JP2002038142A - Polymer fluorescent substance and polymer luminous element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer fluorescent substance or a polymer fluorescent substance solution capable of stably achieving a high luminous efficiency when formed into a polymer light-emitting diode(LED). SOLUTION: [I] This polymer fluorescent substance has a fluorescence in a solid state, 103-107 number-average molecular weight expressed in terms of polystyrene and <=10,000 ppm (wt.) sum total of the amount of a contained poor solvent measured by using a gas chromatography. [II] The polymer fluorescent substance solution is obtained by dissolving the polymer fluorescent substance having the fluorescence in the solid state and 103-107 number-average molecular weight expressed in terms of polystyrene at >=0.1 and <=5 wt.% concentration in an organic solvent and has <=10,000 ppm (wt.) sum total of the amount of the poor solvent in the solution measured by using the gas chromatography.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymeric fluorescent substance and a polymeric light emitting device (hereinafter sometimes referred to as polymeric LED) using the same.

[0002]

2. Description of the Related Art A high molecular weight light emitting material (polymer fluorescent substance) is different from that of a low molecular weight type and is soluble in a solvent, so that a light emitting layer in a light emitting device can be formed by a coating method. (P-phenylene vinylene)
[WO9013148 publication specification, JP-A-3-244
630, Applied Physics Letters (Appl. Phys. Lett. 58, 1982).
Page (1991), Polyfluorene (Japanese Journal of Applied Physics (J
pn. J. Appl. Phys. ) Volume 30, L194
1 (1991)], polyparaphenylene derivatives (Advanced Materials (Adv. Mater.) Vol. 4, p. 36 (1992)) and the like are disclosed.

However, even if a polymeric LED is manufactured using polymeric fluorescent substances having the same structure, the luminous efficiency of the polymeric LED may differ depending on the polymeric fluorescent substance or the polymeric fluorescent substance solution used for coating. There has been a demand for a polymeric fluorescent substance or a polymeric fluorescent substance solution that can more stably achieve higher luminous efficiency when a polymeric LED is used.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymeric fluorescent substance or a polymeric fluorescent substance solution, which can more stably achieve higher luminous efficiency when a polymeric LED is used. A polymer LED and a method for manufacturing the same are provided.

[0005]

Means for Solving the Problems The inventors of the present invention have made earnest studies to achieve the above-mentioned object, and as a result, the polymeric fluorescent substance in which the total amount of the poor solvent contained is a specific amount or less, or the polymeric fluorescent substance Was dissolved in an organic solvent at a specific concentration, and when a polymer LED was produced using a polymer fluorescent substance solution containing a poor solvent in a specific amount or less, it was found that the luminous efficiency was stably high. Invented.

That is, the present invention provides the following [1] to [1]
0]. [1] It has fluorescence in a solid state, has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁷ , and has a total amount of poor solvent contained of 100 measured by a gas chromatography method.
A polymeric fluorescent substance having a concentration of 00 ppm (weight) or less. [2] A polymeric fluorescent substance that has fluorescence in a solid state and has a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁷ is dissolved in an organic solvent at a concentration of 0.1% by weight or more and 5% by weight or less. And the total amount of poor solvents measured by gas chromatography in the solution is 10,000 p.
A polymeric fluorescent substance solution having a pm (weight) or less. [3] Polymer light emission having at least a light emitting layer between a pair of electrodes consisting of an anode and a cathode, at least one of which is transparent or semitransparent, and the light emitting layer using the polymer fluorescent substance of the above [1] element. [4] At least one light emitting layer is provided between a pair of electrodes consisting of an anode and a cathode, at least one of which is transparent or semitransparent, and the light emitting layer is prepared by using the polymeric fluorescent substance solution according to the above [2]. Polymer light emitting device. [5] At least one light emitting layer is provided between electrodes composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent, the light emitting layer has fluorescence in a solid state, and has a polystyrene-equivalent number average molecular weight. A method for producing a polymer light-emitting device containing the polymer fluorescent substance of 10 ³ to 10 ⁷ , wherein the light emitting layer is formed using a solution prepared by dissolving the polymer fluorescent substance of [1] above in an organic solvent. A method for manufacturing a polymer light-emitting device, which comprises the step of forming. [6] At least a light emitting layer is provided between an electrode composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent, the light emitting layer has fluorescence in a solid state, and has a polystyrene-equivalent number average molecular weight. A method for producing a polymer light-emitting device containing the polymer phosphor of 10 ³ to 10 ⁷ , comprising the step of forming the light-emitting layer using the polymer phosphor solution according to [2] above. Manufacturing method. [7] A planar light source using the polymer light emitting device according to the above [3] or [4]. [8] A segment display device using the polymer light emitting device according to the above [3] or [4].

[9] A dot matrix display device using the polymer light emitting device according to the above [3] or [4]. [10] A liquid crystal display device using the polymer light emitting device according to the above [3] or [4] as a backlight.

[0007]

[Here, Ar ₁ is an arylene group or a divalent heterocyclic compound group, and the arylene group or the divalent heterocyclic compound group may have one or more substituents. Further, R ₁ and R ₂ each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic compound group and a cyano group. The group may have one or more substituents. n is 0 or 1. ]

The total of the repeating units represented by the above formula (1) is usually 10 mol% or more and 100 mol% or more of all the repeating units.
It is below, but depending on the structure of the repeating unit, it is preferably 50 mol% or more and 100 mol% or less.

In the polymeric fluorescent substance of the present invention, the total amount of the poor solvent contained measured by a gas chromatography method is 10000 ppm (weight) or less, and 5000 ppm.
It is preferably less than (weight), more preferably 35
It is not more than 00 ppm (weight). Further, the lower limit of the amount of the poor solvent contained is not particularly limited, but 100 ppm or more is preferable from the viewpoint of the labor of removing the poor solvent. In the gas chromatography method, the amount of the poor solvent contained in the polymeric fluorescent substance is determined by dissolving the polymeric fluorescent substance in a high-purity solvent whose content of impurities has been measured in advance to prepare a solution. Can be determined by subjecting it to a gas chromatographic analysis. The poor solvent is a solvent having a small ability to dissolve the polymeric fluorescent substance, and examples thereof include alcohol. Among alcohols, methanol, ethanol and 2-propanol can be mentioned.

As a method for reducing the poor solvent contained in the polymeric fluorescent substance, various methods can be adopted in each step such as taking out, washing, and drying during the production of the polymeric fluorescent substance. For example, at the time of production, a method of synthesizing the polymeric fluorescent substance and then taking it out using a solvent that easily volatilizes at the time of taking out may be considered. Further, as a cleaning method, a method of cleaning the polymeric fluorescent substance using a solvent that easily volatilizes can be considered. Further, as the drying method, heat drying, reduced pressure or vacuum drying, and further combinations thereof can be considered.

In the above formula (1), Ar ₁ is an arylene group or a divalent heterocyclic compound group. Further, the arylene group and the divalent heterocyclic compound group may have one or more substituents.

In the present invention, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon.
Here, the aromatic hydrocarbon is a hydrocarbon that is a base of an aromatic compound and is a hydrocarbon containing a benzene ring,
Those having a condensed ring, and those having an independent benzene ring or a condensed ring directly or through a group such as vinylene are included.

The arylene group usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, and has a phenylene group (for example, formulas 1 to 3 in the following figure) and a naphthalenediyl group (formulas 4 to 1 in the following figure).
3), anthracenylene group (formulas 14 to 19 in the figure below), biphenylene group (formulas 20 to 25 in the figure below), terphenylene group (formulas 26 to 28 in the figure below), condensed ring compound group (formulas 29 to 38 in the figure below) and the like. Is exemplified. The carbon number of the arylene group does not include the carbon number of the substituent.

[0014]

[0015]

[0016]

[0017]

[0018]

In the present invention, the divalent heterocyclic compound group means an atomic group remaining after removing two hydrogen atoms from the heterocyclic compound and has a carbon number of usually 4 to 60, preferably 4 to 2.
It is 0. The carbon number of the divalent heterocyclic compound group does not include the carbon number of the substituent. Here, the heterocyclic compound is
Among organic compounds having a cyclic structure, it means that the element constituting the ring contains not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring.

Examples of the divalent heterocyclic compound group include the following. A divalent heterocyclic compound group containing nitrogen as a hetero atom; a pyridine-diyl group (formulas 39 to 44 in the following figure), a diazaphenylene group (formulas 45 to 4 in the following figure)
8), a quinolinediyl group (formulas 49 to 63 in the following figure), a quinoxalinediyl group (formulas 64 to 68 in the following figure), an acridinediyl group (formulas 69 to 72 in the following figure), a bipyridyldiyl group (formulas 73 to 75 in the following figure), Phenanthrolinediyl group (formula 76 to 78 in the following figure), and the like. A group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom and having a fluorene structure (formula 79 to 93 in the following figure). A 5-membered heterocyclic compound group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a hetero atom: (Formulas 94 to 100 in the following figure). 5-membered condensed heterocyclic compound group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom: (Formulas 101 to 11 in the following figure)
0) can be mentioned. A 5-membered heterocyclic compound group containing silicon, nitrogen, sulfur, selenium or the like as a hetero atom, which is bonded to the hetero atom at the α-position to form a dimer or oligomer: (Formulas 111 to 112 in the following figure) Is mentioned. A 5-membered ring heterocyclic compound group containing silicon, nitrogen, sulfur, selenium or the like as a hetero atom, which is bonded to a phenyl group at the α-position of the hetero atom: (formulae 113 to 119 in the following figure).

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

Here, R is independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl. A group selected from the group consisting of a group, an arylalkynyl group, an arylamino group, a heterocyclic compound group and a cyano group. In the above example, although a plurality of Rs are included in one structural formula, they may be the same or different groups, and they are independently selected. When Ar ₁ has a plurality of substituents, they may be the same or different. In order to improve the solubility in a solvent, it is preferable to have one or more substituents, and it is preferable that the shape of the repeating unit including the substituents has little symmetry.

The alkyl group may be linear, branched or cyclic, and 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,
Examples thereof include an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a 3,7-dimethyloctyl group and a lauryl group, and a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, 3,7- A dimethyloctyl group is preferred.

The alkoxy group may be linear, branched or cyclic and has a carbon number of 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, hexyloxy group, cyclohexyloxy group, heptyloxy group,
Examples thereof include an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group and a lauryloxy group, and a pentyloxy group, a hexyloxy group, an octyloxy group, 2
-Ethylhexyloxy group, decyloxy group, 3,7-
A dimethyloctyloxy group is preferred.

The alkylthio group may be linear, branched or cyclic, and the carbon number 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, cyclohexylthio group, heptylthio group,
Octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group and the like, pentylthio group,
Hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group and 3,7-dimethyloctylthio group are preferable.

The alkylsilyl group may be linear, branched or cyclic and has a carbon number of usually about 1 to 60. Specifically, a methylsilyl group, an ethylsilyl group, a propylsilyl group and an i-propylsilyl group. , Butylsilyl group, i-butylsilyl group, t-butylsilyl group, pentylsilyl group, hexylsilyl group, cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7- Dimethyloctylsilyl group, laurylsilyl group, trimethylsilyl group, ethyldimethylsilyl group,
Propyldimethylsilyl group, i-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group Group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group and the like, pentylsilyl group, hexylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, Decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2
-Ethylhexyl-dimethylsilyl group, decyldimethylsilyl group, and 3,7-dimethyloctyl-dimethylsilyl group are preferable.

The alkylamino group may be linear, branched or cyclic, may be a monoalkylamino group or a dialkylamino group, and has a carbon number of usually about 1 to 40. Specifically, a methylamino group, Dimethylamino group,
Ethylamino group, diethylamino group, propylamino group, i-propylamino 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-
Examples thereof include a dimethyloctylamino group and a laurylamino group, and a pentylamino group, a hexylamino group, an octylamino group, a 2-ethylhexylamino group, a decylamino group, and a 3,7-dimethyloctylamino group are preferable.

The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon and usually has 6 to 60 carbon atoms.
And specifically, a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (wherein C _{1 to} C ₁₂ have ₁ to ₁₂ carbon atoms, and the same shall apply hereinafter), C ₁ to. Examples include a C ₁₂ alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a C ₁ -C ₁₂ alkoxyphenyl group, a C _1-
A C ₁₂ alkylphenyl group is preferred.

The aryloxy group usually has 6 to 6 carbon atoms.
0, specifically, a phenoxy group, C _{1 to} C ₁₂
Examples thereof include an alkoxyphenoxy group, a C _{1 to} C ₁₂ alkylphenoxy group, a 1-naphthyloxy group and a 2-naphthyloxy group, and a C _{1 to} C ₁₂ alkoxyphenoxy group,
C ₁ -C ₁₂ alkylphenoxy group are preferable.

The arylalkyl group usually has 7 to 7 carbon atoms.
It is about 60, specifically, a phenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group. 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
_{A 12} alkylphenyl-C ₁ -C ₁₂ alkyl group is preferred.

The arylalkoxy group usually has 7 carbon atoms.
To about 60, specifically, phenyl-C _{1 to} C ₁₂
Alkoxy group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C
₁₂ alkoxy groups, C ₁ -C ₁₂ alkylphenyl-C ₁ -C
₁₂ alkoxy group, 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ ~C ₁₂ Alkylphenyl-C ₁ -C ₁₂ alkoxy groups are preferred.

The arylamino group usually has 6 to 6 carbon atoms.
It is about 0, and is a phenylamino group, a diphenylamino group, a C _{1 to} C ₁₂ alkoxyphenylamino group, a di(C ₁ to
C ₁₂ alkoxyphenyl)amino group, di(C ₁ -C ₁₂ alkylphenyl)amino group, 1-naphthylamino group, 2
Examples thereof include a naphthylamino group, and a C _{1 to} C ₁₂ alkylphenylamino group and a di(C _{1 to} C ₁₂ alkylphenyl)amino group are preferable.

The monovalent heterocyclic compound group means an atomic group remaining after removing one hydrogen atom from the heterocyclic compound, and the number of carbon atoms is usually about 4 to 60. Specifically, a thienyl group,
Examples thereof include a C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group, and the like. A thienyl group, a C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, C ₁ -C _{A 12} alkylpyridyl group is preferred.

Among the examples of R, in the substituent containing an alkyl chain, they may be linear, branched or cyclic, or a combination thereof, and when they are not linear, for example, an isoamyl group. , 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group,
Examples include 4-C ₁ -C ₁₂ alkylcyclohexyl groups. In order to enhance the solubility of the polymeric fluorescent substance in a solvent, it is preferable that one or more of the substituents of Ar ₁ contain a cyclic or branched alkyl chain. Further, a part of carbon atoms of the alkyl chain may be replaced with a hetero atom, and examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom. Furthermore, R
In the above examples, when an aryl group or a heterocyclic compound group is included in a part thereof, they may further have one or more substituents.

In the above formula (1), n is 0 or 1.

R ₁ and R ₂ in the above formula (1) each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic compound group and a cyano group.

The case where R ₁ and R ₂ are a hydrogen atom or a substituent other than a cyano group will be described.
It may be linear, branched or cyclic, and the carbon number is usually about 1 to 20, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Examples thereof include a heptyl group, an octyl group, a nonyl group, a decyl group and a lauryl group, and a methyl group, an ethyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group are preferable.

The aryl group usually has about 6 to 60 carbon atoms, specifically, a phenyl group and a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ have ₁ to ₁₂ carbon atoms. The same shall apply to the following.), C ₁ -C ₁₂ alkylphenyl groups, 1-naphthyl groups, 2-naphthyl groups, etc. are exemplified, and C ₁ -C ₁₂ alkoxyphenyl groups, C ₁ -C ₁₂
Alkylphenyl groups are preferred.

The monovalent heterocyclic compound group usually has 4 carbon atoms.
To about 60, specifically, a thienyl group, C _{1 to} C
Examples thereof include a ₁₂ alkylthienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C _{1 to} C ₁₂ alkylpyridyl group,
A thienyl group, a C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group and a C ₁ -C ₁₂ alkylpyridyl group are preferred.

In addition, the end groups of the polymeric fluorescent substance are protected by stable groups, because if the polymerization active groups remain as they are, the emission characteristics and life of the device may be reduced. Is also good. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure bonded to an aryl group or a heterocyclic compound group via a vinylene group. Specific examples thereof include the substituents described in Chemical formula 10 in JP-A-9-45478. The polymeric fluorescent substance has a number average molecular weight of 10 ³ to 1 in terms of polystyrene.
0 ^7, their degree of polymerization will vary depending repeating structure and rate. From the viewpoint of film-forming property, the total number of repeating structures is preferably 20 to 10,000, more preferably 30 to 10,000, and particularly preferably 50 to 5.
It is 000.

In the present invention, as a method for synthesizing the polymeric fluorescent substance, when the main chain has a vinylene group, for example, the method described in JP-A-5-202355 can be mentioned. That is, polymerization of a dialdehyde compound and a diphosphonium salt compound and Horner-Wadsworth-Emm of a dialdehyde compound and a diphosphate ester compound.
polymerization by Wittig reaction such as polymerization by ons method, polymerization by Heck reaction of divinyl compound and dihalogen compound or vinyl halogen compound alone,
Polycondensation of a compound having two halogenated methyl groups by the dehydrohalogenation method, polycondensation of a compound having two sulfonium bases by a sulfonium salt decomposition method, Knoeven of a dialdehyde compound and a diacetonitrile compound
A method such as polymerization by agel reaction is exemplified. Of these, disclosed in JP-A-3-244630,
Polymerization by the Wittig reaction, polycondensation by the dehydrohalogenation method, and polycondensation by the sulfonium salt decomposition method are easy to carry out.

When the main chain does not have a vinylene group, for example, a method of polymerizing the corresponding monomer by Suzuki coupling reaction, a method of polymerizing by Grignard reaction, a method of polymerizing by Ni(0) catalyst, FeCl ₃ Examples of the method include a method of polymerizing with an oxidizing agent such as, an electrochemical method of oxidative polymerization, and a method of decomposing an intermediate polymer having a suitable leaving group.

The polymeric fluorescent substance may contain a repeating unit other than the repeating unit represented by the formula (1) as long as the fluorescent property and the charge transporting property are not impaired. Further, the repeating unit represented by the formula (1) or another repeating unit may be linked by a non-conjugated unit, or the non-conjugated portion thereof may be contained in the repeating unit. Examples of the bond structure include those shown below, combinations of the following with vinylene groups, and combinations of two or more of the following. Here, R is a group selected from the same substituents as those described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

[0052]

Further, the polymeric fluorescent substance may be a random, block or graft copolymer, or a polymer having an intermediate structure between them, for example, a random copolymer having a block property. May be. From the viewpoint of obtaining a polymeric fluorescent substance having a high fluorescence quantum yield, a random copolymer having a block property or a block or graft copolymer is preferable to a completely random copolymer. It also includes a case where the main chain is branched and has three or more terminal portions, and a dendrimer.

Further, since the light emission from the thin film is utilized, the polymeric fluorescent substance which has fluorescence in the solid state is preferably used.

When these polymeric fluorescent substances are used as a light emitting material for a polymeric LED, the purity thereof affects the light emitting characteristics. Therefore, the monomer before polymerization is purified by a method such as distillation, sublimation purification and recrystallization. Is preferably polymerized into
Further, after the synthesis, it is preferable to carry out purification treatment such as reprecipitation purification and fractionation by chromatography.

Next, the polymeric fluorescent substance solution of the present invention will be described. The polymeric fluorescent substance solution of the present invention has fluorescence in a solid state and has a polystyrene-equivalent number average molecular weight of 10 ³ to 1
The polymeric fluorescent substance is 0 ^7, in an organic solvent, a solution prepared by dissolving at a concentration of less than 5 wt% 0.1 wt%, was measured by gas chromatography in the solution,
The total amount of the poor solvent is 10000 ppm (weight) or less, preferably 5000 ppm (weight) or less, more preferably 3
It is characterized in that it is 500 ppm (weight) or less.

Above all, it is preferable that the high fluorescent substance contains at least one repeating unit represented by the above formula (1). The total of the repeating units represented by the above formula (1) is usually 10 mol% or more and 100 mol% or less of all the repeating units, and depending on the structure of the repeating units, 50 mol%
It is preferably 100 mol% or more.

Organic solvents used for dissolving the polymeric fluorescent substance include chloroform, methylene chloride, dichloroethane,
Tetrahydrofuran, toluene, xylene, mesitylene, decalin, n-butylbenzene and tetramethylbenzene are preferable, and toluene, xylene and chloroform are more preferable. The polymeric fluorescent substance is usually added to these solvents in an amount of 0.
It can be dissolved by 1% by weight or more. The amount of the poor solvent in the polymeric fluorescent substance solution of the present invention can be measured by a gas chromatography method. In the polymeric fluorescent substance solution of the present invention, the amount of the poor solvent is 10,000 ppm (weight).
Those produced by dissolving the polymeric fluorescent substance in the following organic solvents are preferable.

As a method for obtaining the polymeric fluorescent substance solution of the present invention, the amount of the poor solvent in the solution is 10,000 ppm (weight).
The method is not particularly limited as long as it is the following method. For example, the amount of the poor solvent of the polymeric fluorescent substance solution is 10,000 in advance.
Examples include a method in which a polymeric fluorescent substance solution is prepared by mixing a polymeric fluorescent substance in which a poor solvent is adjusted to be ppm to a solvent and a solvent. Above all, it is preferable to use an organic solvent in which the amount of the poor solvent is 10,000 ppm or less, and it is more preferable to use a method in which the polymeric fluorescent substance of the present invention and an organic solvent in which the amount of the poor solvent is 10,000 ppm (weight) or less are used.

Next, the polymer LED of the present invention will be described. The structure of the polymer LED of the present invention is a polymer LED having a light emitting layer between a pair of an anode and a cathode, at least one of which is transparent or semitransparent, and the light emitting layer is the polymer fluorescent substance of the present invention. Alternatively, it is necessary to use a polymeric fluorescent substance solution. As the polymer LED of the present invention, a polymer LED having an electron transport layer provided between a cathode and a light emitting layer, a polymer LED having a hole transport layer provided between an anode and a light emitting layer, Examples thereof include a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer. For example, specifically, the following structures a) to d) are exemplified. a) Anode/light emitting layer/cathode b) Anode/hole transport layer/light emitting layer/cathode c) Anode/light emitting layer/electron transporting layer/cathode d) Anode/hole transporting layer/light emitting layer/electron transporting layer/cathode (Here, / means that each layer is laminated adjacently. The same applies hereinafter.)

Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a function of transporting electrons. Is a layer having. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The light emitting layer, the hole transporting layer and the electron transporting layer may be independently used in two or more layers.

Of the charge transport layer provided adjacent to the electrode, it has a function of improving the efficiency of charge injection from the electrode,
Those having an effect of lowering the driving voltage of the element are generally called a charge injection layer (hole injection layer, electron injection layer) in general.

Further, in order to improve the adhesion to the electrode and the charge injection from the electrode, the above-mentioned charge injection layer or an insulating layer having a film thickness of 2 nm or less may be provided adjacent to the electrode.
A thin buffer layer may be inserted at the interface of the charge transport layer or the light emitting layer in order to improve the adhesion at the interface, prevent mixing, and the like. The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of luminous efficiency and device life.

In the present invention, the polymer LED provided with the charge injection layer (electron injection layer, hole injection layer) is a polymer LED provided with the charge injection layer adjacent to the cathode and the charge adjacent to the anode. An example is a polymer LED provided with an injection layer.
For example, the following structures e) to p) are specifically mentioned. e) Anode/charge injection layer/light emitting layer/cathode f) Anode/light emitting layer/charge injection layer/cathode g) Anode/charge injection layer/light emitting layer/charge injection layer/cathode h) Anode/charge injection layer/hole Transport layer/light emitting layer/cathode i) Anode/hole transport layer/light emitting layer/charge injection layer/cathode j) Anode/charge injection layer/hole transport layer/light emitting layer/charge injection layer/cathode k) Anode/charge Injection layer/light emitting layer/electron transport layer/cathode l) anode/light emitting layer/electron transport layer/charge injection layer/cathode m) anode/charge injection layer/light emitting layer/electron transport layer/charge injection layer/cathode n) anode /Charge injection layer/hole transport layer/light emitting layer/electron transport layer/cathode o) anode/hole transport layer/light emitting layer/electron transport layer/charge injection layer/cathode p) anode/charge injection layer/hole transport Layer/light-emitting layer/electron transport layer/charge injection layer/cathode

As a specific example of the charge injection layer, a layer containing a conductive polymer, provided between the anode and the hole transport layer,
A layer containing a material having an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer, provided between the cathode and the electron transport layer, and included in the cathode material and the electron transport layer. Examples thereof include a layer including a material having an electron affinity that is an intermediate value with respect to the electron transport material.

When the charge injection layer is a layer containing a conductive polymer, the electric conductivity of the conductive polymer is 10 ⁻⁵ S/cm.
It is preferably 10 ³ or more and 10 ³ or less, and 10 ⁻⁵ S/cm or more 1 in order to reduce the leak current between the light emitting pixels.
0 ² or less is more preferable, and 10 ⁻⁵ S/cm or more and 10 ¹ or less is further preferable. Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S/cm or more and 10 ³ or less, the conductive polymer is doped with an appropriate amount of ions.

The types of ions to be doped are anions for the hole injection layer and cations for the electron injection layer.
Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion, and the like, and examples of the cation include lithium ion, sodium ion, potassium ion, tetrabutylammonium ion, and the like. The thickness of the charge injection layer is, for example, 1 nm to 100 nm, preferably 2 nm to 50 nm.

The material used for the charge 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, polyphenylenevinylene and its derivatives, polythienylenevinylene and its derivatives. Examples include conductive polymers such as derivatives, metal phthalocyanines (copper phthalocyanine, etc.), carbon, and the like.

The insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material of the insulating layer include metal fluorides, metal oxides, organic insulating materials, and the like. Polymer LE with an insulating layer having a thickness of 2 nm or less
Examples of D include a polymer LED in which an insulating layer having a film thickness of 2 nm or less is provided adjacent to a cathode, and a polymer LED in which an insulating layer having a film thickness of 2 nm or less is provided adjacent to an anode.

Specific examples include the following structures q) to ab). q) Anode/insulating layer having a thickness of 2 nm or less/light emitting layer/cathode r) Anode/light emitting layer/insulating layer having a thickness of 2 nm or less/cathode s) Anode/insulating layer having a thickness of 2 nm or less/light emitting layer/thickness 2n
m or less insulating layer/cathode t) Anode/insulating layer with a thickness of 2 nm or less/hole transport layer/light emitting layer/cathode u) Anode/hole transport layer/light emitting layer/insulating layer with a thickness of 2 nm or less/cathode v ) Anode/insulating layer with a thickness of 2 nm or less/hole transport layer/light emitting layer/insulating layer with a thickness of 2 nm or less/cathode w) Anode/insulating layer with a thickness of 2 nm or less/light emitting layer/electron transport layer/cathode x) Anode/light-emitting layer/electron transport layer/insulating layer with a thickness of 2 nm or less/cathode y) Anode/insulating layer with a thickness of 2 nm or less/light-emitting layer/electron transport layer/insulating layer with a thickness of 2 nm/cathode z) anode/ Insulating layer having a thickness of 2 nm or less/hole transport layer/light emitting layer/electron transport layer/cathode aa) anode/hole transport layer/light emitting layer/electron transport layer/thickness 2n
m or less insulating layer/cathode ab) Anode/insulating layer having a thickness of 2 nm or less/hole transporting layer/light emitting layer/electron transporting layer/insulating layer having a thickness of 2 nm or less/cathode

When a polymer LED is used to form a film from a solution by using these polymer solvent-soluble polymer fluorescent substances, it is sufficient to remove the solvent by coating and drying the solution. The same method can be applied when a transport material and a light emitting material are mixed, which is very advantageous in manufacturing. As a film forming method from a solution, a spin coating method, a casting method, a microgravure coating method,
Coating methods such as 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, a flexographic printing method, an offset printing method and an inkjet printing method can be used.

The film thickness of the light emitting layer varies depending on the material used, and may be selected so that the driving voltage and the light emitting efficiency have appropriate values. For example, it is 1 nm to 1 μm, preferably 2 nm to 500 nm. And more preferably 5 nm to 200 nm.

In the polymer LED of the present invention, a light emitting material other than the above polymer phosphor may be used for the light emitting layer,
You may mix and use them. Further, in the polymer LED of the present invention, a light emitting material other than the above polymer phosphor may be mixed and used in the light emitting layer. Known materials can be used as the light emitting material. Examples of low-molecular compounds include naphthalene derivatives, anthracene or its derivatives, perylene or its derivatives, polymethine-based, xanthene-based, coumarin-based, cyanine-based dyes, 8-
A metal complex of hydroxyquinoline or a derivative thereof, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used. In particular,
For example, JP-A-57-51781 and 59-19439.
Known materials such as those described in Japanese Patent No. 3 can be used.

When the polymer LED of the present invention has a hole transport layer, the hole transport material used is polyvinylcarbazole or its derivative, polysilane or its derivative, and polysiloxane derivative having an aromatic amine in the side chain. , A pyrazoline derivative, an arylamine derivative,
Examples thereof include stilbene derivatives, triphenyldiamine derivatives, polyaniline or its derivatives, polythiophene or its derivatives, poly(p-phenylene vinylene) or its derivatives, or poly(2,5-thienylene vinylene) or its derivatives.

Specifically, as the hole transport material, there are disclosed in Japanese Patent Laid-Open Nos. 63-70257, 63-175860, 2-135359 and 2-13536.
No. 1, gazette 2-209988 gazette, and gazette 3-3799.
Examples include those described in Japanese Patent Publication No. 2 and Japanese Patent Publication No. 3-152184.

Among these, as a hole transport material used in the hole transport layer, polyvinylcarbazole or its derivative, polysilane or its derivative, polysiloxane derivative having an aromatic amine compound group in the side chain or main chain, polyaniline or Derivatives thereof, polythiophene or derivatives thereof, poly(p-phenylene vinylene)
Alternatively, a polymer hole transport material such as a derivative thereof, poly(2,5-thienylenevinylene) or a derivative thereof is preferable, and more preferably polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof,
It is a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low molecular weight hole transport material, it is preferable to use it by dispersing it in a polymer binder.

Polyvinylcarbazole or a derivative thereof can be obtained, for example, from a vinyl monomer by cationic polymerization or radical polymerization.

As the polysilane or its derivative,
Chemical Review (Chem. Rev.) Vol. 89,
1359 (1989), British Patent GB230019
The compounds and the like described in No. 6 publication are exemplified. As the synthetic method, the methods described therein can be used, but the Kipping method is particularly preferably used.

Since polysiloxane or its derivative has almost no hole transporting property in the siloxane skeleton structure,
Those having the structure of the above-mentioned low molecular weight hole transport material in the side chain or the main chain are preferably used. Particularly, those having a hole-transporting aromatic amine in the side chain or main chain are exemplified.

The method for forming the hole transport layer is not limited,
For the low molecular weight hole transport material, a method of forming a film from a mixed solution with a polymer binder is exemplified. For the polymer hole transport material, a method of forming a film from a solution is exemplified.

The solvent used for film formation from the solution is not particularly limited as long as it dissolves the hole transport material.
As the solvent, chlorine-based solvents such as chloroform, methylene chloride and dichloroethane, ether-based solvents such as tetrahydrofuran, aromatic hydrocarbon-based solvents such as toluene and xylene, ketone-based solvents such as acetone and methyl ethyl ketone,
Ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate are exemplified.

As a film forming method from a solution, a spin coating method from a solution, 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. Method, screen printing method, flexo printing method,
A coating method such as an offset printing method or an inkjet printing method can be used.

As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption for visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

The film thickness of the hole transport layer varies depending on the material used, and may be selected so that the driving voltage and the luminous efficiency have appropriate values, but at least a thickness that does not cause pinholes. Is necessary, and if it is too thick,
This is not preferable because the driving voltage of the element becomes high. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

When the polymer LED of the present invention has an electron-transporting layer, known electron-transporting materials can be used, including an oxadiazole derivative, anthraquinodimethane or its derivative, benzoquinone or its derivative, Examples thereof include naphthoquinone or its derivative, anthraquinone or its derivative, tetracyanoanthraquinodimethane or its derivative, fluorenone derivative, diphenyldicyanoethylene or its derivative, diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or its derivative.

Concretely, JP-A-63-70257, JP-A-63-175860, and JP-A-2-1353.
No. 59, No. 2-135361, No. 2-209.
No. 988, No. 3-37992, and No. 3-152.
Examples include those described in Japanese Patent No. 184.

Of these, oxadiazole derivatives,
A metal complex of benzoquinone or a derivative thereof, anthraquinone or a derivative thereof, or 8-hydroxyquinoline or a derivative thereof is preferable, and 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,3 is preferable.
4-Oxadiazole, benzoquinone, anthraquinone and tris(8-quinolinol)aluminum are more preferable.

The method for forming the electron transport layer is not particularly limited, but for low molecular weight electron transport materials, the vacuum deposition method from powder or the method by film formation from a solution or a molten state is used as a polymer electron transport material. Then, a method of forming a film from a solution or a molten state is exemplified. When forming a film from a solution or a molten state, a polymer binder may be used together.

The solvent used for film formation from the solution is not particularly limited as long as it can dissolve the electron transport material and/or the polymer binder. As the solvent, chlorine-based solvents such as chloroform, methylene chloride and dichloroethane, ether-based solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone-based solvents such as acetone and methyl ethyl ketone, ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

The film formation method from a solution or a molten state includes spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating. A coating method such as a method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method or the like can be used.

As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption for visible light are suitably used. As the polymer binder, poly(N-vinylcarbazole), polyaniline or its derivative, polythiophene or its derivative, poly(p-phenylene vinylene) or its derivative, poly(2,5-thienylene vinylene) or its derivative, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the driving voltage and the light emission efficiency have appropriate values. Is necessary, and if it is too thick,
This is not preferable because the driving voltage of the element becomes high. Therefore, the film thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

The substrate for forming the polymer LED of the present invention is
An electrode is formed, a layer made of a conductive polymer is formed by coating, and any material that does not change during electrolytic doping,
For example, glass, plastic, polymer film, silicon substrate, etc. are exemplified. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

In the present invention, the anode side is preferably transparent or semitransparent, but as the material of the anode, a conductive metal oxide film, a semitransparent metal thin film or the like is used. Specifically, a film (NESA) formed using a conductive glass made of indium oxide, zinc oxide, tin oxide, and a composite material thereof such as indium tin oxide (ITO) and indium zinc oxide.
Etc.), gold, platinum, silver, copper, etc. are used, and ITO, indium/zinc/oxide, and tin oxide are preferable. Examples of the manufacturing method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a plating method and the like. Also,
As the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used. The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1
μm, and more preferably 50 nm to 500 nm. In addition, on the anode, in order to facilitate charge injection,
A layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like and having an average film thickness of 2 nm or less may be provided.

As the material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example,
Lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium,
Metals such as samarium, europium, terbium, ytterbium, and alloys of two or more of them, or one or more of them with gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten,
Alloys with one or more of tin, graphite or graphite intercalation compounds, etc. are used. Examples of alloys include
Magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-
Aluminum alloy etc. are mentioned. The cathode may have a laminated structure of two or more layers. The film thickness of the cathode can be appropriately selected in consideration of electrical conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1
μm, and more preferably 50 nm to 500 nm.

As a method for producing the cathode, a vacuum vapor deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. In addition, a layer made of a conductive polymer or a layer having an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic layer. A protective layer for protecting the polymer LED may be attached. In order to stably use the polymer LED for a long term, it is preferable to attach a protective layer and/or a protective cover in order to protect the device from the outside.

As the protective layer, polymer compounds, metal oxides, metal fluorides, metal borides and the like can be used. Further, as the protective cover, a glass plate, a plastic plate whose surface has been subjected to low water permeability treatment, or the like can be used, and a method in which the cover is bonded to the element substrate with a heat-effect resin or a photocurable resin and sealed is preferable Used for. If the space is maintained by using the spacer, it is easy to prevent the element from being scratched. If an inert gas such as nitrogen or argon is filled in the space, oxidation of the cathode can be prevented. Further, by installing a desiccant such as barium oxide in the space, moisture adsorbed in the manufacturing process can be prevented. It becomes easy to suppress that the element gives an image. It is preferable to take any one or more of these measures.

The method for producing a polymer LED of the present invention has at least a light emitting layer between electrodes composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent, and the light emitting layer is fluorescent in a solid state. A method for producing a polymeric light emitting device comprising a polymeric fluorescent substance having a polystyrene-reduced number average molecular weight of 10 ³ to 10 ^7, which is prepared by dissolving the polymeric fluorescent substance of the present invention in an organic solvent. The method is characterized by including the step of forming the light emitting layer using the above solution.

The method for producing a polymer LED of the present invention has at least a light emitting layer between electrodes composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent, and the light emitting layer is in a solid state. A method for producing a polymeric light emitting device comprising a polymeric fluorescent substance having fluorescence and having a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁷ , wherein the polymeric fluorescent substance solution of the present invention is used to form the light emitting layer. It is characterized by including the process of forming. In the method for producing a polymer LED of the present invention,
The high fluorescent substance contains 1 repeating unit represented by the formula (1).
It is preferable to include one or more kinds.

In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. Further, in order to obtain a patterned light emission, a method of providing a mask having a patterned window on the surface of the planar light emitting element, an organic layer of a non-light emitting portion is formed to be extremely thick and There is a method of emitting light, a method of forming either one of the anode or the cathode, or both electrodes in a pattern. Further, in order to form a dot matrix device, both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors or a method of using a color filter or a fluorescence conversion filter. The dot matrix device can be driven passively, and
Active driving may be performed in combination with FT or the like. These display elements are used for computers, televisions, mobile terminals,
It can be used as a display device for mobile phones, car navigation systems, video camera viewfinders, and the like. Further, the planar light emitting element is a self-luminous thin type and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar light source for illumination.
Further, if a flexible substrate is used, it can be used as a curved light source or a display device.

[0101]

EXAMPLES Examples will be shown below for illustrating the present invention further in detail, but the present invention is not limited thereto.

Example 1 <Synthesis of polymeric fluorescent substance 1> 1.83 g of 2,5-bis(chloromethyl)-4'-(3,7-dimethyloctyloxy)biphenyl and 2-methyl-5-(3 ,7-Dimethyloctyl)-p-xylylene dibromide 1.63
g and 2-methoxy-5-(2-ethylhexyloxy)
0.244 g of -p-xylylene dichloride was dissolved in 660 g of dehydrated 1,4-dioxane. This system was bubbled with nitrogen for 20 minutes to replace the inside of the system with nitrogen, and then heated to 95° C. in a nitrogen atmosphere. To this liquid, in advance, dehydrated 1,4-dioxane 80 g,
A solution in which 4.7 g of potassium-t-butoxide was dissolved was added dropwise over about 10 minutes. After dropping, at 97° C. 2.
Polymerized for 5 hours. After the polymerization, the polymerization solution was cooled to 50° C., and acetic acid was added to neutralize the solution. After cooling to room temperature, this polymerization liquid was poured into 800 g of methanol, and the generated precipitate was recovered. The precipitate was dried under reduced pressure, dissolved in tetrahydrofuran, and poured into methanol for reprecipitation recovery. It was dried under reduced pressure to obtain 1.4 g of a polymer. This polymer is called polymeric fluorescent substance 1. The number average molecular weight of polymeric fluorescent substance 1 was 2×10 ⁵ .

Example 2 A 0.48% (by weight) chloroform solution of polymeric fluorescent substance 1 was prepared and the amount of the poor solvent was measured by a gas chromatography method. As a result, the poor solvent methanol was 12.6 pp.
m (weight) was included. Tetrahydrofuran, which is not a poor solvent, was 6.31 ppm (weight). Since the contents of methanol and tetrahydrofuran in chloroform used were below the detection limit, the polymeric fluorescent substance 1 contained about 2600 ppm (weight) of methanol, which is a poor solvent, and about 1300 ppm (weight) of tetrahydrofuran, which was not a poor solvent.
It was found that it was contained.

Example 3 <Production and Evaluation of Element> 150 nm by sputtering method
To the glass substrate with the ITO film attached at the thickness of
4) Ethylenedioxythiophene/polystyrene sulfonic acid (PEDOT: manufactured by Bayer, Bytron P TP AI 4
The suspension (083) was filtered through a 0.5 μm membrane filter, and then spin-coated to form a film having a thickness of 70 nm, and dried on a hot plate at 120° C. for 10 minutes.
The polymeric fluorescent substance 1 was dissolved in a toluene solvent (Kanto Kagaku EL grade) to prepare a 0.6% solution. The content of methanol, which is a poor solvent, in this polymeric fluorescent substance solution was 16 ppm. Using the solution, the above PEDOT
8 by spin coating on the substrate with ITO film coated with
A light emitting layer was formed to a thickness of 0 nm. Further, this was dried under reduced pressure at 80° C. for 1 hour, and then lithium fluoride corresponding to about 0.4 nm and then 40 n of calcium were used as a cathode.
m, aluminum is further deposited to 70 nm to form polymer L
An ED element was produced. The degree of vacuum during vapor deposition is all 8
It was not more than ×10 ^-6 Torr. When a voltage of 4.0 V was applied to the obtained device, yellow EL light emission was observed. The luminous efficiency at this time was 7.2 cd/A, and the emission spectrum of the device had a peak at 556 nm.

Comparative Example 1 0.2 g of ethanol was added to 10 g of toluene to prepare a toluene solution containing 19600 ppm (weight) of ethanol. The polymeric fluorescent substance 1 is dissolved in this solution,
A 0.6% solution of the polymeric fluorescent substance 1 was prepared. A polymer LED device was produced in the same manner as in Example 3 except that this polymer fluorescent substance solution was used. A voltage of 4.0 is applied to the obtained device.
When V was applied, yellow EL emission was observed. At this time, the emission efficiency was 5.9 cd/A, and the emission spectrum of the device had a peak at 556 nm.

[0106]

Industrial Applicability The polymer LED manufactured by using the polymeric fluorescent substance or the polymeric fluorescent substance solution of the present invention stably has high luminous efficiency. Therefore, the polymer LED can be preferably used for a device such as a curved or planar light source as a backlight, a segment type display element, or a dot matrix flat panel display.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Sasaki 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd. F-term (reference) 3K007 AB03 BA06 BB06 CA01 CB01 DA00 DB03 EB00 FA01 FA03 5C094 AA10 AA21 BA29 CA15 CA19

Claims (20)

[Claims] 1. A solid-state fluorescent substance having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁷ and a total amount of poor solvent contained measured by gas chromatography of 10000 ppm (weight). A polymeric fluorescent substance characterized by the following: 2. A repeating unit represented by the following formula (1) is 1
The polymeric fluorescent substance according to claim 1, wherein the polymeric fluorescent substance comprises at least one kind. -Ar ₁ -(CR ₁ =CR ₂ ) _n -(1) [wherein Ar ₁ is an arylene group or a divalent heterocyclic compound group, and the arylene group or the divalent heterocyclic compound group is 1 It may have one or more substituents. Also R ₁ ,
R ₂ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic compound group and a cyano group, and one aryl group and one monovalent heterocyclic compound group It may have the above substituents. n is 0
Or 1. ] 3. The total amount of poor solvent contained is 5000 pp.
It is less than m (weight), The claim 1 or 2 characterized by the above-mentioned.
The polymeric fluorescent substance described. 4. The polymeric fluorescent substance according to claim 1, wherein the poor solvent contained is alcohol. 5. The polymeric fluorescent substance according to claim 4, wherein the alcohol is selected from the group consisting of methanol, ethanol and 2-propanol. 6. A polymeric fluorescent substance having fluorescence in a solid state and having a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁷ in an organic solvent at a concentration of 0.1% by weight or more and 5% by weight or less. And the total amount of poor solvent measured by gas chromatography in the solution is 1
A polymeric fluorescent substance solution characterized by being 0000 ppm (weight) or less. 7. The polymeric fluorescent substance solution according to claim 6, wherein the high fluorescent substance contains one or more kinds of repeating units represented by the formula (1) of claim 2. 8. The organic solvent is chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene,
1 selected from the group consisting of xylene, mesitylene, decalin, n-butylbenzene and tetramethylbenzene.
8. The polymeric fluorescent substance solution according to claim 6, wherein the polymeric fluorescent substance solution is more than one kind. 9. The polymeric fluorescent substance according to claim 1, which has at least a light emitting layer between an electrode composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent. A polymer light-emitting device comprising a body. 10. The polymeric fluorescent substance according to claim 6, which has at least a light emitting layer between an electrode composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent. A polymer light emitting device, characterized by being prepared using a body solution. 11. The polymer light emitting device according to claim 9, wherein a layer made of an electron transporting compound is provided between the cathode and the light emitting layer adjacent to the light emitting layer. 12. The polymer light emitting device according to claim 9, wherein a layer made of a hole transporting compound is provided between the anode and the light emitting layer adjacent to the light emitting layer. 13. A layer formed of an electron transporting compound between a cathode and a light emitting layer adjacent to the light emitting layer, and a hole transporting property adjacent to the light emitting layer between an anode and the light emitting layer. 11. The polymer light emitting device according to claim 9, further comprising a layer made of a compound. 14. At least one light emitting layer is provided between an electrode composed of a pair of an anode and a cathode, at least one of which is transparent or semi-transparent, and the light emitting layer has fluorescence in a solid state and has a polystyrene equivalent number average. A method for producing a polymer light emitting device comprising a polymer fluorescent substance having a molecular weight of 10 ³ to 10 ⁷ , comprising:
A method for producing a polymer light emitting device, comprising the step of forming the light emitting layer using a solution prepared by dissolving the polymer fluorescent substance according to claim 1 in an organic solvent. 15. At least one light emitting layer is provided between an electrode composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent, and the light emitting layer has fluorescence in a solid state and has a polystyrene equivalent number average. A method for producing a polymer light emitting device comprising a polymer fluorescent substance having a molecular weight of 10 ³ to 10 ⁷ , comprising:
A method for producing a polymer light emitting device, comprising the step of forming the light emitting layer using the polymer fluorescent substance solution according to claim 6. 16. The high phosphor is represented by the formula (1) according to claim 2.
16. The polymeric fluorescent substance solution according to claim 14 or 15, comprising one or more kinds of repeating units represented by. 17. A planar light source using the polymer light emitting device according to claim 9. 18. A segment display device comprising the polymer light emitting device according to claim 9. 19. A dot matrix display device comprising the polymer light emitting device according to claim 9. 20. A liquid crystal display device comprising the polymer light emitting device according to claim 9 as a backlight.