JP2007266586A - Organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element which can easily change a luminescent color (obtains any light emission pattern) in a short process. <P>SOLUTION: The organic electroluminescent element includes a first transparent or translucent electrode, a second electrode, and a layer which is provided between the electrodes, contains two or more light emitting components having different peak wavelengths of light emission, and has the function of emitting light. The layer having the function of emitting light is partly or entirely heated at 50°C to 450°C and thus changes the ratio between the maximum luminous intensities of the two or more light emitting components contained in the heated part. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an organic electroluminescence device capable of easily changing the emission color.

  The organic electroluminescence element is suitable for uses such as a display because it has a feature that light emission of many colors can be easily obtained in addition to low voltage driving and high luminance. As such an organic electroluminescence element, for example, a polymer light emitting element using a polymer light emitting material has been proposed (Patent Documents 1 and 2, Non-Patent Document 1).

  In order to use the organic electroluminescence device in a multi-color or full-color display, the light-emitting material is placed in a different place, for example, by separately coating light-emitting materials having different emission colors in order to obtain an arbitrary light emission pattern from the device. It is necessary to apply a method that uses different methods, a method that uses a color filter, a method that uses a color conversion material, and the like.

International Publication No. 90/013148 Pamphlet JP-A-3-244630 Applied Physics Letters (Appl. Phys. Lett.), 58, 1982 (1991).

However, in order to obtain an arbitrary light emission pattern from the device, the method of creating a light emitting material in a different place is usually that when a low molecular light emitting material is used, a mask is used during vapor deposition, and a polymer light emitting material is used. In the case of the ink jet method, the photolithographic process is repeatedly performed to manufacture a patterned substrate. Therefore, these methods require a long and complicated manufacturing process. In addition, the method using a color filter and the method using a color conversion material require a process of repeating the photolithography process for each color, so that the process is also long and complicated. Therefore, the yield tends to decrease and it is difficult to make a free pattern at low cost.
Accordingly, an object of the present invention is to provide an organic electroluminescence element capable of easily changing the emission color (obtaining an arbitrary emission pattern) in a short process.

As a result of intensive studies to solve the above problems, the inventors have found that the following organic electroluminescence elements and manufacturing methods can solve the problems, and have achieved the present invention.
That is, the present invention firstly
An organic electro having a transparent or translucent first electrode, a second electrode, and a layer having a light emitting function, which is provided between these electrodes and contains two or more light emitting components having different emission peak wavelengths A luminescence device, wherein a part or all of the layer having a light emitting function is heated at 50 to 450 ° C., whereby each of the two or more light emitting components contained in the heated portion has a maximum light emission intensity. Provided is an organic electroluminescence device having a property of changing the ratio.
The present invention secondly,
(1) a step of forming a first electrode and a layer having a light emitting function comprising two or more light emitting components having different light emission peak wavelengths;
(2) forming a second electrode on the opposite side of the first electrode with respect to the layer having a light emitting function;
(3) A method for producing an organic electroluminescence device comprising a step of heating a part or all of the layer having a light emitting function at 50 to 450 ° C. is provided.
Thirdly, the present invention provides a planar light source, a flexible sheet, and a display device using the organic electroluminescent element or the organic electroluminescent element obtained by the manufacturing method.

Although the organic electroluminescent element of the present invention emits light with a substantially uniform color, the luminescent color changes when a part or all of the layer having a light emitting function is heated at a specific temperature, Change color and increase color depending on the shape pattern of the heated part. This discoloration / multicoloring by heating can be performed during the production of the organic electroluminescence element, or after the organic electroluminescence element is produced once, and can be carried out by a process that is significantly easier than before. . Therefore, a color / multicolor light emission pattern according to the purpose can be freely formed at an arbitrary timing, so that the application range is wide and useful. Specifically, for example, an organic electroluminescence device having a desired color / multicolor emission pattern can be easily produced by the production method of the present invention.
Therefore, the organic electroluminescence element of the present invention or the organic electroluminescence element obtained by the production method of the present invention can add display contents to a display such as a poster or a show window as well as a multicolor or full color display element. In view of the above, it is particularly useful for a planar light source, a flexible sheet, a display device and the like.

  Hereinafter, the present invention will be described in detail.

<Organic electroluminescence device>
The organic electroluminescence device of the present invention is a light emission comprising a transparent or translucent first electrode, a second electrode, and two or more kinds of light emitting components with different emission peak wavelengths provided between these electrodes. An organic electroluminescent device having a functional layer, wherein two or more of the layers having the light emitting function are contained in a heated portion by being heated at 50 to 450 ° C. The ratio of the maximum light emission intensity of each of the light emitting components is such that the ratio changes.

  Here, the “heated part” means a part of the layer having a light emitting function, which receives heat energy directly or indirectly. In addition, “the ratio of the maximum emission intensity of each of the two or more light-emitting components changes” means that the ratio of the maximum light emission intensity at the emission peak wavelength of each of the two or more light-emitting components included (that is, the light emission component is When there are two types, [maximum emission intensity at emission peak wavelength of emission component 1]: [maximum emission intensity at emission peak wavelength of emission component 2], and when there are three emission components, [emission The maximum emission intensity at the emission peak wavelength of component 1: [the maximum emission intensity at the emission peak wavelength of emission component 2]: [the maximum emission intensity at the emission peak wavelength of emission component 3]. . And when the ratio changes, discoloration or multicolorization occurs.

  The layer having the light emitting function may be composed of only one layer or may be composed of two or more layers.

  The heating is preferably 70 to 400 ° C, more preferably 80 to 300 ° C, still more preferably 80 to 250 ° C, particularly preferably 110 to 220 ° C, and particularly preferably 140 to 210 ° C. When the heating temperature is within such a range, the ratio of the maximum light emission intensity of the light emitting component in the layer having a light emitting function changes, and the light emission color of the element can be changed more efficiently. Moreover, although a heating method is not specifically limited, Usually, it is performed by the method etc. which are demonstrated at the process (3) of the manufacturing method of the below-mentioned organic electroluminescent element.

-First electrode-
The first electrode is transparent or translucent. The first electrode may be an anode or a cathode, but is usually an anode. The first electrode may be composed of only one layer or may be composed of two or more layers.

  For the first electrode, for example, a metal oxide having a high electrical conductivity, a metal sulfide having a high electrical conductivity, a metal having a high electrical conductivity, etc., preferably having a high transmittance in the visible light region. However, the organic layer may be appropriately selected depending on the organic layer to be combined (for example, a layer having a light emitting function, or a hole transport layer, an electron transport layer, a hole injection layer, an electron injection layer, or the like depending on circumstances). As a specific example, a film made of indium oxide, zinc oxide, tin oxide, and a conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc., which is a composite thereof (for example, , NESA, etc.), gold, platinum, silver, copper, and the like, preferably ITO, indium / zinc / oxide, and tin oxide. In addition, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used for the first electrode (these are collectively referred to as “first electrode material”). These may be used alone or in combination of two or more.

  The thickness of the first electrode can be appropriately selected in consideration of light transmittance and electrical conductivity, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. The first electrode is usually a thin film having such a thickness.

  In order to facilitate charge injection adjacent to the first electrode, for example, conductive polymers such as phthalocyanine derivatives and polythiolene derivatives, molybdenum oxide, amorphous carbon, carbon fluoride, polyamine compounds, etc. 1 to 200 nm Alternatively, a layer having an average film thickness of 5 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided.

-Second electrode-
The second electrode is not particularly limited, and may be transparent, translucent, or opaque. The second electrode may be an anode or a cathode, but is usually a cathode. The second electrode may be composed of only one layer or may be composed of two or more layers.

  It is preferable to use a material having a small work function for the second electrode. Specific examples include alkaline metals such as lithium, sodium, potassium, rubidium and cesium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; aluminum, scandium, vanadium, zinc, yttrium, indium, cerium and samarium , Europium, terbium, ytterbium, etc .; two or more of them; one or more of them; one of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin Alloys with the above: graphite, graphite intercalation compounds and the like are used. Specific examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy. (These are collectively referred to as “second electrode material”.) These may be used alone or in combination of two or more.

  The thickness of the second electrode can be appropriately selected in consideration of electric conductivity and durability, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. The second electrode is usually a thin film having such a thickness.

  From the conductive polymer between the second electrode and the organic layer (for example, a layer having a light emitting function, and in some cases, a hole transport layer, an electron transport layer, a hole injection layer, an electron injection layer, etc.) A layer having an average film thickness of 5 nm or less, a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like and having an average film thickness of 5 nm or less may be provided.

  The order in which the first electrode and the second electrode are formed (usually, these electrodes are formed on the base material) is not particularly limited, and is appropriately selected according to the top emission type or bottom emission type element structure. can do.

-Layer with light emitting function-
-Light emitting component The light emitting component contained in the layer having a light emitting function needs to be two or more having different emission peak wavelengths. When this light emitting component is only one type or when there are two or more types having the same emission peak wavelength, no change in emission color occurs even when the resulting device is heated. The light emitting component is not particularly limited as long as it has a combination with different emission peak wavelengths, but a combination of a high molecular compound having a light emitting property and a low molecular compound having a light emitting property is preferable.

  For example, when there are two types of light-emitting components contained in the layer having a light-emitting function, usually, the longer wavelength from the excited state of the light-emitting component having the emission peak wavelength on the shorter wavelength side of the two types The energy level can be transferred to the ground state of the light emitting component having the emission peak wavelength on the side, and the energy level relationship is difficult for the opposite energy transfer. When there are three types of light-emitting components contained in the layer having a light-emitting function, usually, light is emitted from the excited state of the light-emitting component A having the emission peak wavelength on the shortest wavelength side of the three types to the longest wavelength side. Energy transfer is possible to the ground state of the light-emitting component B having a peak wavelength, and the energy level relationship is difficult for the reverse energy transfer. Further, from the excited state of the light emitting component A having the light emission peak wavelength on the shortest wavelength side, the basis of the light emitting component C having the light emission peak wavelength between the light emission peak wavelength of the light emission component A and the light emission peak wavelength of the light emission component B Energy transfer to a state is possible, and the energy level relationship is difficult for the reverse energy transfer.

  The combination of the component having the emission peak wavelength on the shorter wavelength side and the component having the emission peak wavelength on the longer wavelength side includes a polymer and a low molecule, a low molecule and a polymer, a low molecule and a low molecule, a high molecule Examples of molecules and polymers include "a polymer compound having a light emission property" having a light emission peak wavelength on a shorter wavelength side and "a low molecular compound having a light emission property" having a light emission peak wavelength on a longer wavelength side. A combination of a “polymer compound having luminescence” having an emission peak wavelength on the shorter wavelength side and a “compound exhibiting light emission from a triplet excited state” having an emission peak wavelength on the longer wavelength side Is more preferable.

  Hereinafter, a combination of a light-emitting polymer compound and a light-emitting low molecular compound, which is a preferred embodiment of the present invention, will be described as an example. Here, “a high molecular compound having a light emitting property” and “a low molecular compound having a light emitting property” mean that electrons in a compound (that is, a high molecular compound or a low molecular compound) are excited from the ground state by an external stimulus. , And emits light when returning to the ground state again.

・ Luminescent component (polymer compound with luminescence)
The polymer compound having luminescence has a polystyrene-equivalent number average molecular weight of usually 1 × 10 ³ to 1 × 10 ⁸ , preferably 1 × 10 ⁴ to 1 × 10 ⁶ , more preferably 1 × 10 ⁵ to. It is 5 × 10 ⁵ and has a light emitting property. This light-emitting polymer compound usually has an emission peak wavelength on the short wavelength side as compared with a light-emitting low-molecular compound. In addition, the high molecular compound which has luminescent property may be used individually by 1 type, or may use 2 or more types together.

  The ratio of the polymer compound having light emitting property to the total light emitting component contained in the layer having a light emitting function is usually 50 to 99.9% by weight, preferably 80 to 99% by weight, more preferably 90 to 98% by weight. %. When this range is satisfied, the light emission intensity of the electroluminescence of the device is increased, and the light emission efficiency is improved.

  The high molecular compound having luminescence has a quantum yield of fluorescence or phosphorescence of preferably 10% or more, more preferably 50 to 100%. When this range is satisfied, the light emission intensity of the electroluminescence of the device is increased, and the light emission efficiency is improved.

  The glass transition temperature of the light-emitting polymer compound is not particularly limited, but is preferably 70 ° C. or higher, and particularly preferably 100 ° C. or higher.

  The polymer compound having a light emitting property is preferably a compound having a liquid crystal state. And the said heating can be performed in the temperature range which shows this liquid crystal state. The temperature range showing this liquid crystal state varies depending on the polymer compound to be selected, but is usually 50 ° C. to 450 ° C., preferably 70 to 400 ° C., more preferably 80 to 300 ° C., further preferably 80 to 250 ° C. Particularly preferred is 110 to 220 ° C, particularly preferred 140 to 210 ° C.

  Among the polymer compounds having luminescent properties, conjugated polymer compounds are preferable. Here, the conjugated polymer compound means a polymer compound in which delocalized π electron pairs exist along the main chain skeleton of the polymer compound. As this delocalized electron, an unpaired electron or a lone electron pair may participate in resonance instead of a double bond.

  The polymer compound having a light-emitting property may be a homopolymer or a copolymer. For example, polyfluorene (for example, Japanese Journal of Applied Physics Vol. 30, L1941 P. (1991)), polyparaphenylene (for example, Advanced Materials (Adv. Mater.) Vol. 4, p. 36 (1992)), polyarylenes such as polypyrrole, polypyridine, polyaniline, polythiophene; polypara; Polyarylene vinylenes such as phenylene vinylene and polythienylene vinylene (for example, WO98 / 27136 published specification); polyphenylene sulfide, polycarbazole and the like can be mentioned (for example, “Advanced Materials Vol.12 1737-1750 ( 2000) ”,“ Organic EL Display Technology Monthly Display December Special Issue P68-73 ”, etc.). Among these, a polyarylene-based polymer compound having a light emitting property is preferable.

  Examples of the repeating unit contained in the polyarylene-based polymer compound having a light-emitting property include an arylene group and a divalent heterocyclic group. Those containing 20 to 100 mol% of these repeating units are preferred, and those containing 50 to 99 mol% are more preferred.

  Here, the number of carbon atoms constituting the ring of the arylene group is usually about 6 to 60. Specific examples thereof include a phenylene group, a biphenylene group, a terphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrene diyl group, and a pentarange. Yl group, indenediyl group, hepterenediyl group, indacenediyl group, triphenylenediyl group, binaphthyldiyl group, phenylnaphthylenediyl group, stilbenediyl group, fluorenediyl group (for example, in the following formula (1), A = -C (R ′) (R ′) —).

  The number of carbon atoms constituting the ring of the divalent heterocyclic group is usually about 3 to 60. Specific examples include pyridine-diyl group, diazaphenylene group, quinolinediyl group, quinoxalinediyl group, acridinediyl group, bipyridyldiyl. Group, phenanthrolinediyl group, in the following formula (1), A = —O—, —S—, —Se—, —NR′—, —C (R ′) (R ′) —, or —Si (R ′) ) (R ')-and the like. R ′ is as described later.

  As the repeating unit contained in the polyarylene-based polymer compound having a light emitting property, a repeating unit represented by the following formula (1) is more preferable. The polymer compound may contain only one type of repeating unit represented by the following formula (1) or two or more types.

（式中、Ａは、該式中の２個のベンゼン環上の４個の炭素原子と一緒になって５員環又は６員環を形成する原子又は原子群を表し、Ｒ^1a、Ｒ^1b、Ｒ^1c、Ｒ^2a、Ｒ^2b及びＲ^2cは、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールアルコキシカルボニル基、ヘテロアリールオキシカルボニル基又はカルボキシル基を表し、或いはＲ^1bとＲ^1c、及びＲ^2bとＲ^2cは、それぞれ一緒になって環を形成していてもよい。）

(In the formula, A represents an atom or a group of atoms that form a 5-membered ring or a 6-membered ring together with four carbon atoms on the two benzene rings in the formula; R ^1a , R ^1b , R ^1c , R ^2a , R ^2b and R ^2c are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group , Arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio Group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkoxy group Represents a sulfonyl group, an aryloxycarbonyl group, an arylalkoxycarbonyl group, a heteroaryloxycarbonyl group or a carboxyl group, or R ^1b and R ^1c , and R ^2b and R ^2c , together form a ring, May be.)

Examples of the halogen atom represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , and R ^2c include fluorine, chlorine, bromine, and iodine.

The alkyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl. Group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, Examples include perfluorooctyl group, and pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group are preferable.

The alkoxy group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyl. Oxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, Examples include perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy. Group, 7,7-dimethyloct Aryloxy group is preferred.

The alkylthio group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexyl. Examples include thio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group, and the like. Pentylthio group, hexylthio group, octylthio group 2-ethylhexylthio group, decylthio group, and 3,7-dimethyloctylthio group are preferable.

The aryl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent and usually has about 3 to 60 carbon atoms. a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C ₁₂ indicates that it is 1 to 12 carbon atoms. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1 - naphthyl, 2-naphthyl group, pentafluorophenyl group, a pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, etc. triazyl group and the like, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group Is preferred.

The aryloxy group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms. There, specifically, phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group, pyridyloxy group, Examples include a pyridazinyloxy group, a pyrimidyloxy group, a pyrazyloxy group, and a triazyloxy group, and a C _{1 to} C ₁₂ alkoxyphenoxy group and a C _{1 to} C ₁₂ alkylphenoxy group are preferable.

The arylthio group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms. , specifically, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group , pyrimidylthio group, pyrazylthio group, etc. Toriajiruchio group and the like, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio group are preferable.

The arylalkyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent, and usually has about 7 to 60 carbon atoms. the phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkyl groups are preferred.

The arylalkoxy group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent, and usually has about 7 to 60 carbon atoms. the phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkoxy group are preferable.

The arylalkylthio group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent, and usually has about 7 to 60 carbon atoms. the phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkoxy group are preferable.

The alkenyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent and usually has about 2 to 20 carbon atoms. Specific examples thereof include vinyl group, 1-propylenyl group, 2-propylenyl group, 3-propylenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, cyclohexenyl group and the like.

The alkynyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent and usually has about 2 to 20 carbon atoms. Specific examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptenyl group, octynyl group, and cyclohexylethynyl group.

The arylalkenyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent and usually has about 8 to 50 carbon atoms. The aryl group (namely, aryl moiety) and alkenyl group (namely, alkenyl moiety) constituting the arylalkenyl group are the same as the above aryl group and alkenyl group. Specific examples of the arylalkenyl group include 1-arylvinyl group, 2-arylvinyl group, 1-aryl-1-propylenyl group, 2-aryl-1-propylenyl group, 2-aryl-2-propylenyl group, 3- An aryl-2-propylenyl group etc. are mentioned.

The arylalkynyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c usually has about 7 to 60 carbon atoms. Specifically, phenyl-C _{1 to} C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkynyl group, 1-naphthyl -C ₁ -C ₁₂ alkynyl group, 2-naphthyl -C ₁ etc. -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkynyl group are preferred.

  The amide group usually has about 2 to 20 carbon atoms, and specifically includes a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diamide group. Examples include an acetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, a succinimide group, and a phthalimide group.

The arylalkenyl group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl group, 1-naphthyl -C ₁ -C ₁₂ alkenyl groups, 2-naphthyl -C ₁ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

The acyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c usually has about 2 to 20 carbon atoms, and specifically includes an acetyl group, a propionyl group, and a butyryl group. , Isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, pentafluorobenzoyl group and the like.

The acyloxy group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c has about 2 to 20 carbon atoms, and specifically includes an acetyloxy group, a trifluoroacetyloxy group, and propionyl. Examples include an oxy group, a benzoyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a pentafluorobenzoyloxy group.

The amide group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent and usually has about 2 to 20 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamido group, dipropioamide group, dibutyroamide group, dibenzamide group, ditriamide. Examples include a fluoroacetamide group and a dipentafluorobenzamide group.

The acid imide group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent, except for a hydrogen atom bonded to the nitrogen atom from the acid imide. The residue obtained is usually about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms.

The imine residue represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c may have a substituent, and the imine compound (that is, —N═C— Examples thereof include aldimine, ketimine, and compounds in which the hydrogen atom on N is substituted with an alkyl group or the like.) A residue obtained by removing one hydrogen atom from The number of carbon atoms is usually about 2 to 60, and preferably 2 to 20.

As the substituted amino group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c , the substituted amino group includes an alkyl group, an aryl group, an arylalkyl group, and a heterocyclic skeleton 1 And an amino group substituted with one or two groups selected from valent organic groups. Note that the monovalent organic group having an alkyl group, an aryl group, an arylalkyl group or a heterocyclic skeleton may have a substituent. The substituted amino group usually has about 1 to 40 carbon atoms. Specific examples thereof include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, t-butylamino. Group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group , cyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, bis (trifluoromethyl) amino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl Amino group, bis (C ₁ -C ₁₂ alkoxyphenyl) amino group, bis (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, a bis (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, bis (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) Examples include an amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group, and the like.

The substituted silyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c is 1, 2 or 2 selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group Represents a silyl group substituted with three groups. Carbon number is about 1-60 normally, Preferably it is 3-30. Note that the monovalent organic group having an alkyl group, an aryl group, an arylalkyl group or a heterocyclic skeleton may have a substituent. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-i-propylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, and tri-p-xylylsilyl group. , Tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

The substituted silyloxy group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c is selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent organic group having a heterocyclic skeleton. Examples thereof include a silyloxy group (H ₃ SiO—) substituted with 1, 2 or 3 groups. The monovalent organic group having an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic skeleton may have a substituent. The substituted silyloxy group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri-i-propylsilyloxy group, t-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, tri- Examples thereof include a p-xylylsilyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a t-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

The substituted silylthio group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c is selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent organic group having a heterocyclic skeleton. Examples thereof include a silylthio group (H ₃ SiS—) substituted with 1 to 3 groups. Note that the monovalent organic group having an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic skeleton may have a substituent. The substituted silylthio group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri-i-propylsilylthio group, t-butylsilyldimethylsilylthio group, triphenylsilylthio group, tri- Examples thereof include a p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a t-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

The substituted silylamino group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c is 1 selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent organic group having a heterocyclic skeleton. And a silylamino group (that is, H ₃ SiNH— or (H ₃ Si) ₂ N—) substituted with ˜6 groups. The monovalent organic group having an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic skeleton may have a substituent. The substituted silylamino group usually has about 1 to 120 carbon atoms, preferably 3 to 60 carbon atoms. Specific examples thereof include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri-i-propylsilylamino group, t-butylsilyldimethylsilylamino group, triphenylsilylamino group, tri- p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino group, dimethylphenylsilylamino group, bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, bis (Tri-n-propylsilyl) amino group, bis (tri-i-propylsilyl) amino group, bis (t-butyldimethylsilyl) amino group, bis (triphenylsilyl) amino group, bis (tri-p-xylylsilyl) Amino group, bis (tribenzylsilyl) Amino group, bis (diphenylmethylsilyl) amino group, bis (t-butyldiphenylsilyl) amino group, such as bis (dimethylphenylsilyl) amino group.

The monovalent heterocyclic group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and the number of carbon atoms is usually about 4 to 60, specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

The heteroaryloxy group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c usually has about 4 to 60 carbon atoms, preferably 5 to 48 carbon atoms. Specifically, a thienyl group, C ₁ -C ₁₂ alkoxide Shichie alkenyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyloxy group, a pyridyloxy group, etc. isoquinolyloxy group and the like, C ₁ -C ₁₂ alkoxy a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified. C ₁ -C ₁₂ alkyl pyridyl group as such as methyl pyridyl group, ethyl pyridyloxy group, dimethylpyridyl group, propyl pyridyloxy group, 1,3,5-trimethyl-pyridyl group, methyl ethyl pyridyl group I-propylpyridyloxy group, butylpyridyloxy group, i-butylpyridyloxy group, t-butylpyridyloxy group, pentylpyridyloxy group, isoamylpyridyloxy group, hexylpyridyloxy group, heptylpyridyloxy group, octylpyridyloxy group Group, nonylpyridyloxy group, decylpyridyloxy group, dodecylpyridyloxy group and the like.

The heteroarylthio group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c usually has about 4 to 60 carbon atoms, preferably 5 to 48 carbon atoms. Specifically, pyridylthio, C ₁ -C ₁₂ alkoxy pyridylthio group, C ₁ -C ₁₂ alkylpyridylthio group, isoquinolylthio group and the like, C ₁ -C ₁₂ alkoxy pyridylthio group, C ₁ -C ₁₂ Alkylpyridylthio groups are preferred.

Examples of the alkoxycarbonyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c include a group formed by bonding the exemplified group and a carbonyl group to the above alkoxy group.

Examples of the aryloxycarbonyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c include groups in which the above-mentioned aryloxy group is bonded to the exemplified group and a carbonyl group. .

Examples of the arylalkoxycarbonyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , and R ^2c include groups in which the exemplified group and a carbonyl group are bonded to the arylalkoxy group. .

Examples of the heteroaryloxycarbonyl group represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c include a group in which the exemplified group and a carbonyl group are bonded to the heteroaryloxy group. Can be mentioned.

  Specific examples of A include, but are not limited to, the following.

（式中、Ｒ、Ｒ’、Ｒ’’はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基又は１価の複素環基を表す。）

(Wherein R, R ′ and R ″ are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, Arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group Represents a substituted silylamino group, a cyano group, a nitro group or a monovalent heterocyclic group.)

The atoms, residues, and groups represented by R, R ′, and R ″ have the same meaning as described and exemplified as the above R ^1a , R ^1b , R ^1c , R ^2a , R ^2b, and R ^2c .

  As A, -O-, -S-, -Se-, -NR'-, -CR'R'- or -SiR'R'- is preferred, -O-, -S-, -CR'R. '-Is more preferred.

  Examples of the repeating unit represented by the above formula (1) include the following structures.

（式中、Ｒ、Ｒ’及びＲ’’は、前記と同じ意味を有する。また、式中、ベンゼン環上の水素原子は、それぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールアルコキシカルボニル基、ヘテロアリールオキシカルボニル基又はカルボキシル基に置換されていてもよく、ベンゼン環の隣接位に２個の置換基が存在する場合、それらが互いに結合して環を形成してもよい。）

(Wherein R, R ′ and R ″ have the same meaning as described above. In the formula, each hydrogen atom on the benzene ring is independently a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, Aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imido group, imine Residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkoxycarbonyl group, Aryloxycarbonyl group, arylalkoxycarbonyl group, heteroaryl It may be substituted by oxy carbonyl group or a carboxyl group, if two substituents are present at the adjacent position of the benzene ring, may form them combine with each other to form a ring.)

  The polymer compound having a light emitting property may contain, for example, a repeating unit derived from an aromatic amine in addition to an arylene group and a divalent heterocyclic group. In this case, hole injection property and hole transport property can be imparted to the light-emitting polymer compound. When the luminescent polymer compound includes a repeating unit composed of an arylene group and / or a divalent heterocyclic group and a repeating unit derived from an aromatic amine (an arylene group and / or a divalent complex). The repeating unit consisting of a cyclic group): (the repeating unit derived from an aromatic amine) is usually in the range of 99: 1 to 20:80 in molar ratio.

  As the repeating unit derived from an aromatic amine, a repeating unit represented by the following formula (2) is preferable.

（式中、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶及びＡｒ⁷は、それぞれ独立に、置換されていてもよいアリーレン基又は置換されていてもよい２価の複素環基を表す。Ａｒ⁸、Ａｒ⁹及びＡｒ¹⁰は、それぞれ独立に、置換されていてもよいアリール基又は置換されていてもよい１価の複素環基を表す。ｏ及びｐはそれぞれ独立に０又は１を表し、０≦ｏ＋ｐ≦２である。）

(In the formula, Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ each independently represent an optionally substituted arylene group or an optionally substituted divalent heterocyclic group. Ar ⁸ , Ar ⁹ And Ar ¹⁰ each independently represents an optionally substituted aryl group or an optionally substituted monovalent heterocyclic group, o and p each independently represent 0 or 1, and 0 ≦ o + p ≦ 2)

In the above formula (2), the definitions and specific examples of the arylene group and the divalent heterocyclic group represented by Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are as described above. In description of the repeating unit which a molecular compound contains, it is the same as what was demonstrated and illustrated as an arylene group and a bivalent heterocyclic group.

In the above formula (2), the definition and specific examples of the aryl group and the monovalent heterocyclic group represented by Ar ⁸ , Ar ⁹ and Ar ¹⁰ are the above R ^1a , R ^1b , R ^1c , R ^2a , R ^The aryl group represented by ^2b and R ^2c is the same as described and exemplified as the monovalent heterocyclic group.

  Specific examples of the repeating unit represented by the above formula (2) include the following structures.

（式中、芳香環上の水素原子は、それぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールアルコキシカルボニル基、ヘテロアリールオキシカルボニル基又はカルボキシル基で置換されていてもよい。）

(In the formula, each hydrogen atom on the aromatic ring is independently a halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, Alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group , Cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkoxycarbonyl group, aryloxycarbonyl group, arylalkoxycarbonyl group, heteroaryloxycarbonyl group or carboxyl group Even It has.)

  Among the repeating units represented by the above formula (2), a repeating unit represented by the following formula (3) is particularly preferable.

（式中、Ｒ³、Ｒ⁴及びＲ⁵は、それぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールアルコキシカルボニル基、ヘテロアリールオキシカルボニル基又はカルボキシル基を表す。ｘ及びｙは、それぞれ独立に、０〜４の整数を示す。ｚは０〜２の整数を示す。ｗは０〜５の整数を示す。）

Wherein R ³ , R ⁴ and R ⁵ are each independently a halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio Group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted Represents a silylamino group, a cyano group, a nitro group, a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylalkoxycarbonyl group, a heteroaryloxycarbonyl group or a carboxyl group. X and y are Each independently represents an integer of 0 to 4. z represents an integer of 0 to 2. w represents an integer of 0 to 5.)

In the above formula (3), the atoms, residues and groups represented by R ³ , R ⁴ and R ⁵ are specifically the above R ^1a , R ^1b , R ^1c , R ^2a , R ^2b and R ^2c. It has the same meaning as described and exemplified as.

  The polymer compound having a light emitting property may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. Good. From the viewpoint of obtaining a polymer compound having high light emission quantum yield and light emission property, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  The terminal group of the light-emitting polymer compound may be protected with a stable group, because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and lifetime when the device is made may be reduced. . Those having a conjugated bond continuous with the conjugated structure of the main chain are preferred, and examples thereof include a structure bonded to an aryl group or heterocyclic group via a carbon-carbon bond. Specifically, substituents described in Chemical formula 10 of JP-A-9-45478 are exemplified.

  Moreover, since the light emission from a thin film is utilized, a polymer compound having light emission in a solid state is preferably used as the light emitting polymer compound.

Examples of methods for synthesizing luminescent polymer compounds include, for example, a method of polymerizing a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, an oxidation of FeCl ₃ or the like. Examples thereof include a method of polymerizing with an agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like. Among these, the method of polymerizing by Suzuki coupling reaction, the method of polymerizing by Grignard reaction, and the method of polymerizing by Ni (0) catalyst are preferable because the reaction control is easy.

  Since the purity of the luminescent polymer compound affects the luminescent properties, it is preferable to polymerize after purifying the monomer before polymerization by a method such as distillation, sublimation purification, recrystallization, etc. A purification treatment such as precipitation purification or fractionation by chromatography is preferred.

  Examples of the light-emitting polymer compound include polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative. , Polyaniline or a derivative thereof, polythiophene or a derivative thereof, polypyrrole or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, or poly (2,5-thienylenevinylene) or a derivative thereof. Specifically, JP-A 63-70257, 63-175860, JP 2-135359, 2-135361, 2-209988, 3-37992, Examples described in JP-A-3-152184 are exemplified.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of polysilane or derivatives thereof include compounds described in Chemical Review (Chem. Rev.), 89, 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  As the polymer compound having a light emitting property, a polymer compound composed of a repeating unit derived from an aromatic amine is particularly preferable. The repeating unit derived from an aromatic amine is preferably represented by the above formula (2), and more preferably represented by the above formula (3).

  Among the light-emitting polymer compounds, known compounds can be used, and examples thereof include polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof.

  Examples of the polymer compound having luminescent properties include materials described in “Polymer EL Materials” (co-authored by Toshihiro Onishi and Tamami Koyama, Kyoritsu Publishing Co., Ltd., published in 2004, first edition, first print), pages 33-58. .

  Furthermore, as a polymer compound having specific light emitting properties, WO99 / 13692 published specification, WO99 / 48160 published specification, GB2340304A, WO00 / 53656 published specification, WO01 / 19834 published specification, WO00 / 55927 published specification, GB2348316, WO00 / 46321 published specification, WO00 / 06665 published specification, WO99 / 54943 published specification, WO99 / 54385 published specification, US5777070, WO98 / 06773 published specification , WO97 / 05184 published specification, WO00 / 35987 published specification, WO00 / 53655 published specification, WO01 / 34722 published specification, WO99 / 24526 published specification, WO00 / 22027 published specification, WO00 / 22026 published specification, WO98 / 27136 published specification, US573636, WO98 / 21262 published specification, US5741921, WO97 / 09394 published specification, WO96 / 29356 published specification, WO96 / 10617 published specification EP0707020, WO95 / 07955 published specification, JP2001-181618, JP2001-123156, JP2001-3045, JP2000-351967, JP2000-303066 JP, 2000-299189, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, Polyfluorenes, derivatives and copolymers thereof, polyarylenes, derivatives and copolymers, polyarylenes disclosed in JP-A-10-114891, JP-A-9111233, JP-A-9-45478, etc. Examples include arylene vinylene, derivatives and copolymers thereof, (co) polymers of aromatic amines and derivatives thereof, and the like.

・ Luminescent materials (low molecular weight compounds with luminescent properties)
A low molecular light emitting material having a light emitting property has a light emitting property. The low molecular weight light emitting material having light emitting property preferably has a molecular weight of less than 1 × 10 ³ . Specific examples include a compound that emits light from a triplet excited state, preferably a triplet light emitting complex compound (that is, a complex compound that emits light from a triplet excited state), a dendrimer, and the like. It is a term luminescent complex compound. In the low molecular weight compound having light emitting property, the emission peak wavelength is usually observed on the long wavelength side as compared with the polymer compound having light emitting property. In addition, a low molecular light-emitting material may be used individually by 1 type, or may use 2 or more types together.

  The ratio of the low molecular weight compound having a light emitting property among all the light emitting components contained in the layer having a light emitting function is usually 0.1 to 50% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 10% by weight. %.

  Furthermore, the low molecular weight compound having luminescence has a quantum yield of fluorescence or phosphorescence of preferably 10% or more, more preferably 50 to 100%.

  In this specification, a compound that emits light from a triplet excited state includes a complex that exhibits fluorescence in addition to phosphorescence, in addition to a complex that exhibits phosphorescence.

  Examples of the triplet light-emitting complex compound include metal complex compounds that have been conventionally used as low-molecular EL light-emitting materials. For example, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light- Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998 ), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, Jpn.J.Appl.Phys., 34, 1883 (1995) and the like.

  The central metal of the triplet light emitting complex compound is usually a metal having an atomic number of 50 or more, and the complex has a spin-orbit interaction and can cause an intersystem crossing between the singlet state and the triplet state. . More specifically, for example, rhenium, iridium, osmium, scandium, yttrium, platinum, gold, and lanthanoids such as europium, terbium, thulium, dysprosium, samarium, praseodymium, gadolinium and the like, iridium, platinum, Gold and europium are preferable, iridium, platinum and gold are particularly preferable, and iridium is most preferable.

  Examples of the ligand of the triplet light emitting complex compound include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, 2-phenyl- Examples thereof include benzoxazole and derivatives thereof, porphyrin and derivatives thereof.

Examples of triplet light-emitting complex compounds include the following (Tris (8-quinolinol) aluminum, Ir (ppy) ₃ , Btp ₂ Ir (acac) with iridium as the central metal, PtOEP with europium as the central metal, Europium And triplet light-emitting complexes such as Eu (TTA) ₃ phen) having a central metal.

（式中、Ｒは、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アルキルアミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、１価の複素環基、又はシアノ基を表す。）

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, An arylalkynyl group, an arylamino group, a monovalent heterocyclic group, or a cyano group is represented.)

  In the above examples, in order to increase the solubility of the triplet light emitting complex compound in the solvent, R is preferably an alkyl group or an alkoxy group, and has little symmetry in the shape of the repeating unit including the substituent. It is preferable.

Another example of the triplet light-emitting complex compound is a structure represented by the following formula (4).
(J) _s -M- (K) _t (4)
(In the formula, M represents a metal atom, and J and K are independently a ligand containing an atom bonded to one or more M selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom, Represents a halogen atom or a hydrogen atom, s is an integer of 0-5, and t is an integer of 1-5.)

  Examples of the ligand represented by K that includes one or more atoms bonded to M selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom, and a phosphorus atom include an alkyl group, an alkoxy group, and an acyloxy group. Group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, sulfonate group, cyano group, heterocyclic coordination And the like, carbonyl compounds, ethers, amines, imines, phosphines, phosphites and sulfides. The bond between the ligands K and M may be a coordination bond or a covalent bond. Moreover, the multidentate ligand which combined these may be sufficient.

An alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, and an arylalkylthio group, which are ligands K containing an atom bonded to M, are the above R ^1a , This is the same as described and exemplified as being represented by R ^1b , R ^1c , R ^2a , R ^2b , R ^2c .

  The alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. Specifically, a methylamino group or a dimethylamino group , Ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t-butylamino group, pentylamino group, hexylamino group Cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group , Dicyclohexylamino group Pyrrolidyl group, piperidyl group, etc. ditrifluoromethylamino group, and a pentylamino group, hexylamino group, octyl amino group, 2-ethylhexyl amino group, decylamino group, 3,7-dimethyloctylamino group.

The arylamino group may have a substituent on the aromatic ring, the number of carbon atoms is usually about 3 to 60, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinyl amino group, pyrimidylamino group, Pirajiruamino group, etc. triazyl amino group and the like, C ₁ -C ₁₂ alkylphenyl group, di (C ₁ -C ₁₂ alkylphenyl) amino group are preferable.

The aryl alkyl amino group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁₎ -C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups and the like, C ₁ -C ₁₂ alkylphenyl -C ₁ -C _{A 12} alkylamino group and a di (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group are preferred.

  Examples of the sulfonate group include a benzene sulfonate group, a p-toluene sulfonate group, a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.

  Heterocyclic ligands include ligands composed of pyridine rings, pyrrole rings, thiophene rings, oxazole, furan rings and other heterocyclic rings and benzene rings, specifically phenylpyridine, 2- (Paraphenylphenyl) pyridine, 7-bromobenzo [h] quinoline, 2- (4-thiophen-2-yl) pyridine, 2- (4-phenylthiophen-2-yl) pyridine, 2-phenylbenzoxazole, 2- (Paraphenylphenyl) benzoxazole, 2-phenylbenzothiazole, 2- (paraphenylphenyl) benzothiazole, 2- (benzothiophen-2-yl) pyridine, 1,10-phenanthroline, 2,3,7,8, Examples include 12,13,17,18-octaethyl-21H, 23H-porphyrin, which may be a coordination bond or a covalent bond.

  Examples of the carbonyl compound are those that coordinately bond with M through an oxygen atom, and examples include ketones such as carbon monoxide, acetone, and benzophenone, and diketones such as acetylacetone and acenaphthoquinone.

  Examples of ethers include those that coordinate with M through an oxygen atom, and examples thereof include dimethyl ether, diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane.

  The amine is coordinated with M at the nitrogen atom, and monoamines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, triphenylamine, dimethylphenylamine, methyldiphenylamine, 1,1,2,2- Examples thereof include diamines such as tetramethylethylenediamine, 1,1,2,2-tetraphenylethylenediamine, and 1,1,2,2-tetramethyl-o-phenylenediamine.

  The imine has a coordinate bond with M at the nitrogen atom, and is a monoimine such as benzylideneaniline, benzylidenebenzylamine, benzylidenemethylamine, dibenzylideneethylenediamine, dibenzylidene-o-phenylenediamine, 2,3-bis (anilino). ) Diimines such as butane.

  Examples of the phosphine are those having a coordinate bond with M at a phosphorus atom, and examples thereof include triphenylphosphine, diphenylphosphinoethane, and diphenylphosphinopropane. Examples of the phosphite are those having a coordinate bond with M at a phosphorus atom, and examples thereof include trimethyl phosphite, triethyl phosphate, and triphenyl phosphite.

  Examples of the sulfide are those having a coordinate bond with M at a sulfur atom, and examples thereof include dimethyl sulfide, diethyl sulfide, diphenyl sulfide, and thioanisole.

  The metal atom represented by M is usually a metal atom having an atomic number of 50 or more and can cause an intersystem crossing between a singlet state and a triplet state in the present compound by spin-orbit interaction. Specifically, rhenium atom, osmium atom, iridium atom, platinum atom, gold atom, lanthanum atom, cerium atom, praseodymium atom, neodymium atom, promethium atom, samarium atom, europium atom, gadolinium atom, terbium atom, dysprosium atom, etc. And are preferably rhenium atom, osmium atom, iridium atom, platinum atom, gold atom, samarium atom, europium atom, gadolinium atom, terbium atom, dysprosium atom, and more preferably iridium atom, platinum in terms of luminous efficiency. Atom, gold atom, europium atom.

  J represents a ligand containing one or more atoms selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom as an atom bonded to M. The ligand containing one or more atoms selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom as the atom bonded to M is the same as that exemplified for K.

  Examples of the ligand J include the following.

（式中、＊はＭと結合する原子を表す。Ｒは、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルアミノ基、アルキルシリル基、アリール基、アリールオキシ基、アリールチオ基、アリールアミノ基、アリールシリル基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルキルアミノ基、アリールアルキルシリル基、アシル基、アシルオキシ基、イミン残基、アミド基、アリールアルケニル基、アリールアルキニル基、シアノ基、又は１価の複素環基を示す。Ｒは互いに結合して環を形成してもよい。）

(In the formula, * represents an atom bonded to M. Each R independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an alkylsilyl group, an aryl group, or an aryloxy group. , Arylthio group, arylamino group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxy group, imine residue, amide group, arylalkenyl group An arylalkynyl group, a cyano group, or a monovalent heterocyclic group, R may be bonded to each other to form a ring.)

In the above formula, the halogen atom represented by R, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyloxy group, acyl group, imine The residue, amide group, arylalkenyl group, arylalkynyl group, cyano group, or monovalent heterocyclic group is represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c above. The same as those explained and exemplified as atoms, residues and groups.

  In the above formula, the alkylamino group, arylamino group, and arylalkylamino group represented by R are the same as those described and exemplified as the group represented by the ligand K bonded to M in the above.

  In the above formula, the alkylsilyl group represented by R may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. Specifically, the trimethylsilyl group, triethylsilyl group, Propylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, Examples include octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, pentyldimethylsilyl group, hexyldimethyl Silyl group, octyldimethylsilyl group 2-ethylhexyl - dimethylsilyl group, decyldimethylsilyl group, a 3,7-dimethyl silyl group.

  In the above formula, the arylsilyl group represented by R may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms, and is a triphenylsilyl group or tri-p-xylylsilyl group. Group, tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

In the above formula, the aryl alkyl silyl group represented by R, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl silyl groups, such as phenyl -C ₁ -C ₁₂ alkyldimethylsilyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl A silyl group is preferred.

  In the above formula, in order to enhance the solubility of the triplet light emitting complex compound in the solvent, it is preferable that at least one of R includes a long-chain alkyl group.

  In the above formula, J is preferably bonded to M at least one nitrogen atom or carbon atom in terms of stability of the triplet light emitting complex compound, and more preferably J is bonded to M in a multidentate manner. More preferably, J is represented by the following formula (J-1) or (J-2).

（式中、Ｒ⁶〜Ｒ¹³は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルアミノ基、アルキルシリル基、アリール基、アリールオキシ基、アリールチオ基、アリールアミノ基、アリールシリル基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルキルアミノ基、アリールアルキルシリル基、アシル基、アシルオキシ基、イミン残基、アミド基、アリールアルケニル基、アリールアルキニル基、シアノ基、１価の複素環基を示し、＊はＭと結合する部位を表す。）

Wherein R ^{6 to} R ¹³ are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilyl group, aryl group, aryloxy group, arylthio group, arylamino Group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxy group, imine residue, amide group, arylalkenyl group, arylalkynyl group, cyano Group represents a monovalent heterocyclic group, and * represents a site bonded to M.)

（式中、Ｔは酸素原子又は硫黄原子を示す。Ｒ¹⁴〜Ｒ¹⁹は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルアミノ基、アルキルシリル基、アリール基、アリールオキシ基、アリールチオ基、アリールアミノ基、アリールシリル基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルキルアミノ基、アリールアルキルシリル基、アシル基、アシルオキシ基、イミン残基、アミド基、アリールアルケニル基、アリールアルキニル基、シアノ基を示し、＊はＭと結合する部位を表す。）

(In the formula, T represents an oxygen atom or a sulfur atom. R ^{14 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an alkylsilyl group, or an aryl group. , Aryloxy group, arylthio group, arylamino group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxy group, imine residue, amide group , An arylalkenyl group, an arylalkynyl group, and a cyano group, and * represents a site bonded to M.)

In the above formula, the atoms and groups represented by R ^{6 to} R ¹⁹ are specifically described as those represented by R ^1a , R ^1b , R ^1c , R ^2a , R ^2b , R ^2c in the above. And those exemplified and exemplified as the group represented by the ligand K that binds to M.

  The compound showing light emission from the triplet excited state used for the layer having a light emitting function may contain only one kind or two or more kinds. In addition, when the compound that emits light from the triplet excited state is two or more triplet light emitting complex compounds, they may have the same metal or different metals. Good. Moreover, each metal complex structure may have mutually different luminescent color. At this time, it is preferable to design so that an appropriate amount of the metal complex is included because the emission color can be controlled.

  Furthermore, a dendrimer compound is mentioned as a compound which shows light emission from a triplet excited state. Regarding dendrimer compounds, JP-A-11-140180, JP-A-2002-220468, “Dendritic Molecules” published in 1996 by VCH Publishing Company, June 1998, Hyundai Kagaku, pp. 20-40 “Molecular design of dendrimers”, “Dendrimer- In the present invention, the dendrimer compound refers to the core (nuclear core). ) And a dendritic compound having a chemical structure in which a dendritic structure including a branching unit is three-dimensionally repeated.

  As low-molecular compounds having luminescent properties, “Organic EL Display” (Co-authored by Shizuo Tokito, Chinami Yasada, Hideyuki Murata, Ohmsha, 2004, 1st edition, 1st edition), pages 83-99, 101 Phosphorescent materials described on page 120 can also be used.

  The thickness of the layer having a light emitting function is usually 30 nm to 3 μm, preferably 50 nm to 1 μm, more preferably 60 nm to 300 nm, and still more preferably 60 nm to 100 nm.

-Arbitrary layer-
In addition to the first electrode, the second electrode, and the layer having a light emitting function, the organic electroluminescence device of the present invention includes a charge transport layer [that is, a hole transport layer (usually containing a hole transport material). And an electron transport layer (usually containing an electron transport material). ], A charge injection layer [that is, a generic term for a hole injection layer and an electron injection layer. ] Or the like.

  In the present specification, the “hole transport layer” means a layer having a function of transporting holes, and the “electron transport layer” means a layer having a function of transporting electrons. “Hole injection layer” means a layer having a function of injecting holes, and “electron injection layer” means a layer having a function of injecting electrons. Note that the hole injection layer and / or the hole transport layer may have an electron block function for preventing electrons injected from the cathode from passing through the layer having a light emitting function, and the electron injection layer. Alternatively, the electron transport layer or both may have a hole blocking function that prevents holes injected from the anode from passing through the layer having a light emitting function.

As a charge transport material (that is, a generic term for a hole transport material and an electron transport material), a material in which the layer structure does not substantially collapse and the function does not substantially decrease by heat treatment can be appropriately selected. . The number average molecular weight of the charge transport material is preferably about 1 × 10 ³ to 1 × 10 ^{8 in} terms of polystyrene, and more preferably about 1 × 10 ⁴ to 1 × 10 ⁶ .

  Examples of the hole transport material include aromatic amine compounds such as N, N-diphenyl-N, N-bis (3-methylphenyl) -1,1-biphenyl-4,4-diamine (TPD), hydrazone Compounds, metal phthalocyanines, porphyrins, styrylamine compounds, polyvinyl carbazole, polysilane (Appl. Phys. Lett. 59, 2760 (1991)), poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (HC Starck B-Tech) Manufactured by the company, trade name: Bytron P TP AI 4083), and suspensions thereof are preferably used. As the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988, JP-A-2- Examples include those described in Japanese Patent Nos. 311591, 3-37992, 3-152184, 11-35687, 11-217392, and Japanese Patent Application Laid-Open No. 2000-80167. . Note that a material used for the hole injection layer, such as metal phthalocyanine, may be used as a material used for the hole transport layer in relation to the electrode and the material of the adjacent layer.

  The thickness of the hole transport layer differs depending on the material used, and may be adjusted so that the drive voltage and the light emission efficiency are appropriate, but at least a thickness that does not cause pinholes is required. . If this thickness is too thick, the driving voltage of the device becomes high, which is not preferable. Therefore, the thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

  Examples of electron transport materials include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, Various metals typified by metal complexes of distyrylpyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, benzoxazole and benzothiazole ligands Complex, benzoquinone or its derivative, naphthoquinone or its derivative, anthraquinone or its derivative, diphenyldicyanoethylene or its derivative, diphenoquinone derivative , Polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, or polyfluorene or derivatives thereof, bathocuproine or derivatives thereof. Further, as an electron transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, 2-135361, 2-209988, 3-37992 And those described in Japanese Patent Publication No. 3-152184.

  The thickness of the electron transport layer differs depending on the material used, and may be adjusted so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If this thickness is too thick, the driving voltage of the device becomes high, which is not preferable. Therefore, the thickness of the electron transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

  Other charge transport materials include “Organic EL Display” (co-authored by Shizuo Tokito, Chibaya Adachi, Hideyuki Murata, Ohm Co., Ltd., published in 2004, first edition, first print), pages 17-48, 83 The hole transport material, electron transport material, etc. which are described in -99 pages and 101-120 pages can be utilized.

  The hole injection layer is, for example, a layer containing a conductive polymer, provided between the anode and the hole transport layer, and having an intermediate value between the anode material and the hole transport material contained in the hole transport layer. Examples thereof include a layer containing a material having an ionization potential.

When the hole injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm. Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  If the kind of ion to dope is a hole injection layer, it is an anion. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and the like. Examples of the cation include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.

  As a film thickness of a positive hole injection layer, they are 1 nm-100 nm, for example, and 2 nm-50 nm are preferable.

  The material used for the hole injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene Examples include vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon. The

  The electron injection layer is, for example, provided between the cathode and the layer having a light emitting function or the electron transport layer, and the electron affinity or electron transport layer of the light emitting material included in the layer having the work function and the light emitting function of the cathode material. A layer containing a material having an electron affinity with an intermediate value with respect to the contained electron transporting material is preferably used.

When the electron injection layer is a layer containing a conductive polymer, the electron injection layer is provided adjacent to the cathode between the cathode and the layer having a light emitting function. The electric conductivity of the conductive polymer is preferably 10 ⁻⁷ S / cm or more and 10 ³ S / cm or less. In order to reduce the leakage current between the light emitting pixels, 10 ⁻⁵ S / cm or more and 10 or less. ² S / cm or less is more preferable, and 10 ⁻⁵ S / cm or more and 10 ¹ S / cm or less is more preferable. Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions. The kind of ion to dope is a cation, and examples thereof include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.

  The thickness of the electron injection layer is, for example, 1 nm to 150 nm, and preferably 2 nm to 100 nm.

  As a method for forming the electron injection layer, film formation from a solution is exemplified, and it is only necessary to remove the solvent by drying after coating the solution, which is very advantageous in production. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Coating methods such as flexographic printing, offset printing, nozzle coating, capillary coating, and inkjet printing can be used. Also, an electron injection material that is in the form of an emulsion and dispersed in water or alcohol can be formed into a film by the same method as that for a solution.

-Element structure-
Specific examples of the organic electroluminescence element of the present invention include, for example, an element having an anode and a cathode, a hole injection layer in contact with the anode between the electrodes, and a layer having a light emitting function ( For example, an EL element in which a hole transport layer is provided adjacent to the layer having a light emitting function between the hole injection layer and the layer having a light emitting function (for example, the following b); An element in which an electron transport layer is provided adjacent to the layer having a light emitting function (for example, c); and the light emitting function between the cathode and the layer having the light emitting function. An element in which an electron transport layer is provided adjacent to the layer having a hole transport layer adjacent to the layer having a light emitting function between the hole transport layer and the layer having a light emitting function (for example, d below) ); Between the cathode and the layer having a light emitting function, an electron injection adjacent to the cathode. An electron transport layer provided adjacent to the layer having a light emitting function, and a hole transport layer adjacent to the layer having a light emitting function between the hole transport layer and the layer having a light emitting function. And the like (for example, e) described below.
a) Anode / hole injection layer / layer having light emission function / cathode b) Anode / hole injection layer / hole transport layer / layer having light emission function / cathode c) Anode / hole injection layer / light emission function Layer / electron transport layer / cathode d) anode / hole injection layer / hole transport layer / layer having light emitting function / electron transport layer / cathode e) anode / hole injection layer / hole transport layer / light emitting function Layer / electron transport layer / electron injection layer cathode (where / indicates that the layers are laminated adjacent to each other. The same applies hereinafter).

-Board-
In producing the device of the present invention, a substrate is usually used. This substrate is usually positioned under the first electrode, the second electrode, the layer having a light emitting function, and other layers (for example, a protective layer formed in some cases). The substrate may be any substrate that does not change when these electrodes and layers are formed, and examples thereof include a substrate made of glass, plastic, a polymer film, silicon, a metal substrate such as stainless steel, and the like. In the case where the substrate is opaque, the electrode located on the opposite side of the substrate with respect to the layer having a light emitting function is preferably transparent or translucent.

-Ink composition-
The light-emitting component used for the production of the device of the present invention can be used as an ink composition by mixing with a solvent or a dispersion medium, if necessary. The viscosity of the ink composition varies depending on the printing method. However, when the ink composition passes through a discharge device, such as an ink jet printing method, the viscosity is 1 at 25 ° C. to prevent clogging and flight bending at the time of discharge. It is preferably in the range of ˜20 mPa · s.

  Although there is no restriction | limiting in particular as a solvent used for an ink composition, What can melt | dissolve or uniformly disperse | distribute materials other than the solvent which comprises this ink composition is preferable. When the material constituting the ink composition is soluble in a nonpolar solvent, the solvent is a chlorine solvent such as chloroform, methylene chloride, dichloroethane, an ether solvent such as tetrahydrofuran, toluene, xylene, tetralin, Aromatic hydrocarbon solvents such as anisole, n-hexylbenzene, cyclohexylbenzene, aliphatic hydrocarbon solvents such as decalin, bicyclohexyl, etc., ketone solvents such as acetone, methyl ethyl ketone, 2-heptanone, ethyl acetate, butyl acetate And ester solvents such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate.

  In an organic electroluminescence device made using an ink composition, the optimum value of the film thickness of the charge transport layer or the layer having a light emitting function varies depending on the material used, and the drive voltage and the light emission efficiency are appropriate. What is necessary is just to select, for example, it is 1 nm-1 micrometer, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

  In addition, since the element of the present invention undergoes heat treatment to change its emission color and become multicolored, if the region to be heat-treated is arbitrarily designated, the emission color will change only in that region and patterned to any emission color. An organic electroluminescence device can be obtained.

-Protective layer After forming the first electrode, the second electrode, and the layer having a light emitting function, the obtained polymer light emitting device may have a protective layer for protecting the polymer light emitting device. Good.

  In general, for example, after the second electrode is manufactured, a protective layer that protects the organic electroluminescent element from the second electrode side may be attached so as to be sandwiched between the stacked substrates. In order to use the organic electroluminescence element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the material of the protective layer, polymer compounds typified by curable resins such as epoxy resins, metal oxides, metal fluorides, metal borides and the like can be used (collectively, “protective layer” Called "materials"). Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Moreover, the film | membrane which protects an organic electroluminescent element can also be formed by forming one or more laminated films of an organic layer / inorganic layer on an organic electroluminescent element. Among these, it is preferable to take any one or more measures.

-Manufacturing method of organic electroluminescence element-
Next, the manufacturing method of this invention is demonstrated. Discolored and multi-colored organic electroluminescence elements
(1) a step of forming a first electrode and a layer having a light emitting function comprising two or more light emitting components having different light emission peak wavelengths;
(2) forming a second electrode on the opposite side of the first electrode with respect to the layer having a light emitting function;
(3) A part or all of the layer having a light emitting function can be manufactured by a method comprising heating at 50 to 450 ° C. In addition to these steps, (4) a step of forming a protective layer on the second electrode may be performed, and other steps may be performed.

  The above-described organic electroluminescence device of the present invention may be produced by any method, but the method having the steps (1) and (2) (in some cases, further having the step (4) in some cases). Preferably, it is manufactured by the method.

  Hereinafter, each process will be described in detail.

・ Process (1)
The first electrode (usually a transparent or translucent electrode) and a layer having a light emitting function containing two or more light emitting components having different emission peak wavelengths may be formed continuously. Other layers may be formed before and after the formation of one electrode and a layer having a light emitting function containing two or more kinds of light emitting components having different emission peak wavelengths. Specifically, for example, after forming the first electrode, another layer is formed, and then a layer having a light emitting function including two or more kinds of light emitting components having different emission peak wavelengths is formed. Further, after that, other layers may be formed. The layer having the light emitting function may be composed of only one layer or may be composed of two or more layers.

  Examples of the other layers include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and other layers having a light emitting function.

  The method for forming the first electrode is not particularly limited, and can be performed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like.

  A method for forming a layer having a light emitting function containing two or more kinds of light emitting components having different emission peak wavelengths is not particularly limited. For example, the layer can be formed from a solution. Examples of the method for forming a film from a solution include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing. Examples thereof include coating methods such as a method, a flexographic printing method, an offset printing method, a nozzle coating method, a capillary coating method, and an ink jet printing method. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

  The thicknesses of the first electrode and the layer having a light emitting function containing two or more kinds of light emitting components having different light emission peak wavelengths are as described in the above-mentioned section of organic electroluminescence.

・ Process (2)
There is no particular limitation except that the first electrode and the second electrode are formed on opposite sides with respect to the layer having the light emitting function. That is, another layer may exist between the layer having the light emitting function and the first electrode, and another layer may be present between the layer having the light emitting function and the second electrode. Also good.

  Examples of the other layers include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and other layers having a light emitting function.

  The formation method of said 2nd electrode is not specifically limited, For example, it can carry out by the vacuum deposition method, sputtering method, the lamination method etc. which thermocompression-bonds a metal thin film.

  The thicknesses of the second electrodes are as described in the above-mentioned organic electroluminescence section.

・ Process (3)
Heating of a part or all of the layer having a light emitting function may be performed by any method, but may be performed once or a plurality of times. Further, this heating may be performed directly or indirectly. In order to perform desired discoloration / multicolorization, the heating is performed at 50 to 450 ° C., preferably 70 to 400 ° C., more preferably 80 to 300 ° C., further preferably 80 to 250 ° C., particularly preferably. Is carried out at 110 to 220 ° C, particularly preferably 140 to 210 ° C. If the temperature is too high, the device itself may be destroyed. The heating time is not particularly limited, but is preferably 30 minutes or less, more preferably 5 minutes or less, and even more preferably 30 seconds or less in order to shorten the tact time. By setting the heating temperature and the heating time in such a range, the ratio of the maximum emission intensity of each of the two or more kinds of light emitting components contained in the layer having a light emitting function can be controlled.

  The heating method is not particularly limited, and examples thereof include methods using heat conduction, heat radiation, and the like. Specifically, energization to the first electrode and the second electrode (ie, Joule heat), It can be performed with a thermal head, light such as electromagnetic waves and infrared rays, laser, etc., and preferably performed with a thermal head, light such as infrared rays and laser. Further, heating may be performed by directly or indirectly contacting a heated material such as a metal with a layer having a light emitting function.

  Specifically, for example, in the case of heating with electromagnetic waves, a target pattern having a light emission color different from the location masked on the light emitting surface of the element can be easily obtained by using a mask or the like.

  In the case of heating with a laser or a thermal head, the fine area can be easily heated, so that a color change can be freely generated in the fine area. A thermal head is a device that can selectively heat a heat generating resistor to generate heat by selectively applying a potential, and can selectively heat a target location with the obtained thermal energy. When a laser is used, patterning can be performed by scanning with a polygon mirror, a galvanometer mirror, or the like.

  In addition to these, a heat medium with good thermal conductivity in a line shape, mesh shape, or a fixed shape pattern is placed on a hot plate, and an organic electroluminescence element is placed on the heat medium. The temperature distribution can be formed and the colors can be created according to the desired pattern.

  Therefore, an organic electroluminescence element before heat treatment is prepared in advance, and if necessary, the element is subjected to heat treatment each time, and can be easily and freely patterned with a desired emission color. A light emitting element can be obtained. For example, by using a laser printer, a thermal head printer, or the like, a light emission pattern having an intended light emission color can be drawn on the element so as to be printed on paper.

  Although it is difficult to accurately measure the actual temperature of the layer having the light emitting function (or the light emitting component contained in this layer), the temperature that can be used as an indicator, such as the surface temperature of a thermal head, hot plate, heater, etc., is used. Thus, the temperature can be controlled by examining the temperature at which the light emission characteristics change in advance. Moreover, temperature control by laser irradiation is also possible by considering beforehand the output of the laser, the focused spot size, the irradiation time, and the change in the light emission characteristics.

・ Process (4)
The step of forming the protective layer on the second electrode may be performed by any method. Here, forming the protective layer on the second electrode includes not only the upper surface of the second electrode but also an aspect in which the upper surface of the second electrode is covered with the protective layer.

-Order of each process The above processes (1) to (3) or processes (1) to (4) may be performed in any order. Typically, the step (3) is performed before the step (2), after the step (2), simultaneously with the step (2), or a combination thereof. “Before step (2)” includes not only immediately before step (2), but also includes other steps between step (3) and step (2). Further, “after step (2)” includes not only immediately after step (2) but also a case of having other steps between step (2) and step (3).

Specifically, for example,
A. A method of performing step (2) and step (3) in this order after performing step (1);
B. A method of performing step (3) and step (2) in this order after performing step (1);
Etc. Moreover, when performing the said process (4), for example,
C. A method of performing step (2), step (3), step (4) in this order after performing step (1):
D. A method of performing step (3), step (2), step (4) in this order after performing step (1);
E. A method of performing step (2), step (4), step (3) in this order after performing step (1);
F. A method of performing step (3), step (4), step (2) in this order after performing step (1);
Etc. In the above process, you may have another process between each process.

  An organic electroluminescent device manufactured by the manufacturing method of the present invention (herein, the organic electroluminescent device that can be manufactured by the step (1) and the step (2), and further a step (4) in some cases). Can be discolored and multicolored by producing a heat-treated organic electroluminescent element having a protective layer formed thereon. After the protective layer is formed, it is advantageous because the device is easy to handle. Therefore, in the manufacturing method of this invention, it is preferable to heat-process after protective layer formation.

  In addition, the organic electroluminescent element manufactured by the manufacturing method of this invention may have a board | substrate. The production of the substrate is usually performed before the step (1).

-Application-
The organic electroluminescence element of the present invention and the organic electroluminescence element manufactured by the manufacturing method of the present invention are, for example, a planar light source (that is, a curved or planar light source, specifically, for example, a liquid crystal Examples thereof include a curved or flat light source for display backlight or illumination, and display devices (for example, advertisement display devices, segment display devices, dot matrix display devices (for example, flat panel displays). .), Liquid crystal display devices (in this case, particularly preferably used as a backlight), and the like. Moreover, it is useful also in manufacturing a sheet-like flexible organic electroluminescent element by forming the element on a flexible substrate.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples. Hereinafter, the unit of intensity is W / (m ² · nm · sr).

<Synthesis Example 1>
-Synthesis of polymer compound 1-
26 g (0.048 mol) of 2,7-dibromo-9,9-dioctylfluorene, 5.6 g (0.012 mol) of 2,7-dibromo-9,9-diisopentylfluorene and 22 g of 2,2′-bipyridyl ( 0.14 mol) was dissolved in 1600 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, 56 g (0.20 mol) of bis (1,5-cyclooctadiene) nickel (0) was added to this solution, and the temperature was raised to 60 ° C. and reacted for 8 hours. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25 wt% ammonia water 1200 mL / methanol 1200 mL / ion-exchanged water 1200 mL, and stirred for 30 minutes, and then the deposited precipitate was filtered. After washing with methanol, it was dried under reduced pressure for 2 hours. Thereafter, the resultant was dissolved in 2500 mL of toluene, followed by filtration. After 2600 mL of 1N hydrochloric acid was added to the filtrate and stirred for 1 hour, the aqueous layer was removed, 2600 mL of 2 wt% aqueous ammonia was added to the organic layer, and the mixture was stirred for 1 hour. The aqueous layer was removed. After adding 900 mL of water and stirring for 1 minute and removing the aqueous layer twice, the organic layer was dropped into 2900 mL of methanol and stirred for 1 hour, and the deposited precipitate was filtered and washed with methanol. After drying under reduced pressure for 2 hours, the product was dissolved in 2300 mL of toluene, purified through an alumina column (alumina amount 450 g), the recovered toluene solution was dropped into 4500 mL of methanol and stirred for 1 hour, and the deposited precipitate was filtered for 2 hours. By drying under reduced pressure, the following structural formula:

で表される２種類の繰り返し単位からなる共重合体（以下、「高分子化合物１」という。）２０ｇを得た。

20 g of a copolymer consisting of two types of repeating units represented by the following (hereinafter referred to as “polymer compound 1”) was obtained.

The polymer compound 1 had a polystyrene-equivalent number average molecular weight Mn of 1.4 × 10 ⁵ , a polystyrene-equivalent weight average molecular weight Mw of 4.3 × 10 ⁵ , and an emission peak wavelength of 422 nm.

<Synthesis Example 2>
-Synthesis of polymer compound 2-
Synthesis of Compound C (Dibenzothiophene Derivative) a) Synthesis of Compound C-1 In a 1 L four-necked flask under an inert atmosphere, 7 g of 2,8-dibromodibenzothiophene and 280 ml of THF were added and stirred and dissolved at room temperature. Then, it cooled to -78 degreeC. 29 ml of n-butyllithium (1.6 molar hexane solution) was added dropwise. After completion of the dropping, the mixture was stirred for 2 hours while maintaining the temperature, and 13 g of trimethoxyboronic acid was added dropwise. After completion of dropping, the temperature was slowly returned to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% by weight sulfuric acid and stirred at room temperature for 12 hours. Water was added for washing, and the organic layer was separated. After replacing the solvent with ethyl acetate, 5 ml of 30 wt% aqueous hydrogen peroxide was added and stirred at 40 ° C. for 5 hours. Thereafter, the organic layer was separated, washed with a 10% by weight aqueous ammonium iron (II) sulfate solution, dried, and the solvent was distilled off to obtain 4.43 g of a brown solid. By-products such as a dimer were produced from LC-MS measurement, and the purity of Compound C-1 was 77% (LC area percentage).
MS (APCI (-)) :( M-H) - 215

（化合物Ｃ−１）

(Compound C-1)

b) Synthesis of Compound C-2 4.43 g of the above Compound C-1, 25.1 g of n-octyl bromide, and 12.5 g (23.5 mmol) of potassium carbonate were added to a 200 ml three-necked flask under an inert atmosphere. Then, 50 ml of methyl isobutyl ketone was added as a solvent, and the mixture was heated to reflux at 125 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off, chloroform and water were added, the organic layer was separated, and further washed twice with water. After drying over anhydrous sodium sulfate, purification was performed with a silica gel column (developing solvent: toluene / cyclohexane = 1/10) to obtain 8.49 g (LC area percentage 97%, yield 94%) of compound C-2. .
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.91 (t, 6H), 1.31-1.90 (m, 24H), 4.08 (t, 4H), 7.07 (dd, 2H), 7.55 (d, 2H), 7 .68 (d, 2H)

（化合物Ｃ−２）

(Compound C-2)

c) Synthesis of Compound C-3 6.67 g of Compound C-2 and 40 ml of acetic acid were placed in a 100 ml three-necked flask, and the temperature was raised to 140 ° C. with an oil bath. Subsequently, 13 ml of 30 wt% aqueous hydrogen peroxide was added from the condenser, and after stirring vigorously for 1 hour, the reaction was terminated by pouring into 180 ml of cold water. After extraction with chloroform and drying, the solvent was distilled off to obtain 6.96 g (LC area percentage 90%, yield 97%) of compound C-3.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.87 (m, 24H), 4.06 (t, 4H), 7.19 (dd, 2H), 7.69 (d, 2H), 7 .84 (d, 2H)
MS (APCI (+)): (M + H) ^<+> 473

（化合物Ｃ−３）

(Compound C-3)

d) Synthesis of Compound C-4 3.96 g of Compound C-3 and 15 ml of a 1: 1 mixture of acetic acid / chloroform were added to a 200 ml four-necked flask under an inert atmosphere, and the mixture was stirred and dissolved at 70 ° C. Subsequently, 6.02 g of bromine was dissolved in 3 ml of the above solvent and stirred for 3 hours. A sodium thiosulfate aqueous solution was added to remove unreacted bromine, chloroform and water were added, and the organic layer was separated and dried. The solvent was distilled off and the residue was purified by a silica gel column (developing solvent: chloroform / hexane = 1/4) to obtain 4.46 g (LC area percentage 98%, yield 84%) of compound C-4.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.95 (t, 6H), 1.30 to 1.99 (m, 24H), 4.19 (t, 4H), 7.04 (s, 2H), 7.89 (s, 2H)
MS (FD +) M + 630

（化合物Ｃ−４）

(Compound C-4)

e) Synthesis of Compound C (Dibenzothiophene Derivative) In an inert atmosphere, 3.9 g of Compound C-4 and 50 ml of diethyl ether were placed in a 200 ml three-necked flask, heated to 40 ° C. and stirred. Lithium aluminum hydride 1.17 g was added little by little and allowed to react for 5 hours. Excess lithium aluminum hydride was decomposed by adding water little by little and washed with 5.7 ml of 36 wt% hydrochloric acid. Chloroform and water were added, and the organic layer was separated and dried. Purification by a silica gel column (developing solvent: chloroform / hexane = 1/5) yielded 1.8 g (LC area percentage 99%, yield 49%) of Compound C.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.97 (m, 24H), 4.15 (t, 4H), 7.45 (s, 2H), 7.94 (s, 2H)
MS (FD ⁺ ) M ⁺ 598

（化合物Ｃ：ジベンゾチオフェン誘導体）

(Compound C: dibenzothiophene derivative)

-Synthesis of compound D (phenylenediamine derivative) f) Synthesis of compound D-1 In an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. It was. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours. The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of a white solid (Compound D-1).
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 1.3 [s, 9H], 2.4 [s, 6H], 7.1 [s, 2H]
MS (FD ⁺ ) M ⁺ 241

（化合物Ｄ−１）

(Compound D-1)

g) Synthesis of Compound D-2 Under an inert atmosphere, 36 ml of degassed dehydrated toluene was placed in a 100 ml three-necked flask, and 0.63 g of tri (t-butyl) phosphine was added. Subsequently, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of the above compound D-1, 5.2 g of sodium t-butoxy, and 4.7 g of N, N′-diphenyl-1,4-phenylenediamine were added. And then reacted at 100 ° C. for 3 hours. The reaction solution was added to 300 ml of saturated brine and extracted with 300 ml of chloroform warmed to about 50 ° C. After the solvent was distilled off, 100 ml of toluene was added, and the mixture was heated and allowed to cool until the solid was dissolved, and then the precipitate was filtered to obtain 9.9 g of a white solid (Compound D-2).

（化合物Ｄ−２）

(Compound D-2)

h) Synthesis of Compound D (Phenylenediamine Derivative) Under an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask and the above N, N′-diphenyl-N, N′-bis was added. After dissolving 5.2 g of (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine (Compound D-2), 3.5 g of N-bromosuccinimide / N, N in an ice bath -The dimethylformamide solution was dripped and it was made to react for a whole day and night. 150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of Compound D white solid (Compound D).
¹ H-NMR (300 MHz / THF-d8):
δ (ppm) = 1.3 [s, 18H], 2.0 [s, 12H], 6.6 to 6.7 [d, 4H], 6.8 to 6.9 [br, 4H], 7 .1 [s, 4H], 7.2 to 7.3 [d, 4H]
MS (FD ⁺ ) M ⁺ 738

（化合物Ｄ：フェニレンジアミン誘導体）

(Compound D: phenylenediamine derivative)

In a nitrogen atmosphere, 1.95 g of the compound C (dibenzothiophene derivative), 2.39 g of the compound D (phenylenediamine derivative), and 2.33 g of 2,2′-bipyridyl were dissolved in 462.6 g of dehydrated tetrahydrofuran, The temperature was raised to 60 ° C., and 4.10 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added to this solution and reacted for 5 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25 wt% aqueous ammonia 85.2 g / methanol 168.8 g / ion-exchanged water 319.8 g, and stirred for 2 hours, and then the deposited precipitate was filtered. And dried under reduced pressure. After drying, the product was dissolved in 162.2 g of toluene. After dissolution, 8.3 g of radiolite was added, and the insoluble material was filtered. The obtained filtrate was purified through an alumina column, and then the purified solution was added to a mixed solution of ion-exchanged water 135.2 g / 25 wt% ammonia water 20.4 g and stirred for 0.5 hour, and then the aqueous layer was removed. . Further, 135.2 g of ion-exchanged water was added to the organic layer and stirred for 0.5 hour, and then the aqueous layer was removed. After carrying out vacuum concentration for a part of the obtained organic layer, the organic layer was poured into 341.8 g of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure to obtain the following structural formula:

で表される２種類の繰り返し単位からなる共重合体（以下、「高分子化合物２」という。）２．３５ｇを得た。

2.35 g of a copolymer composed of two types of repeating units represented by the following (hereinafter referred to as “polymer compound 2”) was obtained.

The number average molecular weight Mn in terms of polystyrene of the polymer compound 2 was 1.2 × 10 ⁴ , the weight average molecular weight Mw in terms of polystyrene was 7.7 × 10 ⁴ , and the emission peak wavelength was 461 nm.

<Metal complex 1>
As the triplet light emitting complex compound, the following formula:

で表されるIridium(III) bis-(2-(2'-benzothienyl)pyridinatoN,C³)(acetyl-acetonate)（アメリカン ダイ ソース社製、商品名：ELECTROPHOSPHORESCENT METAL COMPLEX、カタログ番号：ADS067RE）（金属錯体１）を用いた。金属錯体１の発光ピーク波長は、約６１５ｎｍであった。

Iridium (III) bis- (2- (2'-benzothienyl) pyridinatoN, C ³ ) (acetyl-acetonate) (product name: ELECTROPHOSPHORESCENT METAL COMPLEX, catalog number: ADS067RE) (metal) Complex 1) was used. The emission peak wavelength of the metal complex 1 was about 615 nm.

<Example 1>
-Fabrication of light-emitting elements-
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by HC Starck B-Tech, trade name: CH8000 LVW176 / 3) was filtered through a 0.5 μm filter. A filtered suspension is formed to a thickness of about 60 nm by spin coating on a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and dried at about 200 ° C. for 10 minutes using a hot plate in the atmosphere. By doing this, the glass substrate A was produced.

  Next, the polymer compound 1 obtained in Synthesis Example 1 and the polymer compound 2 obtained in Synthesis Example 2 were mixed so that the weight ratio was 8: 2, and dissolved in xylene. Solution 1 was prepared. At this time, the xylene solution 1 was prepared so that the total concentration of the polymer compound 1 and the polymer compound 2 would be about 0.9% by weight. Moreover, the metal complex 1 obtained above was dissolved in chloroform, and the chloroform solution 2 was prepared so that the density | concentration of the metal complex 1 might be 0.45 weight%. Further, the xylene solution 1 and the chloroform solution 2 are mixed, and the weight of the metal complex 1 in the chloroform solution 2 with respect to the total weight of the polymer compound 1 and the polymer compound 2 in the xylene solution 1 is about 6.5% by weight. Thus, a mixed solution 3 of xylene and chloroform was prepared. Using this mixed solution 3, a film was formed on the glass substrate A at 600 rpm by spin coating. The film thickness was about 80 nm.

Further, this was heated to about 70 ° C. to remove residual solvent under reduced pressure (the degree of vacuum was 1 × 10 ⁻⁴ Pa or less), dried for 60 minutes, and then sequentially deposited by vacuum deposition with about 10 nm of barium and then with aluminum. A device A was fabricated by vapor deposition so as to have a thickness of about 150 nm. Note that after the degree of vacuum reached 2 × 10 ⁻⁵ Pa or less, metal deposition was started. Barium was deposited using a resistance heating method, and aluminum was deposited using an electron beam method.

  Further, a photo-curing resin is applied to the four sides of the glass plate, bonded to the element A in an inert gas (that is, nitrogen gas), sealed by irradiation with ultraviolet light and photo-curing, and a protective layer is provided. Thus, the device B was produced.

-Element evaluation before heating-
When a voltage of 8 V was applied to the device B thus obtained, EL (electroluminescence) emission was exhibited. The CIE chromaticity coordinate value (before heating) of the luminescence was measured. The results are shown in Table 1.
Next, when a voltage of 10 V was applied to the element B, EL light emission was exhibited. The EL spectrum had a peak showing the maximum emission intensity of blue and a peak showing the maximum emission intensity of red. The wavelength that showed these peaks was about 450 nm (blue light emitting component (the polymer compound 1 and the polymer compound 2); the spectra of these compounds overlapped, and a peak with a maximum intensity appeared at about 450 nm. Wavelength 1), about 615 nm (red light-emitting component (Iridium (III) bis- (2- (2′-benzothienyl) pyridinatoN, C ³ ) (acetyl-acetonate)); wavelength 2). Table 2 shows the maximum emission intensity (intensity at wavelength 1) of the blue emission component, the maximum emission intensity (intensity at wavelength 2) of the red emission component, and the ratio thereof (intensity at wavelength 1 / intensity at wavelength 2). .
Before applying the voltage, the device B was irradiated with UV light having a peak wavelength of 365 nm, and PL (photoluminescence) was measured. The PL spectrum had two peaks (wavelength 1 and wavelength 2) as described above. Table 3 shows the maximum emission intensity (intensities at wavelengths 1 and 2) and the ratio (intensity at wavelength 1 / intensity at wavelength 2) at these two peaks.

-Heat treatment of a layer having a light emitting function-
Next, the device B was placed on a hot plate having a surface temperature of 150 ° C. and heated for about 3 minutes, and then the device was allowed to cool to room temperature.

-Element evaluation after heating-
Thereafter, in the same manner as the measurement method for element B before heating, (1) “value of CIE chromaticity coordinates (after heating)” and (2) “maximum of blue light emitting component” of EL spectrum. Emission intensity (intensity at wavelength 1), maximum emission intensity of red emission component (intensity at wavelength 2), ratio thereof (intensity at wavelength 1 / intensity at wavelength 2) ", (3)" blue emission component of PL spectrum " Maximum emission intensity (intensity at wavelength 1), maximum emission intensity of red light-emitting component (intensity at wavelength 2), and ratio thereof (intensity at wavelength 1 / intensity at wavelength 2) "were measured and calculated. The obtained results are shown in Table 1, Table 2, and Table 3, respectively.

-Evaluation-
It was confirmed that the ratio of the maximum light emission intensity was changed by heat-treating the layer having a light emitting function at 150 ° C. within the range of 50 to 450 ° C. Here, the greater the ratio of the maximum emission intensity, the stronger the blue light emission, and the smaller the maximum emission intensity ratio, the stronger the red light emission. Therefore, in the element of Example 1, the emission color changed from red to blue before and after the heat treatment.

<Examples 2 to 4>
In Example 1, the surface temperature of the hot plate was changed from 150 ° C. to 100 ° C. (Example 2), 200 ° C. (Example 3), and 230 ° C. (Example 4). , (1) “CIE chromaticity coordinate value (after heating)”, (2) EL spectrum “maximum emission intensity of blue emission component (intensity at wavelength 1), maximum emission intensity of red emission component (intensity at wavelength 2) ), Ratio thereof (intensity at wavelength 1 / intensity at wavelength 2), (3) “maximum emission intensity of blue light-emitting component (intensity at wavelength 1), maximum emission intensity of red emission component (at wavelength 2) of PL spectrum” Intensity) and their ratio (intensity at wavelength 1 / intensity at wavelength 2) "were measured and calculated. The obtained results are shown in Table 1, Table 2, and Table 3, respectively.

^*「強度比」とは、"波長１における強度／波長２における強度"を意味する。

^* “Intensity ratio” means “intensity at wavelength 1 / intensity at wavelength 2”.

^*「強度比」とは、"波長１における強度／波長２における強度"を意味する。

^* “Intensity ratio” means “intensity at wavelength 1 / intensity at wavelength 2”.

<Comparative Example 1>
In Example 1, except that the surface temperature of the hot plate was changed from 150 ° C. to 40 ° C., the same as in Example 1, (1) “value of CIE chromaticity coordinates (after heating)”, (2) EL Spectrum “maximum emission intensity of blue emission component, maximum emission intensity of red emission component, ratio thereof (intensity at wavelength 1 / intensity at wavelength 2)”, (3) “maximum emission intensity of blue emission component, An attempt was made to measure and calculate the maximum emission intensity of the red light-emitting component and the ratio thereof (intensity at wavelength 1 / intensity at wavelength 2). However, visually, no change in emission color was observed in the obtained device. From this, it is considered that the ratio of the maximum emission intensity did not change before and after heating in the EL spectrum and the PL spectrum.

<Example 5>
-Patterning-
Two aluminum blocks (width 4 mm x depth 10 mm x height 10 mm) are arranged on a hot plate having a surface temperature of 342 ° C., and element B is placed thereon, and a part of the light-emitting portion of element B is placed on it. The block was touched, and a part of the light emitting site was locally heated for about 7 seconds. Next, the obtained element was allowed to cool to room temperature. When a voltage of 8 V was applied to the resulting device, only the portion in contact with the block emitted blue light, and the other portions emitted red light. Therefore, it was confirmed that the desired patterning can be easily performed by using the element B which is the element of the present invention.

Claims (10)

  An organic electro having a transparent or translucent first electrode, a second electrode, and a layer having a light emitting function, which is provided between these electrodes and contains two or more light emitting components having different emission peak wavelengths A luminescence device, wherein a part or all of the layer having a light emitting function is heated at 50 to 450 ° C., whereby each of the two or more kinds of light emitting components contained in the heated portion has a maximum light emission intensity. An organic electroluminescence device having the property of changing the ratio of.   The organic electroluminescence device according to claim 1, wherein the light-emitting component is a combination of a light-emitting polymer compound and a light-emitting low molecular compound.   The organic electroluminescent element according to claim 2, wherein the light-emitting polymer compound includes a liquid crystal state.   4. The organic electroluminescence device according to claim 2, wherein at least one of the light-emitting polymer compound and the light-emitting low molecular compound is a compound that emits light from a triplet excited state. (1) forming a layer having a light emitting function, comprising a first electrode and two or more light emitting components having different emission peak wavelengths;
(2) forming a second electrode on the opposite side of the first electrode with respect to the layer having a light emitting function;
(3) A method for producing an organic electroluminescent element, comprising: heating a part or all of the layer having a light emitting function at 50 to 450 ° C.   The manufacturing method according to claim 5, wherein the step (3) is performed before the step (2), after the step (2), simultaneously with the step (2), or a combination thereof.   The manufacturing method according to claim 5 or 6, wherein the heating is performed by energizing the first electrode and the second electrode, a thermal head, infrared rays, or a combination thereof.   The planar light source using the organic electroluminescent element as described in any one of Claims 1-4, or the organic electroluminescent element obtained by the manufacturing method as described in any one of Claims 5-7.   The flexible sheet using the organic electroluminescent element as described in any one of Claims 1-4, or the organic electroluminescent element obtained by the manufacturing method as described in any one of Claims 5-7.   The display apparatus using the organic electroluminescent element as described in any one of Claims 1-4, or the organic electroluminescent element obtained by the manufacturing method as described in any one of Claims 5-7.