TW201311780A - Method for manufacturing patterned phase retardation film - Google Patents
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- 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
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Abstract
Description
本發明涉及一種圖案化相位延遲膜之製造方法,更具體地,涉及一種僅透過單次配向製程就能夠製備相位延遲膜之相位延遲膜的製備方法,以及圖案化相位延遲膜。 The present invention relates to a method of fabricating a patterned phase retardation film, and more particularly to a method of preparing a phase retardation film capable of preparing a phase retardation film by a single alignment process, and a patterned phase retardation film.
隨著資訊社會之發展,對顯示裝置之要求也以各種形態逐漸增加,目前已有多種平面顯示裝置被開發利用。其中,液晶顯示裝置為具有多樣化用途而被廣泛使用的平面顯示裝置。為了使液晶顯示裝置能在各種領域作為圖像顯示裝置使用,已有許多與之相關的技術已經發展,目前以具備重量輕、薄型與耗電低等特徵,以及能實現一定程度之高品質圖像為目的,正在進行技術開發。根據液晶之排列狀態和驅動方式,液晶顯示裝置可分為扭轉向列型(Twisted Nematic,TN)液晶顯示裝置、垂直配向型(Vertically Aligned,VA)液晶顯示裝置、平面切換型(In Plane Switching,IPS)液晶顯示裝置、以及光學補償彎曲型(Optically Compensated Bend,OCB)液晶顯示裝置等。這些液晶顯示裝置受到配向膜影響或者液晶本身性質影響,液晶初期形成預定排列,當施加電場時,液晶排列會改變,如此,因液晶具有光學各向異性,透過液晶之光線的偏光狀態隨著液晶排列狀態變化,利用偏光板將其顯示為透光量的差異,藉以顯示圖像。 With the development of the information society, the requirements for display devices have gradually increased in various forms, and various flat display devices have been developed and utilized. Among them, the liquid crystal display device is a flat display device which is widely used and has various uses. In order to enable liquid crystal display devices to be used as image display devices in various fields, many related technologies have been developed, and at present, they are characterized by light weight, thinness, low power consumption, and a high degree of quality image. For the purpose, technology development is underway. According to the arrangement state and driving mode of the liquid crystal, the liquid crystal display device can be classified into a twisted nematic (TN) liquid crystal display device, a vertically aligned (VA) liquid crystal display device, and a plane switching type (In Plane Switching, IPS) liquid crystal display device, and optically compensated bend (OCB) liquid crystal display device. These liquid crystal display devices are affected by the alignment film or the properties of the liquid crystal itself. The liquid crystal is initially formed in a predetermined arrangement. When an electric field is applied, the liquid crystal alignment changes. Thus, since the liquid crystal has optical anisotropy, the polarization state of the light transmitted through the liquid crystal follows the liquid crystal. The arrangement state changes, and it is displayed as a difference in the amount of light transmission by using a polarizing plate, thereby displaying an image.
在利用雙折射性之超扭轉向列型液晶顯示裝置 (STN-LCD)中,由於液晶單元本身具有雙折射性,因此可透過液晶單元之光線產生相位延遲(光線之畸變)。為此,STN面板中之相位延遲膜同時作為色補償膜來使用。起初,相位延遲膜係作為對橢圓偏光引起之稱為藍色模式(blue mode)或者黃色模式(yellow mode)之STN特有之干涉色(著染色)的光學色補償膜來開發。雖然薄膜電晶體液晶顯示裝置(TFT-LCD)不需要使用作為色補償膜之相位膜,但是,近來為了擴大視角或是提高清晰度,必須層疊使用各種相位延遲膜,因此需要開發一種具有多種功能之相位延遲膜。而且,隨著3D立體影像再現技術之發展,使用圖案化相位延遲膜使左眼影像和右眼影像之偏光方向不同之技術得到發展。相位延遲膜的製備技術包括有延伸技術和配向技術,當考慮所有偏光、反射、折射、干涉、衍射、散射之技術問題,需要使用配向技術。 Super twisted nematic liquid crystal display device using birefringence In (STN-LCD), since the liquid crystal cell itself has birefringence, a phase delay (distortion of light) is generated by light passing through the liquid crystal cell. For this reason, the phase retardation film in the STN panel is simultaneously used as a color compensation film. Initially, the phase retardation film was developed as an optical color compensation film for an interference color (staining) unique to an STN called a blue mode or a yellow mode caused by ellipsometry. Although a thin film transistor liquid crystal display device (TFT-LCD) does not require a phase film as a color compensation film, recently, in order to enlarge the viewing angle or improve the definition, various phase retardation films must be laminated, and thus it is necessary to develop a plurality of functions. Phase retardation film. Moreover, with the development of 3D stereoscopic image reproduction technology, a technique of using a patterned phase retardation film to make the polarization directions of the left-eye image and the right-eye image different has been developed. Phase retardation film preparation techniques include extension techniques and alignment techniques. When considering all the technical issues of polarization, reflection, refraction, interference, diffraction, and scattering, alignment techniques are required.
決定液晶初期排列之配向,主要係透過使用摩擦(rubbing)方法朝特定方向摩擦配向膜來完成。但是摩擦方法屬於機械性方法,很難精密地調整液晶初期配向狀態,且很難使液晶在各細微區域具有相互不同之傾斜角(Pretilt Angle)。因此,為了使基板之配向膜在每個微小單位區域均顯示不同方向,一般必須進行兩次配向製程,且該製程通常使用光罩來進行。 The alignment of the initial arrangement of the liquid crystals is mainly determined by rubbing the alignment film in a specific direction by using a rubbing method. However, the rubbing method is a mechanical method, and it is difficult to precisely adjust the initial alignment state of the liquid crystal, and it is difficult to make the liquid crystals have mutually different tilt angles in the respective fine regions. Therefore, in order for the alignment film of the substrate to display different directions in each of the minute unit regions, it is generally necessary to perform two alignment processes, and the process is usually performed using a photomask.
如日本授權專利第2650205號中揭示一種技術,其首先向一側方向實施摩擦製程後,以圖案化形態塗覆光罩,並朝向與第一次摩擦方向之相反方向進行摩擦,從而可在 塗覆之光罩上形成與第一次配向部分相反方向的開口部分。如此,第一次摩擦之後,在上層配向膜層上塗覆抗蝕劑(resist),並以具有圖案之形態照射光線,顯影以圖案曝光之抗蝕劑(resist),則上層側配向層被該顯影液蝕刻(etching),而下層側配向層被曝光,雖然經過第二次摩擦能夠形成與第一次摩擦不同方向之配向膜,然而製造過程複雜,且由於使用含有化學成分的顯影液,因此存有可能降低液晶配向性能的問題,以及具有以圖案化形態黏貼光罩過程中,難以精巧黏貼之缺點。 A technique disclosed in Japanese Patent No. 2650205, which firstly applies a rubbing process in one side direction, coats the photomask in a patterned form, and rubs in a direction opposite to the first rubbing direction, thereby enabling An opening portion in a direction opposite to the first alignment portion is formed on the coated photomask. Thus, after the first rubbing, a resist is applied on the upper alignment film layer, and the light is irradiated in a pattern to develop a pattern-exposed resist, and the upper layer side alignment layer is coated with the resist. The developing solution is etched, and the lower layer side alignment layer is exposed. Although the alignment film in a direction different from the first rubbing can be formed by the second rubbing, the manufacturing process is complicated, and since the developer containing the chemical component is used, There is a problem that it is possible to lower the alignment property of the liquid crystal, and it is difficult to be intimately adhered during the process of sticking the mask in a patterned form.
此外,日本授權專利第3596727號中揭示,在圖案化第一區域與第二區域中,首先用光罩塗覆第一區域,而對第二區域進行曝光後,進行第一次摩擦以去除光罩,之後設置雙折射層並進行第二次摩擦,以製備圖案化相位延遲膜。然而,製程步驟複雜,且圖案化光罩時,不同配向之區域間的分界線可能形成得不明確。 In addition, in Japanese Patent No. 3,596,727, it is disclosed that in the patterned first region and the second region, the first region is first coated with a photomask, and after the second region is exposed, the first rubbing is performed to remove the light. The cover was then provided with a birefringent layer and subjected to a second rub to prepare a patterned phase retardation film. However, the process steps are complicated, and when the reticle is patterned, the boundary between the regions of different alignments may be unclear.
每增加一次單次配向製程,就會使製程速度變慢,此為生產效率下降之主要原因,如此會導致產品價格提高。 Each additional one-time alignment process will slow down the process, which is the main reason for the decline in production efficiency, which will lead to an increase in product prices.
為解決如上問題,本發明研究出藉由印製不同種類之配向劑,並使其以一定間隔交錯,再透過單次配向製程製備圖案化相位延遲膜,其圖案之分界點的直線性優秀,因此可形成精巧之圖案,還可使製程簡化,進而完成本發明。 In order to solve the above problems, the present invention has been made to prepare a patterned phase retardation film by printing different kinds of alignment agents and interlacing them at regular intervals, and then through a single alignment process, and the boundary of the pattern is excellent in linearity. Therefore, a delicate pattern can be formed, and the process can be simplified to complete the present invention.
本發明之目的在於提供一種透過單次配向製程製備圖案化相位延遲膜之方法,以及一種圖案化相位延遲膜。 It is an object of the present invention to provide a method of preparing a patterned phase retardation film by a single alignment process, and a patterned phase retardation film.
本發明提供一種圖案化相位延遲膜(patterned phase retardation film)之製造方法,以及利用該方法所製備之圖案化相位延遲膜。該製備方法包括有下列步驟:(a)在基板上形成不同種類之配向劑,並使其以一定間隔交錯;(b)在形成有該配向劑之基板上進行配向劑之配向;以及(c)在該配向劑已完成配向之基板上,塗覆並硬化一光硬化性液晶單體組成物。 The present invention provides a method of fabricating a patterned phase retardation film, and a patterned phase retardation film prepared by the method. The preparation method comprises the steps of: (a) forming different kinds of alignment agents on the substrate and interlacing them at intervals; (b) performing alignment of the alignment agent on the substrate on which the alignment agent is formed; and (c) Applying and hardening a photocurable liquid crystal monomer composition on the substrate on which the alignment agent has been aligned.
根據本發明之圖案化相位延遲膜之製造方法,其係利用印刷技術在基板上形成具有不同配向性之兩種配向劑,並使其以一定間隔交錯,因此,與先前利用光罩之製程相比,本發明製得之圖案的直線性顯著提高,從而能夠製備精巧的相位延遲膜,而且僅透過單次配向性形成製程就能夠製備圖案化相位延遲膜,與先前技術相比,製程時間減少一半,因此其製程簡化以及降低成本之效果突出。 A method for fabricating a patterned phase retardation film according to the present invention, which uses a printing technique to form two kinds of alignment agents having different alignment properties on a substrate, and interlaces them at intervals, thereby, in contrast to the process of using the photomask Compared with the pattern obtained by the present invention, the linearity of the pattern is remarkably improved, so that a delicate phase retardation film can be prepared, and the patterned phase retardation film can be prepared only by a single alignment formation process, and the process time is reduced as compared with the prior art. Half, so its process simplification and cost reduction are outstanding.
圖1顯示以偏光顯微鏡觀察由實施例1所製備之圖案化相位延遲膜的圖像。 Fig. 1 shows an image of the patterned phase retardation film prepared in Example 1 observed with a polarizing microscope.
圖2顯示以偏光顯微鏡觀察由實施例2所製備之圖案化相位延遲膜的圖像。 2 shows an image of the patterned phase retardation film prepared in Example 2 observed by a polarizing microscope.
圖3顯示以偏光顯微鏡觀察由比較例1所製備之圖案化相位延遲膜的圖像。 Fig. 3 shows an image of the patterned phase retardation film prepared by Comparative Example 1 observed with a polarizing microscope.
只要未特別定義,本說明書中所使用之所有技術及科學用語,皆與本發明所屬技術領域中具有通常知識者所理 解者具有相同的含義。本說明書中所使用之命名法及下面描述之實驗方法係為本技術領域普遍使用之方法。 Unless otherwise defined, all technical and scientific terms used in the present specification are relevant to those of ordinary skill in the art to which the present invention pertains. The solver has the same meaning. The nomenclature used in the present specification and the experimental methods described below are methods generally used in the art.
本發明形成相位延遲膜之圖案時,並未使用光罩,而是使用兩種不同種類的配向劑,透過單次配向性形成製程來製備圖案化相位延遲膜。因此,本發明係有關於一種圖案化相位延遲膜(patterned phase retardation film)之製備方法,該方法包括有下列步驟:(a)在基板上形成不同種類之配向劑,並使其以一定間隔交錯;(b)在形成有該配向劑之基板上進行配向劑之配向;以及(c)在該配向劑完成配向之基板上,塗覆並硬化一光硬化性液晶單體組成物。 When the pattern of the phase retardation film is formed by the present invention, the patterned phase retardation film is prepared through a single alignment formation process using two different kinds of alignment agents without using a photomask. Accordingly, the present invention is directed to a method of preparing a patterned phase retardation film, the method comprising the steps of: (a) forming different kinds of alignment agents on a substrate and interlacing them at intervals (b) performing alignment of the alignment agent on the substrate on which the alignment agent is formed; and (c) coating and curing a photocurable liquid crystal monomer composition on the substrate on which the alignment agent is aligned.
為製備所需圖案間隔之相位延遲膜,應該考慮相位延遲膜所要求之圖案間隔,以形成以一定間距交錯之不同種類的配向劑。本發明之特徵在於,相互不同種類之配向劑所形成之間距可為40 μm至1000 μm,此係根據製備之圖案化相位延遲膜所需之圖案間隔,而可機動調整之間距。若將本發明之圖案化相位延遲膜安裝於液晶顯示面板上使用,需調整相位延遲膜之圖案間隔,使其能夠配合液晶顯示面板的圖像顯示線。作為用於實現立體影像之圖案化相位延遲膜之一具體例,本發明中係形成,例如印製以一定間隔交錯之不同種類的配向劑,前述間隔優選為180 μm至220 μm。所述以一定間隔交錯之不同種類的配向劑,意指本發明實施例中所製備的兩種配向劑,係按行交替且形成一定間隔。 To prepare a phase retardation film of the desired pattern spacing, the pattern spacing required for the phase retardation film should be considered to form different types of alignment agents that are staggered at a certain pitch. The present invention is characterized in that the distance between the mutually different kinds of alignment agents may be from 40 μm to 1000 μm, which is maneuverable according to the pattern interval required for the prepared patterned phase retardation film. When the patterned phase retardation film of the present invention is mounted on a liquid crystal display panel, the pattern interval of the phase retardation film needs to be adjusted to match the image display line of the liquid crystal display panel. As a specific example of the patterned phase retardation film for realizing a stereoscopic image, in the present invention, for example, different types of alignment agents which are staggered at regular intervals are formed, and the interval is preferably 180 μm to 220 μm. The different kinds of alignment agents which are staggered at a certain interval mean that the two kinds of alignment agents prepared in the examples of the present invention are alternately arranged in a row and formed at a certain interval.
印刷不同種類之配向劑的技術可利用噴墨印刷(inkjet)、微凹版印刷(micro-gravure)、平版印刷(offset)、以及網版(screen)印刷等。噴墨印刷為噴射墨或者凝聚墨後進行噴射之方法;微凹版印刷為凹版印刷法之一種,能夠顯示細微之深淺,屬於一種適合照片印刷之印刷法;平版印刷並不是在板上直接對被印刷物進行印刷,而是先在作為中間載體之橡膠布上轉印之後,再印刷到紙上的方法;網版印刷屬於不使用大規模機器之手動印刷的一種,係指在網版上黏貼材料,並一張一張地進行印刷,網版印刷也稱木版印刷。此外,亦可使用一種在透明基板上根據圖案間隔來選擇可進行印刷之技術,並能夠賦予相同效果之印刷法。本發明透過使用這種印刷法,精巧地以一定間隔印刷不同種類的配向劑,從而可製備出分界點之直線性優秀且圖案精巧的圖案化相位延遲膜。 Techniques for printing different types of alignment agents can utilize inkjet, micro-gravure, offset, and screen printing. Inkjet printing is a method of ejecting ink or ejecting ink and then ejecting it; microgravure printing is a kind of gravure printing method, which can display subtle shades, and belongs to a printing method suitable for photo printing; lithographic printing is not directly on the board. The printed matter is printed, but is first printed on the rubber cloth as the intermediate carrier, and then printed on the paper; the screen printing is a type of manual printing that does not use a large-scale machine, which means that the material is pasted on the screen. Printing is done one by one, and screen printing is also called woodblock printing. Further, a printing method in which a technique capable of printing is selected according to a pattern interval on a transparent substrate and which can impart the same effect can be used. According to the present invention, by using such a printing method, different types of alignment agents are finely printed at regular intervals, whereby a patterned phase retardation film having excellent linearity and fine pattern of a boundary point can be prepared.
若使在基板上以一定間隔印刷之不同種類的配向劑產生配向性,由於每種配向劑產生之配向性的方向不同,因此能夠形成交錯、間隔一定且具有不同方向之配向性的配向劑。這是由於不同種類之配向劑透過相同方向之配向性產生製程後,就會產生不同方向之配向性的理論。因此,若要形成具有一定間隔且相互正交之配向性,優選地,不同種類之配向劑中,其中一種配向劑具有平行於配向性形成方向的配向性,另一種配向劑具有垂直於配向性形成方向的配向性。 When the different types of alignment agents printed on the substrate at regular intervals are oriented, the direction of the alignment of each of the alignment agents is different, so that an alignment agent having a uniform interdigitation and a different orientation can be formed. This is due to the fact that different types of alignment agents produce processes in different directions through the alignment of the same direction. Therefore, in order to form an alignment with a certain interval and mutual orthogonality, preferably, among the different kinds of alignment agents, one of the alignment agents has an alignment parallel to the orientation of the alignment formation, and the other alignment agent has an orientation perpendicular to the alignment. Forming the orientation of the orientation.
根據配向性形成製程,會使用不同種類的配向劑。若 為產生配向性而使用摩擦(rubbing)製程,則應使用與其匹配的摩擦配向劑。摩擦製程係透過朝向一側方向以物理方式摩擦基板,而產生配向性的製程。由於其係使用一種如布或者尼龍材質之摩擦布直接接觸基板而賦予配向的方式,因此會產生如靜電、灰塵等透過接觸方式配向所致之問題,但是,與其他非接觸方式,如光配向、離子束等方式相比,卻展現出較快的製程速度。本發明之特徵在於,為進行配向性形成製程而使用摩擦製程時,該彼此不同之配向劑可分別為在與摩擦方向平行的方向上形成配向性的配向劑,以及在與摩擦方向垂直的方向上形成配向性的配向劑。 Different types of alignment agents are used depending on the alignment formation process. If To use an rubbing process to create an alignment, a matching anti-aligning agent should be used. The rubbing process creates a aligning process by physically rubbing the substrate toward one side. Since it uses a rubbing cloth such as cloth or nylon to directly contact the substrate to impart alignment, it may cause problems such as static electricity, dust, etc. through alignment, but other non-contact methods such as optical alignment Compared with the way of ion beam, it shows a faster process speed. The present invention is characterized in that, when a rubbing process is used for performing the alignment forming process, the mutually different alignment agents may respectively form an alignment agent in an direction parallel to the rubbing direction, and a direction perpendicular to the rubbing direction. An aligning alignment agent is formed on the surface.
本發明中,在與摩擦方向平行的方向上形成配向性的配向劑可選自由聚醯亞胺(polyimide)、聚乙烯醇(poly vinyl alcohol)、聚醯胺酸(polyamic acid)、聚醯胺(polyamide)以及聚氧乙烯(polyoxyethylene)構成之群組;在與摩擦方向垂直的方向上形成配向性的配向劑可選自由下面化學式1所示之聚苯乙烯(Polystyrene)、化學式2所示之聚-(4,4’-(9,9-芴基)二亞苯基環丁烷基四羧醯亞胺)(poly-(4,4’-(9,9-fluorenyl)diphenylene cyclobutanyltetracarboximide),以下簡稱CBDA-FDA PI)、化學式3所示之聚{對-亞苯基3,6-雙[4-(正-丁氧基)苯氧基]苯均四甲酸二醯亞胺}(poly{p-phenylene 3,6-bis[4-(n-butoxy)phenyloxy]pyromellitimide}, C4-PMDA-PDA PI)、化學式4所示之聚(2,7-(9,9’-螺二芴環丁基四羧醯亞胺)(poly(2,7-(9,9’-spirobifluorene cyclobutyltetracarboximide)),SBF-CBDA PI)、以及化學式5所示之聚(2,7-(9,9’-螺二芴4,4’-(六氟異丙烯)二鄰苯二甲醯亞胺)(poly(2,7-(9,9’-spirobifluorene 4,4’-(hexafluoroisopropylidene)diphthalimide)),SBF-6FDA)構成之群組,然而,本發明不限於此,只要是在與摩擦方向垂直的方向上形成配向性的配向劑,皆屬於本發明之範圍。本發明之一實施例中,當透過使用CBDA-FDA PI進行摩擦配向時,可確認在與摩擦方向垂直的方向上形成配向性。 In the present invention, an alignment agent which forms an alignment in a direction parallel to the rubbing direction may be selected from a polyimide, a polyvinyl alcohol, a polyamic acid, and a polydecylamine. a group composed of (polyamide) and polyoxyethylene; an alignment agent which forms an alignment in a direction perpendicular to the rubbing direction may be selected from polystyrene represented by the following Chemical Formula 1, and Chemical Formula 2 Poly-(4,4'-(9,9-fluorenyl)diphenylene cyclobutanyltetracarboximide), Hereinafter referred to as CBDA-FDA PI), poly{p-phenylene 3,6-bis[4-(n-butoxy)phenoxy]benzenetetracarboxylic acid diimide] (poly) {p-phenylene 3,6-bis[4-(n-butoxy)phenyloxy]pyromellitimide}, C4-PMDA-PDA PI), poly(2,7-(9,9'-spirobicyclobutyltetracarboxylic quinone imine) of formula 4 (poly(2,7-(9,9'-) Spirobifluorene cyclobutyltetracarboximide), SBF-CBDA PI), and poly(2,7-(9,9'-spirobifluorene 4,4'-(hexafluoroisopropene)) a group of amines (poly(2,7-(9,9'-spirobifluorene 4,4'-(hexafluoroisopropylidene)diphthalimide), SBF-6FDA), however, the invention is not limited thereto, as long as it is in friction with It is within the scope of the present invention to form an aligning alignment agent in the direction perpendicular to the direction. In one embodiment of the present invention, when the friction alignment is performed by using CBDA-FDA PI, it is confirmed that it is formed in a direction perpendicular to the rubbing direction. Orientation.
[化學式3]
本發明中該(b)步驟之配向性的產生,除了透過前述之摩擦製程以外,也可透過照射朝向一側方向偏光之光線,而產生配向性之光配向製程來實現。該製程係為僅透過光線照射製程就能夠產生配向之非接觸方式製程,一般可分為光可聚合化反應(photo-dimerization)、光致異構化反應(photo-isomerization)、以及光裂解(photo-decomposition)反應。尤其,光裂解反應之原理係 透過利用300 nm以下之短波長偏光光線,使配向膜之高分子鏈裂解,從而形成配向力。亦即,若將朝向一側方向偏光的光線照射於光配向劑上,則光配向劑之分子結構會變形而產生一定之配向性。用於光配向之光線可使用以10 mW/cm2至200 mW/cm2偏光的紫外線。惟,用於產生光配向的最小光強度,係可根據光配向劑之分子結構和光引發劑而改變。換言之,可使光配向劑之分子結構變形或是可活化引發劑的最小光能量,就可被稱作用於產生光配向的最小光強度。 In the present invention, the alignment of the step (b) can be achieved by, in addition to the above-described rubbing process, by illuminating the light that is polarized in one direction to produce an aligning optical alignment process. The process is a non-contact process capable of producing alignment only through a light irradiation process, and is generally classified into photo-dimerization, photo-isomerization, and photolysis (photolysis). Photo-decomposition) reaction. In particular, the principle of the photocleavage reaction is to cleave the polymer chain of the alignment film by using a short-wavelength polarized light of 300 nm or less to form an alignment force. That is, when light that is polarized toward one side is irradiated onto the photo-aligning agent, the molecular structure of the photo-aligning agent is deformed to produce a certain alignment property. For the light for photoalignment, ultraviolet rays polarized at 10 mW/cm 2 to 200 mW/cm 2 can be used. However, the minimum light intensity used to produce the optical alignment can vary depending on the molecular structure of the photoalignment agent and the photoinitiator. In other words, the molecular structure of the photo-aligning agent can be deformed or the minimum light energy of the activatable agent can be referred to as the minimum light intensity for generating the optical alignment.
當產生配向性之製程透過光配向來實現時,應使用與其匹配的光配向劑。本發明中,彼此不同之配向劑可分別為在與所照射之光線之偏光方向平行的方向上形成配向性的配向劑,以及在與所照射之光線之偏光方向垂直的方向上形成配向性的配向劑。前述在與所照射之光線之偏光方向平行的方向上形成配向性的配向劑可選自由聚醯亞胺(polyimide)、聚醯胺酸(polyamic acid)、聚降冰片烯(polynorbornene)、苯基馬來醯亞胺共聚物(phenylmaleimide copolymer)、聚偶氮苯(polyazobenzene)、聚乙烯亞胺(polyethyleneimide)、聚乙烯醇(polyvinyl alcohol)、聚乙烯(polyethylene)、聚苯乙烯(polystyrene)、聚亞苯基鄰苯二甲醯胺(polyphenylenephthalamide)、聚酯(polyester)、聚甲基丙烯酸甲酯(polymethyl methacrylate)、以及聚-(4,4’-(9,9-芴基)二亞苯基環丁烷基四羧醯亞胺 (poly-(4,4’-(9,9-fluorenyl)diphenylene cyclobutanyltetracarboximide),CBDA-FDA PI)構成之群組。前述在與所照射之光線之偏光方向垂直的方向上形成配向性的配向劑可選自由下面化學式6所示之氯甲基化聚醯亞胺(Chloromethylated polyimide,CMPI)以及化學式7所示之聚乙烯醇肉桂酸酯(polyvinylcinnamate,PVCi)構成之群組。然而,本發明並不限於此,只要是形成與照射之光線的偏光方向垂直之配向性的配向劑,均屬於本發明之範圍。 When an alignment process is achieved through light alignment, a matching optical alignment agent should be used. In the present invention, the mutually different alignment agents may respectively form an alignment agent in an orientation parallel to the polarization direction of the irradiated light, and form an alignment in a direction perpendicular to the polarization direction of the irradiated light. An aligning agent. The above-mentioned alignment agent which forms an alignment in a direction parallel to the polarization direction of the irradiated light may be selected from polyimide, polyamic acid, polynorbornene, and phenyl. Phenylmaleimide copolymer, polyazobenzene, polyethyleneimide, polyvinyl alcohol, polyethylene, polystyrene, poly Polyphenylenephthalamide, polyester, polymethyl methacrylate, and poly-(4,4'-(9,9-fluorenyl) diphenylene Butane-alkyltetracarboxylic quinone imine (Group of poly-(4,4'-(9,9-fluorenyl)diphenylene cyclobutanyltetracarboximide), CBDA-FDA PI). The above-mentioned alignment agent which forms an alignment in a direction perpendicular to the direction of polarization of the irradiated light may be selected from the group consisting of a chloromethylated polyimide (CMPI) represented by the following Chemical Formula 6 and a polymerization represented by Chemical Formula 7. A group consisting of polyvinylcinnamate (PVCi). However, the present invention is not limited thereto, and any alignment agent that forms an alignment perpendicular to the direction of polarization of the irradiated light is within the scope of the present invention.
氯甲基化聚醯亞胺(CMPI)係於現有之聚醯亞胺(Polyimide,PI)上置換氯甲基基團(chloromethyl group),具有比現有之聚醯亞胺溶解性優秀之優點,且溶劑之沸點高,因此在將膜硬化時,具有可使製程變容易之優點,且若照射偏光之UV,分子透過此光線會進行各向異性分解,而透過所生成之各向異性結構使液晶完成配向。與其 他光配向劑相比,聚醯亞胺(PI)一般具有熱穩定性高之優點。將4,4’-(六氟異丙烯)二酞酸酐(4,4’-(Hexafluoroisopropylidene)diphthalic anhydride,6FDA)和4,4’-二胺基二苯醚(4,4’-Diaminodiphenylether)溶解於N-甲基吡咯酮(NMP)並聚合後,使用吡啶(pyridine)和乙酸酐(Acetic anhydride)進行化學亞醯胺化反應(chemical imidization),之後使用氯甲基甲基醚(chloromethyl methyl ether,CMME)和四氯化錫(tin(IV)chloride)並經由氯甲基化反應(chloromethylation)之方法獲得氯甲基化聚醯亞胺(CMPI)。 Chloromethylated polyimine (CMPI) is a chloromethyl group substituted on the existing polyimide (PI), which has the advantage of being superior to the existing polyimine. Since the boiling point of the solvent is high, when the film is cured, there is an advantage that the process can be easily made, and if the polarized UV is irradiated, the molecules transmit the light to undergo anisotropic decomposition, and the anisotropic structure formed by the transmission is made. The liquid crystal completes the alignment. Instead of Compared to his photo-alignment agent, polyimine (PI) generally has the advantage of high thermal stability. Dissolve 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-diaminodiphenylether (4,4'-Diaminodiphenylether) After N-methylpyrrolidone (NMP) is polymerized, chemical imidization is carried out using pyridine and Acetic anhydride, followed by chloromethyl methyl ether. , CMME) and tin(IV) chloride and obtain chloromethylated polyimine (CMPI) via chloromethylation.
雖然作為光配向材料之聚乙烯醇肉桂酸酯(PVCi)被廣泛地認為屬於一種若照射偏光光線,則會在與光線之偏光方向垂直的方向上進行配向的材料,然而其光配向機制仍存在爭議,其爭議點為例如光照射引起之順反異構化(cis/trans isomerization)和二聚體(dimer)中苯基團(bezene group)之配向性。儘管存在前述爭議,關於光配向機制所主張的多個共同點為,配向是由於配向膜結構之各向異性與液晶之間的相互作用而產生。前述聚乙烯醇肉桂酸酯(PVCi)係透過醚化反應(etherification),在聚乙烯醇(Polyvinylalcohol)上置換肉桂酸酯基團(cinnamate group)而獲得。 Although polyvinyl cinnamate (PVCi), which is a photo-alignment material, is widely considered to be a material that aligns in a direction perpendicular to the direction of polarization of light when irradiated with polarized light, the optical alignment mechanism still exists. Controversy, the controversial points are, for example, the cis/trans isomerization caused by light irradiation and the alignment of the bezene group in the dimer. Despite the foregoing controversy, a number of in common with respect to the optical alignment mechanism is that the alignment is due to the interaction between the anisotropy of the alignment film structure and the liquid crystal. The polyvinyl cinnamate (PVCi) is obtained by dissolving a cinnamate group on polyvinyl alcohol by etherification.
本發明中可使用之基板優選為具有85%以上之光學透明度的基材,其材質係可選自由聚醚碸(polyether sulfone,PES)、聚醯亞胺(polyimide,PI)、環烯烴聚合物 (cyclo olefin polymer,COP)、聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、三醋酸纖維素(triacetyl cellulose,TAC)、聚碳酸酯(poly carbonate,PC)、以及玻璃構成之群組。該所限定之材料係為所屬技術領域一般可使用之材料,且屬於所屬技術領域中具有通常知識者可易於變換使用之材料,然而,前揭者並非固定條件。 The substrate usable in the present invention is preferably a substrate having an optical transparency of 85% or more, and the material thereof is optionally selected from polyether sulfone (PES), polyimide (PI), and cycloolefin polymer. (cyclo olefin polymer, COP), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polycarbonate (PC), and glass group. The materials defined herein are materials that are generally used in the art and are readily adaptable to those of ordinary skill in the art, however, the foregoing are not fixed conditions.
若欲賦予印刷於基板上之配向劑圖案化配向性,則可透過塗覆光硬化性液晶單體組成物,並進行硬化製程來完成相位延遲膜。將光硬化性液晶單體(reactive mesogen,RM)塗覆於圖案化配向之基板上,並照射紫外線使其硬化而形成光硬化性液晶單體層,使該光硬化性液晶單體層發揮使偏光光線之相位延遲的作用。本發明提供之圖案化相位延遲膜,其相位延遲方向及尺寸係根據圖案化部分而改變,並且,其相位延遲方向/尺寸係以一定間隔交替。 If the alignment agent to be printed on the substrate is to be patterned, the phase retardation film can be completed by applying a photocurable liquid crystal monomer composition and performing a curing process. A photocurable liquid crystal monomer (RM) is applied onto a patterned alignment substrate, and is irradiated with ultraviolet rays to be cured to form a photocurable liquid crystal monomer layer, and the photocurable liquid crystal monomer layer is allowed to function. The effect of the phase delay of the polarized light. The patterned phase retardation film provided by the present invention has a phase retardation direction and a size which are changed according to the patterned portion, and whose phase retardation direction/size is alternated at regular intervals.
本發明中,該光硬化性液晶單體組成物為具有聚合性基團之液晶化合物,尤其,可具有丙烯基、乙烯基醚基或者環氧化物之官能團,並且,為了增加聚合體之交聯,光硬化性液晶單體組成物的組成混合物可混合使用2個以上之聚合性官能團,例如具有單反應性對雙反應性化合物及/或非極性對極性化合物之聚合性液晶基團化合物,另外,還可透過改變其組成比例來變更排列分布。 In the present invention, the photocurable liquid crystal monomer composition is a liquid crystal compound having a polymerizable group, and particularly, may have a functional group of a propenyl group, a vinyl ether group or an epoxide, and in order to increase crosslinking of the polymer. a composition mixture of the photocurable liquid crystal monomer composition may be a mixture of two or more polymerizable functional groups, for example, a polymerizable liquid crystal group compound having a single reactive pair of a bireactive compound and/or a nonpolar polar compound, and You can also change the arrangement by changing the composition ratio.
可透過調整光硬化性液晶單體層之厚度來調整相位延遲大小,當相位延遲大小為λ/4時,可將線偏光轉換為圓偏光。該λ表示延遲相位之光線的波長符號。光硬化性 液晶單體之相位延遲在分子結構中係透過長軸和短軸之折射率來實現,其差異優選為0.7至3。此外,由於需要在基材上進行塗覆,因此應將一定量混合於有機溶劑中使用。該比例優選為5%~50%,顯而易見地,前述比例僅為易於塗覆之比例,並非固定值。 The phase delay can be adjusted by adjusting the thickness of the photo-curable liquid crystal cell layer. When the phase delay is λ/4, the linearly polarized light can be converted into circularly polarized light. This λ represents the wavelength symbol of the light of the delayed phase. Photohardenability The phase retardation of the liquid crystal monomer is achieved in the molecular structure by the refractive indices of the major axis and the minor axis, and the difference is preferably 0.7 to 3. Further, since it is necessary to coat the substrate, a certain amount should be mixed and used in an organic solvent. The ratio is preferably from 5% to 50%, and it is obvious that the aforementioned ratio is only a ratio which is easy to apply, and is not a fixed value.
本發明中,光硬化性液晶單體層可利用旋轉塗布(spin)、刮刀塗布(comma)、凹版塗布(gravure)、浸漬塗布(dip)、狹縫模具式塗布(slot die)、絹印(silk screen),噴墨印刷(inkjet printing)等習知塗覆製程進行。進行旋轉塗布時,利用以400 rpm至1000 rpm的轉速旋轉20秒至25秒,並以2500 rpm至3500 rpm的轉速旋轉70秒至80秒之方法,塗布0.5 μm至5 μm的厚度。塗覆後,在60℃條件下乾燥1分鐘後,利用照射20 mW/cm2之紫外線1分鐘來實現硬化製程,前揭條件係根據光硬化性液晶單體材料的特性而變。 In the present invention, the photocurable liquid crystal monomer layer can be subjected to spin coating, comma, gravure, dip coating, slot die coating, and stencil printing. Silk screen), inkjet printing, etc. are carried out by a conventional coating process. For spin coating, a thickness of 0.5 μm to 5 μm is applied by rotating at 400 rpm to 1000 rpm for 20 seconds to 25 seconds and rotating at 2500 rpm to 3500 rpm for 70 seconds to 80 seconds. After the coating, after drying at 60 ° C for 1 minute, the curing process was carried out by irradiating ultraviolet rays of 20 mW/cm 2 for 1 minute, and the pre-extraction conditions were changed depending on the characteristics of the photocurable liquid crystal monomer material.
本發明中,係使具有一定間隔圖案化之配向的方向相互垂直,當在此基板上塗覆及硬化液晶單體層,使其具有λ/4相位延遲效果時,所製備之圖案化相位延遲膜可將線偏光之光線轉換為左圓偏光和右圓偏光。將如此製得之相位延遲膜安裝於分離左眼圖像和右眼圖像之平面顯示器上,並使用左圓偏光與右圓偏光分離之偏光眼鏡,則可實現3D立體影像。 In the present invention, the direction in which the alignment is patterned with a certain interval is perpendicular to each other, and the patterned phase retardation film is prepared when the liquid crystal cell layer is coated and hardened on the substrate to have a λ/4 phase retardation effect. The linearly polarized light can be converted into a left circular polarized light and a right circular polarized light. The phase retardation film thus obtained is mounted on a flat-panel display that separates the left-eye image and the right-eye image, and the polarized glasses separated by the left circular polarized light and the right circular polarized light are used to realize a 3D stereoscopic image.
以下,透過實施例更詳細地說明本發明。對於所屬技術領域中具有通常知識者來說,應理解這些實施例僅係為 了例示本發明,而非限定本發明之範圍。 Hereinafter, the present invention will be described in more detail by way of examples. It will be understood by those of ordinary skill in the art that these embodiments are only The invention is illustrated by way of example and not of limitation.
本實施例中,係印刷具有不同配向方向性的兩種摩擦配向劑,透過單次摩擦製程製備圖案化相位延遲膜。 In this embodiment, two kinds of rubbing alignment agents having different alignment directions are printed, and a patterned phase retardation film is prepared through a single rubbing process.
準備尺寸5 cm x 5 cm的PI膜,利用噴墨印刷(inkjet printing)裝置(Inkjet Printer,Dimatix co.Ltd.供售)以200 μm之間隔進行帶狀印刷,使聚醯亞胺(polyimide)和CBDA-FDA PI兩種配向劑的寬度比達到1:1。將γ-丁內酯(gamma-Butyrolactone,GBL)、N-甲基吡咯酮(N-Methl-2-Pyrrolidone,NMP)以及2-丁氧基乙醇(2-Butoxyethanol,BC)以7:2:1的比例混合成溶液,若將其總合之質量比視為100時,將聚醯亞胺以2%之質量比溶解於前述溶液進行使用,並將CBDA-FDA-PI以2%之質量比溶解於γ-丁內酯(GBL)進行使用。 A PI film of 5 cm x 5 cm in size was prepared, and tape printing was performed at 200 μm intervals using an inkjet printing apparatus (Inkjet Printer, available from Dimatix co. Ltd.) to make polyimide. The width ratio of the two alignment agents to CBDA-FDA PI is 1:1. Γ-butyrolactone (GBL), N-Methl-2-Pyrrolidone (NMP) and 2-butoxyethanol (BC) at 7:2: The ratio of 1 is mixed into a solution, and if the mass ratio of the total is considered to be 100, the polyimine is dissolved in the above solution at a mass ratio of 2%, and the CBDA-FDA-PI is 2% by mass. It is used in comparison with γ-butyrolactone (GBL).
為了使該溶劑(solvent)充分焙燒,在200℃進行乾燥15分鐘後,對於所塗覆之條紋狀配向劑,以斜線方向實施摩擦製程。亦即,對該PI膜以45°的機械方向(Machanical direction)實施摩擦製程,該摩擦製程係於1 mm摩擦深度(depth)、600 rpm之輥旋轉速度、以及20 mm/sec之台階(stage)移動速度的條件下進行。 In order to sufficiently sterilize the solvent, after drying at 200 ° C for 15 minutes, a rubbing process was performed in a diagonal direction on the applied stripe-shaped alignment agent. That is, the PI film was subjected to a rubbing process in a 45° mechanical direction, which was at a depth of 1 mm, a roll rotation speed of 600 rpm, and a step of 20 mm/sec (stage). ) Under the condition of moving speed.
在已進行摩擦製程之配向劑頂面塗覆液晶單體(型號RMS-013C,Merck co.Ltd.供售)後,在60℃下乾燥1分鐘,使溶劑(solvent)充分揮發,並使用波長為365 nm的 紫外線以20 mW/cm2之強度進行1分鐘曝光製程,使光硬化性液晶單體固著於配向劑上。 After coating the top surface of the alignment agent that has been subjected to the rubbing process with a liquid crystal monomer (Model RMS-013C, available from Merck Co. Ltd.), it is dried at 60 ° C for 1 minute to sufficiently solvate the solvent and use the wavelength. The 365 nm ultraviolet light was subjected to a 1 minute exposure process at an intensity of 20 mW/cm 2 to fix the photocurable liquid crystal monomer to the alignment agent.
利用雙折射測定裝置(型號REMS-100,Sesim co.Ltd.供售)對由此所製備之相位延遲膜進行雙折射的測定,且透過偏光顯微鏡確認其寬度及分界點之直線特性。實驗反覆進行5次,下表1顯示測定之結果,圖1顯示以偏光顯微鏡所觀察之照片。 The phase retardation film thus prepared was subjected to measurement of birefringence by a birefringence measuring apparatus (Model REMS-100, available from Sesim Co. Ltd.), and the linear characteristics of the width and the boundary point were confirmed by a polarizing microscope. The experiment was repeated five times. Table 1 below shows the results of the measurement, and Figure 1 shows the photograph observed by a polarizing microscope.
圖1所示者為印刷有在與摩擦方向垂直之方向上進行配向之配向劑,以及在與摩擦方向平行之方向上進行配向之配向劑,且該等配向劑以一定間隔交錯,並僅利用單次摩擦配向製程所製得之圖案化相位延遲膜。 Fig. 1 shows an alignment agent printed in a direction perpendicular to the rubbing direction, and an alignment agent which is aligned in a direction parallel to the rubbing direction, and the alignment agents are staggered at regular intervals and used only A patterned phase retardation film produced by a single rubbing alignment process.
表1中之圖案寬度表示以單次摩擦配向製程製得之相位延遲膜之各圖案寬度的平均值,當將圖案之間的分界線視為直線時,分界點表示偏離前述直線的程度,以μm單位表示,而雙折射值表示對於550 nm之入射光的相位 延遲值。圖案寬度值顯示有5次實驗超出基準值200 μm的程度,以及是否具有均勻之平均值及標準偏差值。分界點及雙折射值則顯示有5次實驗的平均值。 The pattern width in Table 1 represents the average value of the pattern widths of the phase retardation films produced by the single rubbing alignment process. When the boundary line between the patterns is regarded as a straight line, the boundary point indicates the degree of deviation from the aforementioned straight line, The μm unit is expressed, and the birefringence value indicates the phase of the incident light for 550 nm. Delay value. The pattern width value shows the extent to which 5 experiments exceeded the reference value of 200 μm and whether there was a uniform average and standard deviation value. The cut-off point and birefringence value show the average of 5 experiments.
本實施例係以一定間隔印刷具有不同配向方向性的兩種光配向劑,透過單次光配向製程製備圖案化相位延遲膜。 In this embodiment, two kinds of photoalignment agents having different alignment directions are printed at regular intervals, and a patterned phase retardation film is prepared through a single photo-alignment process.
準備尺寸5 cm x 5 cm的PI膜,利用噴墨印刷(inkjet printing)裝置(Inkjet Printer,Dimatix co.Ltd.供售)以200 μm之間隔進行帶狀印刷,使聚-(4,4’-(9,9-芴基)二亞苯基環丁烷基四羧醯亞胺(poly-(4,4’-(9,9-fluorenyl)diphenylene cyclobutanyltertracarboximide),以下簡稱CBDA-FDA PI)和氯甲基化聚醯亞胺(Chloromethylated Polyimide,以下簡稱CMPI)兩種配向劑的寬度比達到1:1。將該CBDA-FDA-PI以2%之質量比溶解於γ-丁內酯(GBL)進行使用,且將CMPI以2%之質量比溶解於環己酮(cyclohexanone)進行使用。 A PI film of 5 cm x 5 cm in size was prepared, and tape printing was performed at 200 μm intervals using an inkjet printing apparatus (Inkjet Printer, supplied by Dimatix co. Ltd.) to make poly-(4, 4' -(9,9-fluorenyl)diphenylene cyclobutanyltertracarboximide (hereinafter referred to as CBDA-FDA PI) and The width ratio of the two kinds of alignment agents of Chloromethylated Polyimide (CMPI) is 1:1. The CBDA-FDA-PI is dissolved in γ-butyrolactone at a mass ratio of 2% (GBL). It was used, and CMPI was dissolved in cyclohexanone at a mass ratio of 2% for use.
為了使該溶劑(solvent)充分焙燒,在200℃進行乾燥15分鐘後,對所塗覆之條紋狀(stripe)配向劑,將光線偏光方向為斜線方向之波長254 nm之紫外線以30 mW/cm2之強度曝光5分鐘。 In order to sufficiently calcine the solvent, after drying at 200 ° C for 15 minutes, the applied stripe alignment agent was irradiated with ultraviolet rays having a wavelength of 254 nm in a diagonal direction at 30 mW/cm. The intensity of 2 is exposed for 5 minutes.
在透過曝光形成配向性之該配向劑頂面塗覆光硬化 性液晶單體(RM)(型號RMS-013C,Merck co.Ltd.供售)後,在60℃下乾燥1分鐘,使溶劑(solvent)充分揮發,並使用波長為365 nm的紫外線以20 mW/cm2之強度進行1分鐘曝光製程,使光硬化性液晶單體(RM)固著於在配向劑上。 The photocurable liquid crystal monomer (RM) (Model RMS-013C, available from Merck co. Ltd.) was coated on the top surface of the alignment agent formed by the exposure to form an alignment, and then dried at 60 ° C for 1 minute to obtain a solvent ( The solvent is sufficiently volatilized and exposed to ultraviolet light having a wavelength of 365 nm at a strength of 20 mW/cm 2 for 1 minute to fix the photocurable liquid crystal monomer (RM) to the alignment agent.
利用雙折射測定裝備(型號REMS-100,Sesim co.Ltd.供售)對由此製備之相位延遲膜進行雙折射的測定,且透過偏光顯微鏡確認其寬度及分界點之直線特性。實驗反覆進行5次,下表2顯示測定之結果,圖2顯示以偏光顯微鏡所觀察之照片。 The phase retardation film thus prepared was subjected to measurement of birefringence using a birefringence measuring apparatus (Model REMS-100, available from Sesim co. Ltd.), and the linear characteristics of the width and the boundary point were confirmed by a polarizing microscope. The experiment was repeated five times. Table 2 below shows the results of the measurement, and Figure 2 shows the photographs observed with a polarizing microscope.
圖2所示者為印刷有在與照射之偏光方向垂直之方向上進行配向之配向劑,以及在與照射之偏光方向平行之方向上進行配向之配向劑,且該等配向劑以一定間隔交錯,並僅利用單次光配向製程所製得之圖案化相位延遲膜。 Fig. 2 shows an alignment agent printed in a direction perpendicular to the direction of polarization of the irradiation, and an alignment agent which is aligned in a direction parallel to the direction of polarization of the irradiation, and the alignment agents are interlaced at regular intervals. And using only a single photo-alignment process to produce a patterned phase retardation film.
表2中之圖案寬度表示以單次光配向製程製得之相位延遲膜之各圖案寬度的平均值,當將圖案之間的分界線視為直線時,分界點表示偏離前述直線的程度,以μm單位表示,而雙折射值表示對於550 nm之入射光的相位延遲值。圖案寬度值顯示有5次實驗超出基準值200 μm的程度,以及是否具有均勻之平均值及標準偏差值。分界點及雙折射值則顯示有5次實驗的平均值。 The pattern width in Table 2 represents the average value of the pattern widths of the phase retardation films produced by the single-time optical alignment process. When the boundary line between the patterns is regarded as a straight line, the boundary point indicates the degree of deviation from the aforementioned straight line, The μm unit represents, and the birefringence value represents the phase delay value for incident light at 550 nm. The pattern width value shows the extent to which 5 experiments exceeded the reference value of 200 μm and whether there was a uniform average and standard deviation value. The cut-off point and birefringence value show the average of 5 experiments.
本比較例係利用先前技術製備圖案化相位延遲膜,並與根據本發明之製備方法所製備之圖案化相位延遲膜進行比較。 This comparative example uses a prior art technique to prepare a patterned phase retardation film and compare it to a patterned phase retardation film prepared in accordance with the preparation method of the present invention.
準備尺寸5 cm x 5 cm的PI膜,在頂面塗覆顯示平行於摩擦方向之配向特性的配向劑,亦即實施例1中使用的聚醯亞胺(polyimide),對於所塗覆之配向膜以1 mm摩擦深度(depth)、600 rpm之輥旋轉速度、以及20 mm/sec之台階(stage)移動速度的條件進行第一次摩擦之後,將開口部具有200 μm之寬度,非開口部具有150 μm之寬度,且顯示條紋狀(stripe)圖案之50 μm厚度的摩擦光罩置於其上,然後在與第一次摩擦方向垂直的方向上進行第二次摩擦。使用開口部與非開口部之寬度不同之光罩的原因在於,由於放置光罩後進行第二次摩擦時,因光罩之厚度導致第二次摩擦未能對非開口部之前側施加效果。因此,將光罩之開口部寬度製作得比非開口部寬度更寬。 A PI film having a size of 5 cm x 5 cm was prepared, and an alignment agent showing an alignment characteristic parallel to the rubbing direction, that is, a polyimide used in Example 1, was applied to the top surface for the applied alignment. The film was subjected to the first rubbing with a depth of 1 mm, a roll rotation speed of 600 rpm, and a step movement speed of 20 mm/sec, and the opening was 200 μm wide, and the non-opening portion was opened. A rubbing reticle having a width of 150 μm and exhibiting a thickness of 50 μm in a stripe pattern was placed thereon, and then a second rub was performed in a direction perpendicular to the first rubbing direction. The reason why the mask having a different opening width than the non-opening portion is used is that the second rubbing does not exert an effect on the front side of the non-opening portion due to the thickness of the mask when the second rub is performed after the mask is placed. Therefore, the width of the opening of the mask is made wider than the width of the non-opening.
在該摩擦配向之配向劑頂面塗覆液晶單體(型號RMS-013C,Merck co.Ltd.供售)後,在60℃下乾燥1分鐘,使溶劑(solvent)能夠充分揮發,並使用波長為365 nm的紫外線以20 mW/cm2之強度進行1分鐘曝光製程,使光硬化性液晶單體(RM)固著於配向劑上。 After the liquid crystal monomer (Model RMS-013C, available from Merck co. Ltd.) was coated on the top surface of the rubbing alignment agent, it was dried at 60 ° C for 1 minute to allow the solvent to be sufficiently volatilized, and the wavelength was used. The 365 nm ultraviolet light was subjected to a 1 minute exposure process at an intensity of 20 mW/cm 2 to fix the photocurable liquid crystal monomer (RM) to the alignment agent.
將以上述過程製備之圖案化相位延遲膜之圖案寬度、分界點、以及雙折射值顯示在表3中,實驗反覆進行5次。圖3係顯示以偏光顯微鏡(型號BX51,Olympus co.Ltd.供售)所觀察之結果。 The pattern width, the boundary point, and the birefringence value of the patterned phase retardation film prepared by the above procedure are shown in Table 3, and the experiment was repeated five times. Fig. 3 shows the results observed with a polarizing microscope (Model BX51, available from Olympus Co. Ltd.).
表3中之圖案寬度表示以兩次摩擦配向製程製得之相位延遲膜之各圖案寬度的平均值,當將圖案之間的分界線視為直線時,分界點為偏離前述直線的程度,以μm單位表示,雙折射值表示對於550 nm之入射光的相位延遲值。圖案寬度值顯示有5次實驗超出基準值200 μm的程度,以及是否具有均勻之平均值及標準偏差值。分界點及 雙折射值則顯示有5次實驗的平均值。 The pattern width in Table 3 represents the average value of the pattern widths of the phase retardation films obtained by the two rubbing alignment processes. When the boundary line between the patterns is regarded as a straight line, the boundary point is a degree of deviation from the aforementioned straight line, The μm unit indicates that the birefringence value represents the phase retardation value for incident light at 550 nm. The pattern width value shows the extent to which 5 experiments exceeded the reference value of 200 μm and whether there was a uniform average and standard deviation value. Demarcation point and The birefringence value shows the average of 5 experiments.
如表1、2及3所示,根據本發明之製備方法所製得之圖案化相位延遲膜與先前技術相比,圖案寬度能夠非常穩定地形成,且分界點值明顯低於先前技術,因此分界點之直線性顯著提高。 As shown in Tables 1, 2 and 3, the patterned phase retardation film produced by the preparation method of the present invention can form a pattern width very stably as compared with the prior art, and the boundary value is significantly lower than that of the prior art, The linearity of the demarcation point is significantly improved.
更具體而言,對於以200 μm為基準之圖案寬度,雖然實施例和比較例之平均值均顯示出沒有大幅超出200 μm,然而透過標準偏差比較可知,實施例1之圖案寬度的標準偏差為14.9,實施例2為6.2,而比較例1超過40,因此可知利用本發明之製備方法所製得之圖案化相位延遲膜的圖案寬度能夠非常均勻地形成。此外,從分界點偏離直線性的程度來看,實施例均低於15 μm,而比較例超過40 μm,因此可知本發明之相位延遲膜之分界點的直線性與先前技術相比顯著提高。由於圖案寬度及分界點會受到所選位置使用之印刷技術影響,因此可確認利用精巧之印刷技術進行該製程將會獲得良好效果。 More specifically, for the pattern width based on 200 μm, although the average values of the examples and the comparative examples all showed no significant exceeds 200 μm, the standard deviation of the pattern width of Example 1 was found to be 14.9, in Example 2, it was 6.2, and Comparative Example 1 exceeded 40. Therefore, it was found that the pattern width of the patterned phase retardation film obtained by the production method of the present invention can be formed very uniformly. Further, from the viewpoint of the degree of deviation of the boundary point from the linearity, the examples were all lower than 15 μm, and the comparative examples exceeded 40 μm, so that the linearity of the boundary point of the phase retardation film of the present invention was remarkably improved as compared with the prior art. Since the pattern width and the demarcation point are affected by the printing technology used in the selected location, it can be confirmed that the process using the delicate printing technology will achieve good results.
以上,詳細地描述了本發明內容之具體部分,對於所屬技術領域中具通常知識者而言,此種具體技術僅為優選實施例而已,本發明之範圍並不受限於此。換言之,本發明之實質範圍係藉由所附之申請專利範圍及其均等物予以定義。 The specific details of the present invention have been described in detail above, and the specific technology is only a preferred embodiment for those skilled in the art, and the scope of the present invention is not limited thereto. In other words, the true scope of the invention is defined by the scope of the appended claims and their equivalents.
圖1顯示以偏光顯微鏡觀察由實施例1所製備之圖案化相位延遲膜的圖像。 Fig. 1 shows an image of the patterned phase retardation film prepared in Example 1 observed with a polarizing microscope.
圖2顯示以偏光顯微鏡觀察由實施例2所製備之圖案化相位延遲膜的圖像。 2 shows an image of the patterned phase retardation film prepared in Example 2 observed by a polarizing microscope.
圖3顯示以偏光顯微鏡觀察由比較例1所製備之圖案化相位延遲膜的圖像。 Fig. 3 shows an image of the patterned phase retardation film prepared by Comparative Example 1 observed with a polarizing microscope.
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW101121586A TW201311780A (en) | 2011-06-16 | 2012-06-15 | Method for manufacturing patterned phase retardation film |
Country Status (3)
Country | Link |
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KR (1) | KR20120138991A (en) |
TW (1) | TW201311780A (en) |
WO (1) | WO2012173431A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109803995A (en) * | 2017-01-31 | 2019-05-24 | 株式会社Lg化学 | Polyimides and the polyimide film prepared therefrom for flexible display |
US10892428B2 (en) | 2017-10-31 | 2021-01-12 | Yungu (Gu'an) Technology Co., Ltd. | Flexible substrate and manufacturing method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR0175023B1 (en) * | 1995-10-31 | 1999-03-20 | 김광호 | Liquid crystal display and its fabrication method |
KR100969148B1 (en) * | 2003-05-30 | 2010-07-08 | 엘지디스플레이 주식회사 | A method of fabricating retardation film using of polarized uv |
KR20050004455A (en) * | 2003-07-02 | 2005-01-12 | 엘지.필립스 엘시디 주식회사 | A method of fabricating retardation film using of ion beam |
KR20110043459A (en) * | 2009-10-19 | 2011-04-27 | 주식회사 엘지화학 | Patterned retardation film and method for manufacturing the same |
-
2011
- 2011-06-16 KR KR1020110058485A patent/KR20120138991A/en not_active Application Discontinuation
-
2012
- 2012-06-15 TW TW101121586A patent/TW201311780A/en unknown
- 2012-06-15 WO PCT/KR2012/004753 patent/WO2012173431A2/en active Application Filing
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109803995A (en) * | 2017-01-31 | 2019-05-24 | 株式会社Lg化学 | Polyimides and the polyimide film prepared therefrom for flexible display |
CN109803995B (en) * | 2017-01-31 | 2021-11-02 | 株式会社Lg化学 | Polyimide and polyimide film for flexible display prepared therefrom |
US11319409B2 (en) | 2017-01-31 | 2022-05-03 | Lg Chem, Ltd. | Polyimide and polyimide film, prepared therefrom, for flexible display |
US10892428B2 (en) | 2017-10-31 | 2021-01-12 | Yungu (Gu'an) Technology Co., Ltd. | Flexible substrate and manufacturing method thereof |
Also Published As
Publication number | Publication date |
---|---|
KR20120138991A (en) | 2012-12-27 |
WO2012173431A3 (en) | 2013-03-28 |
WO2012173431A2 (en) | 2012-12-20 |
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