JP4956174B2 - Organic electroluminescence device and display system using fluorescent complex - Google Patents

Description

  The present invention relates to a long-life and bright organic electroluminescence device using a specific fluorescent complex. The present invention also relates to a display system using a specific complex.

  In recent years, electroluminescence elements have been actively developed. When a phosphorescent material is used as the light emitting material, the light emitting efficiency of the element is dramatically improved. Therefore, various phosphorescent materials have been developed and applied to electroluminescence elements. Among them, the europium complex, a rare earth complex, has attracted a great deal of attention because its emission spectrum is sharp and its color purity is high, and when it is used as a dopant in the emission layer, the emission spectrum does not depend on the type of host material. For example, it is reported in patent documents 1 and 2.

  The europium complexes shown in these patent documents have β-diketone and phenanthroline as ligands, but their emission intensity and dispersion characteristics as a dopant have room for improvement as far as the present inventors know. . In addition, an example in which a europium complex having only β-diketone as a ligand is used for an electroluminescence device has been reported, but this device also has room for improvement in order to realize sufficient light emission intensity (Patent Document 2). .

  Thus, it is thought that the cause which there was room for improvement as an electroluminescent element was that the solubility and amorphous property of the fluorescent complex used were not enough. In other words, when these characteristics are low, even when trying to form a thinner thin film when forming an electroluminescent element, a crystal larger than the film thickness is formed, and the layer structure is destroyed. is there.

  On the other hand, general electroluminescent elements are being studied for various uses, particularly for applications requiring a flat and lightweight illuminant. For example, a method has been proposed in which an organic electroluminescence element is attached to a windshield of an automobile to perform various displays. In addition, the electroluminescence element can be applied to an emergency light installed in a building. However, the electroluminescence element is particularly expensive when it has a large area, and it is difficult to realize a sufficient life due to deterioration of the cathode. In addition, since the power consumption is large and heat is generated, its application is limited. Furthermore, since the moving image display is not necessarily required for the above-described applications, there is a lot of waste.

  In such applications, it may be sufficient to apply a fluorescent film to an appropriate object and irradiate light from a light source instead of an electroluminescence element. However, when a conventional inorganic phosphor is used as a light-emitting thin film, problems such as a change in visibility due to light scattering occur, and the purpose cannot often be achieved. Further, when a general organic phosphor is used, transparency can be realized, but since it is colored, the visibility is still inferior, and the object may not be sufficiently achieved. In order to achieve these objects, a fluorescent complex having sufficient solubility, amorphousness, transparency, and durability for a film-forming substance is required.

For example, a rare earth complex coordinated with crown ether is also known (Patent Document 1). However, such a conventionally known complex has an oxygen group constituting an ether group as a coordinating group. However, since the coordination ability is relatively low, there is room for improvement in stability as a complex. The complex having the crown ether described in Document 1 as a ligand has room for improvement in the shielding effect against C—H or O—H bonds existing in the vicinity when the complex is dissolved in a resin or the like. .
JP-A-11-260563 Japanese Patent Laid-Open No. 10-158639 Journal of the Chemical Society, Abstract, 4685-7, 1956. Journal of Organic Chemistry, 30 (1), 101-5, 1965. Tetrahedron 1991, V47 (3) p403-10

  The present invention has been made in view of the above problems, and an object of the present invention is to realize an organic electroluminescence element and a display element exhibiting excellent characteristics by using a fluorescent complex having high solubility.

式中、Ｒ^１〜Ｒ^６およびＲ^１１〜Ｒ^１３は、水素原子、重水素原子、置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基またはアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、および置換または非置換のヘテロ環基からなる群から選ばれるものであり、ｐは２〜２０の整数であるが、式（１）においてはＲ^１〜Ｒ^６のすべてが、式（２）においてはＲ^１〜Ｒ^４のすべてが、同一である場合を除く。 A first organic electroluminescence device according to the present invention comprises at least an anode, an organic light emitting layer, and a cathode as constituent elements, and the organic light emitting layer comprises a dopant and a host material, The dopant is a rare earth complex represented by the following formula (1) or (2), and the host material is at least selected from the group consisting of aromatic amine derivatives, carbazole derivatives, thiophene oligomers and polymers, and zinc complexes. It is characterized by comprising 1 type.

In the formula, R ^{1 to} R ⁶ and R ^{11 to} R ¹³ are each a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group or an alkoxy group having a linear or branched structure having 20 or less carbon atoms, a substituted or It is selected from the group consisting of an unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group, and p is an integer of 2 to 20 However, the case where all of R ^{1 to} R ⁶ in Formula (1) and all of R ^{1 to} R ⁴ in Formula (2) are the same is excluded.

式中、Ｘは、Ｐ、ＳおよびＣからなる群から選ばれる原子であり、分子中のそれぞれのＸは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
Ｒは、結合するＸがＰである場合には、置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基およびアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、ならびに置換または非置換のヘテロ環基からなる群から選ばれる置換基であり、Ｃ原子である場合には存在せず、Ｓ原子である場合には存在しないか、Ｓ原子と二重結合を介して結合する酸素であり、分子中のＲは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
Ｙは、水素、炭素数２０以下のアルキル基またはアルコキシ基であり、分子中のそれぞれのＹは同一であっても異なっていてもよく、また、Ｙは分子中の他のＹとの間で酸素を含んでいてもよい炭素鎖により相互に結合して架橋環構造を形成していてもよく、
Ｚは、−Ｏ−、−ＮＹ^ａ−、−Ｓ−、および−Ｓｅ−からなる群から選ばれる２価基であり、ここでＹ^ａは置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基およびアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、ならびに置換または非置換のヘテロ環基からなる群から選ばれる置換基であり、また、Ｙ^ａは分子中の他のＹまたはＹ^ａとの間で酸素を含んでいてもよい炭素鎖により相互に結合して架橋環構造を形成していてもよく、分子中のそれぞれのＺは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
ｍ１およびｍ３はそれぞれ０を含む整数であり、
ｍ１＋ｍ３は２〜１２の整数であり、
ｍ２はｍ１＋ｍ３以上の整数であり、
式中の−Ｘ（＝Ｏ）Ｒ−、−ＣＹ_２−、および−Ｚ−はランダムに配列され、互いに環状に結合されている。 The second organic electroluminescence device according to the present invention comprises at least an anode, an organic light emitting layer, and a cathode as constituent elements, and the organic light emitting layer comprises a dopant and a host material, The dopant comprises a rare earth atom and a ligand, and at least one of the ligands is a rare earth complex which is a cyclic multidentate ligand represented by the following formula (3), and the host material is an aromatic It is composed of at least one selected from the group consisting of amine derivatives, carbazole derivatives, thiophene oligomers and polymers, and zinc complexes.

In the formula, X is an atom selected from the group consisting of P, S, and C, and when there are a plurality of each X in the molecule, they may be the same or different,
R is a substituted or unsubstituted alkyl group and alkoxy group having a straight chain or branched structure having 20 or less carbon atoms, a substituted or unsubstituted phenyl group, a substituted or non-substituted group when X to be bonded is P; A substituent selected from the group consisting of a substituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group, which is not present when it is a C atom, but when it is an S atom Is oxygen which is not present or is bonded to the S atom via a double bond, and when there are a plurality of R in the molecule, they may be the same or different,
Y is hydrogen, an alkyl group having 20 or less carbon atoms or an alkoxy group, and each Y in the molecule may be the same or different, and Y is different from other Y in the molecule. A carbon chain that may contain oxygen may be bonded to each other to form a bridged ring structure,
Z is a divalent group selected from the group consisting of —O—, —NY ^a —, —S—, and —Se—, wherein Y ^a is a substituted or unsubstituted straight chain having 20 or less carbon atoms. Selected from the group consisting of alkyl and alkoxy groups having a chain or branched structure, substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted naphthyl groups, and substituted or unsubstituted heterocyclic groups And Y ^a may be bonded to each other by a carbon chain which may contain oxygen with other Y or Y ^a in the molecule to form a bridged ring structure, Each Z in the molecule may be the same or different when there are multiple occurrences,
m1 and m3 are integers each including 0;
m1 + m3 is an integer of 2 to 12,
m2 is an integer greater than or equal to m1 + m3,
In the formula, —X (═O) R—, —CY ₂ —, and —Z— are randomly arranged and bonded to each other cyclically.

式中、Ｒ^１〜Ｒ^６およびＲ^１１〜Ｒ^１３は、水素原子、重水素原子、置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基またはアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、および置換または非置換のヘテロ環基からなる群から選ばれるものであり、ｐは２以上の整数であるが、式（１）においてはＲ^１〜Ｒ^６のすべてが、式（２）においてはＲ^１〜Ｒ^４のすべてが、同一である場合を除く。 The first display system according to the present invention can irradiate the transparent fluorescent film made of a rare earth complex and polymer represented by the following formula (1) or (2) with ultraviolet light or near ultraviolet light. And a light source.

In the formula, R ^{1 to} R ⁶ and R ^{11 to} R ¹³ are each a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group or an alkoxy group having a linear or branched structure having 20 or less carbon atoms, a substituted or Selected from the group consisting of an unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group, and p is an integer of 2 or more. In the formula (1), all of R ^{1 to} R ⁶ are the same, and in the formula (2), all of R ^{1 to} R ⁴ are the same.

式中、Ｘは、Ｐ、ＳおよびＣからなる群から選ばれる原子であり、分子中のそれぞれのＸは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
Ｒは、結合するＸがＰである場合には、置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基およびアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、ならびに置換または非置換のヘテロ環基からなる群から選ばれる置換基であり、Ｃ原子である場合には存在せず、Ｓ原子である場合には存在しないか、Ｓ原子と二重結合を介して結合する酸素であり、分子中のＲは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
Ｙは、水素、炭素数２０以下のアルキル基またはアルコキシ基であり、分子中のそれぞれのＹは同一であっても異なっていてもよく、また、Ｙは分子中の他のＹとの間で酸素を含んでいてもよい炭素鎖により相互に結合して架橋環構造を形成していてもよく、
Ｚは、−Ｏ−、−ＮＹ^ａ−、−Ｓ−、および−Ｓｅ−からなる群から選ばれる２価基であり、ここでＹ^ａは置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基およびアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、ならびに置換または非置換のヘテロ環基からなる群から選ばれる置換基であり、また、Ｙ^ａは分子中の他のＹまたはＹ^ａとの間で酸素を含んでいてもよい炭素鎖により相互に結合して架橋環構造を形成していてもよく、分子中のそれぞれのＺは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
ｍ１およびｍ３はそれぞれ０を含む整数であり、
ｍ１＋ｍ３は２〜１２の整数であり、
ｍ２はｍ１＋ｍ３以上の整数であり、
式中の−Ｘ（＝Ｏ）Ｒ−、−ＣＹ_２−、および−Ｚ−はランダムに配列され、互いに環状に結合されている。 A second display system according to the present invention comprises a rare earth complex and a polymer comprising a rare earth atom and a ligand, wherein at least one of the ligands is a cyclic multidentate ligand represented by the following formula (3). And a light source capable of irradiating the transparent fluorescent film with ultraviolet light or near-ultraviolet light.

In the formula, X is an atom selected from the group consisting of P, S, and C, and when there are a plurality of each X in the molecule, they may be the same or different,
R is a substituted or unsubstituted alkyl group and alkoxy group having a straight chain or branched structure having 20 or less carbon atoms, a substituted or unsubstituted phenyl group, a substituted or non-substituted group when X to be bonded is P; A substituent selected from the group consisting of a substituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group, which is not present when it is a C atom, but when it is an S atom Is oxygen which is not present or is bonded to the S atom via a double bond, and when there are a plurality of R in the molecule, they may be the same or different,
Y is hydrogen, an alkyl group having 20 or less carbon atoms or an alkoxy group, and each Y in the molecule may be the same or different, and Y is different from other Y in the molecule. A carbon chain that may contain oxygen may be bonded to each other to form a bridged ring structure,
Z is a divalent group selected from the group consisting of —O—, —NY ^a —, —S—, and —Se—, wherein Y ^a is a substituted or unsubstituted straight chain having 20 or less carbon atoms. Selected from the group consisting of alkyl and alkoxy groups having a chain or branched structure, substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted naphthyl groups, and substituted or unsubstituted heterocyclic groups And Y ^a may be bonded to each other by a carbon chain which may contain oxygen with other Y or Y ^a in the molecule to form a bridged ring structure, Each Z in the molecule may be the same or different when there are multiple occurrences,
m1 and m3 are integers each including 0;
m1 + m3 is an integer of 2 to 12,
m2 is an integer greater than or equal to m1 + m3,
In the formula, —X (═O) R—, —CY ₂ —, and —Z— are randomly arranged and bonded to each other cyclically.

  The organic electroluminescent device and the display system according to the present invention comprise a specific fluorescent complex. Such a fluorescent complex is highly soluble or compatible with a host material in an organic electroluminescence device and a polymer material in a display device, and also has a high amorphous property. Therefore, a thin thin film containing the fluorescent complex is uniformly formed. Can be formed. As a result, the layer structure defect due to crystallization of the fluorescent complex is eliminated in the organic electroluminescence element, the emission intensity and the long life are achieved, and the display element has a transparent fluorescent film exhibiting strong emission for a wide variety of uses. It can be easily formed according to the above, and various display systems can be realized.

式中、Ｌｎは希土類原子であり、Ｒ^１〜Ｒ^６およびＲ^１１〜Ｒ^１３は、水素原子、重水素原子、置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基またはアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、および置換または非置換のヘテロ環基からなる群から選ばれるものであり、ｐは２以上の整数であるが、式（１）においてはＲ^１〜Ｒ^６のすべてが、式（２）においてはＲ^１〜Ｒ^４のすべてが、同一である場合を除く。 Rare earth complex The rare earth complex used as a fluorescent complex in the present invention comprises a rare earth atom and a specific ligand coordinated thereto. One of the rare earth complexes that can be used in the present invention is represented by the following formula (1) or (2).

In the formula, Ln is a rare earth atom, and R ^{1 to} R ⁶ and R ^{11 to} R ¹³ are a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl having a straight chain or branched structure having 20 or less carbon atoms. A group or an alkoxy group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group, and p is Although it is an integer greater than or equal to 2, in the formula (1), R ^{1 to} R ⁶ are all the same, and in the formula (2), all of R ^{1 to} R ⁴ are the same.

  Here, Ln is a rare earth atom, and an appropriate light emission intensity or light emission wavelength can be selected according to the use, but europium or terbium is preferable, and europium is particularly preferable.

In addition, all of R ^{1 to} R ⁶ in (1) and all of R ^{1 to} R ⁴ in Formula (2) need not be the same. Under this condition, the complex becomes asymmetrical, and the solubility or amorphousness with respect to the polymer material or the host material becomes sufficient.

  Moreover, p in Formula (2) is an integer of 2-20. Here, p is preferably 7 or less in order to coordinate to a single rare earth atom. In addition, when p is an odd number, there is fluorescence that improves the solubility in the polymer material or the host material. .

式中、Ｘは、Ｐ、ＳおよびＣからなる群から選ばれる原子であり、分子中のそれぞれのＸは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
Ｒは、結合するＸがＰである場合には、置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基およびアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、ならびに置換または非置換のヘテロ環基からなる群から選ばれる置換基であり、Ｃ原子である場合には存在せず、Ｓ原子である場合には存在しないか、Ｓ原子と二重結合を介して結合する酸素であり、分子中のＲは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
Ｙは、水素、炭素数２０以下のアルキル基またはアルコキシ基であり、分子中のそれぞれのＹは同一であっても異なっていてもよく、また、Ｙは分子中の他のＹとの間で酸素を含んでいてもよい炭素鎖により相互に結合して架橋環構造を形成していてもよく、
Ｚは、−Ｏ−、−ＮＹ^ａ−、−Ｓ−、および−Ｓｅ−からなる群から選ばれる２価基であり、ここでＹ^ａは置換または非置換の、炭素数が２０以下の直鎖または分岐構造を有するアルキル基およびアルコキシ基、置換または非置換のフェニル基、置換または非置換のビフェニル基、置換または非置換のナフチル基、ならびに置換または非置換のヘテロ環基からなる群から選ばれる置換基であり、また、Ｙ^ａは分子中の他のＹまたはＹ^ａとの間で酸素を含んでいてもよい炭素鎖により相互に結合して架橋環構造を形成していてもよく、分子中のそれぞれのＺは複数存在する場合にはそれぞれ同一であっても異なっていてもよく、
ｍ１およびｍ３はそれぞれ０を含む整数であり、
ｍ１＋ｍ３は２〜１２の整数、好ましくは２〜８の整数であり、
ｍ２はｍ１＋ｍ３以上の整数であり、
式中の−Ｘ（＝Ｏ）Ｒ−、−ＣＹ_２−、および−Ｚ−はランダムに配列され、互いに環状に結合されている。 Another rare earth complex that can be used in the present invention comprises a rare earth atom and a ligand, and at least one of the ligands is a cyclic multidentate ligand represented by the following formula (3). It is a complex.

In the formula, X is an atom selected from the group consisting of P, S, and C, and when there are a plurality of each X in the molecule, they may be the same or different,
R is a substituted or unsubstituted alkyl group and alkoxy group having a straight chain or branched structure having 20 or less carbon atoms, a substituted or unsubstituted phenyl group, a substituted or non-substituted group when X to be bonded is P; A substituent selected from the group consisting of a substituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group, which is not present when it is a C atom, but when it is an S atom Is oxygen which is not present or is bonded to the S atom via a double bond, and when there are a plurality of R in the molecule, they may be the same or different,
Y is hydrogen, an alkyl group having 20 or less carbon atoms or an alkoxy group, and each Y in the molecule may be the same or different, and Y is different from other Y in the molecule. A carbon chain that may contain oxygen may be bonded to each other to form a bridged ring structure,
Z is a divalent group selected from the group consisting of —O—, —NY ^a —, —S—, and —Se—, wherein Y ^a is a substituted or unsubstituted straight chain having 20 or less carbon atoms. Selected from the group consisting of alkyl and alkoxy groups having a chain or branched structure, substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted naphthyl groups, and substituted or unsubstituted heterocyclic groups And Y ^a may be bonded to each other by a carbon chain which may contain oxygen with other Y or Y ^a in the molecule to form a bridged ring structure, Each Z in the molecule may be the same or different when there are multiple occurrences,
m1 and m3 are integers each including 0;
m1 + m3 is an integer of 2 to 12, preferably an integer of 2 to 8,
m2 is an integer greater than or equal to m1 + m3,
In the formula, —X (═O) R—, —CY ₂ —, and —Z— are randomly arranged and bonded to each other cyclically.

式中、ＸおよびＲの定義は前記したとおりであり、ｎ１〜ｎ６はそれぞれ０以上の整数であり、好ましくは１〜３、好ましくは１である。 The cyclic multidentate ligand represented by the formula (3) includes an atomic group having an O atom having a lone electron pair, such as P═O, S═O, O═S═O, and C═O, and an isolated An N atom having an electron pair and a Se atom are coordinated to a rare earth atom to form a complex. Here, in the rare earth complex used in the present invention, a ring formed by a plurality of coordination groups is preferably not too large. From such a viewpoint, what has a structure in any one of following formula (3A)-(3C) is preferable.

In the formula, the definitions of X and R are as described above, and n1 to n6 are each an integer of 0 or more, preferably 1 to 3, and preferably 1.

  These ligands are selected according to the type of rare earth atom that is the central metal of the rare earth complex, and the molecular weight of the ligand is generally 2000 or less, preferably 1000 or less. Conventionally, it is known that a dendrimer having a very high molecular weight is used as a ligand of a rare earth complex. By using such a dendrimer or the like as a ligand of a rare earth complex, the shielding effect of central rare earth ions is enhanced. You can also. However, the molecular weight of dendrimers reaches several thousand, and it is often impossible to obtain an effective fluorescent layer due to its huge structure, and the effects of the present invention cannot be achieved sufficiently.

  These cyclic multidentate ligands may be knotted with each other via chemical bonds, if necessary. That is, it may be a dimer or trimer in which cyclic multidentate ligands are linked by a molecular chain, or a polymer. Specifically, they may be bonded via an alkylene group extended from R or Y in the above general formula, an ether bond, an ester bond, or the like.

  The cyclic bidentate ligands of formulas (3A) to (3C) are capable of forming a coordination bond with a rare earth ion that is Lewis acidic because the oxygen atom of X = O is Lewis basic. .

  When such a cyclic bidentate ligand is coordinated to a rare earth atom, the ring surrounds the rare earth atom. At this time, it is preferable that the center of the rare earth atom does not coincide with the surface constituted by a plurality of coordination groups. When there are 4 or more coordinating groups of the cyclic bidentate ligand, not all the coordinating groups are located on a single plane depending on the structure (comformation) of the cyclic bidentate ligand. A structure in which rare earth atoms jump out of the ligand plane determined from the center of gravity at the position of the coordinating group is preferred. In other words, it is preferable that each ligand does not exist in a symmetrical position with respect to the center of the rare earth atom. Such a structure is likely to occur when the space defined by each ligand is small, in other words, when the ring formed by the ligand is small. For this reason, it is preferable that the ring of the cyclic multidentate ligand is not too large.

  Since the rare earth complex used in the present invention has such a structure, the ligand field has asymmetry. For this reason, the absorption efficiency of the rare earth complex is increased, and as a result, the light emission efficiency is high.

  This luminous efficiency tends to be further increased by combining a plurality of types of ligands and coordinating with rare earth atoms. For example, two or more kinds of cyclic multidentate ligands each having the structure described above can be combined, or a cyclic multidentate ligand having the structure described above can be combined with other ligands. As a ligand different from the cyclic bidentate ligand having the above-described structure, any conventionally known coordination compound can be used. For example, phosphine oxide compounds, carbonyl compounds, pyridine compounds , Sulfoxide compounds, and sulfone compounds. Such a combination of ligands tends to improve the solubility or dispersibility of the rare earth complex in a resin or the like, or increase the luminous efficiency due to the asymmetry of the ligand field.

  The above-mentioned cyclic multidentate ligand can be prepared by any method. For example, it can be obtained by oxidizing the phosphorus atom (trivalent) of the hetero crown by the technique used for the oxidation of phosphine. As the oxidation reaction, for example, the method described in Non-Patent Document 1 or 2 can be used. It can also be obtained by a cyclization reaction as shown in Non-Patent Document 3.

  The rare earth complex according to the present invention is one in which the above-described ligand is coordinated to a rare earth atom. As the rare earth atom that can be used, any one can be selected, but europium is particularly preferable from the viewpoint of luminous efficiency and red color rendering. The rare earth complex used in the present invention is prepared by reacting a salt containing such a rare earth atom, for example, chloride, nitrate, hydroxide, etc., in the above-described ligand and solvent, if necessary, by heating. Can be prepared. As the solvent, water, alcohols, ester solvents, etc. are generally used.

  A rare earth complex containing a cyclic bidentate ligand has a very high solubility in a polymer material due to the effect of the cyclic bidentate ligand, and is a factor that exerts a remarkable effect in the present invention.

これに対して、配位子が対称に配位する希土類錯体は非常に溶解性が低く、実質的に溶解しない。具体的には、上記のＲ１〜Ｒ４がすべてフェニル基である場合には、溶解度が０．０１μｍｏｌ／ｇ以下である。 The solubility of the rare earth complexes represented by these formulas (1) to (3) is as shown in Table 1.

In contrast, rare earth complexes in which ligands are coordinated symmetrically have very low solubility and do not substantially dissolve. Specifically, when all of R1 to R4 are phenyl groups, the solubility is 0.01 μmol / g or less.

Organic electroluminescent device The organic electroluminescent device according to the present invention comprises the above rare earth complex as a dopant, and the host material is selected from the group consisting of aromatic amine derivatives, carbazole derivatives, and thiophene oligomers and polymers. It is composed of at least one kind. For the rare earth complex of formula (3), a zinc complex can also be used as a host material.

式中、Ａｒ^１〜Ａｒ^４は、フェニル基、ビフェニル基、複素芳香族基からなる群から選択される置換基であり、Ａは、置換又は非置換の、フェニレン基、ビフェニレン基、およびチオフェニレン基からなる群から選択される２価基である。 The aromatic amine derivative used as the host material in the present invention can be arbitrarily selected according to the use, but those represented by the following formula (4) are preferable.

In the formula, Ar ^{1 to} Ar ⁴ are substituents selected from the group consisting of a phenyl group, a biphenyl group, and a heteroaromatic group, and A is a substituted or unsubstituted phenylene group, biphenylene group, and thiophenylene. A divalent group selected from the group consisting of groups.

Here, in Formula (4), Ar ^{1 to} Ar ⁴ may be the same or different, but the combination of Ar ¹ and Ar ² may be different from the combination of Ar ³ and Ar ^4. preferable. This is because if the structure of such an aromatic amine derivative is asymmetric, the amorphousness increases and crystallization is difficult.

式中、Ｒ^２１、およびＲ^２２は、直鎖又は分岐鎖の、アルキル基、アルコキシ基、アミノ基、およびニトロ基からなる群から選択される置換基であり、ｑは２以上の整数である。ここでｑは任意に選択できるが、通常、カルバゾール誘導体の分子量が数千のものが好適に用いられる。 As the carbazole derivative, a polymer represented by the following formula (5) is preferable.

In the formula, R ²¹ and R ²² are linear or branched substituents selected from the group consisting of alkyl groups, alkoxy groups, amino groups, and nitro groups, and q is an integer of 2 or more. . Here, q can be arbitrarily selected, but usually a carbazole derivative having a molecular weight of several thousand is preferably used.

式中、ｒは重合度を示す２以上の整数である。ここでｒはより大きいものが好ましく、分子量が１，０００以上になるように選択されるが、通常、分子量が１００，０００程度までのものが用いられる。 Furthermore, as the thiophene oligomer or polymer, those represented by the following formula (6) are preferable.

In the formula, r is an integer of 2 or more indicating the degree of polymerization. Here, r is preferably larger, and is selected so that the molecular weight is 1,000 or more. Usually, a molecular weight of up to about 100,000 is used.

式中、ｒ０は重合度を示す２以上の整数である。ここでｒ
はより大きいものが好ましく、分子量が１，０００以上になるように選択されるが、通常、分子量が１００，０００程度までのものが用いられる。 When the host material is a thiophene oligomer or polymer, the host material preferably further comprises a sulfonic acid polymer. In particular, the sulfonic acid polymer of the following formula (7) is preferable, but the mixture of the thiophene polymer of the formula (6) and the sulfonic acid polymer of the formula (7) is well known as PEDOT-PSS and is inexpensive. preferable.

In the formula, r0 is an integer of 2 or more indicating the degree of polymerization. Where r
Is preferably selected so that the molecular weight is 1,000 or more, but those having a molecular weight of up to about 100,000 are usually used.

Furthermore, when the rare earth complex has a cyclic multidentate ligand of the formula (3), a zinc complex can be used as the host material. Such a zinc complex can be arbitrarily selected from those known as host materials, and examples thereof include those represented by the following formula (10).

  The rare earth complex used in the present invention has an absorption spectrum in the ultraviolet region (300 to 380 nm) in the near ultraviolet (380 to 380 nm) due to the asymmetry of the structure, that is, the coordination sites of a plurality of phosphine oxides and the like. 405 nm), a long wavelength shift to the blue-violet region, and when a hole transport material having an emission spectrum in this region is used as a host material, energy transfer proceeds efficiently, resulting in a bright and long-life organic electroluminescence device. can get.

  Furthermore, the relationship between the host material of the present invention and the dopant energy level is that the LUMO level of the host material is lower than the LUMO level of the dopant material, and the HOMO level of the host material is lower than the HOMO level of the dopant material. It is more desirable from the viewpoint of efficient energy transfer.

  The structure of the organic electroluminescent element by this invention is shown, for example in FIGS. That is, the organic electroluminescence element of FIG. 1 includes a glass substrate 1, an anode 2 made of ITO, a hole transport layer 3, a light emitting layer 4, and a cathode 5. The organic electroluminescence element of FIG. 2 includes a glass substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 6, and a cathode 5. The organic electroluminescence element of FIG. 3 includes a glass substrate 1, an anode 2, a light emitting layer 4, a hole blocking layer 7, an electron transport layer 6, and a cathode 5. The organic electroluminescent element in FIG. 4 is composed of a glass substrate 1, an anode 2, a light emitting layer 4, an electron transport layer 6, and a cathode 5. The organic electroluminescence device of FIG. 5 includes a glass substrate 1, an anode 2, a hole injection layer 8, a hole transport layer 3, a light emitting layer 4, a hole blocking layer 9, an electron transport layer 6, an electron injection layer 10, and a cathode 5. Is done.

  As the anode of the organic electroluminescence device according to the present invention, gold, copper iodide, bell oxide, or indium oxide bell (ITO) can be used. The cathode material includes metals of Group 1 and 2 of the periodic table such as sodium, lithium, magnesium and calcium, and metals of Group 3 of the periodic table such as gallium and indium. Examples of the hole transport material include arylamine derivatives, carbazole derivatives, thiophene oligomers or polymers, and copper phthalocyanine. This hole transport layer material can be used as a host material of a light emitting layer, and a rare earth complex can be dispersed therein as a dopant to form a light emitting layer.

  In addition to the rare earth complex of the present invention, the light emitting layer can be used as a dopant for the hole transport material described above.

The light-emitting layer, in addition to Alq ₃ as Al oxine complex, perylene compounds, naphthalene-based compounds, coumarin based compounds, oxadiazole-based compounds, aldazine-based compounds, bis benzoxathiol gelsolin compounds, bisstyryl compounds, pyrazine-based A compound, a CPD compound, an In oxine complex, a Zn complex, a Fe oxine complex, or a Ga imine complex can be used. The material used for the hole-blocking layer has a large ionization potential. The material must have a low hole mobility, and there are triazole compounds and derivatives thereof. Examples of the electron transport layer material include metal chelate compounds containing Alq3, benzoxador, benzothiazole, tris (8-hydroxyquinolinol) bismuth, and perylene compounds.

Display system A transparent fluorescent film composed of a rare earth complex and a polymer as described above is installed on the surface or inside of a transparent object such as transparent glass or plastic, or on a non-transparent object such as a wall or floor, By installing an excitation light source that can irradiate ultraviolet light or near ultraviolet light on the transparent fluorescent film, it is possible to construct a display system that is colorless and transparent when not excited, has no visibility, and can emit strong light when excited. it can.

  Here, the rare earth complex used in the present invention is highly soluble or dispersible in the polymer material as described above, but by using a specific material as the polymer material, the effect is further strongly expressed. be able to. The polymer used is preferably a polymer selected from the group consisting of fluorine-based polymers, silicon-based polymers, and mixtures thereof. When these polymer materials are used, in addition to the effect that the solubility of the rare earth complex is high, the durability of the polymer material tends to be improved when used as a display element.

式中、Ｘはハロゲン原子、好ましくはフッ素または塩素であり、Ｒ^ａ１〜Ｒ^ａ３はそれぞれ独立に アルキル基であり、ｘ１〜ｘ３およびｙ１〜ｙ６はそれぞれ重合度を表す数であって、ｘ１＋ｘ２＋ｘ３およびｙ１＋ｙ２＋ｙ３＋ｙ４＋ｙ５＋ｙ６はそれぞれ０では無く、各繰り返し単位はランダムに配列していてもよい。 When a fluorine-based polymer is used as the polymer material, those represented by the following formula (8A) or (8B) are preferable.

In the formula, X is a halogen atom, preferably fluorine or chlorine, R ^{a1 to} R ^a3 are each independently an alkyl group, x1 to x3 and y1 to y6 are numbers each representing a degree of polymerization, and x1 + x2 + x3 and y1 + y2 + y3 + y4 + y5 + y6 is not 0, and each repeating unit may be arranged at random.

式中、ｚは１以上の整数である。 Moreover, when using a silicon-type polymer as a polymer material, what is shown by following formula (9A)-(9C) is preferable.

In the formula, z is an integer of 1 or more.

  The display system according to the present invention includes a phosphor or a phosphor that is a combination of the rare earth complex and the polymer, and the phosphor is installed in accordance with various uses, and emits light by light from an excitation light source. Various displays.

  For example, as one embodiment according to the present invention, a transparent phosphor thin film formed by dissolving a rare earth complex of each color or a mixture thereof in a polymer is formed on a windshield of a passenger car, and an LED element serving as an excitation light source is formed at a location separated from the thin film. By installing, a speed display system as shown in FIG. 6 can be realized. FIG. 6A shows an example of a display state by a display element, and FIG. 6B is a cross-sectional view of an automobile including a display system. A transparent phosphor thin film 64 is installed on the windshield 63 of the automobile, and the light emitted from the excitation light source 62 changes according to information output from a speedometer (not shown) that detects the speed of the automobile. The light emission change is as illustrated in FIG. 6A, and the speed change is displayed on the windshield. Since the transparent phosphor thin film 64 is colorless and transparent when not emitting light, the presence of the thin film is not perceived, and when excited, it is possible to emit strong light in a see-through state while maintaining transparency. The driver can see a speedometer with excellent visibility without obstructing the field of view and without having to face down. Therefore, accidents due to excessive speed can be prevented.

  Furthermore, as shown in FIG. 7, the effect of preventing overspeed is further enhanced by increasing the light emission pattern in the high-speed region, or in a system that clearly emits light such as red as a warning color in the high-speed region. In the sense of warning the driver, it is desirable to blink in the high speed region.

  The display system illustrated in FIGS. 6 and 7 can display not only the absolute speed but also the road information such as the speed limit and display a deviation from the designated driving condition.

  The present invention can also be applied to automobile navigation systems. The current car navigation system has room for improvement because it is necessary to confirm the position and direction on the screen when the vehicle stops. However, if the display system according to the present invention is used to awaken a car navigation system in which information output from the navigation system is displayed by a phosphor installed on the windshield, the outside scenery and direction indication are integrated. Therefore, it is not necessary to change the viewpoint and it is easy to understand. That is, a navigation system including a GPS or the like is combined with the display element according to the present invention, and the information is displayed by a phosphor as shown in FIG. 8 installed on the windshield of an automobile. FIG. 8 is an example of the display when the direction in which the vehicle should travel is displayed with an arrow. The route that reaches the destination inputted in advance is selected by the navigation system. For example, when turning left, the route is displayed as shown in FIG. Further, as shown in FIGS. 8C and 8D, changing the emission color according to the distance has the effect of further enhancing the driver's understanding. In such a case, the phosphor can be placed inside the surface of the transparent object, or can be placed inside. For example, two glasses can be bonded with the phosphor sandwiched therebetween. In addition, a phosphor can be placed on the glass surface, and a protective layer can be placed on the surface to improve the durability of the phosphor.

  Furthermore, as shown in FIG. 9, it is possible to provide a system in which a phosphor is installed in a window or a vehicle body of an automobile, and a driver sends a specific message to surrounding drivers as necessary. For example, in a city where a streetcar runs, if you are unfamiliar with the priority relationship, you can temporarily display the message on a part of the car body.

  In addition, as shown in FIG. 10, in one embodiment of the display system according to the present invention, for example, when a phosphor 101 that notifies an emergency is installed on a window or an outer wall of an elderly person's house 100 and an emergency occurs, A phosphor can send a message to the outside by light automatically or manually by excitation light from the light source 102 to obtain a system for rescue.

  In addition, as shown in FIG. 11, one embodiment of the display system according to the present invention includes a phosphor 111 and an excitation light source 112 that are not visible in daily life and emit light in an emergency such as a fire, and are provided with a floor surface 110, a wall surface, a door, etc. It is something to be installed in. In other words, in the event of an emergency such as a fire, the display system indicates the retreat path based on information from the control circuit 113. At this time, in order to input information to the control circuit 113, the source of the fire or the fire situation is identified from the operation state of the fire detector such as the smoke detector, the heat detector, or the sprinkler, and the evacuation for selecting a safe evacuation route It is more desirable to combine the route selection system 114 to display the optimal evacuation route in a light-emitting manner.

  Further, in one embodiment of the display system according to the present invention, as shown in FIG. 12, the phosphor 121 is installed at the edge of the obstacle 120 placed in the passage or the like, or the edge of the passage having a low frontage. When a human body sensor 123 including a control circuit detects that a person is approaching an obstacle, the light source 123 irradiates the phosphor with light and the edge of the obstacle Is used to call attention.

  Further, as shown in the sectional view of FIG. 13A, a smoke detector 131, a phosphor (display plate) 132 for displaying a smoking cessation message made of the transparent fluorescent thin film, and an excitation light source 133 are installed on the wall surface 130 of the smoking cessation room. Thus, when smoking, the smoke is detected by the smoke detector, and the smoking cessation mark blinks from the wall (FIG. 13B), thereby enabling a display system. It can be expected to suppress smoking in non-smoking areas.

  The display system according to the present invention is a display system that is colorless and transparent at the time of non-light emission, has no visibility, and can emit brightly bright light at the time of light emission, such as a transparent part (glass window), a corridor or an object of a vehicle or a house. By installing a transparent fluorescent thin film and sending a necessary light message when necessary, it becomes possible to realize safety and convenience that have been difficult to realize in the past.

The organic electroluminescence device according to the present invention will be described below using an example.
Example 1
ITO was laminated on a glass substrate by sputtering or the like to form an anode, and the compounds of the formulas (E1) and (E2) were vacuum-deposited so as to have a molar ratio of 1:20 and a thickness of 50 nm. On top of this, magnesium was deposited as a cathode to a thickness of 50 nm to produce an organic electroluminescence device.

By applying a voltage of 12 V between the electrodes, a luminance of 150 cd / m ² was obtained, and the time required for the luminance to halve in the continuous lighting test was as good as 30000 h.

Example 2
An organic electroluminescence device having the same configuration as in Example 1 was produced except that the dopant represented by the formula (E3) was used.

By applying a voltage of 12 V between the electrodes, a luminance of 200 cd / m ² was obtained, and the time required for the luminance to be halved in the continuous lighting test was as good as 50000 h.
Example 3

An organic electroluminescence device exactly the same as in Example 2 was produced except that the compound represented by the formula (5) was used as the host material.
By applying a voltage of 12 V between the electrodes, a luminance of 180 cd / m ² was obtained, and the time required for the luminance to halve in the continuous lighting test was as good as 40000 h.
Example 4

An organic electroluminescence device identical to that of Example 1 was prepared except that the compound represented by the formula (5) was used as the host material.
By applying a voltage of 12 V between the electrodes, a luminance of 170 cd / m ² was obtained, and the time required for the luminance to be halved in the continuous lighting test was as good as 30000 h.

Example 5
An organic electroluminescence device exactly the same as that of Example 1 was produced except that the compound represented by the formula (E4) was used as the host material.

By applying a voltage of 12 V between the electrodes, a luminance of 220 cd / m ² was obtained, and the time required for the luminance to halve in the continuous lighting test was as good as 60000 h.

Example 6
A europium complex represented by the following formula (E5) was synthesized by the method shown in the text.
Furthermore, ITO was laminated | stacked on the glass substrate by 200 nm sputtering, and the said glass substrate was wash | cleaned one by one using acetone and 2-propanol. Thereafter, (E6) as a luminescent material and (E5) as a dopant were laminated to a thickness of 50 nm at a deposition rate ratio of 5: 1 as a fluorescent layer using a vacuum deposition method. Further thereon, a triazole compound shown in (E7) as a hole blocking layer was laminated to a thickness of 15 nm, and further, Alq _{3 with} a thickness of 30 nm as an electron transport layer and magnesium with a thickness of 150 nm as a cathode were sequentially laminated, The organic electroluminescent element shown in FIG. 1 was created. The luminance when a voltage of 12 V was applied to the organic electroluminescence element exceeded 150 cd / m ² . Next, the time required to halve the luminance with a voltage of 15 V applied was 60000 h.

Example 7
Except using (E4) as the host material, an organic electroluminescence device exactly the same as in Example 1 was produced.
The luminance when a voltage of 12 V was applied to the organic electroluminescence element exceeded 160 cd / m ² . Next, the time required to halve the luminance with a voltage of 15 V applied was 40000 h.

Example 8
A 1 wt% benzene solution of polyvinyl carbazole (5) was formed on the glass substrate with ITO of Example 6 by spin coating. On top of this, a solution of europium complex (E5) (10 mg / 1 ml) and polyvinylcarbazole (5) (10 mg / 1 ml) dissolved in benzene was similarly spin-coated and sufficiently dried. Next, 60 nm of the compound represented by the formula (E8) was deposited as an electron transporting layer, and Al—Li was deposited as a cathode by a 200 nm vacuum deposition method, and the organic electroluminescence device shown in FIG.
The luminance when a voltage of 12 V was applied to the organic electroluminescence element exceeded 160 cd / m ² . Next, the time required to reduce the luminance in half with a voltage of 15 V applied was 35000 h.

Example 9
Example PEDOT-PSS, which is a mixture of the thiophene polymer of formula (6) and the sulfonic acid polymer of formula (7), was formed on the ITO-coated glass substrate of Example 6 by spin coating. An organic electroluminescence element exactly the same as that of No. 6 was produced as a prototype.
The luminance when a voltage of 12 V was applied to the organic electroluminescence element exceeded 180 cd / m ² . Next, the time required to halve the luminance with a voltage of 15 V applied was 30000 h.

Example 10
An organic electroluminescence device exactly the same as in Example 1 was prepared, except that the zinc complex of formula (10) was used as the luminescent material.
The luminance when a voltage of 12 V was applied to the organic electroluminescence element exceeded 200 cd / m ² . Next, the time required for halving the luminance with a voltage of 15 V applied was 25000 h.

Comparative Example 1
An organic electroluminescence device exactly the same as in Example 1 was produced except that the compound represented by the formula (E9) was used as the europium complex.
By applying a voltage of 12 V between the electrodes, a luminance of 100 cd / m ² was obtained, and the time required for the luminance to be halved in the continuous lighting test was insufficient at 4000 h.

Example 11
ITO was laminated on the glass substrate by sputtering at 200 nm, and the glass substrate was sequentially washed with acetone and 2-propanol. Thereafter, (E10) was deposited to 60 nm by vacuum deposition, and (E5) (light emitting layer) was laminated to a thickness of 60 nm as a fluorescent layer thereon, and 2000-A Al-Li was further laminated (FIG. 2). . The luminance when a voltage of 12 V was applied to the organic electroluminescence element exceeded 130 cd / m ² . Next, the time required to halve the luminance with a voltage of 15 V applied was 30000 h.

Example 12
An organic electroluminescence element shown in FIG. 4 was prototyped. Al as the cathode, Li ₂ O as the electron injection layer, Alq ₃ as the electron transport layer, the compound of formula (E13) as the hole blocking layer, the compound of (E11) and the compound of (E5) as the red light emitting layer ( The compound of E11) and the compound of (E12) are formed as a green light emitting layer, the compound of (E11) and the compound of (E14) are formed as a blue light emitting layer, and each co-deposited film is formed, and (E2), Copper phthalocyanine was used as the hole injection layer, and ITO was used as the anode. The initial luminance when a voltage of 12 V was applied to the organic electroluminescence element was 150 cd / m ² or more, and the time required to reduce the luminance by half when the voltage of 15 V was applied was 30000 h.

The display system according to the present invention will be described with reference to an example.
Example 13
A europium complex represented by the formula (E1) and a terbium complex represented by the formula (E15) were synthesized as red phosphors.

These complexes were dissolved in xylene together with the polymer represented by the formula (8B) at the following ratio to prepare an ink.
Red light emitting transparent fluorescent thin film (E1) 2 wt%
Orange light-emitting transparent fluorescent thin film (E1) 2 wt%, (E15) 8 wt%
Yellow light-emitting transparent fluorescent thin film (E1) 2 wt%, (E15) 16 wt%
Light green light-emitting transparent fluorescent thin film (E1) 2 wt%, (E15) 32 wt%
Green light-emitting transparent fluorescent thin film (E15) 8wt%
When these inks were pattern-printed on a glass substrate and each was irradiated with UV-LED light, very strong light emission of a desired color was obtained. No change in brightness was observed after 1000 hours.

Example 14
A transparent fluorescent thin film was prepared in the same manner as in Example 13 except that the europium complex represented by the formula (E3) and the terbium complex represented by the formula (E16) were used as the red phosphor, and very strong emission of each color was confirmed. did. Even after 1000 hours, no decrease in brightness was observed.

Example 15
A transparent fluorescent thin film was prepared in the same manner as in Example 14 except that the europium complex represented by the formula (E5) and the terbium complex represented by the formula (E16) were used as the red phosphor, and very strong light emission of each color. It was confirmed. Even after 1000 hours, no decrease in brightness was observed.

Example 16
A transparent fluorescent thin film was prepared in the same manner as in Example 13 except that the polymer represented by the formula (8A) was used as a polymer and ethyl acetate was used as a solvent, and very strong luminescence of each color was confirmed. Even after 1000 hours, no decrease in brightness was observed. Even after 1000 hours, no decrease in brightness was observed.

Example 17
Using the polymers of the formulas (9A), (9B) and (9C) as the polymer, each phosphor is dissolved in this solution at the same concentration as in Example 13, and printed and polymerized to create a transparent fluorescent thin film of each color The emission of each color was confirmed. The emission of each color was very strong. Even after 1000 hours, no decrease in brightness was observed.

Example 18
The transparent fluorescent thin film of Example 13 was coated with a chloroethylene trifluoride resin thin film and exposed to conditions of 85 ° C. and 85% humidity (accelerated aging test) for 300 hours. It was found to be about 95% and sufficiently durable. Furthermore, no decrease in brightness was observed after 1000 hours.

Comparative Example 2
Except for using the compound represented by the formula (E9) as the europium complex, an ink exactly the same as in Example 13 was prepared and evaluated. However, the emission intensity was not sufficient as compared with Example 13, and the brightness decreased. It was written.

Sectional drawing of one embodiment of the organic electroluminescent element by this invention. Sectional drawing of one embodiment of the organic electroluminescent element by this invention. Sectional drawing of one embodiment of the organic electroluminescent element by this invention. Sectional drawing of one embodiment of the organic electroluminescent element by this invention. Sectional drawing of one embodiment of the organic electroluminescent element by this invention. The schematic diagram which shows one embodiment of the display system by this invention. The schematic diagram which shows one embodiment of the display system by this invention. The schematic diagram which shows one embodiment of the display system by this invention. The schematic diagram which shows one embodiment of the display system by this invention. The schematic diagram which shows one embodiment of the display system by this invention. The schematic diagram which shows one embodiment of the display system by this invention. The schematic diagram which shows one embodiment of the display system by this invention. The schematic diagram which shows one embodiment of the display system by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Anode 3 Hole transport layer 4 Light emitting layer 5 Cathode 6 Electron transport layer 7 Hole blocking layer 8 Hole injection layer 9 Hole blocking layer 10 Electron injection layer 61 Transparent phosphor thin film 62 Excitation light source 63 Front glass 64 Handle 100 Housing 101 Phosphor 102 Light source 110 Floor 111 Phosphor 112 Excitation light source 113 Control circuit 114 Evacuation route selection system 120 Obstacle 121, 122 Phosphor 123, 124 Human sensor 125, 126 Light source 130 Wall 131 Smoke detector 132 Phosphor 133 Excitation light source

Claims (22)

An organic electroluminescence device comprising at least an anode, an organic light emitting layer, and a cathode as constituent elements, wherein the organic light emitting layer comprises a dopant and a host material, and the dopant is represented by the following formula (1) or ( 2) and the host material is composed of at least one selected from the group consisting of aromatic amine derivatives, carbazole derivatives, thiophene oligomers and polymers, and zinc complexes. Organic electroluminescence device.

In the formula, Ln is a rare earth atom, and R ^{1 to} R ⁶ and R ^{11 to} R ¹³ are a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl having a straight chain or branched structure having 20 or less carbon atoms. Selected from the group consisting of a group , a substituted or unsubstituted phenyl group, and a substituted or unsubstituted heterocyclic group, and in formula (1), at least one of R ^{1 to} R ⁶ is represented by formula (2) Is an alkyl group having a linear or branched structure having 20 or less carbon atoms, wherein at least one of R ^{1 to} R ⁴ is substituted or unsubstituted, and p is an integer of 2 to 20, Except that R ^{1 to} R ⁶ are all the same in formula (2), and all of R ^{1 to} R ⁴ are the same in formula (2).   The organic electroluminescent element of Claim 1 whose p in Formula (2) is an odd number.   R in the formula (1) ¹ ~ R ⁶ At least one of R in formula (2) ¹ ~ R ⁴ The organic electroluminescent element according to claim 1, wherein at least one of the groups is a substituted or unsubstituted phenyl group. R in the formula (1) ¹ ~ R ⁶ At least one of R in formula (2) ¹ ~ R ⁴ The organic electroluminescent element according to claim 1 or 2, wherein at least one of the above is a substituted or unsubstituted heterocyclic group.   The organic electroluminescent element according to claim 1, wherein the rare earth atom is europium. The electroluminescent element of any one of Claims 1-5 whose said aromatic amine derivative is what is shown by following formula (4).

In the formula, Ar ^{1 to} Ar ⁴ are substituents selected from the group consisting of a phenyl group, a biphenyl group, and a heteroaromatic group, and A is a substituted or unsubstituted phenylene group, biphenylene group, and thiophenylene. A divalent group selected from the group consisting of groups. The organic electroluminescent element according to claim 6, wherein in formula (4), the combination of Ar ¹ and Ar ² is different from the combination of Ar ³ and Ar ⁴ . The organic electroluminescent element according to any one of claims 1 to 5, wherein the carbazole derivative is a polymer represented by the following formula (5).

In the formula, R ²¹ and R ²² are linear or branched substituents selected from the group consisting of alkyl groups, alkoxy groups, amino groups, and nitro groups, and q is an integer of 2 or more. . The organic electroluminescent element according to any one of claims 1 to 5, wherein the thiophene oligomer or polymer has a structure represented by the following formula (6).

In the formula, r is an integer of 2 or more indicating the degree of polymerization. The organic electroluminescent element according to claim 9 , wherein the host material further contains a sulfonic acid polymer represented by the following formula (7).

In the formula, r0 is an integer of 2 or more indicating the degree of polymerization. A transparent fluorescent film comprising a rare earth complex and a polymer represented by the following formula (1) or (2), and a light source capable of irradiating the transparent fluorescent film with ultraviolet light or near ultraviolet light. Display system.

In the formula, Ln is a rare earth atom, and R ^{1 to} R ⁶ and R ^{11 to} R ¹³ are a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl having a straight chain or branched structure having 20 or less carbon atoms. Selected from the group consisting of a group , a substituted or unsubstituted phenyl group, and a substituted or unsubstituted heterocyclic group, and p is an integer of 2 to 20, but in formula (1), R ^{1 to} R all ⁶ of, in the formula (2) all ^R 1 to R ⁴ are, unless the same. The display system according to claim 11 , wherein p in formula (2) is an odd number. 13. At least one of R ^{1 to} R ⁶ in formula (1) and at least one of R ^{1 to} R ⁴ in formula (2) is a substituted or unsubstituted phenyl group according to claim 11 or 12. Display system . 13. At least one of R ^{1 to} R ⁶ in formula (1) and at least one of R ^{1 to} R ⁴ in formula (2) is a substituted or unsubstituted heterocyclic group. display system. The display system according to claim 11, wherein the rare earth atom is europium.   The display system according to claim 11, wherein the polymer is selected from the group consisting of a fluorine-based polymer, a silicon-based polymer, and a mixture thereof. The display system according to claim 16, wherein the polymer is a fluorine-based polymer represented by the following formula (8A) or (8B).

In the formula, X is a halogen atom, R ^{a1 to} R ^a3 are each independently an alkyl group, x1 to x3 and y1 to y6 are numbers representing the degree of polymerization, and x1 + x2 + x3 and y1 + y2 + y3 + y4 + y5 + y6 are not 0, respectively. Each repeating unit may be arranged at random. The display system according to claim 16, wherein the polymer is a silicon-based polymer represented by the following formulas (9A) to (9C).

In the formula, z is an integer of 1 or more.   The display system according to claim 11, wherein a surface of the transparent fluorescent film is covered with a moisture-proof layer.   A control circuit that changes at least one of the light intensity, irradiation range, and wavelength of the light source over time, thereby changing at least one of the light emission pattern, light emission color, and light emission intensity of the transparent phosphor film over time; The display system according to any one of claims 11 to 19.   The display system according to any one of claims 11 to 20, further comprising a speedometer for measuring a speed of the automobile, wherein the light source is irradiated with light according to a speed measured by the speedometer. The transparent fluorescent film is installed on the windshield of the automobile, and the speed of the automobile is adjusted by changing the information displayed by the transparent fluorescent film according to the speed of the automobile. Display system to display.   21. The display system according to any one of claims 11 to 20, further comprising a fire detector installed in a building, wherein the display system is safe based on information obtained by the fire detector. A display system for displaying an evacuation route in a building by the transparent fluorescent film.

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