JP4900560B2 - Novel diamine compound, polymer and liquid crystal aligning agent - Google Patents

Description

  The present invention relates to a novel diamine compound, a polyamic acid, an imidized polymer thereof, a liquid crystal aligning agent, and a liquid crystal display element. More specifically, a liquid crystal display comprising a novel diamine compound, a polyamic acid using the same, an imidized polymer thereof, a liquid crystal alignment agent containing at least one of these polymers, and a liquid crystal alignment film obtained from the liquid crystal alignment agent It relates to an element.

Conventionally, a cell of a sandwich structure is formed by forming a nematic liquid crystal layer having positive dielectric anisotropy between two substrates having a liquid crystal alignment film formed on the surface via a transparent conductive film, There is known a TN liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell in which the major axis of liquid crystal molecules is continuously twisted by 90 degrees from one substrate toward the other substrate.
Further, the addition of a chiral agent achieves a state in which the major axis of the liquid crystal molecules is continuously twisted between the substrates by 180 degrees or more, and an STN (Super Twisted Nematic) type liquid crystal display element utilizing the birefringence effect generated thereby. Is also present. More recently, a homeotropically aligned nematic liquid crystal layer having negative dielectric anisotropy between opposing substrates and a cholesteric liquid crystal layer in which the helical axis is parallel to the substrate normal are formed. A guest-host type reflective liquid crystal display element in which a dye is added to the above has also been developed. The alignment of the liquid crystal in these liquid crystal display elements is usually expressed by a liquid crystal alignment film subjected to a rubbing treatment. Here, as a material for the liquid crystal alignment film constituting the liquid crystal display element, polyimide, polyamide, polyester, and the like are conventionally known. In particular, polyimide is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like.

Up to now, studies have been made on improving display quality, such as higher definition of liquid crystal display elements, and lowering power consumption. As a result, remarkable progress has been made as a high-performance display element. Liquid crystal display elements having a high retention rate and high reliability have been developed. However, in recent years, in addition to the conventional transmissive type, the range of use of liquid crystal display elements such as reflective type and transflective type has been expanded, and devices and production lines have been greatly enlarged along with the increase in substrate size. As well as high reliability, the required performance for the process condition dependency of the pretilt angle is becoming stricter. Among liquid crystal alignment films composed of polyamic acid, which is a precursor of conventional polyimide, and imide-based polymers having a structure obtained by dehydrating and cyclizing it, a liquid crystal display element is formed using the liquid crystal alignment film. When fabricated, there were many that had problems with the stability of the pretilt angle with respect to the process conditions even if a high voltage holding ratio and high reliability were obtained.
JP-A-11-349864

  The objective of this invention is providing the novel diamine compound suitable for manufacture of the polyamic acid used for manufacture of a liquid crystal aligning film.

  Another object of the present invention is to provide a polyamic acid and an imidized polymer thereof using the novel diamine compound of the present invention.

  Still another object of the present invention is a liquid crystal alignment film comprising a polyamic acid and / or an imidized polymer thereof, and having a good pretilt angle dependency on process conditions while maintaining a high voltage holding ratio and high reliability. Is to provide.

  Still another object of the present invention is to provide a liquid crystal aligning agent comprising the liquid crystal aligning film of the present invention and having excellent high voltage holding ratio as described above.

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are:
First, the following formula (I)

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, or a halogen atom, and X and Y are each independently represented by the following formula ( a) to (d)

Z is a group represented by each of the above (a) to (d) or an oxygen atom, and a is an integer of 0 to 4. ) (Hereinafter referred to as “specific diamine compound”).

According to the present invention, the above objects and advantages of the present invention are:
Secondly, a polyamic acid obtained by reacting a specific diamine compound and tetracarboxylic dianhydride (hereinafter referred to as “specific polymer I”) and an imidized polymer obtained by subjecting it to dehydration and ring closure (hereinafter referred to as “ A specific polymer II ”).

According to the present invention, the above object and advantage of the present invention are as follows.
Thirdly, it is achieved by a liquid crystal aligning agent containing a polyamic acid (specific polymer I) and / or an imidized polymer (specific polymer II).

Furthermore, according to the present invention, the above objects and advantages of the present invention are as follows:
Fourthly, it is achieved by a liquid crystal display device provided with a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.

The alignment film formed from the polyamic acid and / or imidized polymer synthesized by using the diamine compound of the present invention has an excellent pretilt angle dependency on the process margin while maintaining a high voltage holding ratio as compared with the conventional alignment film. And can be suitably used to construct various liquid crystal display elements such as a TN liquid crystal display element, an STN liquid crystal display element, a reflective liquid crystal display element, and a transflective liquid crystal display element.
The liquid crystal display element of the present invention can be effectively used in various devices, and is suitable for display devices such as desk calculators, watches, table clocks, mobile phones, counting display boards, word processors, personal computers, and liquid crystal televisions. Can be used.

  Hereinafter, the present invention will be described in detail.

Specific diamine compound The specific diamine compound used in the present invention is a compound represented by the above formula (I). In the formula (I), R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, or a halogen atom, and X and Y are independently selected from the above formulae. It is an ester group or an amide group represented by each of (a) to (d), Z is a group or oxygen atom represented by each of the above formulas (a) to (d), and a is 0 to 4 It is an integer. Also, when a is an integer from 2 to 4, a plurality of R ¹ may be the same or different.
The alkyl group having 1 to 12 carbon atoms representing R ¹ and R ² is preferably a lower alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. , N-butyl group, tert-butyl group and the like. The hull alkyl group having 1 to 12 carbon atoms representing the R ^1, R ^2, can be cited as an example preferred the trifluoromethyl group. Examples of the halogen atom representing R ¹ include a fluorine atom.
The specific diamine compound represented by the above formula (I) can be obtained by, for example, the following method.
[Compound wherein X is a group represented by the above formula (a) and Y is a group represented by the above formula (b)]
Step (i). Following formula (II)

(Wherein A is a halogen atom) a dinitrobenzoic acid halide compound is reacted with dihydroxycyclohexane to give the following formula (III)

The compound containing the hydroxyl group represented by this is obtained.
Step (ii). In the compound (III) having a hydroxyl group produced in the step (i), the following formula (IV)

(Wherein the definitions of R ¹ , R ² , Z, A and a are the same as above) are reacted to give the following formula (V)

(Wherein the definitions of R ¹ , R ² , Z and a are the same as above).
Step (iii). The dinitro compound (V) obtained in step (ii) is reduced, and the following formula (VI)

(Here, the definition of R < ¹ >, R < ² >, Z, and a is the same as above.) The specific diamine compound represented by this is obtained.

[When X is a group represented by the above formula (c) and Y is represented by the above formula (d)]
Step (i). The dinitrocyclohexane halide represented by the above formula (II) is reacted with diaminocyclohexane to give the following formula (VII)

The compound which has an amino group represented by these is obtained.
Step (ii). The compound represented by the above formula (IV) is reacted with the compound (VII) having an amino group produced in the step (i), and the following formula (VIII)

(Here, the definitions of R ¹ , R ² , Z and a are the same as above.) Are obtained.
Step (iii). The dinitro compound (VIII) obtained in step (ii) is reduced, and the following formula (IX)

(Here, the definitions of R ¹ , R ² , Z and a are the same as above.) Are obtained.

In the synthesis reaction of the specific diamine compound, a solvent can be used as necessary. The solvent is not particularly limited as long as it can dissolve the specific diamine compound and does not inhibit the reaction. For example, aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and other dimethylsulfoxide, dimethylformamide and dimethylacetamide it can. Examples of the basic catalyst used in the above reaction include sodium hydroxide, potassium hydroxide, pyridine, triethylamine and the like.
The ratio of the dinitrobenzoic acid halide compound represented by the above formula (II) in the step (i) and the compound having a cyclohexane structure is such that the compound having a cyclohexane structure is 2 to 1 mol of the dinitrobenzoic acid halide compound. 20 moles are preferred. The ratio of the compound represented by the above formula (IV) or (VIII) to 1 mol of the compound (III) or (VII) obtained in the step (i) in the above step (ii) is 1 to 1.2 mol. Is preferred.

  In the reduction of the dinitro compound in the step (iii), a reducing agent such as hydrogen gas, hydrazine, or hydrochloric acid can be used in the presence of a known catalyst. Examples of the catalyst include a group VIII metal, that is, a metal catalyst mainly composed of a metal such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium and platinum, specifically, when the metal is supported on a support. And the above-mentioned metal complex catalysts. The reduction reaction may be homogeneous or heterogeneous.

The amount of the catalyst used can be used at an appropriate ratio. For example, when the catalyst is mainly composed of the group VIII metal, the catalyst is used in an amount of 0.0001 to 100 parts by weight, particularly 0.001 to 100 parts by weight based on 100 parts by weight of the dinitro compound. It is preferably used in the range of 20 parts by weight. In addition, as the reduction reaction, a method using a reducing agent such as zinc, tin, tin (II) carbide, sodium sulfide, sodium hydrosulfide, sodium dithionite, or ammonium sulfide can be used. In this case, the reducing agent is preferably used in the range of 0.001 to 10 mol with respect to 1 mol of the nitro group of the dinitro compound.
As the solvent used in the reduction reaction, those which dissolve both the dinitro compound and the diamine compound and are not altered by the reduction reaction are preferable. For example, alcohols such as methanol, ethanol, propanol and butanol; diethyl ether, 1,2-dimethoxy Examples include ethers such as ethane, tetrahydrofuran, dioxane, and anisole.
A specific diamine compound can be used individually or in combination of 2 or more types, The compound of following formula (X)-(XVII) is illustrated as a preferable thing.

  In addition to the specific diamine compound, other diamine compounds can be used in combination with the diamine compound used in the present invention as long as the effects of the present invention are not impaired.

Examples of other diamine compounds include the compounds shown below. p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfone, 3,3′- Dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 5 -Amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'- Diaminodiphenyl ether, 3,3′-diaminobenzophenone, 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) hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (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'-di Mino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenylene) Isopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) Aromatic diamines such as biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, aliphatic such as 4,4′-methylenebis (cyclohexylamine) And alicyclic diamines;
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-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 Intramolecular such as phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas (XVIII) and (XIX) A diamine having two primary amino groups and a nitrogen atom other than the primary amino group;

(Wherein R ³ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ represents a divalent organic group.)

(Wherein X ² represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, R ⁴ represents a divalent organic group, and there are a plurality of them. X ² may be the same or different.)
Mono-substituted phenylenediamines represented by the following formula (XX); diaminoorganosiloxanes represented by the following formula (XXI);

(Wherein R ⁵ represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ⁶ represents a steroid skeleton, A monovalent organic group having a group selected from a fluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms is shown.)

(Wherein R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁷ may be the same or different, p is an integer of 1 to 3, and q is 1 to 20) Is an integer.)
And compounds represented by the following formulas (XXII) to (XXVI). These diamine compounds can be used alone or in combination of two or more.

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)
Among these, 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-amino) Enoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, compounds represented by the above formulas (XXII) to (XXVI), 2,6-diaminopyridine, 3,4-diaminopyridine, 2 1,4-diaminopyrimidine, 3,6-diaminoacridine, a compound represented by the following formula (XXVII) among the compounds represented by the above formula (XVIII), and the following formula among the compounds represented by the above formula (XIX) Of the compounds represented by (XXVIII) and the compounds represented by the above formula (XX), compounds represented by the following formulas (XXIX) to (XXXIV) are preferred.

Tetracarboxylic dianhydride Examples of the tetracarboxylic dianhydride used in the present invention include the compounds shown below. Butanetetracarboxylic 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 dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic 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- Chlohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2 .1] Aliphatics and fats such as octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), compounds represented by the following formulas (1) and (2) Cyclic tetracarboxylic dianhydrides;

(Wherein R ⁸ and R ¹⁰ represent a divalent organic group having an aromatic ring, R ⁹ and R ¹¹ represent a hydrogen atom or an alkyl group, and a plurality of R ⁹ and R ¹¹ are the same. But it may be different.)
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (Phthalic acid) phenylphosphine oxide dianhydride, 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 (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate) 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydride) Trimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formulas (3) to (6) An aromatic tetracarboxylic dianhydride such as a compound represented by each of the above can be exemplified. These may be used alone or in combination of two or more.

  Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5 − Oxo-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] -oct-7-ene-2,3,5,6-tetracarboxylic Acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Of the anhydrides, compounds represented by the above formula (1) Of the compounds represented by the formulas (7) to (9) and the compound represented by the above formula (2), the compound represented by the following formula (10) exhibits good liquid crystal orientation. Are preferable from the viewpoint of being capable of producing 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, , 2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran) -2 ', 5'-dione), pyromellitic dianhydride and compounds represented by the following formulas (7) to (10).

[Synthetic reaction of polyamic acid]
The specific polymer I (polyamic acid) used in the present invention is obtained by reacting a diamine compound containing a specific diamine compound with tetracarboxylic dianhydride. The use ratio of the specific diamine compound preferably occupies 0.1 to 100 mol%, and more preferably 5 to 30 mol% in all diamine compounds. The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.

  The synthetic reaction of polyamic acid is preferably carried out in an organic solvent under a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the specific polymer I to be synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Examples include aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of the organic solvent used (a) is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable that

[Poor solvent]
For the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination as long as the polyamic acid to be produced does not precipitate. be able to. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene Glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n- Chill ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene 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.
As described above, a reaction solution obtained by dissolving the specific polymer I is obtained. And the specific polymer I can be obtained by pouring this reaction solution in a lot of poor solvents, obtaining a deposit, and drying this deposit under reduced pressure. Further, the specific polymer I can be purified by dissolving the specific polymer I in an organic solvent and then precipitating with a poor solvent once or several times.
The specific polymer I of the present invention thus obtained has the following formula (11)

Where R ¹ , R ² , X, Y, Z and a are the same as defined above, and A is a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Having repeating units represented.

Imidized polymer The specific polymer II (imidized polymer) used in the present invention can be synthesized by dehydrating and ring-closing the specific polymer I described above. The imidized polymer used in the present invention may be partially dehydrated and ring-closed with an imidation rate of less than 100%. The “imidation rate” as used herein means the ratio of the number of imide bond units to the total number of units of imide bond units and amic acid bond units, that is, the ratio of repeat units having an imide ring or an isoimide ring in all repeating units of the polymer. The value is expressed as a percentage. An alignment film made of an imidized polymer having an imidization ratio of 30 to 100% can be evaluated to have high image sticking and high reliability, particularly when used in a TFT type device. The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C., the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease.

On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. In addition, the imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained.
The specific polymer II of the present invention thus obtained has the following formula (12)

(Wherein R ¹ , R ² , X, Y, Z, A and a have the same definition as above).

<End-modified polymer>
The specific polymer I and the specific polymer II may be of a terminal modified type with a controlled molecular weight. By using this terminal-modified polymer, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified type can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic anhydride and the like. Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecylamine. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. Can do. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

[Logarithmic viscosity]
<Logarithmic viscosity of polymer>
The polyamic acid and imide group-containing polyamic acid obtained as described above preferably have a logarithmic viscosity (η _ln ) of 0.05 to 10 dl / g, more preferably 0.05 to 5 dl / g.
The value of the logarithmic viscosity (η _ln ) in the present invention is determined by measuring the viscosity at 30 ° C. for a solution having a concentration of 0.5 g / 100 ml using N-methyl-2-pyrrolidone as a solvent. ).

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is constituted by dissolving and containing an active ingredient comprising the polyamic acid and / or imidized polymer of the present invention in an organic solvent.
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 a polyamic acid can be mentioned. Moreover, the poor solvent illustrated as what can be used together in the case of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together.

The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the coating film thickness is It is too small to obtain a good liquid crystal alignment film. When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases to easily deteriorate the coating characteristics. . Moreover, the temperature at the time of preparing the liquid crystal aligning agent of this invention, Preferably, it is 0 to 200 degreeC, More preferably, it is 20 to 60 degreeC.
The liquid crystal aligning agent that forms the liquid crystal alignment film of the present invention contains a compound having at least one epoxy group in the molecule (hereinafter also referred to as “epoxy group-containing compound”) from the viewpoint of improving the adhesion to the substrate surface. May be.

Examples of the epoxy group-containing 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-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′ - tetraglycidyl -m- xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', N' - -4,4'- tetraglycidyl Gia Minodiphenylmethane and the like can be mentioned as preferable ones. The blending ratio of these epoxy group-containing compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the specific polymer.

Moreover, the liquid crystal aligning agent of this invention may contain the functional silane containing compound. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. can be mentioned.
The blending ratio of these functional silane-containing compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the specific polymer.

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

(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spinner method, a printing method, an ink jet method, etc. Is heated to form a coating film. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask in advance is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. In addition, the liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film that becomes an alignment film by removing the organic solvent after coating, but further proceeds with dehydration ring closure by further heating, and is further imidized. It can also be set as a coating film. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) A rubbing process is performed in which the formed coating film surface is rubbed in a certain direction with a roll wound with a cloth made of a fiber such as nylon, rayon, or cotton. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film.
Further, by partially irradiating the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. A resist film is partially formed on the surface of the liquid crystal alignment film that has been subjected to a treatment for changing the pretilt angle or a rubbing treatment as disclosed in JP-A-5-107544, which is different from the previous rubbing treatment. The visibility characteristics of the liquid crystal display element can be improved by removing the resist film after performing the rubbing treatment in the direction and changing the liquid crystal alignment ability of the liquid crystal alignment film.

(3) Two substrates on which the liquid crystal alignment film is formed as described above are manufactured, and the two substrates are separated by a gap (cell gap) so that the rubbing directions in the respective liquid crystal alignment films are orthogonal or antiparallel. ), And the periphery of the two substrates are bonded together using a sealant, and liquid crystal is injected and filled in the cell gap defined by the substrate surface and the sealant, and the injection hole is sealed. A liquid crystal cell is constructed. And a liquid crystal display element is obtained by arrange | positioning a polarizing plate to the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell.
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.

Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal. Liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films. The polarizing plate which consists of itself can be mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The voltage holding ratios in the examples and comparative examples were evaluated by the following methods.

[Imidation rate]
From the peak area ratio of absorption near 1381 cm ⁻¹ (C—N—C bending vibration = absorption of imide bond) and absorption near 1503 cm ⁻¹ (absorption of amic acid bond) in FT-IR measurement, The imidization rate was calculated by
Imidation ratio = {α ₁ / (α ₁ + α ₂ )} × 100 (%)
α _1: 1381cm ^-1 vicinity of the absorption peak area alpha _2: peak area of absorption around 1503cm ^-1 Incidentally, alpha ₂ is the absorption in the vicinity of 1303cm ^-1 but was heated for 10 minutes on a hot plate at 300 ° C. The coating The value obtained by calculating the peak area as 0.

[Voltage holding ratio]
A voltage of 5 V was applied to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from release of application was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation. The case where the voltage holding ratio was 90% or more was judged as good, and the other cases were judged as bad.

[Reliability test]
A liquid crystal display element is placed in a constant temperature bath at 100 ° C., and continuously driven for 24 hours with a drive waveform generator “Function / arbitrary waveform generator” (manufactured by Hewlett Packard).

Example 1 ( Synthesis of specific diamine compound)
Step (i): 23.06 g (100 mmol) of 3,5-dinitrobenzoyl chloride and 34.85 g (300 mmol) of 1,4-dihydroxycyclohexane were dissolved in 400 g of tetrahydrofuran. Next, 7.91 g (100 mmol) of pyridine was gradually added dropwise while stirring and cooling with ice. After reacting for 6 hours, the reaction solution was poured into a large excess of water, and the precipitate was filtered off and recrystallized from methyl ethyl ketone to obtain a white dinitro compound.
Step (ii): 24.82 g (80 mmol) of the dinitro compound obtained in step (i) and 19.6 g (80 mmol) of p-trifluoromethoxybenzoyl chloride were dissolved in 400 g of tetrahydrofuran. Next, 6.33 g (80 mmol) of pyridine was gradually added dropwise while stirring and cooling with ice. After reacting for 6 hours, the reaction solution was poured into a large excess of water, and the precipitate was filtered off and recrystallized from methyl ethyl ketone to obtain a white dinitro compound.
Step (iii): 37.35 g (72 mmol) of the dinitro compound obtained in step (ii) was dissolved in 400 g of ethanol, and 0.3 g of a 5 wt% palladium-carbon catalyst and 5.6 g of hydrazine monohydrate ( 100 mmol) was added and the reaction was refluxed for 6 hours. The reaction solution was poured into a large excess of water, and the precipitate was filtered off and recrystallized from ethanol to obtain 24.44 g of a white specific diamine (I) represented by the above formula (X). The NMR spectrum of the obtained specific diamine compound is shown in FIG. Elemental analysis _{(C 21 H 21 N 2 O} 5 F 3, molecular weight 438.4): Calculated C: 57.48%, H: 4.79 %, N: 6.39%, O: 18.25%, F: 13.09%. Found C: 57.39%, H: 4.74%, N: 6.45%, O: 18.32%, F: 13.10%.

Example 2 (Synthesis of specific polymer IIa)
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.09 g (0.5 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine as a diamine compound 90.03 g (0 8325 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 26.3 g (0.06 mol) of the specific diamine compound (I), 1.396 g (0.015 mol) of aniline as a monoamine Was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 400 g of a specific polymer Ia having a logarithmic viscosity of 0.81 dl / g. 30 g of the obtained specific polymer Ia was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, dehydrating and ring-closing at 110 ° C. for 4 hours, and precipitation and washing were performed in the same manner as above. The pressure was reduced to obtain 18.2 g of the specific polymer IIa having a logarithmic viscosity of 0.75 dl / g. The NMR spectrum of the obtained specific polymer IIa is shown in FIG.

Example 3 (Synthesis of specific polymer IIb)
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound and a specific diamine compound (I) 52.61 g (0.12 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 380 g of a specific polymer Ib having a logarithmic viscosity of 0.78 dl / g. 30 g of the obtained specific polymer Ib was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours. The pressure was reduced to obtain 20.1 g of a specific polymer IIb having a logarithmic viscosity of 0.76 dl / g. The NMR spectrum of the obtained specific polymer IIb is shown in FIG.

Example 4 (Synthesis of specific polymer IIc)
1,2.09 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine 82.46 g (0 as diamine compound) 7625 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, 35.07 g (0.08 mol) of the specific diamine compound (i) represented by formula (X), and 4,4 9.91 g (0.05 mol) of '-diaminodiphenylmethane and 1.396 g (0.015 mol) of aniline as a monoamine were added to N-methyl-2-pyrrolidone 4500 Dissolved in, and reacted for 6 hours at 60 ° C.. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Then washed with methyl alcohol, and dried 15 hours in vacuo at 40 ° C., a specific polymer I c logarithmic viscosity 0.79 dl / g was obtained 350 g. 30 g of the obtained specific polymer Ic was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation and washing in the same manner as above. The pressure was reduced to obtain 18.8 g of a specific polymer IIc having a logarithmic viscosity of 0.78 dl / g. The NMR spectrum of the obtained specific polymer IIc is shown in FIG.

Synthesis Example 1 (Synthesis of polyamic acid (A-1))
196.12 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl 212 as diamine compound .3 g (1.0 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 390 g of a polyamic acid having a logarithmic viscosity of 0.91 dl / g (referred to as “polyamic acid (A-1)”).

Synthesis Example 2 (Synthesis of polyimide B-1)
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound and 4- ( 4'-trifluoromethyl-acetoxyphenyl) cycloalkyl f Kishiru 3,5-aminobenzoate 50.69g (0.12 mol) was dissolved in N- methyl-2-pyrrolidone 4500 g, it was reacted for 6 hours at 60 ° C.. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 390 g of polyamic acid having a logarithmic viscosity of 0.79 dl / g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 18.7 g of polyimide having a logarithmic viscosity of 0.77 dl / g (referred to as “polyimide B-1”).

Synthesis Example 3 (Synthesis of polyamic acid A-2 and polyimide B-2)
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound, and 4- 50.69 g (0.12 mol) of (4′-trifluoromethylbenziloxy) cyclohexyl 3,5-diaminobenzoate was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 390 g of a polyamic acid having a logarithmic viscosity of 0.79 dl / g (referred to as “polyamic acid A-2”). 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 18.7 g of polyimide having a logarithmic viscosity of 0.77 dl / g (referred to as “polyimide B-2”).

Synthesis example 4
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound, and cholestanyl- 7.842 g (0.015 mol) of 3,5-diaminobenzoate was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 400 g of a polyamic acid having a logarithmic viscosity of 0.75 dl / g (referred to as “polyamic acid A-3”). 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 19.2 g of polyimide having a logarithmic viscosity of 0.78 dl / g (referred to as “polyimide B-3”).

Synthesis example 5
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.08 g (0.5 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine 95.71 g (0 mol) as the diamine compound 865 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, and 12.86 g (0.02 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, N- 8.09 g (0.03 mol) of octadecylamine was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 340 g of polyamic acid having a logarithmic viscosity of 0.84 dl / g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.4 g of a polyimide having a logarithmic viscosity of 0.65 dl / g (referred to as “polyimide (B-4)”).

Example 5
The specific polymer IIa obtained in Example 2 and the polyamic acid (A-1) obtained in Synthesis Example 1 were converted into γ− so that the specific polymer IIa: polyamic acid = 20: 80 (weight ratio). Dissolve in butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 72/15/13) to make a solution with a solid content concentration of 4% by weight, and after thorough stirring, filter the solution with a pore size of 1 μm. It filtered using, and the liquid crystal aligning agent of this invention was prepared. The liquid crystal aligning agent was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner (rotation speed: 2500 rpm, application time: 1 minute), and 200 A film having a dry film thickness of 0.08 μm was formed by drying at 0 ° C. for 1 hour. When the imidization rate of this film was measured, the imidation rate was 52%. A rubbing machine having a roll in which a rayon cloth was wound around this film was subjected to a rubbing treatment at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / second, and a hair foot pushing length of 0.4 mm. The liquid crystal alignment film-coated substrate was dipped in isopropyl alcohol for 1 minute and then dried on a hot plate at 100 ° C. for 5 minutes. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of transparent electrodes / transparent electrode substrates having the liquid crystal alignment film of the liquid crystal alignment film coated substrate, the liquid crystal alignment film The adhesive was cured by overlapping and pressing so that the surfaces were opposed. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarizing plates are formed on both sides of the substrate. Were laminated to prepare a liquid crystal display element. The voltage holding ratio of the obtained liquid crystal display element was evaluated. The voltage holding ratio was as high as 99%, and contrast unevenness and display defects were not observed.

  Further, the liquid crystal aligning agent was applied on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner (application time: 1 minute). A film having a dry film thickness shown in Table 1 was formed by drying for 1 hour at each drying temperature under Conditions 1 to 5. After the coating was formed, the substrate was rubbed in the same manner as described above, and an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 17 μm was applied to the outer edge of the liquid crystal alignment film coated substrate of a pair of transparent electrodes / transparent electrode substrates. After that, the liquid crystal alignment film surfaces were overlapped so as to face each other and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC-5081, manufactured by Merck & Co., Inc.) is filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive. Were laminated to prepare a liquid crystal display element. The pretilt angle of the obtained liquid crystal display element was evaluated, and the process condition dependency of the pretilt angle was judged. The results are shown in Table 2.

Examples 6 and 7 and Comparative Examples 1 to 6
The polyimide and polyamic acid obtained in Synthesis Examples 1 to 5 are dissolved in a mixed solvent containing γ-butyllactone as a main component to obtain a solution having a solid content concentration of 4.0%, and this solution is filtered through a filter having a pore size of 1 μm. By doing so, a liquid crystal aligning agent was prepared. Using each of the liquid crystal aligning agents thus adjusted, a film was formed on the substrate surface in the same manner as in Example 5, and the imidization ratio of the film was measured. A liquid crystal display element was produced using the substrate on which the liquid crystal alignment film was formed. Then, the voltage holding ratio and the pretilt angle were evaluated. The results are shown in Table 2. In Example 7 and Comparative Example 6, polyamic acid and polyimide were used in such a ratio that polyamic acid: polyimide = 4: 1 (weight ratio).

1 is an NMR spectrum diagram of a specific diamine compound obtained in Example 1. FIG. 2 is an NMR spectrum diagram of the specific polymer IIa obtained in Example 2. FIG. 2 is an NMR spectrum diagram of the specific polymer IIb obtained in Example 3. FIG. 4 is a NMR spectrum diagram of the specific polymer IIc obtained in Example 4. FIG.

Claims (7)

The following general formula (I)

(In the formula, R ¹ and R ² are an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, or a halogen atom, and X and Y are independently represented by the following formulas (a) to (d).

Z is a group represented by each of the above (a) to (d) or an oxygen atom, and a is an integer of 0 to 4. The diamine compound represented by this. The following formula (II) or (III)

A diamine compound represented by:
A polyamic acid obtained by reacting the diamine compound according to claim 1 and claim 2 with tetracarboxylic dianhydride. A polyimide obtained by dehydrating and ring-closing the polyamic acid according to claim 3. A liquid crystal alignment film containing the polyamic acid according to claim 3 and / or the polyimide according to claim 4. 6. The liquid crystal alignment film according to claim 5, wherein the percentage ratio of the number of imide bond units to the total number of bond units of imide bond units and amic acid bond units in the polymer is 30 to 100%. A liquid crystal display element comprising the liquid crystal alignment film according to claim 5.

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