TW210378B - - Google Patents
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- TW210378B TW210378B TW080109258A TW80109258A TW210378B TW 210378 B TW210378 B TW 210378B TW 080109258 A TW080109258 A TW 080109258A TW 80109258 A TW80109258 A TW 80109258A TW 210378 B TW210378 B TW 210378B
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- Taiwan
- Prior art keywords
- patent application
- item
- polymeric materials
- refractive index
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- Prior art date
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- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 4
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- 239000004429 Calibre Substances 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
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- 210000000689 upper leg Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
- G02B5/0825—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
- G02B5/0841—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0883—Mirrors with a refractive index gradient
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/516—Oriented mono-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2369/00—Polycarbonates
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
- G02F1/133545—Dielectric stack polarisers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S359/00—Optical: systems and elements
- Y10S359/90—Methods
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
Λ fi Ιί 6 2103^3 五、發明説明() 本發明偽闋於一種多層的雙折射干涉偏光鏡,持別是 關於一種多層共押出的聚合裝置,其被設計成可藉著構造 上的光學干涉而將選定之波長的光偏振。 雙折射偏光鏡在此項技藉裡已為習知者,並且在過去 即己被使用於偏振並且過濾選定波長的光。例如,雙折射 偏光鏡可被使用於拒絶(反射)被特定偏振的狹窄波長範圍 而傳送其餘的入射光,以便降低從其他光源來之眩目的光 ,並且作用為光束分離器。 有許多自然形成的結晶化合物作用為雙折射偏光鏡。 例如,方解石(5庚酸鈣)結晶體即具有己知之雙折射性質。 不管如何,單一結晶物葆為昂貴的材料並且無法針對特定 應用所需而隨時形成所欲得到的形狀或者構造。此技藝之 其他者,例如Hokas的美國專利第691號案,即曾經 從板狀或片狀的雙折射聚合物例如^二酸乙二酯併入
Vv 一種各向同性的矩陣聚合物裡來構造$折射偏光鏡。 在許多個例子裡,聚合物可嘲著單軸拉伸而將該聚合 物定向至分子的階層,例如Rogers et al.之美國專利第 4,525,4 13號案所掲示者。包含高度雙折射聚合物以及具 有較大折射率偏差所構成之交替層的多重光學裝置即曾被 Rogers et al.所提出。不管如何,該種Rogers et al. 裝置必須使用在分子構造以及電子密度分佈之間具有特定 數學關偽之特定的高度雙祈射聚合物。 因此,在此技藝裡對於雙折射干涉偏光鏡仍然有一需 要,其必須可以使用現存之技術與随時可得之材料來製造 本紙尺度逍用中國Η家標毕(CNS)TM規格(210X297公址) -3 - (請先閲讀背而之注意1ε項#塡^厶. 裝- .線* 經濟部中央標準局β工消许合作社印製 210373 經濟部屮央標準局β工消伢合作社印製 Λ 6 Π 6 五、發明説明() 。再者,在此技藝裡對於雙折射干涉偏光鏡亦存在另一需 要,其必須僅吸收很少的光。甚且,在此技藝裡對於雙折 射干涉偏光鏡復有一需要,其必須被構造成可以偏振具有 所希望之特定波長的光。 本發明藉著提供一種具有多層板片或薄膜之形態的雙 折射干涉偏光鏡而能符合該等需要,其可以使用現有之共 押出技術而從随時可得之材料被構造完成。本發明的偏光 .鏡具有之光吸收的程度接近零並且被構造成可以偏振和反 射持定波長的光而僅傳送其餘波長的光。該種偏光鏡亦將 僅偏振具有那些波長之所傳送的光,而其餘所傳送的光仍 然不會被镉振。 在本文中所使用之偏光鏡、偏振的光、以及褊振作用 傜指一種光的狀態,其中在不同的平面裡光線的横向振動 假設具有不同的形態。本文中所使用的偏振作用,包括直 交平面裡不相等的#反^並且包含光的橢圓和圓形的偏振 以及平面偏振。而光”,不僅指可見光譜者,並且 亦包括紫外線及紅外光。當本文中討論到聚合材料之定向 的平面時,乃偽指該聚合材料由於材料沿X和/或Y方向之 單軸或雙軸拉伸的定向方向以便用以定義該等材料的偏振 效應。本文中所指的光進入或侵入聚合材料之各層的平而 偽為一垂直於各層之主要表面的平面(亦即Z軸方向)。 依據本發明的一値特點,所提出之雙祈射干涉偏光鏡 包含値別地具有非零應力光學傜數的至少第一和第二種聚 合材料之多重交替定向的材料層,而該等非零應力光學偽 本紙ft尺度逍用中國國家標準(CNS) Ή規格(210x297公*) 4 .........................裝· · . ·訂.....線 (請先閲讀背而之注意市項#植^:« 210373 Λ 6 η 6 經濟部十央·標準灼A工消伢合作社印製 五、發明説明() 數具有充分的差異以便在一第一痼平面裡第一及第二種聚 合材料之間産生一折射率偏差,該折射率偏差係不同於一 垂直於第一锢平面的第二個平面裡第一及第二種聚合材料 之間的折射率偏差。 本發明的雙折射干涉偏光鏡亦可包含各種聚合材料所 構成的三或更多交替的積層。例如,一値第三層的圖案可 以使用重覆的單元ABCBA,其中Β單元為一種Α及C重覆單元 的共聚物或可溶混的摻合物。在一些例子裡,B層將不僅 貢獻本發明的光偏振性質,亦作用為一種將A及C層黏合在 一起的黏著劑層。 再者,第三個聚合物層亦被發現到可做為一種ABABAB 重覆體之一或兩主要外部表面的表皮層或者做為一内靥。 其表皮層可為具有犧牲性者,或者可為永久性者並且做為 防止刮擦或耐候的保護層。甚且,這種表皮層可在共押出 之後再被塗佈於偏光鏡上。例如,一表皮層可以噴霧塗佈 在塗蓋層上而將偏光鏡的表面補平以便增進光學的性質並 且賦予抗刮擦的能力,抗化學性和/或耐候性。該種表皮 層亦可被積層於多層結構的偏光鏡上。以積層的方法就那 些無法容易地共押出之聚合物而言乃為霈要的。 在本發明的一個具體實施例裡,第一及第二種聚合材 料在未被定向時大致上具有相等的折射率。其折射率偏差 傜發生於該等材料被拉伸時所定向的平面裡。在另一個具 體實施例裡,第一及第二種聚合材料於未被定向時即具有 不同的折射率。藉著拉伸來定向該等聚合物導致該等平面 (請先閱讀背而之注意市項#项穷/ X). 裝· -線· 本紙張尺度逍用中a®家標準(CNS)T4規格(210X297公龙) -5 - 10378 A (1 \\ 6 五、發明説明() 之一裡個別地折射率之間的偏差降低,而在男一平面上的 偏差則保持不變或者增大。該種偏光鏡可為單軸或雙軸定 向者。 在本發明的一橱較佳形態裡,第一種聚合材料具有一 正的應力光學僳數,而第二種聚合材料具有一負的應力光 學偽數。較適宜者,在第一個平面裡的折射率偏差至少為 0.03,並且最適宜者傜為0.05或者更大。 較適宜者,毎一聚合層的光學厚度偽為0.09微米到 〇.70徹米。光學厚度,nd,偽被定義為積層(d)之物理厚 度與其折射率(η)的乘積。在本發明的一値較佳形態裡, 各層厚度隨著薄膜的厚深而單向逐漸地增便産生一種 聲' 積層厚度的悌度,使其能反射並且偏振較寬 Υ範掘之波長的 光。 i. 兩種聚合材料可為任何不同的聚合物,具有非零的應 力光學俗數,在該等材料被定向時提供必需的折射率偏差 。所謂之非零的應力光學偽數,意即該種聚合物的折射率 在其被定向時沿一正或負的方向變動者。具有零應力光學 偽數之各向同性的材料缺乏雙祈射。 經濟部屮央樣準局A工消件合作社印製 例如,第一種聚合材料可為一聚碩酸酯,例如一種以 雙苯酚Α為基礎的聚磺酸酯,或者一種聚對苯二酸乙二酯 ,該兩者皆具有正的應力光學偽數。第二種聚合材料可為 —種聚苯乙烯,其具有負的應力光學係數。大體上為無定 形的無規聚苯乙烯或者晶狀的間規聚苯乙烯都可適用。其 他適合用做第二種聚合材料的聚合物包括苯乙烯與丙烯腈 本紙尺度边用中HB家標準(CNS)TM規格(210x297公龙) _ 6 _ 210373 Λ f5 B 6 經濟部屮央梂準局A工消伢合作社印製 五、發明説明() 的共聚物,苯乙烯與異丁烯酸甲酯的共聚物,以及聚萘酸 乙二酯,這些全都具有負的應力光學僳數。 本發明的镉光鏡反射並且镐振入射於其表面之光的一 部份而傳送其餘的入射光。在構造之時,其可被設計成為 僅傳送一狹小範圍的波長而反射一寬廣範圍的波長,或者 正好相反。本發明的偏光鏡亦可被設計成為大致上反射並 且偏振所有入射於該裝置之一個平面的光而且大致上傳送 所有入射於與該平面垂直之另一平面的光。 在本發明的一些具體實施例裡,其可能需要加入色劑 例如染料或顔料於該雙折射偏光鏡的一或多層裡。此可以 被完成於其主體之外或表皮層之一或兩者,或者可替換地 ,色劑亦可被加入於偏光鏡之内層的一層或者數層。顔料 或染料的使用容許特定波長的光被偏光鏡選擇性地吸收。 而未加顔料或未加染料的多層薄膜將反射被特定偏振的波 長並且傳送其餘的入射光,顔料及染料復可被使用於控制 所反射之偏振光的光帶寬度以及所傳送之光的波長範圍。 例如,所有被傳送的光可藉著將一黑色層共押出於雙祈射 偏光鏡的背面而被吸收。再者,染料可被使用於藉箸吸收 選定之波長而縮小所反射之光以及所傳送之光的波長帶。 所選定的聚合物將決定折射率偏差、個別地應力光學 偽數、以及玻璃轉化溫度。積層的數目、定向的程度、積 層的厚度、以及顔料#$料的使用全部可以被調整(控制) 以便提供一種具有所徽以供持定之用途的偏光鏡。此 一點傜不同於先前的技術,其偽受限於設計與偏振持徵者 it 閲 背 而 之 .注 意 事 項 Λ m 装
ST 線 本紙尺度遑用中SB家標準(CNS)T4規格(210x297公;«:) 2ΐ〇3'ί3 經濟部屮央標準而Μ工消费合作社印製 Λ ίϊ Π 6 五、發明説明() Ο 在本發明的另一錮具箱實施例裡提供了一種可諏節的 雙折射干涉偏光鏡,包含具有锢別地非零應力光學#數之 第一及第二種撣性體材料所構成的多重交替地積層,其非 零應力光學偽數傜為充分的不同以便能在一第一個平面裡 的第一及第二種彈性體材料之間産生一折射率偏差,而該 折射率偏差傜不同於一垂直於第一個平面的第二辉平面裡 之第一及第二種彈性體材料之間的折射率偏差。由於形成 偏光鏡的個別積層偽為彈性體,偏光鏡可依據彈性體伸長 的程度可變動地偏振光的波長。除此之外,由於各積層偽 為彈性體.當該裝置被回復到一放鬆的狀態時該偏光鏡將 為可調節地以及可逆轉地。 本發明亦提供一種製造雙祈射干涉偏光鏡的方法,包 括共押出在多重積層裡至少第一及第二種聚合材料具有個 別地非零應力光學偽數的步驟。該等積層可被拉伸而將聚 合材料定向並且在一第一個平面裡産生一折射率偏差,此 折射率偏差偽不同於一個與第一個平面垂直的第二個平面 裡第一及第二種聚合材料之間的折射率偏差。雖然許多聚 合物組合可在高於玻璃轉移溫度但低於其熔點的溫度下被 拉伸,有一些聚合物組合卻可披“冷拉”,其中該聚合物 的:一或多種可於低於其玻璃轉移溫度的溫度下被拉伸。 在本發明的一個具體實施例裡,第-及第二種聚合材 料在未被定向時大致上具有相等的祈射率,且一祈射率偏 差會随著定向作用而發生於~平面上。在另一個具體實施 本紙尺度遑用中SB家標準(CNS)T4規格(210x297公龙) -8 - (請先間請背而之注意事項#项^«> 裝- Λ β η 6 五、發明説明() 例裡,於被定向時,第一及第二種聚合材料在第一及第二 倨平面之一裡具有大致上相等的折射率,但是在另一平面 裡會有一折射率偏差。該等聚合材料的定向作用可以為單 軸或者雙軸的。 較適宜者,在第一値平面裡的折射率偏差至少約為 0.03,並且最適宜者至少為Q.05或者更大,且每一層的光 學厚度為G.09微米到Q.7Q徹米之間。在一値具體實施例裡 ,該等積層的厚度隨著薄膜的厚深單向地逐漸增加以便提 供一種可反射較寬廣波長範圍的偏光鏡。在本發明的一個 較佳具體實施例裡,第一種聚合材料具有一正的應力光學 係數,並且第二種聚合材料具有一負的應力光學偽數。 據此,本發明的一個目的僳在於提供一種雙折射干涉 偏光鏡以及製造方法,其可以從易於得到之材料使用既有 的共押出技術來被構造,使其吸收光的程度接近零,並且 被構造成可以反射和偏振特定波長的光而傳送其他波長的 光。本發明的這一痼以及其他目的和優點從下面的詳細說 明、隨附的圖式和附加的請求專利範圍中將變成顯而易知 者。 經浒部屮央楳準局ΚΧ工消费合作社印虹 第1圖偽為依據本發明所製成的多層光學干涉偏光鏡 之反射對光波長的一個圖。 本發明提供具有多層薄膜形狀之改良的光學干涉偏光 鏡,其具有許多必要的性質包括使該裝置可以偏振選定之 光波長的能力。與本發明相關之基本的光學原理係為那些 和被具有不同折射率的薄膜層所為之光的反射有關者。這 9 (請先閲讀背而之注意事項#项^/-· 本紙張尺度逍用中国國家猱準(CNS)T4規格(210x297公:it) 210373 Λ ίί Π 6 經濟部屮央樣準局A工消费合作社印製 五、發明説明() 些原理驗證了材料之個別層厚度與折射率兩者間之作用的 從屬關係。請參考Radford et al所著的“虹彩之共押出 多層塑膠薄膜的反射性”,13聚合物工程及科學216(1973 )。 在該文獻裡描述了-一種薄膜,其厚度d小於約0.5微米 或者其光學厚度nd (在此η俗為該材料之折射率)係小於約 0.7 撤米。請見 Vasicek 所著的 Optics of Thin Films(‘1 96 0) ,第100和139頁。 干涉薄膜,其依賴光之構造上的光學干涉以便在電磁 光譜之可見光、紫外線或紅外光部份産生強的光學干涉, 曾被描述於先前的技術裡。請見,例如,Alfrey, Jr. et al.,的美國專利第3,711,176號案。這種干涉薄膜依據下 列公式而作用: λ id= (2/m)(NiDi+ H2D2) 在此λ n俗為所反射的波長,單位為nanometer(10-3米), I及}為交替之聚合物的折射率,卩*及卩2為個別之聚合物 層的厚度,單位為113110111616]:(1(3_3米),並且B為反射的次 序(Π=1, 2力3, 4, 5)。此一公式適用於入射的光垂直於 薄膜的表面。若為其他的入射角度,該公式將被修正以將 角度列入考慮,如習知技術者。本發明的偏光鏡對所有的 入射光角度皆為可操作的。該公式的每一値答案決定一個 波長,在此波長皆期望有一相對於周圍區域之強烈的反射 。反射的強度ί%為“卜比率”的一値函數,其中, Ni D. f =-—- N, D. + Na Da (請先閲讀背而之注意事項洱项.:'3. 本紙張尺度逍用中a Η家楳準(CNS) Ή規格(2丨0X297公;it) lOciVb Λ β ___η 6 _ 五、發明説明() 藉箸適當選擇f-比率,可以對各種較高次數之反射的反射 強度進行某一程度的控制,例如,紫色(約為Q. 38 W波長) 到红色(約為0.68 w波長)的第一次可見光的反射可以用具 有之光學厚度為〇 . 075到0 . 25徹米之間的積層來獲得。 不管如何,從先前技術之薄層干涉薄膜所反射的光並 未被偏振。從本發明之交替的聚合物層所反射的光由於薄 膜之雙折射性質基本上傜被偏振的。因此,在其較佳的形 態裡,本發明的雙折射干涉偏光鏡包含至少第一及第二種 具有個別之非零應力光學傜數的聚合材料所構成的多重交 替定向的積層,其非零應力光學係數乃為充分地不同以便 在一第一値平面的第一及第二種聚合材料之間産生一折射 率偏差,而此折射率偏差係不同於一個與第一個平面垂直 的第二個平面裡第一及第二種聚合材料之間的折射率偏差 。此一折射率偏差較適宜者至少約0.03,並且最適宜的是 至少Q.G5或者更大。此一構造形成一種偏光鏡,其在一第 一個平面.例如定向的平面上造成光學的干涉,並且在一 垂直於該平面的第二値平面上造成近於零的光學干涉。 經濟部屮央梂準灼Α工消f合作社印51 較適宜者,每一聚合物層的光學厚度偽在0.09到0.70 微米的範圍裡。適用於本發明之應用的聚合物包括具有應 力光學偽數之大致上為透明的熱可塑性聚合物,當該等聚 合物被定向時,其應力光學俗數在至少一個平面上提供了 必要的祈射率偏差。除此之外,從製程的觀點而言,該等 聚合物必須為可相容共押出者。 11 (請先間讀背而之注意本項洱埙?·'、κ> .線· 本紙張尺度逍用中Η S家猱準(CNS)肀4規格(210x297公:«:) ό A 6 η 6 經濟部屮央櫺準局员工消费合作社印Μ 五、發明説明() 一個適當的聚合物配對之實例偽為聚磺酸酯與聚苯乙 烯。間規聚苯乙烯被認為是特別適用者。聚硪酸酯具有一 正的應力光學傜數,而聚苯乙烯具有一負的應力光學傜數 。兩者具有之折射率(未定向時)約為1.6。其他適用於本 發明之大致上為透明的熱可塑性聚合物包括例如名稱為“ 彈性體的光學干涉薄膜”,於1990年6月26日所掲露之美 國專利第4 , 937 , 134號案裡所一般指定的那些彈性髖。 除此之外,其他聚合物及共聚物例如以聚2,6萘酸乙 二酯、1,4-琛己烷二甲烯對苯二酸酯(PCTG)為基礎的共聚 物、以及戊二亞胺和異丁酸甲酯(KAMAX樹脂,可從Rohn及 Haas取得)的共聚物,亦適合於本發明的應用。再者,聚 合物之可溶混的摻合物可被使用於調整偏光鏡所使用之積 層的折射率、應力光學係數、以及玻璃轉移溫度。其他可 被用於本發明之應用的熱可塑性樹脂之實例,以及其代表 性的折射率包括有,但未限於:金氟烷氣基樹脂(折射率 = 1.35)、聚四氟乙烯(1.35)、氟化的乙烯-丙烯共聚物 1-34)、硅_樹脂(1.41)、聚偏二氟乙烯(1.42)、聚氣三 氟乙烯(1.42)、環氣樹脂(1.45)、聚丁基丙酸酯(1.46)、 聚4-甲基戊烯-1(1.46)、療醋酸乙烯酯(1.47)、乙基纖維 素(1.47)、聚甲醛(1.48)、聚異丁基丙烯酸甲酯(1.48)、 聚甲基丙烯酸酯(1.48)、聚丙基丙烯酸甲酯(1.48)、聚乙 基丙烯酸甲酯(1.48)、聚醚成塊醯胺(1.49)、聚甲基丙烯 酸甲酯(1.49)、醋酸纖維素(1.49)、丙酸酯纖維素(1,49) 、醋酸丁酸纖維素(1.49)、硝酸纖維素(1.4 9)、聚乙烯醇 (請先閲讀背而之注意事項#塡.βνθ> 本紙張尺度逍用中a ffl家楳準(CNS) Τ4規格(210x297公;Jt) 12 A 6 η 6 經濟部中央?4準灼员工消费合作社印製 五、發明説明() 缩丁醛(1.49)、聚丙烯(1.49)、聚丁烯(1.50)、離子化樹 脂例如Surlyn(商標名)(1.51)、低密度聚乙烯(1.51)、聚 丙烯膀(1.51)、聚異丁烯(1.51)、熱可塑性的聚酷例如 Ecdel(商標)(1.52)、天然橡膠(1.52)、丁腈橡膠(1.52) 、聚丁二酯(1.52)、尼龍(1.53),聚丙烯亞胺(1.53)、聚 醋酸氣乙烯(1.54)、聚氯乙烯(1.54)、高密度聚乙烯(1.54) 、異丁烯酸甲酷與苯乙烯的共聚物(1.54)、透明的丙烯腈 -丁二烯-苯乙烯的三聚物(1.54)、烯丙二甘醇樹脂(1.55) 、聚偏二氯乙烯和聚氯乙烯的摻合物例如Saran樹脂(商標 名)(1.55)、聚-α-甲基苯乙烯(1.56)、苯乙烯-丁二烯膠 乳例如D0W-512-K(商標名)(1.56)、聚氨基甲酸酯(1,56) 、氣丁二烯橡膠(1.56)、苯.乙烯和丙烯腈的共聚物例如 Tyril樹脂(商標)(1.57)、苯乙烯和丁二烯的共聚物品 (1.57)、其他熱可塑性聚酯例如聚對苯二酸乙酯以及聚對 苯二酸乙二醇酯(1.60)、聚亞胺(1.61)、聚偏二氣乙烯 (1.61)、聚二氯苯乙烯(1.62)、聚理(1.63)、聚醚理(1.65) 、以及聚醚亞胺(1.66)。 上面聚合物之共聚物和可溶混的摻合物亦可被使用於 本發明的應用。這種共聚物和摻合物可被使用以便提供無 數種不同的折射率,使其互相配合而逹成最佳的偏振效應 。除此之外,該等聚合物之共聚物和可溶混之摻合物的使 用可被用以增進共押出以及定向作用時交替積層的可加工 性。再者,共聚物以及可溶混之摻合物的使用可容許該等 聚合物之應力光學偽數與玻璃轉移溫度的調整。 請 先 閲 背 而 之 注 意 事 項 # 裝 玎 線 本紙张尺度遑用中SK家標準(CNS)T4規格(210x297公货) 13 2i〇仰 Λ β Π 6 經濟部屮央.#準局貝工消赀合作社印製 五、發明説明() 依據本發明之多層的雙折射干涉偏振薄膜藉著使用一 種如美國專利第3, 773,882號案與第3,884,606號案所描述 的多層共押出裝置可以非常優越地被製備完成。這種裝置 提供一種方法,用於製備多層的,同時押出的熱可塑性材 料,其毎一層皆具有大致上均勻的積層厚度。較適宜者, 如美國專利第3,859,647案所描述之一糸列的多重層積裝 置亦可被使用。 該共押出裝置的進料區從一來源例如一加熱塑化押出 機接收不同的熱可塑性聚合材料。該等樹脂狀的材料流入 進料區内的一値機械操作的區段。此一區段將原始的原料 流重新整理成具有最终主體所需之積層數目的多層排列的 原料流。較適宜者,此一多層排列的原料流大髏上可被流 經一糸列的多重層積裝置,以便再增加最終主體之積層的 數目。 該一多層排列的原料流然後流入一個押出模,其係被 如此構造以及安排使得原料流被保持於其内。這種押出裝 置傜如美國專利第3,55 7,2 65號案所描述者。最终的産品 被押出而形成一多層的主體,其中毎一層大致上平行於相 郯層的主表面。 該押出模的構造可以改變並且可以例如降低毎層的厚 度和尺寸。從機械定向區段傳送來之各層厚度縮減的精確 度、押出模的構造、以及押出後主體之機诚工作的量偽為 所有影蜜最终主體之個別積層厚度的因素。 在押出以及積層之後,所得到之多層薄層於一溫度 (請先閲讀背而之注意事項孙项炙 3 本紙张尺Αϋ用中a國家標準(CNS)T4規格(210X297公龙) 14 2i〇抑 Λ 6 H 6 經濟部屮央梂準而β工消赀合作社印製 五、發明説明() 高於聚合物之値別玻璃轉移溫度但低於其艏別熔點下,沿 單軸或者雙軸而被拉伸。可替換地,該多層薄膜可於一溫 度低於該薄膜裡之至少一種聚合物的玻璃轉移溫度之下被 冷拉和拉伸。此導致該等聚合物起定向作用並且由於聚合 物之間應力光學傜數和/或折射率的差異而在該偏光鏡的 至少一傾平面裡産生一折射率偏差。 選定波長之光的偏振作用俗藉著因為偏光鏡之至少一 個平面裡折射率偏差所造成的構造性光學干涉來逹成的。 該偏光鏡可被構造使得不同的波長可依需要而被偏振 。折射率偏差的控制、薄膜内相關積層之厚度、以及薄膜 内發生之定向作用的量決定了何種波長的光學將被偏振。 而就其他干涉薄膜而言,被偏振之光的波長亦端賴入射光 相對於偏光鏡之表面的入射角度而定。 本發明的雙折射干涉镰光鏡反射並且偏振一部份人射 於其表面的光,並且傳送其餘的入射光。實質上並沒有光 被偏光鏡所吸收。在構造的期間,交替之聚合物積層的厚 度可被控制使得偏光鏡僅傳送狹小的波長範圍而反射並且 偏振一較寬廣的波長範圍。例如,在多層薄膜裡的積層可 被安排使得它們的厚度隨著薄膜的厚度做單向漸進的增加 以便産生一積層厚度梯度。此賦予了該偏光鏡寬廣的光帶 反射性質。這種偏光鏡可被使用做為僅傳送一狹小範圍之 波長的光帶過濾器。 可替換地,該薄膜可被構造成僅偏振和反射一狹窄的 波長範圍而對入射光的其餘部份保持為可穿透的。如果使
(諳先閱讀背而之汰意卞項#填JT'i HV 本紙張尺度边用中S®家標準(CNS)T 4規格(210父297公;«:) -15 - Λ 6 Π 6 五、發明説明() 用白光做為光源,本發明的偏光鏡依據其積層之光學厚度 將在一平面上將特定波長之被偏振的光反射回去,而傳送 剩下的光。 本發明之偏光鏡的一痼用途傜裝設於飛機或汽車的擋 風玻璃上,有一 “警示”的顯示可被投射於其上。該偏光 鏡將降低飛機或汽車外面,或者飛機或汽車本身内部來的 眩目光線,而此眩目的光線之入射角度偽相同於所投射之 “警示”影像的角度。本發明的使用造成了其他入射光增 進的傳送,在其上面亦可使用至少吸收一些入射光的傳统 偏光鏡。本發明之偏光鏡的另一個用途偽做為一掘光束分 離器。 為了使本發明更能易於瞭解,請參考下面的實例,其 俱用於描述本發明,但不是用來限制其範圍。 啻例1 經濟部屮央標準灼A工消1V合作社印製 使用一種如美國專利第3,7 7 3, 88 2號案及3,7 5 9,6 4?號 案所描逑的装置,製備一片雙折射干涉偏振薄膜。此Η之 厚度約為0.008公分( 0.0 0 3英吋),並且具有由聚碩酸酯 (Calibre 300- 15 , DOW化學公司之商標)以及聚苯乙烯 (Styron 685D, DOW化學公司之商標)所構成之385層交替 的積層(ABABAB)。 一片2.54公分(1英时)乘2.54公分(1吳时)乘0.008公 分(0 . 00 3英吋)的薄膜樣品然後於160V (高於該兩聚合物 之玻璃轉移溫度)以448N/Cm2 ( 650 1 b/in2)的力量沿箸單軸 方向將其從原先的2.54公分長(1英时)泣伸至一最终長度 本紙尺度逍用中國Η家楳準(CNS)肀4規格(210X297公;«:) 6 Λ Γ) Π 6 五、發明説明() 7.6公分(3英吋),並且然後迅速地以水使其驟冷而將該等 聚合物定向。最終樣品的厚度平均0.004公分(0.0015英吋 ),並且其最小的寬度為1.27公分(0.50英吋)。 後拉伸的狀況被控制使得聚碩酸酯層最終的平均積層 厚度為856.8埃而聚苯乙烯層為873.1埃。這些積層的厚度 被算出以便得到一種偏振薄膜,可偏振位於可見光譜之中 間地帶(λ = 550 0埃)而具有如上定義之f-比率為0.5的光 線。 兩種聚合物在未定向狀態下測得之折射率約為1. 6。 不管如何,該種聚碩酸酯測得之正應力光學偽數約為+5000 Brewsters而聚苯乙烯測得之負應力光學係數約為-50 00 Brewsters。後拉伸的程度被控制使得定向作用的平面裡 兩聚合物之間的折射率偏差成為0 . 03。 經濟部屮央標準工消奸合作社印奴 為了決定該薄膜是否作用為一個偏光鏡,兩片385層 的薄膜於單軸拉伸而將聚合物定向於薄膜裡之前被積層完 成。一給定波長的反射量被測定於一値與單軸拉伸平行的 平面以及一個與單軸拉伸垂直的平面。如第1圖中所顯示 者,在平行與垂直平面裡一寬廣範圍之波長反射量的差異 驗證了該薄膜確實作用於將光線偏振。 由於一些代表性的具體實施例及細節已經被描述用以 說明本發明,其對於熟識此項技藝的人士而言將變得顯而 易知者的是各種掲露於此之方法及裝置的變動可被執行而 仍不脱離本發明的範圍,而此範圍係定義於隨附的申I青專 利範圍裡者。 17 (請先間-背而之注意市項#填^頁) 本紙張尺度逍用中國國家楳準(CNS)T4規格(210父297公龙)
Claims (1)
- Α7 Β7 C7 D7 經濟部中央標準局員工消費合作杜印製 六、申請專利範圍 第80109258號專利申請案申請專利範圍修正本 修正日期:82年4月 1. 一種包含多重交替定向的積層之雙折射干涉偏光鏡, 特擻為至少第一及第二聚合材料具有個別地非零應力 光學係數,而該等非零應力光學侈數係為充分地不同 而足Μ在該第一及第二聚合材料之間產生一在第一平 面中之折射率偏差,且該折射率偏差係不同於在垂直 於該第一平面之一第二平面中之該第一與第二聚合材 料之間之折射率偏差;且其中該聚合材料經共擠塑出 成多重積層,再拉伸Μ定向該材料,而產生一折射率 偏差。 2. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該第一及第二聚合材料未被定向時具有大致上相等的 折射率。 3. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該被定向的第一及第二聚合材料在該等平面之一中 具有大致上相等的折射率。 4. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該第一及第二聚合材料係為沿著單軸被定向者。 5. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該第一聚合材料具有一正的應力光學係數,且該第二 聚合材料具有一負的應力光學係數。 6 .依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 於該第一平面中的該折射率偏差為至少0.03。 (請先閲讀背面之注意事項再塡寫本頁) 丨裝· 訂. .線. 本紙張尺度適用中國國家標準(CKS)甲4说格(210 X 297公贫) 3 Α7 Β7 C7 D7 六、申請專利範園 7 .侬據申請專利範圍第1項的雙折射干涉偏光鏡,其中 每一積層的光學厚度係爲0.09撤米到0.70徹米。 8. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該積層的厚度單向逐漸地增加Μ造成一個層厚梯度 〇 9. 依據申請專利範圍第1項的雙折射千涉偏光鏡,其中 該第一聚合材料係從聚碩酸酯和聚對苯二酸乙二酯所 構成的族群中所選出者。 10·依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該第二聚合材料係從聚苯乙烯、苯乙烯與丙烯腈之共 聚物、苯乙烯與甲基丙烯酸甲酯之共聚物、Μ及聚萘 睃乙二酯所構成的族群中所選出者。 11. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該的第二聚合材料爲一間規聚苯乙烯。 12. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該第一及第二聚合材料包含共聚物或可溶混的聚合物 摻合物以便調整該等聚合材料之値別的折射率、應力 光學係數、Μ及玻璃轉化溫度。 13. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 一著色劑被加入於該雙折射偏光鏡的至少一層中。 14. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該著色劑係從顔料和染料所構成的族群中所選出者。 15. 依據申請專利範圍第1項的雙折射干涉偏光鏡,其中 該的偏光鏡可依據該彈性體伸長的程度藉由可變地偏 •紙張尺度適用中國國家標準(CNS)甲4規格(210 X 297公發 (請先閲讀背面之注意事項再填寫本頁) Γ 4'^ 烴濟部中央標準局員工消費合作社印製 烴濟部中央標準局w工消費合作社印製 A7 -. B7 . C7 _D7_ 六、申請專利範圍 振各棰波長的光而調節。 16.—種製造一雙折射干涉镐光鏡的方法,包含下列步驟 提供至少第一及第二具有値別地非零應力光學係 數的聚合材料, 共擠出該第一及第二聚合材料成爲多重交替的積 層,並且 拉伸上述的積層以使該第一及第二聚合材料成為 定向並且在第一平面中產生一折射率偏差,而該折射 率偏差係不同於在垂直於該第一平面之第二平面中之 該第一與第二聚合材料之間之折射率鴒差。 17·依據申請專利範圍第16項所述的方法,其中該第一及 第二聚合材料具有一玻璃轉化溫度,且其中該拉伸步 驟係在一高於該聚合材料的玻璃轉化溫度但是低於其 熔解溫度之溫度下進行。 18. 依據申請專利範圍第16項所述的方法,其中該第一及 第二聚合材料未被定向時具有大致上相等的折射率。 19. 依據申請專利範圍第16項所述的方法,其中在該等平 面之一中之折射率偏差增加,而另一平面中之折射率 偏差減少,以致被定向的第一及第二種聚合材料於其 中一個平面中具有大致上相等的折射率。 20·依據申請專利範圍第16項所述的方法,其中該第一及 第二聚合材料係沿著單軸被定向者。 21.依據申請專利範圍第16項所述的方法,其中該第一聚 (請先閲讀背面之注意事項再填寫本頁) .裝· 訂 •線· 本紙張尺度適用中國國家樣準(CNS)甲4規格(210 X 297公釐) Α7 Β7 C7 D7 六、申請專利範圍 合材料具有一正的應力光學係數並且該第二聚合材料 具有一負的應力光學係數。 22. 依據申請專利範圍第16項所述的方法,其中於第一平 面中的折射率镉差為至少0.03。 23. 依據申請專利範圍第16項所述的方法,其中每一積屬 的光學厚度係為〇.〇9撒米到0.70撒米。 24 _依據申請專利範圍第16項所述的方法,其中該積層的 厚度單向逐漸地增加以造成一値層厚梯度。 25.依據申請專利範圍第16項所述的方法,其中該第一聚 合材料係從聚碩酸酯和聚對苯二酸乙二酯所構成的族 群中所選出者。 〆 26·依據申請專利範圔第16項所、述的方法,其中該第二聚 合材料係從聚苯乙烯、苯乙烯與丙烯腈之共聚物、苯 乙烯與甲基丙烯酸甲酯之共聚物、Μ及聚萘酸乙二酯 所構成的族群中所選出者。 27·依據申請專利範圍第16項所述的方法,其中該的第二 聚合材料爲一間規聚苯乙烯。 f #先閱讀背面之注意事項再填寫本頁) 丨裝_ 訂. .線. 煙濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)甲4规格(210 X 297公货)
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| DE69329945T2 (de) * | 1992-07-14 | 2001-06-07 | Seiko Epson Corp., Tokio/Tokyo | Polarisierendes element, optisches element und optischer kopf |
| US5333072A (en) * | 1992-12-31 | 1994-07-26 | Minnesota Mining And Manufacturing Company | Reflective liquid crystal display overhead projection system using a reflective linear polarizer and a fresnel lens |
| US6483612B2 (en) | 1998-04-15 | 2002-11-19 | Duke University | Projection screen apparatus including holographic optical element |
| US6788460B2 (en) | 1998-04-15 | 2004-09-07 | Duke University | Projection screen apparatus |
| US20030206342A1 (en) * | 1993-05-12 | 2003-11-06 | Bright View Technologies, Inc. | Micro-lens array based light transmission screen |
| RU2047643C1 (ru) | 1993-05-21 | 1995-11-10 | Хан Ир Гвон | Материал для поляризующих покрытий |
| US5946431A (en) | 1993-07-30 | 1999-08-31 | Molecular Dynamics | Multi-functional photometer with movable linkage for routing light-transmitting paths using reflective surfaces |
| US6096375A (en) * | 1993-12-21 | 2000-08-01 | 3M Innovative Properties Company | Optical polarizer |
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- 1991-11-08 DE DE69128613T patent/DE69128613T2/de not_active Expired - Lifetime
- 1991-11-08 EP EP91310336A patent/EP0488544B1/en not_active Expired - Lifetime
- 1991-11-12 JP JP29588991A patent/JP3704364B2/ja not_active Expired - Lifetime
- 1991-11-25 CA CA002056153A patent/CA2056153A1/en not_active Abandoned
- 1991-11-25 KR KR1019910021065A patent/KR920010316A/ko not_active Withdrawn
- 1991-11-25 TW TW080109258A patent/TW210378B/zh not_active IP Right Cessation
-
1995
- 1995-05-30 US US08/452,832 patent/US5612820A/en not_active Expired - Lifetime
-
1996
- 1996-12-18 US US08/768,525 patent/US5872653A/en not_active Expired - Lifetime
-
1998
- 1998-12-23 US US09/220,210 patent/US6583930B1/en not_active Expired - Fee Related
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2004
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-
2005
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- 2005-10-28 JP JP2005315254A patent/JP2006178418A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004171025A (ja) | 2004-06-17 |
| JP2006178419A (ja) | 2006-07-06 |
| EP0488544B1 (en) | 1998-01-07 |
| US6583930B1 (en) | 2003-06-24 |
| ES2110981T3 (es) | 1998-03-01 |
| US5486949A (en) | 1996-01-23 |
| KR920010316A (ko) | 1992-06-26 |
| JP4037835B2 (ja) | 2008-01-23 |
| US5612820A (en) | 1997-03-18 |
| JP3704364B2 (ja) | 2005-10-12 |
| US5872653A (en) | 1999-02-16 |
| CA2056153A1 (en) | 1992-05-27 |
| DE69128613D1 (de) | 1998-02-12 |
| DE69128613T2 (de) | 1998-08-13 |
| JP2006178418A (ja) | 2006-07-06 |
| EP0488544A1 (en) | 1992-06-03 |
| JPH04268505A (ja) | 1992-09-24 |
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| MK4A | Expiration of patent term of an invention patent |