201121999 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種高分子液晶配向添加物及具有高分 子液晶配向添加物的液晶顯示裝置的製造方法，尤指一種 無突起結構的基板上協同配向層使液晶材料產生一預傾 角。 【先前技術】 液晶顯示器具有輕薄化以及節能等特性，遂為取代傳 統陰極射線管（Cathode Ray Tube, CRT)顯示器，隨著不同尺 寸製造上的發展，已廣泛為市場所接受並應用於各式電子 產品，包含行動通訊裝置、筆記型電腦、以及家庭影音撥 放裝置等。然而，相較於前述陰極射線管顯示器，液晶顯 示器仍具有可視角上的限制以及反應時間延遲等問題。 為能克服前述液晶顯示器的問題，一種多重垂直配向 型液晶顯示裝置（Multi-domain Vertically Aligned Liquid Crystal Display, MVA-LCD)已被開發出來，如中華民國第 1308660號專利案、第1299057號專利案、第1275883號專 利案、第1249061號等。該種多重垂直配向型液晶顯示裝 置係利用容置液晶材料的二基板表面，增設複數個突起結 構（protrusion)，使液晶材料於未受電壓驅動下即可產生一 預傾角（pretilt angle)。如此，當施加電壓時，各個液晶單體 依據電場而產生相應偏轉，藉由不同偏轉方向的液晶單體 相互補強，來增加視角，避免傳統液晶螢幕因為僅具有單 一偏轉方向使觀賞者由不同角度觀看產生亮度差而限制視 角的問題。 一般多重垂直配向型液晶顯示裝置須依賴基板上設置 複數突起結構使液晶單體產生預傾角，因此，於製造上往 201121999 在透過薄膜沉積、黃光製程或㈣等方式來形成突起結 構。如此-來’勢必增加工業製造上的複雜度以及加工成 本。另外’設置於基板上的突起結構亦會導致光線穿透上 的障礙，降低液晶顯示器晝面亮度的均勻。 【發明内容】 -本發明之主要目的，在於去除多重垂直配向型液晶顯 不裝置中基板上的突起結構，並且避免因去除突起結構後 影響多重垂直配向能力的表現所造成視角狹小的問題。為 達上述㈣’本發明提供一種高分子液晶配向添加物 括有：201121999 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a liquid crystal alignment additive and a liquid crystal display device having a polymer liquid crystal alignment additive, and more particularly to a substrate-free synergistic structure. The alignment layer produces a pretilt angle for the liquid crystal material. [Prior Art] The liquid crystal display has the characteristics of light weight and energy saving, and has replaced the traditional cathode ray tube (CRT) display. With the development of different sizes, it has been widely accepted by the market and applied to various types. Electronic products, including mobile communication devices, notebook computers, and home audio and video playback devices. However, compared with the aforementioned cathode ray tube display, the liquid crystal display still has problems such as limitation in viewing angle and delay in reaction time. In order to overcome the problems of the aforementioned liquid crystal display, a multi-domain Vertically Aligned Liquid Crystal Display (MVA-LCD) has been developed, such as the Patent No. 1308660 of the Republic of China, and the Patent No. 1299057 , Patent No. 1275883, No. 1249061, and the like. The multi-vertical alignment type liquid crystal display device utilizes a plurality of protrusion structures on the surface of the two substrates for accommodating the liquid crystal material, so that the liquid crystal material can generate a pretilt angle without being driven by a voltage. Thus, when a voltage is applied, each liquid crystal cell is deflected according to an electric field, and the liquid crystal cells of different deflection directions are complementary to each other to increase the viewing angle, thereby avoiding the conventional liquid crystal screen having different angles for the viewer to have different angles. Watch the problem of producing a difference in brightness and limiting the viewing angle. Generally, a multi-vertical alignment type liquid crystal display device relies on a plurality of protrusion structures on a substrate to cause a pretilt angle of a liquid crystal cell. Therefore, in 201121999, a protrusion structure is formed by a film deposition, a yellow light process, or a (four) process. Such a “come” will inevitably increase the complexity of manufacturing and the cost of processing. In addition, the protrusion structure disposed on the substrate also causes an obstacle to light penetration, which reduces the uniform brightness of the liquid crystal display. SUMMARY OF THE INVENTION - The main object of the present invention is to remove the protrusion structure on the substrate in the multi-vertical alignment type liquid crystal display device, and to avoid the problem that the viewing angle is narrow due to the influence of the multiple vertical alignment ability after removing the protrusion structure. In order to achieve the above (four) 'the present invention, a polymer liquid crystal alignment additive is provided:
H-C 如式（I)的聚合單體：丄 L+U-H-C Polymeric monomer of formula (I): 丄 L+U-
士 〇Xie“ 式(I) 其中，R為氫基或甲烷基，x為氫基、甲烷基或氟基， n、m為相同或相異go的整數，m+n>();或者 如式（II)的聚合單體：士〇Xie " Formula (I) wherein R is hydrogen or methyl, x is hydrogen, methyl or fluoro, n, m is an integer of the same or different go, m + n >(); or Polymeric monomer of formula (II):
CasC-H 式(II) 其中’ R為氫基或甲烷基，n、m為相同或相異的 整數，m+n>0，但m+n不等於2。 該式（I)或式（II)的聚合單體係利用能量光照射而進行 聚合反應，該能量光係為可見光或紫外光，且該能量光照 射波長介於280nm至380nm之間，而其照射強产 gO.lmj/cm2。此外，若欲加速聚合速度並減少能量光照射 時間’本發明所述高分子液晶配向添加物，更包含有— 201121999 化起始劑。 此外，本發明更提供一種液晶顯示裝置的製造方法， 包括步驟有： a) 提供一第一基板以及一第二基板，該第一基板以及 該第二基板分別具有相互對應且平行的第一表面 以及一第二表面，該第一表面與該第二表面分別具 有一配向層； b) 注入一液晶組合物於該第一基板與該第二基板之 間，該液晶組合物包含有一液晶材料以及一高分子 液晶配向添加物，該高分子液晶配向添加物中所包 含有如前述式（I)或式（II)的聚合單體； c) 聚合該式⑴或式（II)的聚合單體於該配向層上以形 成一高分子液晶配向聚合層。 其中，於步驟b)中，該液晶組合物係以灌注法（Injection) 或液晶滴下法（One Drop Fill, ODF)注入於該第一基板與該 第二基板之間。 另外，於注入一液晶組合物於該第一基板與該第二基 板之間後，更具有一施加電壓於該液晶組合物的步驟，使 該液晶材料、式（I)或式（II)的聚合單體均偏轉至一預定方 向，再經過步驟c)聚合形成垂直配向，來增強錨定力 (anchoring force) ° 再者，為了能使該式（I)或式（Π)的聚合單體反應完全， 避免剩餘聚合單體而造成殘影，於聚合該式（I)或式（II)的聚 合單體於該配向層上以形成一高分子液晶配向聚合層之後 更具有一加熱固化該式（I)或式（II)的聚合單體步驟，其中該 加熱固化步驟中的溫度介於90°C至160°C之間。 201121999 藉由本發明所揭露的奇分子液晶配向添加物，多重垂 直配向型液晶顯示裝置（MVA-LCD)無須於基板上設置複數 犬起結構，減少製程上於基板上形成突起結構的工序以及 成本。由式（I)或式（II)的聚合單體聚合反應產生的高分子液 晶配向聚合層足以取代傳統多重垂直配向型液晶顯示裝置 基板上的突起結構，使液晶材料於未受電壓驅動下即亦可 產生一預傾角（pre-tilt angle)。除此之外，由於面板上無突 起結構的設置，有效增加光線穿透基板的能力，且由式⑴ 或式（II)的聚合單體聚合反應產生的高分子液晶配向聚合 層设置於配向層上，使得液晶顯示器於暗態時更暗，以增 加液晶面板顏色顯示的對比程度。 【實施方式】 有關本發明之詳細說明及技術内容，現就配合圖式說 明如下： 本發明的高分子液晶配向添加物·，其較佳的態樣包 括有： 如式（I)的聚合單體：CasC-H Formula (II) wherein 'R is a hydrogen group or a methyl group, n, m are the same or different integers, m + n > 0, but m + n is not equal to 2. The polymerization single system of the formula (I) or the formula (II) is subjected to polymerization by energy light irradiation, which is visible light or ultraviolet light, and the energy light irradiation wavelength is between 280 nm and 380 nm, and Irradiation strong production gO.lmj/cm2. Further, if the polymerization rate is to be accelerated and the energy light irradiation time is reduced, the polymer liquid crystal alignment additive of the present invention further contains - 201121999. In addition, the present invention further provides a method for fabricating a liquid crystal display device, comprising the steps of: a) providing a first substrate and a second substrate, the first substrate and the second substrate respectively having first surfaces that are corresponding to each other and parallel And a second surface, the first surface and the second surface respectively have an alignment layer; b) injecting a liquid crystal composition between the first substrate and the second substrate, the liquid crystal composition comprising a liquid crystal material and a polymer liquid crystal alignment additive comprising a polymerizable monomer of the above formula (I) or formula (II); c) polymerizing the polymerizable monomer of the formula (1) or formula (II) The alignment layer is formed to form a polymer liquid crystal alignment polymerization layer. Wherein, in the step b), the liquid crystal composition is injected between the first substrate and the second substrate by an injection method or a One Drop Fill (ODF) method. In addition, after injecting a liquid crystal composition between the first substrate and the second substrate, a step of applying a voltage to the liquid crystal composition is further provided to make the liquid crystal material, the formula (I) or the formula (II) The polymerized monomers are all deflected to a predetermined direction, and then polymerized in step c) to form a vertical alignment to enhance the anchoring force. Further, in order to enable the polymerization monomer of the formula (I) or formula (Π) The reaction is complete, and the residual polymerization monomer is avoided to cause image sticking. After polymerizing the polymerizable monomer of the formula (I) or (II) on the alignment layer to form a polymer liquid crystal alignment polymerization layer, there is a heat curing. A polymerization monomer step of the formula (I) or formula (II), wherein the temperature in the heat curing step is between 90 ° C and 160 ° C. 201121999 With the odd molecular liquid crystal alignment additive disclosed in the present invention, the multiple vertical alignment type liquid crystal display device (MVA-LCD) does not need to have a plurality of canine structures on the substrate, and the process and cost for forming the protrusion structure on the substrate in the process are reduced. The polymer liquid crystal alignment polymerization layer produced by the polymerization of the polymerized monomer of the formula (I) or the formula (II) is sufficient to replace the protrusion structure on the substrate of the conventional multiple vertical alignment type liquid crystal display device, so that the liquid crystal material is driven by no voltage. A pre-tilt angle can also be produced. In addition, due to the absence of the protrusion structure on the panel, the ability of light to penetrate the substrate is effectively increased, and the polymer liquid crystal alignment polymerization layer produced by polymerization of the polymerized monomer of the formula (1) or the formula (II) is disposed on the alignment layer. In the above, the liquid crystal display is made darker in the dark state to increase the contrast of the color display of the liquid crystal panel. [Embodiment] The detailed description and technical contents of the present invention will now be described with reference to the following drawings: The polymer liquid crystal alignment additive of the present invention, and preferred aspects thereof include: an aggregation sheet of the formula (I) body:
式⑴ η 其中，R為氫基Μ烧基，X為氫基、甲絲或氣基， m為相同或相異go的整數，m+n>〇 ;或者 如式（Π)的聚合單體：Wherein R is a hydrogen-based fluorenyl group, X is a hydrogen group, a methyl or gas group, m is an integer of the same or different go, m+n>〇; or a polymerizable monomer of the formula (Π) :
式(II) 其中，R為氫基或曱烷基，η m為相同或相異的 201121999 整數，m+n>〇 ’但m+n不等於2。 前述式（I)或式（II)的聚合單體經能量光照射後可相互 聚合’該能量光選擇性使用可見光或紫外光，而該能量光 的照射波長介於280nm至380nm之間，而其照射強度則 SO.lmj/cm2。此外，若欲加速該聚合單體的反應時間，或 者減少能量光的照射時間，該高分子液晶配向添加物中更 可具有一硬化起始劑。 另外一方面，本發明揭露一種使用前述高分子液晶配 向添加物的液晶顯示裝置的製造方法，包括步驟有··Wherein R is a hydrogen group or a decyl group, and η m is the same or different 201121999 integer, m+n>〇' but m+n is not equal to 2. The polymerized monomers of the above formula (I) or (II) can be polymerized by irradiation with energy light. The energy light selectively uses visible light or ultraviolet light, and the irradiation wavelength of the energy light is between 280 nm and 380 nm. The irradiation intensity is SO.lmj/cm2. Further, in order to accelerate the reaction time of the polymerized monomer or to reduce the irradiation time of the energy light, the polymer liquid crystal alignment additive may further have a hardening initiator. In another aspect, the present invention discloses a method of fabricating a liquid crystal display device using the polymer liquid crystal alignment additive, including steps including
a) 提供一第一基板以及一第二基板，該第一基板以及 該第二基板分別具有相互對應且平行的第一表面 以及一第二表面’該第一表面與該第二表面分別具 有一配向層； b) 注入一液晶組合物於該第一基板與該第二基板之 間’該液晶組合物包含有一液晶材料以及一高分子 液晶配向添加物’該高分子液晶配向添加物中所包 含有如式（I)或式（II)的聚合單體；以及 c) 聚合該式（I)或式（π)的聚合單體於該配向層上以 形成一高分子液晶配向聚合層。 請參閱『圖1-1』至『圖1-4』所示，係本發明液晶顯 示裝置的製造方法之較佳實施例製造流程示意圖。首先， 以製造多重垂直配向型液晶顯示裝置為例，如『圖1_丨』所 示，將一第一基板11與一第二基板12相應置放，該第一 基板11與該第二基板12各具有一相互平行的第一表面 以及一第二表面121。該第一基板π與該第二基板12可選 為玻璃、石英或軟性塑膠（如PET)等透明材料。該第一基板 11與該第二基板12的第一表面111與該第二表面121分別 201121999 設有一導電層13,該導電層13電性連接至一薄膜電晶體（圖 中未示），該導電層13可選用氧化銦錫或氧化銦鋅等透明 導電材料。並於該第一表面111與該第二表面121上的導 電層13增設有配向層14(alignment layers)，具有用來誘導 後續注入液晶分子定向排列。該配向層14所使用的材料可 為聚苯乙燦、聚酿亞胺、聚乙稀醇、聚酯、環氧樹脂、聚 胺酯、聚矽烷等；其中，較佳選擇為聚醯亞胺（p〇lyimide)。 再請參閱『圖1-2』所示，於該第一基板11與該第二基 板12之間注入一液晶組合物，該液晶組合物包含有一液晶 材料20以及一南分子液晶配向添加物，該高分子液晶配向 添加物中所包含有如式（I)或式（II)的聚合單體3〇的所聚合 形成。該液晶組合物可以灌注法（Injection)或液晶滴下法 (One Drop Fill, ODF)注入於該第一基板u與該第二基板 12。其中，該式（I)或式（Π)的聚合單體3〇相對於該液=材 料20的重量百分比為〇.i%_2〇/〇。 若欲提升液晶顯示器的對比能力，可選擇性於注入該液 晶組合物至該第一基板U與該第二基板12之間後施加一 電壓，該電壓是由薄膜電晶體驅動該導電層13所產生，該 液晶組合物内的液晶材料20以及該式⑴或式（π)的聚合單 體30依據電場方向相應偏轉至一預定方向如『圖I」 所示》於此步驟中所施加的電壓介於M〇伏特之間。 當液晶組合物完成注入於第一基板11與第二基板12之 間，可直接或者如前述先施加一電壓後，才進行該式⑴或 式(Π)的聚合單體3〇的聚合反應。由於本發明該式⑴或式 (II)的聚合單體3()屬於具有雙_壓克力單體，可利用能 量光40照射進行聚合反應，該能量光4〇可選擇性使用‘ 201121999 見光或紫外光’該能量光40照射強度20.lmj/cm2。若欲增 加該聚合單體30反應的速度，或者減少能量光4〇照射時 間’該高分子液晶配向添加物更具有一硬化起始劑，如一 種紫外光硬化起始劑（ultraviolet curing agent)。聚合後的該 式（1)或式（II)的聚合單體30於該第一基板π與該第二基板 12的配向層14上形成一高分子液晶配向聚合層31，如『圖 1-4』所示。為避免於此步驟中反應不完全而剩餘未反應之 該式（I)或式（II)的聚合單體30，造成液晶顯示器產生殘影 (image sticking)的問題，本發明可選擇性於聚合該式⑴或 鲁 式（11)的聚合單體於該配向層14上以形成一高分子液晶配 向聚合層31之後加熱固化該式⑴或式（„)聚合單體3〇，所 施加的溫度介於90°C至160°C之間。 综上所述’本發明高分子液晶配向添加物以及具有前 述高分子液晶配向添加物的液晶顯示裝置的製造方法主要 係提供一種如前述式（丨）或式（11)聚合單體相互聚合後形 成尚分子液晶配向聚合層，該高分子液晶配向聚合層使液 晶材料產生預傾角，而達到多重垂直配向的效果，足以取 # 代傳統基板所設置的突起結構。如此，可省去突起結構形 成於基板的製程，減少加工工序以及製造成本；且因無突 起結構，有效提升面板穿透度。由於基板上除了配向層外 更增設一高分子液晶配向聚合層，使得面板暗態更暗，並 提升晝面對比程度。因此本發明極具進步性及符合申請發 明專利之要件，爰依法提出申請，祈鈞局早日賜准專利， 實感德便。 以上已將本發明做一詳細說明，惟以上所述者，僅爲本 發明之一較佳實施例而已，當不能限定本發明實施之範 201121999 皆 二：凡依本發明申請範圍所 應仍屬本發明之專利涵蓋範㈣。&糾飾專 【圖式簡單說明】 圖1-1至圖1-4，係本發明液 實施例製造流程示意圖 曰曰顯示裝置的製造方法之較佳 【主要元件符號說明】 第一基板 •第一表面 12 .............第二基板 121..... .第二表面 13 .............導電層 ...............配向層 2〇...... •液晶材料 ...............聚合單體 ................分子液晶配向聚合層 ...............能量光a) providing a first substrate and a second substrate, the first substrate and the second substrate respectively having a first surface corresponding to and parallel to each other and a second surface having a first surface and a second surface respectively The alignment layer; b) injecting a liquid crystal composition between the first substrate and the second substrate, the liquid crystal composition comprises a liquid crystal material and a polymer liquid crystal alignment additive, and the polymer liquid crystal alignment additive is included a polymerizable monomer of the formula (I) or formula (II); and c) polymerizing the polymerizable monomer of the formula (I) or (π) on the alignment layer to form a polymer liquid crystal alignment polymerization layer. Referring to Figures 1-1 through 1-4, there is shown a schematic diagram of a manufacturing process of a preferred embodiment of a method of fabricating a liquid crystal display device of the present invention. First, in the case of manufacturing a multi-vertical alignment type liquid crystal display device, a first substrate 11 and a second substrate 12 are disposed correspondingly, as shown in FIG. 1_丨, the first substrate 11 and the second substrate. Each has a first surface that is parallel to each other and a second surface 121. The first substrate π and the second substrate 12 may be made of a transparent material such as glass, quartz or soft plastic (such as PET). The first substrate 11 and the first surface 111 of the second substrate 12 and the second surface 121 are respectively provided with a conductive layer 13 respectively. The conductive layer 13 is electrically connected to a thin film transistor (not shown). The conductive layer 13 may be made of a transparent conductive material such as indium tin oxide or indium zinc oxide. And an alignment layer 14 is disposed on the first surface 111 and the conductive layer 13 on the second surface 121 to induce alignment of the subsequently injected liquid crystal molecules. The material used for the alignment layer 14 may be polystyrene, polyamidiamine, polyethylene glycol, polyester, epoxy resin, polyurethane, polydecane, etc.; among them, polyimine (p) is preferred. 〇lyimide). Referring to FIG. 1-2, a liquid crystal composition is injected between the first substrate 11 and the second substrate 12, and the liquid crystal composition comprises a liquid crystal material 20 and a south molecular liquid crystal alignment additive. The polymer liquid crystal alignment additive contains a polymerized monomer of the formula (I) or the formula (II). The liquid crystal composition may be implanted into the first substrate u and the second substrate 12 by an injection method or a One Drop Fill (ODF). Here, the weight percentage of the polymerizable monomer 3〇 of the formula (I) or the formula (Π) relative to the liquid = material 20 is 〇.i% _2 〇 / 〇. If the contrast property of the liquid crystal display is to be improved, a voltage may be selectively applied after the liquid crystal composition is injected between the first substrate U and the second substrate 12, and the voltage is driven by the thin film transistor. Producing, the liquid crystal material 20 in the liquid crystal composition and the polymerized monomer 30 of the formula (1) or (π) are correspondingly deflected according to the direction of the electric field to a predetermined direction as shown in FIG. 1 and the voltage applied in this step. Between M volts. When the liquid crystal composition is completely injected between the first substrate 11 and the second substrate 12, the polymerization of the polymerized monomer 3 of the formula (1) or the formula (?) can be carried out directly or after a voltage is applied as described above. Since the polymerized monomer 3() of the formula (1) or the formula (II) of the present invention belongs to a monomer having a double-acrylic force, the polymerization can be carried out by irradiation with energy light 40, and the energy light can be selectively used as '201121999. Light or ultraviolet light 'The energy light 40 is irradiated with a intensity of 20.lmj/cm2. If it is desired to increase the rate of reaction of the polymerized monomer 30, or to reduce the irradiation time of the energy light, the polymer liquid crystal alignment additive further has a hardening initiator such as an ultraviolet curing agent. The polymerized monomer 30 of the formula (1) or the formula (II) after polymerization is formed on the first substrate π and the alignment layer 14 of the second substrate 12 to form a polymer liquid crystal alignment polymerization layer 31, as shown in FIG. 4" is shown. In order to avoid the unreacted reaction of the polymerizable monomer 30 of the formula (I) or the formula (II) in this step, the problem of image sticking of the liquid crystal display is caused, and the present invention can be selectively polymerized. The polymerization monomer of the formula (1) or the ruthenium (11) is heated on the alignment layer 14 to form a polymer liquid crystal alignment polymerization layer 31, and then the temperature of the polymerized monomer (3) or (3) is cured. Between 90 ° C and 160 ° C. In summary, the method for producing a liquid crystal alignment additive of the present invention and a liquid crystal display device having the polymer liquid crystal alignment additive described above mainly provides a formula (如) Or the polymerized monomer of the formula (11) is polymerized to form a molecular liquid crystal alignment polymerization layer, and the polymer liquid crystal alignment polymerization layer causes a pretilt angle of the liquid crystal material to achieve multiple vertical alignment effects, which is sufficient for the conventional substrate to be set. The protrusion structure can eliminate the process of forming the protrusion structure on the substrate, reduce the processing procedure and the manufacturing cost, and effectively improve the panel penetration due to the non-protrusion structure. A polymer liquid crystal alignment polymer layer is added outside the alignment layer to make the dark state of the panel darker and enhance the face-to-face ratio. Therefore, the invention is highly advanced and meets the requirements of the invention patent application, and the application is made according to law. The invention has been granted a patent as soon as possible. The above description of the present invention has been made in detail. However, the above description is only a preferred embodiment of the present invention, and the embodiment of the present invention is not limited to 201121999. The patents of the present invention are still included in the scope of the application of the present invention. (4) & 纠 专 【 图 图 图 图 图 图 图 图 图 图 图 图 图 图 制造 制造 制造 制造 制造 制造制造Preparation of the manufacturing method of the display device [Main component symbol description] First substrate • First surface 12 . . ....... Second substrate 121...... Second surface 13 .............Conductive layer...............Alignment layer 2〇... •Liquid crystal material....... ........polymerized monomer................molecular liquid crystal alignment polymerization layer...............energy light