TW201313748A

TW201313748A - Optical compensation films based on fluoropolymers

Info

Publication number: TW201313748A
Application number: TW100134267A
Authority: TW
Inventors: xiao-liang Zheng; Dong Zhang; Jiao-Kai Jing; Frank W Harris; Brian Michael King; Ted Calvin Germroth; Thauming Kuo
Original assignee: Akron Polymer Systems Inc
Priority date: 2011-09-23
Filing date: 2011-09-23
Publication date: 2013-04-01

Abstract

An optical compensation film composition is disclosed herein having a polymer film and a substrate, wherein the polymer film has a positive birefringence greater than 0.005 throughout the wavelength range of 400 nm < λ < 800 nm, the film having been cast from a polymer solution comprising a solvent and a polymer having a moiety of wherein R1, R2, and R3 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens, wherein at least one of R1, R2, and R3 is a fluorine atom, and wherein R is hydrogen or a substituent on the styrenic ring.

Description

以含氟聚合物製成之光學補償膜Optical compensation film made of fluoropolymer

本申請案為2008年8月22日提出申請之美國專利第12/229,401號之部分沿續申請案，且為2007年3月29日提出申請之美國專利第11/731,367號之部分沿續申請案。本發明係關於在400 nm<λ<800 nm波長範圍間正雙折射率大於0.005之光學補償膜，其可用於需受控光線管理之光學設備，如液晶顯示器(LCD)裝置、光學開關，以及導波管。更詳而言之，本發明之光學補償膜係供面內(in-plane)切換LCD(IPS-LCD)所使用。This application is a continuation-in-part application of U.S. Patent No. 12/229,401, filed on Aug. 22, 2008, which is incorporated herein by reference. case. The present invention relates to an optical compensation film having a positive birefringence greater than 0.005 in a wavelength range of 400 nm < λ < 800 nm, which can be used for optical devices requiring controlled light management, such as liquid crystal display (LCD) devices, optical switches, and Guide tube. More specifically, the optical compensation film of the present invention is used for an in-plane switching LCD (IPS-LCD).

美國專利申請第2008/0239491號揭露一在400 nm<λ<800 nm波長範圍間正雙折射率大於0.002之聚合物薄膜，其中該薄膜係以一聚合物之溶液澆鑄於基質上而成，所述聚合物具有以下基元U.S. Patent Application No. 2008/0239491 discloses a polymer film having a positive birefringence of greater than 0.002 in the wavelength range of 400 nm < λ < 800 nm, wherein the film is formed by casting a solution of a polymer onto a substrate. The polymer has the following primitives

其中R¹、R²及R³係各自為氫原子、烷基、取代烷基或鹵素，其中OASU為一盤狀基群或一液晶基元，且其中OASU係經單一共價鍵連附於聚合物主鏈。Wherein R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group, a substituted alkyl group or a halogen, wherein OASU is a discotic group or a liquid crystal unit, and wherein OASU is attached via a single covalent bond Polymer backbone.

聚苯乙烯為最常見具有盤狀OASU之聚合物，其溶液澆鑄薄膜通常具有0.001-0.002之雙折射率。491申請案教示在苯環上併入如溴基或硝基等雙折射率加強取代基(BES)可提高聚苯乙烯之雙折射率。例如，聚硝基苯乙烯之雙折射率可高達約0.016，而聚溴基苯乙烯可高達約0.007。Polystyrene is the most common polymer having a discotic OASU, and its solution cast film usually has a birefringence of 0.001 to 0.002. The application of the 491 application teaches the incorporation of a birefringent reinforcing substituent (BES) such as a bromo group or a nitro group on the benzene ring to increase the birefringence of the polystyrene. For example, polynitrostyrene can have a birefringence of up to about 0.016, while polybromostyrene can be as high as about 0.007.

對照之下，本案發明人意外發現，藉由在聚苯乙烯分子主鏈上併入氟原子，可大幅提高聚苯乙烯薄膜之雙折射率。此種聚合物薄膜之雙折射率高達約0.015-0.02。此外，該聚合物薄膜之機械性質遠優於聚苯乙烯薄膜。高雙折射率使得薄膜於基質上之澆鑄可產生具有理想延遲率之補償薄膜，而改良之機械性質使得製成之無襯薄膜具有高強度，可便於拉伸、捲繞和貼合。In contrast, the inventors of the present invention unexpectedly found that the birefringence of the polystyrene film can be greatly improved by incorporating a fluorine atom into the main chain of the polystyrene molecule. The polymer film has a birefringence of up to about 0.015-0.02. In addition, the polymer film is much more mechanical than the polystyrene film. The high birefringence allows the casting of the film onto the substrate to produce a compensation film having a desired retardation, and the improved mechanical properties allow the resulting linerless film to have high strength for ease of stretching, winding and lamination.

在一實施例中，一光學補償膜組成物包括一聚合物薄膜及一基質，其中該聚合物薄膜之正雙折射率在400 nm<λ<800 nm之波長範圍內大於0.005，該薄膜係以一含溶劑及聚合物之聚合物溶液澆鑄於而成，所述聚合物具有以下基元In one embodiment, an optical compensation film composition includes a polymer film and a substrate, wherein the polymer film has a positive birefringence greater than 0.005 in a wavelength range of 400 nm < λ < 800 nm, and the film is a polymer solution containing a solvent and a polymer having the following primitives

其中R¹、R²及R³係各自為氫原子、烷基、取代烷基，或鹵素，其中R¹、R²及R³中之至少一者為氟原子，且其中R為氫或苯乙烯系環上之一取代基。Wherein R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group, a substituted alkyl group, or a halogen, wherein at least one of R ¹ , R ² and R ³ is a fluorine atom, and wherein R is hydrogen or benzene One of the substituents on the vinyl ring.

熟悉此技藝人士將可藉由以下之詳細說明瞭解本發明之其他益處與優點。Other benefits and advantages of the present invention will be apparent from the following detailed description.

在一實施例中，一種光學補償膜組成物係包含一聚合物薄膜及一基質，其中該聚合物薄膜之正雙折射率在400 nm<λ<800 nm之波長範圍內大於0.005，該薄膜係以一包含一溶劑及一聚合物之聚合物溶液澆鑄而成，所述聚合物具有以下基元In one embodiment, an optical compensation film composition comprises a polymer film and a substrate, wherein the polymer film has a positive birefringence greater than 0.005 in a wavelength range of 400 nm < λ < 800 nm, and the film system is Casting from a polymer solution comprising a solvent and a polymer having the following motifs

其中R¹、R²及R³係各自為氫原子、烷基、取代烷基，或鹵素，其中R¹、R²及R³中之至少一者為氟原子，且其中R為氫或苯乙烯系環上之一取代基。在一觀點中，至少R¹、R²及R³中之兩者為氟原子；在另一觀點中，R¹、R²及R³皆為氟原子。Wherein R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group, a substituted alkyl group, or a halogen, wherein at least one of R ¹ , R ² and R ³ is a fluorine atom, and wherein R is hydrogen or benzene One of the substituents on the vinyl ring. In one aspect, at least two of R ¹ , R ² and R ³ are fluorine atoms; in another aspect, R ¹ , R ² and R ³ are each a fluorine atom.

苯乙烯系環上取代基R之範例包括烷基、取代烷基、鹵素、羥基、羧基、硝基、烷氧基、胺基、磺酸鹽、磷酸鹽、醯基、醯氧基、苯基、烷氧羰基及氰基等等中之一或多者。Examples of the substituent R on the styrene ring include an alkyl group, a substituted alkyl group, a halogen, a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an amine group, a sulfonate group, a phosphate group, a decyl group, a decyloxy group, and a phenyl group. One or more of an alkoxycarbonyl group, a cyano group and the like.

在一實施例中，該聚合物溶液係澆鑄於該基質上以形成一在該基質上之聚合物塗層薄膜。該溶液澆鑄聚合物薄膜在溶劑蒸發時能夠形成面外(out-of-plane)非等向性配向，而不需經過熱處理、光輻射或拉伸，且其正雙折射率在400 nm<λ<800 nm之波長範圍內大於0.005，大於0.01，或大於0.015。In one embodiment, the polymer solution is cast onto the substrate to form a polymer coated film on the substrate. The solution cast polymer film can form an out-of-plane anisotropic alignment when the solvent evaporates without heat treatment, light irradiation or stretching, and its positive birefringence is 400 nm<λ <800 nm in the wavelength range is greater than 0.005, greater than 0.01, or greater than 0.015.

正雙折射率(Δn)定義為n_z>(n_x+n_y)/2，其中n_x及n_y代表面內折射率，而n_z代表薄膜之厚度方向折射率(Δn=n_z-(n_x+n_y)/2)。此等聚合物製成之光學補償膜其正雙折射率在400 nm<λ<800 nm波長範圍內皆大於0.005，而不需經過熱處理、光輻射或拉伸。然而，在特定實施例中，可採用熱處理、光輻射或拉伸以進一步加強正雙折射率。在至少一實施例中，該補償薄膜之雙折射率在400 nm<λ<800 nm波長範圍內大於0.01或0.015。The positive birefringence (Δn) is defined as n _z >(n _x +n _y )/2, where n _x and n _y represent in-plane refractive indices, and n _z represents refractive index in the thickness direction of the film (Δn=n _z - (n _x +n _y )/2). The optical compensation film made of these polymers has a positive birefringence of more than 0.005 in the wavelength range of 400 nm < λ < 800 nm without heat treatment, light irradiation or stretching. However, in certain embodiments, heat treatment, optical radiation, or stretching may be employed to further enhance the positive birefringence. In at least one embodiment, the compensation film has a birefringence greater than 0.01 or 0.015 in the wavelength range of 400 nm < λ < 800 nm.

雙折射率(Δn)之測量方式為以不同增量判定薄膜在約400 nm至約800 nm波長範圍內之雙折射率。或者，可如本技藝中慣用之方式，測量薄膜於633 nm之雙折射率。以633 nm之Δn為參考值之原因在於具有正雙折射率之薄膜在633 nm以下波長之雙折射率通常高於633 nm時之雙折射率，且波長633 nm以上之雙折射率通常與633 nm時之雙折射率相等或僅略低於此值。因此，在此技藝中，對波長633 nm時雙折射率之理解為400 nm<　<800 nm波長範圍內之雙折射率大於或約略相當於633 nm時之雙折射率。The birefringence (Δn) is measured by varying the birefringence of the film in the wavelength range from about 400 nm to about 800 nm in different increments. Alternatively, the birefringence of the film at 633 nm can be measured as is conventional in the art. The reason why Δn at 633 nm is used as a reference value is that the birefringence of a film having a positive birefringence at a wavelength below 633 nm is usually higher than the birefringence at 633 nm, and the birefringence at a wavelength of 633 nm or more is usually 633. The birefringence at nm is equal or only slightly lower than this value. Therefore, in this technique, the birefringence at a wavelength of 633 nm is understood to be a birefringence in the wavelength range of 400 nm < < 800 nm greater than or approximately equivalent to the birefringence at 633 nm.

在另一實施例中，待該溶液澆鑄聚合物薄膜乾燥後將之自基質取下，形成一無襯薄膜，可經單軸或雙軸拉伸。該無襯薄膜可經貼合附加於一基質。In another embodiment, the solution cast polymer film is dried and then removed from the substrate to form a linerless film that can be uniaxially or biaxially stretched. The linerless film can be attached to a substrate via a laminate.

將聚合物溶液澆鑄於基質上之作業可採用本技藝中習知之方法，例如，旋轉塗佈、噴灑塗佈、捲式塗佈、淋幕塗佈或浸泡塗佈。基質為本本技藝中所習知者，包括三醋酸纖維素(TAC)、環烴烯聚合物(COP)、聚酯、聚乙烯醇、纖維酯、醋酸丙酸纖維素(CAP)、聚碳酸酯、聚丙烯酸酯、聚烯烴、聚氨酯、聚苯乙烯、玻璃及其他常用於LCD顯示器之材料。The casting of the polymer solution onto the substrate can be carried out by methods known in the art, for example, spin coating, spray coating, roll coating, curtain coating or immersion coating. Substrates are well known in the art and include cellulose triacetate (TAC), cyclic hydrocarbon polymers (COP), polyesters, polyvinyl alcohols, cellulose esters, cellulose acetate propionate (CAP), polycarbonates. , polyacrylates, polyolefins, polyurethanes, polystyrene, glass and other materials commonly used in LCD displays.

在本發明另一實施例中，該聚合物組成物可溶於一溶劑，如甲苯、甲基異丁基酮、環戊酮、二氯甲烷、1,2-二氯乙烷、甲基戊基酮、甲基乙基酮、甲基異丁基酮及其混合物。In another embodiment of the invention, the polymer composition is soluble in a solvent such as toluene, methyl isobutyl ketone, cyclopentanone, dichloromethane, 1,2-dichloroethane, methyl pentane Ketone, methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof.

本發明之聚合物薄膜可為一同聚物或一共聚物。該同聚物可由具有以下結構之含氟單體進行聚合作用而製成。The polymer film of the present invention may be a homopolymer or a copolymer. The homopolymer can be produced by polymerization of a fluorine-containing monomer having the following structure.

其中R¹、R²及R³係各自為氫原子、烷基、取代烷基，或鹵素且其中R¹、R²及R³中之至少一者為氟原子，且其中R為氫或苯乙烯系環上之一取代基。Wherein R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group, a substituted alkyl group, or a halogen and wherein at least one of R ¹ , R ² and R ³ is a fluorine atom, and wherein R is hydrogen or benzene One of the substituents on the vinyl ring.

此種含氟單體之範例包括但不限於，α,β,β-三氟苯乙烯、α,β-二氟苯乙烯、β,β-二氟苯乙烯、α-氟苯乙烯，以及β-氟苯乙烯。在一實施例中，該同聚物為聚(α,β,β-三氟苯乙烯)。Examples of such fluoromonomers include, but are not limited to, α,β,β-trifluorostyrene, α,β-difluorostyrene, β,β-difluorostyrene, α-fluorostyrene, and β. - Fluorostyrene. In one embodiment, the homopolymer is poly(α,β,β-trifluorostyrene).

該共聚物可經一或多種含氟單體與一或多種乙烯性不飽和單體之共聚作用製備而成。乙烯性不飽和單體之範例包括但不限於，丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、異丙烯酸丁酯、異甲基丙烯酸丁酯、乙基己基丙烯酸酯、2-甲基丙烯酸乙基己酯、2-乙基己基丙烯酸酯、異戊二烯、丙烯酸辛酯、甲基丙烯酸辛酯、丙烯酸異辛酯、甲基丙烯酸異辛酯、三甲基丙基三丙烯酸酯、苯乙烯、α-甲基苯乙烯、硝基苯乙烯、溴苯乙烯、碘苯乙烯、氰基苯乙烯、氯苯乙烯、4-叔丁基苯乙烯、4-甲基苯乙烯、乙烯基聯苯、乙烯基三苯基、乙烯基甲苯、氯甲基苯乙烯、丙烯酸，甲基丙烯酸、亞甲基丁二酸、反式丁烯酸、順丁烯二酸酐、四氟乙烯(及其他氟乙烯)、甲基丙烯酸縮水甘油酯、碳化二亞胺甲基丙烯酸、C₁-C₁₈烷基丁烯酸酯、馬來酸二正丁酯、馬來酸二辛酯、甲基丙烯酸烯丙酯、馬來酸二烯丙酯、丙二酸二烯丙酯、甲基丙烯酸甲氧基丁酯、異冰片甲基丙烯酸酯、甲丙烯醯酸羥基丁酯、甲基丙烯酸羥乙酯、甲基丙烯酸羥丙酯、乙醯基乙醯氧基甲基丙烯酸乙酯、乙醯基乙醯氧基丙烯酸乙酯、丙烯清、氯乙烯、二氯乙烯、醋酸乙烯酯、乙烯基碳酸乙烯酯、環氧丁烷、3,4-二羥基丁烷、甲基丙烯酸羥乙酯、甲基丙烯醯胺、丙烯醯胺、丁基丙烯醯胺、乙基丙烯醯胺、二丙酮丙烯醯胺、丁二烯、乙烯酯單體、甲基丙烯酸乙烯酯、甲基丙烯酸異丙酯、脂環環氧甲基丙烯酸酯、乙基甲醯胺、4-乙烯基-1,3-二氧戊環-2-酮、2,2-二甲基-4-乙烯基-1,3-二氧戊環、3,4-二醋酸基-1-丁烯及單乙烯基己二酸叔丁基胺基甲基丙烯酸乙酯、二甲基胺基甲基丙烯酸乙酯、二乙基胺基甲基丙烯酸乙酯、N,N-二甲基胺基丙基甲基丙烯醯胺、2-叔丁基胺基甲基丙烯酸乙酯、N,N-二甲基胺基丙烯酸乙酯、N-(2-甲基丙烯醯氧乙基)乙烯脲，以及甲基丙烯醯胺基乙基乙烯脲。其他單體可參照The Brandon Associates,2nd edition,1992 Merrimack,N.H.以及Polymers and Monomers,the 1966-1997 Catalog from Polyscience,Inc.,Warrington,Pa.,U.S.A。The copolymer can be prepared by copolymerization of one or more fluoromonomers with one or more ethylenically unsaturated monomers. Examples of ethylenically unsaturated monomers include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, butyl isoacrylate, and isoforms. Butyl acrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, isooctyl acrylate, A Isooctyl acrylate, trimethyl propyl triacrylate, styrene, α-methyl styrene, nitrostyrene, bromostyrene, iodine styrene, cyanostyrene, chlorostyrene, 4-tert Butylstyrene, 4-methylstyrene, vinylbiphenyl, vinyltriphenyl, vinyltoluene, chloromethylstyrene, acrylic acid, methacrylic acid, methylene succinic acid, transbutene Acid, maleic anhydride, tetrafluoroethylene (and other vinyl fluoride), glycidyl methacrylate, carbodiimide methacrylic acid, C ₁ -C ₁₈ alkyl crotonate, maleic acid Butyl ester, dioctyl maleate, allyl methacrylate, diene maleate Ester, diallyl malonate, methoxybutyl methacrylate, isobornyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acetamidine Ethyl ethoxy methacrylate, ethyl acetoacetate, propylene, vinyl chloride, dichloroethylene, vinyl acetate, vinyl ethylene carbonate, butylene oxide, 3, 4 -dihydroxybutane, hydroxyethyl methacrylate, methacrylamide, acrylamide, butyl acrylamide, ethyl acrylamide, diacetone acrylamide, butadiene, vinyl ester monomer, Vinyl methacrylate, isopropyl methacrylate, alicyclic epoxy methacrylate, ethyl formamide, 4-vinyl-1,3-dioxolan-2-one, 2,2- Dimethyl-4-vinyl-1,3-dioxolane, 3,4-diacetoxy-1-butene and tert-butylaminoethyl methacrylate, dimethyl methacrylate Ethyl methacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylamide, 2-tert-butylaminoethyl methacrylate, N,N-dimethylamino group Ethyl acrylate, N-(2-methylpropenyloxyethyl)ethylene urea, and methacrylamidoethylethylene urea. Other monomers can be found in The Brandon Associates, 2nd edition, 1992 Merrimack, NH and Polymers and Monomers, the 1966-1997 Catalog from Polyscience, Inc., Warrington, Pa., USA.

在一實施例中，該聚合物為α,β,β-三氟苯乙烯與一或多種乙烯性不飽和單體之共聚物，所述乙烯性不飽和單體係選自由苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、2-乙基己基丙烯酸酯、丙烯酸、甲基丙烯酸、α-甲基苯乙烯、4-甲基苯乙烯、乙烯基聯苯、丙烯清以及異戊二烯所構成之群組。In one embodiment, the polymer is a copolymer of alpha, beta, beta-trifluorostyrene and one or more ethylenically unsaturated monomers selected from the group consisting of styrene and acrylic acid. Ester, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, α-methylstyrene, 4-methylstyrene, vinyl biphenyl A group consisting of propylene and isoprene.

可以本技藝中所習知之任一方法實施聚合，如本體聚合、溶液聚合、乳液聚合或懸浮聚合。該反應可為自由基、陽離子、陰離子、兩性離子、齊格勒納塔(Ziegler-Natta)，或原子轉移自由基類之聚合作用。若欲達成高分子量，則可採用乳液聚合。高分子量聚合物可產生較佳之薄膜品質與較高之正雙折射率。製備單氟、二氟及三氟苯乙烯同聚物和共聚物之方法可參考Progress in Polymer Science,Volume 29(2004),pages 75-106,Elsevier Ltd.,MO,USA，其內容於此合併參照。The polymerization can be carried out by any of the methods known in the art, such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. The reaction can be a polymerization of a free radical, a cation, an anion, a zwitterion, a Ziegler-Natta, or an atom transfer radical. If high molecular weight is desired, emulsion polymerization can be employed. High molecular weight polymers produce better film quality and higher positive birefringence. For the preparation of monofluoro, difluoro and trifluorostyrene homopolymers and copolymers, see Progress in Polymer Science , Volume 29 (2004), pages 75-106, Elsevier Ltd., MO, USA, the contents of which are incorporated herein by reference. Reference.

可使用一含氟同聚物溶液進行溶液薄膜澆鑄，此溶液為含氟同聚物與其他聚合物或一含氟共聚物之混合物，其他聚合物及含氟共聚物之作用在於改善薄膜品質並降低成本。聚合物溶液可進一步包含其他成分，如其他聚合物或添加劑。塑化劑為常用之薄膜形成添加劑，具有改善薄膜性質之功用。Solution film casting can be carried out using a fluorine-containing homopolymer solution which is a mixture of a fluorine-containing homopolymer and another polymer or a fluorine-containing copolymer, and other polymers and fluorine-containing copolymers function to improve film quality and cut costs. The polymer solution may further comprise other ingredients such as other polymers or additives. The plasticizer is a commonly used film forming additive and has the function of improving the properties of the film.

適用於本發明之塑化劑範例包括可購自Eastman Chemical Company之Abitol E(氫化松香)、Permalyn 3100(季戊四醇之妥爾油松香酯)、Permalyn 2085(甘油之妥爾油松香酯)、Permalyn 6110(季戊四醇之松香酯)、Foralyn 110(季戊四醇之氫化松香酯)、Admex 523(一種雙質子酸乙二醇聚酯)以及光學薄膜加強劑400(一種專利低VOC低臭接合劑)；以及可購自Unitex Chemical Corp.之Uniplex 552(季戊四醇四苯甲酸酯)、Uniplex 280(蔗糖苯甲酸酯)和Uniplex 809(PEG二-2-乙基己酸酯)；以及三苯基磷酸鹽、三(乙烯乙二醇)雙(2-乙基己酸酯)、三(乙烯乙二醇)雙(正辛酸酯)，及其混合物。Examples of plasticizers suitable for use in the present invention include Abitol E (hydrogenated rosin) available from Eastman Chemical Company, Permalyn 3100 (tall oil rosin ester of pentaerythritol), Permalyn 2085 ( tall oil rosin ester of glycerol), Permalyn 6110 (rosin ester of pentaerythritol), Foralyn 110 (hydrogenated rosin ester of pentaerythritol), Admex 523 (a biprotonic acid ethylene glycol polyester), and optical film enhancer 400 (a patented low VOC low odor cement); Uniplex 552 (pentaerythritol tetrabenzoate), Uniplex 280 (sucrose benzoate) and Uniplex 809 (PEG di-2-ethylhexanoate) from Unitex Chemical Corp.; and triphenyl phosphate, three (ethylene glycol) bis(2-ethylhexanoate), tris(ethylene glycol) bis(n-octanoate), and mixtures thereof.

在另一實施例中，該聚合物溶液更包含一或多種選自以下項目所構成群組之塑化劑：三苯基磷酸鹽、三(乙烯乙二醇)雙(2-乙基己酸酯)、三(乙烯乙二醇)雙(正辛酸酯)；Eastman Chemical Company所供應之光學薄膜加強劑400、Abitol E以及Admex 523；以及Unitex Chemical Corp.所供應之Uniplex 552、Uniplex 809及Uniplex 280。In another embodiment, the polymer solution further comprises one or more plasticizers selected from the group consisting of triphenyl phosphate, tris(ethylene glycol) bis(2-ethylhexanoic acid). Ester), tris(ethylene glycol) bis(n-octanoate); optical film enhancer 400, Abitol E and Admex 523 supplied by Eastman Chemical Company; and Uniplex 552, Uniplex 809 supplied by Unitex Chemical Corp. Uniplex 280.

依據組成物，本發明之聚合物可溶於，例如，甲苯、甲基異丁基酮、環戊酮、二氯甲烷、1,2-二氯乙烷、甲基戊基酮、甲基乙基酮、甲基異丁基酮或其混合物。Depending on the composition, the polymer of the present invention is soluble, for example, toluene, methyl isobutyl ketone, cyclopentanone, dichloromethane, 1,2-dichloroethane, methyl amyl ketone, methyl ethyl Ketone, methyl isobutyl ketone or a mixture thereof.

在一實施例中，用以澆鑄該聚合物薄膜之原料為一包含聚(α,β,β-三氟苯乙烯)與選自環戊酮、二氯甲烷及甲苯中一或多種溶劑之溶液。以此製成之聚(α,β,β-三氟苯乙烯)薄膜其正雙折射率在400 nm<λ<800 nm之波長範圍中大於0.015。在一觀點中，係將聚(α,β,β-三氟苯乙烯)之環戊酮溶液澆鑄於COP薄膜上以形成一具有加強黏性之塗層。在另一觀點中，係將聚(α,β,β-三氟苯乙烯)之甲苯溶液或聚(α,β,β-三氟苯乙烯)之甲苯與二氯甲烷及/或環戊酮混合溶液澆鑄於TAC薄膜上以形成一具有加強黏性之塗層，其中該溶劑之甲苯含量為約80-100%重量比(包括但不限於80、81、82、83、84、85、86、87、88、89、90、91、92、93、94、95、96、97、98、99及100)。In one embodiment, the material used to cast the polymer film is a solution comprising poly(α,β,β-trifluorostyrene) and one or more solvents selected from the group consisting of cyclopentanone, dichloromethane, and toluene. . The poly(α,β,β-trifluorostyrene) film thus produced has a positive birefringence of more than 0.015 in a wavelength range of 400 nm < λ < 800 nm. In one aspect, a solution of poly(α,β,β-trifluorostyrene) in cyclopentanone is cast onto a COP film to form a coating having enhanced adhesion. In another aspect, a toluene solution of poly(α,β,β-trifluorostyrene) or poly(α,β,β-trifluorostyrene) toluene with dichloromethane and/or cyclopentanone The mixed solution is cast on the TAC film to form a viscous coating, wherein the solvent has a toluene content of about 80-100% by weight (including but not limited to 80, 81, 82, 83, 84, 85, 86 , 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 and 100).

本發明之特點在於以一含氟聚合物溶液澆鑄形成一高面外雙折射率(Δn=n_z-(n_x+n_y)/2)之薄膜。製作時係於一基質上澆鑄薄塗層膜以產生一具有理想之面外延遲率(R_th)之補償薄膜。如本技藝中所週知，光學薄膜之延遲率定義為R=Δn x d，其中d為薄膜之厚度。在一實施例中，一基質上用以製造光學薄膜之塗層之厚度為約3-15 μm(包括但不限於3、4、5、6、7、8、9、10、11、12、13、14及15)，而在另一實施例中，該厚度為約8-12 μm。The invention is characterized in that a film having a high out-of-plane birefringence (Δn = n _z - (n _x + n _y ) / 2) is formed by casting a fluoropolymer solution. The thin coating film is cast on a substrate to produce a compensation film having a desired out-of-plane retardation (R _th ). As is well known in the art, the retardation rate of an optical film is defined as R = Δn xd, where d is the thickness of the film. In one embodiment, the thickness of the coating used to fabricate the optical film on a substrate is about 3-15 μm (including but not limited to 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15), and in another embodiment, the thickness is about 8-12 μm.

雙折射聚合物薄膜具有厚度方向之面外延遲率(R_th=(n_z-(n_x+n_y)/2) x d)及/或面內延遲率(R_e=(n_x-n_y) x d)，其中n_x及n_y代表面內折射率，而n_z代表薄膜之厚度方向折射率。本發明之聚合物薄膜中R_th>0且Re接近零；此種薄膜通常稱為正C板。IPS-LCD之光學補償膜結構即包含之塗佈於正A板(n_x>n_y=n_z)上之正C板(折射率範圍：n_z>n_x=n_y)。在此種結構中，C板之R_th為約45 nm至約150 nm而A板之Re為約50至約200 nm。The birefringent polymer film has an out-of-plane retardation ratio in the thickness direction (R _th =(n _z -(n _x +n _y )/2) xd) and/or an in-plane retardation rate (R _e =(n _x -n _y Xd), where n _x and n _y represent in-plane refractive indices, and n _z represents refractive index in the thickness direction of the film. The polymer film of the present invention has R _th > 0 and Re is close to zero; such a film is commonly referred to as a positive C plate. The optical compensation film structure of the IPS-LCD includes a positive C plate (refractive index range: n _z > n _x = n _y ) coated on a positive A plate (n _x > n _y = n _z ). In such a structure, the _Rth of the C plate is from about 45 nm to about 150 nm and the Re of the A plate is from about 50 to about 200 nm.

因此，在另一實施例中，本發明提供一種光學補償膜組成物，其包含一面外延遲率(R_th)為約45 nm至約150 nm之聚合物薄膜，該薄膜係以溶液澆鑄於一折射率範圍為n_x>n_y=n_z且面內延遲率(R_e)為約50 nm至約200 nm之基質上，其中該塗層之厚度為約3-10 μm(包括但不限於3、4、5、6、7、8、9，and 10)。此種基質之範例包括拉伸COP及拉伸聚碳酸酯。Accordingly, in another embodiment, the present invention provides an optical compensation film composition comprising a polymer film having an outer retardation ( _Rth ) ratio of from about 45 nm to about 150 nm, the film being solution cast in a solution a refractive index in the range of n _x >n _y = n _z and an in-plane retardation (R _e ) of from about 50 nm to about 200 nm, wherein the thickness of the coating is about 3-10 μm (including but not limited to 3, 4, 5, 6, 7, 8, 9, and 10). Examples of such substrates include stretched COP and stretched polycarbonate.

IPS-LCD之另一光學補償膜結構為具有一塗佈於雙軸薄膜(n_x>n_y>n_z)上之正C板。在此種結構中，C板之R_th為約150 nm至約250 nm而雙軸薄膜之延遲率為R_e=約60-100 nm且R_th=約-100nm至-200 nm.Another optical compensation film structure of the IPS-LCD has a positive C plate coated on a biaxial film (n _x > n _y > n _z ). In such a structure, R C plates of _th is from about 150 nm to about 250 nm and the retardation film was biaxially about R _e = R _th = 60-100 nm and about -100nm to -200 nm.

因此，在另一實施例中，本發明提供一種光學補償膜組成物，其包含一面外延遲率(R_th)為約150 nm至約250 nm之聚合物薄膜，該薄膜係以溶液澆鑄於一折射率範圍為n_x>n_y>n_z、面內延遲率(R_e)為約60 nm至約100 nm且面外延遲率(R_th)為約-100 nm至約-200 nm之基質上，其中該塗層之厚度為約8-12 μm。此種基質之範例包括拉伸纖維酯薄膜如CAP(醋酸丙酸纖維素)和TAC薄膜以及拉伸聚亞醯胺薄膜。Accordingly, in another embodiment, the present invention provides an optical compensation film composition comprising a polymer film having an outer retardation ( _Rth ) ratio of from about 150 nm to about 250 nm, the film being solution cast in a solution a matrix having a refractive index range of n _x >n _y >n _z , an in-plane retardation ratio (R _e ) of from about 60 nm to about 100 nm, and an out-of-plane retardation ratio (R _th ) of from about -100 nm to about -200 nm The thickness of the coating is about 8-12 μm. Examples of such substrates include stretched fibrous ester films such as CAP (cellulose acetate propionate) and TAC films and stretched polyamidamide films.

在上述兩種結構中，本發明之聚合物薄膜是以溶液澆鑄於如COP、聚碳酸酯、TAC和CAP之拉伸薄膜上，以取得所需之R_th與R_e組合。或者，該聚合物薄膜是澆鑄於上述材質之未拉伸薄膜上；再將產生之塗佈後基質拉伸至指定之整體R_th與R_e值。In both structures, the polymer solution of the present invention is cast on a film such as COP, polycarbonate, and the TAC of CAP stretched film, R _th _e in order to obtain the desired composition of the R. Alternatively, the polymer film is cast on the texture of the unstretched film; after coating the substrate and then stretched to produce a whole designated R _e and R _th value.

在另一實施例中，本發明之聚合物薄膜係經拉伸以產生一折射率範圍為n_x<n_y<n_z之雙軸薄膜或折射率範圍為n_x<n_y=n_z之負A板。製備此種薄膜之方法可參考美國專利申請公開案第2009/0068380號，其內容於此合併參照。In another embodiment, the polymer film of the present invention is stretched to produce a biaxial film having a refractive index range of n _x <n _y < n _z or a refractive index range of n _x <n _y = n _z Negative A plate. A method of preparing such a film is described in U.S. Patent Application Publication No. 2009/0068380, the disclosure of which is incorporated herein by reference.

在另一實施例中，該補償薄膜係用於一液晶顯示裝置，該液晶顯示裝置包括一面內切換液晶顯示裝置。該液晶顯示裝置可做為電視或電腦螢幕。In another embodiment, the compensation film is used in a liquid crystal display device including an in-plane switching liquid crystal display device. The liquid crystal display device can be used as a television or a computer screen.

範例example 範例1：聚合物薄膜製備與雙折射率測量Example 1: Polymer film preparation and birefringence measurement

將聚(α,β,β-三氟苯乙烯)(PTFS)聚合物之樣本以5%重量/體積濃度溶解於二氯甲烷中。利用葉片澆鑄法以20 mils之間距將溶液澆鑄於一平坦玻璃基質。將薄膜在空氣中靜置一夜放乾，而後置於室溫之真空烘箱8小時。乾燥後，將薄膜小心剝下。此無襯PTFS薄膜之雙折射率經Metricon型號2010/M稜鏡耦合器以單一薄膜模式在633nm之波長下測定為0.0190。A sample of the poly(α,β,β-trifluorostyrene) (PTFS) polymer was dissolved in dichloromethane at a concentration of 5% by weight/volume. The solution was cast into a flat glass substrate at a distance of 20 mils using blade casting. The film was allowed to stand in the air overnight and allowed to dry, and then placed in a vacuum oven at room temperature for 8 hours. After drying, the film was carefully peeled off. The birefringence of this linerless PTFS film was determined to be 0.0190 at a wavelength of 633 nm in a single film mode using a Metricon Model 2010/M 稜鏡 coupler.

範例2：PTFS薄膜之雙折射率與薄膜厚度之關係Example 2: Relationship between birefringence and film thickness of PTFS film

此範例說明薄膜厚度對於溶液澆鑄PTFS薄膜之雙折射率有何影響。利用範例1之方法，將以甲苯為溶劑之PTFS溶液藉由設定不同之澆鑄葉片間距澆鑄為不同厚度之PTFS薄膜，而後分別測量其雙折射率。雙折射率與厚度之關係示於圖1。如圖中可見，厚度小於2 μm時，薄膜之雙折射率隨著厚度降低而快速增加；而當厚度大於2 μm時，隨著厚度增加，薄膜之雙折射率逐步減少至一穩定值。This example illustrates the effect of film thickness on the birefringence of a solution cast PTFS film. Using the method of Example 1, the PTFS solution with toluene as a solvent was cast into PTFS films of different thicknesses by setting different casting blade pitches, and then the birefringence was measured separately. The relationship between birefringence and thickness is shown in Fig. 1. As can be seen from the figure, when the thickness is less than 2 μm, the birefringence of the film increases rapidly as the thickness decreases; and when the thickness is greater than 2 μm, the birefringence of the film gradually decreases to a stable value as the thickness increases.

範例3：PTFS薄膜之雙折射率與溶劑之關係Example 3: Relationship between birefringence and solvent of PTFS film

此範例說明溶劑對於溶液澆鑄PTFS薄膜雙折射率之影響。利用範例1之方法，分別以二氯甲烷、環戊酮及甲苯之溶液澆鑄不同厚度之PTFS薄膜，而後測量其雙折射率。雙折射率資料示於圖2。與採用甲苯者相較，以環戊酮溶液澆鑄而成之薄膜具有較高之雙折射率，而以二氯甲烷澆鑄而成之薄膜具有最高之雙折射率。This example illustrates the effect of solvent on the birefringence of a solution cast PTFS film. Using the method of Example 1, PTFS films of different thicknesses were cast with solutions of dichloromethane, cyclopentanone and toluene, respectively, and then the birefringence was measured. The birefringence data is shown in Figure 2. The film cast from the cyclopentanone solution has a higher birefringence than the one using toluene, and the film cast from methylene chloride has the highest birefringence.

範例4：PTFS薄膜之雙折射率與澆鑄條件之關係Example 4: Relationship between birefringence of PTFS film and casting conditions

此範例說明澆鑄條件對於溶液澆鑄PTFS薄膜雙折射率之影響。利用範例1之方法，以PTFS之環戊酮溶液澆鑄成不同厚度之PTFS薄膜，而後使其於不同條件下乾燥。1號薄膜首先在空氣中靜置一夜放乾而後於真空烘箱中乾燥8小時。2號薄膜首先覆蓋於盤下靜置一夜放乾而後於真空烘箱中乾燥8小時。3號薄膜首先覆蓋於盤下靜置一夜放乾，盤下另放置一杯環戊酮以產生環戊酮蒸氣，而後於真空烘箱中乾燥8小時。雙折射率資料示於圖3。未覆蓋薄膜雙折射率值最高，覆蓋薄膜雙折射率值較低，而蒸氣處理薄膜之雙折射率值最低。This example illustrates the effect of casting conditions on the birefringence of a solution cast PTFS film. Using the method of Example 1, a PTFS film of different thickness was cast with a cyclopentanone solution of PTFS, and then dried under different conditions. Film No. 1 was first allowed to stand overnight in the air and then dried in a vacuum oven for 8 hours. Film No. 2 was first placed under the pan for one night to dry and then dried in a vacuum oven for 8 hours. Film No. 3 was first placed under the pan and allowed to stand overnight to be allowed to dry. A cup of cyclopentanone was placed under the pan to produce cyclopentanone vapor, which was then dried in a vacuum oven for 8 hours. The birefringence data is shown in Figure 3. The uncovered film has the highest birefringence value, the cover film has a lower birefringence value, and the vapor treated film has the lowest birefringence value.

範例5：塑化劑對PTFS薄膜之影響Example 5: Effect of plasticizer on PTFS film

此範例說明塑化劑對於溶液澆鑄PTFS薄膜雙折射率之影響。於PTFS之二氯甲烷溶液中以5或10%之比率加入TPP(三苯基磷酸鹽)或OE-400(Eastman Chemical Company所售之光學薄膜加強劑400)做為塑化劑，按照範例1之方式澆鑄不同厚度之PTFS薄膜。如圖4所示，TPP與OE400比例增加皆會降低PTFS薄膜之雙折射率。This example illustrates the effect of a plasticizer on the birefringence of a solution cast PTFS film. TPP (triphenyl phosphate) or OE-400 (optical film enhancer 400 sold by Eastman Chemical Company) was added as a plasticizer in a ratio of 5 or 10% in a PTFS dichloromethane solution, according to Example 1. The PTFS film of different thickness is cast in the same manner. As shown in Figure 4, an increase in the ratio of TPP to OE400 reduces the birefringence of the PTFS film.

範例6：PTFS薄膜之拉伸Example 6: Stretching of PTFS film

此範例說明薄膜拉伸對面外延遲率(R_th)與面內延遲率(R_e)之影響；其亦驗證在何種拉伸率下可達成理想之R_th與R_e值。按照範例1之方式以二氯甲烷為溶劑製作PTFS薄膜；將製成之薄膜用於拉伸。以20mm/min之速率在220℃下進行單軸拉伸。測量拉伸薄膜在三正交方向上之折射率並將結果示於圖5。下標x代表拉伸方向；y代表面內垂直方向；而z代表薄膜法線方向。拉伸時，n_x減少而n_y與n_z皆呈現增加。面內與面外雙折射率兩者之絕對值皆隨拉伸增加而上升，如圖6所示。This example illustrates the effect of film stretching on the out-of-plane retardation (R _th ) and in-plane retardation (R _e ); it also verifies at which elongation ratios the desired R _th and R _e values can be achieved. A PTFS film was prepared in the same manner as in Example 1 using dichloromethane as a solvent; the resulting film was used for stretching. Uniaxial stretching was carried out at 220 ° C at a rate of 20 mm/min. The refractive index of the stretched film in the three orthogonal directions was measured and the results are shown in Fig. 5. The subscript x represents the stretching direction; y represents the in-plane vertical direction; and z represents the film normal direction. When stretched, n _x decreases while n _y and n _{z both} increase. The absolute values of both in-plane and out-of-plane birefringence increase with increasing tensile, as shown in FIG.

範例7：聚合物塗層之製備與雙折射率測量Example 7: Preparation and Birefringence Measurement of Polymer Coatings TAC基質上之PTFS塗層：PTFS coating on TAC substrate:

將PTFS聚合物以5%重量/體積濃度溶解於甲苯。利用葉片澆鑄法以8 mils之間距將溶液澆鑄於一平坦TAC基質。將塗層在空氣中靜置一夜放乾，而後置於真空烘箱8小時。此PTFS/TAC塗層之雙折射率經Metricon型號2010/M稜鏡耦合器以單一薄膜模式在633nm之波長下測定為0.0189。由於PTFS之折射率高於TAC，以單一薄膜模式測量頂部PTFS塗層不會受到TAC基質所影響。The PTFS polymer was dissolved in toluene at a concentration of 5% by weight/volume. The solution was cast into a flat TAC substrate by blade casting at a distance of 8 mils. The coating was allowed to stand overnight in the air and allowed to dry in a vacuum oven for 8 hours. The birefringence of this PTFS/TAC coating was determined to be 0.0189 in a single film mode at a wavelength of 633 nm using a Metricon Model 2010/M(R) coupler. Since the refractive index of PTFS is higher than TAC, the top PTFS coating measured in a single film mode is not affected by the TAC matrix.

COP基質上之PTFS塗層：PTFS coating on COP substrate:

將PTFS聚合物以5%重量/體積濃度溶解於環戊酮(Cp)。利用葉片澆鑄法以8mils之間距將溶液澆鑄於一平坦COP基質。將塗層在空氣中靜置一夜放乾，而後置於真空烘箱8小時。此PTFS/COP塗層之雙折射率經Metricon型號2010/M稜鏡耦合器以單一薄膜模式在633nm之波長下測定為0.0190。The PTFS polymer was dissolved in cyclopentanone (Cp) at a concentration of 5% by weight/volume. The solution was cast into a flat COP matrix at a distance of 8 mils using blade casting. The coating was allowed to stand overnight in the air and allowed to dry in a vacuum oven for 8 hours. The birefringence of this PTFS/COP coating was determined to be 0.0190 at a wavelength of 633 nm in a single film mode using a Metricon Model 2010/M(R) coupler.

範例8：不同PTFS塗層之雙折射率Example 8: Birefringence of different PTFS coatings

此範例比較利用不同基質及/或不同溶劑製成之PTFS塗層其雙折射率數值。利用範例7所述之方式，分別以甲苯、甲苯/CH₂Cl₂(9/1重量比)及甲苯/Cp(9/1重量比)為溶劑在TAC上製備三種PTFS塗層，測定其不同厚度之雙折射率。將結果與COP上之PTFS塗層(溶劑：Cp)和以甲苯溶液澆鑄成之無襯薄膜比較。如圖7所示，TAC上以甲苯和甲苯/CH₂Cl₂摻合物製成之PTFS塗層其雙折射率值相仿，皆略高於無襯薄膜，TAC上以甲苯/Cp摻合物製成之塗層其雙折射率值低於無襯薄膜。甲苯或甲苯/CH₂Cl₂在COP上與在TAC上之PTFS塗層其雙折射率相當。This example compares the birefringence values of PTFS coatings made with different matrices and/or different solvents. Three PTFS coatings were prepared on TAC using toluene, toluene/CH ₂ Cl ₂ (9/1 by weight) and toluene/Cp (9/1 by weight) as solvents in the manner described in Example 7, and the differences were determined. The birefringence of the thickness. The results were compared to a PTFS coating on COP (solvent: Cp) and a linerless film cast in a toluene solution. As shown in Figure 7, the PTFS coatings on TAC with toluene and toluene/CH ₂ Cl ₂ blends have similar birefringence values, slightly higher than linerless films, and toluene/Cp blends on TAC. The resulting coating has a lower birefringence value than the linerless film. Toluene or toluene/CH ₂ Cl ₂ is comparable in COP to the birefringence of the PTFS coating on TAC.

範例9：PTFS薄膜與塗層之延遲率及波長分散Example 9: Delay rate and wavelength dispersion of PTFS film and coating

以 Ellipsometer(J. A. Woollam Co.,Inc.販售)測量二氯甲烷所製PTFS無襯薄膜之與COP上兩種不同厚度PTFS塗層(溶劑：Cp)之延遲率。各樣本之面外延遲率示於圖8。圖8中PTFS薄膜之延遲率曲線以550nm之延遲率值常態化，以利說明波長分散。如圖9所示，PTFS薄膜之Rth/Rth₅₅₀值在400nm-800nm之波長範圍中於1.09至0.95間微幅變化。圖9繪示理論適配，其與實驗曲線完全重疊。理論適配係基於式Rth ，其中G為一材料和程序相關常數，而λ _r為材料基本光原單元之共振波長。160nm為PTFS之最佳λ _r配適值。Take Ellipsometer (sold by JA Woollam Co., Inc.) measures the retardation of two different thickness PTFS coatings (solvent: Cp) on a PTFS linerless film made of methylene chloride and COP. The out-of-plane retardation rate of each sample is shown in Fig. 8. The retardation curve of the PTFS film in Fig. 8 is normalized with a retardation value of 550 nm to illustrate the wavelength dispersion. As shown in FIG. 9, the Rth/Rth ₅₅₀ value of the PTFS film varies slightly from 1.09 to 0.95 in the wavelength range of 400 nm to 800 nm. Figure 9 depicts the theoretical adaptation, which completely overlaps the experimental curve. Theoretical adaptation is based on the formula Rth Where G is a material and a program-dependent constant, and λ _r is the resonant wavelength of the material's basic photon unit. 160 nm is the optimum λ _r matching value for PTFS.

以上已就實施例加以說明。熟悉此技藝人士應知可在不脫離本發明範疇之原則下就上述方法與設備進行變更及調整。在所附申請專利範圍或其相等物之範疇內所為任何變更與調整均應包含於本發明之中。雖然以上敘述包含諸多具體內容，但其僅為說明本發明之部分實施例，而不應對本發明之範疇構成限制。本發明更應包含其他各種實施例與實施方式。The embodiments have been described above. It will be apparent to those skilled in the art that changes and modifications may be made in the above methods and apparatus without departing from the scope of the invention. Any changes and modifications within the scope of the appended claims or their equivalents are intended to be included in the invention. The description above contains many specifics, and is merely illustrative of some embodiments of the invention and should not be construed as limiting the scope of the invention. The invention should include other various embodiments and implementations.

此外，雖然特定範例中所列舉之數字已力求精確，但任何數值因其各自測試方式標準偏差之故，必然包含一定之誤差，是以應知設定本發明範圍之數值範圍及參數乃為近似值。In addition, although the numerical values set forth in the specific examples are intended to be accurate, any numerical values are necessarily inconsistent with the standard deviations of the respective test methods, and the numerical ranges and parameters that set the scope of the invention are approximations.

本案說明與附圖係說明本發明之至少一實施例，且各實施例係於所附申請專利範圍中具體明確指出。The description and drawings are intended to be illustrative of the embodiments of the invention

圖1顯示PTFS薄膜(以甲苯溶液經葉片澆鑄而成)雙折射率與薄膜厚度之關係。Figure 1 shows the relationship between the birefringence of a PTFS film (casted in a toluene solution by a blade) and the film thickness.

圖2顯示PTFS薄膜雙折射率與溶劑之關係。Figure 2 shows the relationship between the birefringence of a PTFS film and a solvent.

圖3顯示PTFS薄膜雙折射率與澆鑄條件之關係。Figure 3 shows the relationship between the birefringence of the PTFS film and the casting conditions.

圖4顯示塑化劑對於PTFS薄膜雙折射率之影響。Figure 4 shows the effect of plasticizer on the birefringence of PTFS films.

圖5顯示拉伸PTFS薄膜之折射率。Figure 5 shows the refractive index of a stretched PTFS film.

圖6顯示拉伸PTFS薄膜之雙折射率。Figure 6 shows the birefringence of a stretched PTFS film.

圖7顯示基質上PTFS塗層之雙折射率。Figure 7 shows the birefringence of the PTFS coating on the substrate.

圖8顯示PTFS薄膜與COP上塗層之延遲率。Figure 8 shows the retardation of the PTFS film and the COP topcoat.

圖9顯示PTFS薄膜常態化延遲率與理論適配。Figure 9 shows the theoretical adaptation of the normalization delay rate of PTFS films.

Claims

一種光學補償膜組成物，其係包含一聚合物薄膜以及一基質，其中該聚合物薄膜之正雙折射率於400 nm<λ<800 nm之波長範圍內係大於0.005，該薄膜係以一包含一溶劑及一聚合物之聚合物溶液澆鑄而成，所述聚合物具有以下基元其中R¹、R²及R³係各自為氫原子、烷基、取代烷基，或鹵素，其中R¹、R²及R³中之至少一者為氟原子，且其中R為氫或苯乙烯系環上之一取代基。An optical compensation film composition comprising a polymer film and a substrate, wherein the polymer film has a positive birefringence of more than 0.005 in a wavelength range of 400 nm < λ < 800 nm, and the film is included a solvent and a polymer solution of a polymer having the following primitives Wherein R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group, a substituted alkyl group, or a halogen, wherein at least one of R ¹ , R ² and R ³ is a fluorine atom, and wherein R is hydrogen or benzene One of the substituents on the vinyl ring.

如申請專利範圍第1項所述之光學補償膜，其中R¹、R²及R³中至少二者為氟原子。The optical compensation film of claim ¹ , wherein at least two of R ¹ , R ² and R ³ are fluorine atoms.

如申請專利範圍第1項所述之光學補償膜，其中R¹、R²及R³皆為氟原子。The optical compensation film of claim 1, wherein R ¹ , R ² and R ³ are each a fluorine atom.

如申請專利範圍第1項所述之光學補償膜，其中R¹、R²及R³為氟原子而R為一氫原子。The optical compensation film of claim 1, wherein R ¹ , R ² and R ³ are a fluorine atom and R is a hydrogen atom.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物係選自包含以下同聚物之群組：α,β,β-三氟苯乙烯、α,β-二氟苯乙烯、β,β-二氟苯乙烯、α-氟苯乙烯，以及β-氟苯乙烯。The optical compensation film of claim 1, wherein the polymer is selected from the group consisting of: α,β,β-trifluorostyrene, α,β-difluorostyrene, ,,β-difluorostyrene, α-fluorostyrene, and β-fluorostyrene.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物係選為聚(α,β,β-三氟苯乙烯)。The optical compensation film of claim 1, wherein the polymer is selected from the group consisting of poly(α,β,β-trifluorostyrene).

如申請專利範圍第1項所述之光學補償膜，其中該溶劑係選自包含以下溶劑之群組中之一或多種溶劑：甲苯、甲基異丁基酮、環戊酮、二氯甲烷、1,2-二氯乙烷、甲基戊基酮、甲基乙基酮，以及甲基異丁基酮。The optical compensation film of claim 1, wherein the solvent is selected from one or more of the group consisting of toluene, methyl isobutyl ketone, cyclopentanone, dichloromethane, 1,2-dichloroethane, methyl amyl ketone, methyl ethyl ketone, and methyl isobutyl ketone.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物薄膜之正雙折射率在400 nm<λ<800 nm之波長範圍內係大於0.01。The optical compensation film of claim 1, wherein the positive refractive index of the polymer film is greater than 0.01 in a wavelength range of 400 nm < λ < 800 nm.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物薄膜之正雙折射率在400 nm<λ<800 nm之波長範圍內係大於0.015。The optical compensation film of claim 1, wherein the positive refractive index of the polymer film is greater than 0.015 in a wavelength range of 400 nm < λ < 800 nm.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物薄膜之正雙折射率在400 nm<λ<800 nm之波長範圍內係大於0.015，該薄膜係以一溶液澆鑄而成，所述溶液包含聚(α,β,β-三氟苯乙烯)及一或多種溶劑，該一或多種溶劑係選自包含甲苯、環戊酮及二氯甲烷之群組。The optical compensation film according to claim 1, wherein the positive refractive index of the polymer film is greater than 0.015 in a wavelength range of 400 nm < λ < 800 nm, and the film is cast in a solution. The solution comprises poly(α,β,β-trifluorostyrene) and one or more solvents selected from the group consisting of toluene, cyclopentanone, and dichloromethane.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物薄膜之製作係於該基質上進行澆鑄以於該基質上形成一塗層。The optical compensation film of claim 1, wherein the polymer film is produced by casting on the substrate to form a coating on the substrate.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物薄膜之正雙折射率在400 nm<λ<800 nm之波長範圍內係大於0.015，該薄膜之製作係以一包含聚(α,β,β-三氟苯乙烯)之溶液澆鑄於該基質上而形成一塗層。The optical compensation film of claim 1, wherein the positive refractive index of the polymer film is greater than 0.015 in a wavelength range of 400 nm < λ < 800 nm, and the film is formed by a poly ( A solution of α,β,β-trifluorostyrene) is cast onto the substrate to form a coating.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物薄膜之正雙折射率在400 nm<λ<800 nm之波長範圍內係大於0.015，該薄膜之製作係以一溶液澆鑄於該基質上而形成一塗層，所述溶液包含聚(α,β,β-三氟苯乙烯)及一或多種溶劑，該一或多種溶劑係選自包含甲苯、環戊酮及二氯甲烷之群組。The optical compensation film of claim 1, wherein the polymer film has a positive birefringence of more than 0.015 in a wavelength range of 400 nm < λ < 800 nm, and the film is produced by casting a solution. Forming a coating on the substrate, the solution comprising poly(α,β,β-trifluorostyrene) and one or more solvents selected from the group consisting of toluene, cyclopentanone and dichloromethane Group of.

如申請專利範圍第13項所述之光學補償膜，其中該溶劑為環戊酮，且該基質為一環烴烯聚合物(COP)。The optical compensation film of claim 13, wherein the solvent is cyclopentanone, and the substrate is a cyclic hydrocarbon polymer (COP).

如申請專利範圍第13項所述之光學補償膜，其中該溶劑係選自由甲苯、甲苯摻合二氯甲烷、甲苯摻合環戊酮，及其混合物所構成之群組，且該基質為一纖維酯薄膜或三醋酸纖維素(TAC)薄膜，其中該溶劑之甲苯含量為約80-100%重量比。The optical compensation film according to claim 13, wherein the solvent is selected from the group consisting of toluene, toluene blended with dichloromethane, toluene blended with cyclopentanone, and a mixture thereof, and the substrate is a A fibrous ester film or a cellulose triacetate (TAC) film, wherein the solvent has a toluene content of about 80 to 100% by weight.

如申請專利範圍第12項所述之光學補償膜，其中該基質為A板，其折射率範圍為n_x>n_y=n_z，且面內延遲率(R_e)為約50 nm至約200 nm，其中該塗層之面外延遲率(R_th)為約45 nm至約150 nm且厚度為約3-10 μm。The optical compensation film of claim 12, wherein the substrate is an A plate having a refractive index range of n _x >n _y = n _z and an in-plane retardation ratio (R _e ) of from about 50 nm to about 200 nm, wherein the coating has an out-of-plane retardation ( _Rth ) of from about 45 nm to about 150 nm and a thickness of about 3-10 μm.

如申請專利範圍第12項所述之光學補償膜，其中該基質為一雙軸薄膜，其折射率範圍為n_x>n_y>n_z，面內延遲率(R_e)為約60-100 nm，且面外延遲率(R_th)為約-100 nm至-200 nm，其中該塗層之面外延遲率(R_th)為約150 nm至約250 nm且厚度為約8-12 μm。The optical compensation film of claim 12, wherein the substrate is a biaxial film having a refractive index range of n _x >n _y >n _z and an in-plane retardation ratio (R _e ) of about 60-100. Nm, and the out-of-plane retardation rate (R _th ) is about -100 nm to -200 nm, wherein the coating has an out-of-plane retardation (R _th ) of about 150 nm to about 250 nm and a thickness of about 8-12 μm. .

如申請專利範圍第1項所述之光學補償膜，其中該溶液澆鑄聚合物薄膜係貼合於該基質之上。The optical compensation film of claim 1, wherein the solution cast polymer film is attached to the substrate.

如申請專利範圍第1項所述之光學補償膜，其中該溶液澆鑄聚合物薄膜係經單軸或雙軸拉伸後貼合於該基質之上。The optical compensation film of claim 1, wherein the solution cast polymer film is uniaxially or biaxially stretched and attached to the substrate.

如申請專利範圍第11項所述之光學補償膜，其中該塗佈後之基質再經單軸或雙軸拉伸。The optical compensation film of claim 11, wherein the coated substrate is further uniaxially or biaxially stretched.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物係一α,β,β-三氟苯乙烯與一或多種乙烯性不飽和單體之共聚物。The optical compensation film of claim 1, wherein the polymer is a copolymer of α,β,β-trifluorostyrene and one or more ethylenically unsaturated monomers.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物係一α,β,β-三氟苯乙烯與一或多種乙烯性不飽和單體之共聚物，所述乙烯性不飽和單體係選自包含以下項目之群組：丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、異丙烯酸丁酯、異甲基丙烯酸丁酯、乙基己基丙烯酸酯、2-甲基丙烯酸乙基己酯、2-乙基己基丙烯酸酯、異戊二烯、丙烯酸辛酯、甲基丙烯酸辛酯、丙烯酸異辛酯、甲基丙烯酸異辛酯、三甲基丙基三丙烯酸酯、苯乙烯、α-甲基苯乙烯、硝基苯乙烯、溴苯乙烯、碘苯乙烯、氰基苯乙烯、氯苯乙烯、4-叔丁基苯乙烯、4-甲基苯乙烯、乙烯基聯苯、乙烯基三苯基、乙烯基甲苯、氯甲基苯乙烯、丙烯酸、甲基丙烯酸、亞甲基丁二酸、反式丁烯酸、順丁烯二酸酐、四氟乙烯、氟乙烯、甲基丙烯酸縮水甘油酯、碳化二亞胺甲基丙烯酸、C₁-C₁₈烷基丁烯酸酯、馬來酸二正丁酯、馬來酸二辛酯、甲基丙烯酸烯丙酯、馬來酸二烯丙酯、丙二酸二烯丙酯、甲基丙烯酸甲氧基丁酯、異冰片甲基丙烯酸酯、甲丙烯醯酸羥基丁酯、甲基丙烯酸羥乙酯、甲基丙烯酸羥丙酯、乙醯基乙醯氧基甲基丙烯酸乙酯、乙醯基乙醯氧基丙烯酸乙酯、丙烯清、氯乙烯、二氯乙烯、醋酸乙烯酯、乙烯基碳酸乙烯酯、環氧丁烷、3,4-二羥基丁烷、甲基丙烯酸羥乙酯、甲基丙烯醯胺、丙烯醯胺、丁基丙烯醯胺、乙基丙烯醯胺、二丙酮丙烯醯胺、丁二烯、乙烯酯單體、甲基丙烯酸乙烯酯、甲基丙烯酸異丙酯、脂環環氧甲基丙烯酸酯、乙基甲醯胺、4-乙烯基-1,3-二氧戊環-2-酮、2,2-二甲基-4-乙烯基-1,3-二氧戊環、3,4-二醋酸基-1-丁烯，及單乙烯基己二酸叔丁基胺基甲基丙烯酸乙酯、二甲基胺基甲基丙烯酸乙酯、二乙基胺基甲基丙烯酸乙酯、N,N-二甲基胺基丙基甲基丙烯醯胺、2-叔丁基胺基甲基丙烯酸乙酯、N,N-二甲基胺基丙烯酸乙酯、N-(2-甲基丙烯醯氧乙基)乙烯脲，以及甲基丙烯醯胺基乙基乙烯脲。The optical compensation film of claim 1, wherein the polymer is a copolymer of α,β,β-trifluorostyrene and one or more ethylenically unsaturated monomers, the ethylenic unsaturated The single system is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, butyl isoacrylate, isomethyl Butyl acrylate, ethylhexyl acrylate, ethylhexyl 2-methyl acrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, isooctyl acrylate, methyl Isooctyl acrylate, trimethyl propyl triacrylate, styrene, α-methyl styrene, nitrostyrene, bromostyrene, iodine styrene, cyanostyrene, chlorostyrene, 4-tert-butyl Styrene, 4-methylstyrene, vinylbiphenyl, vinyltriphenyl, vinyltoluene, chloromethylstyrene, acrylic acid, methacrylic acid, methylene succinic acid, transbutenoic acid , maleic anhydride, tetrafluoroethylene, vinyl fluoride, methacrylic acid shrinkage Oily esters, carbodiimide methacrylate, C ₁ -C ₁₈ alkyl crotonate, n-butyl maleate, dioctyl maleate, allyl methacrylate, diallyl maleate Propyl ester, diallyl malonate, methoxybutyl methacrylate, isobornyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, B Ethyl mercapto ethoxyethyl methacrylate, ethyl ethoxylated ethyl acrylate, propylene, vinyl chloride, dichloroethylene, vinyl acetate, vinyl ethylene carbonate, butylene oxide, 3, 4-dihydroxybutane, hydroxyethyl methacrylate, methacrylamide, acrylamide, butyl acrylamide, ethyl acrylamide, diacetone acrylamide, butadiene, vinyl ester monomer , vinyl methacrylate, isopropyl methacrylate, alicyclic epoxy methacrylate, ethyl formamide, 4-vinyl-1,3-dioxolan-2-one, 2, 2 - dimethyl-4-vinyl-1,3-dioxolane, 3,4-diacetoxy-1-butene, and tert-butylaminoethyl methacrylate, monovinyl adipate, Dimethylamino group Ethyl acrylate, diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylamide, 2-tert-butylaminoethyl methacrylate, N,N- Ethyl dimethyl methacrylate, N-(2-methylpropenyl oxyethyl) ethylene urea, and methacrylamidoethylethylene urea.

如申請專利範圍第22項所述之光學補償膜，其中該聚合物係一α,β,β-三氟苯乙烯與一或多種乙烯性不飽和單體之共聚物，所述乙烯性不飽和單體係選自由苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、2-乙基己基丙烯酸酯、丙烯酸、甲基丙烯酸、α-甲基苯乙烯、4-甲基苯乙烯、乙烯基聯苯、丙烯清以及異戊二烯所構成之群組。The optical compensation film of claim 22, wherein the polymer is a copolymer of α,β,β-trifluorostyrene and one or more ethylenically unsaturated monomers, the ethylenic unsaturated The single system is selected from the group consisting of styrene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, α-methyl styrene, 4 a group consisting of methyl styrene, vinyl biphenyl, propylene clear and isoprene.

如申請專利範圍第1項所述之光學補償膜，其中R為選自包含烷基、取代烷基、鹵素、羥基、羧基、硝基、烷氧基、胺基、磺酸鹽、磷酸鹽、醯基、醯氧基、苯基、烷氧羰基以及氰基之群組中之一或多種取代基。The optical compensation film of claim 1, wherein R is selected from the group consisting of an alkyl group, a substituted alkyl group, a halogen, a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an amine group, a sulfonate salt, a phosphate salt, One or more substituents in the group of anthracenyl, anthracenyloxy, phenyl, alkoxycarbonyl, and cyano groups.

如申請專利範圍第1項所述之光學補償膜，其中該聚合物溶液更包含一塑化劑，塑化劑係選自包含三苯基磷酸鹽、三(乙烯乙二醇)雙(2-乙基己酸酯)、三(乙烯乙二醇)雙(正辛酸酯)、氫化松香、雙質子酸乙二醇聚酯、季戊四醇四苯甲酸酯、聚乙烯乙二醇二-2-乙基己酸酯以及蔗糖苯甲酸酯之群組。The optical compensation film according to claim 1, wherein the polymer solution further comprises a plasticizer, and the plasticizer is selected from the group consisting of triphenyl phosphate and tris(ethylene glycol) bis (2- Ethylhexanoate), tris(ethylene glycol) bis(n-octanoate), hydrogenated rosin, diprotic acid ethylene glycol polyester, pentaerythritol tetrabenzoate, polyethylene glycol di-2- Group of ethyl hexanoate and sucrose benzoate.

如申請專利範圍第1項所述之光學補償膜，其中該薄膜不經過熱處理、光輻射或拉伸。The optical compensation film of claim 1, wherein the film is not subjected to heat treatment, light irradiation or stretching.