TW200405095A - Transflective liquid crystal display device - Google Patents
Transflective liquid crystal display device Download PDFInfo
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- TW200405095A TW200405095A TW092121964A TW92121964A TW200405095A TW 200405095 A TW200405095 A TW 200405095A TW 092121964 A TW092121964 A TW 092121964A TW 92121964 A TW92121964 A TW 92121964A TW 200405095 A TW200405095 A TW 200405095A
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- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials
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- 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
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/04—Number of plates greater than or equal to 4
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- 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
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/08—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates with a particular optical axis orientation
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- 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
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/10—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates with refractive index ellipsoid inclined, or tilted, relative to the LC-layer surface O plate
- G02F2413/105—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates with refractive index ellipsoid inclined, or tilted, relative to the LC-layer surface O plate with varying inclination in thickness direction, e.g. hybrid oriented discotic LC
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Polarising Elements (AREA)
Abstract
Description
200405095 玖、發明說明: 【發明所屬之技術領域】 本發明係關於文字處理機或個人電腦等0A機器、電子 手冊、行動電話等行動資訊機器、或具備液晶顯示器之照 相機體型VTR等方面所採用,兼具反射型或透過型的液晶 顯示元件。 【先前技術】 近年,液晶顯示元件在大幅活用其薄型輕量特徵之情況 下,已逐漸提高當作行動型資訊終端機器顯示器用的市場 需求擴大期待。因為行動式資訊終端機器通常屬於電池驅 動,抑制消耗電力便成為重要的課題。因此,行動式用途 的液晶顯示元件等,便特別著眼於未使用電力消耗較大的 背光源,或未經常使用,且可達低消耗電力化、薄型化、 輕量化的反射型液晶顯示元件。 反射型液晶顯示元件係利用一對偏光板挾置液晶單 元,再於外側配置反射板的偏光板二片式反射型液晶顯示 元件,廣泛使用於黑白顯示用。此外,最近利用偏光板與 反射板挾置液晶層的偏光板一片式反射型液晶顯示元件, 因為較諸於偏光板二片式之下,在原理上較為明亮,亦較 容易彩色化,因此已正實用化。偏光板一片式反射型液晶 顯示元件,為使偏光板與液晶單元之間所配置的相位差板 擁有略圓偏光板機能,因此使用1 / 4波長板,更藉由將液 晶單元内的液晶層厚度形成大致1 / 4波長程度的厚度,俾 可實現正常白型反射型液晶顯示元件(譬如參照曰本專利 6 312/發明說明書(補件)/92-10/92121964 200405095 特開6 - 1 1 7 1 1號公報、國際公開第9 8 / 4 3 2 0號小冊等)。 在相位差板方面,使用1 / 4波長板可賦予良好的圓偏光 板特性,因此便有提案使用至少由:在5 5 0 n m單色光的複折 射光相位差為大致1 / 4波長的1 / 4波長板,及在5 5 0 n m單 色光的複折射光相位差為大致1 / 2波長的1 / 2波長板所構 成的二片以上相位差薄膜(譬如參照日本專利特開平 1 0 - 6 8 8 1 6 號公報)。 但是,該等反射型液晶顯示元件,通常乃因為利用外界 光而執行顯示,因此當在較昏暗環境下使用的情況時,便 具有較不易觀看到顯示的缺點。解決此問題的技術,有提 案在偏光板一片式反射型液晶顯示元件中,取代反射板, 而改為採用具有透過部分入射光之性質的半透過反射板, 且具備背光源的半透過反射型液晶顯示元件(譬如參照曰 本專利特開平1 0 - 2 0 6 8 4 6號公報)。此情況下,在背光源非 點亮的狀態下,可使用為利用外界光的反射型(反射模 式),而在較昏暗的環境下,則可使用為點亮背光源的透過 型(透過模式)。 此偏光板一片式半透過反射型液晶顯示元件,在透過模 式中,必須通過半透過反射層並將略圓偏光射入於液晶單 元中,因此在一片或複數片之以聚碳酸酯為代表的高分子 延伸薄膜、與由偏光板所構成圓偏光板,便必須配置於半 透過反射層與背光源之間。但是,在透過模式的液晶顯示 元件中,因為液晶分子所擁有的折射率各向異性,因此當 從斜向觀看時,便本質上無法避免顯示色變化、或顯示對 7 312/發明說明書(補件)/92-10/92121964 200405095 比降低的視野角問題,在採用高分子延伸薄膜的圓偏光 板,本質上頗難擴大視野角度。 再者,在行動式資訊終端機器方面,近年對薄型化、輕 量化的需求逐漸提高,行動式資訊終端機器的顯示器中所 使用的組件,亦強烈要求薄型化、輕量化,但是高分子延 伸薄膜不僅在製造面問題,且在薄型化方面亦有極限。 有鑑於斯,本發明之目的在於提供一種透過模式下的顯 示明亮且高對比,並可設計呈較薄厚度,視野角依存性較 少的半透過反射型液晶顯示元件。 【發明内容】 本發明之第1發明乃關於半透過反射型液晶顯示元件, 係具備有:具透明電極的第1基板;含有由具反射機能區域 與具透過機能區域所形成半透過反射性電極的第2基板; 挾置於該第1基板與該第2基板間的向列液晶層;設置在 鄰接該第1基板液晶層之面的背面上之第1光學各向異性 (anisotropic)元件與1片偏光板;以及設置在鄰接該第2 基板液晶層之面的背面上之第2光學各向異性元件與1片 偏光板;其特徵在於: 上述第1光學各向異性元件係由1片高分子配向膜所構 成的相位差薄膜,當將在波長(久)450nm、550nm、及650nm 中的延遲值,分別設定為Re(450)、Re(550)及Re(650)之 時,由滿足下述式(I )與(Π )的相位差薄膜所構成,200405095 发明 Description of the invention: [Technical field to which the invention belongs] The present invention is applied to 0A devices such as word processors or personal computers, mobile information devices such as electronic manuals and mobile phones, or camera-type VTRs equipped with liquid crystal displays. Both reflective and transmissive liquid crystal display elements. [Prior art] In recent years, liquid crystal display devices have gradually increased their market demand for displays for mobile information terminal devices, while making the most of their thin and lightweight features. Because mobile information terminals are usually battery-driven, reducing power consumption has become an important issue. Therefore, liquid crystal display elements such as mobile applications are particularly focused on reflective liquid crystal display elements that do not use a backlight that consumes a large amount of power, or that are not frequently used, and can achieve low power consumption, thinness, and light weight. A reflective liquid crystal display element is a two-plate reflective liquid crystal display element that uses a pair of polarizing plates to set up a liquid crystal cell, and a reflective plate on the outside. It is widely used for black and white displays. In addition, recently, a polarizing plate one-piece reflective liquid crystal display element using a polarizing plate and a reflecting plate in which a liquid crystal layer is disposed, is brighter in principle and easier to colorize than the polarizing plate two-piece type. It is practical. A polarizing plate is a one-piece reflective liquid crystal display element. In order to make the retardation plate disposed between the polarizing plate and the liquid crystal cell have a slightly circular polarizing plate function, a 1/4 wavelength plate is used, and the liquid crystal layer in the liquid crystal cell is further used. The thickness is approximately 1/4 wavelength, and a normal white reflective liquid crystal display element can be realized (for example, refer to Japanese Patent 6 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 JP 6-1 1 7 1 Bulletin, International Publication No. 9 8/4 3 2 0, etc.). In terms of retardation plates, the use of a 1/4 wavelength plate can impart good circular polarizing plate characteristics. Therefore, it has been proposed to use at least: the phase difference of the birefringent light of monochromatic light at 5 50 nm is approximately 1/4 wavelength Two or more retardation films composed of a 1/4 wave plate and a 1 / 2-wave plate with a birefringent light phase difference of approximately 1/2 wavelength at 550 nm for monochromatic light (for example, refer to Japanese Patent Laid-Open No. 1) 0-6 8 8 16). However, such reflective liquid crystal display elements usually perform display by using external light. Therefore, when used in a relatively dim environment, they have the disadvantage that the display is not easy to see. As a technique for solving this problem, there is a proposal to replace a reflective plate in a polarizing plate one-piece reflective liquid crystal display element with a transflective reflective plate having a property of transmitting a part of incident light and a transflective reflective type having a backlight source. A liquid crystal display element (for example, refer to Japanese Patent Application Laid-Open No. 10-2 0 6 8 4 6). In this case, the reflection type (reflection mode) that uses external light can be used when the backlight is not lit, and the transmission type (transmission mode) that lights the backlight can be used in a dim environment. ). This polarizing plate is a one-piece transflective reflective liquid crystal display element. In the transmission mode, it is necessary to pass through the transflective reflective layer and emit slightly circular polarized light into the liquid crystal cell. Therefore, one or more pieces of polycarbonate are represented The polymer stretched film and the circular polarizing plate composed of a polarizing plate must be disposed between the semi-transmissive reflective layer and the backlight. However, in a transmission mode liquid crystal display element, because the refractive index anisotropy possessed by the liquid crystal molecules, when viewed from an oblique direction, it is essentially impossible to avoid a change in display color or display. ()) / 92-10 / 92121964 200405095 The problem of reduced viewing angle, in the circular polarizer using polymer stretch film, it is difficult to enlarge the viewing angle in essence. In addition, in terms of mobile information terminal equipment, the demand for thinness and lightening has been increasing in recent years. The components used in the display of mobile information terminal equipment have also strongly demanded to be thin and lightweight, but the polymer stretch film There are limits not only to manufacturing aspects, but also to thinness. In view of the foregoing, an object of the present invention is to provide a transflective reflective liquid crystal display element which has a bright and high-contrast display in a transmission mode and can be designed to have a thin thickness and a small viewing angle dependency. [Summary of the Invention] The first invention of the present invention relates to a transflective liquid crystal display element, comprising: a first substrate having a transparent electrode; and a transflective reflective electrode formed by a region having a reflective function and a region having a transmissive function A second substrate; a nematic liquid crystal layer interposed between the first substrate and the second substrate; a first optically anisotropic element disposed on a back surface of a surface adjacent to the liquid crystal layer of the first substrate and One polarizing plate; and a second optical anisotropic element and one polarizing plate provided on the back surface of the surface adjacent to the liquid crystal layer of the second substrate; the first optical anisotropic element is composed of one When a retardation film composed of a polymer alignment film is set to Re (450), Re (550), and Re (650), the retardation values at the wavelengths (long) of 450 nm, 550 nm, and 650 nm are determined by A retardation film composed of the following formulae (I) and (Π),
Re( 4 5 0 ) < Re( 5 5 0 )< Re( 6 5 0 )(I) 0. 2 ^ Re( λ )/ λ ^0.3 (Π ) 8 312/發明說明書(補件)/92-10/92121964 200405095 上述第2光學各向異性元件係由至少1片顯示光學正單 軸性之液晶性高分子物質所實質形成,且該液晶性高分子 物質係含有將在液晶狀態下所形成向列混合配向予以固定 化的液晶薄膜(A)。 再者,本發明第2發明乃上述半透過反射型液晶顯示元 件,其中,上述第2光學各向異性元件係由下述所構成: 由至少1片顯示光學正單軸性之液晶性高分子物質所實質 形成,且該液晶性高分子物質係含有將在液晶狀態下所形 成向列混合配向予以固定化的液晶薄膜(A );以及至少1 片高分子延伸薄膜。 再者,本發明第3發明乃上述半透過反射型液晶顯示元 件,其中,上述第2光學各向異性元件係由下述所構成: 由至少1片顯示光學正單軸性之液晶性高分子物質所實質 形成,且該液晶性高分子物質係含有將在液晶狀態下所形 成向列混合配向予以固定化的液晶薄膜(A );以及由至少1 片顯示光學正單軸性之液晶性高分子物質所實質形成,且 該液晶性高分子物質係含有將在液晶狀態下所形成向列配 向予以固定化的液晶薄膜(B)。 再者,本發明第4發明乃上述半透過反射型液晶顯示元 件’其中’上述液晶薄膜(A)係使液晶材料在液晶狀怨下進 行向列混合配向,再從此狀態進行冷卻,俾將向列混合偏 向予以玻璃固定化的液晶薄膜。 再者,本發明第5發明乃上述半透過反射型液晶顯示元 件’其中’上述液1晶薄膜(A )係使液晶材料在液晶狀息下進 9 312/發明說明書(補件)/92-10/92121964 200405095 行向列混合配向,再利用交聯反應將向列混合偏向予以固 定化的液晶薄膜。 再者,本發明第6發明乃上述半透過反射型液晶顯示元 件,其中,上述具反射機能區域與具透過機能區域的液晶 層厚係不同,具反射機能區域的液晶層厚度較薄於具透過 機能區域的液晶層厚。 再者,本發明第7發明乃上述半透過反射型液晶顯示元 件,係採用電控雙折射(Electrically Controlled Birefringence,ECB)方式。 再者,本發明第8發明乃上述半透過反射型液晶顯示元 件,係採用扭轉向列(T w i s t e d N e m a t i c,T N )方式。 再者,本發明第9發明乃上述半透過反射型液晶顯示元 件,係採用混合配向向列(H y b r i d A 1 i g n e d N e m a 1: i c,H A N ) 方式。 【實施方式】 以下,詳細說明本發明。 本發明的半透過反射型液晶顯示元件,由觀看者端觀 之,係由偏光板、第1光學各向異性元件、液晶單元、第 2光學各向異性元件、偏光板、背光源所構成,配合需要 可再追加光擴散層、光控制薄膜、導光板、稜鏡薄片(p r i s m s h e e t )等。此形式的液晶顯示元件乃藉由在後方設置背光 源,便可使用反射模式與透過模式的二種模式。 其次,針對本發明中所使用的液晶單元進行說明。 本發明中所使用的液晶單元係由下述組件所構成:具透 10 312/發明說明書(補件)/92-10/92121964 200405095 明電極的第1基板;含有由具反射機能區域與具透過機能 區域所形成半透過反射性電極的第2基板;以及挾置於該 第1基板與該第2基板間的向列液晶層。 該液晶單元乃含有由具反射機能區域與具透過機能區 域所形成半透過反射層,而具反射機能區域將成為執行反 射顯示的反射顯示部,具透過機能區域將成為執行透過顯 示的透過顯示部。 該液晶單元的反射顯示部之液晶層厚,最好較薄於透過 顯示部。理由說明如下。 首先,針對當將液晶層厚設定為適於反射顯示之層厚 時,透過顯示部的透過顯示進行說明。當執行適於反射顯 示的液晶層設定之情況時,隨液晶層電場等外場所產生配 向變化衍生出的偏光狀態變化量,乃為從觀察者端通過液 晶層而所射入光將在反射層被反射之後,再度通過液晶層 之後,再從觀察者端射出,藉此可往返液晶層而獲得充分 對比的程度。但是,在此設定中,於透過顯示部,通過液 晶層的光,在偏光狀態下的變化量將嫌不足。因此,即便 在使用於反射顯示之液晶單元的觀察者端追加設置偏光 板,從觀察者端觀看僅使用於透過顯示的偏光板,呈設置 於液晶單元背面狀態,但是在透過顯示部仍無法獲得充分 的顯示。即,當將液晶配向條件設定為適於反射顯示部的 液晶層配向條件之情況時,在透過顯示部將呈現亮度不足 現象,或即便亮度足夠,但是較暗顯示的透過率並未降低, 使顯示無法獲得充分地對比。 11 312/發明說明書(補件)/92-10/92121964 200405095 再者,若詳細說明的話,當執行反射顯示的情況時 依對僅單次通過液晶層的光賦予大概1 / 4波長的相位 方式’利用所施加的電壓控制者上述液晶層内的液晶 狀態。如此若適於反射顯示的液晶層厚,即施行賦予 波長相位調變的電壓調變(m 〇 d u 1 a t i ο η )並施行透過顯 話,於使透過顯示部在暗顯示時的透過率充分降低之 下,透過顯示部在亮顯示時,光射出端的偏光板將吸 一半光度的光,而無法獲得充分的亮顯示。此外,若 顯示部為增加亮顯示時的明亮度,而施行偏光板、相 補償板等光學元件的的配置的話,透過顯示部在較暗 時的明亮度,將為較亮顯示時之明亮度的約1 / 2明亮 顯示的對比將呈不足現象。 反之,在將液晶層厚度設定為適於透過顯示之條件 面,必須依對透過於液晶層的光賦予1 / 2波長相位差 式,對上述液晶層施行電壓調變。所以,在利用於反 與透過光均為高解析度且辨識性優越之顯示方面,反 示部的液晶層厚度,便必須較小於透過顯示部的液晶 度。較理想的話,反射顯示部的液晶層厚度最好為透 示部液晶層厚度的約1 / 2。 上述液晶單元的方式,可舉例如:扭轉向列(T w i s t e Nematic, TN)方式、超扭轉向列型(Super Twisted Nematic,STN)方式、電控雙折射(Electrically Controlled Birefringence,ECB)方式、橫向電場切 (In-Plane Switching, IPS)方式、垂直 S己向(Vertic 312/發明說明書(補件)/92-10/92121964 ,便 差之 配向 1/4 示的 情況 收約 透過 位差 顯示 度, 方 之方 射光 射顯 層厚 過顯 d 換 al 12 200405095Re (4 5 0) < Re (5 5 0) < Re (6 5 0) (I) 0.2 ^ Re (λ) / λ ^ 0.3 (Π) 8 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 The second optical anisotropic element is substantially formed of at least one liquid crystalline polymer substance exhibiting optical positive uniaxiality, and the liquid crystalline polymer substance contains A liquid crystal film (A) in which a nematic mixed alignment is fixed is formed. Furthermore, the second invention of the present invention is the above-mentioned transflective liquid crystal display element, wherein the second optically anisotropic element is composed of: at least one liquid crystalline polymer exhibiting optical positive uniaxiality The substance is substantially formed, and the liquid crystalline polymer substance contains a liquid crystal film (A) in which a nematic mixed alignment formed in a liquid crystal state is immobilized; and at least one polymer stretched film. Furthermore, the third invention of the present invention is the transflective liquid crystal display device described above, wherein the second optically anisotropic element is composed of: at least one liquid crystalline polymer exhibiting optical positive uniaxiality Substance is formed substantially, and the liquid crystalline polymer substance contains a liquid crystal film (A) in which a nematic hybrid alignment formed in a liquid crystal state is immobilized; and at least one piece has high liquid crystallinity showing optical uniaxiality The molecular substance is formed substantially, and the liquid crystalline polymer substance contains a liquid crystal film (B) in which a nematic alignment formed in a liquid crystal state is fixed. Furthermore, the fourth invention of the present invention is the above-mentioned semi-transmissive reflective liquid crystal display element, wherein the above-mentioned liquid crystal film (A) is a liquid crystal material that performs nematic mixing and alignment under the state of liquid crystal, and then cools from this state. The column mixing is biased toward the glass-immobilized liquid crystal film. Furthermore, the fifth invention of the present invention is the above-mentioned semi-transmissive reflective liquid crystal display element 'wherein' the above-mentioned liquid 1 crystal thin film (A) is a liquid crystal material that advances in a liquid crystal state 9 312 / Invention Specification (Supplement) / 92- 10/92121964 200405095 Liquid crystal film with row-nematic hybrid alignment, and then cross-linking reaction will be used to immobilize the nematic hybrid. In addition, the sixth invention of the present invention is the transflective liquid crystal display element described above, wherein the thickness of the liquid crystal layer between the reflective function region and the transmissive function region is different, and the thickness of the liquid crystal layer with the reflective function region is thinner than that of the transmissive liquid crystal layer. The liquid crystal layer in the functional region is thick. Furthermore, the seventh invention of the present invention is the above-mentioned transflective liquid crystal display element, and adopts an electrically controlled birefringence (ECB) method. Furthermore, the eighth invention of the present invention is the transflective liquid crystal display element described above, and adopts a twisted nematic (T w i s t e d N e m a t i c, T N) method. Furthermore, the ninth invention of the present invention is the above-mentioned transflective liquid crystal display element, which adopts a hybrid alignment nematic (Hy b r d A 1 i g n e d N e m a 1: i c, H A N) method. [Embodiment] Hereinafter, the present invention will be described in detail. The transflective liquid crystal display element of the present invention is composed of a polarizing plate, a first optically anisotropic element, a liquid crystal cell, a second optically anisotropic element, a polarizing plate, and a backlight. If necessary, a light diffusion layer, a light control film, a light guide plate, a prism sheet, etc. may be further added. This type of liquid crystal display element can be used in two modes of reflection mode and transmission mode by providing a backlight in the rear. Next, a liquid crystal cell used in the present invention will be described. The liquid crystal cell used in the present invention is composed of the following components: a first substrate having a transparent electrode 10 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095; A second substrate having a transflective reflective electrode formed in the functional region; and a nematic liquid crystal layer interposed between the first substrate and the second substrate. The liquid crystal cell includes a semi-transmissive reflective layer formed by a reflective function region and a transmissive function region, and the reflective function region will become a reflective display section that performs reflective display, and the transmissive function region will become a transmissive display section that performs transmissive display. . The liquid crystal layer of the reflective display portion of the liquid crystal cell is preferably thicker than the transmissive display portion. The reason is explained below. First, when the liquid crystal layer thickness is set to a layer thickness suitable for reflective display, the transmission display of the transmission display section will be described. When the setting of the liquid crystal layer suitable for reflective display is performed, the amount of change in the polarization state derived from the alignment change in the external field such as the electric field of the liquid crystal layer is for the incident light to pass through the liquid crystal layer from the observer's end on the reflective layer. After being reflected, after passing through the liquid crystal layer again, it is emitted from the viewer's end, whereby the degree of sufficient contrast can be obtained by going back and forth to the liquid crystal layer. However, in this setting, the amount of change in the polarization state of the light transmitted through the liquid crystal layer through the display portion is insufficient. Therefore, even if a polarizing plate is additionally provided on the observer side of the liquid crystal cell used for reflective display, and the polarizing plate used only for the transmissive display is viewed from the observer side, it is arranged on the back of the liquid crystal cell, but it is still not available on the transmissive display portion. Full display. That is, when the liquid crystal alignment conditions are set to the liquid crystal layer alignment conditions suitable for the reflective display section, the transmission display section will show insufficient brightness, or even if the brightness is sufficient, the transmittance of the dark display is not reduced, so that The display cannot be fully contrasted. 11 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 Furthermore, if it is explained in detail, when performing a reflective display, a phase method of giving approximately 1/4 wavelength to light that passes through the liquid crystal layer only once is performed. 'The liquid crystal state in the liquid crystal layer is controlled by the applied voltage. In this way, if the thickness of the liquid crystal layer suitable for reflective display is to perform voltage modulation (m 0du 1 ati ο η) that imparts wavelength phase modulation and perform transmissive display, the transmittance of the transmissive display portion during dark display is sufficient. Below this, during the bright display through the display portion, the polarizing plate at the light emitting end will absorb half of the light, and a sufficient bright display cannot be obtained. In addition, if the display unit is configured to increase the brightness during bright display, and the arrangement of optical elements such as polarizing plates and phase compensation plates is adopted, the brightness of the display unit when it is dark will be the brightness during bright display. The contrast of bright display of about 1/2 will be insufficient. Conversely, when the thickness of the liquid crystal layer is set to a condition suitable for transmission display, it is necessary to apply a voltage modulation to the liquid crystal layer by applying a 1/2 wavelength retardation formula to the light transmitted through the liquid crystal layer. Therefore, the thickness of the liquid crystal layer of the reflective portion must be smaller than that of the liquid crystal transmitted through the display portion in a display with high resolution and excellent visibility both in reflected and transmitted light. Preferably, the thickness of the liquid crystal layer in the reflective display portion is about 1/2 of the thickness of the liquid crystal layer in the transparent portion. Examples of the liquid crystal cell method include: a twisted nematic (TN) method, a super twisted nematic (STN) method, an electrically controlled birefringence (ECB) method, and a horizontal direction. In-Plane Switching (IPS) method, vertical S direction (Vertic 312 / Invention Specification (Supplement) / 92-10 / 92121964, the difference between the direction of the difference is 1/4, and the degree of transmission is displayed.) , Fang Zhifang's thickness of the light-emitting layer is too high. Al 12 200405095
Alignment,VA)方式、光學互補雙折射(Optically Compensated Birefringence, 0CB)方式、混合配向向列 (Hybrid Aligned Nematic,HAN)方式、軸對稱對齊(Axially Symmetric Aligned Microcell, ASM)、中間調灰階 (halftone grayscale)方式、分割酉己向 >去(domain divided) 方式、或利用強介電性液晶、反強介電性液晶的顯示方式 等各種方式。 當TN方式之情況時,液晶層的扭轉方向可為左旋亦可 為右旋。扭轉角度最好在9 0度以下,尤以7 0度以下為佳。 當大於9 0度的情況時,恐將發生液晶顯示元件附著不需要 顏色的不良現象。 再者,液晶單元的驅動方式亦無特別的限制,可為 如:STN-LCD等之中所採用的被動矩陣方式、及TFT(Thin Film Transistor)電極、TFD(Thin Film Doide)電極等採 用主動電極(active electrode)的主動矩陣方式、電漿定 址方式等任何驅動方式。 構成液晶單元的透明電極係僅要漿顯示構成液晶層之 液晶性的材料,配向呈特定配向方向的話便可,並無特別 的限制。具體而言,具使液晶配向之性質的透明基板,雖 基板本身雖欠缺配向能力,但是可採用將具有使液晶配向 性質的配向膜等,設置於其上的透明電極等任何者。此外, 液晶單元的電極亦可使用如I T 0等週知者。電極通常可設 置於鄰接液晶層的透明基板面上,當使用具配向膜之基板 的情況時,可設置於基板與配向膜之間。 13 312/發明說明書(補件)/92-10/92121964 200405095 顯不出形成液晶層之液晶性的材料’並無特別的限制’ 可舉例如.·可構成各種液晶單元之普通各種低分子液晶物 質、高分子液晶物質、及該等混合物。此外,在該等不損 及液晶性的範圍下,亦可添加色素、對掌劑(c h i r a 1 agent)、非液晶性物質等。 半透過反射性電極中所含具反射機能的區域(以下稱 「反射層」),並無特別限制,可例示如:铭、銀、金、鉻、 鉑等金屬、含該等的合金、氧化鎂等氧化物、介電質多層 膜、顯示出選擇反射的液晶、或該等組合等。該等反射層 可為平面,亦可為曲面。另外,反射層可為施行加工為凹 凸形狀等表面形狀俾使具擴散反射性者、兼具液晶單元之 觀察者端與背面端之該電極基板上的電極者、或該等組合。 本發明中所採用的偏光板,僅要可達成本發明目的者的 話便可,並無特別的限制,可適當使用液晶顯示元件中所 採用的普通者。具體而言,可在如聚乙烯醇(P V A )或部分縮 醛化P V A之類P V A系、或乙烯-醋酸乙烯共聚物之部分皂化 物等所構成親水性高分子薄膜中,使用由吸附著碘及/或雙 色性色素並延伸的偏光膜、如PVA脫水處理物或氯乙烯脫 鹽酸處理物之類聚烯烴配向薄膜等所構成偏光膜。此外, 亦可使用反射型偏光膜。 該偏光板可單獨使用偏光膜,在提昇強度、提昇耐濕 性、提昇耐熱性等目的之下,亦可在偏光膜的單面或雙面 上設置透明保護層等。透明保護層可舉例如:將聚酯、三乙 醯纖維素等透明塑膠薄膜,直接或透過黏著層層積者、透 14 312/發明說明書(補件)/92-10/92121964 200405095 明樹脂塗佈層、丙烯酸系或環氧系等光硬化型樹脂層等。 當將該等透明保護層披覆於偏光膜雙面上的情況時,亦可 二側設置不同的保護層。 本發明中所採用的第1光學各向異性元件係由當將在波 長(λ)450ηιη、550nm、及650nm中的延遲值,分別設定為 Re(450)、Re(550)及Re(650)之時,由滿足下述式(I)與(Π) 的1片高分子配向膜所構成相位差薄膜。Alignment (VA) method, Optically Compensated Birefringence (0CB) method, Hybrid Aligned Nematic (HAN) method, Axially Symmetric Aligned Microcell (ASM), halftone grayscale (halftone) grayscale) method, domain division method, or a display method using a ferroelectric liquid crystal or an anti-ferroelectric liquid crystal. In the case of the TN method, the twist direction of the liquid crystal layer may be left-handed or right-handed. The twisting angle is preferably below 90 degrees, especially below 70 degrees. When it is more than 90 degrees, there is a fear that an undesirable phenomenon in which the liquid crystal display element is attached with an unnecessary color may occur. In addition, the driving method of the liquid crystal cell is not particularly limited, and may be, for example, a passive matrix method used in STN-LCD, etc., and a TFT (Thin Film Transistor) electrode, TFD (Thin Film Doide) electrode, etc. Any driving method, such as active matrix method and plasma addressing method. The transparent electrode system constituting the liquid crystal cell is only required to display the liquid crystal material constituting the liquid crystal layer, and the orientation is not particularly limited as long as the orientation is in a specific orientation direction. Specifically, a transparent substrate having the property of aligning liquid crystals, although the substrate itself lacks the ability to align, can be any transparent electrode provided with an alignment film or the like having the property of aligning liquid crystals. In addition, the electrode of the liquid crystal cell may be a known one such as I T 0. The electrode can usually be placed on the surface of the transparent substrate adjacent to the liquid crystal layer. When a substrate with an alignment film is used, it can be placed between the substrate and the alignment film. 13 312 / Explanation of the Invention (Supplement) / 92-10 / 92121964 200405095 The material that does not show the liquid crystal properties of the liquid crystal layer is not particularly limited. Examples include: · Common low molecular liquid crystals that can form various liquid crystal cells Substances, polymer liquid crystal substances, and mixtures thereof. In addition, as long as the liquid crystallinity is not impaired, a pigment, a c h i r a 1 agent, a non-liquid crystal substance, or the like may be added. There are no particular restrictions on the area of the transflective reflective electrode that has a reflective function (hereinafter referred to as the "reflective layer"). Examples include metals such as Ming, silver, gold, chromium, platinum, alloys containing them, and oxidation. An oxide such as magnesium, a dielectric multilayer film, a liquid crystal exhibiting selective reflection, or a combination thereof. The reflective layers may be flat or curved. In addition, the reflective layer may be processed into a surface shape such as a concave-convex shape so as to have a diffuse reflectance, an electrode on the electrode substrate that has both an observer end and a back end of the liquid crystal cell, or a combination thereof. The polarizing plate used in the present invention is not limited as long as it can reach the purpose of the present invention, and ordinary ones used in liquid crystal display elements can be appropriately used. Specifically, a hydrophilic polymer film composed of a PVA system such as polyvinyl alcohol (PVA) or a partially acetalized PVA, or a saponified product of an ethylene-vinyl acetate copolymer, etc., can be used by adsorbing iodine. And / or a polarizing film in which a dichroic pigment is stretched, and a polarizing film composed of a polyolefin alignment film such as a PVA dehydration treatment product or a vinyl chloride dehydrochlorination treatment product. Alternatively, a reflective polarizing film may be used. This polarizing plate can use a polarizing film alone, and for the purpose of improving the strength, improving the moisture resistance, and the heat resistance, a transparent protective layer or the like can be provided on one or both sides of the polarizing film. The transparent protective layer may be, for example, a transparent plastic film such as polyester or triethyl cellulose, laminated directly or through an adhesive layer, 14 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 clear resin coating Fabric layer, light-curable resin layer such as acrylic or epoxy. When these transparent protective layers are coated on both sides of the polarizing film, different protective layers may be provided on both sides. The first optically anisotropic element used in the present invention is configured by setting retardation values at wavelengths (λ) of 450 nm, 550 nm, and 650 nm to Re (450), Re (550), and Re (650), respectively. At this time, a retardation film is composed of one polymer alignment film satisfying the following formulae (I) and (Π).
Re( 4 5 0 ) < Re( 5 5 0 ) < Re( 6 5 0 )(I) 0.2^Re(A)/A^0.3(n) 滿足上述式(I ),即由波長越短延遲值越小的1片高分 子配向膜所構成相位差薄膜,可利用滿足下述(A)或(B )之 條件的高分子配向膜而獲得。 (A) 具有下述(1)〜(3)配向膜,(1)由含有:形成具正折射 率各向異性之高分子化合物的單體單位(以下稱「第1單體 單位」)、與形成具負折射率各向異性之高分子化合物的單 體單位(以下稱「第2單體單位」)的高分子化合物所構成 的薄膜;(2 )基於該第1單體單位而成的高分子化合物之 Re(450)/Re(550),較小於基於該第2單體單位而成的高分 子化合物之Re(450)/Re(550);且(3)具正折射率各向異 性。 (B) 具有下述(1)〜(3)配向膜,(1)由含有:形成具正折射 率各向異性之高分子化合物的單體單位(以下稱「第1單體 單位」)、與形成具負折射率各向異性之高分子化合物的單 體單位(以下稱「第2單體單位」)的高分子化合物所構成 15 312/發明說明書(補件)/92-10/92121964 200405095 的薄膜;(2 )基於該第1單體單位而成的高分子化合物之 Re(450)/Re(550),較大於基於該第2單體單位而成的高分 子化合物之Re(450)/Re(550);且(3)具負折射率各向異 性。 滿足上述(A )、( B )條件之態樣的例子,有如滿足下述條 件(C )、( D )者。 (C) 具有下述(1)〜(3)配向膜,(1)由具正折射率各向異 性之高分子化合物、與具負折射率各向異性之高分子化合 物所構成高分子化合物的摻合聚合物、及/或由形成具正折 射率各向異性之高分子化合物的單體單位、與形成具負折 射率各向異性之高分子化合物的單體單位所構成共聚物所 構成的薄膜;(2 )該具正折射率各向異性之高分子化合物的 R e ( 4 5 0 ) / R e ( 5 5 0 ),較小於該具負折射率各向異性之高分子 化合物的R e ( 4 5 0 ) / R e ( 5 5 0 );且(3 )具正折射率各向異性。 (D) 具有下述(1)〜(3)配向膜,(1)由具正折射率各向異 性之高分子化合物、與具負折射率各向異性之高分子化合 物所構成高分子化合物的摻合聚合物、及/或由形成具正折 射率各向異性之高分子化合物的單體單位、與形成具負折 射率各向異性之高分子化合物的單體單位所構成共聚物所 構成的薄膜;(2 )該具正折射率各向異性之高分子化合物的 R e ( 4 5 0 ) / R e ( 5 5 0 ),較大於該具負、折射率各向異性之高分子 化合物的R e ( 4 5 0 ) / R e ( 5 5 0 );且(3 )具正折射率各向異性。 此處所謂「具正或負折射率各向異性之高分子化合 物」,係指賦予具正或負折射率各向異性之配向膜的高分子 16 312/發明說明書(補件)/92-10/92121964 200405095 化合物。 在本發明中,第1光學各向異性元件所採用的高分子配 向膜係如上述,可為摻合聚合物所構成者,亦可採用由共 聚物所構成者。 構成高分子配向膜的高分子材料,僅要屬於滿足上述條 件的摻合聚合物或共聚物的話便可,可為耐熱性優越、光 學性能佳,且可溶液製膜的熱可塑性聚合物。譬如可從聚 丙烯酸酯系、聚酯系、聚碳酸酯系、聚烯烴系、聚醚系、 聚硫系、聚石蘇系、聚醚石致系等聚合物之中,適當選擇1種 或2種以上。其中,因為配向膜之吸水率若非低於1重量% 以下的話,當作相位差薄膜用時,在實用上將發生問題, 因此薄膜材料最好依滿足薄膜吸水率在1重量%以下(尤以 0 · 5重量%以下)條件之方式進行選擇,此乃重要的一環。 若屬於摻合聚合物的話,就從需要光學性透明的觀點而 言,最好為相溶摻合物、或各個高分子化合物的折射率略 等。摻合聚合物之具體組合可舉例如.·具負光學各向異性之 高分子化合物的聚甲基丙烯酸甲酯、與具正光學各向異性 之高分子化合物的聚偏二氟乙烯、聚環氧乙烷、或偏二氣 乙烯-三氟乙烯共聚物的組合;具正光學各向異性之高分子 化合物的聚苯醚、與具負光學各向異性之高分子化合物的 聚苯乙烯、苯乙烯-月桂醯馬來醯亞胺共聚物、苯乙烯-環 己基順丁烯二醯亞胺共聚物、或苯乙烯-苯基順丁烯二醯亞 胺共聚物的組合;具負光學各向異性的苯乙烯-順丁烯二酸 酐共聚物、與具正光學各向異性的聚碳酸酯;或具正光學 17 312/發明說明書(補件)/92-10/92121964 200405095 各向異性的丙烯腈-丁二烯共聚物、與具負光學各向異性的 丙烯腈-苯乙烯共聚物等,惟並不僅限定於該等。特別就透 明性的觀點而言,最好為聚苯乙烯、與聚(2,6 -二曱基-1,4 -苯醚)等聚苯醚的組合。當此種組合的情況時,該聚苯乙烯 的比率最好佔總體的6 7重量%以上、且7 5重量%以下。 再者,共聚物可採用如:丁二烯-苯乙烯共聚物、乙烯-苯乙烯共聚物、丙烯腈-丁二烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、聚碳酸酯共聚物、聚酯共聚物、聚酯碳酸 酯共聚物、聚丙烯酸酯共聚物等。特別係為使具有芴骨架 的片段變為負光學各向異性,最好採用具芴骨架的聚碳酸 酯共聚物、聚酯共聚物、聚酯碳酸酯共聚物、聚丙烯酸酯 共聚物等。 使雙酚類、與光氣(P h 〇 s g e n e )或碳酸二苯等碳酸醋形成 性化合物進行反應而所製得聚碳酸酯共聚物,透明性、耐 熱性、生產性優越,特別適於使用。聚碳酸酯共聚物最好 含有具芴骨架之構造的共聚物。 本發明之配向膜材料較佳者有如:由下述式(1 )所示重 複單位、與下述式(2 )所示重複單位所構成聚碳酸酯的配向 膜所形成,且式(1 )所示重複單位係佔聚碳酸酯總體之 3 0〜9 0莫耳%,式(2 )所示重複單位係佔聚碳酸酯總體之 7 0〜1 0莫耳%的材料。Re (4 5 0) < Re (5 5 0) < Re (6 5 0) (I) 0.2 ^ Re (A) /A^0.3 (n) satisfies the above formula (I), that is, the shorter the wavelength A retardation film composed of one polymer alignment film having a smaller retardation value can be obtained by using a polymer alignment film that satisfies the following conditions (A) or (B). (A) having the following (1) to (3) alignment films, (1) a monomer unit (hereinafter referred to as a "first monomer unit") containing: a monomer compound forming a polymer compound having positive refractive index anisotropy; A thin film composed of a polymer compound (hereinafter referred to as a "second monomer unit") that forms a polymer unit having a negative refractive index anisotropic polymer compound; (2) a film based on the first monomer unit The Re (450) / Re (550) of the polymer compound is smaller than the Re (450) / Re (550) of the polymer compound based on the second monomer unit; and (3) each has a positive refractive index Anisotropy. (B) the following (1) to (3) an alignment film, (1) a monomer unit (hereinafter referred to as a "first monomer unit") comprising: a polymer compound having a positive refractive index anisotropy; Formed with polymer units that form polymer units with negative refractive index anisotropy (hereinafter referred to as "second monomer units") 15 312 / Explanation of the Invention (Supplement) / 92-10 / 92121964 200405095 Film; (2) Re (450) / Re (550) of the polymer compound based on the first monomer unit is larger than Re (450) of the polymer compound based on the second monomer unit / Re (550); and (3) has negative refractive index anisotropy. An example of a condition that satisfies the conditions (A) and (B) above is the one that satisfies the following conditions (C) and (D). (C) It has the following (1) to (3) alignment films, (1) a polymer compound composed of a polymer compound having a positive refractive index anisotropy and a polymer compound having a negative refractive index anisotropy A polymer and / or a copolymer composed of a monomer unit forming a polymer compound having positive refractive index anisotropy and a monomer unit forming a polymer compound having negative refractive index anisotropy Thin film; (2) Re (4 50) / Re (550) of the polymer compound having positive refractive index anisotropy is smaller than that of polymer compound having negative refractive index anisotropy R e (4 5 0) / R e (5 5 0); and (3) has positive refractive index anisotropy. (D) having the following (1) to (3) alignment films, (1) a polymer compound composed of a polymer compound having a positive refractive index anisotropy and a polymer compound having a negative refractive index anisotropy A polymer and / or a copolymer composed of a monomer unit forming a polymer compound having positive refractive index anisotropy and a monomer unit forming a polymer compound having negative refractive index anisotropy Thin film; (2) Re (4 50) / Re (550) of the polymer compound having positive refractive index anisotropy is larger than that of polymer compound having negative, refractive index anisotropy R e (4 5 0) / R e (5 5 0); and (3) has positive refractive index anisotropy. The “polymer compound with positive or negative refractive index anisotropy” here refers to the polymer 16 312 / Invention Specification (Supplement) / 92-10 that imparts an alignment film with positive or negative refractive index anisotropy. / 92121964 200405095 compounds. In the present invention, as described above, the polymer alignment film used in the first optically anisotropic element may be composed of a polymer blend or a copolymer. The polymer material constituting the polymer alignment film need only belong to a blended polymer or copolymer satisfying the above-mentioned conditions. The polymer material can be a thermoplastic polymer having excellent heat resistance, excellent optical properties, and solution-forming films. For example, one can be appropriately selected from polymers such as polyacrylate-based, polyester-based, polycarbonate-based, polyolefin-based, polyether-based, polysulfide-based, polystone-based, and polyetherstone-based polymers. 2 or more. Among them, if the water absorption of the alignment film is not less than 1% by weight, it will cause practical problems when used as a retardation film. Therefore, it is best for the film material to meet the water absorption of the film below 1% by weight (especially 0 · 5% by weight or less). This is an important part. If it is a blended polymer, from the viewpoint of requiring optical transparency, it is preferably a miscible blend or a refractive index of each polymer compound. The specific combination of the blended polymer may include, for example, polymethyl methacrylate of a polymer compound having negative optical anisotropy, polyvinylidene fluoride, and a polycyclic ring of a polymer compound having positive optical anisotropy. Ethylene oxide, or combination of vinylidene oxide-trifluoroethylene copolymers; polyphenylene ethers with polymer compounds with positive optical anisotropy, polystyrenes with polymer compounds with negative optical anisotropy, benzene Ethylene-lauric acid maleimide copolymer, styrene-cyclohexyl maleimide diimide copolymer, or styrene-phenyl maleimide diimide copolymer; with negative optical isotropy Anisotropic styrene-maleic anhydride copolymer, and polycarbonate with positive optical anisotropy; or positive optical 17 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 anisotropic propylene The nitrile-butadiene copolymer and the acrylonitrile-styrene copolymer having negative optical anisotropy are not limited to these. In particular, in terms of transparency, a combination of polystyrene and polyphenylene ether such as poly (2,6-difluorenyl-1,4-phenylene ether) is preferred. In the case of such a combination, the proportion of the polystyrene is preferably 67% by weight or more and 75% by weight or less. Furthermore, the copolymer may be used, for example, butadiene-styrene copolymer, ethylene-styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and polycarbonate copolymer. Polymers, polyester copolymers, polyester carbonate copolymers, polyacrylate copolymers, etc. In particular, in order to make a segment having a fluorene skeleton into negative optical anisotropy, it is preferable to use a polycarbonate copolymer, polyester copolymer, polyester carbonate copolymer, polyacrylate copolymer, or the like having a fluorene skeleton. Polycarbonate copolymers prepared by reacting bisphenols with carbonate-forming compounds such as phosgene (Ph osgene) or diphenyl carbonate, which are excellent in transparency, heat resistance, and productivity, and are particularly suitable for use . The polycarbonate copolymer preferably contains a copolymer having a fluorene skeleton structure. The alignment film material of the present invention is preferably formed by an alignment film of a polycarbonate composed of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and the formula (1) The repeating unit shown represents 30 to 90 mole% of the entire polycarbonate, and the repeating unit represented by formula (2) is a material of 70 to 10 mole% of the overall polycarbonate.
312/發明說明書(補件)/92-10/92121964 18 200405095312 / Invention Specification (Supplement) / 92-10 / 92121964 18 200405095
在上述式(1 )中,R!〜R 8係指從分別獨立的氫原子、鹵原 子、及碳數1〜6之碳化氫基中所選擇的基;X係指式(3 )所 示基。此外,在上述式(2 )中,R 9〜R ! 6係指從分別獨立的氫 原子、鹵原子、及碳數1〜2 2之碳化氫基中所選擇的基;Y 係指從式(4 )所示基中選擇出的基。In the above formula (1), R! To R 8 refer to groups independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 6 carbon atoms, respectively; X refers to the formula (3) base. In addition, in the above formula (2), R 9 to R! 6 refer to a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having a carbon number of 1 to 22, respectively; and Y refers to the formula (4) The base selected from the bases shown.
——C—0—R20-〇——C——一Si————R23~ Ο Ο , R22 在上述式(4 )中,R I 7〜R 1 9、R 2 1及R 2 2係指從分別獨立的氳i 原子、鹵原子、及碳數1〜2 2之碳化氫基中所選擇的基;R 2 〇 及R 2 3係指從分別獨立的碳數1〜2 0之碳化鼠基中所選擇的 基;AI*係碳數6〜1 0芳基。 19 312/發明說明書(補件)/92-10/92121964 200405095 此材料係由上述式Π)所示具芴骨架之重複單位、與上 述式(2 )所示重複單位所構成聚碳酸酯共聚物,以及由上述 式〇)所示具芴骨架之重複單位所構成聚碳酸酯、與上述式 (2 )所示重複單位所構成聚碳酸酯共聚物的摻合聚合物。當 屬於共聚物的情況時,上述式(1 )與(2 )所示重複單位可分 別組合2種以上,當屬於組成物的情況時,上述重複單位 亦可分別組合2種以上。 在上述式(1 )中,R!〜R 8係指從分別獨立的氫原子、鹵原 子、及碳數1〜6之碳化氫基中所選擇的基。此碳數1〜6之 碳化氫基可舉例如:曱基、乙基、異丙基、環己基等烷基、 苯基等芳基。其中,最好為氫原子甲基。 在上述式(2 )中,R 9〜R! 6係指從分別獨立的氫原子、鹵原 子、及碳數1〜2 2之碳化氫基中所選擇的基。此碳數1〜2 2 之碳化氫基可舉例如:甲基、乙基、異丙基、環己基等碳數 1〜9之烷基;苯基、聯苯基、三聯苯基等芳基。其中,最 好為氫原子、甲基。 在上述式(4 )中,R 1 7〜R 1 9、R 2 1及R 2 2係指從分別獨立的氫 原子、i原子、及碳數1〜2 2之碳化氫基中所選擇的基。此 碳數1〜2 2之碳化氫基可舉例如:甲基、乙基、異丙基、環 己基等碳數1〜9之烷基;苯基、聯苯基、三聯苯基等芳基。 其中,最好為氫原子、甲基。R20及R23係指從分別獨立的 碳數1〜2 0之碳化氫基中所選擇的基,且A r係如苯基、f 基等碳數6〜1 0芳基。 上述式(1 )含有率(即,共聚物之情況時為共聚物組成、 20 312/發明說明書(補件)/92-10/92121964 200405095 組成物之情況時為摻合組成比),係聚碳酸酯整體的3 0〜9 0 莫耳%。當在偏離此範圍之外的情況時,則在測量波長 4 0 0〜7 0 0 n m中,相位差絕對值並非波長越短越小。上述式 (1 )含有率,最好為聚碳酸酯總體的3 5〜8 5莫耳%,尤以 4 0〜8 0莫耳%為佳。其中,上述莫耳比係無關共聚物、摻合 聚合物,可在構成配向膜的聚碳酸酯整體總體中,利用如 核磁共振(N M R )元件而求得。 此材料的聚碳酸酯最好為由下述式(5 )所示重複單位、 與下述式(6 )所示重複單位所構成的聚碳酸酯共聚物及/或 聚碳酸酯組成物(摻合聚合物)。——C-0—R20-〇——C——One Si ———— R23 ~ Ο Ο, R22 In the above formula (4), RI 7 ~ R 1 9, R 2 1 and R 2 2 refer to R 2 0 and R 2 3 are independently selected from a 氲 i atom, a halogen atom, and a hydrocarbon group having 1 to 2 carbon atoms; R 2 0 and R 2 3 are each independently a carbonized rat having 1 to 20 carbon atoms. The selected group among the groups; AI * is an aryl group having 6 to 10 carbon atoms. 19 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 This material is a polycarbonate copolymer composed of a repeating unit with a fluorene skeleton shown in the above formula Π) and a repeating unit shown in the above formula (2) And a blend polymer of a polycarbonate composed of a repeating unit having a fluorene skeleton represented by the above formula 0) and a polycarbonate copolymer composed of a repeating unit represented by the above formula (2). In the case of a copolymer, two or more kinds of repeating units represented by the formulae (1) and (2) may be combined, and in the case of a composition, the two or more kinds of repeating units may be combined respectively. In the above formula (1), R! To R 8 are groups selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 6 carbon atoms, which are independent of each other. Examples of the hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as fluorenyl, ethyl, isopropyl, and cyclohexyl, and aryl groups such as phenyl. Among them, a hydrogen atom methyl group is preferred. In the above formula (2), R 9 to R! 6 refer to a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 22 carbon atoms, which are independent of each other. Examples of the hydrocarbon group having 1 to 2 carbon atoms include alkyl groups having 1 to 9 carbon atoms such as methyl, ethyl, isopropyl, and cyclohexyl; aryl groups such as phenyl, biphenyl, and terphenyl . Among these, a hydrogen atom and a methyl group are preferred. In the above formula (4), R 1 7 to R 1 9, R 2 1 and R 2 2 are selected from a hydrogen atom, an i atom, and a hydrocarbon group having 1 to 2 2 carbon atoms, which are each independently selected. base. Examples of the hydrocarbon group having 1 to 2 carbon atoms include alkyl groups having 1 to 9 carbon atoms such as methyl, ethyl, isopropyl, and cyclohexyl; aryl groups such as phenyl, biphenyl, and terphenyl . Among these, a hydrogen atom and a methyl group are preferred. R20 and R23 refer to groups independently selected from hydrocarbon groups having 1 to 20 carbon atoms, and A r is an aryl group having 6 to 10 carbon atoms such as a phenyl group and an f group. The content ratio of the above formula (1) (that is, the composition of the copolymer in the case of a copolymer, and the blending composition ratio in the case of a composition of 20 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095) 30 to 90 mole% of the whole carbonate. When it is out of this range, the absolute value of the phase difference is not shorter and shorter at the measurement wavelength of 400 to 700 nm. The content ratio of the formula (1) is preferably 35 to 85 mol% of the entire polycarbonate, and more preferably 40 to 80 mol%. Among them, the above-mentioned molar ratio-independent copolymers and blended polymers can be obtained by using, for example, a nuclear magnetic resonance (N M R) element in the entire polycarbonate as a whole to form an alignment film. The polycarbonate of this material is preferably a polycarbonate copolymer and / or a polycarbonate composition (doped with a repeating unit represented by the following formula (5) and a repeating unit represented by the following formula (6) Polymer).
(6) 在上述式(5 )中,R 2 4及R 2 5係指從分別獨立的氫原子或甲 基中所選擇的基;在上述式(6 )中,R 2 6及R 2 7係指從分別獨 立的氫原子或曱基中所選擇的基;Ζ係指從式(7 )所示基中 所選擇的基。(6) In the above formula (5), R 2 4 and R 2 5 refer to a group selected from a separate hydrogen atom or a methyl group; in the above formula (6), R 2 6 and R 2 7 Refers to a group selected from independently independent hydrogen atoms or fluorenyl groups; Z refers to a group selected from the groups represented by formula (7).
312/發明說明書(補件)/92-10/92121964 21 200405095 再者,在下述式(8 )〜(1 2 )所示重複單位所構成的共聚物 中,重複單位(1 2 )的比率最好為4 0〜7 5莫耳%;在下述式(9 ) 與(1 2 )所示重複單位所構成的共聚物中,(1 2 )的比率最好 為3 0〜7 0莫耳% ;在下述式(1 0 )與(1 2 )所示重複單位所構成 的共聚物中,(12)的比率最好為30〜70莫耳%;在下述式(8) 與(11 )所示重複單位所構成的共聚物中,(1 1 )的比率最好 為4 0〜7 5莫耳%。312 / Description of the Invention (Supplement) / 92-10 / 92121964 21 200405095 Furthermore, among the copolymers composed of the repeating units represented by the following formulae (8) to (1 2), the ratio of the repeating unit (1 2) is the most It is preferably 40 to 75 mole%. In a copolymer composed of repeating units represented by the following formulae (9) and (1 2), the ratio of (1 2) is preferably 30 to 70 mole%. In a copolymer composed of repeating units represented by the following formulae (1 0) and (1 2), the ratio of (12) is preferably 30 to 70 mole%; in the following formulae (8) and (11), In the copolymer composed of repeating units, the ratio of (1 1) is preferably 40 to 75 mole%.
最好的材料係含雙酚A [ B P A、對應上述式(8 )]與雙甲酚 芴[B C F、對應上述式(1 2 )]的共聚物或高分子摻合物、或者 22 312/發明說明書(補件)/奶10/92121964 200405095 該等的混合物,該等成分的調配比係BCF含有率55〜75莫 耳%,最好為5 5〜7 0莫耳%。該等材料可獲得更接近理想的 λ/4板或λ/2板。 上述共聚物及/或摻合聚合物係可利用週知方法進行製 得。聚碳酸酯可適當的採用如:二羥基化合物與光氣進行縮 聚合的方法、熔融縮聚合法等。當摻合的情況時,最好為 相溶性摻合物,即便未完全相溶,若配合成分間之折射率 的話,便可抑制成分間的光散亂現象,可提升透明性。 本發明之高分子配向膜的材料高分子化合物極限黏 度,最好為0 . 3〜2 . 0 d 1 / g。若黏度低於此的話,將變脆弱 造成無法保有機械強度的問題;反之,若黏度高於此的話, 因為溶液黏度將過度提昇,造成在溶液製膜中,產生模線 (d i e Π ne )等問題,且聚合結束時的精製亦將趨於困難的 問題。 本發明的高分子配向膜最好為透明,濁度值(h a z e v a 1 u e ) 最好在3 %以下,總光線透過率最好在8 5 %以上。此外,上 述高分子配向膜材料的玻璃轉移溫度最好在1 0 0 °C以上, 尤以在1 2 0 °C以上為佳。此外,亦可添加如:苯基水揚酸、 2 -羥基二苯曱酮、三聯苯基磷酸酯等紫外線吸收劑,或供 改變顏色的藍色油墨劑(b 1 u i n g a g e n t),抗氧化劑等。 本發明的高分子配向膜係採用將上述碳酸酯等薄膜,利 用延伸等而配向的薄膜。此薄膜之製造方法,可採用如周 知的溶融擠出法、溶液澆注法等,但就從膜厚不均、外觀 等觀點而言,最好採用溶液澆注法。溶液澆注法中的溶劑, 23 312/發明說明書(補件)/92-10/92121964 200405095 可適當的採用如:二氯曱烷 再者,延伸方法雖亦可使 採用縱向單軸延伸。在提昇 可含有周知可塑劑的鄰苯二 酯、鄰苯二甲酸二丁酯等鄰 磷酸酯;脂肪族二鹼基酯、 在延伸時,亦可使上述薄膜 留於薄膜中並施行延伸。此 固形份的1〜2 0質量°/〇。 再者,上述可塑劑或液晶 相位差波長分散產生變化, 的1 0質量%以下,尤以在3 高分子配向膜的膜厚並無 4 0 μπι 〇 在為使高分子配向膜的相 以具特定化學構造為必要條 由此化學構造所決定,但是 狀態等而有所變動。 高分子配向膜特別因為可 存性較少的優越之4分之1 述式(Π )。 0. 2 ^ Re( λ )/ λ ^0.3 本發明中所採用的第2光 性正單軸性之液晶性高分子 二氧戊環等。 用週知的延伸方法,但是最好 薄膜中的延伸性之目的下,亦 曱酸二甲酯、鄰苯二甲酸二乙 苯二甲酸酯;三丁基磷酸酯等 甘油衍生物、二醇衍生物等。 製膜時所採用的有機溶劑,殘 有機溶劑的量,最好為聚合物 等添加劑可使高分子配向膜的 而添加量最好為聚合物固形份 質量%以下為佳。 特別的限制,最好為1 μπι至 位差成為波長越短越小,必須 件’相位差波長分散大部分係 亦應注意將隨延伸條件、摻合 構成擁有1片配向膜且波長依 波長板(λ / 4板),因此滿足下 (Π ) 學各向異性元件係由顯示光學 物質(具體而言,顯示光學性正 312/發明說明書(補件)/92· 10/92121 %4 24 200405095 單軸性之液晶性高分子化合物、或至少含1種該液晶性高 分子化合物之顯示光學性正單軸性液晶性高分子組成物) 所構成,且至少含有將該液晶性高分子化合物或該液晶性 高分子組成物,在液晶狀態下所形成的平均傾斜角為5 ° 〜3 5 °的向列混合配向構造,予以固定化的液晶薄膜(A ), 在可見光區域中具有略4分之1波長的相位差之元件。 此處所謂「向列混合配向」係指液晶分子為向列配向, 此時的液晶分子之指向方向與薄膜平面間的夾角,在薄膜 上面與下面呈不同配向形態。所以,可謂因為在上面界面 附近與下面界面附近,該指向方向與薄膜平面間的夾角角 度不同,因此在該薄膜的上面與下面之間,該角度將連續 變化。 再者,將向列混合配向狀態固定化的薄膜,係液晶分子 指向方向在薄膜厚度方向所有處所均朝不同角度。所以, 該薄膜係當以薄膜的構造體觀之的情況時,還是未存在光 軸〇 再者,本發明中所謂「平均傾斜角」,係指在液晶薄膜 厚度方向中,液晶分子的指向方向與薄膜平面所構成夾角 的平均值。本發明所提供的液晶薄膜係在薄膜其中一界面 附近處,指向方向與薄膜平面所形成夾角的絕對值,通常 為2 0 °〜9 0 ° ,最好為3 0 °〜7 0 °的角度,而在該面的背面 處,則絕對值通常為0 °〜2 0 ° ,最好為0 °〜1 0 °的角度, 平均傾斜角的絕對值,通常為5。〜4 5。,最好為7 °〜4 0 ° , 尤以1 0 °〜3 8 °的角度為佳,更以1 5 °〜3 5 °的角度為佳。 25 312/發明說明書(補件)/92-10/92121964 0 ;1 0 200405095 當平均傾斜角偏離上述範圍的情況時,恐將發生對比降低 等不良現象,因此最好不要。另外,平均傾斜角係可利用 晶體旋轉法(crystal rotation method)求得。 構成本發明中所採用第2光學各向異性元件的液晶薄膜 (A ),係僅要由顯示光學正單軸性的液晶性高分子物質所實 質形成的,且將該液晶性高分子物質在液晶狀態下,所形 成的向列混合配向狀態予以固定化便可,其製造方法並無 特別的限制。譬如,可採用將低分子液晶在液晶狀態中形 成向列混合配向之後,再利用光交聯或熱交聯而固定化所 獲得的液晶薄膜*或者採用將向分子液晶在液晶狀態下形 成向列混合配向之後,再經冷卻而將該配向固定化而所獲 得的液晶薄膜。另外,本發明中所謂「液晶薄膜」係指無 關薄膜本身是否呈液晶性,將低分子液晶、高分子液晶等 液晶物質予以薄膜化而所獲得者。 再者,液晶薄膜(A)在為能顯現出對半透過反射型液晶 顯示元件更佳視野角度改良效果,該薄膜厚度雖因為依存 於對象液晶顯示元件的形式、或各種光學參數,因而不能 一概而論,但是通常為0.2μπι〜ΙΟμπι的範圍,最好為 0.3μπι〜5μπι的範圍,尤以0.5μπι〜2μπι的範圍為佳。當膜厚 低於0 . 2 μ m之時,恐將無法獲得充分的補償效果。反之, 若膜厚超過1 0 μ m的話,顯示器的顯示恐將出現不必要顏 色附著的現象。 其次,採用圖1至圖3,分別將由液晶薄膜(A)所構成的 光學各向異性元件的上下、該光學各向異性元件的傾斜方 26 312/發明說明書(補件)/92-10/92121964 200405095 向、及液晶單元層的預傾斜方向,分別定義如下。 首先,在圖1與圖2所示中,將由液晶薄膜(A)所構成 的光學各向異性元件的上下,若利用構成該光學各向異性 元件的液晶薄膜(A )之薄膜界面附近,由液晶分子指向方向 與薄膜平面所呈夾角而分別定義的話,將液晶分子之指向 方向與薄膜平面所成夾角為銳角端且形成2 0〜9 0度角度的 面設定為b面,將該角度為銳角端且形成0〜20度角度的面 設定為c面。 當從此光學各向異性元件的b面通過液晶薄膜層而看到 c面的情況時,便將液晶分子指向方向、與朝指向方向的c 面的投影成分間所構成角度,成為銳角的方向,且平行於 投影成分的方向定義為光學各向異性元件的傾斜方向。 其次,在圖3中,通常在液晶單元層的單元界面中,驅 動用低分子液晶對單元界面非呈平行狀態而是具有某種角 度的傾斜狀態,一般將此角度稱為預傾斜角;將單元界面 的液晶分子指向方向、與對指向方向界面的投影成分所形 成的角度為銳角的方向,且平行於指向方向投影成分的方 向,定義為液晶單元層的預傾斜方向。 再者,第2光學各向異性元件係可採用組合搭配其他高 分子延伸薄膜或向列配向固定化的液晶薄膜(B )。 高分子延伸薄膜係顯示單軸性或雙軸性的物質,可採用 如:聚碳酸S旨(P C )、聚甲基丙稀酸S旨(Ρ Μ Μ A )、聚乙稀醇 (PVA)、日本合成橡膠(股)製ART ON(商品名)薄膜等延伸薄 膜。此情況下,若顧慮成本提高問題的話,1片液晶薄膜 27 312/發明說明書(補件)/92-10/92121964 200405095 與1片高分子延伸薄膜的組合在實用上最為恰當。 液晶薄膜(B)係僅要向列配向狀態呈固定化狀態者的話 便可,可由任何形式液晶所形成。譬如可採用將低分子液 晶在液晶狀態中形成向列配向之後,再利用光交聯或熱交 聯而固定化所獲得的液晶薄膜,或者採用將高分子液晶在 液晶狀態下形成向列配向之後,再經冷卻而將該配向固定 化而所獲得的液晶薄膜。另外,本發明中所謂「液晶薄膜 (B )」,乃如同液晶薄膜(A ),係指無關薄膜本身是否呈液晶 性,將低分子液晶、高分子液晶等液晶物質予以薄膜化而 所獲得者。 再者,第2光學各向異性元件中所含液晶薄膜亦可使用 為液晶薄膜單體,亦可設計呈支撐基板的透明塑膠薄膜使 用。當使用為液晶薄膜單體的情況時,在製作該偏光板時 所採用的聚酯或三乙醯纖維素等透明塑膠薄膜上,層積液 晶薄膜之後,再經與偏光板呈一體化之後便可製得。 針對本發明之第2光學各向異性元件的延遲值(複折射 △ η與膜厚d的乘積),進行說明。 從液晶薄膜(A )法線方向進行觀看時的面内表觀延遲 值,在向列混合配向的薄膜中,與指向方向平行方向的折 射率(以下稱「n e」)與垂直方向的折射率(以下稱「η 〇」) 係不同,當將從n e除以η 〇的扣除值設定為表觀上複折射 率的情況時,表觀上的延遲值便為表觀上複折射率與絕對 膜厚的乘積。此表觀上的延遲值乃利用橢圓儀 (e 1 1 i p s 〇 m e t r y )等偏光光學測定便可輕易求得。 28 312/發明說明書(補件)/92-10/92121964 200405095 將上述第2光學各向 異性元件,區The best material is a copolymer or polymer blend containing bisphenol A [BPA, corresponding to the above formula (8)] and biscresol hydrazone [BCF, corresponding to the above formula (1 2)], or 22 312 / invention Instruction (Supplement) / Milk 10/92121964 200405095 The blending ratio of these ingredients is a BCF content rate of 55 to 75 mole%, preferably 55 to 70 mole%. These materials can get closer to the ideal λ / 4 plate or λ / 2 plate. The above-mentioned copolymer and / or blended polymer can be produced by a known method. As the polycarbonate, for example, a method of polycondensation polymerization of a dihydroxy compound and phosgene, a melt polycondensation method, or the like can be suitably used. In the case of blending, a miscible blend is preferred. Even if they are not completely miscible, if the refractive index between the components is blended, the phenomenon of light scattering between the components can be suppressed and the transparency can be improved. The limiting viscosity of the polymer compound of the polymer alignment film of the present invention is preferably 0.3 to 2.0 d 1 / g. If the viscosity is lower than this, it will become fragile and the mechanical strength will not be maintained. On the other hand, if the viscosity is higher than this, the solution viscosity will be excessively increased, which will cause die Π ne in the solution filming, etc. Problems, and the refining at the end of polymerization will also tend to be a difficult problem. The polymer alignment film of the present invention is preferably transparent, the haze value (h a z e v a 1 u e) is preferably 3% or less, and the total light transmittance is preferably 85% or more. In addition, the glass transition temperature of the polymer alignment film material is preferably 100 ° C or more, and more preferably 120 ° C or more. In addition, UV absorbers such as phenylsalicylic acid, 2-hydroxybenzophenone, terphenyl phosphate, or blue inks (b 1 u i n g a g e n t) for changing colors, antioxidants, etc. may be added. The polymer alignment film of the present invention is a film in which the above-mentioned thin films such as carbonates are aligned by stretching or the like. As a method for manufacturing the film, a known melt extrusion method, a solution casting method, or the like can be used, but from the viewpoint of uneven film thickness and appearance, the solution casting method is preferably used. The solvent in the solution casting method, 23 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 can be suitably used, such as: dichloromethane. In addition, although the stretching method can also be used to extend uniaxially in the longitudinal direction. It can contain phthalates such as phthalate and dibutyl phthalate, which are well-known plasticizers, and aliphatic dibasic esters. When stretched, the film can be left in the film and stretched. This solid content is 1 to 20 mass ° / 〇. In addition, the above-mentioned plasticizer or liquid crystal retardation wavelength dispersion changes, and is less than 10% by mass, especially in the film thickness of 3 polymer alignment films, which is not 40 μm. The specific chemical structure is determined by the necessary chemical structure, but the state and the like vary. The polymer alignment film is particularly superior to the one-fourth formula (Π) because of its low storability. 0.2 ^ Re (λ) /λ^0.3 The second optically positive uniaxial liquid crystal polymer dioxolane and the like used in the present invention. The well-known stretching method is used, but for the purpose of the best stretchability in the film, dimethyl acetate, phthalic acid diacetate, glycerin derivatives such as tributyl phosphate, and glycols Derivatives, etc. The amount of the organic solvent and residual organic solvent used in film formation is preferably an additive such as a polymer, which allows the polymer alignment film to be added, and the added amount is preferably a polymer solid content of less than mass%. Special limitation, it is best to be 1 μπι until the retardation becomes shorter and shorter. The phase retardation and wavelength dispersion are required. Most of the systems should also pay attention to having an alignment film depending on the extension conditions and the composition. The wavelength depends on the wavelength plate. (Λ / 4 plate), so the following (Π) anisotropic element is composed of a display optical substance (specifically, the display optical property is positive 312 / Invention Specification (Supplement) / 92 · 10/92121% 4 24 200405095 It is composed of a uniaxial liquid crystal polymer compound or an optically positive uniaxial liquid crystal polymer composition containing at least one kind of the liquid crystal polymer compound, and contains at least the liquid crystal polymer compound or The liquid crystal polymer composition has a nematic hybrid alignment structure with an average inclination angle of 5 ° to 35 ° formed in a liquid crystal state, and the liquid crystal film (A) to be immobilized has slightly 4 points in the visible light region. Element with a phase difference of 1 wavelength. The so-called "nematic hybrid alignment" herein means that the liquid crystal molecules are nematically aligned. At this time, the angle between the orientation direction of the liquid crystal molecules and the plane of the film is different from that of the film. Therefore, it can be said that the angle between the pointing direction and the plane of the film is different near the upper interface and near the lower interface, so the angle will continuously change between the upper and lower sides of the film. In addition, the film in which the nematic mixed alignment state is fixed is such that the liquid crystal molecules are directed in different directions in all directions in the film thickness direction. Therefore, when the film is viewed from the structure of the film, the optical axis does not exist. Furthermore, the "average tilt angle" in the present invention refers to the direction in which the liquid crystal molecules point in the thickness direction of the liquid crystal film. The average value of the angle formed with the film plane. The liquid crystal film provided by the present invention is an absolute value of the angle formed between the pointing direction and the plane of the film near one of the interfaces of the film, usually an angle of 20 ° ~ 90 °, preferably an angle of 30 ° ~ 70 ° At the back of the face, the absolute value is usually 0 ° ~ 20 °, preferably 0 ° ~ 10 °, and the absolute value of the average tilt angle is usually 5. ~ 4 5. It is preferably 7 ° ~ 40 °, especially 10 ° ~ 38 °, and more preferably 15 ° ~ 35 °. 25 312 / Invention Specification (Supplement) / 92-10 / 92121964 0; 1 0 200405095 When the average tilt angle deviates from the above range, adverse phenomena such as reduced contrast may occur, so it is best not to. The average tilt angle can be obtained by a crystal rotation method. The liquid crystal film (A) constituting the second optically anisotropic element used in the present invention is only formed substantially from a liquid crystal polymer substance exhibiting optical positive uniaxiality, and the liquid crystal polymer substance is In the liquid crystal state, the formed nematic mixed alignment state may be fixed, and the manufacturing method is not particularly limited. For example, a low-molecular liquid crystal can be formed into a nematic hybrid alignment in a liquid crystal state, and then the obtained liquid crystal film can be fixed by photocrosslinking or thermal crosslinking * or a nematic liquid crystal can be formed in a liquid crystal state. After the alignment is mixed, the liquid crystal film obtained by fixing the alignment is cooled again. The "liquid crystal film" in the present invention refers to a film obtained by thinning a liquid crystal material such as a low-molecular liquid crystal and a high-molecular liquid crystal, regardless of whether the film itself is liquid crystalline. In addition, the liquid crystal film (A) has a better viewing angle improvement effect on the transflective liquid crystal display element. Although the thickness of the film depends on the form of the target liquid crystal display element or various optical parameters, it cannot be generalized. However, it is usually in a range of 0.2 μm to 10 μm, preferably in a range of 0.3 μm to 5 μm, and more preferably in a range of 0.5 μm to 2 μm. When the film thickness is less than 0.2 μm, it may not be able to obtain a sufficient compensation effect. Conversely, if the film thickness exceeds 10 μm, the display may cause unnecessary color adhesion. Next, using FIG. 1 to FIG. 3, the optical anisotropic element composed of the liquid crystal film (A) is placed above and below, and the inclined side of the optical anisotropic element 26 312 / Invention Specification (Supplement) / 92-10 / The 92121964 200405095 direction and the pre-tilt direction of the liquid crystal cell layer are defined as follows. First, as shown in FIG. 1 and FIG. 2, when an optical anisotropic element composed of a liquid crystal film (A) is used above and below the vicinity of a film interface of the liquid crystal film (A) constituting the optical anisotropic element, If the angle between the orientation direction of the liquid crystal molecules and the plane of the film is defined separately, set the angle formed by the orientation direction of the liquid crystal molecules and the plane of the film to be an acute angle end and form an angle of 20 to 90 degrees as the b-plane. The surface at an acute angle end and forming an angle of 0 to 20 degrees is set as the c-plane. When the c-plane is seen from the b-plane of the optically anisotropic element through the liquid crystal film layer, the angle formed between the liquid crystal molecules pointing direction and the projection component of the c-plane toward the pointing direction becomes an acute angle direction. And the direction parallel to the projection component is defined as the oblique direction of the optically anisotropic element. Secondly, in FIG. 3, usually in the unit interface of the liquid crystal cell layer, the driving low-molecular liquid crystal does not have a parallel state to the unit interface but an inclined state with a certain angle. This angle is generally referred to as a pre-tilt angle; The direction formed by the liquid crystal molecules of the cell interface and the angle formed by the projection component on the interface of the pointing direction is an acute angle direction, and the direction of the projection component parallel to the pointing direction is defined as the pre-tilt direction of the liquid crystal cell layer. In addition, the second optical anisotropic element may be a liquid crystal film (B) that is fixed in combination with other polymer stretched films or nematically aligned. The polymer stretched film is a substance that exhibits uniaxiality or biaxiality. For example, polycarbonate carbonate (PC), polymethyl acrylate (PMA), and polyvinyl alcohol (PVA) can be used. , ART ON (trade name) film made by Japan Synthetic Rubber Co., Ltd. and other stretch films. In this case, a combination of a single liquid crystal film 27 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 and a polymer stretched film is most practically practical if the cost increase is a concern. The liquid crystal film (B) is only required to be in a state where the nematic alignment state is fixed, and may be formed of any type of liquid crystal. For example, after the low-molecular liquid crystal is formed into a nematic alignment in a liquid crystal state, the obtained liquid crystal film may be fixed by photo-crosslinking or thermal cross-linking, or after the polymer liquid crystal is formed into a nematic alignment in a liquid crystal state. And the liquid crystal film obtained by fixing the alignment after cooling. In addition, the so-called "liquid crystal film (B)" in the present invention is the same as the liquid crystal film (A), which refers to a person obtained by thinning liquid crystal materials such as low-molecular liquid crystal and high-molecular liquid crystal, regardless of whether the film itself is liquid crystalline. . Furthermore, the liquid crystal film contained in the second optical anisotropic element may be used as a liquid crystal film alone, or a transparent plastic film that is designed to support a substrate may be used. When the liquid crystal film is used alone, after the liquid crystal film is laminated on the transparent plastic film such as polyester or triethyl cellulose used in the production of the polarizing plate, it is integrated with the polarizing plate. Can be made. The retardation value (product of the birefringence Δη and the film thickness d) of the second optically anisotropic element of the present invention will be described. The in-plane apparent retardation value when viewed from the normal direction of the liquid crystal film (A). In a film with nematic hybrid alignment, the refractive index parallel to the direction of orientation (hereinafter referred to as "ne") and the refractive index in the vertical direction. (Hereinafter referred to as "η 〇") is different. When the subtraction value from dividing ne by η 〇 is set as the apparent complex refractive index, the apparent retardation value is the apparent complex refractive index and absolute Product of film thickness. This apparent retardation value can be easily obtained by using polarized optical measurement such as an ellipsometry (e 1 1 i p s 0 m e t r y). 28 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 The above-mentioned second optical anisotropic element, zone
當僅由將向列 >見合偏向的液晶薄膜 區分為僅由將向列混合 況,及液晶薄膜(A) 酉己向固定化的液晶薄膜(B)所 晶薄膜(A )所構成之情況 時,液晶薄膜(A )之表觀上 延遲值,藉由相對於550nm的單 色光,通常設定為70nm〜 I80nm(最好為90nm〜160nm,尤以 在1 2 0 n in〜1 5 0 n m為佳)範圍内,便可獲得優越的圓偏光特 性。當表觀延遲值低於7 〇 n m、或大於丨8 〇 n m之時,液晶| 示元件上恐將發生不需要顏色附著的現象。 當組合液晶薄膜(A )與高分子延伸薄膜或液晶薄膜(B) 的情況時,如日本專利特開平丨〇 — 〇 6 8 8丨6號公報中所記 載’在5 5 0 nm單色光的複折射光相位差為大致丨/ 4波長的 1 / 4波長板’與在5 5 0 n m單色光的複折射光相位差為大致 1 / 2波長的1 / 2波長板,在該等延遲相軸交叉的狀態下進 行貼合,便可獲得良好的圓偏光特性。1 / 4波長板的延遲 值通常為70nm〜180nm之範圍,最好為90nm〜160nm,尤以 120nm〜150nm範圍為佳。1/2波長板的延遲值通常為 180nm〜320nm之範圍,最好為200nm〜300nm,尤以 2 2 0 η πι〜2 8 0 n m範圍為佳。若1 / 4波長板與1 / 2波長板的延 遲範圍偏離上述範圍的情況時,液晶顯示元件上恐將發生 附著不需要顏色的現象。 1 / 4波長板之延遲相軸與1 / 2波長板之延遲相軸所形成 夾角角度,通常在銳角端為40度〜90度,最好為50度〜80 29 312/發明說明書(補件)/92-10/92121964 200405095 度,尤以5 5度〜7 5度範圍内者為佳。 將向列混合配向固定化的液晶薄膜(A)可使用於1 / 4波 長板,亦可使用於1 / 2波長板。 當將液晶薄膜(A )使用於1 / 4波長板的情況時,僅要1 / 2 波長板使用高分子延伸薄膜或液晶薄膜(B )的話便可,而當 將液晶薄膜(A )使用於1 / 2波長板的情況時,僅要1 / 4波長 板使用高分子延伸薄膜或液晶薄膜(B )的話便可。 針對第2光學各向異性元件為僅將1片液晶薄膜(A)使 用於半透過反射型液晶顯示元件的情況,進行說明。液晶 薄膜(A )最好配置於液晶單元的第2基板與偏光板之間。在 此針對液晶薄膜(A )的配置條件,採用圖6進行說明。 在圖6之液晶單元1 5中,分別假設重疊於上方基板預 傾斜方向的直線、及重疊於下方基板預傾斜方向的直線。 將此二直線投影於同一平面上,此時以直線交叉點為中心 所形成的4個角度中,分別拉出銳角端的2個角度形成左 右對稱角度的直線。將此直線在本發明中定義為二等份 線。另外,當重疊於上方基板預傾斜方向之直線、與重疊 於下方基板預傾斜方向之直線,相互重疊的情況時(即,而 直線呈平行狀態),此重疊的直線將成為本發明中所謂的二 等份線。 此二等份線、與以液晶薄膜(A )之傾斜方向為基準的直 線成分間所形成的夾角,通常最好配置呈絕對值0度〜3 0 度(最好為0度〜20度,尤以0度〜10度為佳,更以略呈0 度為佳)。當二者的夾角大於3 0度的情況時,恐將無法獲 30 312/發明說明書(補件)/92-10/92121964 200405095 得充分的視野角補償效果。 其次,針對第2光學各向異性元件為組合 (A)與1片高分子延伸薄膜或1片液晶薄膜, 過反射型液晶顯示元件的情況,進行說明。 液晶薄膜(A )的配置最好如同上述僅採用 相同的配置方式。換句話說,最好液晶薄膜 分子傾斜方向與上述二等份線的方向,大略 傾斜方向與預傾斜方向所成角度最好在0度 尤以0度至2 0度範圍為佳,更以0度至1 0 本發明的半透過反射型液晶顯示元件中, 光源、光控制膜、導光板、稜鏡片並無特別 用周知者。 本發明的半透過反射型液晶顯示元件,除 之外,亦可附設其他構成組件。譬如:藉由將 設於本發明的液晶顯示元件中,便可製作能 高的多色或全彩顯示之彩色液晶顯示元件。 (產業上可利用性) 本發明的半透過反射型液晶顯示元件係透 顯示明亮且高對比,可設計成較薄狀態,並 性較少的特徵。 (較佳實施形態) 以下,利用實施例與比較例更詳盡的說明 發明並不僅限於該等。另外,在本實施例的 無特別限制的前提下,設定為波長5 5 0 n m的 312/發明說明書(補件)/92-10/92121964 1片液晶薄膜 並使用於半透 [片之情況時 中的液晶性南 呈一致狀態。 至3 0度範圍, 度範圍為佳。 光擴散層、背 的限制,可使 上述構成組件 彩色濾光片附 執行色純度較 過模式下的 具有視野依存 本發明,惟本 延遲△ nd ,在 值0 31 200405095 (實施例1 ) 針對本發明的半透過反射型液晶顯示元件的概略,採用 圖4進行說明。相關實施例1構造則採用圖5進行說明。 在第2基板8上設計者由A 1等反射率較南之材料所形 成的反射電極6,與由I T 0等穿透率較高材料所形成的透 明電極7。在第1基板3上設置對向電極4。在反射電極6 及透明電極7、與對向電極4之間夾置著由顯示正介電率 各向異性之液晶材料所構成的液晶層5。在形成第1基板3 之對向電極4側的背面,設置著第1光學各向異性元件2 與偏光板1,在形成第2基板8之反射電極6與透明電極7 之面的背側,設計著第2光學各向異性元件9與偏光板 1 0。在偏光板1 0背面設置著背光源1 1。 製作膜厚方向平均傾斜角為2 8度的向列混合配向,經 固定化的膜厚0 . 7 7 μ m液晶薄膜1 3,利用如圖5所示配置 製作下述TN型半透過反射型液晶顯示元件。 所使用的液晶單元1 5係液晶材料採用Z L I - 1 6 9 5 ( M e r c k 公司製),液晶層厚在反射電極區域6 (反射顯示部)為 3.5μπι,在透明電極區域7(透過顯示部)為4·0μπι。液晶層 之基板雙界面的預傾斜角為2度,液晶單元的扭轉角為左 旋7 0度,液晶單元的△ n d在反射顯示部大致為2 3 0 n m,在 透過顯示部大致為2 6 2 n m。 在液晶單元1 5之觀察者端(圖上方)配置著偏光板1 (厚 度約180μπι ;住友化學工業(股)製SQW- 8 6 2 ),在偏光板1 與液晶單元1 5之間,配置著第1光學各向異性元件2,該 32 312/發明說明書(補件)/92-10/92121964 200405095 第1光學各向異性元件2係滿足本發明要件式(I )與式(Π ) 之帝人(股)製單軸延伸高分子延伸薄膜(產品名:畢亞艾 斯)2。高分子延伸薄膜2的△ n d大約為1 2 0 n m。 再者,第2光學各向異性元件9係在從觀察者所觀看液 晶單元1 5的後方,配置著液晶薄膜1 3及由單軸延伸的聚 碳酸酯薄膜所構成高分子延伸薄膜1 4,更於背面配置著偏 光板1 0。將混合向列偏向構造固定化的液晶薄膜1 3之△ nd為135nm,高分子延伸薄膜14之Δη(1為275nm。 偏光板1與1 0之吸收軸、第1光學各向異性物2與高 分子延伸薄膜1 4的延遲相軸、液晶單元1 5二界面的預傾 斜方向、及液晶薄膜1 3的傾斜方向,係依圖6所示條件進 行配置。 圖7所示係在背光源點亮時(透過模式),將白顯示0 V、 黑顯示6 V的透過率比(白顯示)/(黑顯示)設定為對比,而 全方位的對比圖。 圖8所示係在背光源點亮時(透過模式),從白顯示0 V 至黑顯示6 V,依6色階顯示時的左右方向下之透過率視野 角特性。 圖9所示係在背光源點亮時(透過模式),從白顯示0 V 至黑顯示6 V,依6色階顯示時的上下方向下之透過率視野 角特性。 圖7〜9得知,特別在透過模式中具有優越的視野角特性。 (實施例2 ) 製作膜厚方向平均傾斜角為2 8度的向列混合偏向,經 33 312/發明說明書(補件)/92-10/92121964 200405095 固定化的膜厚0 . 6 0 μ m液晶薄膜1 3,利用如圖5所示配置 製作下述ECB型半透過反射型液晶顯示元件。 所使用的液晶單元1 6係液晶材料採用Z L I - 1 6 9 5 ( M e r c k 公司製),液晶層厚在反射電極區域6 (反射顯示部)為 2 . 1 μ m,在透明電極區域7 (透過顯示部)為4 . 9 μ m。液晶層 之基板雙界面的預傾斜角為2度,液晶單元的△ nd在反射 顯示部大致為1 3 8 n m,在透過顯示部大致為3 2 1 n in的均質 配向。 在液晶單元1 6之觀察者端(圖上方)配置著偏光板1 (厚 度約180μπι ;住友化學工業(股)製SQW- 8 6 2 ),在偏光板1 與液晶單元1 6之間,配置著第1光學各向異性元件2,該 第1光學各向異性元件2係滿足本發明要件式(I )與式(Π ) 之帝人(股)製單軸延伸高分子延伸薄膜(產品名:畢亞艾 斯)2。高分子延伸薄膜2的And大約為115nm。 再者,第2光學各向異性元件9乃將所配置混合向列偏 向構造固定化的液晶薄膜1 3之△ n d為1 0 5 n m,高分子延伸 薄膜14之Δη(1為270nm。 偏光板1與1 0之吸收軸、第1光學各向異性物2與高 分子延伸薄膜1 4的延遲相軸、液晶單元1 6二界面的預傾 斜方向、及液晶薄膜1 3的傾斜方向,係依圖1 0所示條件 進行配置。 圖1 1所示係在背光源點亮時(透過模式),將白顯示0 V、 黑顯示6 V的透過率比(白顯示)/(黑顯示)設定為對比,而 全方位的對比圖。 34 312/發明說明書(補件)/92-10/92121964 200405095 圖1 2所示係在背光源點亮時(透過模式),從ί 至黑顯示6 V,依6色階顯示時的左右方向下之透 角特性。 圖1 3示係在背光源點亮時(透過模式),從白I 黑顯示6 V,依6色階顯示時的上下方向下之透過 特性。 圖1 1〜1 3得知,E C Β型亦如同Τ Ν型,特別在透 具有優越的視野角特性。 (比較例1 ) 如圖1 4之配置圖,除取代液晶薄膜1 3而採用 1 7 ( △ n d大致1 3 0 n m ),將聚碳酸酯1 4的△ n d設3 配置於液晶單元1 5背面側的偏光板1 0吸收轴、 伸薄膜1 4與1 7的延遲相軸,依圖1 5所示條件進 外,其餘均如同實施例1般的製造液晶顯示元件 圖1 6所示係在背光源點亮時(透過模式),將白 黑顯示6 V的透過率比(白顯示)/(黑顯示)設定為 全方位的對比圖。 圖1 7所示係在背光源點亮時(透過模式),從έ 至黑顯示6 V,依,6色階顯示時的左右方向下之透 角特性。 圖1 8所示係在背光源點亮時(透過模式),從έ 至黑顯示6 V,依6色階顯示時的上下方向之透過 特性。 相關視野角特性,將實施例1與比較例1進行 312/發明說明書(補件)/92-10/92121964 ?顯示0V 過率視野 I示0V至 率視野角 過模式中 聚碳酸酯 7 2 6 0 n m » 高分子延 行配置之 〇 顯示0 V、 對比,而 f顯示0V 過率視野 f顯示0V 率視野角 比較。 35 200405095 若就全方位的等對比曲線,依圖7與圖1 6進# 話,得知藉由採用具混合向列構造的液晶薄膜1 3 得較廣的視野角特性。 此外,就構成透過模式之缺點的左右、上下方 性,將圖8,9與圖1 7,1 8進行比較的話,得知藉 混合向列構造的液晶薄膜,便可大幅改善反轉特 (比較例2 ) 如圖1 4之配置圖,除取代液晶薄膜1 3而採用 1 7 ( △ n d大致1 1 0 n m ),將聚碳酸酯1 4的△ n d設肩 配置於液晶單元1 6背面側的偏光板1 0吸收軸、 伸薄膜1 4與1 7的延遲相軸,依圖1 9所示條件進 外,其餘均如同實施例2般的製造液晶顯示元件 圖2 0所示係在背光源點亮時(透過模式),將白 黑顯示6 V的透過率比(白顯示)/(黑顯示)設定為 全方位的對比圖。 圖2 1所示係在背光源點亮時(透過模式),從έ 至黑顯示6 V,依6色階顯示時的左右方向下之透 角特性。 圖2 2所示係在背光源點亮時(透過模式),從έ 至黑顯示6 V,依6色階顯示時的上下方向之透過 特性。 相關視野角特性,將實施例2與比較例2進行 若就全方位的等對比曲線,依圖1 1與圖2 0進 話,得知藉由採用具混合向列構造的液晶薄膜1 3 312/發明說明書(補件)/92-10/92121964 f*比較的 ,便可獲 向色階特 由採用具 性。 聚碳酸酯 〉2 7 0 nm, 高分子延 行配置之 〇 顯示0 V、 對比,而 丨顯示0V 過率視野 丨顯示0V 率視野角 比較。 行比較的 ,便可獲 36 200405095 得較廣的視野角特性。 此外,就構成透過模式之缺點的左右、上下方向色階特 性,將圖1 2,1 3與圖2 1,2 2進行比較的話,得知藉由採用 具混合向列構造的液晶薄膜,便可大幅改善反轉特性。 在本實施例中,雖依無彩色濾光片的型態施行實驗,但 是若在液晶單元中設置彩色濾光片的話,當然亦可進行良 好的多色或全彩顯示。 【圖式簡單說明】 圖1為說明液晶分子之傾斜角與扭轉角的概念圖。 圖2為構成第1光學各向異性元件之液晶薄膜配向構造 的概念圖。 圖3為說明液晶單元之預傾斜方向的概念圖。 圖4為本發明之半透過反射型液晶顯示元件的示意剖視 圖。 圖5為實施例1與實施例2之半透過反射型液晶顯示元 件的示意剖視圖。 圖6為實施例1中,偏光板之吸收軸、液晶單元之預傾 斜方向、高分子延伸薄膜之延遲相軸、及液晶薄膜之傾斜 方向的角度關係平面圖。 圖7為從全方位觀看實施例1之半透過反射型液晶顯示 元件時的對比度圖。 圖8為將實施例1之半透過反射型液晶顯示元件,從0V 至6V依7色階顯示時的左右方位透過率視野角特性圖。When only the nematic liquid crystal film is classified into a mixed liquid crystal film (A) and a liquid crystal film (A) formed by the liquid crystal film (A) which has been fixed to the nematic direction At this time, the apparent retardation value of the liquid crystal film (A) is usually set to 70 nm to I80 nm (preferably 90 nm to 160 nm, especially 1 2 0 n to 1 5 0) relative to 550 nm monochromatic light. nm is preferred), and superior circular polarization characteristics can be obtained. When the apparent retardation value is lower than 7 nm or larger than 8 nm, the phenomenon that color does not need to adhere to the liquid crystal display element may occur. When a liquid crystal film (A) is combined with a polymer stretched film or a liquid crystal film (B), as described in Japanese Patent Laid-Open No. 丨 〇—〇6 8 8 丨 6, monochromatic light at 50 nm The retardation of the birefringent light is approximately 1/4 wavelength plate with a wavelength of ¼ / 4 'and the retardation of the birefringent light with monochromatic light at 550 nm is approximately 1/2 wavelength with a retardation of 1/2 wavelength plate. When the lamination is performed with the retarded axes intersecting, good circular polarization characteristics can be obtained. The retardation value of the 1/4 wavelength plate is usually in the range of 70nm to 180nm, preferably 90nm to 160nm, and more preferably 120nm to 150nm. The retardation value of a 1/2 wavelength plate is usually in a range of 180 nm to 320 nm, preferably 200 nm to 300 nm, and particularly preferably in a range of 2 2 0 η 2 to 2 8 0 m. If the retardation range of the 1/4 wave plate and the 1/2 wave plate deviates from the above range, the liquid crystal display element may adhere to an unwanted color. The angle formed by the retardation axis of the 1/4 wave plate and the retardation axis of the 1/2 wave plate is usually 40 ° ~ 90 ° at the acute angle end, preferably 50 ° ~ 80 29 312 / Invention Specification (Supplementary Document) ) / 92-10 / 92121964 200405095 degrees, especially those in the range of 55 to 75 degrees. The liquid crystal film (A) having the nematic hybrid alignment immobilized can be used for a 1/4 wave plate or a 1/2 wave plate. When the liquid crystal film (A) is used in the case of a 1/4 wave plate, it is only necessary to use a polymer stretch film or a liquid crystal film (B) in the 1/2 wave plate, and when the liquid crystal film (A) is used in In the case of a 1/2 wavelength plate, it is only necessary to use a polymer stretch film or a liquid crystal film (B) for the 1/4 wavelength plate. A case where the second optically anisotropic element uses only one liquid crystal film (A) for a transflective liquid crystal display element will be described. The liquid crystal film (A) is preferably disposed between the second substrate of the liquid crystal cell and the polarizing plate. Here, the arrangement conditions of the liquid crystal film (A) will be described with reference to Fig. 6. In the liquid crystal cell 15 of Fig. 6, a straight line overlapping the pre-tilt direction of the upper substrate and a straight line overlapping the pre-tilt direction of the lower substrate are assumed. The two straight lines are projected on the same plane. At this time, of the four angles formed by the intersection of the straight lines as the center, the two angles at the acute angle ends are respectively drawn to form a straight line with a left-right symmetrical angle. This straight line is defined as a bisector in the present invention. In addition, when a line overlapping the pre-tilt direction of the upper substrate and a line overlapping the pre-tilt direction of the lower substrate overlap each other (that is, the straight lines are in a parallel state), this overlapping straight line will become the so-called in the present invention. Second line. The angle formed between the bisector and the linear component based on the tilt direction of the liquid crystal film (A) is usually preferably arranged at an absolute value of 0 degrees to 30 degrees (preferably 0 degrees to 20 degrees, 0 degrees to 10 degrees is preferred, and slightly 0 degrees is preferred). When the angle between the two is greater than 30 degrees, it may be impossible to obtain a sufficient viewing angle compensation effect of 30 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095. Next, a case where the second optically anisotropic element is a combination of (A) with one polymer stretched film or one liquid crystal film, and a transflective liquid crystal display element will be described. The liquid crystal film (A) is preferably arranged in the same manner as described above. In other words, it is preferable that the oblique direction of the liquid crystal film molecule is in the direction of the above-mentioned bisector. The angle between the roughly oblique direction and the pre-tilt direction is preferably in the range of 0 degrees, especially 0 degrees to 20 degrees, and more preferably 0 In the transflective liquid crystal display device of the present invention, the light source, light control film, light guide plate, and cymbal are not particularly known. In addition to the transflective liquid crystal display element of the present invention, other constituent elements may be attached. For example, by providing the liquid crystal display element of the present invention, a color liquid crystal display element with high multi-color or full-color display can be produced. (Industrial Applicability) The transflective liquid crystal display element of the present invention is characterized in that the transmissive display is bright and has high contrast, and can be designed in a thin state with less flexibility. (Preferred Embodiment) Hereinafter, examples and comparative examples will be used to explain the invention in more detail. The invention is not limited to these. In addition, under the premise that there is no particular limitation in this embodiment, 312 / Invention Specification (Supplement) / 92-10 / 92121964, which is set to a wavelength of 5 50 nm, is a single liquid crystal film and is used in a semi-transparent case. The liquid crystallinity in the medium is in a consistent state. To 30 degree range, the degree range is better. The limitation of the light diffusing layer and the back enables the above-mentioned component color filter to have a field-of-view dependence in the implementation of color purity over mode. However, the present retardation Δ nd is at a value of 0 31 200405095 (Example 1). The outline of the transflective liquid crystal display element of the invention will be described with reference to FIG. 4. The structure of the related embodiment 1 is described with reference to FIG. 5. On the second substrate 8, a reflective electrode 6 made of a material having a relatively low reflectance such as A 1 and a transparent electrode 7 made of a material having a high transmittance such as I T 0 are designed. A counter electrode 4 is provided on the first substrate 3. A liquid crystal layer 5 made of a liquid crystal material showing a positive dielectric anisotropy is interposed between the reflective electrode 6 and the transparent electrode 7, and the counter electrode 4. A first optically anisotropic element 2 and a polarizing plate 1 are provided on the back surface on the side of the counter electrode 4 on which the first substrate 3 is formed, and on the back side of the surface on which the reflective electrode 6 and the transparent electrode 7 of the second substrate 8 are formed, A second optical anisotropic element 9 and a polarizing plate 10 are designed. A backlight 11 is provided on the back of the polarizing plate 10. A nematic hybrid alignment with an average inclination angle of 28 degrees in the film thickness direction was produced, and the fixed film thickness was 0.77 μm liquid crystal film 1 3, and the following TN-type transflective reflection type was produced using the arrangement shown in FIG. 5. Liquid crystal display element. The 15-series liquid crystal material used is ZLI-1 6 9 5 (Merck). The thickness of the liquid crystal layer is 3.5 μm in the reflective electrode region 6 (reflective display), and in the transparent electrode region 7 (transmissive display). ) Is 4.0 μm. The pre-tilt angle of the double interface of the substrate of the liquid crystal layer is 2 degrees, the twist angle of the liquid crystal cell is 70 degrees left-handed, and the Δ nd of the liquid crystal cell is approximately 230 nm in the reflective display portion and approximately 2 6 2 in the transmission display portion. nm. A polarizing plate 1 (thickness of about 180 μm; SQW- 8 6 2 manufactured by Sumitomo Chemical Industries, Ltd.) is disposed on the observer end (above the figure) of the liquid crystal cell 15, and is disposed between the polarizing plate 1 and the liquid crystal cell 15. With the first optical anisotropic element 2, the 32 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 The first optical anisotropic element 2 satisfies the requirements (I) and (Π) of the present invention. Teijin (Strand) uniaxially stretched polymer stretch film (product name: Bias) 2. The Δ n d of the polymer stretched film 2 is approximately 12 0 n m. In addition, the second optical anisotropic element 9 is arranged behind the liquid crystal cell 15 as viewed from an observer, and a liquid crystal film 13 and a polymer stretched film 14 composed of a uniaxially stretched polycarbonate film are arranged. Further, a polarizing plate 10 is arranged on the back. The Δnd of the liquid crystal film 13 fixed with the mixed nematic bias structure is 135 nm, and the Δη of the polymer stretched film 14 (1 is 275 nm. The absorption axes of the polarizing plates 1 and 10, the first optical anisotropic material 2 and The retarded phase axis of the polymer stretched film 14, the pretilt direction of the liquid crystal cell 15 interface, and the tilt direction of the liquid crystal film 13 are arranged according to the conditions shown in Fig. 6. The light source points shown in Fig. 7 are at the backlight point. When it is on (transmission mode), the transmittance ratio of white display 0 V and black display 6 V (white display) / (black display) is set as the contrast, and the comparison chart is comprehensive. Figure 8 shows the backlight source point. When it is on (transmission mode), the viewing angle characteristics of the transmittance in the left-right direction from 0 V to black to 6 V in black are displayed in 6 color steps. Figure 9 shows the backlight when it is lit (transmission mode). From 0 V to black to 6 V to black, the transmittance viewing angle characteristics in the up and down direction when displaying in 6 color levels. Figures 7 to 9 show that it has excellent viewing angle characteristics especially in the transmission mode. (Implementation Example 2) A nematic hybrid deflection with an average inclination angle of 28 degrees in the film thickness direction was produced, after 33 312 / Invention Manual (Supplements) / 92-10 / 92121964 200405095 The fixed thickness of 0.60 μm liquid crystal film 1 3, and the configuration shown in FIG. 5 was used to produce the following ECB-type transflective liquid crystal display element. The 16-series liquid crystal material used is ZLI-1 6 9 5 (Merck). The thickness of the liquid crystal layer is 2.1 μm in the reflective electrode region 6 (reflective display portion), and in the transparent electrode region 7 ( (Transmitting display portion) is 4.9 μm. The pretilt angle of the double interface of the substrate of the liquid crystal layer is 2 degrees, and the Δ nd of the liquid crystal cell is approximately 1 3 8 nm in the reflective display portion and approximately 3 2 1 in the transmissive display portion. A homogeneous alignment of n in. A polarizing plate 1 (thickness of about 180 μm; SQW- 8 6 2 manufactured by Sumitomo Chemical Industries, Ltd.) is arranged at the observer end (above the figure) of the liquid crystal cell 16, and the polarizing plate 1 and the liquid crystal cell are arranged. Between 16 and 16, a first optically anisotropic element 2 is arranged, and the first optically anisotropic element 2 is a uniaxially-stretched polymer made by Teijin (stock) which satisfies the requirements of the present invention in formula (I) and formula (Π). Stretch film (product name: Bias) 2. And of polymer stretch film 2 is about 115n m. In addition, the second optical anisotropic element 9 is a liquid crystal film 13 having a mixed mixed nematic bias structure fixed and having Δnd of 105 nm and Δη of the polymer stretched film 14 (1 is 270nm. The absorption axes of the polarizing plates 1 and 10, the retardation axis of the first optical anisotropic material 2 and the polymer stretched film 14, the pretilt direction of the liquid crystal cell 16 interface, and the tilt direction of the liquid crystal film 13 It is configured according to the conditions shown in Figure 10. Figure 11 shows the transmittance ratio of white display 0 V and black display 6 V (white display) / (black display) as contrast when the backlight is on (transmission mode), and a comprehensive comparison chart . 34 312 / Invention Manual (Supplement) / 92-10 / 92121964 200405095 Figure 1 2 shows when the backlight is on (transmission mode), 6 V is displayed from ί to black, and the left and right directions are displayed in 6 color steps. Lower penetration angle characteristics. Figure 13 shows the transmission characteristics when the backlight is on (transmission mode), displaying 6 V from white I and black, and up and down when displaying in 6 color levels. It can be seen from Figures 1 to 13 that the E C B type is also like the TN type, and has particularly excellent viewing angle characteristics in transmission. (Comparative Example 1) As shown in the layout diagram of FIG. 14, except that instead of the liquid crystal film 13, 17 (Δ nd is approximately 130 nm) is used, and Δ nd of the polycarbonate 14 is set to 3 in the liquid crystal cell 1 5 The polarizing plates 10 on the back side, the absorption axis of 10, and the retardation phase of the stretched film 14 and 17 are in accordance with the conditions shown in FIG. 15 and the rest are manufactured in the same manner as in Example 1. The liquid crystal display element is shown in FIG. 16 When the backlight is on (transmission mode), the transmittance ratio (white display) / (black display) of 6 V for white and black display is set as a comprehensive comparison chart. Figure 17 shows the transmission angle characteristics in the left-right direction when the backlight is on (transmission mode), and 6 V is displayed from έ to black. Figure 18 shows the transmission characteristics when the backlight is on (transmission mode), displaying 6 V from rud to black, and up and down in 6-level display. For viewing angle characteristics, perform Example 1 and Comparative Example 1 312 / Invention Specification (Supplement) / 92-10 / 92121964? Display 0V over-rate field of view I shows 0V to rate field-of-view angle mode Polycarbonate 7 2 6 0 nm »Polymer extended configuration 0 shows 0 V, contrast, while f shows 0 V over-rate field of view f shows 0 V-rate field of view comparison. 35 200405095 If the iso-contrast curves in all directions are shown in FIG. 7 and FIG. 16, it is known that a wide viewing angle characteristic is obtained by using the liquid crystal film 1 3 with a mixed nematic structure. In addition, regarding the left, right, up, and down characteristics of the shortcomings of the transmission mode, comparing Figs. 8 and 9 with Figs. 17 and 18 shows that the liquid crystal film with a mixed nematic structure can greatly improve the inversion characteristics ( Comparative Example 2) As shown in the layout diagram of FIG. 14, except that instead of the liquid crystal film 13, 17 (Δ nd is approximately 110 nm) is used, and Δ nd of the polycarbonate 14 is placed on the back of the liquid crystal cell 16 The polarizing plates 10 on the side, the absorption axis of the polarizing film, and the retardation phase axes of the stretched films 14 and 17 are in accordance with the conditions shown in FIG. 19, and the rest are manufactured as in Example 2. The liquid crystal display element is shown in FIG. When the backlight is turned on (transmission mode), the transmittance ratio (white display) / (black display) of 6 V for white and black display is set as a comprehensive comparison chart. Figure 21 shows the transmission angle characteristics when the backlight is on (transmission mode), displaying 6 V from έ to black, and displaying in the left and right directions according to the 6 color steps. Figure 2 shows the transmission characteristics when the backlight is on (transmission mode), displaying 6 V from έ to black, and up and down in 6-level display. With respect to the viewing angle characteristics, Example 2 and Comparative Example 2 are compared in all directions. If we proceed according to FIG. 11 and FIG. 20, it is learned that by using a liquid crystal film 1 3 312 with a mixed nematic structure / Invention Specification (Supplement) / 92-10 / 92121964 f * Comparison, you can get the characteristic of the color gradation. Polycarbonate〉 270 nm, polymer extended configuration 〇 shows 0 V, contrast, and 丨 shows 0 V over-rate field of view 丨 shows 0 V-rate field of view angle comparison. By comparison, you can get a wide viewing angle characteristic of 36 200405095. In addition, regarding the gradation characteristics of the left and right and up and down directions that constitute the shortcomings of the transmission mode, comparing Figs. 12 and 13 with Figs. 2 and 2 2 shows that by using a liquid crystal film with a mixed nematic structure, Significantly improves reverse characteristics. In this embodiment, although the experiment is performed in the form of a colorless filter, if a color filter is provided in the liquid crystal cell, it is of course possible to perform good multi-color or full-color display. [Brief description of the drawings] FIG. 1 is a conceptual diagram illustrating the tilt angle and twist angle of liquid crystal molecules. Fig. 2 is a conceptual diagram of an alignment structure of a liquid crystal film constituting a first optically anisotropic element. FIG. 3 is a conceptual diagram illustrating a pre-tilt direction of a liquid crystal cell. Fig. 4 is a schematic cross-sectional view of a transflective liquid crystal display element of the present invention. Fig. 5 is a schematic cross-sectional view of a transflective liquid crystal display element of Examples 1 and 2. Fig. 6 is a plan view showing the angular relationship between the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, the retardation axis of the polymer stretched film, and the tilt direction of the liquid crystal film in Example 1. Fig. 7 is a contrast diagram when the transflective liquid crystal display element of Example 1 is viewed from all directions. FIG. 8 is a diagram showing the viewing angle characteristics of the transmittance of left and right directions when the semi-transmissive reflective liquid crystal display element of Example 1 is displayed in 7 color steps from 0V to 6V.
圖9為將實施例1之半透過反射型液晶顯示元件,從0V 37 312/發明說明書(補件)/92-10/92121964 200405095 至6V依7色階顯示時的上下方位透過率視野角特性圖。 圖1 0為實施例2中,偏光板之吸收軸、液晶單元之預 傾斜方向、高分子延伸薄膜之延遲相軸、及液晶薄膜之傾 斜方向的角度關係平面圖。 圖1 1為從全方位觀看實施例2之半透過反射型液晶顯 示元件時的對比度圖。 圖1 2為將實施例2之半透過反射型液晶顯示元件,從 0 V至6 V依7色階顯示時的左右方位透過率視野角特性圖。 圖1 3為將實施例2之半透過反射型液晶顯示元件,從 0V至6V依7色階顯示時的上下方位透過率視野角特性圖。 圖1 4為比較例1與比較例2之半透過反射型液晶顯示 元件的示意剖視圖。 圖1 5為比較例1中,偏光板之吸收軸、液晶單元之預 傾斜方向、及高分子延伸薄膜之延遲相軸的角度關係平面 圖。 圖1 6為從全方位觀看比較例1之半透過反射型液晶顯 示元件時的對比度圖。 圖1 7為將比較例1之半透過反射型液晶顯示元件,從 0V至6V依7色階顯示時的左右方位透過率視野角特性圖。 圖1 8為將比較例1之半透過反射型液晶顯示元件,從 0V至6V依7色階顯示時的上下方位透過率視野角特性圖。 圖1 9為比較例2中,偏光板之吸收軸、液晶單元之預 傾斜方向、及高分子延伸薄膜之延遲相轴的角度關係平面 圖。 38 312/發明說明書(補件)/92-10/92121 %4 200405095 圖 20 為 從全 方 位 觀 ,看 比 較 例 2 之 半 透 過 反 射 型 液 晶 顯 示 元 件時的對1 七> 变1 圖 〇 圖 21 為 將比 較 例 2 之 半 透 過 反 射 型 液 晶 顯 示 元 •件 從 0 V 至 6V 依 7色 階 顯 示 時 的 左 右 方 位 透 過 率 視 野 角 特 性 圖。 圖 22 為 將比 較 例 2 之 半 透 過 反 射 型 液 晶 顯 示 元 件 從 0 V 至 6 V 依 7色 階 顯 示 時 的 上 下 方 位 透 過 率 視 野 角 特 性 圖。 (元件符 號 說明 ) 1, 10 偏 光 板 2 第 1 光 學 各 向 異 性 元 件 2, 14 ,17 高 分 子 延 伸 薄 膜 3 第 1 基 板 4 對 向 電 極 5 液 晶 層 6 反 射 電 極 6 反 射 電 極 區 域 7 透 明 電 極 7 透 明 電 極 區 域 8 第 2 基 板 9 第 2 光 學 各 向 異 性 元 件 11 背 光 源 12 ,1 5, 1 6 液 晶 單 元 13 液 晶 薄 膜 39 312/發明說明書(補件)/92-10/92121964FIG. 9 shows the vertical and horizontal azimuth transmittance viewing angle characteristics when the transflective liquid crystal display element of Example 1 is displayed in 7 color steps from 0V 37 312 / Invention Specification (Supplement) / 92-10 / 92121964 200405095 to 6V Illustration. Fig. 10 is a plan view showing the angular relationship between the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, the retardation phase axis of the polymer stretched film, and the tilt direction of the liquid crystal film in Example 2. Fig. 11 is a contrast diagram when the transflective liquid crystal display element of Example 2 is viewed from all directions. FIG. 12 is a graph showing the viewing angle characteristics of the transmittance of left and right directions when the semi-transmissive reflective liquid crystal display element of Example 2 is displayed from 0 V to 6 V in 7 color steps. FIG. 13 is a view showing the viewing angle characteristics of the transmissive and transmissive liquid crystal display element of Example 2 in the vertical direction when the display is from 0V to 6V in 7 color steps. 14 is a schematic cross-sectional view of a transflective liquid crystal display element of Comparative Examples 1 and 2. Fig. 15 is a plan view showing the angular relationship between the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, and the retardation axis of the polymer stretched film in Comparative Example 1. FIG. 16 is a contrast diagram when the transflective liquid crystal display element of Comparative Example 1 is viewed from all directions. FIG. 17 is a graph showing the viewing angle characteristics of the transmittance of left and right azimuths when the transflective liquid crystal display element of Comparative Example 1 is displayed in 7 color steps from 0V to 6V. FIG. 18 is a diagram showing the viewing angle characteristics of the transmissive and transmissive liquid crystal display elements of Comparative Example 1 in the vertical direction when displaying from 7V to 6V in 7 color steps. Fig. 19 is a plan view showing the angular relationship between the absorption axis of the polarizing plate, the pretilt direction of the liquid crystal cell, and the retardation axis of the polymer stretched film in Comparative Example 2. 38 312 / Description of the Invention (Supplement) / 92-10 / 92121% 4 200405095 Figure 20 shows the pair 1 when the transflective liquid crystal display element of Comparative Example 2 is viewed from an all-round view. 21 is a graph showing the viewing angle characteristics of the transmittance of left and right azimuth when the transflective liquid crystal display element of Comparative Example 2 is displayed from 0 V to 6 V in 7 color steps. Fig. 22 is a view showing the characteristics of the field angle of the transmittance in the upper and lower positions when the transflective liquid crystal display element of Comparative Example 2 is displayed from 0 V to 6 V in 7 color steps. (Description of element symbols) 1, 10 polarizing plate 2 First optically anisotropic element 2, 14, 17 Polymer stretched film 3 First substrate 4 Opposite electrode 5 Liquid crystal layer 6 Reflective electrode 6 Reflective electrode area 7 Transparent electrode 7 Transparent Electrode area 8 Second substrate 9 Second optical anisotropic element 11 Backlight source 12, 1 5, 1 6 Liquid crystal cell 13 Liquid crystal film 39 312 / Invention specification (Supplement) / 92-10 / 92121964
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JP2002285458A JP2004125830A (en) | 2002-09-30 | 2002-09-30 | Transflective liquid crystal display element |
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TWI403797B (en) * | 2004-12-18 | 2013-08-01 | Merck Patent Gmbh | Transflective liquid crystal display |
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JP2006146012A (en) * | 2004-11-24 | 2006-06-08 | Mitsubishi Electric Corp | Liquid crystal display panel |
JP2007072213A (en) * | 2005-09-07 | 2007-03-22 | Nippon Oil Corp | Viewing angle compensation plate for homeotropically oriented liquid crystal display device and homeotropically oriented liquid crystal display device using same |
JP2007219260A (en) * | 2006-02-17 | 2007-08-30 | Nippon Oil Corp | Optical laminate, elliptically polarizing plate and liquid crystal display device |
JP2007241071A (en) * | 2006-03-10 | 2007-09-20 | Fujifilm Corp | Transflective liquid crystal display device |
JP4899153B2 (en) * | 2006-09-05 | 2012-03-21 | Nltテクノロジー株式会社 | Liquid crystal display |
JP4975415B2 (en) | 2006-11-17 | 2012-07-11 | Jx日鉱日石エネルギー株式会社 | Transmission type liquid crystal display device |
JP5072520B2 (en) | 2006-12-19 | 2012-11-14 | 株式会社ジャパンディスプレイセントラル | Liquid crystal display |
WO2008126421A1 (en) * | 2007-04-11 | 2008-10-23 | Fujifilm Corporation | Optical anisotropic film and liquid crystal display device |
JP2008309957A (en) | 2007-06-13 | 2008-12-25 | Nippon Oil Corp | Transmission type liquid crystal display device |
JP5072481B2 (en) * | 2007-08-10 | 2012-11-14 | 株式会社ジャパンディスプレイセントラル | Liquid crystal display |
JP5072480B2 (en) * | 2007-08-10 | 2012-11-14 | 株式会社ジャパンディスプレイセントラル | Liquid crystal display |
WO2010067809A1 (en) | 2008-12-09 | 2010-06-17 | 積水化学工業株式会社 | Retardation element |
TWI420196B (en) | 2008-12-11 | 2013-12-21 | Au Optronics Corp | Liquid crystal display device |
WO2010074048A1 (en) | 2008-12-22 | 2010-07-01 | 積水化学工業株式会社 | Laminate for laminated glass |
WO2013146633A1 (en) * | 2012-03-30 | 2013-10-03 | 日本ゼオン株式会社 | Phase difference film laminated body, method for manufacturing same, and liquid crystal display device |
JP5387725B2 (en) * | 2012-05-18 | 2014-01-15 | 三菱化学株式会社 | Retardation film |
CN102914906B (en) | 2012-10-19 | 2015-02-25 | 京东方科技集团股份有限公司 | Liquid crystal display panel and display device |
CN105676318B (en) * | 2014-12-08 | 2018-06-05 | 三星电子株式会社 | Anti-reflective film and the organic luminescent device for including it |
KR101623086B1 (en) * | 2014-12-08 | 2016-05-20 | 삼성전자 주식회사 | Antireflection film and organic light emitting device provided with the same |
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JPH10332933A (en) * | 1997-05-30 | 1998-12-18 | Nippon Oil Co Ltd | Optical anisotropic element |
JP3406242B2 (en) * | 1998-10-15 | 2003-05-12 | シャープ株式会社 | Liquid crystal display |
JP2001042320A (en) * | 1999-07-30 | 2001-02-16 | Seiko Epson Corp | Liquid crystal device and electronic appliance using the same |
JP2001337222A (en) * | 2000-05-25 | 2001-12-07 | Fuji Photo Film Co Ltd | Optical retardation plate |
JP2002031717A (en) * | 2000-07-14 | 2002-01-31 | Nippon Mitsubishi Oil Corp | Circularly polarizing plate and liquid crystal display device |
JP2002196114A (en) * | 2000-12-26 | 2002-07-10 | Sumitomo Chem Co Ltd | Forward scattering sheet, laminated sheet containing the same and liquid crystal display |
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- 2003-07-15 AU AU2003252650A patent/AU2003252650A1/en not_active Abandoned
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TWI403797B (en) * | 2004-12-18 | 2013-08-01 | Merck Patent Gmbh | Transflective liquid crystal display |
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