TWI320802B - - Google Patents

Description

1320802 (1) 玖、發明說明 【發明所屬之技術領區】 本發明係有關手提電腦，產業用計測器之顯示器所使 用之藍色濾光片及使用其之有機電激發光元件（以下簡稱 有機EL)。 【先前技術】 做爲有機EL顯示器之多彩或全彩化方法之1者如： 吸收有機發光體之發光區的光後，使可視光區螢光所發光 之螢光材料用於過濾器之色彩轉換方式被揭示於特開平3-1 52897號公報，特開平5 -25 8 860號公報等。此方式之有機 發光體發光色彩並未限於白色，因此，更高亮度之有機發 光體可適用於光源，如：利用藍色發光之有機發光體後， 使藍色光呈綠色光，紅色光之波長轉換之色彩轉換方式被 揭示於特開平3- 1 5 2897號，特開平8 -2 8 603 3號，特開平9-208944中。而，含此螢光色素之螢光轉換膜呈高度精細之 透明支撐基板上做成圖案後，即使使用有機發光體之近紫 外光至可視光類之低能量光，仍可構成全彩之發光型顯示 器。 利用濾光片及色轉換濾器以及，有機發光體做爲構成 要素之色轉換方式的有機EL元件中，針對彩色顯示器之 製造步驟所要求之耐熱性，做爲顯示器所使用之耐氣候性 ，以及被要求高精細度之影像以使用顏料分散法所作成之 濾光片爲其主流者，於玻璃基板上塗佈粒徑Ιμηι以下微分 -5- (2) (2)1320802 散紅色，藍色或綠色顏料於感光性樹脂溶液中者後，藉由 照相石版術形成所期待之圖案（特公平4-3 798 7號公報， 特公平4-3 904 1號公報等）。 爲求提昇濾光板之色純度，彩度，光透過量，先行中 以提昇光透過量做爲目的者，採用減少對於形成影像用材 料中感光性樹脂之著色顏料含量，或使形成影像用材料所 形成之影像形成膜之厚度變薄方法。 惟，此等方法中，其濾光片本身之彩度降低，整體顯 示器呈反白現象其必要之色彩鮮豔度變差，反之，若考量 提昇彩度而增加著色顏料含量則整體顯示器變暗，無法確 保明亮度，務必增加背光之光量，而導致顯示器消耗電量 大增之問題產生。 對於此，以提昇光透過量做爲目的者，公知方法有將 顏料粒子之粒徑微分散至其呈色波長之1/2以下爲止（橋 爪清，色材協會誌，1967年12月，p608)，惟，藍色顏料 相較於其他紅色，綠色顏料其呈色波長較短，因此，務必 更進行微分散，而導致成本之提昇，以及分散後之安定性 問題點產生。 做爲藍色顔料者，以具有模，模，模結晶形態之銅酞 菁系藍被廣泛使用之（色材工學手冊，色材協會編集， P.333) ’惟，單獨使用模之銅酞菁藍做爲藍色顏料用於 濾光片時’其著色力低，對於呈目的彩度之感光性樹脂務 必混合極多顔料，造成形成濾光板後其耐熱變色，以及與 玻璃基板相互之密合性出現問題，甚至，波長600nm以上 (3) (3)1320802 透光最大，產生色純度降低之問題。 另外，單獨使用模之銅酞青藍做爲藍色顔料使用時， 其良好著色力對於感光性樹脂雖可減少添加量，惟，取得 目的彩度則漸增加顏料混合量，而提昇感光性樹脂硬化波 長365 ηπι之遮光性，降低光硬化感度後，顯像時出現膜變 薄，圖案晃動之問題產生。 又，模之銅酞菁系藍帶有綠至之藍色者，因此，以此 做爲藍色顏料單獨使用時，將出現與目標之NTSC色相產 生極大落差之問題點。 又，公知者有將銅酞菁系藍中混合二噁嗪系紫之顏料 用於濾光板者（特公平6-95211號公報，特開平1-200353 號公報，特公平4-3 798 7號公報等），利用該3種銅酞菁藍 任一種與二噁嗪系紫之I.C.顏料紫23之混色後，可控制 500~5 50nm之光透射，提昇色純度，惟，目的之藍色領區 420〜5 00之光透射被抑制，而降低做爲顯示器時之亮度問 題出現。更於做爲顯示器時，偏光板之藍色領區光透射率 相較於其他色領區被抑制70〜8 0%，因此，藍色濾器之光 透射量被期待提昇之。 【發明內容】 本發明係以提供一種高度藍色透光率，且，綠色透光 率低之藍色濾光片及藍色純度良好之有機電激發光元件爲 目的者。 本發明爲達成該目的’以藍色濾光片含有結構式（1 (4) (4)1320802 )所示第I色素與粘合劑樹脂，同時，並含有吸收該第1色 素之螢光後’且於可視波長區未具螢光極大之第2色素者1320802 (1) 玖, invention description [Technical domain to which the invention belongs] The present invention relates to a blue filter used in a display of a portable computer, an industrial measuring device, and an organic electroluminescent device using the same (hereinafter referred to as organic EL). [Prior Art] As one of the colorful or full-color methods of the organic EL display, for example, after absorbing the light of the light-emitting area of the organic light-emitting body, the fluorescent material that emits light in the visible light region is used for the color of the filter. The method of the present invention is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The organic illuminant color of the mode is not limited to white. Therefore, the higher brightness organic illuminant can be applied to a light source, such as: after using the blue illuminating organic illuminant, the blue light is green, and the wavelength of the red light The color conversion method of the conversion is disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei. However, after the fluorescent conversion film containing the fluorescent pigment is patterned on the highly fine transparent supporting substrate, even if the near-ultraviolet light of the organic luminous body is used to the low-energy light of the visible light, the full-color light can be formed. Type display. In the organic EL device using a color filter and a color conversion method using an organic light-emitting device as a color conversion method, the heat resistance required for the manufacturing process of the color display is used as the weather resistance used for the display, and High-definition images are required to be the mainstay of filters made using the pigment dispersion method. The particle size is Ιμηι below the differential on the glass substrate -5- (2) (2) 1320802 red, blue or After the green pigment is used in the photosensitive resin solution, the desired pattern is formed by lithography (Japanese Patent Publication No. 4-3798, Japanese Patent Publication No. Hei 4-3904 No. 1). In order to improve the color purity, chroma, and light transmission of the filter, the purpose of improving the light transmission amount in the first step is to reduce the color pigment content of the photosensitive resin in the image forming material, or to form an image material. A method of thinning the thickness of the formed image forming film. However, in these methods, the chroma of the filter itself is lowered, and the overall display is whitened, and the necessary color vividness is deteriorated. Conversely, if the coloring pigment content is increased to increase the chroma, the overall display becomes dark. It is impossible to ensure the brightness, and it is necessary to increase the amount of backlight light, which causes a problem that the display consumes a large amount of power. In view of this, in order to increase the amount of light transmission, a known method is to slightly disperse the particle diameter of the pigment particles to less than or equal to 1/2 of the color wavelength (Qiao Qiqing, Color Materials Association, December 1967, p608) However, the blue pigment has a shorter color wavelength than other red and green pigments. Therefore, it is necessary to perform microdispersion more, resulting in an increase in cost and a problem of stability after dispersion. As a blue pigment, it is widely used as a copper phthalocyanine blue with a mold, a mold, and a mold crystal form. (Color Materials Engineering Handbook, Color Materials Association, P.333) 'However, copper alone is used. When phthalocyanine blue is used as a blue pigment for a filter, its coloring power is low. For a photosensitive resin having a desired color, it is necessary to mix a large amount of pigment, resulting in heat-resistant discoloration after forming a filter, and mutual interaction with a glass substrate. There is a problem with the adhesion, and even the wavelength of 600 nm or more (3) (3) 1320802 has the largest light transmission, resulting in a problem of a decrease in color purity. In addition, when the copper indigo blue is used as the blue pigment alone, the good coloring power can reduce the amount of the photosensitive resin, but the color of the pigment is gradually increased, and the photosensitive resin is increased. The light-shielding property of the hardening wavelength of 365 ηπι reduces the light-hardening sensitivity, and the film becomes thinner at the time of development, and the problem of pattern sway occurs. Further, the copper phthalocyanine blue of the mold has a greenish blue color. Therefore, when it is used alone as a blue pigment, there is a problem that the target NTSC hue is greatly reduced. In addition, it is known that a copper phthalocyanine-blue mixed dioxin-based violet pigment is used for a filter (Japanese Patent Publication No. Hei 6-95211, Japanese Patent Publication No. 1-200353, No. 4-3798 No. 7) In the bulletin, etc., by using any of the three kinds of copper phthalocyanine blue and the color of the dipyridazine-based violet IC pigment violet 23, it is possible to control the light transmission of 500 to 50 nm and improve the color purity, but the blue collar of the purpose The light transmission of the region 420 to 50,000 is suppressed, and the luminance problem when the display is lowered appears. When used as a display, the light transmittance of the blue collar of the polarizing plate is suppressed by 70 to 80% compared with other color collar regions, and therefore, the light transmission amount of the blue filter is expected to be improved. SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a blue color filter having a high blue light transmittance and a low green light transmittance and an organic electroluminescence device having a good blue purity. In order to achieve the object of the present invention, the blue color filter contains the first dye represented by the structural formula (1 (4) (4) 1320802) and the binder resin, and further contains the fluorescent light after absorbing the first pigment. 'And the second color pigment that does not have a very large fluorescence in the visible wavelength region

[結構（1 )中，Ri〜R6分別獨立地代表可被取代之氫 原子，烷基，芳基，或雜環基，R7代表碳數1〜6之鏈式不 飽和烴基。X-爲選自 Γ，Br_，Cl·，F·，C103·，Br03·， ΙΟΓ，C104.，BF4.，PF4·，SbF4·，Br04.，及有機系陰離 子群中之陰離子者] 以上記結構式（1)所示之第1色素做爲藍色濾光片酞 菁之藍色染料使用後，抑制5 00〜600nm之光透射率後，提 昇藍色純度之同時，可做成高度光透射量之藍色濾光片。 又，除第1色素外，並藉由含有在可視波長區之75 Onm以 下不具螢光極大之第2色素，使第丨色素所產生之 60 Onm〜7 OOnm螢光被第2色素吸收後而防止藍色純度之降 低發生。 本發明，其藍色濾光片含有結構式（1)所示第1色素 及粘合劑樹脂之同時’亦含有結構式（2)所示第2色素者 (5) (5)1320802[In the structure (1), Ri to R6 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group which may be substituted, and R7 represents a chain-unsaturated hydrocarbon group having 1 to 6 carbon atoms. X- is selected from the group consisting of ruthenium, Br_, Cl·, F·, C103·, Br03·, ΙΟΓ, C104., BF4., PF4·, SbF4·, Br04., and anions in the organic anion group] When the first dye represented by the structural formula (1) is used as a blue dye of a blue filter phthalocyanine, the light transmittance of 500 to 600 nm is suppressed, and the blue purity is improved, and the high light can be made. Transmittance blue filter. Further, in addition to the first coloring matter, the 60% to 7000 nm fluorescent light generated by the second coloring matter is absorbed by the second coloring matter by containing the second coloring matter which is not fluorescently large at 75 Onm or less in the visible wavelength region. Prevents the decrease in blue purity from occurring. In the present invention, the blue color filter contains the first coloring matter and the binder resin represented by the structural formula (1), and the second coloring matter represented by the structural formula (2) is also contained. (5) (5) 1320802

[結構式（1 )中’ 〜R6分別獨立地代表可被取代之 氫原子’烷基’芳基’或雜環基者，R7代表碳原子ι~6 之鏈式不飽和烴基。X-代表選自1-，8厂，（：1-，？-，（：103-，Br〇3· ’ I03- ’ Cl〇4·，BF4_，PF〆，SbF4·，Βγ〇4·，及有 機系陰離子群中之陰離子][In the structural formula (1), R to R6 each independently represent a hydrogen atom 'alkyl 'aryl' or a heterocyclic group which may be substituted, and R7 represents a chain unsaturated hydrocarbon group of carbon atoms ι to 6. X- represents a plant selected from 1-, 8 plants, (: 1-, ?-, (:103-, Br〇3· ' I03- 'Cl〇4·, BF4_, PF〆, SbF4·, Βγ〇4·, And anions in the organic anion group]

[結構式（2)中，R!代表氫原子，烷基，芳基，或雜 環基者。Χ_表選自 Γ，Br_，Cl·，F·，C103·，Br03·，1〇3_ ’ C104·，BF4·，PF4·，SbF4·，Br04·，及有機系陰離子群 中之陰離子。Y代表〇原子或s原子。a爲1〜6之整數。 ] 本發明藍色濾光片中更可含有使該第1或第2色素登 光消光之驟冷器陰離子者。 又，本發明之有機電激發光元件至少一部份濾光片使 用該藍色濾光片者。 (6) (6)1320802 【實施方式】 [發明實施之形態] 如圖1所不，本實施例有機EL元件1〇〇係於透明支撑 基板10上依序形成藍色濾光片20，有機保護層30,無機氧 化膜40，透明陽極50，正孔注入層51，正孔輸送層52，發 光層53’電子注入層54，及陰極55後，整體構成有機肛 元件者。 以下，針對爲形成本發明藍色濾光片20之調整藍色影 像形成用材料所使用之各材料進行說明。 [第1色素] 本發明藍色濾光片係以含有結構式（1 )所示D奎嘻藍 系色素做爲第1色素者。結構式（1)所示之色素可單獨使 用1種，亦可組合其複數種使用之。結構式（1)所示II奎哮 藍系色素其自體之化學性及熱安定性極高，因此，即使未 藉由顏料分散法其藍色濾光片之耐熱性仍高。更於第1色 素中亦可混合銅酞菁系等其他藍色顔料後使用之。 取得本發明形成藍色影像用材料時，針對結構式（1 )所示曈嚀藍系色素之粘合劑樹脂的混合比以0.1 ~40重量 份者宜。藉此，可抑制500〜5 50nm之光透射，提昇色純度 者。又，結構式（1)所示之喹嚀藍系色素可做成顔料化 後使用之，以公知之方法做爲藍色顏料分散體之製造方法 利用之。如：將銅酞菁系藍與結構式（1 )所示之曈嚀藍 系色素與有機溶劑，意圖分散安定化之顏料衍生物（於必 -10- (7) (7)1320802 要時添加之）以及分散劑同時利用混砂機等分散機進行顏 料之微分散，安定化後，以含有銅酞菁系藍與結構式（1 )所示喹嚀藍系色素做爲藍色顏料分散體者亦可。 [第2色素] 所添加者係吸收第1色素之螢光（ 600nm〜700nm)， 且於可視波長區（ 75 0nm以下）中不具螢光之色素作爲第 2色素。針對第2色素之粘合劑樹脂其混合比以0.1〜40重量 份者宜。又，做爲藍色濾光片機能者以於藍色波長區中不 具吸收之色素者宜。具體而言，添加於濾器時，只要於 45 Onm之透光率爲60%以上之色素者即可使用之。 例如：1，1'-二乙基-4，4’-D奎啉藍色素碘化物（ Cryptocyanine) 、1，1·-二乙基-2，2匕二D奎琳藍色素碘化 物（DDI ) 、3，3·-二甲基噁三鳴啉藍色素碘化物（[In the structural formula (2), R! represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The Χ_ table is selected from the group consisting of ruthenium, Br_, Cl·, F·, C103·, Br03·, 1〇3_ 'C104·, BF4·, PF4·, SbF4·, Br04·, and anions in the organic anion group. Y represents a deuterium atom or an s atom. a is an integer from 1 to 6. The blue filter of the present invention may further comprise a quencher anion which causes the first or second pigment to be matted. Further, at least a part of the filter of the organic electroluminescent device of the present invention uses the blue filter. (6) (6) 1320802 [Embodiment] [Embodiment of the Invention] As shown in Fig. 1, the organic EL element 1 of the present embodiment is sequentially formed on the transparent supporting substrate 10 to form a blue color filter 20, organically The protective layer 30, the inorganic oxide film 40, the transparent anode 50, the positive hole injection layer 51, the positive hole transport layer 52, the light-emitting layer 53' electron injection layer 54, and the cathode 55 constitute the organic anion element as a whole. Hereinafter, each material used for forming the blue image forming material for forming the blue color filter 20 of the present invention will be described. [1st coloring matter] The blue color filter of the present invention contains the D-queen blue coloring matter represented by the structural formula (1) as the first coloring matter. The dyes of the formula (1) may be used singly or in combination of plural kinds. The II quinine blue coloring matter represented by the structural formula (1) has an extremely high chemical property and thermal stability, so that the heat resistance of the blue color filter is not high even by the pigment dispersion method. Further, it is also possible to mix other blue pigments such as copper phthalocyanine in the first coloring matter. When the material for forming a blue image of the present invention is obtained, the mixing ratio of the binder resin of the indigo dye represented by the structural formula (1) is preferably 0.1 to 40 parts by weight. Thereby, light transmission of 500 to 5 50 nm can be suppressed, and color purity can be improved. Further, the quinoxa blue-based dye represented by the structural formula (1) can be used after being pigmented, and is used as a method for producing a blue pigment dispersion by a known method. For example, copper phthalocyanine blue and an indigo pigment represented by structural formula (1) and an organic solvent are intended to disperse the stabilized pigment derivative (Yibi-10-(7) (7)1320802 And the dispersing agent simultaneously uses a dispersing machine such as a sand mixer to perform fine dispersion of the pigment, and after stabilization, the quinoxaline-based dye containing copper phthalocyanine blue and structural formula (1) is used as a blue pigment dispersion. Also available. [Second Pigment] The added one is a pigment which absorbs the fluorescence of the first dye (600 nm to 700 nm) and which does not have fluorescence in the visible wavelength region (75 nm or less). The binder resin for the second pigment is preferably used in an amount of 0.1 to 40 parts by weight. Further, as a blue filter function, it is preferable that the dye is not absorbed in the blue wavelength region. Specifically, when it is added to a filter, it can be used as long as it has a light transmittance of 60% or more at 45 Onm. For example: 1,1'-diethyl-4,4'-D quinine blue pigment iodide (Cryptocyanine), 1,1·-diethyl-2,2匕2 D-quine blue pigment iodide (DDI , 3,3·-dimethyloxanthine blue pigment iodide (

Methyl DOTCI ) 、1，Γ，3，3，3，，3·-六甲基吲哚三喹 啉藍色素碘化物（HITCI) ，IR125(Lambda Phisik 製） 、1，1'-二乙基-4，4·-Π奎啉藍色素碘化物（Cryptocyanine )、IR144( Lambda Phisik 製）、3，3'-二乙基-9，1 卜新 戊烯噻三卩奎啉藍色素碘化物（DNTTCI ) 、1，1’，3，3， 3 1，3 1 -六甲基-4，4 ·，5，5 ’ -二苯-2，2 1 -吲哚三D奎啉藍色 素碘化物（HDITCI) 、1，2^二乙基-4，4·-二喹啉藍色素 碘化物（DDCI-4 )等例者。 或，結構式（2)所示之喹嚀藍系色素亦可做爲第2色 素之使用，具體例如：3，3’-二乙基噻三哮啉藍色素碘化 -11 - (8) (8)1320802 物（DTTCI) 、3，3，-二乙基-4，4’，5，5·-二苯並噻三 D 奎 啉藍色素碘化物（DDTTC1)等例。Methyl DOTCI ), 1, Γ, 3,3,3,,3·-hexamethylguanidinoquinoline blue pigment iodide (HITCI), IR125 (manufactured by Lambda Phisik), 1,1'-diethyl- 4,4·-Π Π 蓝色 蓝色 蓝色 ( ( IR IR IR IR IR IR IR IR IR IR DN DN DN DN DN DN ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( , 1,1',3,3,3 1,3 1 -hexamethyl-4,4 ·,5,5 '-diphenyl-2,2 1 -indole tri D-quinoline blue pigment iodide ( HDITCI), 1,2^diethyl-4,4·-diquinoline blue pigment iodide (DDCI-4) and the like. Alternatively, the quinoxaline-based pigment represented by the structural formula (2) can also be used as the second dye, specifically, for example, 3,3'-diethyl thiatriol blue pigment iodide-11 - (8) (8) 1320802 (DTTCI), 3,3,-diethyl-4,4',5,5--dibenzothiatris- D-quinoline blue pigment iodide (DDTTC1) and the like.

[結構式（2)中，Ri代表氫原子，院基，芳基，或雜 環基。X·表選自 Γ，Br·，Cl—，F·，CI03· ’ Βγ03·，Ι〇3·， Cl〇4·，BF4·，PF4·，SbF4·，Br04_，及有機系陰離子群中 之陰離子。Y代表0原子或s原子。a爲1〜6之整數。] [驟冷器] 所使用色素爲陽離子系色素者，因此，做爲驟冷器者 可使用陰離子系之單獨氧驟冷器者。具體例如：揭示於特 開昭5 9-5 5<795號，特開昭60-234892號等之過渡金屬螯 合劑，雙亞銨鹽等可使用之。 [粘合劑] 本發明藍色濾光片所使用之粘合劑樹脂只要具有可視 光透射性，與基板密合性良好者即可，可使用公知的熱塑 樹脂’熱硬化樹脂，光硬化樹脂等。具有感光性樹脂者較 可以簡便製作濾器之精細圖案爲特別理想者。 -12- (9) (9)1320802 [藍色濾光片及有機EL元件之製作] 將上述各材料所成之藍色形成影像用材料以所期待圖 案塗佈於透明支撐基板10後，形成藍色濾光片層20。塗 佈方法並無特別限定，一般可使用旋轉塗層法，滾輥塗層 法，鑄塑法，網版印刷法，噴墨法等。硬化方法亦無特別 限定，可使用熱硬化（考量螢光材料之劣化，以15(TC爲 止之溫度下進行硬化者宜），濕氣硬化，光硬化（考量螢 光材料之劣化，以可視光進行硬化者宜），更可組合此等 之硬化法等。 形成藍色影像元素之前，或之後，必要時可藉由使用 紅色或/及綠色影像元素形成材料形成紅色或/及綠色濾光 片後，製作多色濾光片。更於此濾光片上介著有機保護層 30及無機氧化膜40層合有機發光體500後可製作多色有 機EL元件。做爲有機發光體5 〇〇層合方法者如：往濾光 片上面依次形成透明陽極50 ’正孔注入層5〗，正孔輸送 層52，發光層53，電子注入層54’及陰極55之方法， 將形成於另一基板上之有機發光體5 00粘合於無機氧化膜 40之方法例者。如此作成之有機EL元件可使用鈍態驅動 方式之有機EL顯示器’亦可使用動態驅動方式之有機顯 示器。 [實施例] [實施例1] [黑罩之製作] -13- (10) 1320802 並未顯示於圖1，對照評定時，於藍色濾光片20 明電極5 0端部爲排除反射光之影響，由透明支撐基杰 面使藍色濾光片2 0端部作成不可視化爲目的者，首 配設黑罩。 於玻璃製透明支撐基板10上以旋轉塗層法全面 塗佈黑罩塗液（CK840 0L，富士軟片ARCH製），於 下進行加熱乾燥後，利用照相石版術取得0.1 3mm間 0.10mm間隙之格子狀黑罩圖案。 [藍色濾光片之製作} 使用做爲粘合劑之透明性光聚合性樹脂（新日鐵 (股份）製，259PAP5 )，針對每100重量份之透明 聚合性樹脂固形份進行添加2重量份之做爲藍色染料 構式（3)所示之色素，更添加1重量份之做爲結構另 )所示之色素（Lambda Physik公司製HDITCI)後， 藍色濾光片用塗液。 ，透 反10 先應 進行 8 or 距， 化學 性光 之結 ：(4 做成[In the structural formula (2), Ri represents a hydrogen atom, a hospital group, an aryl group, or a heterocyclic group. The X· table is selected from the group consisting of ruthenium, Br·, Cl—, F·, CI03· 'Βγ03·, Ι〇3·, Cl〇4·, BF4·, PF4·, SbF4·, Br04_, and the organic anion group. Anion. Y represents 0 atom or s atom. a is an integer from 1 to 6. [Quencher] The pigment used is a cationic dye. Therefore, if it is a quencher, an anion-based individual oxygen quencher can be used. For example, a transition metal chelating agent, a bis-ammonium salt or the like which is disclosed in JP-A-59-9-5 < 795, JP-A-60-234892, and the like can be used. [Binder] The binder resin used in the blue filter of the present invention may have visible light transmittance and may have good adhesion to the substrate, and a known thermoplastic resin 'thermosetting resin, photohardenable may be used. Resin, etc. It is particularly desirable to have a photosensitive resin, and it is more preferable to make a fine pattern of a filter. -12- (9) (9) 1320802 [Production of Blue Filter and Organic EL Element] The blue image forming material made of each of the above materials is applied to the transparent supporting substrate 10 in a desired pattern to form Blue filter layer 20. The coating method is not particularly limited, and a spin coating method, a roll coating method, a casting method, a screen printing method, an ink jet method, or the like can be generally used. The hardening method is not particularly limited, and thermal curing can be used (considering deterioration of the fluorescent material, it is preferable to perform hardening at a temperature of TC), moisture hardening, and photohardening (considering deterioration of the fluorescent material to visible light) For hardening, it is also possible to combine such hardening methods, etc. Before or after forming blue image elements, red or/and green filters can be formed by using red or/and green image element forming materials if necessary. Then, a multi-color filter is produced, and a multi-color organic EL element can be produced by laminating the organic light-emitting body 500 with the organic protective layer 30 and the inorganic oxide film 40 on the filter, and the organic light-emitting element can be produced as an organic light-emitting body. For the lamination method, for example, a transparent anode 50 'positive hole injection layer 5>, a positive hole transport layer 52, a light emitting layer 53, an electron injection layer 54' and a cathode 55 are formed on the filter, and the method is formed on the other. An organic EL device in which the organic light-emitting body 500 on the substrate is bonded to the inorganic oxide film 40 can be used as the organic EL device of the passive driving method, and an organic display of a dynamic driving method can also be used. EXAMPLES [Example 1] [Production of black cover] -13- (10) 1320802 is not shown in Fig. 1. In the comparison evaluation, the end of the bright electrode 50 of the blue filter 20 is excluded from reflected light. The effect is that the transparent support base surface makes the blue filter 20 end portion invisible for the purpose of visualizing the black cover. The black cover is completely coated on the glass transparent support substrate 10 by the spin coating method. The liquid (CK840 0L, Fujifilm ARCH) was heated and dried, and a grid-like black mask pattern of 0.10 mm gap between 0.13 mm was obtained by lithography. [Production of Blue Filter] Used as a bonding The transparent photopolymerizable resin (manufactured by Nippon Steel Co., Ltd., 259PAP5) was added in an amount of 2 parts by weight per 100 parts by weight of the transparent polymerizable resin solid portion as a blue dye configuration (3). The coloring matter was further added with 1 part by weight of the dye (the HDITCI manufactured by Lambda Physik Co., Ltd.), and the coating liquid for the blue filter. , through the reverse 10 should first carry out 8 or distance, chemical light knot: (4 made

ch3chch2ch2 ch3 ch2ch2chch3 ch3 (11) (11)1320802Ch3chch2ch2 ch3 ch2ch2chch3 ch3 (11) (11)1320802

於透明支撐基板〗〇上藉由旋轉塗層進行該藍色濾光片 用塗液之塗膜後，8 0 °C下進行加熱乾燥後，藉由照相石版 術形成〇 . 1 3 m m間距，〇 · 〇〗m m間隙之格子狀藍色濾光片圖 案。 [有機EL元素之製作] 藉由上述方法，於玻璃製透明支撐基板1之單一主面 上形成藍色濾光片2之後，於此上面依序進行有機保護層3 及無機氧化層4之製膜後，更於其上形成有機發光體層500 後製成有機EL元件。有機發光體層500係由透明陽極50/正 孔注入層51/正孔輸送層52/發光層53 /電子注入層54/陰 極55所成之6層構成者。以下，說明具體之製作順序。 於形成該藍色濾光片20之透明支撐基板10進行塗佈透 明性光聚合性樹脂（新日鐵化學（股份）製，25 9PAP5 ) ，乾燥後，於藍色濾光片20上形成厚度爲5 μιη之有機保護 層30，於其上藉由濺射形成由Si02K成厚度lOOnm之無機 氧化層40。再藉由同濺射於該無機氧化層40全面形成由 ITO所成層之膜，進行下述之圖案後，取得透明陽極50。 亦即，於該ITO膜上進行塗佈膜厚〗〇〇nm之光阻劑（東京 應化（股份）製，OFRP- 800 )之後，藉由照相石版術做 -15- (12) (12)1320802 成0.13mm線間距，0.01mm間隙之格子狀透明陽極50。 再將此基板裝置於抵抗加熱蒸銨裝置內，依序使正孔 注入層51，正孔輸送層52，發光層53，電子注入層54及陰 極55不破真空進行成膜。成膜時之真空槽內壓進行減壓至 ll(T4Pa者。具體而言，正孔注入層51做成厚度lOOnm之銅 酞菁（CuPc)層，正孔輸送層52做成厚度20nm之4，4、雙 [N- ( 1-蔡基）-N-苯胺基]雙苯基（-NPD )層，發光層53 做成厚度30nm之4，4’-雙（2，2-二苯基乙烯基）雙苯基 (DPVBi )層，電子注入層54做成厚度20nm之三（8-經基 喹啉）鋁絡合物（Alq )層。陰極爲厚度200nm所成之 Mg/Ag (重量比1 : 10 )，外罩蒸鍍後，做成與陽極線呈垂 直之0.33mm間距，0.05mm間隙之格子狀圖案者。 該各層製膜完成後，由蒸鍍裝置取出有機EL元件100 後，於氮氣氣氛下，使用密封玻璃及UV粘著劑後，使元 件未直接接觸大氣進行密封（未示圖）。所製作之有機 EL元件100於波長470nm具頂點呈藍色光之發光。 [實施例2] 實施例1之藍色濾光片形成中，以結構式（5)所示之 色素取代實施例1所使用之第2色素做爲第2色素後，針對 每1〇〇重量份透明性光聚合性樹脂固形份添加1重量份之外 ，與實施例1同法製成有機EL元件。 -16- (13) 1320802After the coating film of the blue color filter coating liquid is applied to the transparent support substrate by a spin coating layer, after heating and drying at 80 ° C, a 〇. 1 3 mm pitch is formed by photolithography. 〇· 〇〗 A grid-like blue filter pattern with mm gap. [Production of Organic EL Element] After the blue color filter 2 is formed on a single main surface of the glass transparent support substrate 1 by the above method, the organic protective layer 3 and the inorganic oxide layer 4 are sequentially formed thereon. After the film, the organic light-emitting layer 500 is formed thereon to form an organic EL element. The organic light-emitting layer 500 is composed of a transparent anode 50 / a positive hole injection layer 51 / a positive hole transport layer 52 / a light-emitting layer 53 / an electron injection layer 54 / a cathode 55. Hereinafter, the specific production sequence will be described. The transparent supporting substrate 10 on which the blue color filter 20 is formed is coated with a transparent photopolymerizable resin (manufactured by Nippon Steel Chemical Co., Ltd., 25 9 PAP5), and dried to form a thickness on the blue color filter 20. It is an organic protective layer 30 of 5 μm, on which an inorganic oxide layer 40 having a thickness of 100 nm from SiO 2 K is formed by sputtering. Further, a film formed of ITO was formed by sputtering on the inorganic oxide layer 40, and the following pattern was obtained to obtain a transparent anode 50. That is, after applying a photoresist having a film thickness of 〇〇nm (OFRP-800, manufactured by Tokyo Yinghua Co., Ltd.) on the ITO film, -15-(12) (12) was performed by photolithography. 1320802 is a grid-like transparent anode 50 with a 0.13 mm line spacing and a 0.01 mm gap. Further, the substrate device is placed in the heat-resistant ammonium evaporation device, and the positive hole injection layer 51, the positive hole transport layer 52, the light-emitting layer 53, the electron injection layer 54, and the cathode 55 are sequentially formed without being broken. The pressure in the vacuum chamber at the time of film formation was reduced to ll (T4Pa. Specifically, the positive hole injection layer 51 was made of a copper phthalocyanine (CuPc) layer having a thickness of 100 nm, and the positive hole transport layer 52 was made to have a thickness of 20 nm. 4, a double [N-(1-Cetyl)-N-anilino]bisphenyl (-NPD) layer, and the light-emitting layer 53 is made of 4,4'-bis(2,2-diphenyl) having a thickness of 30 nm. a vinyl) bisphenyl (DPVBi) layer, and an electron injecting layer 54 is formed into a layer of tris(8-pyridylquinoline)aluminum complex (Alq) having a thickness of 20 nm. The cathode is Mg/Ag having a thickness of 200 nm. Ratio 1:10), after the vapor deposition of the outer cover, a grid pattern of 0.33 mm pitch and 0.05 mm gap perpendicular to the anode line is formed. After the film formation of each layer is completed, the organic EL element 100 is taken out by the vapor deposition device. After the sealing glass and the UV adhesive were used in a nitrogen atmosphere, the device was not directly exposed to the atmosphere and sealed (not shown). The organic EL device 100 produced was irradiated with blue light at a peak at a wavelength of 470 nm. 2] In the formation of the blue filter of Example 1, the second dye used in Example 1 was replaced by the dye represented by Structural Formula (5) as the second dye, and then 1〇〇 parts by weight of transparency addition photopolymerizable resin solids content of 1 part by weight, the same method as in Example 1 the organic EL element. 16- (13) 1320802

CH3CH2 CH2CH3 [實施例3] 實施例2之藍色濾光片形成中，針對1莫耳第1色素以 0.3莫耳之比率以結構式（6 )所示之鎳絡合體做爲驟冷器 進行添加之外’與實施例2同法調製藍色濾光片用塗液後 ，同法取得有機EL元件。CH3CH2 CH2CH3 [Example 3] In the formation of the blue filter of Example 2, the nickel complex formed by the structural formula (6) was used as a quencher at a ratio of 0.3 mol per 1 mol of the first dye. In addition to the addition, the organic EL device was obtained in the same manner as the coating liquid for the blue filter in the same manner as in Example 2.

[比較例1 ] 以做爲顏料之銅酞菁系藍取代實施例〗所使用之第I色 素及第2色素使用之外，與實施例1同法調製藍色濾光片用 塗料。又，顔料之添加量係於與實施例1同膜厚形成藍色 據光片時，其波長470nm之光透射率與實施例1同法調製 之。 [評定] 針對所製作之試料，進行下記評定。其評定結果如表 1所示。其中’ CIE色度係使所製作元件進行發光後評定其 色度。測定時利用色度計（大塚電子製，MCPD_]〇〇〇)。 階調係針對元件顯示面進行比較由斜角4 5。照射螢光燈光 -17- (14) 1320802 (ΙΟΟΟΙχ)時之階調。表中之値係使比較例結果爲1·〇之 相對値者，値爲1. 〇以上則可提昇階調。透光率係利用吸 光光度計（島津製作所製1；乂-21001><：)後取得吸光光譜之 後進行比較波長470nm及5 1 Onm之光透射率。 [表】] :x 實施例1 實施例2 實施例3 比較例1 ①CIE色度（X，y ) 0.12， 0.12 0.13， 0.16 > 0.09 > 0.10 0.10 0.18 0階調 1.4 1 .4 1.6 1.0 ③透光率（470nm ) 85% 8 5% 8 5% 8 5% (51Onm ) 5 0% 4 8% 4 6% 60% 如表1所示，470nm中整合光透射率形成膜時，其 5 1 Onm之光透射率於實施例中高於比較例。此代表實施例 之濾光片之降低藍色純度波長區中遮光性高於比較例之濾 光片者。又，分散顏料於粘合劑之比較例濾光片易於濾光 片中及界面產生散射。針對此，實施例之濾光片於粘合劑 中色素完全溶解後透明性高，可顯示高度階調値者。 [發明效果] 本發明可提供一種，高度藍色純度及透光率，且，階 調良好之適於有機EL顯示器之藍色濾光片及使用此之有 機EL元件者。 -18- (15) 1320802 【圖式簡單說明】 [圖1]代表備有本發明藍色濾光片之有機EL元件截面 槪略圖者。 [主要元件對照表] 100 有 機 EL元 件 10 透 明 支 撐 基板 20 藍 色 濾 光 片 30 有 機 保 護 層 40 /»>> 機 氧 化 膜 500 有 機 發 光 體 50 透 明 陽 極 5 1 正 孔 注 入 層 52 正 孔 輸 送 層 53 發 光 層 54 電 子 注 入 層 55 陰 極[Comparative Example 1] A blue color filter coating material was prepared in the same manner as in Example 1 except that the copper phthalocyanine blue was used as the pigment in place of the first coloring matter and the second coloring matter used in the examples. Further, when the amount of the pigment added was changed to the film thickness of the same manner as in Example 1, the light transmittance at a wavelength of 470 nm was adjusted in the same manner as in Example 1. [Assessment] For the sample to be produced, the following evaluation is performed. The evaluation results are shown in Table 1. Wherein the 'CIE chromaticity system is used to evaluate the chromaticity of the fabricated component after illuminating. A colorimeter (manufactured by Otsuka Electronics Co., Ltd., MCPD_) 〇〇〇 was used for the measurement. The gradation is compared to the component display surface by an oblique angle of 45. Illuminating the fluorescent light -17- (14) 1320802 (ΙΟΟΟΙχ) when the tone. The enthalpy in the table is such that the result of the comparative example is 1·〇. The relative 値, 値 is 1. 〇 or more can improve the tone. The light transmittance was measured by a spectrophotometer (manufactured by Shimadzu Corporation; 乂-21001><:), and the light transmittances of the wavelengths of 470 nm and 5 1 Onm were compared. [Table]]: x Example 1 Example 2 Example 3 Comparative Example 1 1 CIE chromaticity (X, y) 0.12, 0.12 0.13, 0.16 > 0.09 > 0.10 0.10 0.18 0 tone 1.4 1. 4 1.6 1.0 3 Transmittance (470nm) 85% 8 5% 8 5% 8 5% (51Onm) 5 0% 4 8% 4 6% 60% As shown in Table 1, when 470nm integrated light transmittance forms a film, its 5 1 The light transmittance of Onm is higher in the examples than in the comparative example. This represents a filter in the blue-purity-reducing wavelength region of the filter of the embodiment which is higher in light-shielding than the filter of the comparative example. Further, in the comparative example in which the pigment was dispersed in the binder, the filter was easily scattered in the filter and at the interface. In view of this, the filter of the embodiment has high transparency after the pigment is completely dissolved in the binder, and can exhibit a high degree of tone. [Effect of the Invention] The present invention can provide a blue filter suitable for an organic EL display and a organic EL element using the same, which has a high blue purity and a light transmittance, and has a good step. -18- (15) 1320802 [Simplified description of the drawings] [Fig. 1] shows a cross-sectional view of an organic EL element provided with the blue filter of the present invention. [Main Component Comparison Table] 100 Organic EL Element 10 Transparent Support Substrate 20 Blue Filter 30 Organic Protective Layer 40 /»>> Machine Oxide Film 500 Organic Light Emitting Body 50 Transparent Anode 5 1 Positive Hole Injection Layer 52 Positive Hole Transport layer 53 luminescent layer 54 electron injection layer 55 cathode

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Claims (1)

1320802 Π) 拾、申請專利範圍 I. 一種藍色濾光片，其特徵係在含有結構式（1)所 示第1色素與粘合劑樹脂之同時，並含有吸收該第1色素之 螢光，且於可視波長區中不具螢光極大之第2色素者，1320802 Π) Pickup, Patent Application Area I. A blue color filter characterized in that it contains a first coloring matter represented by the structural formula (1) and a binder resin, and contains fluorescent light absorbing the first coloring matter. And in the visible wavelength region, the second pigment is not fluorescent, [結構式（1 )中’ 分別獨立地代表可被取代之 氫原子’烷基’芳基’或雜環基，R7代表碳數1〜6之鏈 式不飽和烴基。X·代表選自Γ，Br·，Cl·，F-，CIO/， Βγ〇3· ’ Ι〇3· ’ Cl〇4·，BF4-，PF4·，SbF4-，Br〇4·，及有機 系陰離子群中之陰離子]。 2.—種藍色濾光片，其特徵係含有結構式（1)所示 之第1色素與粘合劑樹脂同時含有結構式（2)所示之第2 色素者，[In the structural formula (1), each independently represents a hydrogen atom 'alkyl 'aryl' or a heterocyclic group which may be substituted, and R7 represents a chain-unsaturated hydrocarbon group having 1 to 6 carbon atoms. X· represents Γ, Br·, Cl·, F-, CIO/, Βγ〇3· ' Ι〇3· 'Cl〇4·, BF4-, PF4·, SbF4-, Br〇4·, and organic An anion in the anion group]. 2. A blue color filter characterized in that the first coloring matter represented by the structural formula (1) and the binder resin are simultaneously contained in the second coloring matter represented by the structural formula (2). [結構式（1 )中，R^R6分別獨立地代表可被取代之 -20- (2) (2)1320802 氫原子，烷基，芳基，或雜環基，R?代表碳數1〜6之鏈 式不飽和烴基^ X·代表選自Γ，Br·，cr，F·，C103·， Br03·，l〇3- ’ cl〇4-，bf4-，PF4·，SbF4·，Br04·，及有機 系陰離子群中之陰離子][In the structural formula (1), R^R6 independently represents a -20-(2) (2) 1320802 hydrogen atom, an alkyl group, an aryl group or a heterocyclic group which may be substituted, and R? represents a carbon number of 1~ The chain unsaturated hydrocarbon group of 6 ^ X represents a choice from Γ, Br·, cr, F·, C103·, Br03·, l〇3- ' cl〇4-, bf4-, PF4·, SbF4·, Br04· And anions in the organic anion group] [結構式（2)中，R】代表氫原子，院基，芳基，或雜 環基 ’ X·代表選自1-，8厂，<：1-，？，，（：103-，3^3-，1〇3· ’ CIO，，BF4_，PF4·，SbF4_’ Br04·，及有機系陰離子群 中之陰離子，Y代表〇原子或S原子，a爲1〜6之整數] 〇 3 ·如申請專利範圍第1項或第2項之藍色濾光片，其 中該濾光片爲含有使該第1項或第2項色素之螢光進行消 光之驟冷陰離子者。 4. 一種有機電激發光元件，其特徵係於層合有機發光 體與濾光片而成之有機電激發光元件中，該濾光片之至少 一部份爲如申請專利範圍第1項至第3項之藍色濾光片者。[In the structural formula (2), R] represents a hydrogen atom, a group, an aryl group, or a heterocyclic group 'X· represents a group selected from the group of 1,8, <:1-,? ,, (:103-,3^3-,1〇3· ' CIO,, BF4_, PF4·, SbF4_' Br04·, and anions in the organic anion group, Y represents a germanium atom or an S atom, a is 1 Integer of ~6] 〇3 · For example, the blue filter of claim 1 or 2, wherein the filter is for extinction of the fluorescent light of the pigment of the first or second term Cold anion. 4. An organic electroluminescent device characterized by an organic electroluminescent device formed by laminating an organic illuminant and a filter, at least a portion of which is as claimed in the patent application. The blue filter of items 1 to 3.