keto group, an alkylene group, an alkylidene group, a phenylene group, and 2 represented by the following general formulas 1e and 1f And a coupling group.

-[(CH ₂ ) _r -D ³ ] _s-

-[(C ₆ H ₄ ) -D ⁴ ] _t-

In the formula, r, s and t independently represent an integer of 1 to 6, D ³ and D ⁴ in the group consisting of ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, keto groups and phenylene groups It represents the group selected.

In said Formula (1), the group represented by R <^2> and R <^3> specifically mentions the monovalent organic group illustrated as group represented by a hydrogen atom, a halogen atom, and R <^1> .

Specific examples of the specific tetracarboxylic dianhydride include 1,3,3a, 4,5,9b-hexahydro-4-pentadecyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-heptadecyl-5 (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-nonadecyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-pentadecyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-heptadecyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-nonadecyl-5-methyl-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-pentadecyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-heptadecyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-nonadecyl-8-methyl-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxy-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c]- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxy-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxy-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxy-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxy-5-methyl-5 (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxy-5-methyl-5 ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxy-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxy-8-methyl-5 (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxy-8-methyl-5 ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxycarbonyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxycarbonyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxycarbonyl-5 (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxycarbonyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxycarbonyl-5-methyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxycarbonyl- 5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxycarbonyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxycarbonyl-8-methyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxycarbonyl- 8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (N-hexadecylcarbamoyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (N-stearylcarbamoyl) -5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (N-eicosylcarbamoyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (N-hexadecylcarbamoyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (N-stearylcarbamoyl) -5-methyl-5 (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- ( N-eicosylcarbamoyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (N-hexadecylcarbamoyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho -[1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (N-stearylcarbamoyl) -8-methyl-5 (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (N-Eicosylcarbamoyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoyl-5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoyl-5-methyl-5 (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoyl-8-methyl-5 (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoyloxymethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoyloxymethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naph Tol [1,2-c] -furan-1,3-dione, 1,3, 3a, 4,5,9b-hexahydro-4-stearoyloxymethyl-5 (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoyloxymethyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoyloxymethyl-5-methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoyloxymethyl-5- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoyloxymethyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoyloxymethyl-8-methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoyloxymethyl-8- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoylaminomethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoylaminomethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naph Tol [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoylaminomethyl-5 (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoylaminomethyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoylaminomethyl-5-methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoylaminomethyl-5- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-myristoylaminomethyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-palmitoylaminomethyl-8-methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearoylaminomethyl-8- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxycarbonylmethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxycarbonylmethyl-5 (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxycarbonylmethyl-5 (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxycarbonylmethyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxycarbonylmethyl-5-methyl-5 (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxycarbo Nylmethyl-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-hexadecyloxycarbonylmethyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-stearyloxycarbonylmethyl-8-methyl-5 (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-eicosyloxycarbo Nylmethyl-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (4-hexadecylphenyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-stearylphenyl) -5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-4 (4-eicosylphenyl) -5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (4-hexadecylphenyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-stearylphenyl) -5-methyl-5 (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (4-eicosyl Phenyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (4-hexadecylphenyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-stearylphenyl) -8-methyl-5 (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-eicosylphenyl ) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (4-hexadecyloxyphenyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-stearyloxyphenyl) -5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-eicosyloxyphenyl) -5 (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (4-hexadecyloxyphenyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-stearyloxyphenyl) -5-methyl-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-eico Siloxyphenyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (4-hexadecyloxyphenyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-stearyloxyphenyl) -8-methyl-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (4-eico Siloxyphenyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4-fluoro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-chloro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-fluoro-5-methyl-5 (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-chloro-5-methyl-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4-fluoro- 8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4, 5, 9b-hexahydro-4-chloro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c]- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naph Tol [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5, 9b-hexahydro-4 (trifluoromethyl) -5 (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,1-tri Fluoroethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-4 (1,1,2,2,2-pentafluoroethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethyl) -5-methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethyl) -5- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-4 (1,1,1-trifluoroethyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,1,2,2-pentafluoroethyl) -5-methyl-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethyl) -8-methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethyl) -8- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-4 (1,1,1-trifluoroethyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -fu Lan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,1,2,2-pentafluoroethyl) -8-methyl-5 (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethoxy) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c]- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethoxy) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naph To [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethoxy) -5 (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,1-tri Fluoroethoxy) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-4 (1,1,1,2,2-pentafluoroethoxy) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethoxy) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethoxy) -5-methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethoxy) -5- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-4 (1,1,1-trifluoroethoxy) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c]- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,2,2,2-pentafluoroethoxy) -5-methyl-5 (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethoxy) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethoxy) -8-methyl-5 (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethoxy) -8 -Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-4 (1,1,1-trifluoroethoxy) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,2,2,2-pentafluoroethoxy) -8-methyl-5 (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethoxymethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethoxymethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethoxymethyl) -5 (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1, 1-trifluoroethoxymethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3, 3a, 4,5,9b-hexahydro-4 (1,1,1,2,2-pentafluoroethoxymethyl) -5 (tetrahydro-2,5-dioxo-3-furanyl) -naph Earth [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethoxymethyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethoxymethyl) -5-methyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethoxymethyl) -5-Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-4 (1,1,1-trifluoroethoxymethyl) -5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,2,2, 2-pentafluoroethoxymethyl) -5-methyl -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4 (fluoromethoxymethyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (difluoromethoxymethyl) -8-methyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (trifluoromethoxymethyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-4 (1,1,1-trifluoroethoxymethyl) -8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 (1,1,2,2,2-pentafluoroethoxymethyl) -8-methyl -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

The compound etc. which are represented by following General formula (1)-(168) are mentioned.

Specific tetracarboxylic dianhydride can be synthesize | combined by Diels-Alder-reacting the styrene derivative represented by following formula (4), and maleic anhydride, and further reacting the reaction product with maleic anhydride.

For example, the compound represented by the formula (1) is synthesized according to the following scheme using β-methylstyrene as a styrene derivative.

Moreover, as tetracarboxylic dianhydride used for the synthesis reaction of polyamic acid, tetracarboxylic dianhydride other than specific tetracarboxylic acid can also be used together in the range which does not impair the effect by this invention. Here, the ratio of the specific tetracarboxylic dianhydride to tetracarboxylic dianhydride used for a synthesis reaction is 0.1-100 mol% normally, Preferably it is 5-100 mol%, Especially preferably, it is 50-90 mol %to be.

As tetracarboxylic dianhydride which can be used together, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclo Pentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuranthratecarboxylic dianhydride, 1,3,3a, 4,5 , 9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -Ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2 , 5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, non Aliphatic and alicyclic tetracarboxylic dianhydrides such as chloro [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride and the compounds represented by the following formulas (5) and (6): water;

(Wherein, R ⁴ and R ⁶ represent a divalent organic group having an aromatic ring, R ⁵ and R ⁷ represent a hydrogen atom or an alkyl group, and a plurality of R ⁵ and R ⁷ present may be the same or different. .)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenyl Silanetetracarboxylic dianhydride, 1,2,3,4-furantheracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4 '-Bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4 ' Perfluoroisopropylidenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide Water, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis ( Triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (trimelitate anhydride), propylene glycol-bis (trimelitate anhydride), 1,4-butanediol-bis (trimelitate Anhydride), 1,6-hexanediol-bis (trimelitate anhydride), 1,8-octanediol-bis (trimelitate anhydride), 2,2-bis (4-hydroxyphenyl) propane-bis (tri Mellitate anhydride), 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4-dicarboxyphenyl) pyridine, compounds represented by the following formulas (169) to (172) Aromatic tetracarboxylic dianhydrides, such as these, are mentioned. These are used individually by 1 type or in combination of 2 or more types.

Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naph Earth [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -octo-7-ene-2,3,5, 6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone Tracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the compound represented by the following formulas (173) to (175) of the compound represented by the formula (5) and represented by the formula (6) Among the compounds to be mentioned, compounds represented by the following general formula (176) are preferable from the viewpoint of being able to express good liquid crystal alignment, and particularly preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, pyromellitic dianhydride and the following general formula (173) The compound represented by these is mentioned.

<Diamine Compound>

As a diamine compound used for the synthesis | combination of the said polyamic acid, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl ethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1 , 3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenylether, 3,3'-diaminobenzo Phenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1,3- ratio (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9 , 9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl , 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 ' -(p-phenyleneisopropylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethyl Phenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoro Aromatic diamines such as methyl) phenoxy] -octafluorobiphenyl;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene Aliphatic and alicyclic diamines such as dimethyldiamine and 4,4'-methylenebis (cyclohexylamine);

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine, Two in the molecule, such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, and the compounds represented by the following formulas (7) and (8): Diamines having a primary amino group and a nitrogen atom other than this primary amino group; Mono-substituted phenylenediamines represented by the following formula (9); Diaminoorganosiloxane represented by the following formula (10); The compound etc. which are represented by following General formula (177)-(181) are mentioned. These diamine compounds can be used individually or in combination of 2 or more types.

Wherein X represents a divalent organic group, R ⁸ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and R ⁹ represents pyridine, Represents a monovalent organic group having a ring structure comprising a nitrogen atom selected from pyrimidine, triazine, piperidine and piperazine, and R ¹⁰ is 1 having a group selected from a steroid skeleton, a trifluoromethyl group and a fluoro group Represents an organic group or an alkyl group having 6 to 30 carbon atoms, R ¹¹ represents a hydrocarbon group of 1 to 12 carbon atoms, and a plurality of R ^{11 's} may be the same or different, and p is an integer of 1 to 3, q Is an integer from 1 to 20.

In formula, y is an integer of 2-12 and z is an integer of 1-5.

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4 '-Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4' -(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4, 4'-bis (4-aminophenoxy) biphenyl, the compound represented by the above formulas (177) to (181), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, the compound represented by the following formula (182) among the compound represented by the formula (7), the chemical This to the compound represented by 8 to the compound represented by the formula (9) compounds and represented by the formula 183, a compound represented by the formula (184) to (193) are preferred.

<Polyamic acid>

The use ratio of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid of the present invention is 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group contained in the diamine compound. The ratio which becomes is preferable, and the ratio which becomes 0.3-1.2 equivalent is more preferable.

The synthesis reaction of the polyamic acid is usually carried out in an organic solvent under temperature conditions of -20 ° C to 150 ° C, preferably 0 ° C to 100 ° C. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, can be illustrated. In addition, it is preferable that the usage-amount (a) of an organic solvent is the quantity which normally becomes 0.1-30 weight% with respect to the total amount (a + b) of the reaction solution, for the total amount (b) of tetracarboxylic dianhydride and a diamine compound.

In addition, the organic solvent may be used in combination such that alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like which are poor solvents of polyamic acid are not precipitated. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, lactic acid Butyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, di Ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, die Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.

The reaction solution which melt | dissolves a polyamic acid as mentioned above can be obtained. In addition, the reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the polyamic acid can be obtained by drying the precipitate under reduced pressure. Moreover, polyamic acid can be refine | purified by carrying out the process of dissolving this polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.

<Imidated Polymer>

The imidation polymer of this invention can be manufactured by dehydrating and ring-closing the said polyamic acid. The dehydration ring closure of the polyamic acid is heated by the method of (A) heating the polyamic acid or (B) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst in this solution, and heating as needed. It is done by the method.

The reaction temperature in the method of heating the polyamic acid of said (A) is 50-200 degreeC normally, Preferably it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.                     

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of the polyamic acid of the above (B), for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent is 0.01-20 mol with respect to 1 mol of repeating units of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closure catalyst is 0.01-10 mol with respect to 1 mol of dehydrating agents used. Moreover, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid as an organic solvent used for dehydration ring-closure reaction is mentioned. The reaction temperature of the dehydration ring closure reaction is usually 0 ° C to 180 ° C, preferably 10 ° C to 150 ° C. Moreover, the imidation polymer can be refine | purified by performing the same operation as the purification method of polyamic acid with respect to the reaction solution obtained in this way.

The preferable imidation ratio in the imidation polymer used for the liquid crystal aligning agent of this invention is 10 to 100%, More preferably, it is 30 to 98%. Here, "imidation ratio" shows the ratio of the number of repeating units which form an imide ring with respect to the total number of repeating units in a polymer in%. At this time, a part of the imide ring may be an isoimide ring. The imidation ratio can be controlled by adjusting the reaction conditions of the dehydration ring closure reaction.

<Terminal modified polymer>

The polyamic acid and the imidized polymer of the present invention may be of terminally modified type with controlled molecular weight. By using this terminal-modified polymer, the coating characteristic of a liquid crystal aligning agent, etc. can be improved, without the effect of this invention being impaired. Such terminal-modified ones can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to the reaction system when synthesizing the polyamic acid. Here, examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. have. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine , n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n -Eicosylamine, etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

Logarithmic viscosity of the polymer

As for the polyamic acid and imide group containing polyamic acid obtained by the above, the value of the logarithmic viscosity ((eta) 1n) is 0.05-10 dl / g normally, Preferably it is 0.1-5 dl / g.

The value of the logarithmic viscosity (η1n) in the present invention is measured by using a N-methyl-2-pyrrolidone as a solvent and measuring the viscosity at 30 ° C with respect to a solution having a concentration of 0.5 g / 100 ml, Is saved.                     

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is normally comprised by melt | dissolving and containing the polyamic acid and / or the imidation polymer of this invention in an organic solvent. Moreover, polyamic acid and / or imidation polymer other than the polyamic acid and imidation polymer of this invention can also be used together. In this case, the content of the polyamic acid and / or the imidized polymer of the present invention is preferably 10 to 100% by weight in the prepolymer in the liquid crystal aligning agent.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention is 0 degreeC-200 degreeC normally, Preferably it is 20-60 degreeC.

As an organic solvent which comprises the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of polyamic acid can also be selected suitably, and can be used together.

Although solid content concentration in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is the range of 1 to 10 weight%. That is, although the liquid crystal aligning agent of this invention forms the coating film which becomes a liquid crystal aligning film by apply | coating on the surface of a board | substrate, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal aligning film cannot be obtained, and solid content When the concentration exceeds 10% by weight, the film thickness of the coating film is too large to obtain a good liquid crystal aligning film, the viscosity of the liquid crystal aligning agent is increased and the coating properties are inferior.

The liquid crystal aligning agent of this invention may contain a functional silane containing compound or an epoxy group containing compound from a viewpoint of improving the adhesiveness to the board | substrate surface. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl trie Methoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-tri Methoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyl trimethoxy Silane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, N-bis (oxyethylene) -3 -Aminopropyl trimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane, etc. are mentioned.

As the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3 , 5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycid Dylaminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diaminodiphenylmethane, etc. are mentioned as a preferable thing. The compounding ratio of these functional silane containing compounds and epoxy group containing compounds is 40 weight part or less normally with respect to 100 weight part of polymers, Preferably it is 0.1-30 weight part.

<Liquid crystal display element>

The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured by the following method, for example.

(1) The liquid crystal aligning agent of this invention is apply | coated to one side of the board | substrate with which the patterned transparent conductive film is provided by methods, such as a roll coater method, a spinner method, and a printing method, and then a coating film is heated by heating a coating surface. Form. Here, as a board | substrate, For example, glass, such as a float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and the like can be used. As a transparent conductive film provided on one side of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. In order to pattern these transparent conductive films, a photo etching method or a method using a mask in advance is used. When the liquid crystal aligning agent is applied, a functional silane-containing compound, a functional titanium-containing compound, or the like may be previously applied to the substrate surface in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film. The heating temperature after apply | coating a liquid crystal aligning agent is 80-300 degreeC, Preferably it is 120-250 degreeC. In addition, although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film used as an oriented film by removing an organic solvent after application | coating, it can also be made into the imidized coating film by further heating dehydration ring closure. The film thickness of the coating film formed is usually 0.001 to 1 micron, preferably 0.005 to 0.5 micron.

(2) The rubbing treatment which rubs the formed coating film surface in the fixed direction with the roll wound the cloth which consists of fibers, such as nylon, a rayon, a cotton, for example, is performed. Thereby, liquid crystal aligning ability is provided to a coating film.

In addition, ultraviolet rays as disclosed in, for example, Japanese Patent Application Laid-Open No. 6-222366 or Japanese Patent Application Laid-Open No. 6-281937 are partially added to the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention. A resist film is partially formed on the surface of the liquid crystal alignment film subjected to the treatment of changing the pretilt angle by irradiating with a rubbing treatment or disclosed in JP-A-5-107544, and is different from the rubbing treatment. After the rubbing treatment is performed in the direction, the clock characteristic of the liquid crystal display element can be improved by performing a process of changing the liquid crystal alignment ability of the liquid crystal alignment film by removing the resist film.

In some cases, the liquid crystal alignment ability may be imparted to the coating film by irradiating polarized light or unpolarized ultraviolet light or an ion beam regardless of the rubbing method.

On the other hand, in the case of manufacturing a vertically aligned liquid crystal display element, when the direction in which the liquid crystal molecules fall is controlled by the unevenness and / or the transverse electric field of the substrate surface, it is not necessary to perform the rubbing treatment. The said coating film can also be used as a liquid crystal aligning film as it is.

(3) Two board | substrates with a liquid crystal aligning film were manufactured as mentioned above, and two board | substrates were mutually arrange | positioned through a gap (cell gap) so that the rubbing direction in each liquid crystal aligning film may make a predetermined angle. The periphery of is bonded using a sealant, and the liquid crystal is injected and filled into the cell gap partitioned by the substrate surface and the sealant to seal the injection hole and constitute a liquid crystal cell. Further, the liquid crystal display device is bonded by attaching a polarizing plate to the outer surface of the liquid crystal cell, that is, the other surface of each substrate constituting the liquid crystal cell so that its polarization direction is coincident with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one side of the substrate. You can get it.

Here, as the sealant, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.

Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, a cyanide liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, t-phenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, these liquid crystals are sold, for example, as cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck). It is also possible to add and use a chiral agent. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate called H film which absorbed iodine, and extended | stretched polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

<Examples>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples. In addition, the evaluation method of the polymer, a liquid crystal aligning agent, and a liquid crystal display element in a following example and a comparative example is as follows.

<Voltage retention of liquid crystal display element>

After applying a voltage of 5 V to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention after 167 milliseconds from the release of the application was measured. The measurement apparatus used VHR-1 by Toyo Technica.

<Afterimage erasing time>

After applying a DC voltage of 10 V to the liquid crystal display device for 1 hour, the application of the voltage was canceled, and the display screen was visually observed to measure the time from the release of voltage application until the afterimage on the screen was erased. .                     

<Pretilt Angle of Liquid Crystal Display Element>

It was measured by the crystal rotation method using He-Ne laser light according to the method described in T. J. Scheffer, et.

Synthesis Example 1

Synthesis of Specific Tetracarboxylic Anhydrides

31 g (0.316 mol) of maleic anhydride, 0.6 g of N-nitrosophenylhydroxylamine aluminum salt and 0.08 g of hydroquinone were dissolved in 35 ml of toluene at 100 ° C. 17 g (0.144 mol) of (beta) -methylstyrene was added to this reaction liquid, maintaining at 100 degreeC. The solution was further heated to reflux at 110 ° C. for 10 hours. Subsequently, the reaction solution was cooled to room temperature, 30 ml of methyl isobutyl ketone was added, and the precipitate was separated by filtration and washed three times with 10 ml of methyl isobutyl ketone. Recrystallization from acetic anhydride gave 35 g of specific tetracarboxylic dianhydride represented by the above formula (1).

Synthesis Example 2

Synthesis of Specific Tetracarboxylic Anhydrides

Specific tetracarboxylic dianhydride represented by the formula (13) in the same manner as in Synthesis Example 1, except that 19.3 g (0.144 mol) of β-methoxystyrene was used instead of 17 g (0.144 mol) of β-methylstyrene. 38 g was obtained.

<Example 1>

Synthesis of Polyamic Acid

30.66 g (97.56 mmol) of specific tetracarboxylic dianhydride represented by the formula (1) and 19.34 g (97.56 mmol) of 4,4'-diaminodiphenylmethane were substituted with 450 g of N-methyl-2-pyrrolidone. It dissolved in and reacted at 60 degreeC for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 37.64 g of polyamic acid having a logarithmic viscosity of 0.93 dl / g (this is referred to as “polymer (1a)”).

Synthesis of Imidized Polymer

25.0 g of polymer (1a) was dissolved in 450 g of N-methyl-2-pyrrolidone, and 15.5 g of pyridine and 19.9 g of acetic anhydride were added to this solution, followed by dehydration ring-closure reaction by heating at 115 ° C for 4 hours. The reaction product was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 13.38 g of an imidized polymer having a logarithmic viscosity of 0.95 dl / g (called “polymer (1b)”).

<Example 2>

Synthesis of Polyamic Acid

Poly- mer having a logarithmic viscosity of 0.98 dl / g as in Synthesis Example 1, except that 10.55 g (97.56 mmol) of p-phenylenediamine was used instead of 19.34 g (97.56 mmol) of 4,4'-diaminodiphenylmethane. 28.86 g of amic acid (called "polymer (2a)") was obtained.

Synthesis of Imidized Polymer

12.26 g of an imidized polymer having a logarithmic viscosity of 1.01 dl / g (this is called "polymer (2b)") except that 15.0 g of polymer (2a) was used instead of 25.0 g of polymer (1a) Got.

<Example 3>

Synthesis of Polyamic Acid

10.23 g (94.63 mmol) of p-phenylenediamine and 1.52 g (2.93 mmol) of diamine represented by the above formula (143) were mixed instead of 19.34 g (97.56 mmol) of 4,4'-diaminodiphenylmethane. In the same manner as in Synthesis example 1, 27.84 g of polyamic acid having a logarithmic viscosity of 0.91 dl / g was referred to as "polymer (3a)".

Synthesis of Imidized Polymer

11.37 g of an imidized polymer having a logarithmic viscosity of 0.88 dl / g (this is called "polymer (3b)") except that 15.5 g of polymer (3a) was used instead of 25.0 g of polymer (1a) Got.

<Example 4>

Synthesis of Polyamic Acid

Synthesis except that 32.22 g (97.56 mmol) of the specific tetracarboxylic dianhydride represented by the above formula (13) was used instead of 30.66 g (97.56 mmol) of the specific tetracarboxylic dianhydride represented by the formula (1). In the same manner as in Example 3, 38.57 g of a polyamic acid having a logarithmic viscosity of 0.87 dl / g was referred to as "polymer (4a)".

Synthesis of Imidized Polymer

17.2 g of an imidized polymer having a logarithmic viscosity of 0.83 dl / g (called "polymer (4b)") in the same manner as in Synthesis Example 3, except that 22.0 g of polymer (4a) was used instead of 25.0 g of polymer (1a) Got.

Example 5

Synthesis of Polyamic Acid

Synthesis except that 36.22 g (97.56 mmol) of specific tetracarboxylic dianhydride represented by the above formula (43) was used instead of 30.66 g (97.56 mmol) of the specific tetracarboxylic dianhydride represented by the formula (1). In the same manner as in Example 3, 42.64 g of a polyamic acid having a logarithmic viscosity of 0.84 dl / g was referred to as "polymer (5a)".

Synthesis of Imidized Polymer

16.37 g of an imidized polymer having a logarithmic viscosity of 0.81 dl / g (this is called "polymer (5b)") in the same manner as in Synthesis Example 3, except that 24.0 g of polymer (4a) was used instead of 25.0 g of polymer (1a). Got.

<Example 6>

Synthesis of Polyamic Acid

Specific tetracarboxylic dianhydride 1,3,3a, 4,5,9b-hexahydro-4-heptadecyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione 7.88 g (14.63 mmol), 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo 26.06 g (82.9 mmol) of -3-furanyl) -naphtho [1,2-c] furan-1,3-dione and 19.34 g (97.56 mmol) of 4,4'-diaminodiphenylmethane were N-methyl It was dissolved in 450 g of 2-pyrrolidone and reacted at 60 ° C for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 42.57 g of the polyamic acid of the present invention having a logarithmic viscosity of 0.97 dl / g (this is referred to as “polymer (6a)”).

Synthesis of Imidized Polymer

26.7 g of polymer (6a) was dissolved in 450 g of N-methyl-2-pyrrolidone, and 14.8 g of pyridine and 20.4 g of acetic anhydride were added to the solution, followed by dehydration ring-closure reaction by heating at 115 ° C for 4 hours. Subsequently, the reaction product solution was prepared in the same manner as in the synthesis of the polymer (1a) to precipitate and dry the reaction product, and the imide polymer of the present invention having a logarithmic viscosity of 1.03 dl / g (this is referred to as "polymer (6b)"). 22.3 g were obtained.

<Example 7>

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3) using 9.56 g (17.75 mmol) of specific tetracarboxylic dianhydride -Furanyl) -naphtho [1,2-c] furan-1,3-dione was changed to 31.62 g (100.61 mmol) and p-phenylene was substituted for 4,4'-diaminodiphenylmethane. Except for using 12.80 g (118.36 mmol) of diamine, 42.56 g of an imide polymer of the present invention having a logarithmic viscosity of 1.08 dl / g was obtained in the same manner as in Synthesis example 1 (this is referred to as "polymer (7b)").

Comparative Synthesis Example 1

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione 29.29 g (97.56 mmol) and 19.34 g (97.56 mmol) of 4,4'-diaminodiphenylmethane were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 38.44 g of polyamic acid having a logarithmic viscosity of 1.00 dl / g (this is referred to as “polymer (Aa)”). Subsequently, except for using the polymer (Aa) instead of the polymer (1a), 14.51 g of an imidized polymer having a logarithmic viscosity of 0.89 dl / g (this is referred to as "polymer (Ab)") was obtained in the same manner as in Synthesis example 1. .

Comparative Synthesis Example 2

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione Instead of using 25.82 g (118.36 mmol) of pyromellitic dianhydride and 12.80 g (118.36 mmol) of p-phenylenediamine instead of 4,4'-diaminodiphenylmethane, In the same manner, 32.60 g of a polyamic acid having a logarithmic viscosity of 1.10 dl / g was referred to as "polymer (Ba)".

Comparative Synthesis Example 3

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione Using 29.29 g (97.56 mmol), 2 g of 4,4'-diaminodiphenylmethane 2 g and 1,50- (1,63 mmol) 1- (stearyloxy) -2,4-diaminobenzene Otherwise, in the same manner as in Comparative Synthesis Example 1, 11.8 g of an imidized polymer having a logarithmic viscosity of 0.85 dl / g was referred to as "polymer (Cb)".

<Example 8>

(1) Preparation of liquid crystal aligning agent:

The polymer (1b) obtained in Synthesis Example 1 was dissolved in γ-butyrolactone to give a solution having a solid content of 2.5% by weight, and the solution was filtered with a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent of the present invention.

(2) Preparation of Liquid Crystal Display Device:

(1) The liquid crystal aligning agent of the present invention prepared as described above was applied using a spinner on a transparent conductive film made of an ITO film provided on one side of a glass substrate having a thickness of 1 mm, and dried by drying at 180 ° C. for 1 hour. A coating film having a film thickness of 800 kPa was formed.

(2) The liquid crystal aligning film was manufactured by rubbing the formed coating film surface using the rubbing machine which has the roll wound by the cloth made from nylon. Here, the rubbing treatment conditions were set at the rotational speed of 500 rpm and the stage moving speed of 1 cm / second.

③ Two board | substrates with a liquid crystal aligning film were manufactured as mentioned above, each liquid crystal after apply | coating the epoxy resin adhesive containing the aluminum oxide sphere of diameter 17micrometer by the screen printing method to the outer edge part of each board | substrate. Two board | substrates were opposingly arranged through the space | interval so that the rubbing direction in an oriented film might orthogonally cross, and the outer edge part contacted and crimped | bonded and hardened the adhesive agent.

(4) Nematic liquid crystal "MLC-2001" (manufactured by Merck Co., Ltd.) was filled and filled into the cell gap partitioned by the adhesive on the surface of the substrate and the outer edge portion, and then the injection hole was sealed with an epoxy adhesive to constitute a liquid crystal cell. Then, the liquid crystal display element was manufactured by bonding a polarizing plate to the outer surface of a liquid crystal cell so that a polarization direction may correspond with the rubbing direction of the liquid crystal aligning film formed in one side of the said board | substrate.                     

(5) In the liquid crystal display device manufactured as described above, no abnormal domain was confirmed when voltage was applied to and released from the liquid crystal cell, and the orientation of the liquid crystal was good. Moreover, the voltage retention of the liquid crystal display element was 99%, and the afterimage erase time was very short (0.6 second). The results are shown in Table 1 below.

Example 9

 The liquid crystal display element was produced like Example 8 except having used the polymer (1a) obtained in Example 1 instead of the polymer (1b), and setting the drying temperature after apply | coating a liquid crystal aligning agent to 250 degreeC. The liquid crystal alignment, voltage retention and afterimage erasing time in the manufactured liquid crystal display device were evaluated. The results are shown in Table 1.

<Examples 10 to 13>

A liquid crystal aligning agent was produced in the same manner as in Example 8 except that the polymers (2b) to (5b) obtained in Examples 2 to 5 were used instead of the polymer (1b) to prepare a liquid crystal display element. The orientation, voltage retention, and afterimage erasing time of the liquid crystal in the manufactured liquid crystal display device were evaluated. The results are shown in Table 1.

<Example 14>

A liquid crystal aligning agent was prepared in the same manner as in Example 8 except that 20 parts by weight of the polymer (1b) and 80 parts by weight of the polymer (Ba) obtained in Comparative Synthesis Example 2 were used instead of the polymer (1b). Prepared. The orientation, voltage retention, and afterimage erasing time of the liquid crystal in the manufactured liquid crystal display element were measured. The results are shown in Table 1.                     

<Examples 15 to 18>

Except having used the polymer (2b)-(5b) instead of the polymer (1b), it carried out similarly to Example 14, and manufactured the liquid crystal aligning agent, and manufactured the liquid crystal display element. The orientation, voltage retention, and afterimage erasing time of the liquid crystal in the manufactured liquid crystal display element were measured. The results are shown in Table 1.

&Lt; Example 19 >

A liquid crystal aligning agent was produced in the same manner as in Example 9 except that the polymer (6b) obtained in Example 6 was used instead of the polymer (1b) to prepare a liquid crystal display element. In the obtained liquid crystal display element, the abnormal domain was not confirmed when the voltage was applied to and released from the liquid crystal cell, and the orientation of the liquid crystal was good. In addition, the pretilt angle of the liquid crystal was 5.5 degrees. Moreover, the voltage retention of the liquid crystal display element was 100%, and the afterimage erase time was very short, 0.7 second. In addition, the pretilt angle was measured by changing the rubbing conditions in the range of 200 to 800 rpm of the roll and the moving speed of 0.5 to 5 cm / sec of the stage, but exhibited a variation of 5.5 ± 0.3 °, showing excellent stability of the process conditions. . The results are shown in Table 2 below.

Example 20

A liquid crystal display device was manufactured in the same manner as in Example 19 except that the polymer (6a) obtained in Example 6 was used instead of the polymer (6b) and the drying temperature after the liquid crystal aligning agent was applied to 250 ° C. The orientation, pretilt angle, voltage retention and afterimage erasing time of the liquid crystal in the prepared liquid crystal cell were evaluated. The results are shown in Table 2.

Example 21

A liquid crystal aligning agent was produced in the same manner as in Example 19 except that the polymer (7b) obtained in Example 7 was used instead of the polymer (6b) to prepare a liquid crystal display element. The orientation, pretilt angle, voltage retention and afterimage erasing time of the liquid crystal in the prepared liquid crystal cell were evaluated. The results are shown in Table 2.

<Example 22>

A liquid crystal aligning agent was prepared in the same manner as in Example 19 except that 20 parts by weight of the polymer (6b) and 80 parts by weight of the polymer (Ba) obtained in Comparative Synthesis Example 2 were used instead of the polymer (6b). Prepared. The orientation, pretilt angle, voltage retention and afterimage erasing time of the liquid crystal in the manufactured liquid crystal display element were measured. The results are shown in Table 2.

<Example 23>

A liquid crystal aligning agent was produced and the liquid crystal display element was produced like Example 22 except having used the polymer (7b) obtained in Example 7 instead of the polymer (6b). The orientation, pretilt angle, voltage retention and afterimage erasing time of the liquid crystal in the prepared liquid crystal cell were evaluated. The results are shown in Table 2.

Comparative Example 1

A liquid crystal aligning agent was produced in the same manner as in Example 9 except that the polyimide (Ab) obtained in Comparative Synthesis Example 1 was used instead of the polymer (1b) to prepare a liquid crystal display element. The orientation, voltage retention, and afterimage erasing time of the liquid crystal in the manufactured liquid crystal display element were measured. The results are shown in Table 3 below.

<Comparative Examples 2 and 3>

A liquid crystal aligning agent was produced in the same manner as in Example 9 except that the polymer (Ba) or the polymer (Cb) obtained in Comparative Synthesis Examples 2 and 3 was used instead of the polymer (1b) to prepare a liquid crystal display element. The orientation, voltage retention, and afterimage erasing time (including pretilt angle for Comparative Example 3) of the liquid crystal in the manufactured liquid crystal display device were measured. The results are shown in Table 3.

According to the present invention, novel polyamic acid and imidized polymers useful as liquid crystal aligning agents can be provided.

According to this invention, the liquid crystal aligning agent which can form the liquid crystal aligning film which has favorable orientation characteristic and is short in the afterimage erase time in a liquid crystal display element can be provided.

The liquid crystal aligning film formed by the liquid crystal aligning agent of this invention can be preferably used in order to comprise various liquid crystal display elements, such as a TN type liquid crystal display element, an STN type liquid crystal display element, and a vertical alignment type liquid crystal display element. Moreover, the liquid crystal display element provided with the said liquid crystal aligning film is excellent also in the orientation and reliability of a liquid crystal, and can be effectively used for various apparatuses, for example, a desktop calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer , It can be used suitably as display apparatuses, such as a liquid crystal television.

Claims (6)

delete delete delete delete 1 selected from a polyamic acid having a structure obtained by reacting a tetracarboxylic dianhydride represented by the following formula (1) with a diamine compound represented by the following formula (2), and an imidized polymer having a repeating unit represented by the following formula (3): Liquid crystal aligning agent containing a species or more. <Formula 1>

<Formula 2>

<Formula 3>

[Wherein, R ¹ is a monovalent group represented by the following general formula (1aa), R ² is a hydrogen atom, a halogen atom or a monovalent organic group, R ³ is a halogen atom or a monovalent organic group, and a is 0 to 4 Is an integer of; A is a divalent organic group.] <Formula 1aa>

[Wherein, E is a single bond or a divalent bond group, and R 'is a monovalent group having an alkyl group having 5 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms or a polycyclic structure having 10 to 30 carbon atoms.] The liquid crystal display element which has a liquid crystal aligning film formed using the liquid crystal aligning agent of Claim 5.