TWI390020B - Polymerised lc films with varying thickness - Google Patents
Polymerised lc films with varying thickness Download PDFInfo
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- TWI390020B TWI390020B TW93121208A TW93121208A TWI390020B TW I390020 B TWI390020 B TW I390020B TW 93121208 A TW93121208 A TW 93121208A TW 93121208 A TW93121208 A TW 93121208A TW I390020 B TWI390020 B TW I390020B
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
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- C09K19/00—Liquid crystal materials
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- C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor
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Description
本發明關於一種聚合液晶(LC)材料之薄膜,其具有至少兩個厚度不同之區域,例如,表面光柵之形式。本發明進一步關於一種製備此薄膜之方法,一種用於製備此薄膜之可聚合LC材料,及此薄膜於LC顯示器或其他光學或電子光學組件或裝置、裝飾性或安全應用之用途。The present invention relates to a film of a polymeric liquid crystal (LC) material having at least two regions of differing thickness, for example, in the form of a surface grating. The invention further relates to a method of making the film, a polymerizable LC material for preparing the film, and the use of the film in an LC display or other optical or electro-optical component or device, decorative or security application.
光柵一般用於顯示器工業,例如,將LC分子以較佳定向排列,如WO 01/40853號專利揭示之雙安定顯示器。同樣地,小心地製造之突起(表面浮雕光柵)可用以製造多域垂直排列(VA)顯示器,例如,如US 6,188,457號專利所揭示。通常需要光學微影術步驟以製造這些光柵,其中複雜之結構僅可藉耗時之多處理步驟建立,例如,參見EP 1 186 916及US 6,188,457號專利。此型方法之明顯缺點涉及成本。因此,已努力尋求製造光學及表面光柵之替代方式。Gratings are commonly used in the display industry, for example, to arrange LC molecules in a preferred orientation, such as the dual-amplitude display disclosed in WO 01/40853. Likewise, carefully fabricated protrusions (surface relief gratings) can be used to fabricate multi-domain vertical alignment (VA) displays, for example, as disclosed in U.S. Patent No. 6,188,457. Optical lithography steps are generally required to fabricate these gratings, and the complex structure can be established by only a consuming number of processing steps, for example, see EP 1 186 916 and US Pat. No. 6,188,457. The obvious disadvantage of this type of method involves cost. Therefore, efforts have been made to find alternative ways of fabricating optical and surface gratings.
一種方法已將小金屬球分散至基質中,而且使用高強度雷射將薄膜中切割成中空以製造光柵,如JP 2001-311810號專利所報告。不幸地,此方法仍耗時因此昂貴。一種替代方法為利用直接書寫UV或Ar+ 雷射技術。例如,以此方法在光可異構化偶氮苯為主分子中製造之光柵由,例如,D.Y.Kim、S.K.Tripathy、L.Li、與J.Kumar之Applied Physics Letters 66 1166(1995),P.Rochon、E.Batalla與A.Natansohn之Applied Physics Letters 66 136(1995)之文獻中 得知。以線性偏光可見光(通常來自Ar+ 雷射)照射此偶氮苯化合物造成偶氮鍵之選擇性異構化,導致伴隨之高度增加,因此及可能之表面浮雕光柵。不幸地,偶氮苯材料之顏色濃厚,所以不適合用於顯示器應用。One method has been to disperse small metal spheres into a matrix, and a high-intensity laser is used to cut the film into a hollow to produce a grating, as reported in JP 2001-311810. Unfortunately, this method is still time consuming and therefore expensive. An alternative approach is to use direct writing UV or Ar + laser technology. For example, a grating produced by photo-isomerisable azobenzene as a main molecule in this way is, for example, DYKim, SK Tripathy, L. Li, and J. Kumar, Applied Physics Letters 66 1166 (1995), P. Rochon It is known from E. Batalla and A. Natansohn, Applied Physics Letters 66 136 (1995). Irradiation of the azobenzene compound with linearly polarized visible light (usually from an Ar + laser) results in selective isomerization of the azo bond, resulting in a concomitant increase in height and, therefore, a surface relief grating. Unfortunately, azobenzene materials are thick and therefore not suitable for display applications.
一種替代方法為含可聚合基LC分子(稱為反應性液晶原或RMs)之緩慢光聚合。其亦具有不必使用偏光UV光之優點。在此系統之一個實例中,其揭示於US 4,877,717號專利,含丙烯酸酯RMs經光罩光聚合。此光罩合併兩個使所有或無UV光穿透之不同區域。如此導致UV暴露區域之RM薄膜之光聚合,而避UV光區域仍不聚合。為了試圖保持熱動力平衡,兩區(聚合及不聚合)開始擴散。然而,聚合物之擴散速率遠比單體緩慢。如此造成較多單體存在於UV暴露區域。此單體繼而聚合造成光柵結構,在此薄膜厚遠大於已暴露於UV之區域。不幸地,將此方法商業化之主要缺點為發生擴散製程之緩慢速率。An alternative method is slow photopolymerization of polymerizable LC molecules (referred to as reactive liquid crystals or RMs). It also has the advantage of not having to use polarized UV light. In one example of this system, which is disclosed in U.S. Patent 4,877,717, the acrylate-containing RMs are photopolymerized via a photomask. This reticle combines two different areas that allow all or no UV light to penetrate. This results in photopolymerization of the RM film in the UV exposed region, while the UV-protected region still does not polymerize. In an attempt to maintain thermodynamic equilibrium, the two zones (polymerization and non-polymerization) begin to spread. However, the rate of diffusion of the polymer is much slower than that of the monomer. This causes more monomer to be present in the UV exposed area. This monomer is then polymerized to create a grating structure where the film thickness is much greater than the area that has been exposed to UV. Unfortunately, the main disadvantage of commercializing this method is the slow rate at which diffusion processes occur.
因此,已有製備不具有上述先行技藝方法之缺點的光柵之有利方法之需求。本發明之目標為提供此方法及光柵,特別是具有以下使用不須偏光之汞燈光源、使用適合用於顯示器且提供光柵結構快速製造之材料之有利性質。其他目標由以下之說明而對專家為顯而易知的。Accordingly, there is a need for an advantageous method of fabricating a grating that does not have the disadvantages of the prior art methods described above. It is an object of the present invention to provide such a method and grating, in particular having the following advantageous properties of using a mercury lamp source that does not require polarization, using materials suitable for use in displays and providing rapid fabrication of the grating structure. Other objectives are apparent to the expert by the following description.
本發明之發明人已發現,以上之目標可藉由使用以下揭示之方法而達成。在依照本發明之方法中,可聚合液晶原化合物或反應性液晶原(RM)之混合物在暴露於未偏光或偏光UV光時進行高度變化。相對於先行技藝,此RM混合物 在暴露於UV照射時高度降低。The inventors of the present invention have found that the above objects can be attained by using the methods disclosed below. In the process according to the invention, the mixture of polymerizable liquid crystal precursor compounds or reactive liquid crystal precursors (RM) undergoes a high degree of change upon exposure to unpolarized or polarized UV light. This RM mixture is relative to the prior art It is highly reduced when exposed to UV radiation.
本發明關於一種藉由聚合含至少一種感光化合物之可聚合液晶(LC)材料而得之聚合物薄膜,其特徵為此薄膜包含至少兩個厚度不同之區域。The present invention relates to a polymer film obtained by polymerizing a polymerizable liquid crystal (LC) material containing at least one photosensitive compound, characterized in that the film comprises at least two regions of different thicknesses.
本發明進一步關於一種藉包含以下步驟之方法而得之聚合物薄膜:a)在基材上提供一層包含至少一種感光化合物之可聚合LC材料,b)視情況地將LC材料層排列成均勻定向,c)使此層中或在其選擇區域中之LC材料暴露於造成可異構化化合物之異構化之光射線,其較佳為UV射線,d)將此材料之至少一部份暴露區域中之LC材料聚合,因而將定向固定,及e)視情況地自基材去除聚合薄膜。The invention further relates to a polymer film obtained by the method comprising: a) providing a layer of polymerizable LC material comprising at least one photosensitive compound on a substrate, b) optionally arranging the layer of LC material into a uniform orientation , c) exposing the LC material in the layer or in its selected region to light rays that cause isomerization of the isomerizable compound, preferably UV rays, d) exposing at least a portion of the material The LC material in the region polymerizes, thus orientationally fixed, and e) optionally removes the polymeric film from the substrate.
本發明進一步關於一種以上及以下敘述之聚合物薄膜,其中可聚合液晶(LC)材料包含主體材料,其包含一或多種可聚合液晶原化合物,及至少一種與該主體材料互溶之可聚合感光化合物,而且其中聚合LC薄膜之厚度係藉由改變感光化合物之量及/或型式及/或主體材料之可聚合液晶原化合物之量及型式而控制。The invention further relates to a polymer film as described above and below, wherein the polymerizable liquid crystal (LC) material comprises a host material comprising one or more polymerizable liquid crystal precursor compounds, and at least one polymerizable photosensitive compound that is miscible with the host material And wherein the thickness of the polymerized LC film is controlled by varying the amount and/or type of the photosensitive compound and/or the amount and pattern of the polymerizable liquid crystal precursor compound of the host material.
本發明關於一種可聚合LC材料,其包含至少一種以上及以下敘述之感光化合物。The present invention relates to a polymerizable LC material comprising at least one of the photosensitive compounds described above and below.
本發明進一步關於一種以上及以下敘述之聚合物薄膜在 液晶顯示器(LCDs)或其他光學或電子光學組件或裝置、裝飾性或安全應用之用途。The invention further relates to a polymer film as described above and below Uses of liquid crystal displays (LCDs) or other optical or electro-optical components or devices, decorative or security applications.
本發明進一步關於一種以上及以下敘述之聚合物薄膜作為排列層、光學阻滯薄膜或光學導波器之用途。The invention further relates to the use of one or more of the polymer films described above as an alignment layer, an optical retardation film or an optical waveguide.
本發明進一步關於一種包含以上及以下敘述之聚合物薄膜之LCD。The invention further relates to an LCD comprising the polymer film described above and below.
在本申請案中使用之名詞「薄膜」包括自撐式(即,自由直立式)薄膜,其顯示或多或少明顯之機械安定性與撓性,及在支撐基材上或兩個基材之間之塗層或層。The term "film" as used in this application includes self-supporting (ie, free standing) films that exhibit more or less significant mechanical stability and flexibility, and on a support substrate or on two substrates. A coating or layer between them.
名詞「液晶或液晶原材料」或「液晶或液晶原化合物」應指包含一或多種棒形、板形或碟形液晶原基(即,具誘發液晶相行為之能力之基)之材料或化合物。具棒形或板形基之液晶(LC)化合物在此技藝亦已知為「桿形」液晶。具碟形基之液晶化合物在此技藝亦已知為「盤形」液晶。包含液晶原之化合物或材料本身未必具有液晶相。亦可為其僅在具其他化合物之混合物中,或在將液晶原化合物或材料或其混合物聚合時,顯示液晶相行為。The term "liquid crystal or liquid crystal material" or "liquid crystal or liquid crystal original compound" shall mean a material or compound containing one or more rod-shaped, plate-shaped or dish-shaped liquid crystal primaries (ie, groups having the ability to induce liquid crystal phase behavior). Liquid crystal (LC) compounds having a rod or plate shape are also known in the art as "rod" liquid crystals. Liquid crystal compounds having a dish-shaped basis are also known in the art as "disc-shaped" liquid crystals. The compound containing the liquid crystal or the material itself does not necessarily have a liquid crystal phase. It is also possible to exhibit liquid crystal phase behavior only when it is in a mixture with other compounds or when a liquid crystal original compound or material or a mixture thereof is polymerized.
為了簡化,名詞「液晶材料」在以下用於液晶材料及液晶原材料。For the sake of simplicity, the term "liquid crystal material" is used below for liquid crystal materials and liquid crystal materials.
名詞「反應性液晶原」(RM)表示可聚合液晶原化合物。The term "reactive mesogen" (RM) means a polymerizable liquid crystal original compound.
名詞「指引器」在此技藝為已知的,而且表示液晶材料中液晶原之長分子軸(在桿形化合物之情形)或短分子軸(在 盤形化合物之情形)之較佳定向方向。The term "director" is known in the art and represents the long molecular axis of the liquid crystal material in the liquid crystal material (in the case of rod-shaped compounds) or the short molecular axis (in The preferred orientation direction of the discotic compound).
名詞「平面結構」或「平面定向」指其中光軸實質上平行薄膜平面之薄膜。The term "planar structure" or "planar orientation" refers to a film in which the optical axis is substantially parallel to the plane of the film.
名詞「垂直結構」或「垂直定向」指其中光軸實質上垂直薄膜平面,即,實質上平行薄膜正交面之薄膜。The term "vertical structure" or "vertical orientation" refers to a film in which the optical axis is substantially perpendicular to the plane of the film, i.e., substantially parallel to the plane of the film.
名詞「傾斜結構」或「傾斜定向」指其中光軸以相對薄膜平面為0至90度間之角度θ傾斜之薄膜。The term "inclined structure" or "tilted orientation" refers to a film in which the optical axis is inclined at an angle θ between 0 and 90 degrees with respect to the plane of the film.
名詞「斜面結構」或「斜面定向」表示如以上定義之傾斜定向,其中傾斜角度在垂直薄膜平面之方向另外以0至90°之範圍單調地改變,較佳為由最小值至最大值。The term "beveled structure" or "beveled orientation" means an oblique orientation as defined above, wherein the angle of inclination is monotonically varied in the direction of the vertical film plane by a range of 0 to 90, preferably from a minimum to a maximum.
斜面薄膜之傾斜角度在以下示為平均傾斜角度θave ,除非另有所述。The inclination angle of the bevel film is shown below as the average inclination angle θ ave unless otherwise stated.
平均傾斜角度θave
定義如下
其中θ'(d')為在薄膜內厚度d'之局部傾斜角度,及d為薄膜之總厚度。Where θ'(d') is the local inclination angle of the thickness d' in the film, and d is the total thickness of the film.
在定向均勻之包含單軸正雙折射率液晶材料之平面、垂直及傾斜光學薄膜中,薄膜之光軸係以液晶材料之指引器表示。In a uniformly oriented planar, vertical, and oblique optical film comprising a uniaxial positive birefringence liquid crystal material, the optical axis of the film is represented by a director of liquid crystal material.
名詞「感光」指在光照射時因反應改變其結構或形狀之化合物,其包括但不限於光異構化、光誘發2+2環加成、光燃排列或相似之光降解過程。此外,感光化合物可為可聚合或光可聚合。The term "photosensitive" refers to a compound that changes its structure or shape upon reaction by light, including but not limited to photoisomerization, photoinduced 2+2 cycloaddition, photo-fired alignment, or similar photodegradation processes. Further, the photosensitive compound may be polymerizable or photopolymerizable.
依照本發明之方法適合提供具界定結構(例如,厚度樣式或表面浮雕光柵)之LC薄膜。在聚合時維持LC材料之原始排列,因此可製造具表面浮雕光柵之薄膜及雙折射率增加之薄膜。The method according to the invention is suitable for providing an LC film having a defined structure (for example, a thickness pattern or a surface relief grating). The original alignment of the LC material is maintained during polymerization, so that a film having a surface relief grating and a film having an increased birefringence can be produced.
依照本發明之薄膜較佳為藉由一種包含上述步驟a)至e)之方法製備。步驟a)至e)可依照專家已知且敘述於文獻中之標準步驟進行。The film according to the invention is preferably prepared by a process comprising the steps a) to e) above. Steps a) to e) can be carried out according to standard procedures known to the expert and described in the literature.
此可聚合LC材料包含感光化合物及主體材料。The polymerizable LC material comprises a photosensitive compound and a host material.
感光化合物較佳為液晶原或LC化合物,而且進一步較佳為包含一或多種鍵聯(視情況地經間隔基)至液晶原核之可聚合基之可聚合化合物。The photosensitive compound is preferably a liquid crystal or an LC compound, and further preferably a polymerizable compound containing one or more bond groups (optionally via a spacer) to a polymerizable group of the liquid crystal pronucleus.
主體材料為包含一或多種可聚合液晶化合物(RMs)之液晶原或液晶材料。較佳為,主體材料在聚合前顯示液晶相行為。The host material is a liquid crystal or liquid crystal material comprising one or more polymerizable liquid crystal compounds (RMs). Preferably, the host material exhibits a liquid crystal phase behavior prior to polymerization.
LC材料係如薄薄膜提供於基材上,在此其可藉此技藝已知之工具或方法排列成均勻定向,或在此其可自發地排列。然後使LC材料,或其選擇區域,暴露於造成可異構化化合物改變其形狀(例如,因E-Z異構化)之指定波長之放射線,例如,UV射線。然後藉原處聚合將LC材料在照射區域中或在全部層中之定向固定。異構化及聚合步驟導致LC材料之異構化及聚合區域中厚度之戲劇性減小。The LC material is provided as a thin film on a substrate, where it can be arranged in a uniform orientation by means of tools or methods known in the art, or where it can be spontaneously aligned. The LC material, or a selected region thereof, is then exposed to radiation at a specified wavelength that causes the isomerizable compound to change its shape (eg, due to E-Z isomerization), for example, UV radiation. The orientation of the LC material in the illuminated area or in all layers is then fixed by in situ polymerization. The isomerization and polymerization steps result in isomerization of the LC material and a dramatic reduction in thickness in the polymerization zone.
由於定向LC層之光學阻滯示為LC材料之層厚d與雙折射率△n之積d.△n,厚度及雙折射率之變化亦可造成LC材料之照射部份之阻滯變化。起初LC材料層之阻滯值係藉由層厚 與LC材料個別成分之型式及量之適當選擇而控制。Since the optical retardation of the oriented LC layer is shown as the product of the layer thickness d of the LC material and the birefringence Δn. Δn, the change in thickness and birefringence can also cause a retardation change in the irradiated portion of the LC material. Initially, the retardation value of the LC material layer is determined by the layer thickness. Controlled by appropriate choice of the type and amount of individual components of the LC material.
LC材料層中之異構化程度及厚度範圍可藉由改變LC材料個別成分之型式及量,或藉由改變放射線劑量、強度、時間及/或功率而控制。藉由在放射線來源與LC層間施加光罩,亦可製備具有彼此不同之指定厚度值之區域樣式或像素之薄膜。例如,使用簡單、單色光罩可製造包含兩個不同厚度值之薄膜。使用灰階光罩可製造具多個厚度不同區域之較複雜薄膜。在得到所需之厚度值後,將LC層聚合。以此方式可製造具範圍為起初LC層至較小值之厚度值之聚合物阻滯薄膜。The degree of isomerization and thickness range in the LC material layer can be controlled by varying the type and amount of individual components of the LC material, or by varying the radiation dose, intensity, time, and/or power. A film having a pattern of regions or pixels having a specified thickness value different from each other can also be prepared by applying a photomask between the radiation source and the LC layer. For example, a film containing two different thickness values can be fabricated using a simple, monochromatic mask. A more complex film with multiple regions of different thicknesses can be fabricated using a gray scale reticle. After the desired thickness value is obtained, the LC layer is polymerized. In this way, a polymer retardation film having a thickness value ranging from the initial LC layer to a small value can be produced.
主體材料較佳為可聚合向列或近晶LC材料,特別是向列材料,而且較佳為包含至少一種二或多反應性非對掌RM及視情況地一或超過一種單反應性非對掌RMs。藉由使用二或多反應性RMs而得到交聯之薄膜,其呈現對抗外部影響(如溫度或溶劑)之高機械安定性及高光學性質安定性。包含交聯LC材料之薄膜因此特佳。Preferably, the host material is a polymerisable nematic or smectic LC material, particularly a nematic material, and preferably comprises at least one di- or poly-reactive non-pair RM and optionally one or more than one mono-reactive non-pair Palm RMs. Crosslinked films are obtained by using two or more reactive RMs which exhibit high mechanical stability against high external influences such as temperature or solvent and high optical stability. Films comprising crosslinked LC materials are therefore particularly preferred.
用於本發明之可聚合液晶原單、二與多反應性化合物可藉本質已知且敘述,例如,有機化學之標準作業之方法製備,例如,Houben-Weyl之Methoden der organischen Chemie,Thieme-Verlag,Stuttgart。Polymerizable liquid crystal monomers, di- and poly-reactive compounds for use in the present invention can be prepared by methods known per se and described, for example, by standard methods of organic chemistry, for example, Methoden der organischen Chemie of Houben-Weyl, Thieme-Verlag, Stuttgart.
可與依照本發明之化合物一起在可聚合LC混合物中作為單體或共單體之適當可聚合液晶原化合物之實例揭示於,例如,WO 93/22397、EP 0 261 712、DE 195 04 224、WO 95/22586、WO 97/00600、及GB 2 351 734號專利。然 而,揭示於這些文件中之化合物僅視為實例,其不應限制本發明之範圍。Examples of suitable polymerizable liquid crystal precursor compounds which may be used as monomers or comonomers in the polymerizable LC mixture together with the compounds according to the invention are disclosed, for example, in WO 93/22397, EP 0 261 712, DE 195 04 224, WO 95/22586, WO 97/00600, and GB 2 351 734. Of course However, the compounds disclosed in these documents are only considered as examples, and should not limit the scope of the invention.
特別有用之可聚合液晶原化合物(反應性液晶原)之實例示於以下表,然而,其應僅為描述性且絕不意圖限制,而是解釋本發明:
在上式中,P為可聚合基,較佳為醯基、甲基丙烯酸基、乙烯基、乙烯氧基、丙烯基醚、環氧基、氧環丁烷、或苯乙烯基,x與y為1至12之相同或不同整數,A為1,4-伸苯基,其視情況地經L1 單、二或三取代,或1,4-伸環己基,u與v彼此獨立地為0或1,Z0 為-COO-、-OCO-、-CH2 CH2 -、-CH=CH-、-C≡C-、或單鍵,R0 為極性基或非極性基,Ter為類萜基團,例如,基,Chol為膽固醇基,L、L1 與L2 彼此獨立地為H、F、Cl、CN,或視情況地具1至7個C原子之鹵化烷基、烷氧基、烷基羰基、烷基碳氧基、烷氧基羰基、或烷氧基羰氧基,及r為0、1、2、3、或4。上式中之苯環視情況地經1、2、3、或4個L基取代。In the above formula, P is a polymerizable group, preferably a mercapto group, a methacryl group, a vinyl group, a vinyloxy group, a propenyl ether, an epoxy group, an oxycyclobutane, or a styryl group, and x and y. Is the same or different integer from 1 to 12, and A is a 1,4-phenylene group, which is optionally substituted by L 1 mono-, di- or tri- or 1,4-cyclohexylene, and u and v are independently of each other. 0 or 1, Z 0 is -COO-, -OCO-, -CH 2 CH 2 -, -CH=CH-, -C≡C-, or a single bond, R 0 is a polar group or a non-polar group, and Ter is Quinone-like group, for example, a group, Chol is a cholesteryl group, and L, L 1 and L 2 are, independently of each other, H, F, Cl, CN, or optionally a halogenated alkyl group having 1 to 7 C atoms, an alkoxy group, an alkylcarbonyl group, An alkylcarboxy group, an alkoxycarbonyl group, or an alkoxycarbonyloxy group, and r is 0, 1, 2, 3, or 4. The benzene ring in the above formula is optionally substituted by 1, 2, 3, or 4 L groups.
關於此點,名詞「極性基」表示選自F、Cl、CN、NO2 、OH、OCH3 、OCN、SCN,視情況地具至多4個C原子之氟化烷基羰基、烷氧基羰基、烷基羰氧基、或烷氧基羰氧基,或具1至4個C原子之單、寡或多氟化烷基或烷氧基。名詞「非極性基」表示具1或更多個,較佳為1至12個C原子之視情況地鹵化烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰氧基、或烷氧基羰氧基,其不涵蓋於以上之「極性基」定義中。In this regard, the term "polar group" means a fluorinated alkylcarbonyl group or alkoxycarbonyl group selected from the group consisting of F, Cl, CN, NO 2 , OH, OCH 3 , OCN, SCN, optionally having up to 4 C atoms. An alkylcarbonyloxy group, or an alkoxycarbonyloxy group, or a mono-, oligo or polyfluorinated alkyl or alkoxy group having 1 to 4 C atoms. The term "non-polar group" means, optionally, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group having 1 or more, preferably 1 to 12, C atoms. Or alkoxycarbonyloxy, which is not covered by the definition of "polar group" above.
較佳為,主體材料包含-0至97%,較佳為25至70%之一或多種具一個可聚合基(單反應性)之液晶原化合物,-3至100%,較佳為5至75%,非常較佳為10至50%之一或多種具二或更多個可聚合基(二反應性)之液晶原化合物。Preferably, the host material comprises from 0 to 97%, preferably from 25 to 70%, or a plurality of liquid crystal original compounds having a polymerizable group (single reactivity), from -3 to 100%, preferably from 5 to 75%, very preferably from 10 to 50%, or a plurality of liquid crystal original compounds having two or more polymerizable groups (di-reactive).
特佳為非對掌可聚合液晶原化合物,特別是式R1至R13及R18,非常較佳為式R1及R18。Particularly preferred are non-p-polymerizable liquid crystal original compounds, particularly the formulae R1 to R13 and R18, and very preferably R1 and R18.
如上所述,LC材料層中之厚度變化可藉由改變主體材料中化合物之型式及量而控制。As noted above, the thickness variation in the LC material layer can be controlled by varying the type and amount of compound in the host material.
特佳為主體材料包含不超過75%,非常較佳為不超過50%之二反應性化合物。Particularly preferred is a host material comprising no more than 75%, very preferably no more than 50% of the two reactive compounds.
適當之感光化合物在此技藝為已知的。例如,其為在光照射時顯示光異構化、光燃重組或2+2環加成、或其他光降解過程之化合物。特佳為光可異構化化合物。這些化合物之實例包偶氮苯、苯甲醛肟、偶氮次甲烷、二苯乙烯、螺哌喃、螺崿啶、浮精酐、二芳基乙烯、桂皮酸酯。進一步實例為2-亞甲基茚-1-酮,例如,如EP 1 247 796號專利所述,及(貳-)亞苄基-環烷酮,例如,如EP 1 247 797號專利所述。Suitable photosensitive compounds are known in the art. For example, it is a compound which exhibits photoisomerization, photo-fired recombination or 2+2 cycloaddition, or other photodegradation process upon light irradiation. Particularly preferred are photoisomerizable compounds. Examples of such compounds include azobenzene, benzaldehyde oxime, azomethine, stilbene, spiropyran, spirulina, phlegonic anhydride, diarylethene, cinnamate. Further examples are 2-methyleneindole-1-ones, for example as described in EP 1 247 796, and (贰-)benzylidene-cycloalkanones, for example as described in EP 1 247 797 .
特佳為,光可異構化化合物係選自桂皮酸酯,特別是包含至少一種桂皮酸酯基之可聚合液晶原化合物或反應性液晶原(RMs),例如,如GB 2 314 839、EP 03007236.7、US 5,770,107、或GB 2 388 600號專利所述。非常較佳為LC材料包含一或多種選自下式之桂皮酸酯RMs
其中P、A、R0 、Y、L1 、L2 與v具有上示之意義,及Sp為具1至12個C原子之間隔基,例如,伸烷基或伸烷氧基。Wherein P, A, R 0 , Y, L 1 , L 2 and v have the meanings indicated above, and Sp is a spacer having 1 to 12 C atoms, for example, an alkyl group or an alkylene group.
可聚合或反應性基P較佳為選自乙烯基、丙烯酸基、甲基丙烯酸基、氧雜丁烷基、或環氧基,特佳為丙烯酸基。The polymerizable or reactive group P is preferably selected from the group consisting of a vinyl group, an acryl group, a methacryl group, an oxabutyl group, or an epoxy group, and particularly preferably an acrylic group.
間隔基Sp較佳為具至多10個C原子之伸烷基或伸烷氧基,其為未取代或經F、Cl、Br、I、或CN單或多取代。非常較佳之Sp基為伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、與伸辛基。The spacer Sp is preferably an alkyl or alkylalkoxy group having up to 10 C atoms which is unsubstituted or mono- or polysubstituted by F, Cl, Br, I, or CN. Very preferred Sp groups are exoethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.
Y較佳為CN或Cl或OCH3 。Y is preferably CN or Cl or OCH 3 .
R0 較佳為具3至8個C原子之直鏈烷基或烷氧基,特別是正丙基、正丁基、正己基、正庚基、或正辛基。R 0 is preferably a linear alkyl or alkoxy group having 3 to 8 C atoms, particularly n-propyl, n-butyl, n-hexyl, n-heptyl or n-octyl.
如上所述,LC材料層中之厚度變化可藉由改變感光化合物之型式及量而控制。因此發現,含指定型式及量之感光化合物之可聚合LC材料對於本發明之目的特別有用,因為這些材料可易於控制及調整聚合物薄膜厚度。As described above, the thickness variation in the LC material layer can be controlled by changing the type and amount of the photosensitive compound. Thus, it has been found that polymerizable LC materials containing the specified type and amount of photosensitive compound are particularly useful for the purposes of the present invention because these materials can be easily manipulated and adjusted for polymer film thickness.
特佳為含以上定義之非極性終端基R0 之桂皮酸酯RMs。非常較佳為式IIIa與IVa之桂皮酸酯RMs。進一步較佳為包含二或更多種可聚合基之桂皮酸酯,特別是式V。Particularly preferred is a cinnamic acid ester RMs having a non-polar terminal group R 0 as defined above. Very preferred are the cinnamate RMs of formulae IIIa and IVa. Further preferred is a cinnamic acid ester comprising two or more polymerizable groups, in particular Formula V.
較佳為,可聚合LC材料包含5至90%,非常較佳為10至60%,最佳為15至35%之一或多種感光化合物,較佳為桂皮酸酯RMs,最佳為選自式IIIa、IVa與V。用以造成LC材料中光異構化之光射線視感光化合物之型式而定,而且可易由熟悉此技藝者選擇。顯示以UV射線誘發之光異構化之化合物通常較佳。例如,對於如式III、IV與V之桂皮酸酯化合物,一般使用波長為UV-A範圍(320-400奈米)或波長為365奈米之UV射線。Preferably, the polymerizable LC material comprises from 5 to 90%, very preferably from 10 to 60%, most preferably from 15 to 35%, of one or more photosensitive compounds, preferably cinnamate RMs, most preferably selected from the group consisting of Formula IIIa, IVa and V. The light ray used to cause photoisomerization in the LC material depends on the type of photographic compound and can be readily selected by those skilled in the art. Compounds which exhibit UV-induced photoisomerization are generally preferred. For example, for cinnamate compounds of formulas III, IV and V, UV radiation having a wavelength in the UV-A range (320-400 nm) or a wavelength of 365 nm is generally used.
最適照射時間及射線劑量視使用之LC材料之型式,特別是LC材料中感光化合物之型式及量而定。The optimum irradiation time and radiation dose depend on the type of LC material used, especially the type and amount of the photosensitive compound in the LC material.
依照本發明之薄膜之厚度較佳為0.01至3微米,非常較佳為0.02至0.2微米。The thickness of the film according to the present invention is preferably from 0.01 to 3 μm, very preferably from 0.02 to 0.2 μm.
薄膜內之厚度變化、或高度或表面光柵較佳為0.01至2微米,非常較佳為0.02至0.2微米。The thickness variation, or height or surface grating within the film is preferably from 0.01 to 2 microns, very preferably from 0.02 to 0.2 microns.
依照本發明之薄膜可用於,例如,液晶材料排列用之表面浮雕光柵。The film according to the present invention can be used, for example, as a surface relief grating for aligning liquid crystal materials.
為了製備聚合之LC薄膜,較佳為將可聚合LC混合物塗覆於基材上,較佳為排列成平面定向,及原處聚合,例如,藉由暴露於熱或光化射線,以將LC分子之定向固定。排列及固化係在混合物之LC相中進行。此技術在此技藝為已知的且敘述於,例如,D.J.Broer等人之Angew.Makromol. Chem.183,(1990),45-66。In order to prepare a polymerized LC film, it is preferred to apply the polymerizable LC mixture to a substrate, preferably in a planar orientation, and in situ polymerization, for example, by exposure to heat or actinic radiation to LC The orientation of the molecules is fixed. The alignment and curing are carried out in the LC phase of the mixture. This technique is known in the art and is described, for example, by Angew. Makromol of D.J. Broer et al. Chem. 183, (1990), 45-66.
LC材料之排列可藉由,例如,在塗覆同時或之後使材料剪切,對塗覆材料施加磁或電場,或將表面活性化合物加入LC材料,處理其上塗覆此材料之基材而完成。排列技術之回顧示於,例如,I.Sage之”Thermotropic Liquid Crystals”,G.W.Gray編著,John Wiley & Sons,1987,第75-77頁,及T.Uchida與H.Seki之”Liquid Crystals-Applications and Uses Vol.3”,B.Bahadur編著,World Scientific Publishing,Singapore 1992,第1-63頁。排列材料及技術之回顧示於J.Cognard之Mol.Cryst.Liq.Cryst.78,Supplement 1(1981),第1-77頁。The LC material can be arranged by, for example, shearing the material simultaneously or after coating, applying a magnetic or electric field to the coating material, or adding the surface active compound to the LC material, and processing the substrate on which the material is coated. . A review of alignment techniques is shown, for example, in "Thermotropic Liquid Crystals" by I. Sage, edited by GWGray, John Wiley & Sons, 1987, pp. 75-77, and "Liquid Crystals-Applications by T. Uchida and H. Seki". And Uses Vol. 3", edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pp. 1-63. A review of the alignment materials and techniques is shown in J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pp. 1-77.
在較佳具體實施例中,可聚合LC材料包含誘發或增強LC分子在基材上之平面排列之添加劑。較佳為,此添加劑包含一或多種界面活性劑。適當之界面活性劑敘述於,例如,J.Cognard之Mol.Cryst.Liq.Cryst.78 ,Supplement 1,1-77(1981)。特佳為非離子性界面活性劑,非常較佳為氟烴界面活性劑,例如,市售氟烴界面活性劑Fluorad FC-171®(得自3M Co.),或Zonyl FSN®(得自DuPont),及GB 0227108.8號專利所述之界面活性劑。In a preferred embodiment, the polymerisable LC material comprises an additive that induces or enhances the planar alignment of the LC molecules on the substrate. Preferably, the additive comprises one or more surfactants. Suitable surfactants are described, for example, in J. Cognard, Mol. Cryst. Liq. Cryst. 78 , Supplement 1, 1-77 (1981). Particularly preferred are nonionic surfactants, very preferably fluorocarbon surfactants such as the commercially available fluorocarbon surfactant Fluorad FC-171® (available from 3M Co.) or Zonyl FSN® (available from DuPont) And the surfactant described in the patent GB 0227108.8.
可聚合LC材料較佳為溶解或分散於溶劑中,較佳為有機溶劑中。然後將溶液或分散液塗覆於基材上,例如,藉旋塗或其他已知技術,及在聚合前將溶劑蒸發。The polymerizable LC material is preferably dissolved or dispersed in a solvent, preferably an organic solvent. The solution or dispersion is then applied to the substrate, for example, by spin coating or other known techniques, and the solvent is evaporated prior to polymerization.
可聚合LC材料可另外包含聚合黏合劑或一或多種可形成聚合黏合劑之單體及/或一或多種分散輔劑。適當之黏合 劑及分散輔劑揭示於,例如,WO 96/02597號專利。然而,特佳為不含黏合劑或分散輔劑之LC材料。The polymerizable LC material may additionally comprise a polymeric binder or one or more monomers that form a polymeric binder and/or one or more dispersing adjuvants. Proper bonding Agents and dispersion aids are disclosed, for example, in WO 96/02597. However, it is particularly preferred to be an LC material that does not contain a binder or a dispersing adjuvant.
聚合係藉由暴露於熱或光化射線而發生。光化射線表示以光照射,如UV光、IR光或可見光,以X-射線或γ射線照射,或以高能量粒子照射,如離子或電子。較佳聚合係藉非吸收波長之UV照射進行。至於光化射線之來源,例如,可使用單UV燈或一組UV燈。在使用高燈功率時可減少固化時間。另一種可能之光化射線來源為雷射,例如,UV雷射、IR雷射或可見光雷射。Polymerization occurs by exposure to heat or actinic radiation. The actinic ray means irradiation with light such as UV light, IR light or visible light, irradiation with X-rays or gamma rays, or irradiation with high energy particles such as ions or electrons. Preferably, the polymerization is carried out by UV irradiation at a non-absorption wavelength. As for the source of actinic rays, for example, a single UV lamp or a group of UV lamps can be used. Curing time can be reduced when using high lamp power. Another possible source of actinic radiation is a laser, such as a UV laser, an IR laser or a visible laser.
聚合較佳為在光化射線波長處吸收之引發劑存在下進行。例如,在藉UV光聚合時,可使用在UV照射下分解而產生啟動聚合反應之自由基或離子之光引發劑。在將具丙烯酸或甲基丙烯酸基之可聚合材料固化時,較佳為使用自由基光引發劑,在將具乙烯基、環氧化物與氧雜丁烷基之可聚合材料固化時,較佳為使用陽離子性光引發劑。亦可使用在加熱時產生啟動聚合之自由基或離子之聚合引發劑。至於自由基聚合之光引發劑,例如,可使用市售Irgacure 651、Irgacure 184、Darocure 1173、或Darocure 4205(均得自Ciba Geigy AG),而在陽離子性光聚合之情形,可使用市售UVI 6974(Union Carbide)。可聚合LC材料中之光引發劑濃度較佳為0.1至10%,非常較佳為0.5至5%。The polymerization is preferably carried out in the presence of an initiator which absorbs at the wavelength of the actinic ray. For example, when polymerizing by UV light, a photoinitiator which decomposes under UV irradiation to generate a radical or ion which initiates a polymerization reaction can be used. When curing an acrylic or methacrylic based polymerizable material, it is preferred to use a radical photoinitiator, preferably when curing a polymerizable material having a vinyl group, an epoxide and an oxytetraalkyl group. To use a cationic photoinitiator. It is also possible to use a polymerization initiator which generates a radical or an ion which initiates polymerization upon heating. As the photoinitiator for radical polymerization, for example, commercially available Irgacure 651, Irgacure 184, Darocure 1173, or Darocure 4205 (all available from Ciba Geigy AG) can be used, and in the case of cationic photopolymerization, commercially available UVI can be used. 6974 (Union Carbide). The photoinitiator concentration in the polymerisable LC material is preferably from 0.1 to 10%, very preferably from 0.5 to 5%.
可聚合LC材料可另外包含一或多種其他適當之成分,例如,觸媒、感化劑、安定劑、抑制劑、鏈轉移劑、共反應單體、表面活性化合物、潤滑劑、濕潤劑、分散劑、疏水 性劑、黏著劑、流動改良劑、消泡劑、除氣劑、稀釋劑、反應性稀釋劑、輔劑、著色劑、染料、或顏料。The polymerisable LC material may additionally comprise one or more other suitable ingredients, for example, catalysts, sensitizers, stabilizers, inhibitors, chain transfer agents, co-reactive monomers, surface active compounds, lubricants, wetting agents, dispersants Hydrophobic Agents, adhesives, flow improvers, defoamers, deaerators, diluents, reactive diluents, adjuvants, colorants, dyes, or pigments.
依照本發明之薄膜亦可用於上述以外目的之光學或電子光學裝置,例如,作為排列層、光學濾光器或偏光光束分離器,或裝飾性或安全應用。Films in accordance with the present invention may also be used in optical or electro-optical devices other than those described above, for example, as alignment layers, optical filters or polarized beam splitters, or as decorative or security applications.
例如,其可在裝飾性或安全應用中作為雙折射標記、影像或圖樣。本發明之方法可在薄膜中產生僅在交錯偏光鏡之間可見到之負像。這些薄膜之較佳用途為作為安全標記或安全螺紋以鑑定及防止有價值之文件之偽造,或用於隱藏影像、資訊或圖樣之辨認。因此可應用於消費性產品或家用物體、車體、箔、包裝材料、布料或紡織織物,併入塑膠中,或應用於有價值之文件,如鈔票、信用卡或ID卡、國家ID文件、執照、或任何具金錢價值之產品,如郵票、車票、股票、支票等。For example, it can be used as a birefringence mark, image or pattern in decorative or security applications. The method of the present invention produces a negative image in the film that is only visible between staggered polarizers. The preferred use of these films is as a security mark or security thread to identify and prevent the forgery of valuable documents, or to hide the identification of images, information or graphics. It can therefore be applied to consumer products or household objects, car bodies, foils, packaging materials, fabrics or textile fabrics, incorporated into plastics, or applied to valuable documents such as banknotes, credit cards or ID cards, national ID documents, licenses. Or any product of monetary value, such as stamps, tickets, stocks, checks, etc.
作為雙折射標記之用途特佳為提供於或直接製備於反射性基材上之圖樣化薄膜,例如,金屬或金屬化薄膜或箔,如EP 02019792.7號專利所述。The use as a birefringent marking is particularly preferred as a patterned film provided on or directly on a reflective substrate, for example, a metal or metallized film or foil, as described in EP 02019792.7.
以下之實例應描述本發明而非限制之。The following examples should describe the invention without limitation.
如下調配可聚合LC主體混合物H1。The polymerizable LC host mixture H1 was formulated as follows.
H1:H1:
(1) 39.40%(2) 24.60%(3) 24.60%(4) 9.72% Irgacure 651 1.00% Fluorad FC171 0.60% Irganox 1076 0.08%(1) 39.40% (2) 24.60% (3) 24.60% (4) 9.72% Irgacure 651 1.00% Fluorad FC171 0.60% Irganox 1076 0.08%
藉由將各混合物M1至M5(詳述於表1及2)於二甲苯之50重量%溶液旋塗(3,000 RPM,30秒)於擦光聚醯亞胺(JSR AL1054)/玻璃載物片上,而製造一組兩個薄膜。在一種情形,將薄膜立即光聚合(UV-A,20米瓦公分-2 ,60秒,N2 )而無進一步處理。在另一種情形,將旋塗薄膜在光聚合(UV-A,20米瓦公分-2 ,60秒,N2 )前暴露於光異構化步驟(365奈米,20米瓦公分-2 ,300秒)。By spin coating (3,000 RPM, 30 seconds) of each mixture of M1 to M5 (described in Tables 1 and 2) in a 50% by weight solution of xylene on a polishing polyimine (JSR AL1054) / glass slide And make a set of two films. In one case, the film was immediately photopolymerized (UV-A, 20 mW - 2 , 60 sec, N 2 ) without further processing. In another case, the spin-coated film was exposed to a photoisomerization step (365 nm, 20 mW - 2 ) before photopolymerization (UV-A, 20 mW -2 , 60 sec, N2). 300 seconds).
聚合薄膜之阻滯係藉由在平行偏光鏡之間測量薄膜透光度而測定,薄膜之定向軸對偏光鏡軸為45°之角度。光學透光度係以Oriel Spectrograph測量420-800奈米之波長範圍,其使用鎢燈作為光源。薄膜之阻滯係藉由將觀察之強度測 量代入理論而計算。聚合薄膜中向列指引器之平均傾斜角係藉由在將樣品由-60°轉動至+60°時,測量薄膜之阻滯(如上所述)如光束入射角度之函數而計算(參見O.Parri等人之Mol.Cryst.Liq.Cryst,第332卷,第273頁,1999)。The retardation of the polymeric film was determined by measuring the transmittance of the film between parallel polarizers, the orientation axis of the film being at an angle of 45 to the axis of the polarizer. The optical transmittance is measured by the Oriel Spectrograph in the wavelength range of 420-800 nm, which uses a tungsten lamp as a light source. Film retardation by measuring the intensity of the observation The quantity is substituted into the theory and calculated. The average tilt angle of the nematic director in the polymeric film is calculated by measuring the retardation of the film (as described above) as a function of the angle of incidence of the beam by rotating the sample from -60° to +60° (see O. Parri et al., Mol. Cryst. Liq. Cryst, Vol. 332, p. 273, 1999).
圖1顯示混合物M1之薄膜之阻滯圖,其為(a)不異構化及(b)在光聚合前異構化。其他之混合物M2-5在異構化前後均產生類似之阻滯圖。Figure 1 shows a retardation diagram of a film of mixture M1 which is (a) isomerized and (b) isomerized prior to photopolymerization. The other mixture, M2-5, produced a similar block diagram before and after isomerization.
比較圖1之阻滯圖,顯然異構化及不異構化薄膜均為排列良好之平面薄膜。在基材處及在空氣界面處計算之傾斜角度相同(在實驗誤差內)。測量各薄膜而在基材處得到約1°及在空氣界面處為0°之傾斜角度。兩個阻滯圖間之重要差異為正交入射0°之值。異構化薄膜具較低之值,即,將薄膜異構化可降低阻滯而不改變起初之液晶原排列。Comparing the block diagrams of Figure 1, it is apparent that the isomerized and non-isomerized films are well-aligned planar films. The tilt angles calculated at the substrate and at the air interface are the same (within experimental error). Each film was measured to obtain an angle of inclination of about 1° at the substrate and 0° at the air interface. The important difference between the two block diagrams is the value of the normal incidence of 0°. The isomerized film has a lower value, i.e., isomerization of the film reduces retardation without changing the original alignment of the liquid crystal.
為了證明高度變化,使用KLA-Tencor Alphastep 500外形計測量各混合物M1至M5之異構化及不異構化薄膜之厚度。對於這些測量,將薄薄膜片刮開且得到通過此刮線之外形計軌跡,造成測得薄膜之高度(厚度)。各混合物由於異構化步驟造成之厚度(△d)、阻滯(△R)與雙折射率(△n)之差示於表2。To demonstrate height variations, the isomerization of the various mixtures M1 to M5 and the thickness of the non-isomerized film were measured using a KLA-Tencor Alphastep 500 profiler. For these measurements, the thin film sheet was scraped off and a trajectory was measured through the scratch line to cause the height (thickness) of the film to be measured. The difference between the thickness (Δd), retardation (ΔR) and birefringence (Δn) of each mixture due to the isomerization step is shown in Table 2.
如實例1所述由混合物M4製備異構化薄膜。使此薄膜經含圖2a所示符號之光罩異構化。在符號正下方之薄膜不暴露於UV光因此不異構化,而其餘之薄膜則異構化。在此異構化步驟後,移除光罩且將全部薄膜光聚合。An isomerized film was prepared from mixture M4 as described in Example 1. The film was isomerized via a reticle containing the symbol shown in Figure 2a. The film directly below the symbol is not exposed to UV light and is therefore not isomerized, while the remaining film is isomerized. After this isomerization step, the reticle was removed and the entire film was photopolymerized.
圖2b敘述在交叉偏光鏡之間觀看時,經圖2a之光罩異構化後產生之薄膜影像。Figure 2b illustrates a film image produced by isomerization of the reticle of Figure 2a when viewed between crossed polarizers.
圖2c敘述顯示薄膜之不同區域之厚度而測定高度相對差之外形圖。此外形係使用KLA-Tencor Alphastep 500機及附帶之軟體測量,並且取自圖2b之線所標示,穿越轉移至薄膜中之字母'e'之長度方向。Figure 2c depicts a plot of the relative height difference as a function of the thickness of the different regions of the film. In addition, the KLA-Tencor Alphastep 500 machine and the attached software measurement were used, and as indicated by the line in Figure 2b, the length of the letter 'e' transferred to the film was crossed.
圖2c明確地顯示,使用光罩可製造不同高度之區域。Figure 2c clearly shows that areas of different heights can be made using a reticle.
進一步實驗亦已顯示,薄膜中產生之高度差之程度可藉由控制到達樣品之UV光強度(例如,使用灰階光罩)而控制。以此方式,可建構較詳細之結構。例如,將具有可使0%、50%及100%之入射UV光通過之條之灰階光罩置於樣品與光源之間。將薄膜照射繼而聚合。接收全部UV劑量之薄膜區域薄至接收50%之UV者之約兩倍。同樣地,接收50%劑量之區域薄至不接收UV者之約兩倍。因為UV劑量直接影響薄膜厚,可使用UV透光度之值不同(如代替0%及100%或另增)之具一定範圍區域之光罩在RM薄膜中製造精巧之光柵。Further experiments have also shown that the degree of height difference produced in the film can be controlled by controlling the intensity of the UV light reaching the sample (e.g., using a gray scale mask). In this way, a more detailed structure can be constructed. For example, a gray scale reticle having a strip of 0%, 50%, and 100% incident UV light can be placed between the sample and the light source. The film is irradiated and then polymerized. The area of the film that receives the full UV dose is as thin as about twice that of the 50% UV recipient. Similarly, the area receiving the 50% dose is about twice as thin as the one who does not receive the UV. Since the UV dose directly affects the thickness of the film, a refractory grating can be fabricated in the RM film using a mask having a range of UV transmittance values (eg, instead of 0% and 100% or otherwise).
如下調配可聚合LC主體混合物H2。The polymerizable LC host mixture H2 was formulated as follows.
H2:H2:
(1) 60.00%(2) 11.70%(3) 11.70%(4) 15.00% Irgacure 651 1.00% Fluorad FC171 0.60%(1) 60.00% (2) 11.70% (3) 11.70% (4) 15.00% Irgacure 651 1.00% Fluorad FC171 0.60%
將化合物P3、P4與P6以不同之濃度溶於主體混合物H1與H2中而得不同之可聚合LC混合物。The polymerizable LC mixture was obtained by dissolving the compounds P3, P4 and P6 in different concentrations in the main mixture H1 and H2.
如實例1所述由這些混合物製備聚合物薄膜且測量其厚度。結果敘述於圖3(H1)及圖4(H2)。可見到厚度變化視主體及光可異構化化合物而定,具有非極性終端己基之化合物P4產生最大之厚度減小,及具有極性終端CN基之化合物P6產生最小之厚度減小。A polymer film was prepared from these mixtures as described in Example 1 and the thickness thereof was measured. The results are shown in Fig. 3 (H1) and Fig. 4 (H2). It can be seen that the thickness variation depends on the host and the photoisomerizable compound, and the compound P4 having a non-polar terminal hexyl group produces the greatest thickness reduction, and the compound P6 having a polar terminal CN group produces a minimum thickness reduction.
圖1a與1b顯示得自如本發明實例1所述之異構化(a)與未異構化(b)可聚合混合物之薄膜之阻滯圖。Figures 1a and 1b show block diagrams of films from the isomerized (a) and unisomerized (b) polymerizable mixtures as described in Example 1 of the present invention.
圖2a顯示用於製備依照本發明實例2之薄膜之光罩。Figure 2a shows a reticle for preparing a film according to Example 2 of the present invention.
圖2b顯示依照本發明實例2之薄膜之照片。Figure 2b shows a photograph of a film according to Example 2 of the present invention.
圖2c顯示依照本發明實例2之薄膜之厚度外形。Figure 2c shows the thickness profile of a film according to Example 2 of the present invention.
圖3與4顯示如實例3所述依照本發明之方法,對於由可聚合及光可異構化混合物製備之不同薄膜之厚度變化相對桂皮酸酯濃度。Figures 3 and 4 show the thickness variation versus cinnamate concentration for different films prepared from polymerizable and photoisomerizable mixtures in accordance with the method of the present invention as described in Example 3.
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