KR20080030671A - Poly (aryletherimide) for negative birefringent film of LC - Google Patents

Abstract

 Disclosed is a class of soluble poly (aryletherimides) (PAEIs) having flexible backbones useful for the manufacture of polymeric optical films. Poly (aryletherimide) is dissolved in organic solvents such as ketone and ketone solvent mixtures and coated on various substrates such as triacetyl cellulose (TAC) to form a transparent thin film that exhibits negative birefringence. Thin films can be provided as compensation layers in liquid crystal displays (LCDs) and are combined with other types of optical films such as polarizers, brightness enhancement films, or other compensation films, particularly useful for the manufacture of LCDs. A film can be formed.

Description

Poly (aryletherimide) for negative birefringence film of LCD {POLY (ARYLETHERIMIDES) FOR NEGATIVE BIREFRINGENT FILMS FOR LCDS}

The present invention relates to the production of negative birefringent polymer films for use in compensation layers in liquid crystal displays (LCDs). More specifically, the present invention relates to the preparation and use of poly (aryletherimides) (PAEIs), which can be dissolved in various organic solvents and coated onto various polymer substrates. More specifically, the present invention relates to the preparation of PAEIs, wherein the PAEIs are aromatics comprising dianhydrides and soft ether bonds comprising flexible ether or perfluoroisopropylidene bonds. It is prepared from diaromatic diamines. More specifically, the present invention provides 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropene dianhydride (6FDA) and inexpensive fluorine relates to the preparation of PAEIs based on aromatic ether diamines and the like comprising fluorine, wherein the PAEIs are dissolved in selected solvents such as ketone solvents and / or ketone solvent mixtures and coated onto the desired polymer substrate and consequently Multi-layer polymeric optical films are made.

Liquid crystals are useful for electronic displays because the light traveling through the thin film of the liquid crystal is affected by the birefringence of the film, which can be controlled by the action of a voltage across the film. Liquid crystal displays (LCDs) are desirable because the transmission or reflection of light from an external source, including atmospheric light, can be controlled with much less power than is required for luminescent materials used in other displays. Do.

The following terms have the same definitions as described below.

1. Here, the optical axis refers to a direction in which birefringence is not caused by spreading light.

2. Negative C-plate herein refers to a plate whose optical axis is perpendicular to the plate.

3. The refractive indices in the plane are defined as n _∥ = (n _x + n _y ) / 2, where n _x , n _y are the indices of refraction in the x and y directions, and the xy plane is in the plane of the film. Parallel.

4. In-plane birefringence is defined as Δn _∥ = (n _x -n _y ).

5. The phase retardation of the in-plane phase is defined by R _∥ = (n _x -n _y ) d, where d is the film thickness in the z direction perpendicular to the xy plane.

6. Out of-plane birefringence is defined as _{Δn ⊥} = n _z- (n _x + n _y ) / 2, where n _z is the index of refraction in the z direction.

7. plane out deceleration _{R ⊥ = [n z - (} n x + n y) / 2] is defined as d.

LCDs are now commonly used in peripherals such as digital clocks, calculators, cell phones, portable computers, televisions, and many other types of electronic devices that require long life and small operating space with low power consumption. In particular, portable computers and large screen television LCDs have advantages such as light weight, small space, low power consumption, and long service life. In the near future, CRTs, which are used as monitors and television screens, are expected to be replaced by LCDs.

However, LCDs have inherent viewing angle dependencies, which affect the quality of display performance, such as contrast, hue and / or contrast. The primary factors limiting the quality of LCD performance are the propensity of light to leak through liquid crystal elements or cells and leakage dependence in the direction in which the display is viewed. The best LCD image is only observed in a narrow viewing angle range perpendicular to the display screen.

One common way to widen the viewing angle of an LCD is to apply a compensation film. Several LCD modes, including Twisted Nematic (TN), Super Twisted Nematic (STN), Vertical Alignment (VA), and Optically Compensated Bend (OCB) They show positive C-plate symmetry, with or without an applied field, which can be compensated by a compensation film with negative C-plate symmetry.

In a compensation film with a C-plate symmetry, the out-of-plane refractive index n _⊥ or n _z is less than the in-plane refractive index n _∥ = (n _x + n _y ) / 2 and consequently negative out-of-plane birefringence _{Δn ⊥} = (n _x + n _y ) / 2 <0, thus resulting in a negative out-of-plane deceleration R _⊥ = [n _z- (n _x + n _y ) / 2] d <0. Negative birefringence films are used for fine stretching of polymer films, precisely controlled vapor escape of thin ceramic layers, mixing of expandable inorganic clay layers to crosslinked polymer matrices, and solution casting of thin polymer films. Or by other methods such as, but not limited to, coating. For large size negative birefringent films, solution casting or coating is preferred due to the ease of processing and improved performance. Currently used techniques include stretching of films. The disadvantage of using such film stretching is that the stresses applied to the film can be relaxed, causing the film to warp in the so-called film / screen's corners. The use of poly (aryletherimide) will eliminate the need for stretching when stretching is nearly impossible as well as when it is not simply necessary to achieve the required results.

There are two main methods of applying a negative birefringent film produced by a casting or coating method onto a component of an LCD, which is an integral part of an LCD device such as a polarizer. In the first method, the negative birefringent film is solution cast on a solvent-passive carrier substrate and then an adhesive is applied to the negative birefringent film surface. The combination is thinly spread in a plate shape on the LCD component and the (transported) substrate is removed. In the second method, a negative birefringent film is made by coating a polymer solution directly on an LCD unit component such as a polarizer or a polarizer substrate. This method is preferred because of its simplicity and cost savings. However, this method needs to be easy to dissolve the polymer in the solvent of choice. The solvent must not only dissolve the polymer forming the negative birefringent film, but also must not dissolve or significantly inflate the LCD components. The solvent should also be able to be used in large commercial coating processes. In Japanese Patent 3735361, methylisobutyl ketone (MIBK) is suggested as a preferred solvent for solution coating the cellulose substrate, since it best meets the above requirements. MIBK also does not dissolve triacetylcellulose (TAC), a commonly used substrate.

Previous techniques have suggested that rigid structural units must be incorporated into the backbone of the polymer to make negative birefringent films using solution casting or coating methods. This is thought to be because such groups promote in-plane orientation of the polymer backbone during solution casting or coating processes. Since incorporation of hard groups in the polymer backbone also often results in a decrease in solubility, special steps must be applied to achieve the desired balance between hard and solubility. For example, US Pat. Nos. 5,580,950 and 5,480,964 include polyesters, polyamides, polyimides, etc., based on monomers having twisted 2,2'-diphenyl biphenyl structures. Rigid-rod aromatic polymers are used. The balance between solubility and backbone rigidity is achieved due to the integration of rigid twisted units in the polymer backbone. Twist in hard biphenyl units interferes with chain packing and thus improves solubility.

In US Pat. No. 6,074,709, pendant fluorene groups are added to aromatic polyimide backbones via polymerization of 9,9-bis (4-aminophenyl) fluorene to obtain solubility in useful solvents. Integrate. However, to obtain films with negative birefringence greater than 0.01, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 3,3', 4,4'-tetracarboxylic biphenyl dianhydride Very hard dianhydrides such as (BPDA) or pyromellitic dianhydride (PMDA) should be used to prepare the polyimide. 4,4'-oxydiphthal anhydride (ODPA) and 2,2-bis (3,4-dicarboxylphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride Polyimides using soft dianhydrides such as (6FDA) produce films with negative birefringence less than 0.01. These values can be increased above 0.01 through copolymerization with hard dianhydrides or hard diamines such as p-phenylenediamine.

In US Pat. No. 6,853,424, the compensation layers comprise hard 1,4-dioxophenylene units

It can be obtained in the form of terephthalic acid by the integration of. A particularly useful solubilizing monomer is 4,4 '-(hexahydro-4,7-methanoindan-5-ylidene) bisphenol, which prevents chain packing and maintains solubility while maintaining chain rigidity. Along the polymer backbone to enhance it provides pendant bulky norbornene groups. Solubility can also be improved by copolymerization of monomers containing softer units such as 1,3-dioxophenylene groups or hexafluoroisopropylidene bonds. Although the use of flexiblizing comonomers containing hexafluoroisopropylidine bonds (4,4-hexafluoroisopropylidene diphenol) provides suitable solubility, poly (terephthales) made of this monomer Hydrochloric acid) has a negative birefringence of less than 0.01. 4,4 '-(hexahydro-4,7-melanoindan-5-ylidene) bisphenol should also be used to obtain a polyester chain that is hard enough to make a film having a negative birefringence greater than 0.01. Although harder than other polyesters, they are not as hard as polyimides.

The present invention provides a negative birefringent film made from poly (aryletherimide), wherein the film has a negative birefringence greater than 0.01 at a thickness of less than 15 μm, and the poly (aryletherimide) is solution cast or Coated.

Another embodiment of the present invention includes a film having at least one layer, wherein at least one layer of the film is made of poly (aryletherimide) dissolved in a ketone solvent, wherein at least one layer is a polymeric substrate film The poly (aryletherimide) layer is cast or coated onto a substrate. Possible material for the substrate layer is triacetylcellulose.

Another embodiment of the present invention provides homopoly (aryletherimide) and copoly (aryletherimide) dissolved in a ketone solvent and ketone solvent mixture, which can form a thin film by casting or coating process, Negative birefringence.

Another embodiment of the present invention may coat or cast poly (aryletherimide) dissolved in a ketone solvent and ketone solvent mixture onto another polymer substrate to form a multilayer polymer film.

Another embodiment according to the present invention provides a negative birefringent film made from poly (aryletherimide), wherein the film has a birefringence greater than 0.01 at a thickness of less than 15 μm, and the poly (aryletherimide) is dianhydride. It is a combination of lead and diamine, wherein the poly (aryletherimide) is solution cast or coated on a film.

Another embodiment of the present invention produces a negative birefringent film made from poly (aryletherimide), wherein the film has a negative birefringence greater than 0.01 at a thickness of less than 15 μm, and the poly (aryletherimide)

2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA), bis (3,4-dicarboxyphenyl) ether diane Hydride (ODPA), 4,4 '-[4,4'-(p-phenyleneoxy) isopropylidene] -bis (phthalic anhydride) (Bis- A-DA), 4,4'- [4,4 '-(p-phenyleneoxy) hexafluoroisopropylidene] -bis (phthalic anhydride) (Bis-AF-DA), l, 4-bis (3,4-dicarboxyphenyl Oxy) phenyl dianhydride, and 4,4'-bis (3,4-dicarboxyphenyloxy) biphenyl dianhydride (BPEDA), l, 5-bis (3,4-dicarboxyphenyloxy) naphthyl Dianhydrides selected from the group consisting of dianhydrides

4,4'-diaminophenyl ether, 2-trifluoromethyl-4,4'-diaminophenyl ether, 2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether, 2-trifluoromethyl-2'-methyl-4,4'-diaminophenyl ether, l, 4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'bis (3-aminephenoxy) biphenyl, 4,4 "-bis (4-aminophenoxy) terphenyl, 4,4'-bis (3-aminophenoxy) terphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane, 1,4- Bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino -2-trifluoromethylphenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) -3,3 ', 5,5'-tetra (tert-butyl) biphenyl, 4,4'-bis (3-amino-trifluoromethylphenoxy) Phenyl, 4,4 "-bis (4-amino-2-trifluoromethylphenoxy) terphenyl, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] Propane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] l, l, 3,3,3-hexafluoropropane, and 4,4'- Combination of one diamine selected from the group consisting of bis (4-amino-2-trifluoromethylphenoxy) benzene.

Another embodiment of the present invention provides a liquid crystal display using a negative birefringent film made of poly (aryletherimide) having a negative birefringence greater than 0.01 at a thickness of less than 15 μm, wherein the poly (aryletherimide) is a film Solution that is cast or coated onto the phase.

Preferred solvents such as ketones and ketone mixtures can be used to prepare colorless poly (aryletherimide) films with a negative birefringence greater than 0.01 at a thickness of less than 15 μm via solution coating or casting processes. The film needs to be cast to reach birefringence values and no longer stretched. This value is not expected for poly (aryletherimides) made from dianhydrides containing ductile perfluoroisopropylidene or ether bonds and diamines containing ductile ether bonds. If this combination of monomers is used no hard component is required.

Representative examples of dianhydrides useful in the present invention are as follows:

2,2-bis (3,4-dicarboxyphenyl) -l, l, l, 3,3,3-hexafluoropropane dianhydride (6FDA),

Bis (3,4-dicarboxyphenyl) ether dianhydride (ODPA),

4,4 '-[4,4'-(p-phenyleneoxy) isopropylidene] -bis (phthalic anhydride) (Bis-A-DA),

4,4 '-[4,4'-(p-phenyleneoxy) hexafluoroisopropylidene] -bis (phthalic anhydride) (Bis-AF-DA),

1,4-bis (3,4-dicarboxyphenyloxy) phenyl dianhydride,

4,4'-bis (3,4-dicarboxyphenyloxy) biphenyl dianhydride (BPEDA),

l, 5-bis (3,4-dicarboxyphenyloxy) naphthyl dianhydride.

More preferred dianhydrides include:

2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA),

4,4 '-[4,4'-(p-phenyloxy) -hexafluoroisopropylidene] -bis (phthalic anhydride) (Bis-AF-DA),

4,4'-bis (3,4-dicarboxyphenyloxy) biphenyl ianhydride (BPEDA).

Particularly useful diamines for the present invention are:

4,4'-diaminophenyl ether,

2-trifluoromethyl-4,4'-diaminophenyl ether,

2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether,

2-trifluoromethyl-2'-methyl-4,4'-diaminophenyl ether,

1,4-bis (4-aminophenoxy) benzene,

4,4'-bis (4-aminophenoxy) biphenyl,

4,4'-bis (3-aminophenoxy) biphenyl,

4,4 "-bis (4-aminophenoxy) terphenyl,

4,4'-bis (3-aminophenoxy) terphenyl,

2,2-bis [4- (4-aminophenoxy) phenyl] propane,

2,2-bis [4- (4-aminophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane,

1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene,

4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl,

4,4'-bis (4-amino-2-trifluoromethylphenoxy) -3,3 ', 5,5'tetramethylbiphenyl,

4,4'-bis (4-amino-2-trifluoromethylphenoxy) -3,3 ', 5,5'-tetra (tert-butyl) biphenyl,

4,4'-bis (3-amino-trifluoromethylphenoxy) biphenyl,

4,4 "-bis (4-amino-2-trifluoromethylphenoxy) terphenyl,

2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] propane,

2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] l, l, l, 3,3,3-hexafluoropropane.

More preferred diamines include:

4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl,

4,4'-bis (4-amino-2-trifluoromethylphenoxy) benzene,

2-trifluoromethyl-4,4'-diaminophenyl ether,

2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether,

2-trifluoromethyl-2'-methyl-4,4'-diaminophenyl ether,

2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane,

4,4 "-bis (4-amino-2-trifluoromethylphenoxy) terphenyl.

One embodiment includes one or more ether bonds in a diamine and a combination utilizing two or more perfluoromethyl groups in one perfluoromethyl and dianhydride.

The film of the present invention is soluble in cyclopentanone and MIBK. The solubility of films in cyclopentanone is suitable for a variety of applications and also utilizes MIBK solubility in many applications. As mentioned above, solubility in MIBK is suitable for solution coating on cellulose substrates such as TAC.

In the film of the present invention, the PAEI film may comprise trifluoromethyl (or pefluoromethyl) groups (CF ₃ ) of diamine and dianhydride. Trifluoromethyl groups increase the solubility of the film in MIBK.

The solvent mixture may be a mixture of solvents such as 95% MIBK and 5% ethyl acetate. However, the percentage is not important as long as the MIBK is 50% or more.

Mixtures of dianhydrides and diamines may be used in the present invention. Mixtures of dianhydrides may be used, preferably one of the dianhydrides has a perfluoromethyl group, and suitable remaining dianhydrides which may be used are pyromellitic anhydrides (I):

(I)

And aromatic tetracarboxylic acid dianhydrides of formula (II).

(II)

The mixture of aromatic diamines is preferably diamines encompassed by the present invention.

(III)

And / or in combination with aromatic diamines of formula (IV),

(IV)

Wherein G and F are selected from the group consisting of a covalent bond, a CH ₂ group, a C (CF ₃ ) ₂ group, and a C (CX ₃ ) ₂ group. X is independently selected from the representative and illustrative group consisting of halogen, CO group, O atom, S atom, Si (CH ₂ CH ₃ ) ₂ group or N (CH ₃ ) group; m is an integer of 1-3.

One embodiment comprising a mixture is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4 '. Biphenyl dianhydride and the diamine is 4,4'-bis (4-amino-trifluoromethylphenoxy) biphenyl (6FOBDA). Of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and a 4,4'-biphenyl dianhydride mixture The molar ratio is 99 to 1 (99: 1) to 40 to 60 (40:60). Another embodiment is 2,2-bis (3,4-dicarboxyphenyl-1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4'biphenyl dianhydride. The molar ratio of the mixtures includes 80 to 20 (80:20).

Other embodiments comprising a mixture include 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4 '. A dianhydride mixture of biphenyl dianhydride and the diamine is 2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether (6FODA). Of a mixture of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4'biphenyl dianhydride The molar ratio is 99 to 1 (99: 1) to 40 to 60 (40:60). Another embodiment is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4'biphenyl diane The molar ratio of the hydride mixture is 80 to 20 (80:20).

 The invention will be better understood by the following illustrative and non-limiting examples which illustrate the preparation of polyimide and copolyimide soluble in organic solvents.

Preparation of monomer

Example  One

This example illustrates the preparation of 2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether (6FODA).

300 ml, 3-neck round bottom flask with mechanical stirrer, thermometer, nitrogen inlet and condenser, 2-chloro-5-nitrobenzotrifluoride (480.7 g, 2.132 mol), sodium carbonate (112.96 g, 0.122 mol), m- Nitrobenzoic acid (1.77 g, 0.01 mol) and DMAc (700 ml) were added. The mixture was heated at 150 ° C. for 48 hours. After cooling to room temperature, the mixture was filtered to remove solids. Most of the initial material and DMAc were removed by vacuum distillation. TLC showed many product spots and very few material spots. Recrystallization from ethanol yielded pure small plate crystals (233 g, yield 55%). TLC showed only one product spot. The mother liquor was condensed and an additional 50 g product was obtained. TLC showed only one product spot. The total yield of pure product was 67% (233 + 50 = 283 g). MP: 94-95 degreeC. Quantum NMR (DMSO-d ₆ , δ, ppm): 8.582-8.522 (4H), 7.569-7.450 (2H).

500 ml three-necked round bottom flask equipped with a mechanical stirrer, condenser and bubbler connected gas inlet, dinitro-compound (20 g), ethanol (200 ml), Pd / C (0.3 g Pd concentration: 10%) and hydrazine Monohydrate (8.0 ml) was added. The mixture was stirred at rt overnight. The mixture was filtered and ethanol was removed under reduced pressure. Recrystallization from toluene / hexane mixtures yielded fine crystals .: M.P .: 114-116 ° C. Quantum NMR (DMSO-d6 ,, ppm): 6.870-6.861 (2H), 6.622-6.592 (2H), 5.278 (4H)

Example  2

This example describes the preparation of 2-trifluoromethyl-4,4'-diaminophenyl ether (3FODA).

In a 3000 ml three necked round bottom flask equipped with a mechanical stirrer, condenser and thermometer, 4-nitrophenol (204 g, 1.467 mol), 2-chloro-5-nitrobentosrifluoride (330.7 g, 1.467 mol) and DMAc (800 ml) Was added. The mixture was homogenized and then potassium carbonate (205 g, 1.478 mol) was added. The mixture was heated at 100 ° C. for 20 hours. After cooling, the mixture was poured into 5 l of a methanol / water mixture (10/1, v / v). The precipitate formed was collected by filtration, rinsed in water and filtered again. Recrystallization from a methanol / water mixture gave crystals: 312 g, yield: 64.8%. Melting point: 68 ~ 70 ℃. Proton NMR (DMSO-d ₆ , δ, ppm): 8.568-8.505, (2H). 8.349-8.293, (2H), 7.439-7.408, (3H).

2-trifluoromethyl-4,4'-dinitrobiphenylether (88 g, 0.268 mol), ethanol (600 ml), Pd / C (5) in a 1000 ml three-neck round bottom flask equipped with a mechanical stirrer, condenser and thermometer %, 1.0 g), and hydrazine monohydrate (60 ml) were added. The mixture was heated to reflux for 20 minutes. The reaction was 100% complete. After cooling, the solution was filtered to remove solids. Water was added to the filtrate to precipitate a large amount of crystals. In addition, the crystals are removed from impurities by sublimation. Melting point: 102-104 ° C. Quantum NMR (DMSO-d ₆ , δ, ppm): 6.836 to 6.826 (1H), 6.699 to 6.693 (1H), 6.646 to 6.628 (1H), 6.606 to 6.598 (2H), 6.514 to 6.484 (2H), 5.218 ( 2H), 4.841 (2H).

Example  3

This example illustrates the preparation of 2-trifluoromethyl-2'-methyl-4,4'-diaminophenyl ether (3FHODA).

2-chloro-5-nitrobenzotrifluoride (33.83 g, 0.15 mol), 2-methyl-4-nitrophenol (23 g, 0.15 mol 0, carbonic acid) in a 300 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer, and condenser Potassium (21 g, 0.15 mol), and DMF (100 ml) were added The mixture was heated overnight at 100 ° C. After cooling to room temperature, the mixture was filtered to remove solids. Removed by distillation The residue was poured into water The precipitate formed was collected by filtration and rinsed with water Fine crystals were obtained by recrystallization from ethanol / water: yield-84%; melting point: 96- 98 ° C. Quantum NMR (DMSO-d6, δ, ppm): 8.548 (H1), 8.493-8.453 (1H), 8.175-8.146 (1H), 7.347-7.317 (H1), 7.217-7.187 (1H), and 2.285 (3 H).

500 ml 1-neck flat bottom flask with magnetic stirrer and (bubble connected) condenser in a dinitro-compound (20 g), Pd / C (0.2 g, Pd 5%), ethanol (100 ml) and hydrazine monohydrate (8.0 ml) ). The mixture was stirred at room temperature overnight. The mixture was filtered and the solvent removed on a rotovaporator. Diamine is purified by sublimation. Melting point = 95-97 ° C. Quantum NMR (DMSO-d ₆ , δ, ppm): 6.861 to 6.852 (1H), 6.692 to 6.655 (1H), 6.537 to 6.509 (1H), 6.438 to 6.408 (2H), 6.379 to 6.342 (1H), 5.102 ( 2H), 4.825 (2H), 1.966 (3H).

Example  4

This example describes the preparation of 4,4'bis (4-amino-trifluoromethylphenoxy) biphenyl (6FOQDA).

1,4-dihydroxybenzene (11.62g, 0.106mol), 2-chloro-5-nitrobenzotrifluoride (50.0g, 0.222mol) in a 300ml three-necked round bottom flask equipped with thermometer, mechanical stirrer and condenser and DMAc (100 ml), and dry K ₂ CO ₃ (22.2 g, 0.16 mol) were added. The reaction mixture was heated at 130 ° C. for 10 hours in nitrogen. Upon cooling, a large amount of precipitate formed, filtered by filtration, rinsed with water and dried. (46.03 g, 90.0%). MP: 205-207 degreeC. Proton NMR (δ, ppm, DMSO-d ₆ ): 8.526-8.517 (2H), 8.482-8.443 (2H), 7.388 (4H), 7.255-7.224 (2H). The obtained compound is 4,4'-bis (4-nitro-2-trifluoromethylphenoxy) benzene.

4,4'-bis (4-nitro-2-trifluoromethylphenoxy) biphenyl (20g, 40.98mmole), ethanol (200ml), Pd in 500ml three-neck round bottom flask equipped with thermometer, mechanical stirrer and condenser / C (5% Pd, 0.4 g), and hydrazine mono-hydride (10 ml) were added. The mixture was stirred and heated to reflux for 5 hours and then cooled to room temperature. The mixture was filtered and water (˜200 ml) was poured into the filtrate. The precipitated solid was recrystallized in ethanol / water mixture to yield colorless flake crystals (15.91 g, 90.7%). MP: 112-114 degreeC. Proton NMR (δ, ppm, DMSO-d ₆ ): 6.888-6.880 (2H), 6.833 (4H), 6.805-6.786 (4H), 5.375 (4H). The obtained compound is 4,4'-bis (4-amino-2-trifluoromethylphenoxy) benzene (6FOQDA).

Example  5

This example describes the preparation of 4,4'bis (4-amino-trifluoromethylphenoxy) biphenyl (6FOBDA).

4,4'-biphenyl (18.6 g, 0.1 mol), 2-chloro-5-nitrobenzotrifluoride (46.25 g, 0.205 mol) and DMSO in a 500 ml three-neck round bottom flask equipped with thermometer, mechanical stirrer and condenser (150 ml) was added. The solution was homogeneous and then dry K ₂ CO ₃ (28.3 g, 0.205 mol) was added. The reaction mixture was heated at 130 ° C. for 10 hours. After cooling, a large amount of precipitate was formed, separated by filtration, rinsed with methanol and dried. Recrystallization from the DMF / methanol mixture yielded pale needle crystals (34.35 g, 60.86%). MP: 215-216 degreeC. Proton NMR (δ, ppm, DMSO-d ₆ ): 8.530 (4H), 7.854 (4H), 7.346 (4H), 7.218 (2H). 4,4'-bis (4-nitro-2-trifluoromethylphenoxy) biphenyl compound was obtained.

4,4'-bis (4-nitro-2-trifluoromethylphenoxy) biphenyl (20 g, 0.0373 mol), ethanol (300 ml) in a 500 ml three-neck round bottom flask equipped with thermometer, mechanical stirrer and condenser Pd / C (5% Pd, 0.4 g), and hydrazine mono-hydride (10 ml) were added. The mixture was stirred and heated to reflux overnight and cooled to room temperature. The mixture was filtered and water was added to the filtrate (150 ml). Natural product was recrystallized in ethanol / water mixture to yield colorless flake crystals (15.03 g, 80.0%). MP: 155-156 degreeC. Proton NMR (δ, ppm, DMSO-d ₆ ): 7.550 (4H), 6.912 (8H), 6.835 (2H), 5.425 (4H). 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl (6FOBDA) compound was obtained.

Example  6

This example provides the preparation of 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] 1,1,1,3,3,3-hexafluoropropane (12FOBDA). Explain.

Bisphenol AF (33.6 g, 0.1 mol), 2-chloro-5-nitrobenzotrifluoride (46.25 g, 0.205 mol) and DMSO (500 ml three-necked round bottom flask with thermometer, mechanical stirrer and condenser) 150 ml) was added. The solution was homogenized and then dried K ₂ CO ₃ (28.3 g, 0.205 mol) was added. The reaction mixture was then heated to 100 ° C. for 3 hours. After cooling to room temperature, the mixture was filtered and the filtrate was poured into water (1000 ml). The precipitate formed was collected by filtration, rinsed with water and dried. Recrystallization from DMF / methanol yielded pale fine crystals (43.84 g, 61.37%). MP: 174-175 degreeC. Proton NMR (δ, ppm, DMSO-d ₆ ): 8.531 (4H), 7.517 (4H), 7.371 (6H). 2,2-bis [4- (4-nitro-2-trifluoromethylphenoxy) -phenyl] 1,1,1,3,3,3-hexafluoropropane compound was obtained.

2,2-bis [4- (4-nitro-2-trifluoromethylphenoxy) -phenyl] -hexafluoropropane (29.23 g, 0.041) in a 1000 ml three-necked round bottom flask equipped with thermometer, mechanical stirrer and condenser mol), and ethyl acetate (200 ml) were added. The solution was homogenized and ethanol (200 ml), and ammonium formate (28 g), Pd / C (2 g, Pd 5%) were added. The mixture was homogenized overnight at room temperature and filtered. Solvent was removed from the filtrate by rotary evaporator. The residual solid was dried under reduced pressure to give 20.83 g (77.63%) of a white solid. MP: 65-66 degreeC. Proton NMR (δ, ppm, DMSO-d ₆ ): 7.280 (4H), 6.964 (8H), 6.835 (2H), 5.486 (4H). 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] 1,1,1,3,3,3-hexafluoropropane (12FOBDA) compound was obtained.

Homopolyimide stage 1

Example 7

This example describes the general procedure for preparing homopolyimides of dianhydrides and diamines.

1.00 mmol of dianhydride was added to a solution of 1.00mnole of diamine in 10 ml of m-cresol stirred under nitrogen at ambient temperature. The solution was stirred for 6 hours and 0.05 g isoquinoline was added. The mixture was heated to 200 ° C. and maintained at this temperature for 12 hours. During the application of heat, water by imidization was allowed to evaporate in the reaction mixture. The solution was cooled to ambient temperature and slowly added to 500 ml of stirred methanol. The precipitated polymer was collected by filtration, rinsed with ethanol and dried at 150 ° C. for 24 hours under reduced pressure.

Copolymer  Stage 1

Example  8

This example describes the general procedure for preparing a copolymer from a mixture of dihydrides and one diamine.

1.00 mmol of the dianehydride mixture was added to a diamine 1.00 mmol solution in 10 ml of m-cresol, which was stirred under nitrogen at ambient temperature. The solution was stirred for 6 hours, 0.05 g of isoquinoline was added and the mixture was heated to 200 ° C. and kept at that temperature for 12 hours. During the application of heat, water by imidization was allowed to evaporate in the reaction mixture. The solution was cooled to ambient temperature and added slowly to 500 ml of stirred methanol. The precipitated polymer was obtained by filtration, rinsed with ethanol and dried at 150 ° C. under reduced pressure for 24 hours.

Example  9

This example describes the general procedure for preparing copolymers of one dianhydride and multielement diamines.

1.00 mmol of dianhydride was added to a solution of 1.00 mmol of multielement diamine in 10 ml of m-cresol stirred under nitrogen at ambient temperature. The solution was stirred for 6 hours, 0.05 g of isoquinoline was added and the mixture was heated to 200 ° C. and kept at that temperature for 12 hours. During the application of heat, water by imidization was allowed to evaporate in the reaction mixture. The solution was cooled to ambient temperature and added slowly to 500 ml of stirred methanol. Filtration gave the precipitated polymer, rinsed with ethanol and dried at 150 ° C. under reduced pressure for 24 hours.

Solubility of polyimide and birefringence of film

Polyimide films showing negative birefringence were prepared according to the following method:

The polyimide was dissolved in cyclopentanone or MIBK so that the concentration of solids was 4-5%. After filtration, the solution was poured onto a glass substrate. The solvent was evaporated at ambient temperature. The glass substrate containing the film was dried under reduced pressure at 100 ° C. The substrate glass was immersed in water to remove the polyimide film. The birefringence of the polyimide film was measured with Metricon Prism Coupler 2010 / M. The birefringence of the exemplary embodiment is shown in Tables 1, 2 and 3.

Film coating

The MIBK solution of the poly (aryletherimide) was rod-coated on a glass plate or triacetyl cellulose (TAC) film. In the case of a glass plate, a solution having a content of poly (aryletherimide) of 3 to 5% by weight was used, and in the case of a TAC film, a solution having a content of poly (aryletherimide) of 8 to 20% by weight was used.

Claims (27)

A negative birefringent film made from poly (aryletherimide), wherein the poly (aryletherimide) has a negative birefringence greater than 0.01 at a thickness of less than 15 μm when solution cast or coated onto a substrate. The film of claim 1, which is made from poly (aryletherimide) soluble in ketone solvent and cast or coated onto a substrate. 3. The film of claim 2 wherein at least one layer is a substrate layer made of triacetylcellulose. The film of claim 1 wherein the poly (aryletherimide) is a homopolymer or copolymer of aryletherimide that is soluble in the ketone solvent mixture. The film according to claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine. 6. The film of claim 5 wherein the dianhydride comprises a soft perfluoroisopropylidine bond. The film of claim 1 wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein the diamine comprises a soft ether bond. The film of claim 1 wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein the dianhydride comprises perfluoromethyl groups. 2. The film of claim 1 wherein the poly (aryletherimide) is the reaction product of dianhydride and diamine, wherein the diamine comprises perfluoromethyl groups and soft ether bonds. 2. The film of claim 1 wherein the poly (aryletherimide) is the reaction product of dianhydride and diamine, wherein the dianhydride comprises perfluoromethyl groups and the diamine comprises perfluoromethyl groups. The method of claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein the dianhydride comprises a perfluoromethyl group and the diamine comprises a perfluoromethyl group and a soft ether bond. Characterized by the film. The method of claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3, 3,3-hexafluoropropane dianhydride (6FDA). The method of claim 1, wherein the poly (arylterimide) is a reaction product of dianhydride and diamine, wherein dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3, 3,3-hexafluoropropane dianhydride (6FDA) and 4,4 '[4,4'-(p-phenyleneoxy) hexafluoroisopropylidene] -bis (phthalic anhydride) (Bis -AF-DA) film. The method of claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -l, l, l, 3, 3,3-hexafluoropropane dianhydride (6FDA), bis (3,4-dicarboxyphenyl) ether dianhydride (ODPA), 4,4 '-[4,4'-(p-phenyleneoxy Isopropylidine] -bis (phthalic anhydride) (Bis-A-DA), 4,4 '-[4,4'-(p-phenyleneoxy) hexafluoroisopropylidene] -bis ( Phthalic anhydride) (Bis-AF-D A), l, 4-bis (3,4-dicarboxyphenyloxy) phenyl dianhydride, and 4,4'-bis (3,4-dicarboxyphenyl Oxy) biphenyl dianhydride (BPEDA), l, 5-bis (3,4-dicarboxyphenyloxy) naphthyl dianhydride; Diamines are 4,4'-diaminophenyl ether, 2-trifluoromethyl-4,4'-diaminophenyl ether, 2,2'-bis (trifluoromethyl) -4,4'-diamino Phenyl ether, 2-trifluoromethyl-2'-methyl-4,4'-diaminophenyl ether, l, 4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) Biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4 "-bis (4-aminophenoxy) terphenyl, 4,4'-bis (3-aminophenoxy) terphenyl, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane, 1 , 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis ( 4-amino-2-trifluoromethylphenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy)- 3,3 ', 5,5'-tetra (tert-butyl) biphenyl, 4,4'-bis (3-amino-triflu Romethylphenoxy) biphenyl, 4,4 "-bis (4-amino-2-trifluoromethylphenoxy) terphenyl, 2,2-bis [4- (4-amino-2-trifluoromethylphene Oxy) -phenyl] propane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] l, l, l, 3,3,3-hexafluoropropane, and A film, characterized in that it is selected from the group comprising 4,4'-bis (4-amino-2-trifluoromethylphenoxy) benzene. The method of claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3, 3,3-hexafluoropropane dianhydride (6FDA) and the diamine is 4,4'bis (4-amino-trifluoromethylphenoxy) biphenyl (6FOBDA). The method of claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3, 3,3-hexafluoropropane dianhydride (6FDA) and diamine is 2,2'bis (trifluoromethyl) -4,4'-diaminophenyl ether (6FODA). The method of claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3, It is a mixture of 3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ', 4,4'-tetracarboxylic biphenyl dianhydride and the diamine is 4,4'-bis (4-amino- And trifluoromethylphenoxy) biphenyl (6FOBDA). 18. 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ', 4. A film characterized in that the mixing molar ratio of, 4'-tetracarboxylic biphenyl dianhydride is 99 to 1 (99: 1) to 40 to 60 (40:60). 18. 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ', 4. A film characterized in that the mixing molar ratio of, 4'-tetracarboxylic biphenyl dianhydride is 80 to 20 (80:20). The method of claim 1, wherein the poly (aryletherimide) is a reaction product of dianhydride and diamine, wherein dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3, 3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ', 4,4'-tetracarboxylic biphenyl dianhydride and the diamine is 2,2'-bis (trifluoromethyl)- And 4,4'-diaminophenyl ether (6FODA). 21. 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ', 4. And a 4 'tetracarboxylic biphenyl dianhydride mixed molar ratio of 99 to 1 (99: 1) to 40 to 60 (40:60). 21. The composition of claim 20 wherein 2,2-bis (3,4, -dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ', A film characterized in that the mixing molar ratio of 4,4'-tetracarboxylic biphenyl dianhydride is 50 to 50 (50:50). 2. The poly (aryletherimide) of claim 1, wherein the poly (aryletherimide) is a reaction product of more than one dianhydride and diamine, wherein one of the dianhydrides is polymethyl anhydride and aromatic tetra as shown in formula (I). Selected from the group consisting of carboxylic acid dianhydrides, (I)

Wherein G is independently selected from the group consisting of covalent bonds, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , and C (CX ₃ ) ₂ ; Wherein X is selected from the group consisting of halogen, CO, oxygen, sulfur, SO ₂ , Si (CH ₂ CH ₃ ) ₂ and N (CH ₃ ). The method of claim 23, wherein one of the dianhydrides is 3,3 ', 4,4'-tetracarboxylic biphenyl dianhydride (sym-BPDA) and 2,3,3', 4-tetracarboxylic ratio. Film selected from the group consisting of phenyl dianhydride (asym-BPDA). The method of claim 1, wherein the poly (aryletherimide) is a reaction product of a dianhydride and diamine mixture, wherein one of the diamines is selected from the group consisting of formula (II) and formula (III), (II)

(III)

F is independently selected from the group consisting of a covalent bond, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , and C (CX ₃ ) ₂ ; X is selected from the group consisting of halogen, CO, oxygen, sulfur, SO ₂ , Si (CH ₂ CH ₃ ) ₂ and N (CH ₃ ); m is an integer of 1 to 3, characterized in that the film. Liquid crystals using a negative birefringence film made from poly (aryletherimide) having a negative birefringence greater than 0.01 at a thickness of less than 15 μm, wherein the poly (aryletherimide) is solution cast or coated on a substrate. display. A liquid crystal display using a negative birefringent film made from poly (aryletherimide), wherein the film has a negative birefringence greater than 0.01 at a thickness of less than 15 μm, and poly (aryletherimide) is a combination of dianhydride and diamine , Wherein the poly (aryletherimide) is soluble in the ketone solvent or ketone solvent mixture and the poly (aryletherimide) is solution cast or coated onto the substrate.