JPH08100173A - White fluorescence conversion film and white light emitting element containing the film - Google Patents
White fluorescence conversion film and white light emitting element containing the filmInfo
- Publication number
- JPH08100173A JPH08100173A JP6237558A JP23755894A JPH08100173A JP H08100173 A JPH08100173 A JP H08100173A JP 6237558 A JP6237558 A JP 6237558A JP 23755894 A JP23755894 A JP 23755894A JP H08100173 A JPH08100173 A JP H08100173A
- Authority
- JP
- Japan
- Prior art keywords
- white
- light emitting
- conversion film
- light
- fluorescence conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は白色蛍光変換膜及びそれ
を用いた白色発光素子に関し、さらに詳しくは、青色発
光有機エレクトロルミネッセンス(以下、ELと略記す
る)素子の発光色を高効率で白色に変換できる白色蛍光
変換膜、及びこれと発光素子部とからなり、高効率で高
品質の白色光を発生し、かつ安価で小型化、薄肉化が可
能な白色発光素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a white fluorescent conversion film and a white light emitting device using the same, and more specifically, it is a highly efficient white light emission color of a blue light emitting organic electroluminescent (hereinafter abbreviated as EL) device. The present invention relates to a white fluorescent conversion film capable of converting into white light, and a white light emitting element including the light emitting element portion and the white fluorescent conversion film, capable of generating white light of high efficiency and high quality, inexpensive, downsizing, and thinning.
【0002】[0002]
【従来の技術】OA機器用バックライト,時計用バック
ライト,各種ディスプレイ用バックライトなどの用途に
発光素子を供する場合、発光色としては白色が最も好ま
しい。ところが、単一で白色発光を示すような発光素子
は一般に知られていないため、白色以外の発光色をもつ
発光素子において、発光層と蛍光層や補色発光層とを組
み合わせ、白色発光を得る方法などが試みられている。
例えば、EL発光層に蛍光層を積層方向に配置し、EL
発光色の色調を多様に変化させる方法(特公昭63−1
8319号公報)、分散型EL素子において、透明電極
と対向電極との間に発光層と補色発光層とを配置して、
白色発光を得る方法(特開平5−174974号公報,
特公平5−33514号公報,特公平5−32879号
公報)が開示されている。しかしながら、これらの方法
においては、製造プロセスが煩雑である上、得られる素
子の寿命が短いという欠点を有している。2. Description of the Related Art When a light emitting element is used for applications such as a back light for office automation equipment, a back light for watches, and a back light for various displays, white is most preferable as a light emitting color. However, since a single light emitting device that emits white light is not generally known, a method for obtaining white light emission by combining a light emitting layer with a fluorescent layer or a complementary color light emitting layer in a light emitting device having an emission color other than white. Are being tried.
For example, when a fluorescent layer is arranged in the EL light emitting layer in the stacking direction,
A method of changing the color tone of the emitted light in various ways (Japanese Patent Publication No. 63-1).
8319 gazette), in a dispersion type EL device, a light emitting layer and a complementary color light emitting layer are arranged between a transparent electrode and a counter electrode,
Method for obtaining white light emission (Japanese Patent Application Laid-Open No. 5-174974,
JP-B-5-33514 and JP-B-5-32879) are disclosed. However, these methods have drawbacks that the manufacturing process is complicated and the life of the obtained element is short.
【0003】そこで、素子の寿命を長くし、かつ製造方
法を簡便にするために、透明電極の反対側に蛍光体層を
積層する方法が試みられている。例えば、EL素子の透
明電極の反対側に補色蛍光層を配置することにより、白
色発光を得る方法が提案されており(特公昭63−18
319号公報,特開昭63−19796号公報,実開昭
63−77299号公報)、具体的には、橙黄色発光E
L素子に青色発光系の蛍光染料を用いる方法(特開昭6
2−90897号公報)、青緑色発光EL素子に黄色、
橙色又は赤色発光系の蛍光染料を用いる方法(特開昭6
2−104000,実開平2−95197号公報,実開
平3−104997号公報)、青緑発光EL素子にピン
ク系蛍光顔料を用いる方法(特開平6−163159号
公報)などが提案されている。Therefore, in order to prolong the life of the device and simplify the manufacturing method, a method of laminating a phosphor layer on the opposite side of the transparent electrode has been attempted. For example, a method of obtaining white light emission by arranging a complementary color fluorescent layer on the opposite side of a transparent electrode of an EL element has been proposed (Japanese Patent Publication No. 63-18).
319, Japanese Patent Application Laid-Open No. 63-19796, Japanese Utility Model Application Laid-Open No. 63-77299), specifically, orange-yellow light emission E.
Method of using blue light emitting fluorescent dye for L element
No. 2-90897), a blue-green light emitting EL element has a yellow color,
A method using an orange or red light emitting fluorescent dye (Japanese Patent Laid-Open Publication No. 6-58242)
2-104000, Japanese Utility Model Laid-Open No. 2-95197, Japanese Utility Model Laid-Open No. 3-104997), a method of using a pink fluorescent pigment in a blue-green light emitting EL element (Japanese Patent Application Laid-Open No. 6-163159), and the like.
【0004】しかしながら、これらの方法は、橙黄色発
光EL素子及び青緑色発光EL素子にのみ適用できるも
のであり、青色発光EL素子の発光色を白色に変換する
ことができないという問題がある。また、2色又は3色
の蛍光ストライプ層を透明電極の反対側に積層し、すべ
ての色のストライプを点灯することにより白色発光を得
る方法(特開昭60−84580号公報,特開平1−1
42694号公報,特開平5−258860号公報)も
知られているが、この場合素子の製造法が煩雑であっ
て、安価な素子を製造することができない。他方、式
(II)However, these methods are applicable only to the orange-yellow EL element and the blue-green EL element, and there is a problem that the emission color of the blue-EL element cannot be converted to white. Further, a method of obtaining white light emission by laminating fluorescent stripe layers of two or three colors on the opposite side of the transparent electrode and turning on the stripes of all colors (JP-A-60-84580 and JP-A-1-48580). 1
No. 4,269,94 and Japanese Patent Application Laid-Open No. 5-258860) are known, but in this case, the manufacturing method of the element is complicated and an inexpensive element cannot be manufactured. On the other hand, formula (II)
【化2】 で表される2−〔2−〔4−(N,N−ジメチルアミ
ノ)フェニル〕エテニル〕−4−ジシアノメチレン−6
−メチル−4H−ピラン(DCMと略記する)をポリメ
チルメタクリレート(PMMAと略記する)に分散した
ものを蛍光変換膜として用いることが知られている(特
開平3−152897号公報)。しかしながら、本発明
者らの研究によると、この蛍光変換膜(DCM/PMM
A)を青色発光有機EL素子(色度:x=0.14,y=
0.20,発光極大波長:482nm)に重ねても、黄緑
色(色度:x=0.40,y=0.58)の発光が5%の効
率で得られるのみで、白色光は得られなかった。Embedded image 2- [2- [4- (N, N-dimethylamino) phenyl] ethenyl] -4-dicyanomethylene-6 represented by
It is known to use -methyl-4H-pyran (abbreviated as DCM) dispersed in polymethylmethacrylate (abbreviated as PMMA) as a fluorescence conversion film (JP-A-3-152897). However, according to the study by the present inventors, this fluorescence conversion film (DCM / PMM
A) is a blue light emitting organic EL device (chromaticity: x = 0.14, y =
Even when superposed on 0.20, emission maximum wavelength: 482 nm, yellow-green (chromaticity: x = 0.40, y = 0.58) emission is only obtained with 5% efficiency, and white light is obtained. I couldn't do it.
【0005】[0005]
【発明が解決しようとする課題】本発明は、このような
状況下で、青色発光有機EL素子の発光色を高効率で白
色に変換できる白色蛍光変換膜、及び高効率で高品質の
白色光を発生し、かつ安価で小型化、薄肉化が可能な白
色発光素子を提供することを目的とするものである。SUMMARY OF THE INVENTION Under the circumstances, the present invention provides a white fluorescent conversion film capable of converting the emission color of a blue light emitting organic EL element to white with high efficiency, and high efficiency and high quality white light. It is an object of the present invention to provide a white light emitting device that is capable of producing a light emitting element, is inexpensive, and can be downsized and thinned.
【0006】[0006]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、上記式(II)
で表されるDCMの類縁化合物であって、アミノ基の2
つの置換基がメチル基でなくアリール基である構造の蛍
光色素を光透過性媒体に分散してなる膜が、青色発光有
機EL素子の発光色を高効率で白色に変換しうること、
そしてこの膜と発光素子部とからなる素子は、高効率で
高品質の白色光を発生し、かつ安価で小型化、薄肉化が
可能であることを見出した。本発明は、かかる知見に基
づいて完成したものである。すなわち、本発明は、一般
式(I)The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, the above formula (II)
A compound related to DCM represented by
A film in which a fluorescent dye having a structure in which one substituent is an aryl group instead of a methyl group is dispersed in a light transmissive medium can convert the emission color of a blue light emitting organic EL device to white with high efficiency,
It has been found that an element composed of this film and a light emitting element section can generate white light of high efficiency and high quality, and can be inexpensive, downsized, and thinned. The present invention has been completed based on such findings. That is, the present invention has the general formula (I)
【0007】[0007]
【化3】 Embedded image
【0008】(式中、Ar1 及びAr2 は、それぞれア
リール基を示し、それらはたがいに同一でも異なってい
てもよく、R1 〜R5 は、それぞれ水素原子又は炭素数
1〜3のアルキル基を示し、それらはたがいに同一でも
異なっていてもよく、R6 は炭素数1〜3のアルキル基
を示す。)で表される蛍光色素を、光透過性媒体に分散
してなる白色蛍光変換膜、及びこの白色蛍光変換膜と発
光素子部とからなる白色発光素子を提供するもである。
本発明の白色蛍光変換膜は、光透過性媒体に蛍光色素を
分散してなるものであって、該蛍光色素としては、一般
式(I)(In the formula, Ar 1 and Ar 2 each represent an aryl group, which may be the same or different, and R 1 to R 5 are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Group, which may be the same or different from each other, and R 6 represents an alkyl group having 1 to 3 carbon atoms.) White fluorescent obtained by dispersing a fluorescent dye represented by A white light emitting device including a conversion film and the white fluorescence conversion film and a light emitting device part is provided.
The white fluorescence conversion film of the present invention comprises a fluorescent pigment dispersed in a light transmissive medium, and the fluorescent pigment is represented by the general formula (I).
【0009】[0009]
【化4】 [Chemical 4]
【0010】で表される構造のピラン誘導体が用いられ
る。上記一般式(I)において、Ar1 及びAr2 は、
それぞれアリール基を示す。このアリール基には低級ア
ルキル基、例えばメチル基,エチル基,n−プロピル
基,イソプロピル基などの置換基が導入されていてもよ
い。Ar1 ,Ar2 の具体例としては、フェニル基,2
−メチルフェニル基,3−メチルフェニル基,4−メチ
ルフェニル基,1−ナフチル基,2−ナフチル基,1−
アントラニル基などが挙げられる。このAr1 及びAr
2 はたがいに同一でも異なっていてもよい。R1 〜R5
は、それぞれ水素原子又は炭素数1〜3のアルキル基を
示し、炭素数1〜3のアルキル基としては、メチル基,
エチル基,n−プロピル基及びイソプロピル基が挙げら
れる。このR1 〜R5 はたがいに同一でも異なっていて
もよい。また、R6 は炭素数1〜3のアルキル基で、メ
チル基,エチル基,プロピル基又はイソプロピル基を示
す。A pyran derivative having a structure represented by the following is used. In the general formula (I), Ar 1 and Ar 2 are
Each represents an aryl group. A substituent such as a lower alkyl group, for example, a methyl group, an ethyl group, an n-propyl group or an isopropyl group may be introduced into the aryl group. Specific examples of Ar 1 and Ar 2 include phenyl group and 2
-Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-
Examples thereof include anthranyl group. This Ar 1 and Ar
The two may be the same or different. R 1 to R 5
Are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and as the alkyl group having 1 to 3 carbon atoms, a methyl group,
Examples thereof include ethyl group, n-propyl group and isopropyl group. R 1 to R 5 may be the same or different. R 6 is an alkyl group having 1 to 3 carbon atoms and represents a methyl group, an ethyl group, a propyl group or an isopropyl group.
【0011】上記一般式(I)で表されるピラン誘導体
としては、例えば次に示す構造のものを挙げることがで
きる。Examples of the pyran derivative represented by the above general formula (I) include those having the following structures.
【0012】[0012]
【化5】 Embedded image
【0013】[0013]
【化6】 [Chemical 6]
【0014】[0014]
【化7】 [Chemical 7]
【0015】[0015]
【化8】 Embedded image
【0016】これらの中で、特に一般式(I)における
Ar1 及びAr2 が共にフェニル基、R1 ,R2 ,
R3 ,R4 及びR5 が共に水素原子、及びR6 がメチル
基である2−〔2−〔4−(N,N−ジフェニルアミ
ノ)フェニル〕エテニル〕−4−ジシアノメチレン−6
−メチル−4H−ピランが、性能及び製造の容易さの点
で好適である。また、本発明においては、上記一般式
(I)で表されるピラン誘導体からなる蛍光色素は一種
用いてもよく、二種以上を組み合わせて用いてもよい。
一方、光透過性媒体については、光透過性を有し、かつ
膜形成性を有するものであればよく、特に制限されず、
例えば高分子化合物や無機ガラス、さらには印刷用メジ
ウムなどが用いられる。ここで、高分子化合物として
は、例えばポリビニルピロリジノン,ポリアクリロニト
リル,ポリ(N,N−ジメチルアクリルアミド),ポリ
(N,N−ジメチルメタクリルアミド),ポリビニルア
ルコール,ポリメチルメタクリレート,ポリスチレン,
ポリカーボネート,ポリビニルアセテート,ポリ塩化ビ
ニル,ポリブテン,ポリエチレングリコール、及びこれ
らの共重合体などが挙げられ、また、無機ガラスとして
は、例えばホウ酸ガラスやシリカガラスなどが挙げられ
る。これらの光透過性媒体の中で、特に光透過性,膜形
成性,その他物性などの点からポリビニルピロリジノン
が好適である。また、本発明においては、上記光透過性
媒体は一種用いてもよく、二種以上を組み合わせて用い
てもよい。Of these, particularly Ar 1 and Ar 2 in the general formula (I) are both phenyl groups, R 1 , R 2 ,
2- [2- [4- (N, N-diphenylamino) phenyl] ethenyl] -4-dicyanomethylene-6 in which R 3 , R 4 and R 5 are both hydrogen atoms and R 6 is a methyl group
-Methyl-4H-pyran is preferred in terms of performance and ease of manufacture. Further, in the present invention, one kind of fluorescent dye composed of the pyran derivative represented by the general formula (I) may be used, or two or more kinds thereof may be used in combination.
On the other hand, the light-transmitting medium is not particularly limited as long as it has light-transmitting property and film-forming property.
For example, polymer compounds, inorganic glass, and printing media are used. Here, as the polymer compound, for example, polyvinylpyrrolidinone, polyacrylonitrile, poly (N, N-dimethylacrylamide), poly (N, N-dimethylmethacrylamide), polyvinyl alcohol, polymethylmethacrylate, polystyrene,
Examples thereof include polycarbonate, polyvinyl acetate, polyvinyl chloride, polybutene, polyethylene glycol, and copolymers thereof, and examples of the inorganic glass include borate glass and silica glass. Among these light transmissive media, polyvinylpyrrolidinone is particularly preferable in terms of light transmissivity, film forming property, and other physical properties. In addition, in the present invention, the light-transmitting medium may be used alone or in combination of two or more kinds.
【0017】本発明の白色蛍光変換膜を製造する方法に
ついては特に制限はなく、様々な方法を用いることがで
きる。例えば光透過性媒体に、前記一般式(I)で表さ
れる蛍光色素を混合したのち、これをキャスティング
法,スピンコート法,印刷法,バーコート法,押出し成
形法,ロール成形法,プレス法,スプレー法,ロールコ
ート法などの方法を用いて製膜することにより、所望の
白色蛍光変換膜が得られる。これらの製膜方法において
有機溶媒を用いる場合には、該有機溶媒としては、例え
ば1,2−ジクロロエタン;クロロホルム;アセトン;
シクロヘキサノン;トルエン;キシレン;N,N−ジメ
チルホルムアミド;ジメチルスルホキシド;1,2−ジ
メトキシエタン;ジエチレングリコールジメチルエーテ
ルなどを用いることができる。これらの溶媒は、それぞ
れ単独で用いてもよく、二種以上を混合して用いてもよ
い。例えば、キャスティング法で製膜する場合には、上
記溶媒の中から適当なものを選び、これに蛍光色素と光
透過性媒体を溶かして得られた溶液を、ガラス基板など
の基板上に静かにたらし、シャーレなどで軽く蓋をし
て、溶媒を徐々に蒸発させることにより、薄膜状の白色
蛍光変換膜を得ることができる。The method for producing the white fluorescence conversion film of the present invention is not particularly limited, and various methods can be used. For example, the fluorescent dye represented by the general formula (I) is mixed with a light-transmissive medium, and then the casting method, spin coating method, printing method, bar coating method, extrusion molding method, roll molding method, pressing method is used. A desired white fluorescence conversion film can be obtained by forming a film using a method such as a spray method or a roll coating method. When an organic solvent is used in these film forming methods, examples of the organic solvent include 1,2-dichloroethane; chloroform; acetone;
Cyclohexanone; toluene; xylene; N, N-dimethylformamide; dimethylsulfoxide; 1,2-dimethoxyethane; diethylene glycol dimethyl ether and the like can be used. These solvents may be used alone or in combination of two or more. For example, when a film is formed by the casting method, an appropriate solvent is selected from the above solvents, and the solution obtained by dissolving the fluorescent dye and the light transmissive medium in this is gently placed on a substrate such as a glass substrate. A thin white fluorescence conversion film can be obtained by gently allowing the solvent to gradually evaporate with a pallet, a petri dish, or the like.
【0018】本発明の白色蛍光変換膜は、波長460n
mにおける光線透過率が50%以下であることが好まし
い。この光線透過率が50%を超えると、青色領域(4
20〜485nm)の透過率が高くなり白色の変換光が
得られにくい。好ましい該光線透過率は0〜50%の範
囲であり、特に5〜20%の範囲が好適である。該光線
透過率は、使用する蛍光色素の吸光係数と白色蛍光変換
膜の膜厚とにより左右されるので該吸光係数と膜厚か
ら、必要な蛍光色素濃度を求め、その濃度になるよう
に、光透過性媒体に蛍光色素を分散させればよい。該白
色蛍光変換膜の膜厚は、通常1〜1000μm、好まし
くは2〜100μmの範囲である。本発明の白色発光素
子は、このようにして得られた白色蛍光変換膜と発光素
子部とからなるものであり、該発光素子部としては、例
えば青色発光ダイオードや青色発光有機EL素子などが
用いられるが、これらの中で、420〜485nmの発
光極大波長を有する有機薄膜EL素子が好適である。発
光素子部の発光極大波長が420〜485nmの範囲を
逸脱すると、本発明の構成を用いても、良好な白色光が
得られにくい。The white fluorescent conversion film of the present invention has a wavelength of 460n.
The light transmittance at m is preferably 50% or less. When this light transmittance exceeds 50%, the blue region (4
20 to 485 nm) and the converted white light is difficult to obtain. The preferable light transmittance is in the range of 0 to 50%, and particularly preferably in the range of 5 to 20%. Since the light transmittance depends on the extinction coefficient of the fluorescent dye used and the film thickness of the white fluorescence conversion film, the necessary fluorescent dye concentration is determined from the extinction coefficient and the film thickness so that the concentration is obtained. The fluorescent dye may be dispersed in the light transmissive medium. The thickness of the white fluorescence conversion film is usually 1 to 1000 μm, preferably 2 to 100 μm. The white light emitting element of the present invention comprises the white fluorescence conversion film thus obtained and the light emitting element section, and as the light emitting element section, for example, a blue light emitting diode or a blue light emitting organic EL element is used. Among these, an organic thin film EL element having an emission maximum wavelength of 420 to 485 nm is preferable among them. If the maximum emission wavelength of the light emitting element section deviates from the range of 420 to 485 nm, it is difficult to obtain good white light even with the configuration of the present invention.
【0019】該420〜485nmの発光極大波長を有
する青色発光有機薄膜EL素子は、例えば特開平3−4
7890号公報,特開平3−231970号公報,特開
平5−17765号公報,特開平5−135878号公
報,特開平5−140145号公報,特開平5−247
458号公報,特開平5−247459号公報,特開平
6−100857号公報,特開平6−132080号公
報などに開示された方法に従って作製することができ
る。一例を挙げると、ITO電極を製膜したガラス基板
からなる透明支持基板に、4,4’−ビス〔N−フェニ
ル−N−(3−メチルフェニル)アミノ〕ビフェニル
(TPD);4,4’−ビス(2,2−ジフェニルビニ
ル)ビフェニル(DPVBi)及びMg−Ag電極を順
次真空蒸着し、積層させることによって、青色発光有機
薄膜EL素子が得られる。図1は、本発明の白色発光素
子の構成を示す模式図であり、発光素子部Aからの発光
色は、白色蛍光変換膜Bにより白色光に変換される。The blue light emitting organic thin film EL device having the maximum emission wavelength of 420 to 485 nm is disclosed in, for example, Japanese Patent Laid-Open No. 3-4.
No. 7890, No. 3-231970, No. 5-17765, No. 5-135878, No. 5-140145, No. 5-247.
It can be produced according to the methods disclosed in Japanese Patent Application Laid-Open No. 458, No. 5-247459, No. 6-100857, No. 6-13080, and the like. To give an example, a transparent supporting substrate made of a glass substrate having an ITO electrode formed thereon has 4,4′-bis [N-phenyl-N- (3-methylphenyl) amino] biphenyl (TPD); 4,4 ′. A blue light emitting organic thin film EL device is obtained by sequentially vacuum-depositing -bis (2,2-diphenylvinyl) biphenyl (DPVBi) and Mg-Ag electrodes and stacking them. FIG. 1 is a schematic diagram showing the configuration of the white light emitting element of the present invention, in which the emission color from the light emitting element section A is converted into white light by the white fluorescence conversion film B.
【0020】[0020]
【実施例】次に、本発明を実施例によりさらに詳しく説
明するが、本発明はこれらの例によってなんら制限され
るものではない。 製造例1 2−〔2−〔4−(N,N−ジフェニルアミノ)フェニ
ル〕エテニル〕−4−ジシアノメチレン−6−メチル−
4H−ピランの製造 4−ジシアノメチレン−2,6−ジメチル−4H−ピラ
ン0.6g(3.7ミリモル)及び4−(N,N−ジフェニ
ルアミノ)ベンズアルデヒド1.0g(3.7ミリモル)を
還流エタノール50ミリリットルに溶解し、ピペリジン
0.2ミリリットルを加えて断続的に25時間還流した。
反応混合物を室温まで放冷したのち、生成した固体をろ
別し、エタノール/ジクロロメタン(重量比1/2)5
0ミリリットルから再結晶することにより、黒緑色針状
晶として副生成物0.3g(収率12%)を得た。再結晶
ろ液から溶媒を留去したのち、残渣をカラムクロマトグ
ラフィー(シリカゲル/ジクロロメタン)によって精製
し、赤色針状晶として目的物0.6g(収率38%)を得
た。このものの融点(mp), 1H−NMR,紫外可視
吸収スペクトル及び蛍光スペクトルを測定した。結果を
以下に示す。 mp:217〜218℃1 H−NMR(CDCl3 ,テトラメチルシラン(TM
S)基準):2.38(3H,s),6.4〜6.6(3H,
m),7.0〜7.5(15H,m) 紫外可視吸収スペクトル(1,2−ジクロロエタン中,
濃度1.4×10-6モル/リットル),λmax(log
ε):467nm(4.62) 蛍光スペクトル(1,2−ジクロロエタン中,励起波長
450nm,濃度1.4×10-6モル/リットル),蛍光
極大波長:581nmEXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Production Example 1 2- [2- [4- (N, N-diphenylamino) phenyl] ethenyl] -4-dicyanomethylene-6-methyl-
Preparation of 4H-pyran 4-dicyanomethylene-2,6-dimethyl-4H-pyran 0.6 g (3.7 mmol) and 4- (N, N-diphenylamino) benzaldehyde 1.0 g (3.7 mmol). Dissolve in 50 ml of refluxing ethanol, piperidine
0.2 ml was added and the mixture was refluxed intermittently for 25 hours.
The reaction mixture was allowed to cool to room temperature, the solid formed was filtered off, and ethanol / dichloromethane (weight ratio 1/2) 5
By recrystallization from 0 ml, 0.3 g (yield 12%) of a by-product was obtained as black green needle crystals. After evaporating the solvent from the recrystallization filtrate, the residue was purified by column chromatography (silica gel / dichloromethane) to obtain 0.6 g of the desired product as red needle crystals (yield 38%). The melting point (mp), 1 H-NMR, UV-visible absorption spectrum and fluorescence spectrum of this product were measured. The results are shown below. mp: 217-218 ° C. 1 H-NMR (CDCl 3 , tetramethylsilane (TM
S) standard): 2.38 (3H, s), 6.4 to 6.6 (3H,
m), 7.0-7.5 (15H, m) UV-visible absorption spectrum (in 1,2-dichloroethane,
Concentration 1.4 × 10 -6 mol / liter), λmax (log
ε): 467 nm (4.62) Fluorescence spectrum (in 1,2-dichloroethane, excitation wavelength 450 nm, concentration 1.4 × 10 -6 mol / liter), fluorescence maximum wavelength: 581 nm
【0021】製造例2 有機薄膜EL素子の作製 25mm×75mm×1.1mmのガラス基板上にITO
電極を100nmの厚さで製膜したものを透明支持基板
とした。この透明支持基板をイソプロピルアルコールで
5分間超音波洗浄したのち、純水で5分間洗浄し、再び
イソプロピルアルコールで5分間超音波洗浄した。次い
でこの透明支持基板を真空蒸着装置の基板ホルダーに固
定し、モリブデン製抵抗加熱用ボートに4,4’−ビス
(N−フェニル−N−(3−メチルフェニル)アミノ〕
ビフェニル(TPD)を200mg入れ、他のモリブデ
ン製抵抗加熱用ボートに4,4’−ビス(2,2−ジフ
ェニルビニル)ビフェニル(DPVBi)を200mg
入れて真空チャンバー内を1×10-4Paまで減圧し
た。TPD入りのボートを215〜220℃まで加熱
し、TPDを0.1〜0.3nm/秒の蒸着速度で基板上に
堆積させ、膜厚60nmの正孔注入層を製膜した。この
ときの基板温度は室温であった。得られた正孔注入層を
真空チャンバーから取り出すことなく、この上にDPV
Biをボート温度250℃,蒸着速度0.1〜0.2nm/
秒で基板上に堆積させ、膜厚40nmの発光層を製膜し
た。これを真空チャンバーから取り出し、発光層側にス
テンレススチール製のマスクを設置し、再び基板ホルダ
ーに固定した。次いで、タングステンバスケットに銀
(Ag)ワイヤー0.5gを入れ、モリブデン製ボートに
マグネシウム(Mg)リボン1gを入れ、真空チャンバ
ー内を1×10-4Paまで減圧し、Mg(蒸着速度、0.
8nm/秒)とAg(蒸着速度、0.1nm/秒)を同時
に蒸着し、陰電極を製膜して有機薄膜EL素子を作製し
た。Production Example 2 Preparation of organic thin film EL element ITO on a glass substrate of 25 mm × 75 mm × 1.1 mm
The transparent support substrate was prepared by forming an electrode with a thickness of 100 nm. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then with pure water for 5 minutes, and again with isopropyl alcohol for 5 minutes. Next, this transparent support substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, and 4,4'-bis (N-phenyl-N- (3-methylphenyl) amino] was added to a molybdenum resistance heating boat.
200 mg of biphenyl (TPD) is put into another boat for resistance heating made of molybdenum and 200 mg of 4,4'-bis (2,2-diphenylvinyl) biphenyl (DPVBi).
Then, the inside of the vacuum chamber was depressurized to 1 × 10 −4 Pa. A boat containing TPD was heated to 215 to 220 ° C., TPD was deposited on the substrate at a vapor deposition rate of 0.1 to 0.3 nm / sec, and a hole injection layer having a thickness of 60 nm was formed. At this time, the substrate temperature was room temperature. Without removing the obtained hole injection layer from the vacuum chamber, DPV
Bi at a boat temperature of 250 ° C and a vapor deposition rate of 0.1 to 0.2 nm /
It was deposited on the substrate for 2 seconds to form a light emitting layer having a film thickness of 40 nm. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer side, and it was fixed again to the substrate holder. Next, 0.5 g of silver (Ag) wire was put into a tungsten basket, 1 g of magnesium (Mg) ribbon was put into a boat made of molybdenum, and the inside of the vacuum chamber was decompressed to 1 × 10 −4 Pa, Mg (deposition rate,
8 nm / sec) and Ag (vapor deposition rate, 0.1 nm / sec) were simultaneously vapor-deposited to form a negative electrode to prepare an organic thin film EL device.
【0022】実施例1 製造例1で得られた2−〔2−〔4−(N,N−ジフェ
ニルアミノ)フェニル〕エテニル〕−4−ジシアノメチ
レン−6−メチル−4H−ピラン1.8mgに、ポリビニ
ルピロリジノン〔関東化学(株)製,分子量約360,000
〕0.85gとジクロロメタン8.5ミリリットルを加え
て溶解させた。次いで、この溶液を25mm×75mm
×1mmガラス基板にキャストし、12時間風乾後、5
0℃で真空乾燥して蛍光変換膜を作製した。460nm
における透過率50%以下を達成するための色素濃度
は、Lambert−Beer則〔−log(T/10
0)=εbc、ここでTは%表示の透過率、bは膜厚,
εは分子吸光係数であり4.2×104 cm-1M -1 、c
が必要な色素濃度である。〕に従って計算した。この蛍
光変換膜の膜厚はマイクロメータにより測定したとこ
ろ、50μmであり、460nmにおける透過率は9%
であった。製造例2で得られた有機薄膜EL素子(色度
x=0.161,y=0.150,青色,発光極大波長46
0nm)を電圧7V,電流密度4.2mA/cm2 の条件
で発光させ、これに上記変換膜を重ねて白色発光素子と
し、輝度計(ミノルタ製,CS−100)により出力光
を測定した。変換膜を重ねる前の青色光の輝度が100
cd/m2 であったのに対し、色度x=0.340,y=
0.313の白色光が60cd/m2 の輝度で得られた。
変換効率は60%であった。Example 1 To 1.8 mg of 2- [2- [4- (N, N-diphenylamino) phenyl] ethenyl] -4-dicyanomethylene-6-methyl-4H-pyran obtained in Preparation Example 1 was obtained. , Polyvinylpyrrolidinone [manufactured by Kanto Chemical Co., Inc., molecular weight about 360,000
] 0.85 g and dichloromethane 8.5 ml were added and dissolved. Then add this solution to 25 mm x 75 mm
Cast on × 1mm glass substrate, air-dry for 12 hours, then 5
A fluorescent conversion film was prepared by vacuum drying at 0 ° C. 460 nm
The dye concentration for achieving a transmittance of 50% or less in Lambert-Beer rule [-log (T / 10
0) = εbc, where T is the transmittance in%, b is the film thickness,
ε is a molecular extinction coefficient of 4.2 × 10 4 cm −1 M −1 , c
Is the required dye concentration. ] It calculated according to. The thickness of this fluorescence conversion film was 50 μm as measured by a micrometer, and the transmittance at 460 nm was 9%.
Met. Organic thin film EL device obtained in Production Example 2 (chromaticity x = 0.161, y = 0.150, blue, emission maximum wavelength 46
(0 nm) was caused to emit light under the conditions of voltage 7 V and current density 4.2 mA / cm 2 , and the conversion film was superposed thereon to form a white light emitting device, and the output light was measured by a luminance meter (CS-100 manufactured by Minolta). The brightness of the blue light before the conversion film is stacked is 100
While it was cd / m 2 , chromaticity x = 0.340, y =
White light of 0.313 was obtained at a luminance of 60 cd / m 2 .
The conversion efficiency was 60%.
【0023】実施例2 製造例1で得られた2−〔2−〔4−(N,N−ジフェ
ニルアミノ)フェニル〕エテニル〕−4−ジシアノメチ
レン−6−メチル−4H−ピラン3.0mgに印刷用メジ
ウム〔東洋インキ(株)製,S−800〕1.5gを加え
溶解させた。これを用い、25mm×75mm×1mm
のガラス基板にバーコート法でフィルムを作製し、12
時間風乾後、50℃で真空乾燥して蛍光変換膜を作製し
た。この蛍光変換膜の膜厚は、マイクロメータにより測
定したところ、56μmであり、460nmにおける透
過率は8%であった。製造例2で得られた有機薄膜EL
素子に上記変換膜を重ねて白色発光素子とし、輝度計
(ミノルタ製,CS−100)により出力光を測定した
ところ、変換膜を重ねる前の青色光の輝度が100cd
/m2 であったのに対し、色度x=0.350,y=0.4
20の白色光が60cd/m2 の輝度で得られた。変換
効率は60%であった。なお、製造例2で得られた有機
薄膜EL素子、実施例1及び2で得られた白色発光素子
それぞれの発光色の色度を図2の色度座標図にプロット
した。Example 2 To 3.0 mg of 2- [2- [4- (N, N-diphenylamino) phenyl] ethenyl] -4-dicyanomethylene-6-methyl-4H-pyran obtained in Preparation Example 1 was obtained. 1.5 g of a printing medium [S-800 manufactured by Toyo Ink Co., Ltd.] was added and dissolved. Using this, 25mm x 75mm x 1mm
The film is prepared on the glass substrate of
After air-drying for an hour, it was vacuum dried at 50 ° C. to prepare a fluorescence conversion film. The film thickness of this fluorescence conversion film was 56 μm as measured by a micrometer, and the transmittance at 460 nm was 8%. Organic thin film EL obtained in Production Example 2
When the output film was measured with a luminance meter (CS-100 manufactured by Minolta Co., Ltd.) by stacking the conversion film on the device to form a white light emitting device, the brightness of the blue light before the conversion film was stacked was 100 cd.
/ M 2 , whereas chromaticity x = 0.350, y = 0.4
20 white lights were obtained with a brightness of 60 cd / m 2 . The conversion efficiency was 60%. The chromaticity of the emission color of each of the organic thin film EL device obtained in Production Example 2 and the white light emitting devices obtained in Examples 1 and 2 was plotted in the chromaticity coordinate diagram of FIG.
【0024】[0024]
【発明の効果】本発明の白色蛍光変換膜は、青色発光有
機EL素子の発光色を高効率で白色に変換することがで
き、またこの白色蛍光変換膜と発光素子部とからなる本
発明の白色発光素子は、高効率で高品質の白色光を発生
し、かつ安価で小型化,薄肉化が可能である。したがっ
て、本発明の白色発光素子は、例えばOA機器用バック
ライト,時計用バックライト,各種ディスプレイ用バッ
クライト,ドットマトリックスディスプレイなどに好適
に用いられる。The white fluorescence conversion film of the present invention can convert the emission color of the blue light emitting organic EL element into white with high efficiency, and the white fluorescence conversion film and the light emitting element section of the present invention. The white light emitting element emits white light with high efficiency and high quality, and is inexpensive and can be downsized and thinned. Therefore, the white light emitting element of the present invention is suitably used, for example, in a backlight for office automation equipment, a backlight for watches, a backlight for various displays, a dot matrix display and the like.
【図1】本発明の白色発光素子の構成を示す模式図であ
る。FIG. 1 is a schematic diagram showing a configuration of a white light emitting element of the present invention.
【図2】各色の領域を示す色度座標図であるFIG. 2 is a chromaticity coordinate diagram showing areas of each color.
A 発光素子部 B 白色蛍光変換膜 A light emitting element part B white fluorescent conversion film
Claims (6)
し、それらはたがいに同一でも異なっていてもよく、R
1 〜R5 は、それぞれ水素原子又は炭素数1〜3のアル
キル基を示し、それらはたがいに同一でも異なっていて
もよく、R6 は炭素数1〜3のアルキル基を示す。)で
表される蛍光色素を光透過性媒体に分散してなる白色蛍
光変換膜。1. A compound of the general formula (I) (In the formula, Ar 1 and Ar 2 each represent an aryl group, which may be the same or different from each other;
1 to R 5 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, which may be the same or different from each other, and R 6 represents an alkyl group having 1 to 3 carbon atoms. ) A white fluorescence conversion film obtained by dispersing the fluorescent dye represented by the formula (3) in a light transmissive medium.
ジフェニルアミノ)フェニル〕エテニル〕−4−ジシア
ノメチレン−6−メチル−4H−ピランである請求項1
記載の白色蛍光変換膜。2. The fluorescent dye is 2- [2- [4- (N, N-
Diphenylamino) phenyl] ethenyl] -4-dicyanomethylene-6-methyl-4H-pyran.
The white fluorescence conversion film described.
である請求項1記載の白色蛍光変換膜。3. The white fluorescence conversion film according to claim 1, wherein the light transmissive medium is polyvinylpyrrolidinone.
0%以下である請求項1記載の白色蛍光変換膜。4. The light transmittance at a wavelength of 460 nm is 5
The white fluorescence conversion film according to claim 1, which is 0% or less.
色蛍光変換膜と発光素子部とからなる白色発光素子。5. A white light emitting element comprising the white fluorescence conversion film according to claim 1 and a light emitting element section.
極大波長を有する有機薄膜エレクトロルミネッセンス素
子である請求項5記載の白色発光素子。6. The white light emitting element according to claim 5, wherein the light emitting element section is an organic thin film electroluminescent element having an emission maximum wavelength of 420 to 485 nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6237558A JPH08100173A (en) | 1994-09-30 | 1994-09-30 | White fluorescence conversion film and white light emitting element containing the film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6237558A JPH08100173A (en) | 1994-09-30 | 1994-09-30 | White fluorescence conversion film and white light emitting element containing the film |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH08100173A true JPH08100173A (en) | 1996-04-16 |
Family
ID=17017104
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP6237558A Pending JPH08100173A (en) | 1994-09-30 | 1994-09-30 | White fluorescence conversion film and white light emitting element containing the film |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997029163A1 (en) * | 1996-02-09 | 1997-08-14 | Idemitsu Kosan Co., Ltd. | Fluorescence-reddening membrane and red-emitting device |
JP2001223078A (en) * | 2000-01-27 | 2001-08-17 | General Electric Co <Ge> | Light source provided with organic layer and photo- luminescence layer |
JP2002237381A (en) * | 2001-02-09 | 2002-08-23 | Nagase Inteko Kk | Organic electroluminescence element |
US6464898B1 (en) | 1998-11-20 | 2002-10-15 | Idemitsu Kosan Co., Ltd. | Fluorescence conversion medium and display device comprising it |
WO2003078542A1 (en) * | 2002-03-19 | 2003-09-25 | Neoview Co., Ltd. | Red organic light-emitting compound and organic light-emitting device comprising the same |
JP2005252293A (en) * | 1996-06-26 | 2005-09-15 | Siemens Ag | Semiconductor light emitting element |
JPWO2006132030A1 (en) * | 2005-06-08 | 2009-01-08 | 独立行政法人産業技術総合研究所 | Novel compound, reagent for analysis of peptide or protein containing the compound, and analysis method using the analysis reagent |
JP2013179335A (en) * | 2013-05-08 | 2013-09-09 | Mitsubishi Chemicals Corp | White light emitting element |
-
1994
- 1994-09-30 JP JP6237558A patent/JPH08100173A/en active Pending
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997029163A1 (en) * | 1996-02-09 | 1997-08-14 | Idemitsu Kosan Co., Ltd. | Fluorescence-reddening membrane and red-emitting device |
US9196800B2 (en) | 1996-06-26 | 2015-11-24 | Osram Gmbh | Light-radiating semiconductor component with a luminescence conversion element |
JP2005252293A (en) * | 1996-06-26 | 2005-09-15 | Siemens Ag | Semiconductor light emitting element |
WO2004083339A1 (en) * | 1998-11-20 | 2004-09-30 | Tomoike, Kazuhiro | Phosphorescence converting medium and display using the same |
US6641755B2 (en) | 1998-11-20 | 2003-11-04 | Idemitsu Kosan Co., Ltd. | Fluorescence conversion medium and display device comprising it |
US6464898B1 (en) | 1998-11-20 | 2002-10-15 | Idemitsu Kosan Co., Ltd. | Fluorescence conversion medium and display device comprising it |
JP2001223078A (en) * | 2000-01-27 | 2001-08-17 | General Electric Co <Ge> | Light source provided with organic layer and photo- luminescence layer |
JP2002237381A (en) * | 2001-02-09 | 2002-08-23 | Nagase Inteko Kk | Organic electroluminescence element |
WO2003078542A1 (en) * | 2002-03-19 | 2003-09-25 | Neoview Co., Ltd. | Red organic light-emitting compound and organic light-emitting device comprising the same |
US7211335B2 (en) | 2002-03-19 | 2007-05-01 | Neoviewkolon Co., Ltd. | Red organic light-emitting compound and organic light-emitting device comprising the same |
JPWO2006132030A1 (en) * | 2005-06-08 | 2009-01-08 | 独立行政法人産業技術総合研究所 | Novel compound, reagent for analysis of peptide or protein containing the compound, and analysis method using the analysis reagent |
JP4893964B2 (en) * | 2005-06-08 | 2012-03-07 | 独立行政法人産業技術総合研究所 | Novel compound, reagent for analysis of peptide or protein containing the compound, and analysis method using the analysis reagent |
JP2013179335A (en) * | 2013-05-08 | 2013-09-09 | Mitsubishi Chemicals Corp | White light emitting element |
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