19197 狄、發明說明： 【發明所屬之技術領域】 本發明疋有關於寬頻扭層液晶膜及其製造方法。本發明之 見頻扭層液晶膜可作為圓偏光板（反射型偏光子）。又，本發 5明係有關於使用該圓偏光板之直線偏光子、照明裝置及液晶顯 示裝置。 ^ ji»r 一般而言，液晶顯示器具有在形成透明電極之玻璃板間注 入液晶’並於該玻璃板前後配置偏光子之構造。用於這種液晶 10 顯示器之偏光子係藉由使埃或二色性染料等吸著於聚乙稀醇 膜，將之朝一定方向延伸來製造。如此製造之偏光子其本身乃 是吸收朝一側方向振動之光，僅使朝另一侧方向振動之光通過 來製造直線偏光。因此，偏光子之效率在理論上無法超過50%， 成為使液晶顯示器效率降低之最大主因。又，由於該吸收光 15 線，使得液晶顯示裝置在光源輸出之增大進行到某一程度時， 會因吸收光線之熱變換造成之發熱而使偏光子遭到破壞，又， 由於對晶胞内部之液晶層之熱影響，會導致顯示品質低劣等弊 害。 具有圓偏光分離機能之扭層液晶，係液晶螺旋之旋轉方向 2〇與圓偏光方向一致，其具有只反射波長為液晶螺距之圓偏光之 光這種選擇反射特性。利用這種選擇反射特性，使一定之波長 頻帶之自然光之特定圓偏光透過而分離’並將剩餘光線反射再 利用，藉此可製造高效率之偏光膜。這時，已透過之圓偏光藉 由通過λ/4波長板變換為直線偏光’並使該直線偏光之方向與 5 200419197 用於液晶顯示器之吸收型偏光子之透過方向一致，藉此可得到 高透過率之液晶顯示裝置。亦即，一旦將扭層液晶膜與又/4波 長板組合作為直線偏光子使用，則理論上沒有光的損失，故相 較於單獨使用吸收50%之光之習知吸收型偏光子，在理論上可 5 得到提昇2倍之亮度。 然而’扭層液晶之選擇反射特性僅限定於特定之波長頻 帶，很難涵蓋可見光線全域。扭層液晶之選擇反射波長領域寬 度△ λ係以： △ λ = 2 λ · (ne-no) / (ne+no) 10 no :扭層液晶分子對正常光之折射率 ne :扭層液晶分子對異常光之折射率 λ:選擇反射之中心波長 表示，依存於扭層液晶之分子構造。根據上式，若使 ne-no 較 大則選擇反射波長領域寬度△ λ會變寬，而ne_n〇通常為〇.3 15以下。若使該值變大，則作為液晶之其他機能（定向特性、液 晶溫度等）會變得不充分，實用上很困難。因此，現實上選擇 反射波長領域寬度△又最大也是150nm左右。可實用作為扭層 液晶者最多只有30〜lOOnm。 又，選擇反射中心波長λ係以： 20 λ = ( ne+no) P/2 P:扭層液晶一旋轉扭曲所需螺距長 表示’若螺距固定則依存於液晶分子之平均折射率與螺距長。 因此，要涵蓋可見光全領域，可進行將具有相異之選擇反 射中心波長之多數層積層，或使螺距在厚度方向連續變化以形 6 成選擇反射中心波長之存在分布。 例如’可舉在厚度方向使螺距長連續變化之方法（例如參 考特開平6-281814號公報，特許第3272668號說明書、特開平 11 248943號公報）。該方法係在以紫外線曝光，使扭層液晶組 5成物硬化之際’賦予曝光面侧與出射面側之曝光強度差，並賦 予聚合速度差’藉此在厚度方向設置反應速度不同之液晶組成 物之組成比變化。 該方法之重點在於使取曝光面側與出射面側之曝光強度 之差變大。因此，前述習知技術之實施例之多數情況，係採用 10將紫外線吸收劑混合於液晶組成物，使其在厚度方向發生吸 收，以隨著光程長增加曝光量的方法。 然而，追加試驗前述習知技術所得到之扭層液晶膜，在耐 久試驗（加熱試驗或加濕試驗）中，可看出紫外線吸收劑在扭 層液晶膜表面或與其他層貼合之界面析出的現象。這應是因紫 15外線吸收劑為低分子量，在長期間之耐久試驗中在膜内移動而 凝集之物。若作為一般性的工業材料，則這種程度之表面析出 不會成為外觀異常，並無大礙，即使在界面析出也非會達到界 面剝離之問題。然而，用於液晶顯示裝置之扭層液晶膜位於強 透過光線之光程上，一旦發生這種析出物，不僅可直接目視到 20 析出粒子，且會因析出物之偏光消解造成光利用效率降低，或 因析出物產生之霾而造成光源之光散射分布之變化等光學上 之問題。 扭層液晶膜若在常溫環境下使用，本來幾乎不會有這種析 出物之發生。然而，組裝於液晶顯示裝置時，長期暴露於來自 7 200419197 背光光源之輻射熱，就無法避免紫外線吸收劑之析出。這種析 出物若是在面内均勻地析出則不易被看出，不會被當作是缺 點，但來自光源之輻射熱對液晶顯示裝置面内之不均落差很 大，只有接受大量賴射熱之範圍之析出量會增加，故會成為面 5 内之斑駁而為人看出。且近年之液晶顯示裝置所要求之顯示亮 度超過200燭光，光源侧暴露於1萬燭光程度之光照射強度。 由於該照射強度，液晶顯示裝置之光源側除使用環境溫度外， 還被持續賦予40〜60°C之熱。因此，不僅是加熱可靠性試驗， 在安裝於液晶顯示裝置之連續點燈試驗中也發現紫外線吸收 10 劑之析出。例如，若將得自混合於紫外線吸收劑之扭層液晶組 成物之紫外線聚合體置於80°Cx 500小時、60°C、90% RHx 500 小時之環境下，則可顯著看出白濁、霾度上升、粉體朝表面析 出等問題。 【發明内容】 15 本發明之目的係在提供具有寬頻之反射帶之寬頻扭層液 晶膜及其製造方法。又，本發明之目的係在提供具有寬頻之反 射帶且耐久性良好之寬頻扭層液晶膜及其製造方法。 又，本發明之目的係在提供使用該寬頻扭層液晶膜之圓偏 光板，更在提供利用該圓偏光板之直線偏光子、照明裝置及液 20 晶顯示裝置。 本發明人為了解決上述課題而專心研究之結果，發現藉以 下所示之寬頻扭層液晶膜及其製造方法，可達到上述目的，而 完成了本發明。 亦即，本發明係有關於一種寬頻扭層液晶膜，係將含有聚 8 200419197 合性液晶原化合物（a)、聚合性旋光劑（㈧及光聚合引發劑（c) 之液晶混合物塗布於定向基材上並在不活性氣體環境下進行 紫外線聚合而得者’且該液晶膜具有反射帶寬在2〇〇mn以上。 上述本發明之寬頻扭層液晶膜，係藉由將聚合性之液晶混 5合物以紫外線聚合而得者，其選擇反射波長之反射頻帶寬廣達 200nm以上’具有習知所沒有之寬頻反射帶寬。反射帶寬宜在 300nm以上’尤其適宜在4〇〇nnl以上。又，2〇〇nm以上之反射 帶寬以在可見光範圍 '特別是4〇〇〜8〇〇ηιη之波長範圍為佳。 又，反射帶寬係以分光光度計（大塚電子株式會社製，瞬 10間多測光系統MCPD_2000)測定寬頻扭層液晶膜之反射光譜， 作為具有最大反射率之一半之反射率之反射帶。 前述寬頻扭層液晶膜，其扭層液晶膜之螺距長變化以從紫 外線放射側起連續地變狹窄為佳。 又，前述寬頻扭層液晶膜中，該聚合性液晶原化合物 15以具有1個聚合性官能基為佳，且該聚合性旋光劑（b)以具 有2個以上之聚合性官能基為佳。 如Broer等，Nature,378卷，467項（ 1995)中所揭示的，使 具有螺旋性之液晶原化合物擴散，可得到連續地螺距變化之寬 頻扭層液晶膜。另一方面，在本發明中，由於藉由使具有1個 20 聚合性官能基之液晶原化合物擴散，可得到連續地螺距變化之 寬頻扭層液晶，故螺旋性螺距之變化之序列逆轉。亦即，在本 發明中，可得到螺距長具有從紫外線放射側起連續地變狹窄這 種螺距變化之寬頻扭層液晶膜。又，螺距長之變化最好是紫外 線放射側與其反對側之差至少100nm。又，螺距長係讀取自寬 9 200419197 頻扭層液晶膜之截面TEM像。 所得到之扭層液晶膜係具有grandjean構造，亦即螺距長 有著從一側連續地變狹窄之變化。長螺距長側以連續性或不連 續性地具有顯示紅外線領域之反射之螺距長之螺旋構造或螺 5 旋幾乎被消解之層為佳。上述寬頻扭層液晶膜中，該長螺距長 之螺旋構造或螺旋幾乎被消解之層宜為對於來自正面之入射 光在光學性上具有50〜450nm之相位差值之相位差層。如此， 具有grandjean構造且以扭層液晶而言在可見領域 ( 380〜780nm)中具有顯示選擇反射之部分，而同時，在長螺 10 距長側則具有與顯示選擇反射部分完全不同之螺距之層。該層 在光學特性上為相位差層，其相位差值可控制在50〜450nm之 間。例如，該相位差值為100〜160nm時，通過扭層液晶膜之可 見光域之光顯示直線偏光。另一方面，相位差值為200〜400nm 時，則可變換為與透過扭層液晶之圓偏光狀態相反之旋轉之圓 15 偏光狀態。藉此，可依據寬頻扭層液晶膜所具有之相位差層之 相位差值，來自由地控制透過光之偏光狀態。因此，可輕易地 配合所使用之液晶顯示器類型來作為偏光板使用。 形成前述寬頻扭層液晶膜之液晶混合物亦可不含紫外線 吸收劑。 20 本發明之寬頻扭層液晶膜即使不使用紫外線吸收劑也可 得到寬頻之反射帶寬。因此，可抑制因使用紫外線吸收劑所導 致之霾度上升、偏光透過率降低、析出粒子之目視化等問題， 加熱、加濕環境下之财久性良好，可靠性優異。 在前述寬頻扭層液晶膜中，該聚合性液晶原化合物（a )之 10 200419197 莫耳消光係數以50〜500〇11113111〇1]〇11]@36511111為佳。具有前述 莫耳消光係數者具有紫外線吸收能。莫耳消光係數更適宜為 100〜。若莫耳消光係數小於 $(>(^^(^“(^“@36511111，則無法賦予充分之聚合速度差，而難 5 以寬頻化。另一方面，若大於500dm3m〇r1crrT1@365nm，則可 能聚合無法完全進行，硬化無法完成。又，莫耳消光係數乃是 測定各材料之分光光度光譜，從所得到之365nm之消光度測定 之值。 前述聚合性液晶原化合物（a)係以下述一般式（1):19197. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a wideband twisted layer liquid crystal film and a method for manufacturing the same. The frequency-twisted layer liquid crystal film of the present invention can be used as a circular polarizer (reflective polarizer). The present invention relates to a linear polarizer using a circularly polarizing plate, a lighting device, and a liquid crystal display device. ^ ji »r In general, a liquid crystal display has a structure in which liquid crystal is injected between glass plates forming a transparent electrode, and polarizers are arranged before and after the glass plate. A polarizer used in such a liquid crystal display 10 is manufactured by attracting a film of polyethylene or a dichroic dye or the like and extending it in a certain direction. The polarized photon manufactured in this way absorbs light that vibrates in one direction and passes only light that vibrates in the other direction to produce linearly polarized light. Therefore, the efficiency of polarized photons cannot theoretically exceed 50%, which has become the main cause of the decrease in the efficiency of liquid crystal displays. In addition, due to the 15 lines of light absorption, when the liquid crystal display device increases the output of the light source to a certain extent, the polarized photons will be destroyed due to the heat generated by the thermal conversion of the absorbed light. The thermal effects of the internal liquid crystal layer can cause disadvantages such as poor display quality. The twisted-layer liquid crystal with circular polarization separation function is the rotation direction of the liquid crystal helix 20 is the same as the circular polarization direction. It has the selective reflection characteristic of reflecting only circularly polarized light with a wavelength of the liquid crystal pitch. By using this selective reflection characteristic, a specific circularly polarized light of natural light in a certain wavelength band is transmitted and separated ', and the remaining light is reflected and reused, whereby a highly efficient polarizing film can be manufactured. At this time, the transmitted circularly polarized light is converted into linearly polarized light through a λ / 4 wavelength plate, and the direction of the linearly polarized light is consistent with the transmission direction of the absorption polarizer used in a liquid crystal display. Rate of liquid crystal display device. That is, once the twisted-layer liquid crystal film and the / 4 wavelength plate are used as linear polarizers, there is theoretically no loss of light, so compared to the conventional absorption-type polarizer that absorbs 50% of light alone, Can theoretically get 5 times the brightness. However, the selective reflection characteristic of the 'twisted-layer liquid crystal is limited to a specific wavelength band, and it is difficult to cover the entire range of visible light. The width of the selective reflection wavelength range of the twisted layer liquid crystal △ λ is: △ λ = 2 λ · (ne-no) / (ne + no) 10 no: refractive index of the twisted layer liquid crystal molecules to normal light ne: twisted layer liquid crystal molecules Refractive index λ for anomalous light: The central wavelength of selective reflection is indicated, which depends on the molecular structure of the twisted layer liquid crystal. According to the above formula, if ne-no is made larger, the width Δλ of the selected reflection wavelength range will be wider, and ne_n0 is usually 0.315 or less. If this value is made larger, other functions (alignment characteristics, liquid crystal temperature, etc.) as liquid crystals become insufficient, and practically difficult. Therefore, in reality, the width Δ of the reflection wavelength range is selected to be about 150 nm at the maximum. Can be practically used as a twisted layer. LCDs are limited to 30 ~ 100nm at most. In addition, the reflection center wavelength λ is selected as follows: 20 λ = (ne + no) P / 2 P: The length of the pitch required for the twisted layer liquid crystal to rotate and twist is expressed as' If the pitch is fixed, it depends on the average refractive index and the pitch of the liquid crystal molecules. . Therefore, to cover the entire field of visible light, it is possible to stack most layers with different selective reflection center wavelengths, or continuously change the pitch in the thickness direction to form the existence distribution of the selected reflection center wavelengths. For example, a method of continuously changing the pitch length in the thickness direction (for example, refer to Japanese Patent Application Laid-Open No. 6-281814, Japanese Patent No. 3272668, Japanese Patent Application No. 11 248943). This method is to 'give a difference in exposure intensity between the exposed surface side and the exit surface side and give a difference in polymerization speed' when setting the 5 layers of the twisted layer liquid crystal group to harden by ultraviolet exposure, thereby setting liquid crystals with different reaction speeds in the thickness direction. The composition ratio of the composition changes. The main point of this method is to increase the difference in exposure intensity between the exposure surface side and the exit surface side. Therefore, in most cases of the aforementioned conventional techniques, a method is used in which a UV absorber is mixed with the liquid crystal composition to absorb in the thickness direction to increase the exposure amount as the optical path length increases. However, in the endurance test (heating test or humidification test) of the twisted-layer liquid crystal film obtained by the conventional technique described above, it is seen that the ultraviolet absorber precipitates on the surface of the twisted-layer liquid crystal film or the interface bonded to other layers. The phenomenon. This should be due to the low molecular weight of the purple 15 external absorbent, which has agglutinated during the long-term durability test by moving inside the membrane. As a general industrial material, surface precipitation to such an extent does not cause abnormal appearance, and it is not a big problem, even if it precipitates at the interface, it does not cause the problem of interface peeling. However, the twisted-layer liquid crystal film used for liquid crystal display devices is located on the optical path of strong transmitted light. Once such a precipitate occurs, not only 20 precipitated particles can be directly visualized, but the light utilization efficiency will be reduced due to the polarized light digestion of the precipitate Or optical problems such as changes in the light scattering distribution of the light source caused by the haze generated by the precipitate. If the twisted layer liquid crystal film is used in a normal temperature environment, such a precipitate would hardly occur. However, when assembled in a liquid crystal display device, long-term exposure to radiant heat from a backlight source of 7 200419197 cannot prevent the precipitation of ultraviolet absorbers. This kind of precipitate is not easy to be seen if it is uniformly precipitated in the surface, and it will not be regarded as a disadvantage. However, the radiant heat from the light source has a large difference in the unevenness in the surface of the liquid crystal display device. The amount of precipitation in the range will increase, so it will become mottled within face 5 and be seen. And in recent years, the required display brightness of the liquid crystal display device exceeds 200 candela, and the light source side is exposed to a light irradiation intensity of about 10,000 candela. Due to this irradiation intensity, in addition to the ambient temperature, the light source side of the liquid crystal display device is continuously heated at 40 to 60 ° C. Therefore, not only a heating reliability test, but also a continuous lighting test mounted on a liquid crystal display device, it was found that a UV absorbing agent was precipitated. For example, if an ultraviolet polymer obtained from a twisted layer liquid crystal composition mixed with an ultraviolet absorber is placed in an environment of 80 ° Cx 500 hours, 60 ° C, 90% RHx 500 hours, the cloudiness and haze can be clearly seen Problems such as increasing the temperature and precipitating the powder toward the surface. [Summary of the Invention] 15 The object of the present invention is to provide a wideband twisted layer liquid crystal film having a wideband reflection band and a method for manufacturing the same. Another object of the present invention is to provide a wideband twisted-layer liquid crystal film having a wide reflection band and excellent durability, and a method for manufacturing the same. In addition, the object of the present invention is to provide a circular polarizing plate using the wideband twisted-layer liquid crystal film, and further to provide a linear polarizer, an illuminating device, and a liquid crystal display device using the circular polarizing plate. As a result of intensive research in order to solve the above-mentioned problems, the present inventors have found that the above-mentioned object can be achieved by the broadband twisted-layer liquid crystal film and a manufacturing method thereof as shown below, and completed the present invention. That is, the present invention relates to a wideband twisted-layer liquid crystal film, which is applied to a liquid crystal mixture containing poly 8 200419197 synthetic mesogen compound (a), polymerizable optically active agent (光, and photopolymerization initiator (c)). It is obtained by performing UV polymerization on a substrate and under an inert gas environment, and the liquid crystal film has a reflection bandwidth of more than 2000 nm. The above-mentioned wideband twisted-layer liquid crystal film of the present invention is obtained by mixing polymerizable liquid crystals. The pentamate is obtained by polymerization of ultraviolet rays, and the reflection frequency bandwidth of the selected reflection wavelength is as wide as 200 nm or more. 'It has a wide reflection bandwidth which is not known. The reflection bandwidth should be more than 300 nm.' It is particularly suitable for more than 400 nnl. A reflection bandwidth of 200 nm or more is preferably in a visible light range, particularly a wavelength range of 400 to 800 nm. The reflection bandwidth is measured by a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., and more than 10 instantaneous metering). System MCPD_2000) measures the reflection spectrum of a wideband twisted-layer liquid crystal film as a reflection band having a half of the maximum reflectance. The aforementioned wideband twisted-layer liquid crystal film has a twisted-layer liquid crystal film. It is preferable that the length of the pitch change is narrowed continuously from the ultraviolet radiation side. In the above-mentioned wideband twisted layer liquid crystal film, the polymerizable mesogen 15 preferably has one polymerizable functional group, and the polymerizable optical active agent (B) It is preferable to have two or more polymerizable functional groups. As disclosed in Broer et al., Nature, vol. 378, item 467 (1995), a continuous helix can be obtained by diffusing the helicity of the mesogen compound. Changing wideband twisted-layer liquid crystal film. On the other hand, in the present invention, since a liquid crystalline original compound having one 20 polymerizable functional group is diffused, a wideband twisted-layer liquid crystal having a continuous pitch change can be obtained, so that helix The sequence of the change in the pitch is reversed. That is, in the present invention, a wide-frequency twisted-layer liquid crystal film having a longer pitch and a narrower pitch from the ultraviolet radiation side can be obtained. The change in the longer pitch is preferably ultraviolet rays. The difference between the radiation side and the opposite side is at least 100 nm. In addition, the long pitch is read from the cross-section TEM image of the liquid crystal film with a frequency twist layer of 9 200419197. The obtained twisted layer liquid crystal film has a grandjean structure. That is, the long pitch has a change that continuously narrows from one side. The long pitch long side has a continuous or discontinuous spiral structure or a spiral structure with a long pitch that shows the reflection in the infrared field. In the above-mentioned wideband twisted-layer liquid crystal film, the long spiral structure or the spiral layer whose spiral is almost eliminated is preferably a retardation layer having an optical phase difference of 50 to 450 nm for incident light from the front side. , With a grandjean structure and a twisted layer liquid crystal in the visible area (380 ~ 780nm) has a display selective reflection part, and at the same time, on the long side of the long 10 pitch has a layer with a completely different pitch than the display selective reflection layer . This layer is a retardation layer in optical characteristics, and its retardation value can be controlled between 50 and 450 nm. For example, when the retardation value is 100 to 160 nm, light visible through the twisted layer liquid crystal film shows linearly polarized light. On the other hand, when the retardation value is 200 to 400 nm, it can be converted into a circularly polarized state of rotation 15 opposite to the circularly polarized state of the liquid crystal transmitted through the twisted layer. Thereby, the polarization state of the transmitted light can be freely controlled according to the retardation value of the retardation layer of the wideband twisted-layer liquid crystal film. Therefore, it can be easily used as a polarizing plate with the type of liquid crystal display used. The liquid crystal mixture forming the above-mentioned wideband twisted layer liquid crystal film may not contain an ultraviolet absorbent. 20 The wideband twisted-layer liquid crystal film of the present invention can obtain a wide reflection bandwidth without using an ultraviolet absorber. Therefore, problems such as an increase in haze, a decrease in polarized light transmittance, and visualization of precipitated particles caused by the use of an ultraviolet absorber can be suppressed, and the long-term performance in a heating and humidifying environment is good and the reliability is excellent. In the aforementioned wideband twisted-layer liquid crystal film, the 10 200419197 Molar extinction coefficient of the polymerizable mesogen compound (a) is preferably 50 to 500,001,131,11,1, and 11] @ 36511111. Those having the aforementioned Moire extinction coefficient have ultraviolet absorption energy. The Mohr extinction coefficient is more preferably 100 ~. If the Moire extinction coefficient is less than $ (> (^^ (^ "(^" @ 36511111, it is impossible to give a sufficient polymerization speed difference, and it is difficult to broaden the bandwidth. On the other hand, if it is greater than 500dm3m0r1crrT1 @ 365nm, The polymerization may not be completed, and the hardening may not be completed. In addition, the Moire extinction coefficient is a value measured by measuring the spectrophotometric spectrum of each material from the obtained 365nm extinction. The aforementioned polymerizable mesogen compound (a) is the following State the general formula (1):
表示之化合物為佳（唯，Ri表示氫原子或甲基，η表示1〜5之 整數）。 又，本發明係有關於一種寬頻扭層液晶膜之製造方法，該 方法係將含有聚合性液晶原化合物（a)、聚合性旋光劑（b)及 15 光聚合引發劑（c)之液晶塗布於定向基材上，接著在不活性氣 體環境下使之進行紫外線聚合。本發明之寬頻扭層液晶膜可藉 由控制在紫外線照射時之溫度、紫外線照度、照射時間來製造。 又，本發明係有關於使用上述寬頻扭層液晶膜之圓偏光 板。 20 又，本發明係有關於在上述圓偏光板上積層；1/4板而得到 之直線偏光子。在該直線偏光子中，圓偏光板亦即扭層液晶膜 11 200419197 係積層於λ /4板，以使螺距長連續地變狹窄。 又’本發明係有關於將吸收型偏光子配合上述直線偏光子 之透過軸方向貼合於該透過軸上而得到之直線偏光子。 用於上述直線偏光子之λ/4板宜為當以面内之主折射率為 5 ηχ、町，厚度方向之主折射率為ηζ時，以式（nx—nz) / (ηχ —ny)定義之Νζ係數滿足·〇·5〜-2.5者。 又，本發明係有關於一種照明裝置，係在裡面側具有反射 層之面光源之表面側上，具有上述圓偏光板或直線偏光子者。 更’本發明係有關於一種液晶顯示裝置，係在上述照明裝 10 置之光出射側具有液晶晶胞者。 前述直線偏光子、照明裝置、液晶顯示裝置可使用各形成 層之全部或局部隔著接著層而密著者。 又，本發明之寬頻扭層液晶膜可作為圓偏光板使用，藉組 合λ/4板得到直線偏光子。更，可組合吸收型偏光子等來提高 15 液晶顯示裝置之可靠性。 圖式簡單說明 第1圖是實施例1〜3及比較例1〜3之評價中所使用之偏光 板之概念圖。係1 :偏光板、2 : λ/4板、3 :扭層液晶膜（圓 偏光板）4 :黏著層。 2〇 第2圖是實施例1所製作之扭層液晶膜之反射光譜。 第3圖是實施例2所製作之扭層液晶膜之反射光譜。 第4圖是實施例3所製作之扭層液晶膜之反射光譜。 第5圖是比較例1所製作之扭層液晶膜之反射光譜。 第6圖是比較例2所製作之扭層液晶膜之反射光譜。 12 200419197 第7圖是比較例3所製作之扭層液晶膜之反射光譜。 t 本發明之扭層液晶膜係將含有聚合性液晶原化合物（a)、 聚合性旋光劑（b)及光聚合引發劑（c)之液晶混合物塗布於 5 定向基材上，接著在不活性氣體環境下進行紫外線聚合而得 者。 該聚合性液晶原化合物（a)具有至少1個聚合性官能基， 適宜使用具有由環狀單元等形成之液晶原基者。聚合性官能基 可舉丙烯醯基、甲基丙烯醯基、環氧基、乙烯醚基等，當中又 10 以丙烯醯基、甲基丙烯醯基為佳。又，聚合性液晶原化合物（a) 係如前所述，以莫耳消光係數為50〜500dm3m〇r1crrT1@365nm 者為佳。具有該莫耳消光係數之聚合性液晶原化合物（a)係如 前所述，以下述一般式（1):The compound represented is preferably (only Ri represents a hydrogen atom or a methyl group, and η represents an integer of 1 to 5). The present invention also relates to a method for manufacturing a wideband twisted-layer liquid crystal film. The method is to apply a liquid crystal containing a polymerizable mesogen compound (a), a polymerizable optically active agent (b), and a 15 photopolymerization initiator (c). UV-polymerization was performed on the oriented substrate and then in an inert gas environment. The wideband twisted layer liquid crystal film of the present invention can be manufactured by controlling the temperature, ultraviolet illuminance, and irradiation time during ultraviolet irradiation. The present invention also relates to a circular polarizing plate using the above-mentioned wideband twisted-layer liquid crystal film. 20 The present invention relates to a linearly polarized photon obtained by laminating the above-mentioned circularly polarizing plate and a quarter plate. In this linear polarizer, a circularly polarizing plate, that is, a twisted layer liquid crystal film 11 200419197 is laminated on the λ / 4 plate so that the pitch is continuously narrowed. Furthermore, the present invention relates to a linearly polarized photon obtained by bonding an absorption-type polarized photon to the linearly polarized photon in the transmission axis direction and bonding it to the transmission axis. The λ / 4 plate used for the above-mentioned linear polarizer is preferably when the main refractive index in the plane is 5 ηχ, and the main refractive index in the thickness direction is ηζ, according to the formula (nx-nz) / (ηχ —ny) The definition of the ζ coefficient satisfies · 0.5 ~ -2.5. The present invention also relates to a lighting device having the above-mentioned circular polarizer or linear polarizer on the surface side of a surface light source having a reflective layer on the back side. Furthermore, the present invention relates to a liquid crystal display device having a liquid crystal cell on a light emitting side of the lighting device. As the linear polarizer, the lighting device, and the liquid crystal display device, all or a part of each of the formed layers can be used as an adhesive with the adhesive layer interposed therebetween. In addition, the wideband twisted-layer liquid crystal film of the present invention can be used as a circular polarizer, and a linear polarizer can be obtained by combining a λ / 4 plate. In addition, absorption polarizers can be combined to improve the reliability of 15 liquid crystal display devices. Brief Description of Drawings Figure 1 is a conceptual diagram of a polarizing plate used in the evaluation of Examples 1 to 3 and Comparative Examples 1 to 3. System 1: Polarizing plate, 2: λ / 4 plate, 3: Twisted layer liquid crystal film (circular polarizing plate) 4: Adhesive layer. 2 FIG. 2 is a reflection spectrum of the twisted layer liquid crystal film prepared in Example 1. FIG. FIG. 3 is a reflection spectrum of a twisted layer liquid crystal film produced in Example 2. FIG. FIG. 4 is a reflection spectrum of the twisted-layer liquid crystal film produced in Example 3. FIG. FIG. 5 is a reflection spectrum of a twisted-layer liquid crystal film produced in Comparative Example 1. FIG. FIG. 6 is a reflection spectrum of a twisted-layer liquid crystal film produced in Comparative Example 2. FIG. 12 200419197 FIG. 7 is a reflection spectrum of a twisted layer liquid crystal film produced in Comparative Example 3. FIG. t The twisted layer liquid crystal film of the present invention is a liquid crystal mixture containing a polymerizable mesogen compound (a), a polymerizable optically active agent (b), and a photopolymerization initiator (c) is applied to a 5 orientation substrate, and then inactive It is obtained by ultraviolet polymerization in a gaseous environment. The polymerizable mesogen compound (a) has at least one polymerizable functional group, and a polymer having a mesogen group formed of a cyclic unit or the like is suitably used. Examples of the polymerizable functional group include an acrylfluorenyl group, a methacrylfluorenyl group, an epoxy group, and a vinyl ether group. Among them, an acrylfluorenyl group and a methacrylfluorenyl group are preferred. The polymerizable mesogen compound (a) is as described above, and it is preferable that the molar extinction coefficient is 50 to 500 dm3m0r1crrT1 @ 365nm. The polymerizable mesogen compound (a) having the Moire extinction coefficient is as described above, and has the following general formula (1):
15 所表示之化合物為佳（唯，Ri表示氫原子或甲基，η表示1〜5 之整數）。 該聚合性液晶原化合物（a)之具體例可舉例如以下述所示 之化合物。 20 又，聚合性旋光劑（b)可舉例如BASF社製LC756。 上述聚合性旋光劑（b)之混合量，相對於聚合性液晶原 13 200419197 化合物（a)與聚合性旋光劑（b)之合計100重量份，宜為1〜20 重量份，3〜7重量份更佳。螺旋扭轉力（HTP)可藉由聚合性 液晶原化合物（a)與聚合性旋光劑（b)之比例來控制。藉由 使前述比例在前述範圍内，可選擇反射帶使所得到之扭層液晶 5 膜之反射光譜涵蓋可見光全域。 光聚合引發劑（c)可使用各種種類，而無特別限制。例如， 可舉于〆只人シ亇少于 < 夂S力♦X社製之彳少方年二了 184、彳少力、年二了 907、彳少方年二了 369、彳少力、年二了 651 等。光聚合引發劑（c)之混合量，相對於聚合性液晶原化合物 10 (a)與聚合性旋光劑（b)之合計100重量份，宜為0.01〜10 重量份，0.05〜5重量份更佳。 又，本發明中，可使用將含有聚合性液晶原化合物（a)、 聚合性旋光劑（b)及光聚合引發劑（c)之液晶混合物溶解於 溶劑中之溶液。所使用之溶劑並無特別限制，而以甲基乙基甲 15 酮、環己酮、環戊酮等為佳。溶液之濃度通常為3〜50重量％。 本發明之扭層液晶膜之製造，係將前述液晶混合物塗布於 定向基材上，接著在不活性氣體環境下進行紫外線聚合來進 行。 定向基材可採用習知已知者，例如，可使用：在基材上形 20 成由聚醯亞胺或聚乙烯醇等所形成之薄膜，並將之以人造絲布 等摩擦處理之摩擦膜；斜方蒸鍍膜；在桂皮酸或偶氮苯等具有 光交聯基之聚合物、或聚醯亞胺上照射偏光紫外線之光定向 膜；延伸膜等。此外，亦可藉磁場、電場定向、摩擦應力操作 使之定向。 14 ，419197 又，前述基板可使用聚乙烯對苯二甲酸酯、三乙醯基纖維 素、去甲莰系樹脂、聚乙烯醇、聚醯亞胺、聚烯丙酯、聚碳酸 §旨、聚砜或聚醚颯等由塑膠形成之膜、玻璃板、石英薄片。 前述液晶混合物塗布於定向基材後，將之移行到不活性氣 5 體環境下。當前述液晶混合物為溶液時，係於定向基材塗布該 溶液’乾燥後，將之移行到不活性氣體環境下。使溶劑揮發之 乾燥溫度只要是溶劑之沸點以上之溫度即可。通常在80〜160 C之範圍内，因應溶劑之種類來設定溫度即可。 前述液晶混合物之塗布厚度（溶液之情況係溶劑乾燥後之 10 塗布厚度）以5〜20# m為佳，7〜12/z m更佳。塗布厚度若薄於 5 /z m ’則無法形成僅涵蓋2〇〇nm以上之反射帶寬之螺旋螺距， 若厚於20#m，則定向限制力無法充分作用，可能會產生定向 不良。 不活性氣體可使用不會對前述液晶混合物之紫外線聚合 15 造成影響者，並無特別限制。該不活性氣體可舉氮、氬、氦、 氖、氣、氡等。這當中又以氮最為常用，很適宜。 紫外線照射可從定向基材侧、業已塗布液晶混合物侧之任 一側來進行。 照射紫外線時之聚合溫度一般以140。(：以下為佳。具體來 20說，以60〜140°C為佳，又以8(rC〜12(rc為佳。具有藉加熱促 進單體成分之擴散速度之效果。溫度若低於60°C，則聚合性液 曰曰原化合物（a)之擴散速度非常慢，需要非常長時間來寬頻化。 紫外線照度以〇·1〜20mW/cm2為佳，biOmw/cm2更佳。紫 外線照度若超過20mW/cm2 ,則聚合反應速度大於擴散速度， 15 200419197 而邊付然法見頻化。又’照射時間以5分鐘以下之短時間為佳， 3分鐘以下更佳，而1分鐘以下最佳。 如此得到之扭層液晶膜，不需從基材剝離即可使用，此外 亦可從基材剝離後使用。 5 本發明之寬頻扭層液晶膜可作為圓偏光板使用。圓偏光板 上可積層；1/4板來作為直線偏光子。圓偏光板亦即扭層液晶膜 最好是以使螺距長連續地變狹窄之狀態來積層於λ/4板。 δ玄λ /4板宜為當以面内之主折射率為狀、ny，厚度方向之 主折射率為ΠΖ時，以式（nx—nz) / (nx—ny)定義之Nz係數 10 滿足-〇·5〜-2.5者。 λ/4板可舉：將如聚碳酸酯、去甲莰系樹脂、聚乙烯醇、 聚苯乙烯、聚甲基甲基丙烯酸酯、聚丙烯或其他聚烯烴、聚烯 丙酯、聚醯亞胺這些適宜之聚合物所形成之膜延伸處理所形成 之複折射性膜或液晶聚合物等液晶材料形成之定向膜、以膜支 15持液晶材料之定向層者等。λ/4波長板之厚度通常以〇.5〜2〇〇 /zm為佳，尤以i〜1〇〇/zrn為佳。 在可見光域等之廣波長範圍中作為λΜ波長板來發揮功能 之相位差板，可藉由例如將相對於波長別伽之淡色光作為入 /4波長片發揮功能之相位差層，與顯示其他相位差特性之相位 2〇差㈣如作為^波長板發揮功能之相位差層兩者重叠之方式 等得到。因此，配置於偏光板與亮度提升膜之間之相位差板: 可以是由1層或2層以上之相減層形成者。 、 可將吸_偏光子配合前述直線料子之⑽轴方向貼 合於該透過車由上來使用。 、 16 偏光子並無特別限制，可使用各種。作為偏光子者可舉例 如使聚乙烯醇系膜、部分甲縮醛化聚乙烯醇系膜、乙烯•乙烯 乙酸共聚合物系部分皂化膜等親水性高分子膜内吸著碘或二 色性染料等二色性物質單軸延伸者、聚乙稀醇之脫水處理物或 竣氯乙烯之脫氣酸處理物等多烯系定向膜等。這當中又以聚乙 烯醇系膜與碘等之二色性物質形成之偏光子為佳。這些偏光子 之厚度並無特別限定，一般為5〜8〇/^m。 將聚乙烯醇系膜以蛾染色之單軸延伸之偏光子，可以例如 藉由將聚乙烯醇浸漬於碘水溶液中來染色，並延伸為原長之 10 3〜7倍來製作。亦可因應需要使浸潰於含有喊或硫酸辞、氣 化鋅等之蛾化钾等水溶液中。更可因應需要，於染色前將聚乙 烯醇系膜浸潰於水中水洗。藉由水洗聚乙稀醇系膜，不僅可洗 淨聚乙烯醇系膜表面之污垢或阻塞防止劑，且有使聚乙稀醇系 膜雜來防止染色斑駁等不均之效果。延伸係可在以硬染色後 進行《於*色之同時進行延伸，或於延伸後再以硬染色比 可。也可在爛酸切切等水雜巾或於水財延伸。^ 針通^作為單側或兩側設置有透明保護膜之偏 板來使用。透明保護膜以透明性、機械性域、熱安定性、f 20 分遮蔽性、各向同性性質等皆很優異者為佳。作為透明保^ 者可舉例如聚乙埽對笨二甲㈣、聚、 聚合物、雙乙醯输“ 荨聚S旨系 Λ 纖維素、三乙酿纖維素等纖維素系聚合物、命 她旨系聚合物、聚甲基丙烯酸酯等丙烯酸系聚合物’ 聚合物形成之膜。又， 明 合物等之m 亦叮料本乙杯、丙晞猜·苯乙埽共聚 4之本己烯糸聚合物、具有聚乙烯、聚丙烯環系乃至去 17 200419197 甲莰構造之聚烯烴、乙烯•丙烯共聚合物之聚烯烴系聚合物、 氣乙烯系聚合物、耐綸或芳香族聚醯胺等之醯胺系聚合物等透 明聚合物所形成之膜。更可舉醯亞胺系聚合物、颯系聚合物、 聚醚颯系聚合物、聚醚醚酮系聚合物、聚伸苯基硫化物系聚合 5 物、乙晞醇系聚合物、偏氯乙稀系聚合物、聚乙烯醇縮丁駿系 聚合物、烯丙酯系聚合物、聚甲醛系聚合物、環氧系聚合物、 或前述聚合物之掺合物等之透明聚合物所形成之膜。特別是以 使用光學性上複折射少者為佳。從偏光板之保護膜之觀點來 看，以三乙醯纖維素、聚碳酸酯、丙烯酸系聚合物、環聚埽烴 10 系樹脂、具有去甲莰構造之聚烯烴等適合。 又，特開2001-343529號公報（W001/37007)中所記载之 聚合物膜，可舉例如含有（A)側鏈上具有取代及/或非取代酿 胺基之熱可塑性樹脂、及（B)側鏈上具有取代及/或非取代笨 基以及腈基之熱可塑性樹脂之樹脂組成物。具體例可舉含有由 15異丁烯與曱基順丁烯二醯亞胺形成之交互共聚合物及丙烯 腈•苯乙烯共聚合物之樹脂組成物之膜。膜可使用由樹脂組成 物之混合押出品等所形成之膜。 基於偏光特性或耐久性等點，尤其適合之透明保護膜為表 面以鹼等皂化處理之三乙醯纖維素膜。透明保護膜之厚度可適 20當決定’而一般以強度或處理性等作業性、薄層性等觀點來 看’為10〜500 # Π1，尤以20〜300 μ m為佳，更以30〜200 # m 為佳。 又’透明保護膜以盡可能沒有著色為佳。因此，宜使用： 以Rth=[ (nx+ny) /2-nz] · d (唯，nx、ny為膜平面内之主折射 18 200419197 率、nz為膜厚度方向之折射率、d為膜厚）所表示之膜厚度方向 之相位差值為-90nm〜+75ιπη之保護膜。藉由使用該種厚度方向 之相位差值為-90nm〜+75nm者，可幾乎消除起因於保護膜之偏 光板之著色（光學性染色）。厚度方向之相位差值（Rth)又以 5 _80nm〜+60nm為佳，尤其以-70nm〜+45nm為佳。 前述透明保護膜可在表裡使用由相同聚合物材料所形成 之透明保護膜，亦可使用由不同聚合物材料等形成之透明保護 膜。 前述透明保護膜之未接著偏光子之面，亦可施行以硬罩層 10或反射防止處理、黏結防止或擴散乃至抗眩光為目的之處理。 硬罩處理係以防止偏光板表面之損失為目的所施行者可 藉由將藉丙烯酸系、聚石夕氧系等適宜之紫外線硬化型樹脂形成 之硬度或㈣特性上純異之硬化皮咖加於透縣護膜表 面之方式來形成。反射防止處理係以防止偏光板表面之外光之 15反射為目的而施行者，可按照習知之反射防止膜等之形成來達 成。又，黏結防止處理係以防止與鄰接層之密著為目的而施行 者。 又，抗眩光處理係為了防止外光在偏光板之表面反射而阻 20 礙偏光板透過光之目視辨認等目的而施行者，可藉由例如藉嘖 砂方式或壓紋加工方式等之粗面化方式、或透明微粒子之配合 方式等適且之方式於透龍護臈表面賦予微細凹凸構造來形 成。前述表面微細凹凸構造之形成中，作為其中所含之微粒 —可使用例如平均粒子徑〇 5〜5〇㈣之二氧化矽、氧化鋁、 氧化鈦氧化、氧化錫、氧化銦、氧化鑛、氧化錄等所形 19 200419197 成之具導電性之無機系微粒子，及交聯或未交聯之聚合物等形 成之有機系微粒子等之透明微粒子。形成表面微細凹凸構造 時，微粒子之使用量係相對於形成表面微細凹凸構造之透明樹 脂100重量部，一般為2〜50重量部，又以5〜25重量部為佳。亦 5可使抗眩光層兼作擴散層（擴大可視角機能等），使偏光板透 過光擴散來擴大可視角等。 又’前述反射防止層、黏結防止層、擴散層或抗眩光層等 係可設於透明保護膜，此外亦可作為其他用途光學層而與透明 保護膜作為不同個體來設置。 10 前述直線偏光子之積層，甚至各種光學膜之積層，可藉由 在液晶顯示裝置等之製造過程中依序個別積層之方式來形 成，不過事先積層作成光學膜者則在品質之安定性或裝配作業 等方面很優異’具有可使液晶顯示裝置等之製造步驟提升之優 點。積層可使用黏著層等之適宜接著方法。在接著前述偏光板 15與其他光學層之際，這些膜的光學軸可因應作為目的之相位差 特性等而作成適宜之配置角度。 月ίι述直線偏光子上可没置用以與液晶晶胞等其他構件接 著之黏著層。形成黏著層之黏著劑並無特別限制，例如可適當 選擇丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺甲酸酯、 20聚醯胺、聚醚、氟原子系或橡膠系等之聚合物為基質聚合物者 來使用。特別是丙烯酸系黏著劑，其光學性透明性優異，展顯 出適度之可濕潤性、凝集性與接著性之黏著特性，在耐氣候性 或财熱性等方面優異，尤適宜使用。 又，除上述之外，再加上基於防止因吸濕等造成之發泡現 20 象或剝離現象、防止因熱膨脹等造成之光學特性降低或液曰曰 胞紐曲、進而有高品質且耐久性優異之液晶顯示裝置之形Z 等點，以使用吸濕率低且耐熱性優異之黏著層為佧。 黏著劑層可含有例如天然物或合成物之樹脂類、㈣是如 黏著性賦予樹脂、玻璃纖維、玻璃珠、金屬粉、由其他益機於 末等形成之充填劑、顏料 '著色劑或抗氧化劑等可添加於轉 層之添加劑。X，亦可使其為含讀光擴散性之黏 著劑層等。 < 10 15 20 點著劑層之附設’可以適當之方式進行。例如，可舉調製 使基質聚合物或其組成物溶解或分散於由曱苯或乙酸乙醋等 適宜之溶敎單獨物—所職之溶射而紅爪4〇重 量％左右之黏著劑溶液，將之以延流方式或塗工方式等適宜之 展開方式直接㈣於偏光板上絲學膜上這種方式，或依據前 述於脫模膜上形成轉層，㈣之移著與紐上或光學膜上 之方式等。黏著層亦可作為不同組成或種類等之重疊層設於偏 光板或光學膜之單面或雙面。又，設於雙面之情況亦可在偏 光板或光子膜之表裡作成不同組成、種類或厚度等之黏著層。 黏著層之厚度可因應使用目的或黏著力等適宜地決定，一般為 1 〜500 // m， 又以5〜2〇〇# m為佳 尤以10〜100# m為佳。 在供於用夕 貫用之則，以防止其污染等為目的，對黏著層之露 出暫夺貼附脫拉祺覆蓋住。藉此，在通例之處理狀態下可防 霉著層脫模膜除了上述厚度條件外，可使用例如將塑 膠膜橡膠薄片、紙、布、不織布、網、發泡薄片或金屬薄片、 這些薄片的積層體等之適宜之薄片 因應為要而以秒氧系 長 21 200419197 鏈烷基系、氟元素或硫化鉬等適宜之剝離劑施行塗層處理者等 依據習知之適宜者。 又，在黏著層等各層上，可藉例如柳酸酯系化合物或苯酚 系化合物、苯并三氮σ坐系化合物或氰基丙稀酸系化合物、鎳錯 5 鹽系化合物等之紫外線吸收劑來處理之方式等方式，使其具有 紫外線吸收能等。 本發明之直線偏光子可適當地使用在液晶顯示裝置等各 種裝置之形成等。液晶顯示裝置之形成可以習知為基準來進 行。亦即，液晶顯示裝置一般是藉由將液晶晶胞與黏著型光學 10 膜及因應需要之照明系統等之構成零件適當地組合並裝入驅 動電路等來形成，本發明中，除了使用藉本發明形成之偏光板 或光學膜這點外，並無特別限定，可依據習知之方法。有關液 晶晶胞也可使用例如ΤΝ型、STN型或7Γ型等任意類型者。 可形成在液晶晶胞之單側或兩側配置偏光板或光學膜之 15 液晶顯示裝置、或於照明系統中使用後照燈或反射板者等之適 宜之液晶顯示裝置。這時，藉本發明形成之偏光板或光學膜可 設置於液晶晶胞之單側或兩侧。於兩側設置偏光板或光學膜 時，該等可以相同，也可以不同。更，在液晶顯示裝置形成之 際，可於適宜之位置將例如擴散板、抗眩光層、反射防止膜、 20 保護板、稜鏡陣列、透鏡陣列薄膜、光擴散板、背光等適宜之 零件配置1層或2層以上。 實施例 以下舉實施例、比較例來說明本發明，但本發明並不受這 些實施例之限制。 22 200419197 又，各例中，係使用下述化合物作為聚合性液晶原化合物 (a)〇The compound represented by 15 is preferable (only Ri represents a hydrogen atom or a methyl group, and η represents an integer of 1 to 5). Specific examples of the polymerizable mesogen compound (a) include the following compounds. 20 The polymerizable optically active agent (b) is, for example, LC756 manufactured by BASF Corporation. The blending amount of the polymerizable optically active agent (b) is preferably 1 to 20 parts by weight and 3 to 7 weights relative to 100 parts by weight of the total of the polymerizable mesogen 13 200419197 compound (a) and the polymerizable optically active agent (b). Serve better. The helical twisting force (HTP) can be controlled by the ratio of the polymerizable mesogen compound (a) to the polymerizable optical active agent (b). By making the aforementioned ratio within the aforementioned range, a reflection band can be selected so that the reflection spectrum of the obtained twisted layer liquid crystal 5 film covers the entire visible light range. The photopolymerization initiator (c) can be used in various types without particular limitation. For example, it can be considered that only one person is less than < 夂 S force ♦ The company's system is 184 years old, 280 years old, 907 years old, 369 years old, 369 years old , Year 651 and so on. The mixing amount of the photopolymerization initiator (c) is preferably 0.01 to 10 parts by weight, and more preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total of the polymerizable mesogen compound 10 (a) and the polymerizable optically active agent (b). good. In the present invention, a solution in which a liquid crystal mixture containing a polymerizable mesogen compound (a), a polymerizable optically active agent (b), and a photopolymerization initiator (c) is dissolved in a solvent can be used. The solvent to be used is not particularly limited, but methyl ethyl methyl 15 ketone, cyclohexanone, cyclopentanone and the like are preferred. The concentration of the solution is usually 3 to 50% by weight. The twisted layer liquid crystal film of the present invention is produced by coating the aforementioned liquid crystal mixture on an alignment substrate, and then performing ultraviolet polymerization in an inert gas environment. The oriented substrate may be a known one. For example, a rubbing film formed by forming a thin film of polyimide or polyvinyl alcohol on the substrate and rubbing it with a rayon cloth or the like can be used. Orthorhombic vapor-deposited film; light-directed film irradiated with polarized ultraviolet light on a polymer having a photocrosslinking group such as cinnamic acid or azobenzene; In addition, it can be oriented by magnetic field, electric field orientation, and friction stress operations. 14, 419197 The substrate may be made of polyethylene terephthalate, triethylfluorene cellulose, norfluorene-based resin, polyvinyl alcohol, polyimide, polyallyl ester, polycarbonate, etc. Films made of plastic, such as polysulfone or polyether, etc., glass plates, quartz flakes. After the aforementioned liquid crystal mixture is applied to an alignment substrate, it is moved to an inert gas atmosphere. When the liquid crystal mixture is a solution, the solution is coated on an alignment substrate and dried, and then transferred to an inert gas environment. The drying temperature at which the solvent is volatilized may be a temperature above the boiling point of the solvent. Generally, the temperature can be set within the range of 80 to 160 C according to the type of the solvent. The coating thickness of the aforementioned liquid crystal mixture (in the case of a solution is 10 coating thickness after solvent drying) is preferably 5 to 20 # m, and more preferably 7 to 12 / z m. If the coating thickness is thinner than 5 / z m ′, a spiral pitch that only covers a reflection bandwidth of 200 nm or more cannot be formed. If it is thicker than 20 #m, the orientation restricting force cannot be fully exerted, and orientation failure may occur. There are no particular restrictions on the inert gas that can be used without affecting the UV polymerization of the liquid crystal mixture. Examples of the inert gas include nitrogen, argon, helium, neon, gas, and krypton. Of these, nitrogen is the most commonly used, which is very suitable. The ultraviolet irradiation can be performed from either the alignment substrate side or the side on which the liquid crystal mixture has been applied. The polymerization temperature when irradiating ultraviolet rays is generally 140. (: The following is preferred. Specifically, 20 is preferably 60 to 140 ° C, and 8 (rC to 12 (rc is preferred.) It has the effect of promoting the diffusion rate of monomer components by heating. If the temperature is lower than 60 ° C, the diffusion rate of the polymer compound (a) is very slow, and it takes a long time to widen. The ultraviolet illuminance is preferably 0.1-20 mW / cm2, and the biOmw / cm2 is even better. If the ultraviolet illuminance is When it exceeds 20mW / cm2, the polymerization reaction speed is faster than the diffusion speed. 15 200419197 The side-by-side method is frequently used. The irradiation time is preferably a short time of less than 5 minutes, more preferably less than 3 minutes, and the best of less than 1 minute. The twisted layer liquid crystal film thus obtained can be used without peeling from the substrate, and can also be used after being peeled from the substrate. 5 The broadband twisted layer liquid crystal film of the present invention can be used as a circular polarizing plate. The circular polarizing plate can be used Laminated; 1/4 plate is used as linear polarizer. Circular polarizer, that is, twisted layer liquid crystal film, is preferably laminated on λ / 4 plate in a state where the pitch is continuously narrowed. Δ 玄 λ / 4 plate is preferably When the in-plane principal refractive index is the shape, ny, and the principal refractive index in the thickness direction is ΠZ , Where the Nz coefficient 10 defined by the formula (nx-nz) / (nx-ny) satisfies -0.5 to -2.5. Λ / 4 plate can be exemplified: for example, polycarbonate, norfoamyl resin, polyethylene Alcohol, polystyrene, polymethacrylate, polypropylene or other polyolefins, polyallyl ester, polyfluorene imide, etc. Orientation films made of liquid crystal materials such as polymers, those supporting the alignment layer of liquid crystal materials with film support 15. The thickness of the λ / 4 wavelength plate is usually preferably 0.5 ~ 200 / zm, especially i ~ 1〇 〇 / zrn is preferred. The phase difference plate that functions as a λM wavelength plate in a wide wavelength range such as the visible light range can be used as a phase that functions as a λ / 4 wavelength plate by using light-colored light with a wavelength different from gamma. The retardation layer and the phase difference of 20 which show other retardation characteristics are obtained by overlapping the retardation layer functioning as a wavelength plate, etc. Therefore, the retardation plate disposed between the polarizing plate and the brightness enhancement film : It can be formed by 1 or more subtraction layers. The z-axis direction of the linear material is bonded to the transmission vehicle. 16 Polarizers are not particularly limited, and various types of polarizers can be used. Examples of polarizers include polyvinyl alcohol-based films and partial methylalization. Uniaxial elongation of dichroic materials such as iodine or dichroic dyes in hydrophilic polymer films such as polyvinyl alcohol-based films and ethylene-vinyl-acetic acid copolymerized saponified films, and dehydration products of polyvinyl alcohol Or polyene oriented films such as degassed acid treated products of vinyl chloride, etc. Among them, polarized photons formed of polyvinyl alcohol based films and dichroic materials such as iodine are preferred. The thickness of these polarized photons is not particularly The limitation is generally 5 to 8 // m. The uniaxially-extended polarizer that moth dyes the polyvinyl alcohol film can be dyed by, for example, immersing the polyvinyl alcohol in an iodine aqueous solution, and extended to the original length. 10 3 ~ 7 times to make. If necessary, it may be immersed in an aqueous solution such as potassium moth or the like containing sulfonium sulfate, zinc oxide, or the like. If necessary, the polyvinyl alcohol-based film is immersed in water and washed before dyeing. By washing the polyvinyl alcohol-based film with water, not only the dirt on the surface of the polyvinyl alcohol-based film or an anti-clogging agent can be cleaned, but also the polyvinyl alcohol-based film can be mixed to prevent uneven staining and the like. The stretching system can be carried out after hard dyeing, or at the same time as the color, or after hardening. Can also be cut in rotten acid and other miscellaneous towels or extended in water. ^ Needle pass ^ Used as a polarizing plate with a transparent protective film on one or both sides. The transparent protective film is preferably one having excellent transparency, mechanical properties, thermal stability, f 20-point shielding properties, and isotropic properties. As a transparent protector, for example, polyethylenimine, dimethymethane, poly, polymer, diethylsulfonate, etc., cellulose polymers such as cellulose, triethylcellulose, and so on. It is a film formed by polymers of acrylic polymers such as polymers and polymethacrylates. In addition, m of succinate and the like is also expected to be used in this cup, propylene glycol and phenethyl fluorene copolymer 4 Rhenium polymers, polyethylene, polypropylene ring systems and even 17 200419197 polyolefins with formazan structure, polyolefin polymers of ethylene-propylene copolymers, vinyl polymers, nylon or aromatic polyamides Films made of transparent polymers such as fluorene-based polymers. Fluorine-based polymers, fluorene-based polymers, polyether fluorene-based polymers, polyetheretherketone-based polymers, polyphenylene 5 sulfide polymer, acetohydrin polymer, vinylidene chloride polymer, polyvinyl butyral polymer, allyl ester polymer, polyoxymethylene polymer, epoxy polymer , Or a film formed of a transparent polymer, such as a blend of the foregoing polymers. Especially, From the viewpoint of the protective film of the polarizing plate, triethylfluorene cellulose, polycarbonate, acrylic polymer, cyclopolyfluorene 10-series resin, and norfluorene are preferred. Structured polyolefins are suitable. Also, the polymer film described in JP-A-2001-343529 (W001 / 37007) may include, for example, (A) a substituted and / or unsubstituted amino group having a substituted and / or unsubstituted amino group in a side chain. The thermoplastic resin and the resin composition of (B) a thermoplastic resin having a substituted and / or unsubstituted benzyl group and a nitrile group on the side chain. Specific examples include 15 isobutylene and fluorenyl maleic acid. A film of a resin composition of an amine-based interpolymer and an acrylonitrile-styrene copolymer. The film may be a film formed of a mixed extruded product of a resin composition, etc. Based on the characteristics of polarized light or durability, especially A suitable transparent protective film is a triethyl cellulose cellulose film whose surface is saponified with alkali or the like. The thickness of the transparent protective film can be appropriately determined. 20 Generally, it is considered from the viewpoints of workability and thinness such as strength and handling. 10 ~ 500 # Π1, especially 20 300 μ m is better, and 30 ~ 200 # m is better. Also, the transparent protective film is best not to be colored as much as possible. Therefore, it is suitable to use: Rth = [(nx + ny) / 2-nz] · d (Only, nx, ny are the main refractive index in the film plane, 18 200419197, nz is the refractive index in the film thickness direction, and d is the film thickness.) The protective film has a phase difference in the film thickness direction of -90nm ~ + 75ιπη By using this type of phase difference value of -90nm ~ + 75nm, the coloring (optical dyeing) of the polarizing plate caused by the protective film can be almost eliminated. The phase difference value (Rth) of the thickness direction is also 5 _80nm ~ + 60nm is preferred, especially -70nm ~ + 45nm is preferred. The transparent protective film may be a transparent protective film formed of the same polymer material on the surface or a transparent protective film formed of a different polymer material or the like. The surface of the aforementioned transparent protective film without being polarized may be subjected to a treatment for the purpose of hard cover layer 10 or reflection prevention treatment, adhesion prevention or diffusion, or even anti-glare. The hard cover treatment is to prevent the loss of the surface of the polarizing plate. The implementer can use a hardened skin coffee that has a unique hardness or unique properties formed from suitable UV-curable resins such as acrylic and polylithic oxygen-based resins. It is formed on the surface of the protective film of the county. The anti-reflection treatment is performed for the purpose of preventing 15 reflections of light outside the surface of the polarizing plate, and can be achieved by forming a conventional anti-reflection film or the like. The anti-adhesion treatment is performed for the purpose of preventing adhesion to an adjacent layer. In addition, the anti-glare treatment is performed in order to prevent the reflection of external light on the surface of the polarizing plate, and to prevent the polarizing plate from seeing through the light. For example, the rough surface can be made by sanding or embossing. It is formed by a suitable method such as a chemical conversion method or a combination method of transparent fine particles to impart a fine uneven structure to the surface of the dragon shield. In the formation of the fine uneven structure on the surface, as the fine particles contained therein, for example, silicon dioxide, aluminum oxide, titanium oxide, tin oxide, indium oxide, ore oxide, and oxide having an average particle diameter of 0.05 to 50 Å can be used. 19 200419197 formed by the recording, etc., conductive inorganic fine particles, and organic fine particles formed of crosslinked or uncrosslinked polymers and other transparent fine particles. When forming a fine uneven structure on the surface, the amount of fine particles used is generally 2 to 50 parts by weight and preferably 5 to 25 parts by weight relative to 100 parts by weight of the transparent resin forming the fine uneven structure on the surface. Also, the anti-glare layer can also be used as a diffusion layer (enlargement of viewing angle function, etc.), and the polarizing plate can diffuse the light to expand the viewing angle. The anti-reflection layer, the anti-adhesion layer, the diffusion layer, or the anti-glare layer may be provided on a transparent protective film, or may be provided as an optical layer for other purposes as a separate unit from the transparent protective film. 10 The above-mentioned stack of linear polarizers, and even various optical films, can be formed by sequentially stacking them in order during the manufacturing process of liquid crystal display devices, etc., but those that are laminated in advance to make optical films have a quality It is excellent in assembly work and the like, and has the advantage that the manufacturing steps of the liquid crystal display device and the like can be improved. For the lamination, a suitable bonding method such as an adhesive layer can be used. When the polarizing plate 15 and other optical layers are followed, the optical axis of these films can be formed at an appropriate arrangement angle in accordance with the phase difference characteristics and the like for the purpose. The linear polarizer may not have an adhesive layer for contacting other components such as a liquid crystal cell. The adhesive for forming the adhesive layer is not particularly limited. For example, an acrylic polymer, a silicone polymer, a polyester, a polyurethane, a 20 polyamine, a polyether, a fluorine atom-based system, or a rubber-based system can be appropriately selected. Other polymers are used as matrix polymers. In particular, acrylic adhesives are excellent in optical transparency, exhibit moderate adhesion characteristics such as wettability, agglutination, and adhesion, and are excellent in terms of weather resistance and financial heat resistance, and are particularly suitable for use. In addition to the above, in addition to preventing the phenomenon of foaming or peeling due to moisture absorption, etc., preventing the degradation of optical characteristics due to thermal expansion, etc., or the liquid cells, it has high quality and durability. The shape Z and the like of the liquid crystal display device having excellent properties are based on the use of an adhesive layer having low moisture absorption and excellent heat resistance. The adhesive layer may contain, for example, natural or synthetic resins, such as adhesion-imparting resins, glass fibers, glass beads, metal powder, fillers formed by other beneficial agents, pigments, colorants, or Additives such as oxidants can be added to the transfer layer. X may also be used as an adhesive layer containing reading light diffusivity. < 10 15 20 Attachment of the electrification layer 'can be performed in an appropriate manner. For example, a matrix polymer or a composition thereof can be prepared by dissolving or dispersing an appropriate solvent-solubilized substance such as toluene or ethyl acetate—a dissolving agent, and a red claw adhesive solution of about 40% by weight. It can be directly spread on the silk film on the polarizing plate by a suitable spreading method such as casting method or coating method, or the transfer layer can be formed on the release film according to the foregoing. On the way and so on. The adhesive layer can also be provided on one or both sides of the polarizing plate or optical film as an overlapping layer of different compositions or types. In addition, when it is provided on both sides, it is also possible to make adhesive layers with different compositions, types, or thicknesses on the surface of the polarizer or photonic film. The thickness of the adhesive layer can be appropriately determined according to the purpose of use or adhesive strength, and is generally 1 to 500 // m, and preferably 5 to 2000 # m, especially 10 to 100 # m. In the case of continuous use for the purpose of use, the purpose of preventing contamination, etc., is to temporarily cover the exposure of the adhesive layer with a detachment cover. In this way, in the usual processing state, in addition to the above-mentioned thickness conditions, the mold-proof mold release film can be used, for example, a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet or metal sheet, A suitable thin sheet of a laminated body or the like should be coated with a suitable release agent such as chain alkyl, fluorine or molybdenum sulfide, etc., according to the conventionally suitable ones, if necessary. In addition, on each layer such as an adhesive layer, an ultraviolet absorber such as a salicylate-based compound or a phenol-based compound, a benzotriazine-sigma-based compound, a cyanoacrylic acid-based compound, or a nickel 5 salt-based compound can be used. The method of processing is to make it have ultraviolet absorption energy and the like. The linear polarizer of the present invention can be suitably used in the formation of various devices such as a liquid crystal display device. The formation of a liquid crystal display device can be performed with reference to a conventional method. That is, the liquid crystal display device is generally formed by appropriately combining and constituting components such as a liquid crystal cell, an adhesive optical 10 film, and a lighting system according to need, and incorporating the driving circuit into the driving circuit. In the present invention, in addition to using There is no particular limitation on the polarizing plate or optical film formed by the invention, and conventional methods can be used. As the liquid crystal cell, any type such as a TN type, an STN type, or a 7Γ type may be used. A suitable liquid crystal display device can be formed on one or both sides of the liquid crystal cell, with a liquid crystal display device having a polarizing plate or an optical film, or a backlight or reflection plate used in a lighting system. At this time, the polarizing plate or optical film formed by the present invention can be disposed on one side or both sides of the liquid crystal cell. When polarizing plates or optical films are provided on both sides, these may be the same or different. Furthermore, when the liquid crystal display device is formed, suitable components such as a diffuser plate, an anti-glare layer, an anti-reflection film, a 20 protective plate, a holmium array, a lens array film, a light diffusion plate, and a backlight can be arranged at appropriate positions. 1 or more layers. Examples The following examples and comparative examples are used to illustrate the present invention, but the present invention is not limited by these examples. 22 200419197 In each case, the following compounds were used as the polymerizable mesogen compound (a).
莫耳消光係數為220dm3m〇r1cm〃@365nm。又，聚合性旋光劑 5 (b)係使用BASF社製LC756。The Moire extinction coefficient is 220dm3m0r1cm〃 @ 365nm. As the polymerizable optical active agent 5 (b), LC756 manufactured by BASF was used.
實施例1 調製以上述所示之聚合性液晶原化合物（a) 96重量份、 上述聚合性旋光劑（b) 4重量份及作為光聚合引發劑（c)之 彳少力、夺二了 184 力少文社製）5Example 1 96 parts by weight of the polymerizable mesogen compound (a) shown above, 4 parts by weight of the above-mentioned polymerizable optically active agent (b), and less than 184 as the photopolymerization initiator (c) were prepared. (Li Shaowenshe system) 5
10 重量份所形成之混合物之環戊酮溶液（30重量％固體含有量）。 將上述溶液澆鑄於延伸聚乙烯對苯二甲酸酯基材中，在100°C 使之乾燥2分鐘，除去溶劑。接著，在氮氣環境下以120°c — 面加熱，一面從基材側以3mW/cm2照射紫外線5分鐘，得到目 的之扭層液晶膜。 15 所得到之扭層液晶膜（圓偏光板）之反射光譜顯示於第2 圖。圓偏光板在450〜890nm之範圍有良好的圓偏光分離特性 (反射帶）。扭層液晶層（膜）之綜合厚度約9#m。又，所得 到之扭層液晶層之螺距長在紫外線照射面附近（從紫外線照射 面起l//m下層）為0.54# m，在反對面附近（從反對面起1 20 # m 下層）為 0.27 # m。 將所得到之圓偏光板，以螺距長連續變狹窄之方向，藉丙 23 200419197 稀酸系黏著材（厚25//m)貼合於將聚礙酸酯樹脂膜（厚80 #m)二軸延伸所得到之廣視角；1/4板（Nz係數=-1.2)。再將 之以黏著材積層於日東電工製吸收型偏光板SEG1425DU，得到 寬頻偏光板。 5 實施例2 調製以上述所示之聚合性液晶原化合物（a) 96重量份、 上述聚合性旋光劑（b) 4重量份及作為光聚合引發劑（c)之 /々力年二了 907 (于八只亇，亍彳少S力/vX社製）〇·5 重量份所形成之混合物之環戊酮溶液（3〇重量％固體含有量）。 1〇 將上述溶液澆鑄於延伸聚乙烯對苯二甲酸酯基材中，在l〇〇°C 使之乾燥2分鐘，除去溶劑。接著，在氮氣環境下以i2〇°C — 面加熱，一面從基材側以3mW/cm2照射紫外線5分鐘，接著， 在120 C —面加熱一面以3mW/cm2照射紫外線5分鐘，得到目 的之扭層液晶膜。 15 所得到之扭層液晶膜（圓偏光板）之反射光譜顯示於第3 圖。所得到之圓偏光板在510〜970nm之範圍有良好的圓偏光分 離特性。扭層液晶層（膜）之綜合厚度約9/zm。又，所得到 之扭層液晶層之螺距長在紫外線照射面附近（從紫外線照射面 起1/zm下層）為〇.57/zm，在反對面附近（從反對面起ly m 20 下層）為 0.31 // m。 將所得到之圓偏光板，以螺距長連續變狹窄之方向，藉丙 晞酸系黏著材（厚25# m)貼合於將聚碳酸酯樹脂膜（厚80 /zm)二軸延伸所得到之廣視角λ/4板（Nz係數=-12)。再將 之以黏著材積層於曰東電工製吸收型偏光板SEG1465DU，得到 24 200419197 丸頻偏光板。 實施例3 調製以上述所示之聚合性液晶原化合物（a) 96重量份、 上述聚合性旋光劑（b) 4重量份及作為光聚合引發劑（c)之 5彳瓜力夺二了 369(于八只^^>亇爪亍〆S力少文社製）〇·〇5 重$份所形成之混合物之環戊酮溶液（20重量％固體含有 畺）。將上述溶液澆鑄於延伸聚乙烯對苯二甲酸酯基材中，在 100 C使之乾燥2分鐘，除去溶劑。接著，在氮氣環境下以12〇 °(：一面加熱，一面從基材側以UmW/cm2照射紫外線5分鐘， 10得到目的之扭層液晶膜。 所得到之扭層液晶膜（圓偏光板）之反射光譜顯示於第4 圖。所得到之圓偏光板在520〜920nm之範圍有良好的圓偏光分 離特性。扭層液晶層（膜）之綜合厚度約9/zm。又，所得到 之扭層液晶層之螺距長在紫外線照射面附近（從紫外線照射面 15起Ιβ111下層）為056/zm ,在反對面附近（從反對面起 下層）為0.31am。 將所付到之圓偏光板，以螺距長連續變狹窄之方向，積層 於λ/4板（日東電工製NRF 7彳少厶么11=14〇1^，Nz係數 =-1.2)，'以相對於該軸角度117·5度配置λ/2板（曰東電工製 20 NRZ 7彳少厶Δη=270ηπι，Νζ係數=0.5，視角特性補償型）。 積層係各自使用藉丙烯酸系黏著材（厚25# m)。這時的透過 偏光軸係相對於λ/4板之軸為1〇度，故配合該方向同樣地貼 合日東電工製吸收型偏光板SEG1425DU，得到寬頻偏光板。 比較例1 25 200419197 調製以上述所示之聚合性液晶原化合物（a) 96重量份、 上述聚合性旋光劑（b) 4重量份及作為光聚合引發劑（c)之 彳少力、年二了 184 (S力少又、社製）5 重量份所形成之混合物之環戊酮溶液（30重量％固體含有量）。 5 將上述溶液澆鑄於延伸聚乙烯對苯二甲酸酯基材中，在100°C 使之乾燥2分鐘，除去溶劑。接著，在氮氣環境下以80°C—面 加熱，一面從基材側以50mW/cm2照射紫外線5分鐘，得到目 的之扭層液晶膜。 所得到之扭層液晶膜（圓偏光板）之反射光譜顯示於第5 10 圖。所得到之圓偏光板在710〜880nm之範圍有良好的圓偏光分 離特性。扭層液晶層（膜）之綜合厚度約9 # m。又，所得到 之扭層液晶層之螺距長在紫外線照射面附近（從紫外線照射面 起1 // m下層）為0.52 /zm，在反對面附近（從反對面起1/zm 下層）為0.52 // m。 15 將所得到之圓偏光板，以螺距長連續變狹窄之方向，藉丙 烯酸系黏著材（厚25/zm)貼合於將聚碳酸酯樹脂膜（厚80 #m)二軸延伸所得到之廣視角λ/4板（Nz係數=-1.2)。再將 之以黏著材積層於日東電工製吸收型偏光板SEG1425DU，得到 偏光板。 20 比較例2 調製以上述所示之聚合性液晶原化合物（a) 96重量份、 上述聚合性旋光劑（b) 4重量份及作為光聚合引發劑（c)之 彳少方夸二了 184 (彳少S力少文社製）5 重量份所形成之混合物之環戊酮溶液（30重量％固體含有量）。 26 將上述溶液澆鑄於延伸聚乙烯對苯二甲酸酯基材中，在10(rc 使之乾燥2分鐘，除去溶劑。接著，在氮氣環境下以4〇ι 一面 加熱’一面從基材側以3mw/cm2照射紫外線5分鐘，得到目的 之杻層液晶膜。 5 所得到之扭層液晶膜（圓偏光板）之反射光譜顯示於第6 圖所彳于到之圓偏光板在720〜870nm之範圍有良好的圓偏光分 離特性。扭層液晶層（膜）之綜合厚度約9。又，所得到 之扭層液晶層之螺距長在紫外線照射面附近（從紫外線照射面 起下層）為〇.52//m，在反對面附近（從反對面起l/zm 10 下層）為 0.52#m。 將所得到之圓偏光板，以螺距長連續變狹窄之方向，藉丙 烯酸系黏著材（厚25//m)貼合於將聚碳酸酯樹脂膜（厚80 二軸延伸所得到之廣視角λ/4板（Nz係數=-1.2)。再將 之以黏著材積層於日東電工製吸收型偏光板SEG1425DU，得到 15 偏光板。 比較例3 調製以上述所示之聚合性液晶原化合物（a) 96重量份、 上述聚合性旋光劑（b) 4重量份、作為光聚合引發劑（c)之 彳少力、年二了 184 (テパスパシ亇/レテ彳少s力少文社製）5 20 重篁份及于又匕^ 400 (于〆只\シ十♦亍彳^ s力少又、社 製，紫外線吸收劑）1重量份所形成之混合物之環戊綱溶液（3〇 重量％固體含有量）。將上述溶液澆鑄於延伸聚乙烯對苯二甲酸 酯基材中，在l〇〇°C使之乾燥2分鐘，除去溶劑。接著，在氮 氣環境下以80°C —面加熱，一面從基材側以5〇inW/cm2照射紫 27 200419197 外線5分鐘，得到目的之扭層液晶膜。 所得到之扭層液晶膜（圓偏光板）之反射光譜顯示於第7 圖。所得到之圓偏光板在710〜860nm之範圍有良好的圓偏光分 離特性。扭層液晶層（膜）之綜合厚度約9// m。又，所得到 5 之扭層液晶層之螺距長在紫外線照射面附近（從紫外線照射面 起l//m下層）為0.51/zm，在反對面附近（從反對面起 下層）為0.51 //m。 將所得到之圓偏光板，以螺距長連續變狹窄之方向，藉丙 烯酸系黏著材（厚25//m)貼合於將聚碳酸酯樹脂膜（厚80 10 em)二軸延伸所得到之廣視角λ/4板（Nz係數=-1.2)。再將 之以黏著材積層於曰東電工製吸收型偏光板SEG1425DU，得到 偏光板。 針對以實施例及比較例得到之（寬頻）偏光板進行以下評 價。結果顯示於表1。 15 (亮度提昇率） 藉TOPCON社製BM7來測定將（寬頻）偏光板安裝於15 英吋TFT液晶顯示裝置時之亮度。與無寬頻扭層液晶膜之亮度 相比較，算出提昇之亮度之倍率。 (視角特性：色調變化） 20 視角特性係藉ELDIM社製視角測定機EZ-CONTRAST， 導出Axy而以下述基準評價。 Δχγ= ((x〇^Xl) (y〇-yi) 2) 05 正面色度（xo，y〇)，60。色度（xl5yi ) 良好：視角60。之色調變化^xy在〇·〇4以下。 28 200419197 不良：視角60。之色調變化Axy在〇·〇4以上。 (耐久性） 在80°C及60°C、90% RH之環境下投入寬頻偏光板或偏光 板500小時後，以目視判定有無析出表面之粉狀物質。又，有 5 粉狀物質時，則作為光學用途有問題。 表1 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 聚合性液晶原 化合物（a ) 96 96 96 96 96 96 泵合性旋光劑 (b) 4 4 4 4 4 4 液 晶 混 合 物 光聚合 引發劑 (C) 4 /U 工了 184 5 0 0 5 5 5 ；V 力'牛 工了 907 0 0.5 0 0 0 0 力'年 工了 369 0 0 0.05 0 0 0 紫外線吸收劑 (于又匕° ^ 400) 0 0 0 0 0 1 溶劑（環戊酮） 400 400 400 400 400 400 聚 合 條 件 紫外線照度 (mW/cm2) 3 3 11 50 3 50 溫度（°C ) 120 120 120 80 40 80 扭 層 液 晶 膜 反射帶（nm) 450-890 510-970 520-920 710-880 720-870 710-860 反射帶寬（nm) 440 460 400 170— 150 150 螺距長 (β m) 紫外 線照 射面 0.54 0.57 0.56 0.52 0.52 0.51 反對 面 0.27 0.31 0.31 0.52 0.52 0.51 評 價 亮度才 是昇率 1.3 1.3 1.3 1.1 1.1 1.1 視角特性、色 調變化 良好 良好 良好 不良 不良 不良 财久性（有無 析出物） 無 無 無 無 無 有 29 200419197 產業上可利用性 本發明之寬頻扭層液晶膜可作為圓偏光板（反射型偏光 子）使用。圓偏光板可利用在直線偏光子、照明裝置及液晶顯 示裝置等。 5 【圖式簡單說明】 第1圖是實施例1〜3及比較例1〜3之評價中所使用之偏光 板之概念圖。係1 :偏光板、2 : λ/4板、3 :扭層液晶膜（圓 偏光板）4 :黏著層。10 parts by weight of the formed mixture in a cyclopentanone solution (30% by weight solids content). The above solution was cast into a stretched polyethylene terephthalate substrate and dried at 100 ° C for 2 minutes to remove the solvent. Next, it was heated at 120 ° C under a nitrogen atmosphere, and irradiated with ultraviolet rays at 3 mW / cm2 from the substrate side for 5 minutes to obtain the desired twisted layer liquid crystal film. 15 The reflection spectrum of the twisted layer liquid crystal film (circular polarizing plate) obtained is shown in Figure 2. The circularly polarizing plate has good circularly polarized light separation characteristics (reflection band) in the range of 450 to 890 nm. The overall thickness of the twisted liquid crystal layer (film) is about 9 # m. In addition, the pitch of the obtained twisted liquid crystal layer is 0.54 # m in the vicinity of the ultraviolet irradiated surface (lower layer from the ultraviolet irradiated surface 1 // m), and near the opposite surface (1 20 # m lower layer from the opposite surface) is 0.27 # m. The obtained circular polarizing plate was continuously narrowed in the direction of a long pitch, and a polyacrylic acid resin film (thickness 80 #m) was bonded to the polyacrylic acid ester resin film (thickness 25 // m) by using C23 200419197 dilute acid adhesive material (thickness 25 // m) Wide viewing angle obtained by axis extension; 1/4 plate (Nz coefficient = -1.2). The adhesive material was laminated on the absorption polarizer SEG1425DU made by Nitto Denko to obtain a broadband polarizer. 5 Example 2 96 parts by weight of the polymerizable mesogen compound (a) shown above, 4 parts by weight of the polymerizable optically active agent (b), and 907 as the photopolymerization initiator (c) were prepared. (In Bajiu, Shaoxing Sli / vX Co.) 0.5 parts by weight of a cyclopentanone solution of the resulting mixture (30% by weight solids content). 10. The above solution was cast into an extended polyethylene terephthalate substrate, and dried at 100 ° C for 2 minutes to remove the solvent. Next, in a nitrogen environment, i20 ° C heating was performed, while irradiating ultraviolet rays at 3 mW / cm2 from the substrate side for 5 minutes, and then heating at 120 C, heating was performed at 3 mW / cm2 for 5 minutes. Twisted layer liquid crystal film. 15 The reflection spectrum of the obtained twisted layer liquid crystal film (circular polarizing plate) is shown in Fig. 3. The obtained circularly polarizing plate had good circularly polarized light separation characteristics in a range of 510 to 970 nm. The overall thickness of the twisted liquid crystal layer (film) is about 9 / zm. The pitch of the obtained twisted layer liquid crystal layer is 0.57 / zm near the ultraviolet irradiated surface (1 / zm lower layer from the ultraviolet irradiated surface), and near the opposite surface (lym 20 lower layer from the opposite surface) is 0.31 // m. The obtained circular polarizing plate was continuously narrowed in the direction of a long pitch, and a polycarbonate resin film (thickness 80 / zm) was biaxially stretched with a propionic acid-based adhesive material (thickness 25 # m). Wide viewing angle λ / 4 plate (Nz coefficient = -12). It was then laminated with an adhesive material on an absorption polarizing plate SEG1465DU made by Yuden Denko to obtain 24 200419197 pill-frequency polarizing plate. Example 3 96 parts by weight of the polymerizable mesogen compound (a) shown above, 4 parts by weight of the above-mentioned polymerizable optically active agent (b), and 5 parts of the photopolymerization initiator (c) were prepared to obtain 369. (At eight ^^ > made by 亇 力 亍 〆Selishawensha) 0.05 parts by weight of a cyclopentanone solution of the resulting mixture (20% by weight of solids containing 畺). The solution was cast into an extended polyethylene terephthalate substrate, and dried at 100 C for 2 minutes to remove the solvent. Next, at a temperature of 120 ° (under heating in a nitrogen environment, while irradiating ultraviolet rays at a UmW / cm2 from the substrate side for 5 minutes, 10) was obtained the intended twisted-layer liquid crystal film. The obtained twisted-layer liquid crystal film (circular polarizer) The reflection spectrum is shown in Figure 4. The obtained circularly polarizing plate has good circularly polarized light separation characteristics in the range of 520 to 920 nm. The overall thickness of the twisted liquid crystal layer (film) is about 9 / zm. Also, the obtained twisted The pitch of the liquid crystal layer is 056 / zm in the vicinity of the ultraviolet irradiated surface (from the ultraviolet irradiated surface 15 under the β 1 111), and is near the opposite surface (from the opposite surface from the lower surface) to 0.31 am. Laminated on the λ / 4 plate in the direction of continuous narrowing of the pitch length (NRF 7 made by Nitto Denko Corporation 11 = 14〇1 ^, Nz coefficient = -1.2), 'at an angle of 117.5 degrees with respect to the axis Λ / 2 plate (20 NRZ 7 made by Tohoku Electric Co., Ltd. Δη = 270ηπι, Νζ coefficient = 0.5, viewing angle compensation type). Laminates each use an acrylic adhesive material (thickness 25 # m). Transmission at this time The axis of the polarized light is 10 degrees relative to the axis of the λ / 4 plate, so it fits in the same direction. A wide-band polarizing plate was obtained from Nitto Denko's absorption-type polarizing plate SEG1425DU. Comparative Example 1 25 200419197 The above-mentioned polymerizable mesogen compound (a) 96 parts by weight, the polymerizable optically active agent (b) 4 parts by weight, and A cyclopentanone solution (30% by weight solids content) of a mixture of 5 parts by weight of the photopolymerization initiator (c), which is 184 (S force is low, manufactured by the company). 5 The solution was cast into a stretched polyethylene terephthalate substrate and dried at 100 ° C for 2 minutes to remove the solvent. Then, the surface was heated at 80 ° C in a nitrogen atmosphere, and 50mW from the substrate side on one side. / cm2 is irradiated with ultraviolet rays for 5 minutes to obtain the desired twisted layer liquid crystal film. The reflection spectrum of the obtained twisted layer liquid crystal film (circular polarizing plate) is shown in Fig. 5 and 10. The obtained circular polarizing plate has a range of 710 to 880 nm. Good circular polarized light separation characteristics. The combined thickness of the twisted liquid crystal layer (film) is about 9 # m. Furthermore, the pitch of the obtained twisted liquid crystal layer is longer near the ultraviolet irradiation surface (from the ultraviolet irradiation surface 1 // m lower layer) ) Is 0.52 / zm, attached on the opposite side Near (1 / zm lower layer from the opposite side) is 0.52 // m. 15 The obtained circular polarizing plate is continuously narrowed in the direction of the pitch, and the acrylic polarizing material (thickness 25 / zm) is attached to the Wide viewing angle λ / 4 plate (Nz coefficient = -1.2) obtained by biaxial extension of a polycarbonate resin film (thickness 80 #m). It was laminated with an adhesive on Nitto Denko's absorption-type polarizing plate SEG1425DU to obtain polarized light. 20 Comparative Example 2 96 parts by weight of the polymerizable mesogen compound (a) shown above, 4 parts by weight of the above-mentioned polymerizable optically active agent (b), and less than two as the photopolymerization initiator (c) were prepared. 184 (manufactured by 彳 少 S 利 少 文 社) 5 parts by weight of a cyclopentanone solution (30% by weight of solid content) of the resulting mixture. 26 The above solution was cast into a stretched polyethylene terephthalate substrate, and dried at 10 ° C for 2 minutes to remove the solvent. Then, the substrate was heated under a nitrogen atmosphere at a temperature of 4 m from the substrate side. Irradiate ultraviolet rays at 3mw / cm2 for 5 minutes to obtain the desired pseudo-layer liquid crystal film. 5 The reflection spectrum of the obtained twisted-layer liquid crystal film (circular polarizing plate) is shown in Fig. 6. The obtained circular polarizing plate is 720 to 870 nm. The range has good circular polarization separation characteristics. The overall thickness of the twisted liquid crystal layer (film) is about 9. Also, the pitch of the obtained twisted liquid crystal layer is longer near the ultraviolet irradiation surface (the lower layer from the ultraviolet irradiation surface) is 0. .52 // m, 0.52 # m near the opposing surface (lower 1 / zm 10 from the opposing surface). The obtained circular polarizing plate was continuously narrowed in the direction of the pitch, and the acrylic polarizing material (thick 25 // m) laminated to a wide-angle λ / 4 plate (Nz coefficient = -1.2) obtained by stretching a polycarbonate resin film (thickness 80 biaxially). Then it was laminated with an adhesive material to Nitto Denko's absorption type Polarizing plate SEG1425DU, 15 polarizing plates are obtained. Comparative Example 3 Modulation is as described above. 96 parts by weight of the polymerizable mesogen compound (a), 4 parts by weight of the above-mentioned polymerizable optically active agent (b), as a photopolymerization initiator (c), a small amount of strength, a year of 184 (テ パ ス パ シ 亇 / レ テ 彳 少 s) (Made by Li Shaowen Co.) 5 20 parts by weight and 400% by weight (Yu only \ シ 十 ♦ 亍 彳 ^ s force, by the company, UV absorber) 1 part by weight of cyclopentyl mixture Gang solution (30% by weight solids content). The above solution was cast into a stretched polyethylene terephthalate substrate, dried at 100 ° C for 2 minutes, and the solvent was removed. Next, in a nitrogen atmosphere The surface is heated at 80 ° C, and the purple 27 200419197 is irradiated from the substrate side at 50 inW / cm2 for 5 minutes to obtain the desired twisted layer liquid crystal film. The reflection of the obtained twisted layer liquid crystal film (circular polarizer) The spectrum is shown in Fig. 7. The obtained circularly polarizing plate has good circularly polarized light separation characteristics in the range of 710 to 860 nm. The overall thickness of the twisted layer liquid crystal layer (film) is about 9 // m. Furthermore, the twisted value of 5 obtained The pitch of the liquid crystal layer is longer near the ultraviolet irradiation surface (under the l // m from the ultraviolet irradiation surface) ) Is 0.51 / zm, and it is 0.51 // m in the vicinity of the opposing surface (from the opposing surface to the lower layer). The obtained circular polarizing plate is continuously narrowed in a direction of a long pitch, and an acrylic adhesive material (thickness 25 // m) Laminated on a wide-angle λ / 4 plate (Nz coefficient = -1.2) obtained by biaxially extending a polycarbonate resin film (thickness 80 10 em). It was then laminated with an adhesive material to be absorbed by Yuedong Denko. A polarizing plate of SEG1425DU type was obtained. The following evaluations were performed on the (wideband) polarizing plates obtained in Examples and Comparative Examples. The results are shown in Table 1. 15 (Brightness increase rate) The brightness when a (wideband) polarizer was mounted on a 15-inch TFT liquid crystal display device was measured by TOPCON BM7. Compare the brightness of the liquid crystal film without broadband twist layer, and calculate the magnification of the increased brightness. (Viewing Angle Characteristics: Hue Change) 20 Viewing angle characteristics were derived from an EZ-CONTRAST viewing angle measuring machine manufactured by ELDIM, and Axy was derived and evaluated based on the following criteria. Δχγ = ((x〇 ^ Xl) (y〇-yi) 2) 05 Front chromaticity (xo, y), 60. Chroma (xl5yi) is good: viewing angle 60. The tone change ^ xy is below 0.04. 28 200419197 Bad: Perspective 60. The hue change Axy is above 0.04. (Durability) After putting in a broadband polarizer or polarizer for 500 hours in an environment of 80 ° C, 60 ° C, and 90% RH, visually determine the presence of powdery substances on the surface. In addition, when there are 5 powdery substances, there is a problem in optical use. Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polymerizable mesogen (a) 96 96 96 96 96 96 Pumpable polarimeter (b) 4 4 4 4 4 4 Liquid crystal mixture Photopolymerization Initiator (C) 4 / U worked 184 5 0 0 5 5 5; V force 'cattle worked 907 0 0.5 0 0 0 0 force' worked labor 369 0 0 0.05 0 0 0 UV absorber (in ° ^ 400) 0 0 0 0 0 1 solvent (cyclopentanone) 400 400 400 400 400 400 polymerization conditions UV illumination (mW / cm2) 3 3 11 50 3 50 temperature (° C) 120 120 120 80 40 80 Twisted layer liquid crystal film reflection band (nm) 450-890 510-970 520-920 710-880 720-870 710-860 Reflection bandwidth (nm) 440 460 400 170— 150 150 Long pitch (β m) Ultraviolet irradiation surface 0.54 0.57 0.56 0.52 0.52 0.51 Opposing surface 0.27 0.31 0.31 0.52 0.52 0.52 0.51 Evaluation of brightness is the rate of increase 1.3 1.3 1.3 1.1 1.1 1.1 Viewing angle characteristics, hue changes are good Good Good Bad Bad Financial properties (with or without precipitates) No No No No No No 29 200419197 Industrial Applicability The wideband twisted-layer liquid crystal film of the present invention can Use of a circularly polarizing plate (a polarizer reflective type). Circular polarizers can be used for linear polarizers, lighting devices, and liquid crystal display devices. 5 [Brief description of the drawings] Fig. 1 is a conceptual diagram of a polarizing plate used in the evaluation of Examples 1 to 3 and Comparative Examples 1 to 3. System 1: Polarizing plate, 2: λ / 4 plate, 3: Twisted layer liquid crystal film (circular polarizing plate) 4: Adhesive layer.
第2圖是實施例1所製作之扭層液晶膜之反射光譜。 10 第3圖是實施例2所製作之扭層液晶膜之反射光譜。 第4圖是實施例3所製作之扭層液晶膜之反射光譜。 第5圖是比較例1所製作之扭層液晶膜之反射光譜。 第6圖是比較例2所製作之扭層液晶膜之反射光譜。 第7圖是比較例3所製作之扭層液晶膜之反射光譜。 15 【圖式之主要元件代表符號表】FIG. 2 is a reflection spectrum of a twisted layer liquid crystal film produced in Example 1. FIG. 10 FIG. 3 is a reflection spectrum of the twisted layer liquid crystal film prepared in Example 2. FIG. 4 is a reflection spectrum of the twisted-layer liquid crystal film produced in Example 3. FIG. FIG. 5 is a reflection spectrum of a twisted-layer liquid crystal film produced in Comparative Example 1. FIG. FIG. 6 is a reflection spectrum of a twisted-layer liquid crystal film produced in Comparative Example 2. FIG. FIG. 7 is a reflection spectrum of a twisted-layer liquid crystal film produced in Comparative Example 3. FIG. 15 [Representation of the main components of the diagram]
1…偏光板 3…扭層液晶膜（圓偏光板） 2…又/4板 4…黏著層 301… polarizing plate 3… twisted layer liquid crystal film (circular polarizing plate) 2… and / 4 plate 4… adhesive layer 30