JP2009506349A - Poly (aryl etherimide) for LCD negative birefringence film - Google Patents

Abstract

  Disclosed is a soluble poly (aryl etherimide) (PAEI) that is useful in the production of polymeric optical films and has a flexible backbone. Transparent thin film showing negative birefringence by dissolving poly (aryl ether imide) in organic solvents such as ketones and ketone solvent mixtures and coating on various substrates such as triacetyl cellulose (TAC) Form. This film can be used as a compensation layer in a liquid crystal display (LCD) and combined with an optical film such as a deflector, brightness enhancement film or other compensation film to form a multilayer film that is particularly useful in the manufacture of LCDs. be able to.

Description

Reference to related applications

  This application claims priority based on US Provisional Patent Application No. 60 / 700,169, filed Jun. 18, 2005 entitled "Poly (Aryl Etherimide) for LCD Negative Birefringent Film". To do. The disclosure of US Provisional Patent Application No. 60 / 700,169 is hereby incorporated by reference into the present disclosure.

  The present invention relates to the production of negative birefringent polymer films for use in compensation layers of liquid crystal displays (LCD). More particularly, the present invention relates to the production and use of poly (aryl ether imides) (PAEI) that can be dissolved in various organic solvents and coated on various polymer substrates. More particularly, the present invention relates to the preparation of PAEI made from a dianhydride containing a flexible ether bond or a perfluoroisopropylidene bond and an aromatic diamine containing a flexible ether bond. More particularly, the present invention relates to 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and inexpensive fluorine-containing PAEI's which are formed from aromatic ether diamines and can be dissolved in any solvent, such as ketone solvents and / or ketone solvent mixtures, and can be formed on preferred polymer substrates to form multilayer polymer optical films. Regarding manufacturing.

  Liquid crystals are useful for electronic displays. This is because light transmitted through the liquid crystal thin film is affected by the birefringence of the film, which can be controlled by applying a voltage to the film. In a liquid crystal display (LCD), the transmission or reflection of light from the outside including ambient light can be controlled with much less power than the luminescent materials used in other displays.

Definitions of terms are as follows.
1. The optical axis means a direction in which propagating light is not birefringent.
2. The negative C plate means a plate whose optical axis is perpendicular to the plate.
3. Plane refractive index, n _{|| = (n x + n y)} / 2 (n x and _{n y} is a refractive index in the x-direction and y-direction, x-y plane is parallel to the film plane) by Defined.
4). Plane birefringence is Δn _‖ = is defined by _(n x -n _y).
5. Plane retardation is defined by R _{‖ = (n x -n y) d} (d is the thickness of the film in a direction perpendicular (z direction) the x-y plane).
6). Out-of-plane refractive index, Δn⊥ ₌ n _z - is defined by _{(n x + n y) /} 2 (n z is the refractive index in the z-direction).
7). Out-of-plane retardation, R⊥ ₌ - defined by _{[n z (n x + n} y) / 2] d.

  LCDs are widely used in digital watches, computers, mobile phones, portable computers, televisions, and many electronic devices that require low power consumption, long life, and space-saving operation. In particular, portable computers and large-screen televisions utilize the characteristics of LCD such as light weight, space saving, low power consumption, and long life. In the future, LCDs are expected to replace cathode ray tubes (CRT) as monitors and television screens.

  However, LCDs have a viewing angle dependency that affects the quality of display performance such as contrast, color and / or brightness. The main factor limiting the quality of LCD performance is that light leaks from the liquid crystal element or cell, and the light leakage depends on the direction in which the display is viewed. The highest quality LCD image is obtained only within a narrow viewing angle range centered on an angle perpendicular to the display screen.

  A commonly used method for enlarging the viewing angle of an LCD is to apply a compensation film. Multiple LCD modes, including twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), optically compensated bend (OCB), are positive regardless of the applied electric field. C plate symmetry, and positive C plate symmetry can be compensated by a compensation film having negative C plate symmetry.

In the compensation film with negative C-plate symmetry, out-of-plane refractive index n⊥ or n _z is smaller than the in-plane refractive index n _{|| = (n x + n y)} / 2, as a result, a negative out-of-plane birefringence refractive index _{Δn⊥ = n z - (n x} + n y) / 2 becomes less than 0, a negative out-of-plane retardation _{R⊥ = [n z - (n} x + n y) / 2] d becomes less than 0. Negative birefringent films include but are not limited to precise stretching of polymer films, precisely controlled deposition of thin ceramic layers, mixing of swellable inorganic clay layers into a crosslinked polymer matrix, solution casting or application of thin polymer films, etc. It is manufactured by the method. In the case of a large negative birefringent film, a solution casting method or a solution coating method is preferable from the viewpoint of ease of processing and improvement of performance. Currently used techniques include film stretching. One of the drawbacks of using the stretching technique for negative birefringent films is that stress relaxation occurs that distorts the film (the corner of the film / screen). Poly (aryl ether imide) is almost impossible to stretch, but using poly (aryl ether imide) can achieve the desired result without stretching.

  In order to provide a negative birefringent film formed by casting or coating on an LCD component (such as a polarizing plate) indispensable for an LCD device, two types of methods are mainly used. In the first method, a negative birefringent film is cast on a carrier substrate inert to a solvent, and an adhesive is applied to the surface of the negative birefringent film. They are laminated on the LCD component and the carrier substrate is removed (peeled). In the second method, a negative birefringence film is formed by directly applying a polymer solution onto a component of an LCD device such as a polarizing plate or a base material of the polarizing plate. This method is preferable because it is simple and can reduce the cost. However, this method requires that the polymer be dissolved in the selected solvent. The solvent dissolves the polymer that forms the negative birefringent film, but must not dissolve or significantly swell the LCD components. The solvent must also be usable in large scale industrial coating operations. Japanese Patent No. 3735361 shows that methyl isobutyl ketone (MIBK) is the preferred solvent for solution coating on cellulose substrates because it best meets the above requirements. MIBK does not dissolve triacetyl cellulose (TAC), which is a commonly used base material.

  According to the prior art, in order to form a negative birefringent film using solution casting or solution coating methods, rigid structural units must be introduced into the polymer backbone. This is because the in-plane orientation of the polymer skeleton is considered to be strengthened by the rigid group during the solution casting or solution coating process. In addition, by introducing a rigid group into the polymer skeleton, the solubility is usually reduced, so that special means are required to achieve the desired balance between the rigidity and solubility of the molecular chain. For example, US Pat. Nos. 5,580,950 and 5,480,964 describe rigid rod-like aromatics comprising polyesters, polyamides, and polyimides composed of monomers having a twisted 2,2′-disubstituted biphenyl structure. A polymer is used. A balance between solubility and backbone rigidity is achieved by introducing twist units into the polymer backbone. Rigid biphenyl unit twist prevents molecular chain packing and improves solubility.

  In US Pat. No. 6,074,709, pendant fluorene groups are incorporated into an aromatic polyimide backbone by polymerizing 9,9-bis (4-aminophenyl) fluorene to obtain solubility in useful solvents. It has been introduced. However, in order to obtain a film having a negative birefringence of more than 0.01, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3, Very rigid dianhydrides such as 3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) or pyromellitic dianhydride (PMDA) must be used. 4,4′-oxydiphthalic anhydride (ODPA), 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA), etc. When a flexible dianhydride is used, a polyimide that forms a film having a negative birefringence of less than 0.01 is obtained. Only by copolymerizing a rigid dianhydride such as p-phenylenediamine or a rigid diamine, the negative birefringence can be increased to a value exceeding 0.01.

  In US Pat. No. 6,853,424, the compensation layer is formed by introducing the rigid 1,4-dioxophenylene units shown below into the terephthalic acid ester.

特に有用な可溶性（ｓｏｌｕｂｉｌｉｚｉｎｇ）モノマーは、４，４’−（ヘキサヒドロ−４，７−メタノインダン−５−イリデン）ビスフェノールであり、分子鎖の剛直性を維持しながらも、分子鎖パッキングを防止しかつ溶解性を向上させるペンダント型の嵩高いノルボルネン基がポリマー骨格に沿って形成される。また、１，３−ジオキソフェニレン基またはヘキサフルオロイソプロピリデン結合等のより屈曲性の単位を含むモノマーと共重合することによって、溶解性を向上させることができる。ヘキサフルオロイソプロピリデン結合（４，４−ヘキサフルオロイソプロピリデンジフェノール）を含む屈曲性（ｆｌｅｘｉｂｌｉｚｉｎｇ）コモノマーを使用することによって好適な溶解性が得られるが、このモノマーによって調製されるポリ（テレフタレート）フィルムの負の複屈折率は０．０１未満である。０．０１を超える負の複屈折率を有するフィルムを形成するために十分な剛直性を有するポリエステル鎖を得るためには、４，４’−（ヘキサヒドロ−４，７−メタノインダン−５−イリデン）ビスフェノール等のより剛直性のコモノマーを使用しなければならない。ただし、該コモノマーは、その他のポリエステルよりは剛直性が高いが、ポリイミドほどの剛直性は有していない。

A particularly useful solubilizing monomer is 4,4 ′-(hexahydro-4,7-methanoindan-5-ylidene) bisphenol, which prevents molecular chain packing while maintaining molecular chain rigidity and Pendant bulky norbornene groups that improve solubility are formed along the polymer backbone. Further, the solubility can be improved by copolymerizing with a monomer containing a more flexible unit such as a 1,3-dioxophenylene group or a hexafluoroisopropylidene bond. Poly (terephthalate) films prepared with a flexible solubility can be obtained by using a flexibrizing comonomer containing a hexafluoroisopropylidene bond (4,4-hexafluoroisopropylidenediphenol) The negative birefringence of is less than 0.01. To obtain a polyester chain with sufficient rigidity to form a film having a negative birefringence greater than 0.01, 4,4 ′-(hexahydro-4,7-methanoindan-5-ylidene) A more rigid comonomer such as bisphenol must be used. However, the comonomer is more rigid than other polyesters, but not as rigid as polyimide.

  The present invention is formed from poly (aryl ether imide) and has a negative birefringence greater than 0.01 with a thickness of less than 15 μm, and the poly (aryl ether imide) is solution cast or applied onto a substrate A negative birefringent film is provided.

  In another embodiment, the film has one or more layers, wherein at least one layer is formed from a poly (aryl etherimide) dissolved in a ketone solvent, and at least one layer is a polymer-based film, A poly (aryl etherimide) layer is cast or applied onto the substrate. The material that can be used for the substrate layer may be triacetylcellulose.

  In another embodiment of the present invention, homopoly (aryl etherimides) and copoly (aryl etherimides) that can be dissolved in ketones and ketone solvent mixtures and form thin films that exhibit negative birefringence by casting or coating. I will provide a.

  In another embodiment of the present invention, a poly (aryl etherimide) that dissolves in a ketone and ketone solvent mixture can be applied or cast onto another polymer substrate film to form a multilayer polymer film.

  In another embodiment of the invention, the poly (aryl ether imide) is formed from poly (aryl ether imide), has a negative birefringence greater than 0.01, has a thickness of less than 15 μm, and the poly (aryl ether imide) is dianhydride. The present invention provides a negative birefringent film that is synthesized from a product and a diamine and is solution cast or coated on the film.

  In another embodiment of the present invention, a negative birefringent film made from poly (aryl ether imide), having a negative birefringence greater than 0.01 and having a thickness of less than 15 μm is prepared, and poly (aryl Etherimide) is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA), bis (3,4-dicarboxy). Phenyl) 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 object Selected from the group consisting of 4,4′-bis (3,4-dicarboxyphenyloxy) biphenyl dianhydride (BPEDA) and 1,5-bis (3,4-dicarboxyphenyloxy) naphthyl dianhydride Dianhydride, 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-aminophenyl) Enoxy) 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-to Fluoromethylphenoxy) terphenyl, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) -phenyl] propane, 2,2-bis [4- (4-amino-2-trifluoromethyl) Phenoxy) -phenyl] 1,1,1,3,3,3-hexafluoropropane, and a diamine selected from the group consisting of 4,4′-bis (4-amino-2-trifluoromethylphenoxy) benzene; Is obtained by synthesizing.

  In another embodiment of the present invention, a poly (aryl ether imide) formed from poly (aryl ether imide), having a negative birefringence greater than 0.01 and having a thickness of less than 15 μm is applied onto the film. A liquid crystal display using a negative birefringent film which is cast or solution-coated is provided.

  In another embodiment of the invention, a polymer film comprising one or more layers, wherein at least one layer is formed from a poly (aryl etherimide) that is soluble in a ketone solvent, and at least one layer is a polymer substrate film A liquid crystal display using a polymer film in which a poly (aryl etherimide) layer is cast or coated on the film is provided.

  In another embodiment of the present invention, a negative birefringent film made of poly (aryl ether imide) having a negative birefringence greater than 0.01 and a thickness less than 15 μm, and poly (aryl ether imide) Provides a liquid crystal display using a negative birefringent film synthesized from dianhydride and diamine and solution cast or coated on the film.

  Colorless poly (aryl ether imide) films having a thickness of less than 15 μm and a negative birefringence of greater than 0.01 can be prepared by solution coating or solution flow using the preferred solvent ketone and ketone solvent mixtures. It can be formed by the elongation method. Since these films exhibit the desired birefringence in the cast state, there is no need for further stretching. Since poly (aryl ether imides) are prepared from flexible perfluoroisopropylidene or dianhydrides containing ether linkages and diamines containing flexible ether linkages, these results are unexpected. When using a combination of these monomers, the components need not be rigid.

  Representative examples of dianhydrides useful in the present invention include 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-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), 1,5-bis (3,4-dicarboxyphenyl) Oxy) naphthyl Anhydride, and the like.

  Particularly preferred dianhydrides include 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA), 4,4′- [4,4 ′-(p-phenyleneoxy) -hexafluoroisopropylidene] -bis (phthalic anhydride) (bis-AF-DA), 4,4′-bis (3,4-dicarboxyphenyloxy) biphenyl A dianhydride (BPEDA) is mentioned.

  Particularly useful diamines in the present invention include 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 -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] hexafluoro propane.

  Particularly preferred diamines include 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) benzene, and 2-trifluoro. Methyl-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.

  In one embodiment, the method comprises combining at least one ether linkage of diamine and one perfluoromethyl with at least two perfluoromethyl groups of dianhydride.

  The film of the present invention can be dissolved in cyclopentanone and MIBK. The solubility of the film in cyclopentanone is suitable for many applications, and the solubility in MIBK is also used in a great many applications. As described above, MIBK is a preferred solvent when a solution is applied to a film on a cellulose substrate such as TAC.

In the film of the present invention, the PAEI film can have a trifluoromethyl (or perfluoromethyl) group (CF ₃ ) on the diamine and dianhydride. The presence of the trifluoromethyl group improves the solubility of the film in MIBK.

  The solvent mixture may be a solvent mixture such as 95% MIBK and 5% ethyl acetate. The ratio is not limited as long as MIBK is 50%.

In the present invention, a mixture of dianhydrides and a mixture of diamines can be used. As a mixture of dianhydrides, preferably one of the dianhydrides has a perfluoromethyl group and the other is represented by the pyromellitic acid anhydride represented by the following formula (I) and the following formula (II): Mixtures of dianhydrides including aromatic tetracarboxylic dianhydrides can be used.

芳香族ジアミンの混合物としては、好ましくは、下記式（ＩＩＩ）および／または式（ＩＶ）で表される芳香族ジアミンを含む本発明のジアミンと組み合わせて使用することができる。

The mixture of aromatic diamines can be preferably used in combination with the diamine of the present invention containing an aromatic diamine represented by the following formula (III) and / or formula (IV).

（式中、ＧおよびＦは独立して、共有結合、ＣＨ_２基、Ｃ（ＣＨ_３）_２基、Ｃ（ＣＦ_３）_２基、Ｃ（ＣＸ_３）_２基からなる代表的な基から選択され、Ｘはハロゲン原子、ＣＯ基、酸素原子、硫黄原子、ＳＯ_２基、Ｓｉ（ＣＨ_２ＣＨ_３）_２基またはＮ（ＣＨ_３）基であって、ｍは１〜３の整数である。）

Wherein G and F are independently selected from representative groups consisting of covalent bonds, CH ₂ groups, C (CH ₃ ) ₂ groups, C (CF ₃ ) ₂ groups, C (CX ₃ ) ₂ groups X is a halogen atom, CO group, oxygen atom, sulfur atom, SO ₂ group, Si (CH ₂ CH ₃ ) ₂ group or N (CH ₃ ) group, and m is an integer of 1 to 3. )

  In one embodiment using a mixture, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4 ′ -A dianhydride mixture with biphenyl dianhydride is used and the diamine is 4,4'-bis (4-amino-trifluoromethylphenoxy) biphenyl (6FOBDA). 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: 1 to 40:60. In another embodiment, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4′-biphenyl di- The molar ratio with anhydride is 80:20.

In another embodiment using a mixture, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4 A mixture of dianhydrides with '-biphenyl dianhydride is used, 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: 1 to 40:60. In another embodiment, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4′-biphenyl di- The molar ratio with anhydride is 80:20.
(Example)

The invention is further illustrated with reference to the following non-limiting examples illustrating the preparation of polyimides and copolyimides that are soluble in organic solvents.
Monomer preparation

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

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 charged into a 3000 ml three-necked round bottom flask equipped with a stirrer, thermometer, nitrogen inlet and condenser. 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 starting material and DMAc were removed by vacuum distillation. TLC showed a major product spot and a very small amount of starting material spot. Pure platelet crystals were obtained by recrystallization from ethanol (233 g, 55% yield). Concentration of the mother liquor yielded an additional 50 g of product. TLC showed only one product spot. The total yield of pure product was 67% (233 + 50 = 283 g). Melting point: 94-95 ° C. Proton NMR (DMSO-d _6, δ, ppm): 8.582 to 8.522 (4H), 7.569 to 7.450 (2H).

The dinitro compound (20 g) obtained above, ethanol (200 ml), Pd / C (0.3 g, Pd content: 10%), and hydrazine monohydrate (8.0 ml) were added to a stirrer, condenser, And put into a 500 ml three-necked flask equipped with a gas outlet connected to a bubbler. The mixture was stirred overnight at room temperature. After the mixture was filtered, ethanol was removed under reduced pressure. Fine crystals were obtained by recrystallization from a toluene / hexane mixture. Melting point: 114-116 ° C. Proton NMR (DMSO-d _6, δ, ppm): 6.870 to 6.861 (2H), 6.750 to 6.712 (2H), 6.622 to 6.592 (2H), 5.278 ( 4H).

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

4-nitrophenol (204 g, 1.467 mol), 2-chloro-5-nitrobenzotrifluoride (330.7 g, 1.467 mol), and DMAc (800 ml) were added to a stirrer, condenser, and thermometer. It was put into a 3000 ml three-necked round bottom flask equipped. After the mixture became homogeneous, 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 a 5 L methanol / water mixture (10/1, v / v). The resulting precipitate was collected by filtration, washed with water and filtered again. Crystals were obtained by recrystallization from a methanol / water mixture (312 g, 64.8% yield). Melting point: 68-70 ° C. 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′-dinitrobiphenyl ether (88 g, 0.268 mol), ethanol (600 ml), and Pd / C (5%, 1.0 g), hydrazine monohydrate (60 ml). In a 1000 ml three-necked round bottom flask equipped with a stirrer, condenser, and thermometer. The mixture was heated at reflux for 20 hours. The reaction was 100% complete. After cooling, the solution was filtered to remove solids. Water was added to the filtrate in which a large amount of crystals precipitated. The crystals were further purified by sublimation. Melting point: 102-104 ° C. Proton 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), 6.514-6.484 (2H), 5.218 (2H), 4.841 (2H).

  This example demonstrates 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), potassium carbonate (21 g, 0.15 mol), and DMF (100 ml) was charged into a 300 ml three-necked round bottom flask equipped with a stirrer, thermometer and condenser. The mixture was heated at 100 ° C. overnight. After cooling to room temperature, the mixture was filtered to remove solids. Most of the solvent (DMF) was removed by vacuum distillation. The residue was poured into water. The resulting precipitate was collected by filtration and washed with water. Fine crystals were obtained by recrystallization from an ethanol / water mixture (yield: 84%, melting point = 96-98 ° C.). Proton NMR (DMSO-d _6, δ, ppm): 8.548 (1H), 8.493 to 8.453 (1H), 8.349 (1H), 8.175 to 8.146 (1H), 7 .347-7.317 (1H), 7.217-7.187 (1H), 2.285 (3H).

Dinitro compound (20 g), Pd / C (0.2 g, Pd 5%), ethanol (100 ml), and hydrazine monohydrate (8.0 ml), magnetic stirrer and condenser (connected to bubbler). It was put into a 500 ml single-neck flat bottom flask equipped. The mixture was stirred overnight at room temperature. The mixture was filtered and the solvent was removed on a rotovap. The diamine was purified by sublimation. Melting point = 95-97 ° C. Proton 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), 6.379-6.342 (1H), 5.102 (2H), 4.825 (2H), 1.966 (3H).

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

1,4-dihydroxybenzene (11.62 g, 0.106 mol), 2-chloro-5-nitrobenzotrifluoride (50.0 g, 0.222 mol), DMAc (100 ml), and dried K ₂ CO ₃ (22.2 g, 0.16 mol) was charged into a 300 ml three-necked round bottom flask equipped with a thermometer, stirrer, and condenser. The reaction mixture was then heated at 130 ° C. for 10 hours under a nitrogen atmosphere. A large amount of precipitate formed on cooling, which was separated by filtration, washed with water and dried (46.03 g, 90.0%). Melting point: 205-207 ° C. Proton NMR (δ, ppm, DMSO-d ₆ ): 8.526 to 8.517 (2H), 8.482 to 8.443 (2H), 7.388 (4H), 7.255 to 7.224 ( 2H). The resulting compound was 4,4′-bis (4-nitro-2-trifluoromethylphenoxy) benzene.

4,4′-bis (4-nitro-2-trifluoromethylphenoxy) biphenyl (20 g, 40.98 mmol), ethanol (200 ml), Pd / C (5% Pd, 0.4 g), monohydrogenated hydrazine (10 ml) was charged into a 500 ml three-necked round bottom flask equipped with a thermometer, stirrer and condenser. The mixture was stirred and heated at reflux for 5 hours and cooled to room temperature. The mixture was filtered and the filtrate was added to water (˜200 ml). The precipitated solid was recrystallized with a methanol / water mixture to obtain colorless flaky crystals (15.91 g, 90.7%). Melting point: 112-114 ° C. Proton NMR (δ, ppm, DMSO-d ₆ ): 6.888 to 6.880 (2H), 6.833 (4H), 6.805 to 6.786 (4H), 5.375 (4H). The obtained compound was 4,4′-bis (4-amino-2-trifluoromethylphenoxy) benzene (6FOQDA).

  This example shows 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 (150 ml) were added to a thermometer, stirrer, And a 500 ml three-necked round bottom flask equipped with a condenser. After a homogeneous solution was formed, dry K ₂ CO ₃ (28.3 g, 0.205 mol) was added. The reaction mixture was then heated at 130 ° C. for 10 hours. A large amount of precipitate formed on cooling, which was separated by filtration, washed with methanol and dried. Recrystallization from a DMF / methanol mixture gave pale needle crystals (34.35 g, 60.86%). Melting point: 215-216 ° C. Proton NMR ( _, δ, ppm, DMSO-d ₆ ): 8.530 (4H), 7.854 (4H), 7.346 (4H), 7.218 (2H). The resulting compound was 4,4′-bis (4-nitro-2-trifluoromethylphenoxy) biphenyl.

4,4′-bis (4-nitro-2-trifluoromethylphenoxy) biphenyl (20 g, 0.0373 mol), ethanol (300 ml), Pd / C (5% Pd, 0.4 g), and monohydrogenation Hydrazine (10 ml) was charged into a 500 ml three-necked round bottom flask equipped with a thermometer, stirrer, and condenser. The mixture was stirred and heated at reflux overnight and then cooled to room temperature. The mixture was filtered and the filtrate was added to water (150 ml). The crude product was recrystallized with a methanol / water mixture to obtain colorless flaky crystals (15.03 g, 80.0%). Melting point: 155-156 ° C. Proton NMR ( _, δ, ppm, DMSO-d ₆ ): 7.550 (4H), 6.912 (8H), 6.835 (2H), 5.425 (4H). The resulting compound was 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl (6FOBDA).

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

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

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

  (One-step procedure for homopolyimide)

  This example shows a general procedure for preparing homopolyimides from dianhydrides and diamines.

  1.00 mmol dianhydride was added to a stirred solution of 10 ml m-cresol containing 1.00 mmol diamine at room temperature under nitrogen atmosphere. After the solution was stirred for 6 hours, 0.05 g of isoquinoline was added. The mixture was heated to 200 ° C. and maintained at that temperature for 12 hours. Meanwhile, water generated by imidization was removed from the reaction mixture by distillation. After the solution was cooled to room temperature, the solution was slowly added to 500 ml of stirred methanol. The precipitated polymer was collected by filtration, washed with ethanol, and dried under reduced pressure at 150 ° C. for 24 hours.

  (One step procedure of copolyimide)

  This example shows a general procedure for preparing a copolyimide from a mixture of dianhydrides and one diamine.

  1.00 mmol dianhydride mixture was added to a stirred solution of 10 ml m-cresol containing 1.00 mmol diamine at room temperature under nitrogen. After the solution was stirred for 6 hours, 0.05 g of isoquinoline was added. The mixture was heated to 200 ° C. and maintained at that temperature for 12 hours. Meanwhile, water generated by imidization was removed from the reaction mixture by distillation. After the solution was cooled to room temperature, it was slowly added to 500 ml of stirred methanol. The precipitated polymer was collected by filtration, washed with ethanol, and dried under reduced pressure at 150 ° C. for 24 hours.

  This example illustrates a general procedure for preparing a copolyimide from one dianhydride and multiple diamines.

  1.00 mmol dianhydride was added to a stirred solution of 10 ml m-cresol containing 1.00 mmol diamines at room temperature under nitrogen atmosphere. After stirring the solution for 6 hours, 0.05 g of isoquinoline was added and the mixture was heated to 200 ° C. to maintain the temperature for 12 hours. Meanwhile, water generated by imidization was removed from the reaction mixture by distillation. After the solution was cooled to room temperature, it was slowly added to 500 ml of stirred methanol. The precipitated polymer was collected by filtration, washed with ethanol, and dried under reduced pressure at 150 ° C. for 24 hours.

(Polyimide solubility and birefringence of film)
A polyimide film showing a negative birefringence was produced by the following procedure. The polyimide was dissolved in cyclopentanone or MIBK until the solid content was 4-5%. After filtration, the solution was poured onto a glass substrate. The solvent was evaporated at room temperature. The glass substrate containing the film was dried under reduced pressure at 100 ° C. The polyimide film was removed from the glass by immersing the glass substrate in water. The birefringence of the polyimide film was measured with a prism coupler 2010 / M manufactured by Metricon. Common examples of birefringence are shown in Tables 1, 2 and 3.

(Film application)
A MIBK solution containing poly (aryl ether imide) was rod-coated on a glass plate or a triacetyl cellulose (TAC) film. When coating on a glass plate, a solution containing 3-5% by weight of poly (aryl ether imide) is used, and when coating on a TAC film, 8-20% by weight of poly (aryl ether). A solution containing imide) was used.

Claims (27)

  Formed from poly (aryl ether imide), having a negative birefringence greater than 0.01 with a thickness of less than 15 μm, the poly (aryl ether imide) being solution cast or coated on a substrate , Negative birefringence film. In claim 1,
A film formed from a poly (aryl etherimide) that is soluble in a ketone solvent and solution cast or applied to a substrate. In claim 2,
A film, wherein at least one of the layers is a substrate layer made of triacetylcellulose. In claim 1,
A film wherein the poly (aryl etherimide) is an aryl etherimide homopolymer or copolymer dissolved in a ketone solvent mixture. In claim 1,
A film wherein the poly (aryl etherimide) is a reaction product of a dianhydride and a diamine. In claim 5,
The film wherein the dianhydride comprises a flexible perfluoroisopropylidene bond. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The film wherein the diamine contains a flexible ether bond. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The film wherein the dianhydride contains a perfluoromethyl group. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The film wherein the diamine comprises a perfluoromethyl group and a flexible ether bond. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The dianhydride contains a perfluoromethyl group;
The film wherein the diamine contains a perfluoromethyl group. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The dianhydride contains a perfluoromethyl group;
The film wherein the diamine comprises a perfluoromethyl group and a flexible ether bond. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The film wherein the dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA). In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 4,4 ′-[4 A film selected from the group consisting of 4 '-(p-phenyleneoxy) hexafluoroisopropylidene] -bis (phthalic anhydride) (bis-AF-DA). In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA), bis (3,4-dicarboxy) Phenyl) 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 Product, 4,4′-bis (3,4-dicarboxyphenyloxy) biphenyl dianhydride (BPEDA), and 1,5-bis (3,4-dicarboxyphenyloxy) naphthyl dianhydride Selected
The diamine is 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- (4-amino-2-trifluoromethylphenoxy) benzene, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4-amino-2-trifluoro) Methylphenoxy) -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] , 1,1,3,3,3-hexafluoropropane, and 4,4'-bis (4-amino-2-trifluoromethylphenoxy) is selected from the group consisting of benzene, the film. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine, and the dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 , 3-hexafluoropropane dianhydride (6FDA),
The film wherein the diamine is 4,4'-bis (4-amino-trifluoromethylphenoxy) biphenyl (6FOBDA). In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine, and the dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 , 3-hexafluoropropane dianhydride (6FDA), and the diamine is 2,2′-bis (trifluoromethyl) -4,4′-diaminophenyl ether (6FODA). In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ′, 4,4. A mixture with '-biphenyltetracarboxylic dianhydride,
The film wherein the diamine is 4,4'-bis (4-amino-trifluoromethylphenoxy) biphenyl (6FOBDA). In claim 17,
2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic The film wherein the molar ratio of the mixture with acid dianhydride is 99: 1 to 40:60. In claim 17,
2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic The film, wherein the molar ratio of the mixture with acid dianhydride is 80:20. In claim 1,
The poly (aryl ether imide) is a reaction product of a dianhydride and a diamine,
The dianhydride is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ′, 4,4. A mixture with '-biphenyltetracarboxylic dianhydride,
The film wherein the diamine is 2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether (6FODA). In claim 20,
2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic The film wherein the molar ratio of the mixture with acid dianhydride is 99: 1 to 40:60. In claim 20,
2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic The film, wherein the molar ratio of the mixture with acid dianhydride is 50:50. In claim 1,
The poly (aryl etherimide) is a reaction product of two or more dianhydrides and a diamine;
A film in which one of the dianhydrides is selected from pyromeric anhydride and an aromatic tetracarboxylic dianhydride represented by the following formula (I).

Wherein G 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 a halogen atom, CO , Oxygen atom, sulfur atom, SO ₂ , Si (CH ₂ CH ₃ ) ₂ , and N (CH ₃ ). In claim 23,
One of the dianhydrides is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (sym-BPDA) and 2,3,3′4-biphenyltetracarboxylic dianhydride (asym-BPDA) A film selected from the group consisting of: In claim 1,
The poly (aryl etherimide) is a reaction product of a mixture of dianhydride and diamine,
The film wherein one of the diamines is selected from the group consisting of the following formulas (II) and (III).

Wherein 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 a halogen atom, CO , Oxygen atom, sulfur atom, SO ₂ , Si (CH ₂ CH ₃ ) ₂ , and N (CH ₃ ), and m is an integer of 1 to 3.   Formed from poly (aryl ether imide), having a negative birefringence greater than 0.01 with a thickness of less than 15 μm, the poly (aryl ether imide) being solution cast or coated on a substrate Liquid crystal display using negative birefringence film.   Formed from poly (aryl ether imide), having a negative birefringence greater than 0.01 and having a thickness of less than 15 μm, wherein said poly (aryl ether imide) is synthesized from dianhydride and diamine, Or a liquid crystal display using a negative birefringent film which is dissolved in a ketone solvent mixture and is cast or applied onto a substrate.