TW202231746A - 基於苯乙烯氟聚合物及丙烯酸共聚物之光學膜 - Google Patents
基於苯乙烯氟聚合物及丙烯酸共聚物之光學膜 Download PDFInfo
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- TW202231746A TW202231746A TW110146866A TW110146866A TW202231746A TW 202231746 A TW202231746 A TW 202231746A TW 110146866 A TW110146866 A TW 110146866A TW 110146866 A TW110146866 A TW 110146866A TW 202231746 A TW202231746 A TW 202231746A
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- optical compensation
- compensation film
- film
- weight
- acrylic copolymer
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- 239000004811 fluoropolymer Substances 0.000 title abstract description 9
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 19
- 238000001228 spectrum Methods 0.000 claims description 17
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 12
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 9
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 9
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
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- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
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- AHVOFPQVUVXHNL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C=C AHVOFPQVUVXHNL-UHFFFAOYSA-N 0.000 description 1
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- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- NXMXPVQZFYYPGD-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;methyl prop-2-enoate Chemical compound COC(=O)C=C.COC(=O)C(C)=C NXMXPVQZFYYPGD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
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- C08F112/20—Fluorine
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- G—PHYSICS
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
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- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
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Abstract
本發明提供基於自苯乙烯氟聚合物及丙烯酸共聚物之特定組合物形成之聚合物摻合物之光學補償膜。該等光學補償膜具有所需機械性質及光學性質,諸如霧度、斷裂伸長率、楊氏(Young’s)模量、平面內阻滯及平面外阻滯。該等光學補償膜適用於顯示裝置,諸如於電視、電腦、汽車及行動電話中之彼等。
Description
本發明係關於基於苯乙烯氟聚合物及丙烯酸共聚物之光學補償膜。苯乙烯氟聚合物具有與特定丙烯酸共聚物組合物之特佳相容性。自本文中所揭示之苯乙烯氟聚合物及丙烯酸共聚物組合物製備之聚合物膜提供所需機械性質及光學性質,諸如霧度、斷裂伸長率、楊氏(Young’s)模量、平面內阻滯及平面外阻滯。本發明之聚合物膜可用作顯示裝置(諸如電視、電腦、汽車及行動電話中之彼等)中之光學補償膜。
於此項技術中熟知聚合物膜可用作顯示裝置(諸如行動電話及電視中之彼等)中之光學補償膜以提高觀看品質。此等聚合物膜必須具有特佳光學清晰度以及某些平面內及平面外阻滯值以補償因光以各種角度於顯示裝置(諸如液晶顯示器(LCD))中行進所致之相差異。
為獲得所需阻滯值,通常需要具有不同物理性質及光學性質之兩種聚合物。首先,將兩種聚合物藉由摻合或擠出混合以得到聚合物膜。然後將因此獲得之膜拉伸以產生所需平面內及平面外阻滯值。此可僅藉由使用除了具有所需光學性質外具有特佳相容性之兩種聚合物達成。否則,聚合物膜不可滿足嚴格清晰度要求。美國專利第10,088,615號(下文中「‘615專利」)揭示苯乙烯氟聚合物,諸如聚(α,β,β-三氟苯乙烯),具有與常見聚合物,諸如聚醯亞胺、聚醯胺、聚酯、纖維素酯及環狀聚烯烴(COP)之特差相容性,可能由於其缺少極性基團以與其他聚合物中之官能基相互作用以及其不能形成氫鍵。將苯乙烯氟聚合物溶液與其他聚合物溶液混合之嘗試通常導致不均勻混合物或渾濁溶液;因此,具有良好清晰度之聚合物膜難以製備。‘615專利亦揭示某些丙烯酸聚合物具有與苯乙烯氟聚合物之出人意料良好的相容性。可製備透明均勻溶液,及其澆鑄聚合物膜具有適用於光學裝置中之應用之高的光透射率。然而,‘615專利未揭示能提供具有特定機械性質及光學性質(諸如斷裂伸長率、楊氏模量、平面內阻滯及平面外阻滯)之光學補償膜之聚合物組合物。此外,該膜必須展示良好熱性質及機械性質以忍受嚴峻拉伸條件。最後,僅若該膜滿足阻滯規格,則其可係可用的。因此,此等材料之發現需要技術突破。
本文中揭示基於自聚(α,β,β-三氟苯乙烯)及丙烯酸共聚物之特定組合物形成之聚合物摻合物的光學補償膜。該等光學補償膜提供所需機械性質及光學性質,諸如霧度、斷裂伸長率、楊氏模量、平面內阻滯及平面外阻滯,使得光學補償膜特別可用於各種顯示裝置(諸如電視、電腦、汽車及行動電話中之彼等)中。
根據本發明,揭示光學補償膜。本發明之光學補償膜包含:
a.聚(α,β,β-三氟苯乙烯);及
b.藉由包含以下之單體之聚合製備之丙烯酸共聚物:
i.以基於(i)及(ii)之總重量計70重量%至95重量%之量之甲基丙烯酸甲酯(MMA);及
ii.以基於(i)及(ii)之總重量計5重量%至30重量%之量之一或多種非MMA的乙烯性不飽和單體,該乙烯性不飽和單體選自包含丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正己酯、甲基丙烯酸正己酯、丙烯酸2-甲氧基乙酯、丙烯酸2-乙基己酯及甲基丙烯酸2-乙基己酯之群,
其中該丙烯酸共聚物具有65℃至98℃之玻璃化轉變溫度(T
g),且其中該光學補償膜具有在15 µm至50 µm之膜厚度下量測之小於2.25%之霧度、5%至15%之斷裂伸長率及2 GPa至4 GPa之楊氏模量。
根據本發明,該等光學補償膜可經單軸或雙軸拉伸。於實施例中,該經拉伸之光學補償膜為具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-80 nm至-300 nm之平面內阻滯(R
e)及40 nm至200 nm之平面外阻滯(R
th)的負性A-板或正性雙軸膜。於實施例中,該經拉伸之光學補償膜為具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-100 nm至-200 nm之平面內阻滯(R
e)及50 nm至150 nm之平面外阻滯(R
th)的負性A-板或正性雙軸膜。於實施例中,該經拉伸之光學補償膜為具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-10 nm至10 nm之平面內阻滯(R
e)及50 nm至150 nm之平面外阻滯(R
th)的正性C-板。
根據本發明,提供多層膜。於實施例中,該多層膜包含本發明之光補償膜,其為負性A-板或正性C-板,及具有n
x>n
y=n
z之折射率譜之正性A-板,其中n
x及n
y表示平面內折射率,且n
z表示厚度折射率。於實施例中,該多層膜包含本發明之光學補償膜,其為正性雙軸膜,及具有n
x>n
y>n
z之折射率譜之負性雙軸膜,其中n
x及n
y表示平面內折射率,且n
z表示厚度折射率。
本發明之其他態樣將自以下之描述顯然。
本文中描述基於自聚(α,β,β-三氟苯乙烯)及丙烯酸共聚物之特定組合物形成之聚合物摻合物的光學補償膜。本發明者出人意料地發現,聚(α,β,β-三氟苯乙烯)及丙烯酸共聚物之特定組合物提供具有所需機械性質及光學性質(諸如霧度、斷裂伸長率、楊式模量、平面內阻滯及平面外阻滯)之光學補償膜。
根據本發明,提供光學補償膜,該光學補償膜包含:
a.聚(α,β,β-三氟苯乙烯);及
b.藉由包含以下之單體之聚合製備之丙烯酸共聚物:
i.以基於(i)及(ii)之總重量計70重量%至95重量%之量之甲基丙烯酸甲酯(MMA);及
ii.以基於(i)及(ii)之總重量計5重量%至30重量%之量之一或多種非MMA的乙烯性不飽和單體,該乙烯性不飽和單體選自包含丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正己酯、甲基丙烯酸正己酯、丙烯酸2-甲氧基乙酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯及其組合之群,
其中該丙烯酸共聚物具有65℃至98℃之玻璃化轉變溫度(T
g),且其中該光學補償膜具有在15 µm至50 µm之膜厚度下量測之小於2.25%之霧度、5%至15%之斷裂伸長率及2 GPa至4 GPa之楊氏模量。
根據本發明之一些態樣,提供光學補償膜,該光學補償膜包含:
a.聚(α,β,β-三氟苯乙烯);及
b.藉由包含以下之單體之聚合製備之丙烯酸共聚物:
i.以基於(i)及(ii)之總重量計80重量%至90重量%之量之甲基丙烯酸甲酯(MMA);及
ii.以基於(i)及(ii)之總重量計10重量%至20重量%之量之一或多種非MMA的乙烯性不飽和單體,該乙烯性不飽和單體選自由丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯及其組合組成之群,
其中該丙烯酸共聚物具有85℃至98℃之玻璃化轉變溫度(T
g),且其中該光學補償膜具有在15 µm至50 µm之膜厚度下量測之小於0.5%之霧度、7%至15%之斷裂伸長率及2.5 GPa至3.5 GPa之楊氏模量。
用於製備聚(α,β,β-三氟苯乙烯) (PTFS)之方法係此項技術中已知且已揭示於(例如)美國專利第8,871,882號中,其全文係以引用的方式併入本文中。根據一些態樣,存在於本發明之光學補償膜中之PTFS具有200,000 g/莫耳至800,000 g/莫耳之重量平均分子量(M
w),包含225,000 g/莫耳至750,000 g/莫耳之M
w、250,000 g/莫耳至700,000 g/莫耳之M
w、275,000 g/莫耳至650,000 g/莫耳之M
w、300,000 g/莫耳至600,000 g/莫耳之M
w、325,000 g/莫耳至550,000 g/莫耳之M
w、350,000 g/莫耳至500,000 g/莫耳之M
w、375,000 g/莫耳至450,000 g/莫耳之M
w,及亦包含390,000 g/莫耳至425,000 g/莫耳之M
w,如藉由凝膠滲透層析法(GPC)所量測(聚苯乙烯等效物)。根據一些態樣,存在於本發明之光學補償膜中之PTFS具有200℃至220℃之玻璃化轉變溫度(T
g),包含200℃至215℃之T
g、200℃至210℃之T
g,及亦包含202℃至208℃之T
g,如藉由示差掃描量熱法(DSC)所測定。根據一些態樣,存在於本發明之光學補償膜中之PTFS具有390,000 g/莫耳至425,000 g/莫耳之M
w及202℃至208℃之T
g。
存在於光學補償膜中之丙烯酸共聚物為甲基丙烯酸甲酯(MMA)及一或多種非MMA的乙烯性不飽和單體之共聚物,該乙烯性不飽和單體選自包含以下或由以下組成之群:丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正己酯、甲基丙烯酸正己酯、丙烯酸2-甲氧基乙酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯及其組合。其他適宜單體包括甲基丙烯酸乙酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸異辛酯及甲基丙烯酸異辛酯。期望地,非MMA的丙烯酸酯或甲基丙烯酸酯單體之烷基具有少於8個碳原子。於一個態樣中,存在於光學補償膜中之丙烯酸共聚物為MMA及一或多種選自由丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯及丙烯酸2-乙基己酯組成之群之其他單體之共聚物。
根據本文中所述之光學補償膜之一些態樣,存在於光學補償膜中之聚(α,β,β-三氟苯乙烯)之量可為10重量%至60重量%,包含20重量%至50重量%、25重量%至45重量%,及亦包含30重量%至40重量%,其中該重量%係基於存在於光學補償膜中之聚(α,β,β-三氟苯乙烯)及丙烯酸共聚物之總重量計。相似地,根據本文中所述之光學補償膜之一些態樣,存在於光學補償膜中之丙烯酸共聚物之量可為40重量%至90重量%,包含50重量%至80重量%、55重量%至75重量%,及亦包含60重量%至70重量%,其中該重量%係基於存在於光學補償膜中之聚(α,β,β-三氟苯乙烯)及丙烯酸共聚物之總重量計。根據本文中所述之光學補償膜之一些態樣,存在於光學補償膜中之聚(α,β,β-三氟苯乙烯)之量可為25重量%至45重量%及存在於光學補償膜中之丙烯酸共聚物之量可為55重量%至75重量%,其中該重量%係基於存在於光學補償膜中之聚(α,β,β-三氟苯乙烯)及丙烯酸共聚物之總重量計。根據本文中所述之光學補償膜之一些態樣,存在於光學補償膜中之聚(α,β,β-三氟苯乙烯)之量可為30重量%至45重量%及存在於光學補償膜中之丙烯酸共聚物之量可為55重量%至70重量%,其中該重量%係基於存在於光學補償膜中之聚(α,β,β-三氟苯乙烯)及丙烯酸共聚物之總重量計。
如上所提及,存在於光學補償膜中之丙烯酸共聚物為MMA及一或多種非MMA的乙烯性不飽和單體之共聚物,該乙烯性不飽和單體選自包含以下或由以下組成之群:丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正己酯、甲基丙烯酸正己酯、丙烯酸2-甲氧基乙酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯及其組合。存在於本發明之丙烯酸共聚物中之MMA之量可為70重量%至95重量%,包含75重量%至93重量%,及亦包含80重量%至90重量%,其中該重量%係基於存在於丙烯酸共聚物中之MMA及一或多種非MMA的乙烯性不飽和單體之總重量計。相似地,存在於本發明之丙烯酸共聚物中之一或多種非MMA的乙烯性不飽和單體之量可為5重量%至30重量%,包含7重量%至25重量%,及亦包含10重量%至20重量%,其中該重量%係基於存在於丙烯酸共聚物中之MMA及一或多種非MMA的乙烯性不飽和單體之總重量計。根據本發明之一些態樣,存在於丙烯酸共聚物中之MMA之量可為80重量%至90重量%及存在於丙烯酸共聚物中之一或多種非MMA的乙烯性不飽和單體之量可為10重量%至20重量%,其中該重量%係基於存在於丙烯酸共聚物中之MMA及一或多種非MMA的乙烯性不飽和單體之總重量計。
存在於本發明之光學補償膜中之丙烯酸共聚物具有65℃至98℃之玻璃化轉變溫度(T
g),如藉由示差掃描量熱法(DSC)所測定。根據本發明之一些態樣,該丙烯酸共聚物可具有70℃至98℃之T
g,包含75℃至98℃之T
g、80℃至98℃之T
g、85℃至98℃之T
g及亦包含90℃至93℃之T
g。根據本發明之某些態樣,存在於本發明之光學補償膜中之丙烯酸共聚物具有85℃至98℃之T
g。根據本發明之某些態樣,存在於本發明之光學補償膜中之丙烯酸共聚物具有90℃至93℃之T
g。
本發明之丙烯酸共聚物可使用此項技術中之熟知方法製備。例如,MMA及一或多種乙烯性不飽和單體之丙烯酸共聚物可藉由已知聚合技術,包括(但不限於)本體聚合、溶液聚合、乳液聚合或懸浮液聚合來製備。此外,聚合反應可為自由基聚合、陽離子聚合、陰離子聚合、兩性離子聚合、齊格勒-納塔(Ziegler-Natta)聚合或原子轉移自由基聚合。
本發明之光學補償膜具有使光學補償膜能用於各種顯示裝置(諸如電視、電腦、汽車及行動電話中之彼等,僅舉幾例)中之所需光學性質及機械性質。
藉由本發明之光學補償膜展示之一種所需光學性質為低霧度。根據本發明,該光學補償膜具有小於2.25% (包含0.02%至2.25%)之霧度。於本發明之實施例中,該光學補償膜具有小於1.5% (例如,0.02%至1.5%)之霧度,包含小於1% (例如,0.02%至1%)、小於0.5% (例如,0.02%至0.5%)、小於0.4% (例如,0.02%至0.4%)、小於0.3% (例如,0.02%至0.3%)、小於0.2% (例如,0.02%至0.2%)之霧度,及亦包含小於0.15% (例如,0.02%至0.15%)之霧度。光學補償膜之以上提及之霧度值係在15 µm至50 µm之膜厚度下量測。本文中所述之霧度值係根據ASTM D1003-00測定。
本發明之光學補償膜亦展示優異機械性質。根據本發明,該光學補償膜具有5%至15% (包含7%至15%,及亦包含9%至15%)之斷裂伸長率。本發明之光學補償膜亦具有2 Gpa至4 GPa之楊氏模量,包含2.3 GPa至3.5 GPa、2.5 GPa至3.5 GPa、2.6 GPa至3.5 GPa,及亦包含2.7 GPa至3.5 GPa之楊氏模量。光學補償膜之以上提及之機械性質係在15 µm至50 µm之膜厚度下量測。本文中所述之斷裂伸長率值及楊氏模量值係根據ASTM D882-02測定。
本發明之光學補償膜可藉由聚(α,β,β-三氟苯乙烯) (PTFS)及丙烯酸共聚物之摻合物於溶劑中之溶液澆鑄,或藉由PTFS及丙烯酸共聚物之摻合物之熱熔擠出來製備。聚合物溶液在基板上之澆鑄可藉由此項技術中已知方法,包括(但不限於)旋塗、噴塗、輥塗、簾塗或浸塗進行。熔融擠出可藉由在擠出之前將PTFS及丙烯酸共聚物以粉末或顆粒形式混合或藉由將PTFS及丙烯酸共聚物之固體形式共同擠出來進行。可將PTFS及丙烯酸共聚物以所需比率,諸如,例如,30:70或40:60 PTFS:丙烯酸共聚物混合或共同擠出。為改善相容性,可首先藉由使用更高比率之PTFS,例如,以70:30 PTFS:丙烯酸共聚物製備配混母料。然後可藉由添加另外量之丙烯酸共聚物以達到PTFS:丙烯酸共聚物之最終所需比率重複進行進一步配混。此外,可於擠出製程中使用添加劑以藉由促進流動及混合來減少膜缺陷。用於擠出製程中之一種適宜添加劑為Kynar® PVDF聚合物加工輔助添加劑,其係購自Arkema Inc. (King of Prussia, Pennsylvania)。
用於製備含有PTFS及丙烯酸共聚物之溶液之適宜溶劑包括(但不限於)甲苯、甲基異丁基酮、環戊酮、二氯甲烷、氯仿、1,2-二氯乙烷、甲基戊基酮、甲基乙基酮、甲基異丙基酮、甲基異戊基酮、乙酸乙酯、乙酸正丁酯、丙二醇甲醚乙酸酯及其混合物。用於自含有苯乙烯氟聚合物之溶液澆鑄聚合物膜之方法揭示於美國專利第8,889,043號中,其全文係以引用的方式併入本文中。
本發明之光學補償膜可藉由此項技術中已知方法拉伸以獲得所需平面內阻滯(R
e)值、所需平面外阻滯(R
th)值或所需平面內阻滯(R
e)值及所需平面外阻滯(R
th)值二者。用於拉伸之適宜方法包括單軸拉伸及雙軸拉伸。如與通常太脆而不能經適當拉伸之丙烯酸膜相比,本發明之光學補償膜尤其適用於拉伸。
光學補償膜(或波板)之阻滯(R)經定義為R=Δn × d,其中Δn為雙折射率且d為波板之厚度。雙折射率經分類為平面內雙折射率∆n(in)=n
x-n
y及平面外雙折射率∆n(th)= n
z- (n
x+n
y)/2,其中n
x及n
y表示平面內折射率且n
z表示厚度方向折射率。因此,平面內阻滯由R
e= (n
x- n
y) × d表示,及平面外阻滯由R
th= [n
z- (n
x+n
y)/2] × d表示。
波板之雙折射率(∆n) (或阻滯R)可藉由在約400 nm至約800 nm之波長範圍內以各種增量測定波板之雙折射率來量測。或者,雙折射率可在特定光波長下量測。
已知,用於顯示器(諸如平面內切換(IPS)模式之液晶顯示器(LCD))之正交偏振器需要波板補償斜光線之相位變化。出於此目的,可使用具有負性平面內阻滯之光學補償膜。具有負性平面內阻滯之此光學補償膜通常被稱作負性A板,其具有n
x<n
y=n
z之折射率譜。正交偏振器之一種補償方法為使用負性A板與具有n
x>n
y=n
z之折射率譜之正性A板之組合。
正交偏振器之另一種補償方法為使用具有n
x<n
y<n
z之折射率譜之光學補償膜,其通常被稱作正性雙軸膜。此光學補償膜可提供平面內阻滯以及平面外阻滯。該正性雙軸膜可與具有n
x>n
y>n
z之折射率譜之負性雙軸膜組合使用。
已發現負性A-板可藉由本發明之光學補償膜之非約束單軸拉伸獲得,而正性雙軸膜可藉由具約束之單軸拉伸獲得。
因此,於一些態樣中,本發明之光學補償膜可經拉伸以提供具有n
x<n
y=n
z之折射率譜之負性A-板或具有n
x<n
y<n
z之折射率譜之正性雙軸膜。該負性A-板或正性雙軸膜具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-80 nm至-300 nm之平面內阻滯(R
e)及40 nm至200 nm之平面外阻滯(R
th)。於某些態樣中,本發明之負性A-板或正性雙軸膜具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-100 nm至-200 nm之平面內阻滯(R
e)及50 nm至150 nm之平面外阻滯(R
th)。
本發明之光學補償膜可用於多層光學補償膜中。於某些態樣中,提供包含本發明之負性A-板及具有n
x>n
y=n
z之折射率譜之正性A-板之多層光學補償膜。於某些態樣中,提供包含本發明之正性雙軸膜及具有n
x>n
y>n
z之折射率譜之負性雙軸膜之多重光學補償膜。正性A-板或負性雙軸膜之實例包括(但不限於)經拉伸之聚碳酸酯、環狀烯烴聚合物(COP)、聚酯或纖維素酯之聚合物膜。
用於顯示器中之正交偏振器亦可藉由使用具有n
x=n
y<n
z之折射率譜之光學補償膜(其通常被稱作正性C-板)補償。此光學補償膜可提供正平面外阻滯。該正性C-板亦可與具有n
x>n
y=n
z之折射率譜之正性A-板組合使用。已出人意料地發現,正性C-板可藉由本發明之光學補償膜之雙軸拉伸來獲得。
因此,於一些態樣中,本發明之光學補償膜可經雙軸拉伸以提供具有n
x=n
y<n
z之折射率譜之正性C-板。該正性C-板具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-10 nm至10 nm之平面內阻滯(R
e)及50 nm至150 nm之平面外阻滯(R
th)。
於某些態樣中,提供包含本發明之正性C-板及具有n
x>n
y=n
z之折射率譜之正性A-板之多層光學補償膜。該正性A-板之實例包括(但不限於)經拉伸之聚碳酸酯、環狀烯烴聚合物(COP)、聚酯或纖維素酯之聚合物膜。
本發明之多層光學補償膜可用於顯示裝置,諸如電視、電腦、汽車及行動電話中之彼等中。因此,於另一態樣中,本發明提供包含本發明之多層光學補償膜之平面內切換(IPS)模式液晶顯示器(LCD)。於又一態樣中,本發明提供包含本發明之多層光學補償膜之有機發光二極體(OLED)顯示器。
實例
下列實例描述及證實本文中所述之組合物、膜及方法之實施例。此等實例僅出於說明目的提供且不應解釋為限制本發明,因為許多其變型在不背離本發明之精神及範圍下係可能。
實例 1 :製備聚 (α,β,β- 三氟苯乙烯 ) 及丙烯酸共聚物
聚(α,β,β-三氟苯乙烯) (PTFS)係根據美國專利第8,871,882號中所揭示之方法藉由在存在十二烷基硫酸鈉及鹽酸十二烷胺下乳液聚合α,β,β-三氟苯乙烯來製備。PTFS聚合物之玻璃化轉變溫度(T
g)為208℃,如藉由示差掃描量熱法(DSC)所測得。PTFS聚合物之固有黏度(IV)為1.1 dL/g,如藉由Cannon自動毛細管黏度計使用環戊酮作為溶劑在30℃下所測得。除非另有指定,否則整篇實例所用之PTFS聚合物具有約1.1 dL/g之IV。
丙烯酸共聚物係根據此項技術中已知之常見方法藉由溶液自由基聚合製備。於典型反應中,將特定比率之MMA及另一種單體連同引發劑偶氮雙異丁腈(AIBN) (基於單體之總重量計約1%)溶解於溶劑二甲亞碸(DMSO)中;將所得混合物脫氣及用氮氣再填充。然後將溶液加熱至60℃及允許反應約48小時。於反應後,將混合物於甲醇中沉澱,過濾,用甲醇重複洗滌,及在真空下乾燥。表1至4中列出因此獲得之丙烯酸共聚物。
表1列出以各種比率之甲基丙烯酸甲酯(MMA)與丙烯酸甲酯(MA)之共聚物之組成及其IV及T
g值。
表1:MMA及MA之共聚物 | ||||
丙烯酸共聚物 ID | 按重量(加料)之組成,% | IV (dL/g) | 藉由DSC測得之Tg (℃) | |
MMA | MA | |||
1 | 80 | 20 | 0.62 | 93 |
2 | 78 | 22 | 0.68 | 90 |
3 | 70 | 30 | 0.68 | 78 |
表2列出以各種比率之甲基丙烯酸甲酯(MMA)與丙烯酸乙酯(EA)之共聚物之組成及其IV及T
g值。
表2:MMA及EA之共聚物 | ||||
丙烯酸共聚物 ID | 藉由NMR測得之組成,重量% | IV (dL/g) | 藉由DSC測得之Tg (℃) | |
MMA | EA | |||
4 | 85 | 15 | 0.97 | 97 |
5 | 82 | 18 | 1.19 | 94 |
6 | 84 | 16 | 0.59 | 90 |
7 | 82 | 18 | 0.64 | 88 |
8 | 75 | 25 | 0.60 | 76 |
表3列出以各種比率之甲基丙烯酸甲酯(MMA)與丙烯酸丁酯(BA)之共聚物之組成及其IV及T
g值。
表3:MMA及BA之共聚物 | ||||
丙烯酸共聚物 ID | 藉由NMR測得之組成,重量% | IV (dL/g) | 藉由DSC測得之Tg (℃) | |
MMA | BA | |||
9 | 90 | 10 | 0.53 | 106 |
10 | 87 | 13 | 0.52 | 97 |
11 | 84 | 16 | 0.52 | 90 |
12 | 84 | 16 | 0.62 | 90 |
13 | 82 | 18 | 0.58 | 83 |
表4列出甲基丙烯酸甲酯(MMA)與各種共聚單體之共聚物之組成及其IV及T
g值。
*HA:丙烯酸正己酯;EHA:丙烯酸2-乙基己酯;MeOEA:丙烯酸2-甲氧基乙酯;HMA:甲基丙烯酸正己酯;EHMA:甲基丙烯酸2-乙基己酯
實例 2 :藉由溶液澆鑄製備丙烯酸共聚物膜及其性質
表4:MMA及各種共聚單體之共聚物 | |||||
丙烯酸共聚物 ID | 按重量(加料)之組成 | IV (dL/g) | 藉由DSC測得之Tg (℃) | ||
MMA % | 共聚單體* | % | |||
14 | 85 | HA | 15 | 0.45 | 90 |
15 | 85 | EHA | 15 | 0.47 | 92 |
16 | 85 | MeOEA | 15 | 0.57 | 94 |
17 | 80 | HMA | 20 | 0.44 | 93 |
18 | 80 | EHMA | 20 | 0.45 | 95 |
丙烯酸共聚物溶液係藉由將於實例1中製備之各固體丙烯酸共聚物溶解於甲基乙基酮(MEK)或環戊酮(CPN)中來製備。於徹底混合後,所得溶液係均勻且透明。
使用刮刀澆鑄法將以上製備之丙烯酸共聚物溶液施覆至平坦玻璃基板上以形成塗層膜。允許將塗層膜於空氣中乾燥過夜及隨後放置於真空烘箱中在室溫下(例如,20℃至23℃) 8小時。於乾燥後,剝除膜。
自立膜之雙折射率及厚度係藉由Metricon型號2010/M 棱鏡耦合器使用單膜模式在633 nm之波長下量測。b*及霧度值係藉由HunterLab UltraScan VIS分光光度計根據ASTM D1003-00量測。如表5至8中所示,針對所有膜獲得低b*及霧度值,這指示高的膜清晰度。丙烯酸共聚物膜之平面外雙折射率值(Δn 633 nm)均為稍正性,與純PMMA之膜可相比擬。
*HA:丙烯酸正己酯;EHA:丙烯酸2-乙基己酯;MeOEA:丙烯酸2-甲氧基乙酯;HMA:甲基丙烯酸正己酯;EHMA:甲基丙烯酸2-乙基己酯
表5:MMA及MA之共聚物之澆鑄膜之光學性質 | |||||||
膜 ID | 丙烯酸共聚物 ID | MMA:MA 重量比率 | 厚度 (µm) | n 633 nm | Δn 633 nm | b* | 霧度 (%) |
20 | 1 | 80:20 | 10.1 | 1.4882 | 0.0001 | 0.15 | 0.10 |
21 | 2 | 78:22 | 9.7 | 1.4887 | 0.0005 | 0.15 | 0.12 |
22 | 3 | 70:30 | 10.2 | 1.4879 | 0.0005 | 0.14 | 0.15 |
表6:MMA及EA之共聚物之澆鑄膜之光學性質 | |||||||
膜 ID | 丙烯酸共聚物 ID | MMA:EA 重量比率 | 厚度 (µm) | n 633 nm | Δn 633 nm | b* | 霧度 (%) |
23 | 4 | 85:15 | 8.5 | 1.4894 | 0.0004 | 0.24 | 0.09 |
24 | 5 | 82:18 | 8.0 | 1.4891 | 0.0001 | 0.23 | 0.30 |
25 | 6 | 84:16 | 9.9 | 1.4877 | 0.0002 | 0.15 | 0.20 |
26 | 7 | 82:18 | 9.9 | 1.4881 | 0.0001 | 0.14 | 0.27 |
27 | 8 | 75:25 | 10.3 | 1.4874 | 0.0005 | 0.14 | 0.25 |
表7:MMA及BA之共聚物之澆鑄膜之光學性質 | |||||||
膜 ID | 丙烯酸共聚物 ID | MMA:BA 重量比率 | 厚度 (µm) | n 633 nm | Δn 633 nm | b* | 霧度 (%) |
28 | 9 | 90:10 | 10.0 | 1.4874 | 0.0004 | 0.15 | 0.21 |
29 | 10 | 87:13 | 10.1 | 1.4877 | 0.0004 | 0.16 | 0.15 |
30 | 11 | 84:16 | 9.8 | 1.4880 | 0.0005 | 0.15 | 0.10 |
31 | 12 | 84:16 | 9.3 | 1.4880 | 0.0004 | 0.14 | 0.12 |
32 | 13 | 82:18 | 10.0 | 1.4878 | 0.0007 | 0.16 | 0.28 |
表8:MMA及各種共聚單體之共聚物之澆鑄膜之光學性質 | |||||||
膜 ID | 丙烯酸共聚物 ID | 共聚物 組成*;重量比率 | 厚度 (µm) | n 633 nm | Δn 633 nm | b* | 霧度 (%) |
33 | 14 | MMA:HA 85:15 | 10.8 | 1.4881 | 0.0002 | 0.15 | 0.16 |
34 | 15 | MMA:EHA 85:15 | 10.2 | 1.4886 | 0.0001 | 0.14 | 0.08 |
35 | 16 | MMA:MeOEA 85:15 | 10.6 | 1.4893 | 0.0004 | 0.15 | 0.09 |
36 | 17 | MMA:HMA 80:20 | 12.4 | 1.4879 | 0.0004 | 0.14 | 0.10 |
37 | 18 | MMA:EHMA 80:20 | 10.9 | 1.4884 | 0.0005 | 0.14 | 0.06 |
丙烯酸共聚物膜之機械性質係使用Instron儀器以膜拉伸試驗模式根據ASTM D882-02量測。用於機械測試之膜較用於光學測試之彼等更厚。表9至12中列出丙烯酸共聚物膜之楊氏模量、最大拉伸應力及斷裂伸長率。
*HA:丙烯酸正己酯;EHA:丙烯酸2-乙基己酯;MeOEA:丙烯酸2-甲氧基乙酯;HMA:甲基丙烯酸正己酯;EHMA:甲基丙烯酸2-乙基己酯
實例 3 :藉由溶液澆鑄製備 PTFS/ 丙烯酸共聚物膜及其性質
表9:MMA及MA之共聚物之澆鑄膜之機械性質 | ||||||
膜 ID | 丙烯酸共聚物 ID | MMA:MA 重量比率 | 厚度 (µm) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) |
38 | 1 | 80:20 | 22.0 | 2.8 ± 0.1 | 74 ± 3 | 4.6 ± 0.5 |
39 | 2 | 78:22 | 22.5 | 2.9 ± 0.1 | 72 ± 3 | 7 ± 1 |
40 | 3 | 70:30 | 22.0 | 2.7 ± 0.1 | 67 ± 3 | 6 ± 2 |
表10:MMA及EA之共聚物之澆鑄膜之機械性質 | ||||||
膜 ID | 丙烯酸共聚物 ID | MMA:EA 重量比率 | 厚度 (µm) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) |
41 | 4 | 85:15 | 20.5 | 2.6 ± 0.2 | 70 ± 7 | 7 ± 3 |
42 | 5 | 82:18 | 19.5 | 2.5 ± 0.2 | 66 ± 5 | 9 ± 1 |
43 | 6 | 84:16 | 24.0 | 2.5 ± 0.1 | 69 ± 4 | 5.7 ± 0.6 |
44 | 7 | 82:18 | 22.5 | 2.8 ± 0.1 | 67 ± 2 | 8 ± 3 |
45 | 8 | 75:25 | 22.5 | 2.5 ± 0.2 | 63 ± 4 | 12 ± 3 |
表11:MMA及BA之共聚物之澆鑄膜之機械性質 | ||||||
膜 ID | 丙烯酸共聚物 ID | MMA:BA 重量比率 | 厚度 (µm) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) |
46 | 9 | 90:10 | 22.0 | 2.8 ± 0.2 | 73 ± 4 | 4.1 ± 0.3 |
47 | 10 | 87:13 | 24.0 | 2.7 ± 0.2 | 72 ± 3 | 4.6 ± 0.4 |
48 | 11 | 84:16 | 24.0 | 2.6 ± 0.1 | 68 ± 2 | 5.5 ± 0.3 |
49 | 12 | 84:16 | 22.5 | 2.6 ± 0.1 | 70 ± 2 | 7 ± 2 |
50 | 13 | 82:18 | 23.5 | 2.5 ± 0.2 | 71 ± 2 | 14 ± 3 |
表12:MMA及各種共聚單體之共聚物之澆鑄膜之機械性質 | ||||||
膜 ID | 丙烯酸共聚物 ID | 共聚物 組成*;重量比率 | 厚度 (µm) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) |
51 | 14 | MMA:HA 85:15 | 23.0 | 2.7 ± 0.1 | 72 ± 2 | 4.1 ± 0.2 |
52 | 15 | MMA:EHA 85:15 | 23.5 | 2.6 ± 0.2 | 70 ± 4 | 4.8 ± 0.4 |
53 | 16 | MMA:MeOEA 85:15 | 22.0 | 2.8 ± 0.1 | 72 ± 3 | 5.0 ± 0.5 |
54 | 17 | MMA:HMA 80:20 | 25.0 | 2.6 ± 0.2 | 74 ± 5 | 4.6 ± 0.3 |
55 | 18 | MMA:EHMA 80:20 | 24.5 | 2.4 ± 0.3 | 68 ± 7 | 4.4 ± 0.4 |
聚合物摻合物係使用以各種比率之PTFS及丙烯酸共聚物製備。溶液(10重量%至15重量%)係藉由將PTFS粉末及固體丙烯酸共聚物以各種重量比率(諸如基於丙烯酸共聚物固體及PTFS固體之總重量計60/40重量%、70/30重量%及80/20重量%之丙烯酸共聚物/PTFS重量比率)於環戊酮(CPN)中混合來製備。於充分溶解及混合後,所得溶液係均勻且透明。
使用刮刀澆鑄法將以上製備之聚合物摻合物溶液施覆至平坦玻璃基板以形成塗層膜。允許將塗層膜於空氣中乾燥過夜及隨後放置於真空烘箱中在80℃至100℃下8小時。於乾燥後,剝除膜。
b*及霧度值係藉由HunterLab UltraScan VIS分光光度計根據ASTM D1003-00量測。如表13至16中所示,針對幾乎所有膜獲得低b* (例如,小於1)及低霧度(例如,小於1.5%),這指示高的膜清晰度及兩種聚合物之良好相容性。針對光學測試及機械測試二者使用相同聚合物摻合物膜。聚合物摻合物膜之軟化溫度係藉由熱機械分析(TMA)量測及以「藉由TMA測得之T
g(℃)」列於表13至16中。此等T
g值係用於測定聚合物摻合物膜之拉伸溫度及與藉由DSC量測之表1至4中所列之丙烯酸共聚物之T
g值不相關。PTFS/丙烯酸共聚物膜之機械性質(即,楊氏模量、最大拉伸應力及斷裂伸長率)列於表13至16中及以與實例2之膜相同之方式進行量測。如表13中所見,當MMA及MA之共聚物具有70/30重量%之比率及膜中之丙烯酸共聚物:PTFS之重量比率增加時,膜之霧度亦增加。因此,具有小於70重量% MMA之丙烯酸共聚物不適用於本發明之光學膜。
實例 4 :聚合物膜之拉伸及其性質
表13:PMMA-PMA/PTFS摻合物膜之性質 | ||||||||||
膜 ID | 丙烯酸共聚物 ID | PMMA: PMA 重量比率 | 丙烯酸: PTFS 重量比率 | d (µm) | 藉由TMA測得之Tg (℃) | b* | 霧度 (%) | 楊氏模量 (GPa) | 最大應力 (Mpa) | 斷裂伸長率(%) |
56 | 1 | 80:20 | 60:40 | 41.5 | 148 | 0.21 | 0.11 | 2.9 ± 0.2 | 89 ± 5 | 5.9 ± 0.9 |
57 | 70:30 | 41.5 | 139 | 0.23 | 0.12 | 2.9 ± 0.2 | 82 ± 5 | 7 ± 1 | ||
58 | 80:20 | 34.0 | 134 | 0.25 | 0.24 | 2.9 ± 0.2 | 78 ± 5 | 8 ± 1 | ||
59 | 2 | 78:22 | 60:40 | 39.0 | 142 | 0.28 | 0.14 | 3.1 ± 0.2 | 89 ± 6 | 7.5 ± 0.9 |
60 | 70:30 | 41.5 | 133 | 0.35 | 0.29 | 3.0 ± 0.2 | 82 ± 6 | 9 ± 2 | ||
61 | 80:20 | 32.5 | 127 | 0.23 | 0.61 | 2.9 ± 0.2 | 78 ± 4 | 12 ± 2 | ||
62 | 3 | 70:30 | 60:40 | 38.5 | 142 | 0.46 | 0.45 | 2.9 ± 0.2 | 77 ± 4 | 7 ± 1 |
63 | 70:30 | 40.0 | 136 | 0.32 | 1.32 | 2.9 ± 0.2 | 74 ± 6 | 12 ± 4 | ||
64 | 80:20 | 32.5 | 126 | 0.15 | 2.24 | 3.0 ± 0.3 | 73 ± 7 | 11 ± 2 |
表14:PMMA-PEA/PTFS摻合物膜之性質 | |||||||||||
膜 ID | 丙烯酸共聚物 ID | PMMA: PEA 重量比率 | 丙烯酸: PTFS 重量比率 | d (µm) | 藉由TMA測得之Tg (℃) | b* | 霧度 (%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | |
65 | 4 | 85:15 | 60:40 | 40.1 | 135 | 0.19 | 0.33 | 3.0 ± 0.2 | 89 ± 2 | 10 ± 1 | |
66 | 70:30 | 44.8 | 128 | 0.23 | 0.23 | 2.8 ± 0.2 | 82 ± 4 | 12 ± 2 | |||
67 | 5 | 82:18 | 60:40 | 40.5 | 130 | 0.22 | 0.13 | 2.9 ± 0.1 | 85 ± 3 | 9.2 ± 0.9 | |
68 | 70:30 | 45.8 | 124 | 0.22 | 0.34 | 2.8 ± 0.2 | 80 ± 4 | 15 ± 8 | |||
69 | 6 | 84:16 | 60:40 | 39.4 | 133 | 0.20 | 0.16 | 3.0 ± 0.1 | 88 ± 2 | 7.0 ± 0.5 | |
70 | 70:30 | 43.3 | 126 | 0.18 | 0.19 | 2.8 ± 0.2 | 81 ± 5 | 7.7 ± 0.4 | |||
71 | 7 | 82:18 | 60:40 | 46.0 | 132 | 0.22 | 0.08 | 2.9 ± 0.1 | 85 ± 3 | 8 ± 1 | |
72 | 70:30 | 37.5 | 125 | 0.20 | 0.23 | 2.9 ± 0.1 | 82 ± 4 | 7.8 ± 0.6 | |||
73 | 8 | 75:25 | 60:40 | 39.0 | 125 | 0.18 | 0.15 | 2.9 ± 0.1 | 85 ± 2 | 7.5 ± 0.9 | |
74 | 70:30 | 43.7 | 116 | 0.17 | 0.17 | 2.8 ± 0.1 | 78 ± 3 | 8 ± 2 |
表15:PMMA-PBA/PTFS摻合物膜之性質 | |||||||||||
膜 ID | 丙烯酸共聚物 ID | PMMA: PBA 重量比率 | 丙烯酸: PTFS 重量比率 | d (µm) | 藉由TMA測得之Tg (℃) | b* | 霧度 (%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | |
75 | 9 | 90:10 | 60:40 | 41.5 | 141 | 0.20 | 0.31 | 3.1 ± 0.2 | 92 ± 5 | 5.2 ± 0.3 | |
76 | 70:30 | 49.5 | 136 | 0.19 | 0.20 | 2.9 ± 0.2 | 83 ± 5 | 5.2 ± 0.8 | |||
77 | 80:20 | 38.5 | 129 | 0.18 | 0.25 | 3.0 ± 0.2 | 84 ± 4 | 5.2 ± 0.9 | |||
78 | 10 | 87:13 | 60:40 | 36.5 | 138 | 0.22 | 0.13 | 3.0 ± 0.2 | 83 ± 5 | 6.2 ± 0.8 | |
79 | 70:30 | 41.5 | 132 | 0.21 | 0.13 | 3.0 ± 0.2 | 80 ± 5 | 7 ± 3 | |||
80 | 80:20 | 36.0 | 125 | 0.18 | 0.12 | 2.9 ± 0.2 | 75 ± 5 | 7 ± 2 | |||
81 | 11 | 84:16 | 60:40 | 36.5 | 134 | 0.21 | 0.19 | 3.0 ± 0.2 | 85 ± 7 | 5.8 ± 0.4 | |
82 | 70:30 | 43.5 | 128 | 0.20 | 0.16 | 2.8 ± 0.2 | 78 ± 5 | 7 ± 1 | |||
83 | 80:20 | 36.0 | 120 | 0.18 | 0.10 | 2.8 ± 0.2 | 77 ± 5 | 7 ± 1 | |||
84 | 12 | 84:16 | 60:40 | 38.0 | 144 | 0.22 | 0.14 | 2.9 ± 0.2 | 86 ± 6 | 7 ± 1 | |
85 | 70:30 | 43.0 | 139 | 0.23 | 0.08 | 2.9 ± 0.3 | 82 ± 5 | 9 ± 3 | |||
86 | 80:20 | 35.0 | 130 | 0.23 | 0.18 | 2.7 ± 0.2 | 75 ± 5 | 9 ± 2 | |||
87 | 13 | 82:18 | 60:40 | 45.5 | 135 | 0.23 | 0.31 | 2.9 ± 0.1 | 86 ± 5 | 6.1 ± 0.6 | |
88 | 70:30 | 48.5 | 129 | 0.23 | 0.45 | 3.0 ± 0.3 | 82 ± 9 | 7 ± 1 | |||
89 | 80:20 | 39.5 | 124 | 0.19 | 0.52 | 2.8 ± 0.3 | 71 ± 8 | 7 ± 1 |
表16:各種PMMA基共聚物/PTFS摻合物膜之性質 | |||||||||||
膜 ID | 丙烯酸共聚物 ID | PMMA基共聚物 | 丙烯酸: PTFS 重量比率 | d (µm) | 藉由TMA測得之Tg (℃) | b* | 霧度 (%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | |
90 | 14 | PMMA:PHA 85:15 | 60:40 | 37.5 | 136 | 0.22 | 0.15 | 3.0 ± 0.3 | 87 ± 7 | 7.2 ± 0.7 | |
91 | 70:30 | 43.0 | 130 | 0.20 | 0.19 | 2.9 ± 0.3 | 86 ± 8 | 7.1 ± 0.8 | |||
92 | 80:20 | 35.0 | 124 | 0.17 | 0.12 | 2.8 ± 0.2 | 78 ± 6 | 6 ± 1 | |||
93 | 15 | PMMA: PEHA 85:15 | 60:40 | 39.5 | 151 | 0.24 | 0.20 | 2.9 ± 0.2 | 83 ± 5 | 7.2 ± 0.6 | |
94 | 70:30 | 43.5 | 141 | 0.24 | 0.25 | 2.9 ± 0.3 | 85 ± 8 | 8 ± 1 | |||
95 | 80:20 | 36.5 | 134 | 0.20 | 0.24 | 2.7 ± 0.2 | 77 ± 5 | 9 ± 2 | |||
96 | 16 | PMMA: PMeOEA 85:15 | 60:40 | 37.0 | 146 | 0.22 | 0.25 | 3.2 ± 0.2 | 89 ± 3 | 6.6 ± 0.6 | |
97 | 70:30 | 42.5 | 141 | 0.20 | 0.21 | 3.2 ± 0.2 | 89 ± 5 | 7.0 ± 0.8 | |||
98 | 80:20 | 33.0 | 135 | 0.17 | 0.15 | 3.1 ± 0.2 | 90 ± 5 | 8 ± 1 | |||
99 | 17 | PMMA: PHMA 80:20 | 60:40 | 38.5 | 140 | 0.20 | 0.11 | 2.8 ± 0.3 | 81 ± 7 | 6.7 ± 0.6 | |
100 | 70:30 | 43.5 | 134 | 0.19 | 0.12 | 2.8 ± 0.3 | 83 ± 9 | 8 ± 1 | |||
101 | 80:20 | 37.0 | 128 | 0.16 | 0.17 | 2.7 ± 0.2 | 78 ± 5 | 6.8 ± 0.7 | |||
102 | 18 | PMMA: PEHMA 80:20 | 60:40 | 38.0 | 153 | 0.21 | 0.24 | 2.8 ± 0.3 | 82 ± 8 | 6.9 ± 0.9 | |
103 | 70:30 | 43.0 | 145 | 0.20 | 0.14 | 2.7 ± 0.3 | 83 ± 9 | 6.8 ± 0.5 | |||
104 | 80:20 | 35.0 | 137 | 0.18 | 0.24 | 2.6 ± 0.2 | 78 ± 4 | 7 ± 2 | |||
將自丙烯酸共聚物/PTFS摻合物製備之選定聚合物膜各安裝在配備有加熱室之拉伸機(自Brückner Maschinenbau可得之Karo IV實驗室膜拉伸機)上。將膜預加熱90秒以達到所需拉伸溫度(「拉伸溫度(℃)」)及隨後在所需速度下(一般在1%/秒下)以機器方向(MD)或雙軸拉伸(即,以MD及橫向方向(TD)二者拉伸)至目標拉伸比率L/L0,其中L為最終長度及L0為起始長度。橫向方向(TD)受約束或不受約束。經拉伸膜之相位阻滯(R
e:平面內阻滯;R
th:平面外阻滯)係藉由VASE®橢圓偏光計(自J. A. Woollam Co., Inc.可得)在550 nm之光波長下量測。結果列於表17至22中。
表17列出自以70:30 (丙烯酸共聚物:PTFS)重量比率之表1中之丙烯酸共聚物ID 2 (MMA:MA = 78:22)及PTFS製備之各種經拉伸之聚合物摻合物膜的性質。
NT =未測試
表17:丙烯酸共聚物ID 2 (MMA:MA=78/22):PTFS (70:30)之經拉伸膜之性質 | ||||||||||
膜 ID | 拉伸溫度 (℃) | MD(L/L0) x TD(L/L0) | 受約束,不受約束,或雙軸 | d (µm) | Re (nm) | Rth (nm) | Re/d (nm/µm) | Rth/d (nm/µm) | b* | 霧度 (%) |
105 | n/a | 1 × 1 | n/a | 49.0 | -0.8 | 70.6 | -0.02 | 1.44 | 0.31 | 0.70 |
106 | 125 | 2 | 不受約束 | 36.6 | -217.0 | 113.5 | -5.93 | 3.10 | 0.28 | 1.74 |
107 | 125 | 1.75 × 1 | 受約束 | 27.0 | -85.8 | 97.4 | -3.18 | 3.61 | 0.20 | 0.97 |
108 | 125 | 2 × 1 | 受約束 | 25.0 | -97.6 | 96.6 | -3.90 | 3.87 | 0.22 | 0.75 |
109 | 125 | 2.25 × 1 | 受約束 | 22.3 | -101.3 | 95.3 | -4.54 | 4.27 | 0.20 | 1.05 |
110 | 125 | 1.4 × 1.4 | 雙軸 | 27.5 | -1.4 | 100.2 | -0.05 | 3.64 | 0.19 | 0.85 |
111 | 125 | 1.5 × 1.5 | 雙軸 | 23.5 | -2.8 | 94.1 | -0.12 | 4.01 | 0.17 | 0.99 |
112 | 135 | 2 × 1 | 受約束 | 26.5 | -81.8 | 82.0 | -3.09 | 3.09 | 0.19 | 1.09 |
表17:續 | |||||||
膜 ID | MD | TD | 註釋 | ||||
楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | ||
105 | 2.9 ± 0.2 | 70 ± 4 | 9 ± 1 | 2.9 ± 0.2 | 70 ± 4 | 9 ± 1 | MD,TD相同 |
106 | 3.0 ± 0.2 | 69 ± 4 | 5 ± 2 | NT | NT | NT | 針對TD太小 |
107 | 2.9 ± 0.1 | 67 ± 2 | 16 ± 5 | 2.9 ± 0.1 | 66 ± 2 | 21 ± 5 | |
108 | 2.9 ± 0.1 | 67 ± 3 | 19 ± 7 | 2.9 ± 0.2 | 66 ± 1 | 18 ± 11 | |
109 | 2.9 ± 0.2 | 69 ± 5 | 28 ± 12 | 2.9 ± 0.1 | 64 ± 4 | 22 ± 13 | |
110 | 2.9 ± 0.1 | 67 ± 4 | 29 ± 18 | 2.9 ± 0.1 | 67 ± 4 | 29 ± 18 | MD,TD相同 |
111 | 2.9 ± 0.1 | 67 ± 1 | 21 ± 10 | 2.9 ± 0.1 | 67 ± 1 | 21 ± 10 | MD,TD相同 |
112 | 2.9 ± 0.2 | 70 ± 3 | 27 ± 15 | 2.9 ± 0.2 | 65 ± 5 | 32 ± 32 |
表18列出自以60:40 (丙烯酸共聚物:PTFS)重量比率之表1中之丙烯酸共聚物ID 2 (MMA:MA = 78:22)及PTFS製備之各種經拉伸之聚合物摻合物膜的性質。
表18:丙烯酸共聚物ID 2 (MMA:MA=78:22):PTFS (60:40)之經拉伸膜之性質 | ||||||||||
膜 ID | 拉伸溫度 (℃) | MD(L/L0) x TD(L/L0) | 受約束,不受約束,或雙軸 | d (µm) | Re (nm) | Rth (nm) | Re/d (nm/µm) | Rth/d (nm/µm) | b* | 霧度 (%) |
113 | n/a | 1 × 1 | n/a | 42.3 | -0.5 | 95.6 | -0.01 | 2.26 | 0.24 | 0.29 |
114 | 135 | 2 | 不受約束 | 40.0 | -280.0 | 146.7 | -7.00 | 3.67 | 0.26 | 0.50 |
115 | 135 | 1.75 × 1 | 受約束 | 28.0 | -103.3 | 125.0 | -3.69 | 4.47 | 0.21 | 0.41 |
116 | 135 | 2 × 1 | 受約束 | 23.2 | -113.0 | 118.6 | -4.87 | 5.11 | 0.20 | 0.20 |
117 | 135 | 2.25 × 1 | 受約束 | 21.2 | -127.2 | 121.8 | -6.00 | 5.75 | 0.20 | 0.20 |
118 | 135 | 1.4 × 1.4 | 雙軸 | 23.9 | -0.6 | 117.0 | -0.03 | 4.89 | 0.19 | 0.41 |
119 | 135 | 1.5 × 1.5 | 雙軸 | 20.0 | -1.0 | 112.8 | -0.05 | 5.64 | 0.20 | 0.47 |
表19列出自以70:30 (丙烯酸共聚物:PTFS)重量比率之表2中之丙烯酸共聚物ID 7 (MMA:EA = 82:18)及PTFS製備之各種經拉伸之聚合物摻合物膜的性質。
註釋:膜ID 126及127之拉伸速率為4%/秒。
NT =未測試
表19:丙烯酸共聚物ID 7 (MMA:EA=82:18):PTFS (70:30)之經拉伸膜之性質 | ||||||||||
膜 ID | 拉伸溫度 (℃) | MD(L/L0) x TD(L/L0) | 受約束,不受約束或雙軸 | d (µm) | Re (nm) | Rth (nm) | Re/d (nm/µm) | Rth/d (nm/µm) | b* | 霧度 (%) |
120 | n/a | 1 × 1 | n/a | 46.1 | -0.7 | 53.9 | -0.02 | 1.17 | 0.23 | 0.62 |
121 | 125 | 2 | 不受約束 | 37.6 | -242.0 | 128.2 | -6.44 | 3.41 | 0.21 | 0.38 |
122 | 125 | 2.5 | 不受約束 | 28.0 | -272.2 | 143.1 | -9.72 | 5.11 | 0.20 | 0.39 |
123 | 125 | 1.5 × 1 | 受約束 | 30.9 | -87.6 | 114.8 | -2.84 | 3.71 | 0.20 | 0.56 |
124 | 125 | 2 × 1 | 受約束 | 24.5 | -122.3 | 126.1 | -4.99 | 5.15 | 0.19 | 0.40 |
125 | 125 | 1.3 × 1.3 | 雙軸 | 26.3 | -1.6 | 115.2 | -0.06 | 4.38 | 0.20 | 0.44 |
126 | 125 | 1.4 × 1.4 | 雙軸 | 24.3 | -0.9 | 119.2 | -0.04 | 4.91 | 0.19 | 0.22 |
127 | 135 | 2 × 0.75 | 不受約束 | 33.0 | -203.8 | 109.8 | -6.18 | 3.33 | 0.20 | 0.40 |
128 | 135 | 2 | 不受約束 | 33.6 | -205.2 | 113.5 | -6.11 | 3.38 | 0.20 | 0.43 |
129 | 125 | 1.4 × 1.4 | 雙軸 | 24.5 | -3.9 | 120.7 | -0.16 | 4.99 | NT | NT |
130 | 125 | 1.5 × 1.5 | 雙軸 | 21.5 | -3.6 | 123.9 | -0.17 | 5.76 | NT | NT |
131 | 125 | 1.75 × 1 | 受約束 | 26.0 | -104.6 | 117.1 | -4.02 | 4.51 | NT | NT |
132 | 125 | 2 × 1 | 受約束 | 24.5 | -121.6 | 121.8 | -4.96 | 4.97 | NT | NT |
133 | 135 | 2 × 1 | 受約束 | 24.5 | -97.0 | 98.6 | -3.96 | 4.02 | NT | NT |
表19:續 | |||||||
膜 ID | MD | TD | 註釋 | ||||
楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | ||
120 | 2.8 ± 0.2 | 75 ± 5 | 5 ± 1 | 2.8 ± 0.2 | 75 ± 5 | 5 ± 1 | MD,TD相同 |
123 | 2.8 ± 0.1 | 70 ± 2 | 12 ± 3 | 2.8 ± 0.2 | 70 ± 1 | 8 ± 4 | |
125 | 2.8 ± 0.1 | 66 ± 5 | 6 ± 1 | 2.8 ± 0.1 | 66 ± 5 | 6 ± 1 | MD,TD相同 |
129 | 2.8 ± 0.1 | 69 ± 5 | 41 ± 19 | 2.8 ± 0.1 | 69 ± 5 | 41 ± 19 | MD,TD相同 |
130 | 2.8 ± 0.1 | 69 ± 5 | 38 ± 6 | 2.8 ± 0.1 | 69 ± 5 | 38 ± 6 | MD,TD相同 |
131 | 2.7 ± 0.1 | 69 ± 2 | 33 ± 11 | 2.8 ± 0.1 | 67 ± 2 | 19 ± 4 | |
132 | 2.8 ± 0.1 | 77 ± 5 | 28 ± 10 | 2.8 ± 0.1 | 69 ± 4 | 16 ± 5 | |
133 | 2.8 ± 0.1 | 77 ± 8 | 38 ± 10 | 2.8 ± 0.2 | 70 ± 6 | 33 ± 14 |
表20列出自以60:40 (丙烯酸共聚物:PTFS)重量比率之表2中之丙烯酸共聚物ID 7 (MMA:EA = 82:18)及PTFS製備之各種經拉伸之聚合物摻合物膜的性質。
表20:丙烯酸共聚物ID 7 (MMA:EA=82:18):PTFS (60:40)之經拉伸膜之性質 | ||||||||||
膜 ID | 拉伸溫度 (℃) | MD(L/L0) x TD(L/L0) | 受約束,不受約束,或雙軸 | d (µm) | Re (nm) | Rth (nm) | Re/d (nm/µm) | Rth/d (nm/µm) | b* | 霧度 (%) |
134 | n/a | 1 × 1 | n/a | 36.0 | -0.3 | 88.8 | -0.01 | 2.47 | 0.22 | 0.31 |
135 | 135 | 2 | 不受約束 | 32.0 | -309.5 | 162.2 | -9.67 | 5.07 | 0.21 | 0.47 |
136 | 135 | 2.5 | 不受約束 | 30.5 | -375.8 | 195.1 | -12.32 | 6.40 | 0.22 | 1.51 |
137 | 135 | 1.5 × 1 | 受約束 | 26.3 | -95.3 | 130.9 | -3.62 | 4.98 | 0.21 | 1.11 |
138 | 135 | 2 × 1 | 受約束 | 19.5 | -130.1 | 135.3 | -6.67 | 6.94 | 0.19 | 1.05 |
139 | 135 | 1.3 × 1.3 | 雙軸 | 25.1 | -1.8 | 143.5 | -0.07 | 5.72 | 0.19 | 0.40 |
140 | 135 | 1.4 × 1.4 | 雙軸 | 20.0 | -1.5 | 128.6 | -0.08 | 6.43 | 0.16 | 0.38 |
表20:續 | |||||||
膜 ID | MD | TD | 註釋 | ||||
楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | ||
134 | 2.8 ± 0.1 | 72 ± 4 | 4 ± 1 | 2.8 ± 0.1 | 72 ± 4 | 4 ± 1 | MD,TD相同 |
135 | NT | NT | NT | NT | NT | NT | 太脆而不能測試 |
136 | 2.8 ± 0.1 | 70 ± 2 | 3.9 ± 0.2 | NT | NT | NT | TD太小而不能測試 |
137 | 2.8 ± 0.1 | 64 ± 3 | 4.0 ± 0.8 | 2.8 ± 0.1 | 69 ± 3 | 9 ± 2 | |
138 | NT | NT | NT | NT | NT | NT | |
139 | 2.8 ± 0.2 | 71 ± 2 | 8.7 ± 0.7 | 2.8 ± 0.2 | 71 ± 2 | 8.7 ± 0.7 | MD,TD相同 |
140 | NT | NT | NT | NT | NT | NT |
表21列出自以70:30 (丙烯酸共聚物:PTFS)重量比率之表3中之丙烯酸共聚物ID 12 (MMA:BA = 84:16)及PTFS製備之各種經拉伸之聚合物摻合物膜的性質。
NT =未測試
表21:丙烯酸共聚物ID 12 (MMA:BA=84:16):PTFS (70:30)之經拉伸膜之性質 | ||||||||||
膜 ID | 拉伸溫度 (℃) | MD(L/L0) x TD(L/L0) | 受約束,不受約束,或雙軸 | d (µm) | Re (nm) | Rth (nm) | Re/d (nm/µm) | Rth/d (nm/µm) | b* | 霧度 (%) |
141 | n/a | 1 × 1 | n/a | 45.0 | -0.4 | 76.0 | -0.01 | 1.69 | 0.22 | 0.60 |
142 | 125 | 2 | 不受約束 | 34.3 | -264.8 | 140.8 | -7.72 | 4.10 | 0.22 | 1.21 |
143 | 125 | 2 × 1 | 受約束 | 26.1 | -122.8 | 149.2 | -4.70 | 5.72 | 0.20 | 0.59 |
144 | 125 | 2.25 × 1 | 受約束 | 20.3 | -118.2 | 115.5 | -5.82 | 5.69 | 0.19 | 0.49 |
145 | 125 | 1.75 × 1 | 受約束 | 29.4 | -102.2 | 122.4 | -3.48 | 4.16 | 0.20 | 0.39 |
146 | 125 | 1.4 × 1.4 | 雙軸 | 21.5 | -3.8 | 108.8 | -0.18 | 5.06 | 0.20 | 0.33 |
147 | 125 | 1.5 × 1.5 | 雙軸 | 21.5 | -4.4 | 111.0 | -0.20 | 5.16 | 0.19 | 0.49 |
148 | 125 | 1.6 × 1.6 | 雙軸 | 21.8 | -3.4 | 129.8 | -0.16 | 5.50 | 0.18 | 0.47 |
149 | 125 | 2 × 1 | 受約束 | 23.6 | -114.5 | 120.0 | -4.85 | 5.08 | 0.20 | 0.28 |
表21:續 | |||||||
膜 ID | MD | TD | 註釋 | ||||
楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | ||
141 | 2.7 ± 0.1 | 74 ± 5 | 7.7 ± 0.6 | 2.7 ± 0.1 | 74 ± 5 | 7.7 ± 0.6 | MD,TD相同 |
142 | 2.8 ± 0.1 | 67± 1 | 4.7 ± 0.2 | NT | NT | NT | TD太小而不能測試 |
143 | 3.0 ± 0.2 | 76 ± 2 | 13 ± 8 | 2.7 ± 0.1 | 69 ± 4 | 8 ± 4 | |
144 | 3.0 ± 0.2 | 79 ± 10 | 18 ± 8 | 2.8 ± 0.2 | 67 ± 8 | 14 ± 8 | |
145 | 2.9 ± 0.2 | 74 ± 4 | 12 ± 3 | 2.9 ± 0.2 | 69 ± 2 | 16 ± 10 | |
146 | 2.9 ± 0.1 | 70 ± 2 | 10 ± 3 | 2.9 ± 0.1 | 70 ± 2 | 10 ± 3 | MD,TD相同 |
147 | 2.9 ± 0.2 | 73 ± 4 | 11 ± 4 | 2.9 ± 0.2 | 73 ± 4 | 11 ± 4 | MD,TD相同 |
148 | 2.9 ± 0.2 | 69 ± 5 | 14 ± 5 | 2.9 ± 0.2 | 69 ± 5 | 14 ± 5 | MD,TD相同 |
149 | 3.0 ± 0.2 | 81 ± 9 | 22 ± 9 | 3.0 ± 0.2 | 70 ± 3 | 12 ± 6 |
表22列出自以60:40 (丙烯酸共聚物:PTFS)重量比率之表3中之丙烯酸共聚物ID 12 (MMA:BA = 84:16)及PTFS製備之各種經拉伸之聚合物摻合物膜的性質。
表22:丙烯酸共聚物ID 12 (MMA:BA=84:16):PTFS (60:40)之經拉伸膜之性質 | ||||||||||
膜 ID | 拉伸溫度 (℃) | MD(L/L0) x TD(L/L0) | 受約束,不受約束,或雙軸 | d (µm) | Re (nm) | Rth (nm) | Re/d (nm/µm) | Rth/d (nm/µm) | b* | 霧度 (%) |
150 | n/a | 1 × 1 | n/a | 33.0 | -0.1 | 76.0 | -0.00 | 3.10 | 0.25 | 0.34 |
151 | 135 | 2 | 不受約束 | 29.9 | -301.1 | 140.8 | -10.07 | 5.22 | 0.22 | 0.73 |
152 | 135 | 1.75 × 1 | 受約束 | 19.2 | -104.1 | 149.2 | -5.42µ | 6.59 | 0.20 | 0.46 |
153 | 135 | 2 × 1 | 受約束 | 19.6 | -131.3 | 115.5 | -6.70 | 7.15 | 0.20 | 0.42 |
154 | 135 | 1.4 × 1.4 | 雙軸 | 19.7 | -2.8 | 122.4 | -0.14 | 6.84 | 0.20 | 0.41 |
155 | 135 | 1.5 × 1.5 | 雙軸 | 18.9 | -0.5 | 108.8 | -0.08 | 7.25 | 0.19 | 0.20 |
表22:續 | |||||||
膜 ID | MD | TD | 註釋 | ||||
楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | 楊氏模量 (GPa) | 最大應力 (MPa) | 斷裂伸長率(%) | ||
150 | 3.0 ± 0.1 | 84 ± 2 | 6 ± 1 | 3.0 ± 0.1 | 84 ± 2 | 6 ± 1 | MD,TD相同 |
151 | 3.0 ± 0.1 | 79 ± 1 | 4.6 ± 0.3 | NT | NT | NT | TD太小而不能測試 |
152 | 3.0 ± 0.1 | 76 ± 3 | 23 ± 8 | 3.0 ± 0.2 | 75 ± 2 | 11 ± 3 | |
153 | 3.0 ± 0.2 | 76 ± 6 | 12 ± 4 | 3.0 ± 0.2 | 74 ± 3 | 7 ± 2 | |
154 | 2.9 ± 0.1 | 73 ± 2 | 17 ± 4 | 2.9 ± 0.1 | 73 ± 2 | 17 ± 4 | MD,TD相同 |
155 | 3.0 ± 0.1 | 73 ± 3 | 22 ± 11 | 3.0 ± 0.1 | 73 ± 3 | 22 ± 11 | MD,TD相同 |
如本文中所闡述之術語係僅用於描述本發明之態樣且不應解釋為限制作為整體之本發明。除非由參考之上下文另有相反指定或明確暗示為相反,否則本發明之單數特徵或限制之所有參考應包含對應複數特徵或限制,且反之亦然。除非另有指定,否則「一(a/an)」、「該」及「至少一個」係可互換使用。此外,如該描述及隨附申請專利範圍中所用,除非上下文另有明確指定,否則單數形式「一(a/an)」及「該」包含其複數形式。相反,在適宜之情況下,對複數條項之任何參考應包含單數。
除非另有指定,否則如本文中所用之所有百分比、份數及比率係藉由總組合物之重量計。除非另有指定,否則當其與所列成分有關時,所有此等重量係基於活性含量,及因此不包含可包含於市售材料中之溶劑或副產物。
本文中所揭示之所有範圍及參數,包括(但不限於)百分比、份數及比率應理解為包含其中所假定及歸入之任何及所有子範圍,及端點之間之每個數字。例如,應認為「1至10」之指定範圍包含以1或更大之最小值開始及以10或更小之最大值結束之任何及所有子範圍(例如,1至6.1、2.3至9.4),及該範圍內包含之各整數(1、2、3、4、5、6、7、8、9及10)。
除非由參考組合之上下文另有相反指定或明確暗示為相反,否則如本文中所用之方法或製程步驟之任何組合可以任何順序進行。
就術語「包含(include/includes/including)」用於本說明書或申請專利範圍而言,其意欲以與術語「包括」相似之方式係包含性,因為當採用時,該術語被解釋為於申請專利範圍中之過渡詞。此外,就採用術語「或」(例如,A或B)而言,其意欲意指「A或B或A及B二者」。當申請者意欲指定「僅A或B但是非二者」時,將採用術語「僅A或B但是非二者」。因此,本文中術語「或」之使用係包含性,且非排他性使用。
於本發明之實施例中,利用各種本發明概念彼此組合(例如,各種實施例中之一或多者可彼此組合利用)可係可能。另外,除非特定要素之併入與該態樣之明確條項矛盾,否則關於本發明之特定揭示態樣詳述之任何特定要素應解釋為可用於本發明之所有揭示態樣。另外優點及修改將對熟習此項技術者顯而易見。因此,本發明於其更廣泛態樣中不限於其中呈現之特定細節、所示及所述之代表性裝置或說明性實例。因此,可在不背離一般發明概念之精神或範圍下脫離此等細節。
Claims (23)
- 一種光學補償膜,其包含: (a)聚(α,β,β-三氟苯乙烯);及 (b)藉由包含以下之單體之聚合製備之丙烯酸共聚物: (i)以基於(i)及(ii)之總重量計70重量%至95重量%之量之甲基丙烯酸甲酯(MMA);及 (ii)以基於(i)及(ii)之總重量計5重量%至30重量%之量之一或多種非MMA的乙烯性不飽和單體,該乙烯性不飽和單體選自包含丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正己酯、甲基丙烯酸正己酯、丙烯酸2-甲氧基乙酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯及其組合之群, 其中該丙烯酸共聚物具有65℃至98℃之玻璃化轉變溫度(T g),且其中該光學補償膜具有在15 µm至50 µm之膜厚度下量測之小於2.25%之霧度、5%至15%之斷裂伸長率及2 GPa至4 GPa之楊氏模量。
- 如請求項1之光學補償膜,其中該光學補償膜包含: (a)基於(a)及(b)之總重量計20重量%至50重量%聚(α,β,β-三氟苯乙烯);及 (b)基於(a)及(b)之總重量計50重量%至80重量%丙烯酸共聚物。
- 如請求項1之光學補償膜,其中該光學補償膜包含: (a)基於(a)及(b)之總重量計25重量%至45重量%之該聚(α,β,β-三氟苯乙烯);及 (b)基於(a)及(b)之總重量計55重量%至75重量%之該丙烯酸共聚物。
- 如請求項1之光學補償膜,其中該光學補償膜包含: (a)基於(a)及(b)之總重量計30重量%至45重量%之該聚(α,β,β-三氟苯乙烯);及 (b)基於(a)及(b)之總重量計55重量%至70重量%之該丙烯酸共聚物。
- 如請求項1至4中任一項之光學補償膜,其中該丙烯酸共聚物包含: (i)基於(i)及(ii)之總重量計80重量%至90重量%之該MMA;及 (ii)基於(i)及(ii)之總重量計10重量%至20重量%之該一或多種非MMA的乙烯性不飽和單體。
- 如請求項1至5中任一項之光學補償膜,其中該一或多種非MMA的乙烯性不飽和單體係選自由丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯及其組合組成之群。
- 如請求項1至6中任一項之光學補償膜,其中該丙烯酸共聚物具有85℃至98℃之T g。
- 如請求項1至7中任一項之光學補償膜,其中該光學補償膜具有小於1.5%之霧度。
- 如請求項1至7中任一項之光學補償膜,其中該光學補償膜具有小於1%之霧度。
- 如請求項1至7中任一項之光學補償膜,其中該光學補償膜具有小於0.5%之霧度。
- 如請求項1至10中任一項之光學補償膜,其中該光學補償膜具有7%至15%之斷裂伸長率。
- 如請求項1至11中任一項之光學補償膜,其中該光學補償膜具有2.5 GPa至3.5 GPa之楊氏模量。
- 如請求項1至12中任一項之光學補償膜,其中該光學補償膜藉由溶液澆鑄製備。
- 如請求項1至12中任一項之光學補償膜,其中該光學補償膜藉由擠出製備。
- 如請求項1至14中任一項之光學補償膜,其中該光學補償膜經單軸或雙軸拉伸。
- 如請求項15之光學補償膜,其中該經拉伸之光學補償膜為具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-80 nm至-300 nm之平面內阻滯(R e)及40 nm至200 nm之平面外阻滯(R th)的負性A-板或正性雙軸膜。
- 如請求項15之光學補償膜,其中該經拉伸之光學補償膜為具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-100 nm至-200 nm之平面內阻滯(R e)及50 nm至150 nm之平面外阻滯(R th)的負性A-板或正性雙軸膜。
- 如請求項15之光學補償膜,其中該經拉伸之光學補償膜為具有在15 µm至30 µm之膜厚度下在550 nm之光波長下量測之-10 nm至10 nm之平面內阻滯(R e)及50 nm至150 nm之平面外阻滯(R th)的正性C-板。
- 一種多層膜,其包含如請求項16或請求項17之負性A-板及具有n x>n y=n z之折射率譜之正性A-板。
- 一種多層膜,其包含如請求項16或請求項17之正性雙軸膜及具有n x>n y>n z之折射率譜之負性雙軸膜。
- 一種多層膜,其包含如請求項18之正性C-板及具有n x>n y=n z之折射率譜之正性A-板。
- 一種平面內切換(IPS)模式液晶顯示器(LCD),其包含如請求項19至21中任一項之多層膜。
- 一種有機發光二極體(OLED)顯示器,其包含如請求項19至21中任一項之多層膜。
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US (1) | US20240061149A1 (zh) |
EP (1) | EP4263681A1 (zh) |
KR (1) | KR20230132784A (zh) |
CN (1) | CN116783238A (zh) |
TW (1) | TW202231746A (zh) |
WO (1) | WO2022132755A1 (zh) |
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US6814914B2 (en) * | 2001-05-30 | 2004-11-09 | Konica Corporation | Cellulose ester film, its manufacturing method, optical retardation film, optical compensation sheet, elliptic polarizing plate, and image display |
TWI353461B (en) * | 2004-05-18 | 2011-12-01 | Fujifilm Corp | Optical film, optical compensation film, polarizin |
US8802238B2 (en) * | 2007-03-29 | 2014-08-12 | Akron Polymer Systems, Inc. | Optical compensation films based on fluoropolymers |
US9598570B2 (en) * | 2014-12-08 | 2017-03-21 | Lg Chem, Ltd. | Composition for optical film and optical film prepared by using the same |
US10088615B2 (en) * | 2015-01-23 | 2018-10-02 | Akron Polymer Systems, Inc. | Fluoropolymer-based polymer blends, polymer films, and polarizer protective films |
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- 2021-12-14 CN CN202180092498.7A patent/CN116783238A/zh active Pending
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- 2021-12-14 US US18/260,694 patent/US20240061149A1/en active Pending
- 2021-12-14 EP EP21907622.1A patent/EP4263681A1/en active Pending
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WO2022132755A1 (en) | 2022-06-23 |
CN116783238A (zh) | 2023-09-19 |
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