TWI300093B

TWI300093B - Polymer dispersed liquid crystal composition with improved photo-stability and the device thereof

Info

Publication number: TWI300093B
Application number: TW93141383A
Authority: TW
Inventors: Ching Kuan Lee; Yang Chu Lin; Shih Hsien Liu; Yu Nan Tzeng; Kung Lung Cheng; Ter Young Chern
Original assignee: Ind Tech Res Inst
Priority date: 2004-12-30
Filing date: 2004-12-30
Publication date: 2008-08-21
Also published as: TW200621951A

Description

1300093 九、發明說明：【發明所屬之技術領域】本發明係關於一種高对光之高分子分散型液晶組成物，尤指一種適用於顯示裝置之高耐光之高分子分散型液 5 晶組成物。【先前技術】 10 15 高分子分散型液晶（polymer dispersed liquid crystal，簡稱PDLC)主要是由微米尺寸大小之液晶顆粒分散在高分子基質中所組成；PDLC之操作原理係利用外加電場可控制液晶折射率之變化，在無電場作用下呈不透明狀，而在電場存在下呈透明狀；由於PDLC不需偏光膜及配向膜之協助，且可採用塗佈方式塗佈在含透明導電層（如ITO)之可撓曲基板（如PET)上，因此可應用於製備大尺寸之液晶平面顯不益、廣告看板及汽車、建築物所需之可調光玻璃上。而 -不同特f生之液曰曰、二色性染料（dkhr〇ic办0)及改變液曰曰顆粒之尺寸，可製備出可調整光波波長、受溫度變化感心a光儲存5己憶及全像光學（holography)性質之PDLC裝置，其潛在市場商機實無可限量。戸’由於液晶顯示器可能長期暴露在背光源或外在所，2陽光）之照射，因此液晶中染料分子易產生變解产_ ^員丁放果，目則如能將光穩定度、熱穩定度及溶之材料應用於液晶顯示裝置，可使產品具有較長 20 1300093 製備PDLC膜片的方法主要可分為乳化法 (emulsion)、分相製備法（phase separation)及微膠囊形成 (encapsulation)等三大類；乳化法主要是將液晶乳化分散在可形成膜之高分子（通常為水溶性）水溶液中，然後塗佈在 5 可導電之基材表面（如塗有ITO導電層之PET膜），加熱去除溶劑後，此時高分子形成固體膜而液晶則一顆顆分散在高分子基質中。分相製備法主要可分為溫度成相（thermally-induced phase separation，TIPS)、溶劑成相（solvent-induced phase l〇 separation，SIPS)及聚合成相（polymerization-induced phase separation，PIPS)三種；TIPS方法是在高溫下將液晶與可塑性高分子混合後塗佈在可導電之基材表面，冷卻後可塑性高分子回到固體狀態，而液晶則一顆顆析出分散在高分子基質中；SIPS方法是將液晶及高分子溶入到有機溶劑中形 15 成一均勻相，塗佈在基材表面後再以加熱去除溶劑，此時液晶一顆顆析出分散在高分子基質中；PIPS方法則是將液晶與低分子量之單體或募聚合物均均混合在一起，經過加熱或照光後，因液晶在所形成之高分子中溶解度降低而析出形成PDLC。 20 微膠囊形成是將液晶與反應單體均勻混合在一起，然後塗在含有界面活性劑及可形成膜之水溶性高分子（通常為PVA)水溶液中形成直徑大約1〜10 //之液晶/反應單體顆粒，然後加入架橋劑並加熱使反應單體聚合形成交聯性高分子，此時液晶被困在高分子中形成液晶膠囊顆粒，然後 1300093 :粒分佈較窄之液晶膠囊顆粒；接著將液晶膠囊性高分子水溶液巾，㈣在基材表面後使 /合別揮务掉形成PDLC膜片。影響PDLC膜片性能之參數液晶顆粒之形狀、女……一匕㈣片之厚度、、粒從分佈及液晶的種類、高分子之型怨；高分子之八工曰 _ 曰刀子之刀子置、種類及聚合或交聯的程度；液日日刀子洛解到高分子基質古斟私度，冋子及液晶的折射率比;添加劑(如界面活性劑、流平劑、增稠劑、 10 :“劑寺)及金屬離子含量等。至目前為止，利用高分子分散型液晶之裝置皆在尤射μ 衣置S存在對比不佳與驅動電壓高的問題，且相關應用產品中祐|“ , f ，展口卩Π無评細採时材料之光穩定度問題。發明内容】本發明主要揭示—種具有高耐光之可調光材料製備 15得之高分子分散型液晶顯示裝置，藉由在高分子分散型液日日中加入南耐光之二色性染料與添加劑，增加材料之耐光性:可廣泛的應用於手錶顯示、自動化顯示、標籤、廣告顯不、隱密性隔板如建築用窗戶與車用天窗與側窗，具耐光之特性可抑制液晶分子易因光照黃化之缺點。 20 本發明一種高分子分散型液晶顯示裝置，包括：一上基板；-下基板，·-形成於上基板之第一電極，係夹置於上基板與下基板之間；一形成於下基板之第二電極’係夾 f於上基板舆下基板之間；以及一耐光高分子分散型液晶層，其中，耐光高分子分散型液晶層係包含—高分子基質， 25至少-液晶化合物以及至少一二色性染料，且耐光高分子 1300093 分散型液晶層係夾置於上基板與下基板之間。本發明更包括一種抑制黃化之高分子分散型液晶組成物，係包括：一高分子基質；至少一液晶化合物；以及至少一二色性染料；其中，該液晶化合物係為30個碳以下之 5 液晶化合物。本發明高分子分散型液晶裝置中之第一電極與第二電極較佳係相互垂直；為加強本發明中液晶分子之光耐受力，本發明耐光高分子分散型液晶較佳係更包括一 UV吸收劑；UV吸收劑之種類可以是習用之任何一種，較佳為酚類 10 或苯酚類之UV吸收劑；UV吸收劑之添加量無限制，較佳為佔耐光高分子分散型液晶層中該液晶化合物之0.01 %〜 5%。本發明之耐光高分子分散型液晶層中，適用之液晶化合物可以是習用之液晶組合物，較佳為30個碳以下之液晶 15 組合物。本發明耐光高分子分散型液晶層中之高分子基質可以是習用之任何一種，較佳係選自由聚乙烯醇（polyvinyl alcohol)、聚乙稀醇共聚物（polyvinyl alcohol copolymer)、聚氧化乙稀【poly(ethyleneoxide)】、聚甲基 20 乙稀醚 / 順-丁浠二（polymethyl vinyl ether/maleic anhydride)、聚乙稀σ比洛【poly(vinylpyrrolidone)】、纖維素聚合物（cellulosic polymer)、天然橡膠（natural gums)、聚氨酷（polyurethane)及聚丙烯酸（polyacrylate)所組成之群 1300093 本發明耐光高分子分散型液晶可更包括界面活性劑、流平劑、增稠劑或消泡劑；此外，财光高分子分散型液晶層中之二色性染料不限，較佳係含有如式⑴所示之化合物： 51300093 IX. Description of the Invention: [Technical Field] The present invention relates to a high-light-weight polymer-dispersed liquid crystal composition, and more particularly to a high-light-resistant polymer dispersion type liquid crystal composition suitable for a display device. . [Prior Art] 10 15 Polymer dispersed liquid crystal (PDLC) is mainly composed of micron-sized liquid crystal particles dispersed in a polymer matrix; the operating principle of PDLC is to control liquid crystal refraction by applying an electric field. The change of rate is opaque in the absence of electric field, and transparent in the presence of electric field; since PDLC does not need the assistance of polarizing film and alignment film, it can be coated on transparent conductive layer (such as ITO). On flexible substrates (such as PET), it can be applied to the preparation of large-size LCD flat panels, advertising billboards, and dimmable glass for automobiles and buildings. And - different liquids, dichroic dyes (dkhr〇ic do 0) and change the size of liquid helium particles, can be prepared to adjust the wavelength of light, subject to temperature changes, a light storage 5 recall The holography-type PDLC device has unlimited potential market opportunities.戸 'Because the liquid crystal display may be exposed to the backlight or external environment for a long time, 2 sunlight), so the dye molecules in the liquid crystal are prone to change and produce _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The degree and solubility of the material applied to the liquid crystal display device can make the product have a long 20 1300093. The method for preparing the PDLC film can be mainly divided into emulsion, phase separation and encapsulation. Three major categories; emulsification method is mainly to embed liquid crystal emulsion in a film-forming polymer (usually water-soluble) aqueous solution, and then coated on the surface of 5 conductive substrates (such as PET film coated with ITO conductive layer) After the solvent is removed by heating, the polymer forms a solid film at this time, and the liquid crystal is dispersed in the polymer matrix one by one. The phase separation preparation method can be mainly divided into three types: thermal-induced phase separation (TIPS), solvent-induced phase separation (SIPS) and polymerization-induced phase separation (PIPS); The TIPS method is to mix liquid crystal and plastic polymer at a high temperature and then apply it on the surface of an electrically conductive substrate. After cooling, the plastic polymer returns to a solid state, and the liquid crystal is precipitated and dispersed in a polymer matrix; SIPS method The liquid crystal and the polymer are dissolved in an organic solvent to form a uniform phase, which is coated on the surface of the substrate and then heated to remove the solvent. At this time, the liquid crystal is precipitated and dispersed in the polymer matrix; the PIPS method is The liquid crystal is mixed with the low molecular weight monomer or the polymer, and after heating or illuminating, the liquid crystal is precipitated to form PDLC due to a decrease in solubility of the formed polymer. 20 microcapsule formation is to uniformly mix the liquid crystal and the reactive monomer, and then apply to a water-soluble polymer (usually PVA) aqueous solution containing a surfactant and a film to form a liquid crystal having a diameter of about 1 to 10 // Reactive monomer particles, then adding a bridging agent and heating to polymerize the reactive monomer to form a crosslinkable polymer, at which time the liquid crystal is trapped in the polymer to form liquid crystal capsule particles, and then 1300093: liquid crystal capsule particles having a narrow particle distribution; The liquid crystal capsule polymer aqueous solution towel (4) is allowed to be separated from the surface of the substrate to form a PDLC film. The parameters affecting the performance of the PDLC film, the shape of the liquid crystal particles, the thickness of the film, the thickness of the film, the distribution of the particles, the type of liquid crystal, the type of polymer, the grievance of the polymer, the knives of the knives Type and degree of polymerization or cross-linking; liquid-day knives are resolved to the polymer matrix, the refractive index of scorpion and liquid crystal; additives (such as surfactants, leveling agents, thickeners, 10: "Drug Temple" and metal ion content, etc. Up to now, the devices using polymer-dispersed liquid crystals have a problem of poor contrast and high driving voltage in the special shots, and the related application products are Zhongyou|", f. The light stability of the material is not evaluated during the exhibition. SUMMARY OF THE INVENTION The present invention mainly discloses a polymer-dispersed liquid crystal display device having a high light-resistant tunable material prepared by adding a light-resistant dichroic dye and an additive to the south of the polymer dispersed liquid. , to increase the light fastness of materials: can be widely used in watch display, automatic display, label, advertising display, hidden partitions such as architectural windows and sunroofs and side windows, with light resistance can inhibit liquid crystal molecules Due to the shortcomings of yellowing. 20 A polymer dispersed liquid crystal display device comprising: an upper substrate; a lower substrate, a first electrode formed on the upper substrate, the clip being interposed between the upper substrate and the lower substrate; and being formed on the lower substrate a second electrode 'clamped between the lower substrate and the lower substrate; and a light-resistant polymer dispersed liquid crystal layer, wherein the light-resistant polymer dispersed liquid crystal layer comprises a polymer matrix, 25 at least a liquid crystal compound, and at least A dichroic dye, and the light-resistant polymer 1300093 dispersed liquid crystal layer is sandwiched between the upper substrate and the lower substrate. The present invention further includes a polymer dispersed liquid crystal composition for inhibiting yellowing, comprising: a polymer matrix; at least one liquid crystal compound; and at least one dichroic dye; wherein the liquid crystal compound is 30 carbon or less 5 liquid crystal compounds. In the polymer-dispersed liquid crystal device of the present invention, the first electrode and the second electrode are preferably perpendicular to each other; in order to enhance the light tolerance of the liquid crystal molecules in the present invention, the light-resistant polymer-dispersed liquid crystal of the present invention further includes a The UV absorber; the type of the UV absorber may be any one of the conventional ones, preferably a phenol 10 or a phenolic UV absorber; the amount of the UV absorber added is not limited, preferably the light-resistant polymer dispersed liquid crystal layer 0.01% to 5% of the liquid crystal compound. In the light-resistant polymer-dispersed liquid crystal layer of the present invention, the liquid crystal compound to be used may be a conventional liquid crystal composition, preferably a liquid crystal 15 composition of 30 carbon or less. The polymer matrix in the light-resistant polymer-dispersed liquid crystal layer of the present invention may be any one of conventionally used, and is preferably selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymer, and polyethylene oxide. [poly(ethyleneoxide)], polymethyl vinyl ether/maleic anhydride, poly(vinylpyrrolidone), cellulosic polymer a group consisting of natural gums, polyurethane, and polyacrylate 1300093. The light-resistant polymer dispersed liquid crystal of the present invention may further comprise a surfactant, a leveling agent, a thickener or a defoaming agent. Further, the dichroic dye in the dichroic polymer liquid crystal layer is not limited, and preferably contains a compound represented by the formula (1): 5

X AX A

N- Y 10 式（I)，其中，Α為 I、 I N —N=N—^ >-SR5 — N〇，虽 A 為 V^cr1 時，B 為-COOR2 t -CHC(CN)CO〇R4，且X與γ同為氫原子，其中，r1、r2、及R4獨立為未經取代或可經—或多個氟原子取代之C丨μ傾 N-N ^ Δ ^ >-SR5 基，*為時，B為-NR6R7,且X與γ不相同3 X為Cw烷基，γ為C卜烷基、_〇Ch3、或_〇CA，或X與Y同為C卜Br、I、C“烷基、_〇Ch3、或_〇咖，其中R5為-CH3或42%，及R6與R7獨立為烷基、 ί?N- Y 10 Formula (I), wherein Α is I, IN — N=N—^ > -SR5 — N〇, although A is V^cr1, B is -COOR2 t -CHC(CN)CO〇 R4, and X and γ are each a hydrogen atom, wherein r1, r2, and R4 are independently unsubstituted or C?μp NN ^ Δ ^ >-SR5 groups substituted by - or a plurality of fluorine atoms, * In the meantime, B is -NR6R7, and X is different from γ. 3 X is Cw alkyl, γ is C-alkyl, _〇Ch3, or _〇CA, or X and Y are C, Br, I, C. "Alkyl, _〇Ch3, or _〇, where R5 is -CH3 or 42%, and R6 and R7 are independently alkyl, ί?

B Ο 、 II . N-CR1 或B Ο , II . N-CR1 or

-CH2CH2(CF2)mF-CH2CH2(CF2)mF

• C—OR3• C-OR3

或 ’其中m為1至i〇之整數及以為心烧基；更佳之二色性染料為·· 15 1300093Or 'where m is an integer from 1 to i〇 and is considered to be a heart-burning base; a better dichroic dye is · 15 1300093

G2 Ο G1= —A-Ar^ZrAr^^R! 「 ’n=〇〜2 •B--Ar2(Z2-Ar2+R2 0-2 G2:G2 Ο G1= —A-Ar^ZrAr^^R! ”n=〇~2 •B--Ar2(Z2-Ar2+R2 0-2 G2:

m=CM ”其自t.’ A為氧、硫或氮；B為氣、氧、硫、氮或齒素(氟、 Γ二丨1為、氯、氮氧基或氨基；X2為氫、氯氧基或氨基； Γΐ人Ο刀別為苯基、聯苯、萘基或雜環之芳香環；A。， 5與Ar2分別為苯基、聯苯或雜環之芳香環；&與^分別為 -C00、-oco、〇, s之連接基，且Ri與R2分別為Ci〜C6、-〇ch3〜〇c6H13、 -Cy-Cl〜_Cy-C6、-CF3〜C4F9以及-NCS之末端基。本發明適用之二色性染料係具有高次序性，較佳在 10 〇·4〜〇_9。（次序性高，所得對比較高，次序性為相對液晶量測其不同光軸之吸收度計算得知）【實施方式】本發明實施方式係經由在乳液中加入具有高光穩定 15度之二色性染料與光穩定劑，增加可調光材料之光穩定度。實施例1、PVA純化由於PVA中離子數目過高將造成液晶材料光電特性之改變’所以取得PVA後先以甲醇移除納離子；首先將 PVΑ(如 Celvol 205 or 805)放入圓筒濾紙（extraction thimble) 20内，然後置於索式裝置（Soxhlet)内（以甲醇為溶劑；油鋼溫度設定為170 C )’連續萃取約6小時，然後將PVA倒出，置 1300093 於烘箱内在50°C下烘乾即可得離子含量低於30ppm之 PVA ;曱醇移除鈉離子之效率可參考圖1。實施例2、液晶乳液製備先將2gUCL032液晶配方，以及結構如下式之黃色二 5 色性染料（0.01%〜5%):m = CM "from t. 'A is oxygen, sulfur or nitrogen; B is gas, oxygen, sulfur, nitrogen or dentate (fluorine, ruthenium 1, chlorine, nitrogen or amino; X2 is hydrogen, a chlorooxy group or an amino group; the scorpion scorpion is an aromatic ring of a phenyl group, a biphenyl group, a naphthyl group or a heterocyclic ring; A, 5 and Ar2 are each an aromatic ring of a phenyl group, a biphenyl group or a heterocyclic ring; ^ are -C00, -oco, 〇, s, respectively, and Ri and R2 are Ci~C6, -〇ch3~〇c6H13, -Cy-Cl~_Cy-C6, -CF3~C4F9, and -NCS The dichroic dyes to which the present invention is applied have high order, preferably 10 〇·4~〇_9. (High order, high contrast, order is relative to liquid crystal measurement, different optical axes The calculation of the absorbance is carried out. [Embodiment] The embodiment of the present invention increases the light stability of the light-tunable material by adding a dichroic dye having a high light stability of 15 degrees and a light stabilizer to the emulsion. PVA purification will result in a change in the photoelectric properties of liquid crystal materials due to the high number of ions in the PVA. Therefore, after the PVA is obtained, the nano ions are removed by methanol; first, the PV is enthalpy (such as Celvol 205 or 805). Place it in the extraction thimble 20, then place it in a Soxhlet (with methanol as solvent; the oil temperature is set to 170 C) for continuous extraction for about 6 hours, then pour the PVA. 1300093 can be dried in an oven at 50 ° C to obtain PVA with an ion content of less than 30 ppm. The efficiency of removing sodium ions from decyl alcohol can be referred to Figure 1. Example 2 Preparation of Liquid Crystal Emulsion 2 g UCL032 liquid crystal formulation was first prepared as follows. Yellow dichromatic dye (0.01%~5%):

和添加劑混合物0.01%〜5%(如UV吸收劑、BYK 161、BYK 333、異丙醇等）混合，接著加入5g之10%〜20%之PVA水溶液，然後以均質機攪拌3-5分鐘即得；UV吸收劑於本例中 10 為酚類吸收劑（購自TCI); BYK161、333為溼潤劑或表面助劑。實施例3 將製備好的液晶乳液滴到含ITO之PET基板上，以方形框塗佈器（設定在50 μ、75 //、或100// )塗佈，然後放置在 15 烘箱（溫度設定在90°C，約10分鐘）以去除所含之水份及異丙醇。接著將另一片空白ITO-PET基板貼合在所形成之 PDLC膜片上（有ITO的部份皆需與PDLC膜片接觸），貝占合時儘量用力以去除可能所含的氣泡。另一作法為在空白ITO-PET上塗佈貼合膠如壓克力感 20 光膠NOA65、NOA72，或熱感壓膠如PVA、PVB等，再將之與含有PDLC膜之ITO-ΡΕ 丁互相貼合，即形成可調光薄膜0 11 1300093 實施例4、可調光玻璃製作將製備好之可調光薄膜塗佈單面塗佈以溶劑型壓克力感壓膠1〇〇//m〜_心，放4於1〇0。(：烘箱5分鐘，取出後直接合於透明玻璃上。或將可調光材料夹於兩片玻璃 5間可11周光材料與玻璃間各加入一 pvb膜貼合。實施例5、耐光性測試將所製之可調光材料置於Q U v耐光測試（波長耐光 313mn，45°〇’連續照光至164小時，試片以標準色差計 f測結果如圖2。〇上述實施例僅係為了方便說明而舉例而已，本發明所主張之權利範圍自應以申請專利範圍所述為準，而非僅限於上述實施例。【圖式簡單說明】 15圖1係本發明實施例1之甲醇移除PVA中鈉離子之效率。圖2係本發明抑制黃化高分子分散型液晶組合物之色差計量測結果圖。 °Mix with the additive mixture 0.01%~5% (such as UV absorber, BYK 161, BYK 333, isopropanol, etc.), then add 5g of 10%~20% PVA aqueous solution, then stir with a homogenizer for 3-5 minutes. The UV absorber is in this case 10 is a phenolic absorbent (purchased from TCI); BYK161, 333 is a wetting agent or surface additive. Example 3 The prepared liquid crystal emulsion was dropped onto a PET substrate containing ITO, coated with a square frame applicator (set at 50 μ, 75 //, or 100//), and then placed in a 15 oven (temperature setting) At 90 ° C, about 10 minutes) to remove the water and isopropyl alcohol contained. Next, another blank ITO-PET substrate is attached to the formed PDLC film (the ITO portion needs to be in contact with the PDLC film), and as much as possible to remove the bubbles that may be contained. Another method is to apply a bonding glue such as acrylic 20-gel NOA65, NOA72, or a thermal pressure-sensitive adhesive such as PVA, PVB, etc. to the blank ITO-PET, and then apply it to the ITO-ruthenium containing the PDLC film. Bonding to each other, forming a dimmable film 0 11 1300093 Example 4, dimming glass production The prepared dimmable film coated single-sided coating with solvent-type acrylic pressure sensitive adhesive 1 〇〇 / / m~_heart, put 4 at 1〇0. (: oven for 5 minutes, directly after taking out on the transparent glass. Or sandwiching the dimmable material between the two sheets of glass 5, 11 weeks of light material and glass are added to each pvb film. Example 5, light resistance The test was carried out by placing the tunable material in a QU v light resistance test (wavelength lightfastness 313 mn, 45 ° 〇 'continuous illumination to 164 hours, and the test piece was measured by a standard color difference meter f as shown in Fig. 2. 〇 The above embodiment is only for For convenience of description, the scope of the claims should be based on the scope of the patent application, and is not limited to the above embodiments. [FIG. 1] FIG. 1 is a methanol shift of Example 1 of the present invention. In addition to the efficiency of sodium ion in PVA, Fig. 2 is a graph showing the results of color difference measurement of the yellowing polymer-dispersed liquid crystal composition of the present invention.

【主要元件符號說明】 20 無 12[Main component symbol description] 20 None 12

Claims

十、申請專利範圍： 1. 一種高分子分散型液晶顯示裝置，包括：一上基板；一下基板； 5 一形成於該上基板之第一電極，係夾置於該上基板與該下基板之間；一形成於該下基板之第二電極，係夾置於該上基板與該下基板之間；以及一耐光高分子分散型液晶層，該耐光高分子分散型液 10 晶層係包含一高分子基質、至少一液晶化合物、一 UV吸收劑以及至少一二色性染料，且該耐光高分子分散型液晶層係夾置於該上基板與該下基板之間，該UV吸收劑為酚類或苯酚類之UV吸收劑，且該UV吸收劑之添加量為佔耐光高分子分散型液晶層中該液晶化合物之0.01 %〜5%;該二色 15 性染料具有高次序性0.4〜0.9，且該二色性染料係選自如含式（I)所示之化合物、以及如式（II)所示之化合物所組之群組，其中，該含式（I)所示之化合物為： X α-<0>-ν=νη〇^β γ 式⑴ A為一 ΝΘΝ—^或一Ν=Ν—，當 A為一 Nc^—^時，B 20 為-COOR2或-CHC(CN)COOR4，且X與Y同為氫原子，其中，R1、R2、及R4獨立為未經取代或可經一或多個氟原子 13 13〇〇〇93X. Patent application scope: 1. A polymer dispersed liquid crystal display device comprising: an upper substrate; a lower substrate; 5 a first electrode formed on the upper substrate, being sandwiched between the upper substrate and the lower substrate a second electrode formed on the lower substrate, sandwiched between the upper substrate and the lower substrate; and a light-resistant polymer dispersed liquid crystal layer, the light-resistant polymer dispersed liquid 10 layer comprises a a polymer matrix, at least one liquid crystal compound, a UV absorber, and at least one dichroic dye, and the light-resistant polymer dispersed liquid crystal layer is interposed between the upper substrate and the lower substrate, and the UV absorber is a phenol a UV absorber of the like or a phenol type, and the UV absorber is added in an amount of 0.01% to 5% of the liquid crystal compound in the light-resistant polymer dispersed liquid crystal layer; the two-color 15-type dye has a high order of 0.4 to 0.9. And the dichroic dye is selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II), wherein the compound represented by the formula (I) is: X α-<0>-ν=ν 〇^β γ Formula (1) A is a ΝΘΝ-^ or a Ν=Ν-, when A is a Nc^-^, B 20 is -COOR2 or -CHC(CN)COOR4, and X and Y are both hydrogen atoms Wherein R1, R2, and R4 are independently unsubstituted or may pass through one or more fluorine atoms 13 13〇〇〇93

N—N 取代之烷基；當A為-㈣4s>Sr5時，b為_NRV，且 x與Y不相同，X為Cl_4烷基，γ為cbBr'I'Cw烷基、-〇CH3、或-〇C2H5，或X與γ同為c卜Br、I、Ci.4烷基、_OCH3、或 "〇C2H5’其中R5為-CH3或-C2H5,及R6與R7獨立為(^⑼烷基 CH2CH2(CF2)mF 〇R3 — chN-N substituted alkyl; when A is -(tetra) 4s>Sr5, b is _NRV, and x is not the same as Y, X is Cl_4 alkyl, γ is cbBr'I'Cw alkyl, -〇CH3, or -〇C2H5, or X and γ are the same as Br, I, Ci.4 alkyl, _OCH3, or "〇C2H5' wherein R5 is -CH3 or -C2H5, and R6 and R7 are independently (^(9)alkyl CH2CH2(CF2)mF 〇R3 — ch

或基；該式（II)所示之化合物為：，其中m為1至10之整數及R3為Cb4烧Or a compound represented by the formula (II): wherein m is an integer from 1 to 10 and R3 is a Cb4

G2 〇 X! G1: -A’- Ar^Zi-Ari \ /η=0~2 ίο g2= ' —Β’|αγ2{ζ2-Αγ2'—2 0·ϊ2」 m=(M JL中，A，炎备式（II) ^ ^ T A為氧、硫或氮；B，為氳、氧、硫、氮或鹵素 (氟〃、氣或溴）；Xl為氫、氫氧基或氨基；&為氫、氫氧基或氨基，八“與八!*2分別為苯基、聯苯、萘基或雜環之芳香 15 % ^ΑΓΐ’與ΑΓ2’分別為苯基、聯苯或雜環之芳香環；匕與 Z2 刀別為-C=N·，-NeN·，-COO-，-〇C〇、〇 s 之連接基；且R1與R2分別為CrQ、_〇CH3〜〇C6Hl3、 -Cy-Cl〜-Cy-C6、-CF3〜c4F9以及-NCS之末端基。 2·如申請專利範圍第1項所述之液晶顯示裝置，其中 14 1300093 %年丨曰修(更)正替換頁該第一電極與該第二電極係相互垂直。 3 ·如申請專利範圍第1項所述之液晶顯示裝置，其中該耐光高分子分散型液晶層中之該液晶化合物係為30個碳以下之液晶化合物。 5 4.如申請專利範圍第1項所述之液晶顯示裝置，其中該耐光高分子分散型液晶層中之該高分子基質係選自由聚乙浠醇（polyvinyl alcohol)、聚乙烯醇共聚物（polyvinyl alcohol copolymer)、聚氧化乙烯【poly(ethylene oxide)】、聚甲基乙浠醚 /順-丁烯二（polymethyl vinyl ether/maleic 10 anhydride)、聚乙烯 °比洛【poly(vinyl pyrrolidone)】、纖維素聚合物（cellulosic polymer)' 天然橡膠（natural gums)、聚氨酯（polyurethane)及聚丙稀酸（polyacrylate)所組成之群組0 5. 如申請專利範圍第1項所述之液晶顯示裝置，其中 15 該财光高分子分散型液晶層更包括界面活性劑、流平劑、增稍劑或消泡劑。 6. —種抑制黃化之高分子分散型液晶組成物，係包括：一高分子基質； 20 至少一液晶化合物，該液晶化合物係為30個碳以下之液晶化合物，一 UV吸收劑，該UV吸收劑為酚類或苯酚類之UV吸收劑，且該UV吸收劑之添加量為液晶化，合物之0.01%〜 5% ;以及 15G2 〇X! G1: -A'- Ar^Zi-Ari \ /η=0~2 ίο g2= '-Β'|αγ2{ζ2-Αγ2'—2 0·ϊ2” m=(M JL, A , 炎备式(II) ^ ^ TA is oxygen, sulfur or nitrogen; B, is argon, oxygen, sulfur, nitrogen or halogen (fluorine, gas or bromine); Xl is hydrogen, hydroxyl or amino; & Is hydrogen, hydroxyl or amino, eight "and eight! * 2 respectively phenyl, biphenyl, naphthyl or heterocyclic aromatic 15% ^ ΑΓΐ ' and ΑΓ 2 ' respectively phenyl, biphenyl or heterocyclic Aromatic ring; 匕 and Z2 knives are -C=N·, -NeN·, -COO-, -〇C〇, 〇s linkage; and R1 and R2 are CrQ, _〇CH3~〇C6Hl3, - Cy-Cl~-Cy-C6, -CF3~c4F9, and the terminal group of -NCS. 2. The liquid crystal display device of claim 1, wherein 14 1300.93% of the annual repair (more) replacement page The liquid crystal display device according to the first aspect of the invention, wherein the liquid crystal compound in the light-resistant polymer-dispersed liquid crystal layer is 30 carbon or less. Liquid crystal compound. 5 4. As described in claim 1 In the liquid crystal display device, the polymer matrix in the light-resistant polymer-dispersed liquid crystal layer is selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymer, and poly(ethylene oxide). )], polymethyl vinyl ether/maleic 10 anhydride, polyethylene (poly(vinyl pyrrolidone), cellulose polymer (cellulosic polymer)' natural rubber ( The liquid crystal display device of the first aspect of the invention is the liquid crystal display device of the first aspect of the invention, wherein the financial polymer dispersible liquid crystal layer further comprises a surfactant, a leveling agent, a thinning agent or an antifoaming agent. 6. A polymer dispersed liquid crystal composition for inhibiting yellowing, comprising: a polymer matrix; 20 at least one liquid crystal compound, the liquid crystal compound It is a liquid crystal compound of 30 carbon or less, a UV absorber, which is a UV absorber of phenol or phenol, and the amount of the UV absorber added is liquid crystal. 0.01% to 5% of the composition; and 15

1300093 至少一二色性染料，該二色性染料具有高次序性 0.4〜0.9，且該二色性染料係選自如含式（1)所示之化合物、以及如式（II)所示之化合物所組之群組，其中，該式⑴所示之化合物為·· Χ Α Υ 式⑴ A為 N、〇 N-N 或—當人為 Ν' B為-C00R2或-CHC(CN)C00R4，且X與Y同為氫原子，其中，Ri、R2、及R4獨立為未經取代或可經一或多個氟原子 N—N 取代之Cmo烷基；當A為—Ν=Ν~ν^#時，B為_NR6R7，且 10 X與Y不相同，又為匚“烷基，γ為氣、溴、碘、c1-4烷基、 -OCH3、或-〇C2H5，或X與γ同為氯、漠、蛾、Cu4燒基、 -OCH3、或-〇C2H5，其中 R5為-CH3 或-C2H5，及 R6與 R7獨立 ch21300093 at least one dichroic dye having a high order of 0.4 to 0.9, and the dichroic dye is selected from the group consisting of a compound represented by the formula (1) and a compound represented by the formula (II) The group of the group, wherein the compound represented by the formula (1) is ·· Χ Α Υ (1) A is N, 〇NN or - when the artificial Ν' B is -C00R2 or -CHC(CN)C00R4, and X and Y is a hydrogen atom, wherein Ri, R2, and R4 are independently a Cmo alkyl group which is unsubstituted or may be substituted with one or more fluorine atoms N-N; when A is -Ν=Ν~ν^#, B is _NR6R7, and 10 X is different from Y, and is 匚 "alkyl, γ is gas, bromine, iodine, c1-4 alkyl, -OCH3, or -〇C2H5, or X and γ are both chlorine, Mo, moth, Cu4 alkyl, -OCH3, or -〇C2H5, where R5 is -CH3 or -C2H5, and R6 is independent of R7 and ch2

C〇r3 為 Ci-U)烷基、_CH2CH2(CF2)mFC〇r3 is Ci-U)alkyl, _CH2CH2(CF2)mF

R3 — CH2 、或 15 v_/ ，其中m為1至10之整數，且R34C 燒基，該式（Π)所示之化合物為： 16 1300093 乙月曰修(更)正替換頁R3 — CH2 , or 15 v_/ , where m is an integer from 1 to 10, and R34C is a calcined group. The compound represented by the formula (Π) is: 16 1300093 乙月曰修(more) replacement page

G2= -A-Ar^ZrArV^Ri \ yn=0-2 ，Β’+Α「2{ζ2-Αγ2·)·Ρ{2 η. 0^2 m=0〜1 式（II) 里中，A’為氧、硫或氣，B’為鼠、氧、硫、氣或鹵素（乱、氣或、;臭）；X1為氮、氫氧基或氨基；X2為氫、氳氧基或氨基， Ari與Ar2分別為苯基、聯苯、萘基或雜環之芳香環；ArV 5 與Ar2,分別為苯基、聯苯或雜環之芳香環；心與22分別為 -C=C-, -C=C~) -C=N-5 -Ν=Ν-, -COO-, -OCO-, Ο, S^ 基；且R〗與R2分別為Ci〜C6、_OCH3〜OC6H13、 Cy-Cl^—Cy-C6、-CF3〜C4F9以及-NCS末端基。 7.如申請專利範圍第6項所述之液晶組成物，其中該 10 高分子基質係選自由聚乙烯醇（polyvinyl alcohol)、聚乙烯醇共聚物（polyvinyl alcohol copolymer)、聚氧化乙稀【poly(ethylene oxide)】、聚曱基乙烯謎/順-丁烯二 (polymethyl vinyl ether/maleic anhydride)、聚乙稀 σ比口各【poly(vinyl pyrrolidone)】、纖維素聚合物（cellulosic 15 polymer)、天然橡膠（natural gums)、聚氨醋（polyurethane) 及聚丙烯酸（polyacrylate)所組成之群組。 8 .如申請專利範圍第6項所述之液晶組成物，其中更包括界面活性劑、流平劑、增稠劑或消泡劑。 17 1300093G2= -A-Ar^ZrArV^Ri \ yn=0-2 , Β'+Α"2{ζ2-Αγ2·)·Ρ{2 η. 0^2 m=0~1 In the formula (II), A' is oxygen, sulfur or gas, B' is rat, oxygen, sulfur, gas or halogen (chaotic, gas or, odor); X1 is nitrogen, hydroxyl or amino; X2 is hydrogen, decyloxy or amino , Ari and Ar2 are respectively aromatic rings of phenyl, biphenyl, naphthyl or heterocyclic ring; ArV 5 and Ar2 are respectively aromatic rings of phenyl, biphenyl or heterocyclic ring; and heart and 22 are -C=C- respectively. , -C=C~) -C=N-5 -Ν=Ν-, -COO-, -OCO-, Ο, S^ base; and R and R2 are Ci~C6, _OCH3~OC6H13, Cy- The liquid crystal composition of the sixth aspect of the invention, wherein the 10 polymer matrix is selected from the group consisting of polyvinyl alcohol, Polyvinyl alcohol copolymer, poly(ethylene oxide), polymethyl vinyl ether/maleic anhydride, polyethylene sigma ratio [poly(vinyl pyrrolidone)], cellulosic 15 polymer, natural gums a group of polyurethanes and polyacrylates. 8. The liquid crystal composition of claim 6, which further comprises a surfactant, a leveling agent, a thickener Or defoamer. 17 1300093

L l i〜麵:”正. ΐν'. ο 上一~ττ 離子含量（ppm) —^ ho K) CO CJ cnocnocnocno oooooooo 3 各 5 6 7 8 9aMeOH 噼背 affal(hr)涵一 Na#+命* 1300093 S 2 私年丨二月>〇!^|價)正f涣頁L li~面: "正. ΐν'. ο Previous ~ττ Ion content (ppm) —^ ho K) CO CJ cnocnocnocno oooooooo 3 each 5 6 7 8 9a MeOH 噼backaffal(hr) 涵一Na#+命* 1300093 S 2 Private year 丨 February> 〇!^|Price) 正f涣page