JP5708941B2 - Compound based on dianiline, and polyamic acid composition, polyimide composition, and liquid crystal aligning agent formed therefrom - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority from Taiwanese Application No. 100147994 filed on Dec. 22, 2011.

  The present invention relates to compounds based on dianiline, and more particularly to compounds based on dianiline containing cyclohexylene groups, and polyamic acid compositions and polyimide compositions made from compounds based on dianiline. The present invention also relates to a liquid crystal aligning agent formed from a polyamic acid composition or a polyimide composition.

  In a general liquid crystal display device, the liquid crystal rotates in relation to a change in the surrounding electric field. The orientation of the liquid crystal determines the amount of light that passes through the liquid crystal, thereby displaying an image. Recently, liquid crystal display devices are widely used because of their small volume, light weight, low power consumption, and excellent display quality.

  In a large liquid crystal display size, a thin film transistor (TFT) liquid crystal display element is attached to every pixel in the liquid crystal display. In general, the liquid crystal is injected between two alignment layers arranged at an angle of 90 ° to each other. By controlling the electric field between the alignment layers, the alignment of the liquid crystal can be controlled. The alignment layer can align the liquid crystal at a pretilt angle.

  In the art, conventional methods for forming alignment layers include applying an organic layer to a substrate and then aligning the organic layer by rubbing or other means.

  The polymer used to form the organic layer is selected from polyvinyl alcohol, polyethylene glycol, polyamide, polyamic acid, and polyimide. Polyimide is commonly used to form alignment layers because of its chemical and thermal stability. In general, polyimides are made from the polyhydric acid dehydration and ring closure reactions. Polyamic acid is obtained from the reaction of diamine with tetracarboxylic acid or tetracarboxylic dianhydride. By adjusting the preparation process of polyimide or polyamic acid, or the amount of diamine, tetracarboxylic acid, or tetracarboxylic dianhydride, the properties of the alignment layer can be adjusted.

  The diamine used to prepare the polyimide or polyamic acid is usually selected from aromatic diamines and aliphatic diamines. Examples of aromatic diamines include the following formula:

Etc.

  Japanese Patent Application Laid-Open No. 2010-266847 discloses a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid and derivatives thereof. Polyamic acid and its derivatives are prepared by reacting a diamine compound selected from the diamine group represented by the specific structural formula defined therein or a mixture of a diamine compound and another amine compound with a tetracarboxylic dianhydride compound. It is made by letting.

JP 2010-266847 A

  However, a liquid crystal alignment layer made of the above-described diamine compound used in a liquid crystal display device tends to generate ionic charges that adhere to the liquid crystal alignment layer after an electric field is applied. Ionic charges tend to accumulate in the liquid crystal alignment layer after a long display, and are not easily removed from the liquid crystal alignment layer even after the electric field is no longer applied. Accumulated ionic charges can cause burn-in on the display screen. Accordingly, it is desirable to develop diamines that can reduce the problem of seizure in the art.

  Accordingly, a first object of the present invention is to provide compounds based on dianiline.

  The second object of the present invention is to provide a polyamic acid composition.

  The third object of the present invention is to provide a polyimide composition.

  The fourth object of the present invention is to provide a liquid crystal aligning agent comprising a polyamic acid composition.

  The fifth object of the present invention is to provide a liquid crystal aligning agent containing a polyimide composition.

  The sixth object of the present invention is to provide compounds based on dianiline.

  According to a first aspect of the invention, there is provided a compound based on dianiline of formula (I).

(I)

Wherein ^one of R ¹ -R ⁵ represents amino and one of the other R ¹ -R ⁵ is from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group And the remaining R ¹ -R ⁵ is independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

One of R ⁶ -R ¹⁰ represents amino and one of the other R ⁶ -R ¹⁰ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ⁶ -R ¹⁰ are independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

X ¹ represents the following formula:

and

Selected from the group consisting of

X ² represents the following formula:

and

Selected from the group consisting of

A represents a divalent C ₆ -C ₄₀ group containing at least one 1,4-cyclohexylene group.

  According to the second aspect of the present invention, there is provided a polyamic acid composition obtained by polymerizing a diamine component and a tetracarboxylic acid component or a dianhydride thereof. The diamine component includes compounds based on the above-mentioned dianiline. The polyamic acid composition has a weight average molecular weight in the range of 5,000 to 2,500,000.

  According to the third aspect of the present invention, there is provided a polyimide composition obtained by subjecting a polyamic acid composition to a dehydration / ring-closing reaction.

  According to the fourth aspect of the present invention, there is provided a liquid crystal aligning agent comprising a polyamic acid composition and a solvent for dispersing the polyamic acid composition.

  According to the 5th aspect of this invention, the liquid crystal aligning agent containing the solvent for disperse | distributing a polyimide acid composition and a polyimide acid composition is provided.

  According to a sixth aspect of the invention, there is provided a compound based on dianiline of formula (I).

(I)

  Where A is the following formula:

Or

In the formula, a hydrogen atom can be selectively substituted with halogen.

One of R ¹ -R ⁵ represents amino and one of the other R ¹ -R ⁵ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ¹ -R ⁵ is independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

One of R ⁶ -R ¹⁰ represents amino and one of the other R ⁶ -R ¹⁰ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ⁶ -R ¹⁰ are independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

X ¹ represents the following formula:

and

Wherein R is a hydrogen atom or a C ₁ -C ₃ methyl group,

X ² represents the following formula:

and

Wherein R is a hydrogen atom or a C ₁ -C ₃ methyl group.

  Compounds based on the dianiline of formula (I) are provided.

(I)

Wherein ^one of R ¹ -R ⁵ represents amino and one of the other R ¹ -R ⁵ is from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group And the remaining R ¹ -R ⁵ is independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

One of R ⁶ -R ¹⁰ represents amino and one of the other R ⁶ -R ¹⁰ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ⁶ -R ¹⁰ are independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

X ¹ represents the following formula:

and

Selected from the group consisting of

X ² represents the following formula:

and

Selected from the group consisting of

A represents a divalent C ₆ -C ₄₀ group containing at least one 1,4-cyclohexylene group.

  Preferably, A is a 1,4-cyclohexylene group, and

An unsubstituted or halo substituent selected from the group consisting of G represents a single _bond, is selected from the group consisting of C 1 _{-C 28} alkylene group, and _C 1 _{-C 28} haloalkylene group. More preferably, G is represented by the following formula:

Wherein G ¹ and G ² are independently selected from the group consisting of halogen, C ₁ -C ₁₃ alkyl groups, and C ₁ -C ₁₃ haloalkyl groups. More preferably, G ¹ and G ² are independently selected from the group consisting of methyl, halogen, and halomethyl. In a preferred embodiment of the invention, G ¹ and G ² are both methyl.

Preferably, in formula (I), one of ^{R 2} and ^{R 4} represents amino and the other of ^{R 2} and ^{R 4} represent hydrogen. One of R ⁷ and R ⁹ represents amino and the other R ⁷ and R ⁹ represents hydrogen. R ³ and R ⁸ are independently selected from the group consisting of a C ₁ -C ₃ alkyl group, and a C ₁ -C ₃ haloalkyl group. R ¹ , R ⁵ , R ⁶ , and R ¹⁰ each represent hydrogen.

  Preferably, the dianiline-based compound according to the invention has the following formula:

(N, N '-(cyclohexane-1,4diyl) bis (3-amino-4-methylbenzamide)), and

(4,4 ′-(propane-2,2-diyl) bis (cyclohexane-4,1-diyl) bis (methyl 3-amino-4-benzoate))
Selected from the group consisting of

  Compounds based on the dianiline of formula (I) are provided.

(I)

  Where A is the following formula:

Or

In the formula, a hydrogen atom can be selectively substituted with halogen.

One of R ¹ -R ⁵ represents amino and one of the other R ¹ -R ⁵ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ¹ -R ⁵ is independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

One of R ⁶ -R ¹⁰ represents amino and one of the other R ⁶ -R ¹⁰ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ⁶ -R ¹⁰ are independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen.

X ¹ represents the following formula:

and

Wherein R is a hydrogen atom or a C ₁ -C ₃ methyl group,

X ² represents the following formula:

and

Wherein R is a hydrogen atom or a C ₁ -C ₃ methyl group.

  The compounds based on dianiline according to the invention can be prepared by known methods. Preferably, the dianiline-based compound is obtained by reacting a functional nitrobenzene compound with a bifunctional compound having a cyclohexylene group, followed by hydrogenation. More preferably, the reaction between the nitrobenzene compound and the bifunctional compound is carried out in the presence of a base and an organic solvent. The base serves the purpose of a catalyst that increases the reaction rate and lowers it to the temperature required to carry out the reaction.

  Examples of functional nitrobenzene compounds include, but are not limited to, the following formula:

and

Is mentioned.

  Examples of bifunctional compounds having a cyclohexylene group include, but are not limited to, the following formula:

and

Wherein R represents hydrogen or a C ₁ -C ₃ alkyl group.

When X ¹ and X ² of formula (I) are carbonyl groups, compounds based on dianiline can be prepared, for example, by the following steps.

(1) A carboxylated nitrobenzene compound and SOCl ₂ are reacted to form a nitrobenzene compound having an acyl chloride functional group.

(2) A cyclohexylene-containing dihydroxy compound and PBr ₃ are reacted to form a cyclohexylene-containing dibromide compound, and then reacted sequentially with Li and CuBr to form a cyclohexylene-containing Gilman reagent.

  (3) A nitrobenzene compound having an acyl chloride functional group and a cyclohexylene-containing Gilman reagent are reacted and then hydrogenated.

  The base is preferably an alkali metal and alkaline earth metal (for example, alkali metal and alkaline earth metal carbonates), a tertiary amine (for example, trimethylamine, triethylamine, triisopropylethylenediamine, 4-dimethylaminopyridine, etc.) And basic compounds formed from combinations thereof.

  The organic solvent is preferably an alkyl halide (eg, dichloromethane, dichloroethane, chloroform, etc.), a ketone (eg, acetone, butanone, etc.), tetrahydrofuran, N-methyl-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl. Selected from acetamide, dimethyl sulfoxide, and combinations thereof.

Preferably, the aforementioned hydrogenation is carried out by methods generally well known in the art. For example, the reduction reaction is performed at a suitable pressure and temperature using hydrogen or hydrazine together with a metal catalyst such as Pt, Pd or Raney nickel. In another embodiment, the reduction reaction is performed under concentrated hydrochloric acid using a reducing agent such as SnCl ₂ and Fe. In another embodiment, the reduction reaction is performed in an aprotic solvent using a reducing agent such as LiAlH ₄ .

  The present invention also provides a polyamic acid composition obtained by polymerizing a reaction mixture containing a diamine component and a tetracarboxylic acid component or a dianhydride thereof. The diamine component includes a compound based on the aforementioned dianiline. The polyamic acid composition has a weight average molecular weight in the range of 5,000 to 2,500,000.

  Preferably, the tetracarboxylic acid component or dianhydride thereof is not limited, but includes aromatic tetracarboxylic acid (eg, 1,2,4,5-benzenetetracarboxylic acid, etc.) and dianhydride thereof, Alicyclic tetracarboxylic acids (eg, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, etc.) and their dianhydrides, aliphatic tetracarboxylic acids (eg, butanetetracarboxylic acid, etc.) and their dianhydrides Products, as well as combinations thereof.

  Preferably, the reaction mixture further comprises conventional diamine compounds well known in the art. Examples of conventional diamine compounds include, but are not limited to, aromatic diamines (eg, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, 2,2-diaminodiphenylpropane, bis (3,5-diethyl- 4-aminophenyl) methane, diaminodiphenylsulfone, diaminobenzophenone, diaminonaphthalene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4-bis (4 -Aminophenoxy) diphenylsulfone, 2,2-bis (4,4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (4,4-aminophenoxy) Phenyl) hexafluoropropane), alicyclic Diamine (e.g., bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, etc.), aliphatic diamines (e.g., butanediamine, hexanediamine etc.), and combinations thereof.

  In the reaction mixture, the dianiline-based compound is used in an amount of 1 mol% or more, preferably 10 mol% or more, and more preferably 50 mol% or more with respect to 100 mol% of the combination of dianiline-based compound and the conventional diamine compound. .

  The aforementioned polyamic acid composition has a degree of polymerization in the range of 10 to 5,000, preferably 16 to 250. The polyamic acid composition has a weight average molecular weight in the range of 5,000 to 2,500,000, preferably 8,000 to 125,000.

  The present invention also provides a polyimide composition obtained by subjecting the above-mentioned polyamic acid composition to dehydration / ring-closing reaction.

  The dehydration / ring closure reaction described above is performed by heating the polyamic acid composition to form a polyimide composition. The heating temperature is in the range of 100 ° C to 350 ° C, preferably 120 ° C to 320 ° C. The dehydration / ring closure reaction is carried out in the range of 3 minutes to 6 hours.

  The present invention also provides a liquid crystal aligning agent comprising the aforementioned polyamic acid composition or the aforementioned polyimide composition and a solvent.

  Examples of the solvent used in the liquid crystal aligning agent include, but are not limited to, N-methyl-2-pyrrolidone, m-cresol, γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide , Ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethyl carbitol acetate, and combinations thereof.

  The liquid crystal aligning agent has a solid content adjusted to a range of 3% to 10% in order to control the coating property and the thickness of the alignment layer.

  The liquid crystal aligning agent can be applied to the substrate using a conventional method such as rolling, spin coating, or printing to form a thin film having a thickness in the range of 0.005 to 0.5 μm. The thin film is heated to a temperature in the range of 80 ° C. to 300 ° C., preferably 100 ° C. to 240 ° C., thereby removing the solvent and dehydrating / ring-closing the polyamic acid composition to form a polyimide composition. Is possible.

  The present invention is further described in detail by the following preferred embodiments. It should be understood that the preferred embodiment is for illustrative purposes only and should not be construed as limiting the invention.

Synthesis Example 1: Bis (3-amino-4-methylbenzoic acid) 4,4 ′-(propane-2,2-diyl) bis (cyclohexane-4,1-diyl) ester (Compound P1)
45.29 g (0.25 mol) 4-methyl-3-nitrobenzoic acid (purchased from Acros) and 51.58 g (0.25 mol) dicyclohexylcarbodiimide (DCC) were added to 288.46 g tetrahydrofuran (THF). And mixed uniformly. After 30 minutes, 24.04 g (0.10 mol) of 4,4 ′-(propane-2,2-diyl) dicyclohexanol (purchased from Sigma-Aldrich) and 2.44 g (0.02 mol) of 4- Dimethylaminopyridine (DMAP) was sequentially added and mixed uniformly. The reaction was carried out at room temperature for 8 hours, and the filtrate collected by filtration was concentrated and sufficiently dried. This was followed by three recrystallizations using a solvent mixture of THF and isopropyl alcohol (IPA) (THF to IPA weight ratio of 4 to 6) and after drying 42 g of purified bis (4-methyl-3 Nitrobenzoic acid) 4,4 ′-(propane-2,2-diyl) bis (cyclohexane-4,1-diyl) ester (Compound I1, yield 73%) was obtained as a white solid.

  28.33 g (0.05 mol) of compound I1 was dissolved in 152 g of THF followed by sequential addition of 2.83 g of Pd / C and 28.33 g of hydrazine hydrate (80%). The reaction is carried out at room temperature for 8 hours, and the filtrate collected by filtration is concentrated and sufficiently dried, and 24 g of bis (3-amino-4-methylbenzoic acid) 4,4 ′-(propane-2,2- Diyl) bis (cyclohexane-4,1-diyl) ester (Compound P1, yield 96%) was obtained as a white solid.

NMR data: ¹ H NMR (400 MHz, DMSO-d ₆ ): δ 7.23 (d, 2H, Ar), 7.06 (s, 2H, Ar), 7.03 (d, 2H, Ar), 5 .09 (s, 4H, —NH ₂ ), 4.73 (t, 2H, cyclohexane), 2.08 (s, 6H, —CH ₃ ), 2.00 to 1.00 (m, 18H, cyclohexane) _{, 0.75 (s, 6H, -CH} 3) ppm.

Synthesis Example 2: N, N ′-(cyclohexane-1,4-diyl) bis (3-amino-4-methylbenzamide) (Compound P2)
45.29 g (0.25 mol) of 4-methyl-3-nitrobenzoic acid and 51.58 g (0.25 mol) of DCC were added to 137.03 g of THF and mixed uniformly. After 30 minutes, 11.42 g (0.10 mol) of 1,4-cyclohexanediamine (purchased from Acros) and 2.44 g (0.02 mol) of DMAP were sequentially added and mixed uniformly. The reaction was performed at room temperature for 8 hours, and the filtrate collected by filtration was concentrated and dried sufficiently. Thereafter, recrystallization was carried out three times using a solvent mixture of THF and n-hexane (THF to n-hexane weight ratio of 3 to 7), and after drying, 24 g of purified N, N ′-(cyclohexane -1,4-Diyl) bis (4-methyl-3-nitrobenzamide) (Compound I2, yield 56%) was obtained as a white solid.

  22.02 g (0.05 mol) of compound I2 was dissolved in 114 g of THF and 2.20 g of Pd / C and 22.02 g of hydrazine hydrate (80%) were added sequentially. The reaction was carried out at room temperature for 8 hours, and the filtrate collected by filtration was concentrated and sufficiently dried, and 17 g of N, N ′-(cyclohexane-1,4-diyl) bis (3-amino-4-methylbenzamide) was obtained. ) (Compound P2, yield 91%) was obtained as a white solid.

NMR data: ¹ H NMR (400 MHz, DMSO-d ₆ ): δ 7.63 (d, 2H, —NH), 6.85 (d, 2H, Ar), 6.73 (s, 2H, Ar), 6.60 (d, 2H, Ar) , 4.88 (s, 4H, -NH 2), 4.10 (t, 2H, cyclohexane), 2.03 (s, 6H, -CH 3), 2. 0-0.5 (m, 8H, cyclohexane) ppm.

Example 1:
0.1 mol of compound P1 obtained from the synthesis of Synthesis Example 1 was dissolved in 150 mL of N-methylpyrrolidinone (NMP) followed by 0.1 mol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA, manufactured by Daxin Materials Corp.) and polymerized. More NMP was added until the solid content reached 15 wt%. After the reaction for 8 hours, a polyamic acid solution A1 having a solid content of 15 wt% was obtained.

Comparative Examples 1-6:
The synthesis methods of Comparative Examples 1 to 6 were the same as Example 1 except that 0.1 mol of compound P1 was replaced with 0.1 mol of diamine compounds M1 to M6, respectively. Polyamic acid solutions a1 to a6 having a solid content of 15 wt% were obtained. The structures of the diamine compounds M1 to M6 are shown below.

(M1),

(M2),

(M3),

(M4),

(M5),

(M6)

Application example 1:
The liquid crystal aligning agent B1 is obtained by diluting the polyamic acid solution A1 prepared in Example 1 to a solid content of 6.5 wt% using a NMP / diethylene glycol monobutyl ether (BC) (weight ratio, 1: 1) solvent mixture. It was. Liquid crystal aligning agent B1 was applied to a glass substrate to form a thin film having a thickness of 1200 ± 100 mm, and subsequently heated at 230 ° C. for 30 minutes. Thereafter, the alignment layer was formed by rubbing the thin film in a certain direction. Liquid crystal (purchased from Merck, model name: LCT10477) was injected between the two substrates formed of the alignment layer described above to form a liquid crystal display element D1. The liquid crystal display element D1 includes a pair of alignment layers, a liquid crystal layer disposed between the alignment layers, and a pair of electrodes disposed on the surface of the alignment layer separated from the liquid crystal layer.

Comparative application examples 1 to 6:
Comparative application examples 1 to 6 were performed in the same manner as application example 1 except that the polyamic acid solution A1 obtained in Example 1 was replaced with the polyamic acid solutions a1 to a6, respectively, and the liquid crystal display elements d1 to d6 Respectively.

Ion density measurement:
At 60 ° C., an alternating current of 1.5 V 0.01 Hz was applied to the liquid crystal display element D1 obtained in Application Example 1 and the liquid crystal display elements d1 to d6 obtained in Comparative Application Examples 1 to 6, respectively, followed by ions Density was measured. The results are shown in Table 1.

Measurement of voltage holding ratio:
At 60 ° C., a direct current of 5 V was applied to the liquid crystal display element D1 obtained in Application Example 1 and the liquid crystal display elements d1 to d6 obtained in Comparative Application Examples 1 to 6, respectively, and then the voltage holding ratio was measured. did. The results are shown in Table 1.

  As shown in Table 1, the liquid crystal display element D1 made from the compound P1 based on dianiline according to the present invention has a low ion density (compared to the liquid crystal elements d1 to d6 made from the compounds M1 to M6 based on dianiline). <15000 pC) and high voltage holding ratio (> 90%).

Without being bound by theory, the effects of low ion density and high voltage holding ratio in liquid crystal display elements are obtained using compounds based on dianiline of formula (I) to form liquid crystal aligning agents, and dianiline compounds based on the ^-X 1 ^-A-X 2 ^- is considered ^(X 1, a, X ² is as defined above) is intended to include specific connection group.

  Therefore, according to the present invention, a liquid crystal aligning agent having a polyamic acid composition or a polyimide composition made from a compound based on 1,4-cyclohexylene-containing dianiline can effectively reduce the problem of baking. is there.

  Although the invention has been described in connection with what is considered to be the most practical and preferred embodiments, the invention is not limited to the disclosed embodiments, but is encompassed within the spirit and scope of the broadest interpretation and equivalent construction. It is understood that it is intended to cover various configurations.

Claims (10)

A compound based on the dianiline of formula (I),
(I)
Wherein ^one of R ¹ -R ⁵ represents amino and one of the other R ¹ -R ⁵ is from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group And the remaining R ¹ -R ⁵ is independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen;
One of R ⁶ -R ¹⁰ represents amino and one of the other R ⁶ -R ¹⁰ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ⁶ -R ¹⁰ are independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen;
X ¹ represents the following formula:
and
Is selected from the group consisting of pressurization, et al,
X ² represents the following formula:
and
Is selected from the group consisting of pressurization, et al,
A is a 1,4-cyclohexylene group, and has the following formula:
and
An unsubstituted or halo substituent selected from the group consisting of: wherein G is selected from the group consisting of a single bond, a C ₁ -C ₂₈ alkylene group, and a C ₁ -C ₂₈ haloalkylene group , Compounds based on dianiline. The compound based on dianiline according to claim 1 , wherein said G is represented by the following formula:
Wherein G ¹ and G ² are independently a dianiline-based compound selected from the group consisting of a halogen, a C ₁ -C ₁₃ alkyl group, and a C ₁ -C ₁₃ haloalkyl group. The dianiline-based compound according to claim 2 , wherein G ¹ and G ² are independently selected from the group consisting of methyl, halogen, and halomethyl. A compound based on dianiline according to claim 1, wherein one of R ² and R ⁴ represents amino, the other R ² and R ⁴ represents hydrogen, and R ⁷ and R ^9. One of them represents amino, the other R ⁷ and R ⁹ represent hydrogen, R ³ and R ⁸ independently represent a C ₁ -C ₁₃ alkyl group, and a C ₁ -C ₁₃ haloalkyl. A compound based on dianiline selected from the group consisting of groups wherein R ¹ , R ⁵ , R ⁶ , and R ¹⁰ each represent hydrogen. A compound based on dianiline according to claim 1, which has the following formula:
and
A compound based on dianiline selected from the group consisting of: A polyamic acid composition obtained by polymerizing a diamine component and a tetracarboxylic acid component or a dianhydride thereof, wherein the diamine component comprises the dianiline-based compound according to claim 1, and the polyamic acid composition Is a polyamic acid composition having a weight average molecular weight in the range of 5,000 to 2,500,000. A polyimide composition obtained by subjecting the polyamic acid composition according to claim 6 to a dehydration / ring-closing reaction. A liquid crystal aligning agent comprising the polyamic acid composition according to claim 6 and a solvent for dispersing the polyamic acid composition. A liquid crystal aligning agent comprising the polyimide composition according to claim 7 and a solvent for dispersing the polyimide composition. A compound based on the dianiline of formula (I),
(I)
In the formula, A represents the following formula:
Or
In the formula, a hydrogen atom can be selectively substituted with halogen,
One of R ¹ -R ⁵ represents amino and one of the other R ¹ -R ⁵ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ¹ -R ⁵ are independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen;
One of R ⁶ -R ¹⁰ represents amino and one of the other R ⁶ -R ¹⁰ is selected from the group consisting of a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ haloalkyl group; The remaining R ⁶ -R ¹⁰ are independently selected from the group consisting of hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group, and a halogen;
X ¹ represents the following formula:
and
Is selected from the group consisting of pressurization, et al,
X ² represents the following formula:
and
Ru is selected from the group consisting of pressurized et al, compounds based on dianiline.