JP2003013055A - Method for producing polymeric fluorophor and polymeric light emitting diode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymeric fluorophor having long service life when used in polymeric LED(light emitting diode). SOLUTION: This method for producing a polymeric fluorophor having fluorescence in a solid state is characterized by comprising the step of treating a polymeric fluorophor having a number-average molecular weight of 1×10<4> to 1×10<8> calculated as polystyrene with an acid. The other version of this method is characterized by comprising the steps of treating a polymeric fluorophor having a number-average molecular weight of 1×10<4> to 1×10<8> calculated as polystyrene with an acid and then treating the resultant polymeric fluorophor with an alkali. The other version of this method is characterized by comprising the steps of treating a polymeric fluorophor having a number- average molecular weight of 1×10<4> to 1×10<8> calculated as polystyrene with an acid and then treating the resultant polymeric fluorophor with an alkali and finally treating the resultant polymeric fluorophor with a substance free from both acid and alkali.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Inorganic electroluminescent devices (hereinafter, sometimes referred to as inorganic EL devices) using an inorganic phosphor as a light emitting material are used for display devices such as a planar light source as a backlight and a flat panel display. However, high voltage AC was required to emit light.

In recent years, an organic electroluminescent element (hereinafter referred to as an organic EL element) having a two-layer structure in which an organic fluorescent dye is used as a light emitting layer and an organic charge transporting compound used for a photoconductor for electrophotography is laminated. Have been reported (Japanese Patent Application Laid-Open No. 59-194393). Compared with inorganic EL elements, organic EL elements are characterized in that they can easily emit light of many colors in addition to low voltage driving and high brightness. Therefore, many organic EL elements have a large number of elements, organic fluorescent dyes, and organic charge transport compounds. Attempts have been reported (Japanese Journal of Applied Physics (Jpn. J. Appl. Phys.) No. 27).
Vol., L269 (1988), Journal of.
Applied Physics (J. Appl. Phy
s. ) Volume 65, page 3610 (1989)).

Further, apart from an organic EL element mainly using a low molecular weight organic compound, a polymer LED using a high molecular weight light emitting material is disclosed in WO 9013148, JP-A-3-244630, Applied. Physics Letters (Appl.Phys.Let
t. ) Vol. 58, p. 1982 (1991) and the like, and in WO 9013148, the soluble precursor is converted into a conjugated polymer by film formation on an electrode and heat treatment. It is described that a poly (p-phenylene vinylene) (hereinafter sometimes referred to as PPV) thin film can be obtained and an element using the same.

Further, Japanese Patent Application Laid-Open No. 3-244630 describes a conjugated polymer having a characteristic that it is soluble in a solvent and does not require heat treatment. Also, Applied Physics Letters (Appl.
Phys. Lett. ) 58, 1982 (199)
1 year) describes a solvent-soluble polymer light-emitting material and a polymer LED made using the same.

Since a polymer LED can easily form an organic layer by coating, it is advantageous in increasing the area and cost as compared with the case of depositing a low-molecular phosphor.
Since it is a polymer, it is considered that the mechanical strength of the film is also excellent.

Conventionally, as polymer fluorescent substances used in these polymer LEDs, in addition to poly (p-phenylene vinylene), polyfluorene (Japanese Journal of Applied Physics (Jpn.
Appl. Phys. ) Volume 30, L1941 (19
91)), polyparaphenylene derivatives (Advanced Materials (Adv. Mater.) Vol. 4, 36.
Page (1992)) and the like are reported. There has been a demand for a method for producing a polymeric fluorescent substance that can further extend the life of the polymeric LED.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a polymeric fluorescent substance which has a long life when used for a polymeric LED, and a long lifetime using the polymeric fluorescent substance obtained by the method. It is to provide a polymer LED.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of such circumstances, and as a result, have found that a polymeric fluorescent substance produced by a production method including a step of treating a polymeric fluorescent substance with an acid is used. It was found that a polymer LED device having a long life can be obtained by using it, and the present invention has been completed. That is, the present invention provides [1] a polymeric fluorescent substance comprising a step of treating a polymeric fluorescent substance which has fluorescence in a solid state and has a polystyrene reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ with an acid. Manufacturing method. Further, the present invention [2] has fluorescence in a solid state,
Number average molecular weight in terms of polystyrene is 1 × 10 ⁴ to 1 × 1
0 ⁸ relates to a method for producing a polymeric fluorescent substance comprising a step a step of treating with an alkali for processing polymeric fluorescent substance with an acid is. The present invention also provides [3] a step of treating a polymeric fluorescent substance having fluorescence in a solid state and having a polystyrene reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ with an acid and a step of treating with an alkali. And finally to a method for producing a polymeric fluorescent substance, which comprises a step of treating with a substance containing no acid or alkali. The present invention also provides [4] a polymer light-emitting device having at least one light-emitting layer containing a polymer fluorescent substance between at least one transparent or semi-transparent electrode consisting of an anode and a cathode. The present invention relates to a polymer light emitting device containing the polymer fluorescent substance manufactured by the manufacturing method of [1] to [3]. Further, the present invention relates to [5] a planar light source using the polymer light emitting device according to [4] above. Next, the present invention relates to [6] a segment display device using the polymer light emitting device according to the above [4]. Next, the present invention relates to [7] a dot matrix display device using the polymer light emitting device according to the above [4]. Further, the present invention relates to [8] a liquid crystal display device using the planar light source according to [4] above as a backlight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing a polymeric fluorescent substance of the present invention and a polymeric LED using the polymeric fluorescent substance produced by the producing method will be described in detail.

The method for producing a polymeric fluorescent substance of the present invention is a polymeric fluorescent substance which has fluorescence in a solid state and has a polystyrene-reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ (Sometimes referred to as molecular fluorophore) is treated with an acid.

The method for producing a polymeric fluorescent substance of the present invention is a polymeric fluorescent substance which has fluorescence in a solid state and has a polystyrene reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ (hereinafter (Sometimes called a molecular fluorescent substance) with an acid and an alkali.

The method for producing a polymeric fluorescent substance of the present invention is a polymeric fluorescent substance which has fluorescence in a solid state and has a polystyrene-reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ (Sometimes called a molecular fluorescent substance) with an acid, with an alkali, and finally with a substance containing no acid or alkali.

First, the step of treating with an acid will be described in detail. In the present invention, the acid may be any organic or inorganic substance that exhibits acidity in any sense, for example, an organic acid,
Inorganic acids and the like. Organic acids are preferable because of high treatment efficiency.

As the organic acid, alkanecarboxylic acid, alkenecarboxylic acid, aromatic carboxylic acid, heterocyclic compound carboxylic acid, aromatic alcohol, alkanesulfonic acid, alkenesulfonic acid, aromatic sulfonic acid, heterocyclic compound sulfonic acid, Alkanesulfinic acid, alkensulfinic acid, aromatic sulfinic acid, heterocyclic compound sulfinic acid,
Alkanesulfenic acid, alkensulfenic acid, aromatic sulfenic acid, heterocyclic compound sulfenic acid, alkanephosphonic acid, alkenphosphonic acid, aromatic phosphonic acid, heterocyclic compound phosphonic acid, alkanephosphenic acid, alkenephosphenic acid, Examples thereof include aromatic phosphenic acid, heterocyclic compound phosphinic acid, alkane phosphinic acid, alkene phosphinic acid, aromatic phosphinic acid, and heterocyclic compound phosphinic acid.

More specifically as the organic acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, tartaric acid, maleic acid, phthalic acid, benzoic acid, 4-pyridinecarboxylic acid,
Phenol, methanesulfonic acid, propenesulfonic acid,
Toluenesulfonic acid, 2-thiophenesulfonic acid, ethanesulfenic acid, 1-butenesulfenic acid, toluenesulfenic acid, 2-thiophensulfenic acid, ethanesulfinic acid, 1-butenesulfinic acid, toluenesulfinic acid, 2-
Thiophensulfinic acid, ethylphosphonic acid, propenephosphonic acid, benzenephosphonic acid, 3-thiophenephosphonic acid, ethylphosphenic acid, propenephosphenic acid, benzenephosphenic acid, 3-thiophenephosphenic acid, ethylphosphinic acid, propenephosphine Acid, benzenephosphinic acid, 3-thiophenephosphinic acid, etc. can be exemplified,
Formic acid, acetic acid, propionic acid, oxalic acid, citric acid and tartaric acid are more preferable, and oxalic acid, citric acid and tartaric acid are further preferable.

Examples of the inorganic acid include hydrohalic acid, sulfur oxide hydrogen acid, phosphorus oxide hydrogen acid, nitrogen oxide hydrogen acid and metal oxide hydrogen acid. Specific examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid,
Chlorous acid, nitrous acid, selenious acid, arsenous acid, phosphorous acid, sulfurous acid, periodic acid, chromic acid, silicic acid, hypochlorous acid, hypophosphorous acid, cyanic acid, selenic acid, thiocyanic acid, Examples thereof include thiosulfuric acid, dichromic acid, diphosphoric acid, vanadic acid, hydrofluoric acid, boric acid and iodic acid, and sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid are preferable. In the step of treating with acid,
A single one of these acids or a mixture of two or more acids can be used.

In the present invention, "the step of treating with an acid" refers to the step of bringing the polymeric fluorescent substance into contact with an acid. As a method for treating the raw polymeric fluorescent substance with an acid,
For example, 1) a method of bringing a raw material polymeric fluorescent substance in a liquid state into contact with an acid in a liquid state 2) a method of bringing a raw material polymeric fluorescent substance in a solid state into contact with a liquid state acid 3) a raw material polymeric fluorescent substance in a liquid state 4) a method of contacting the starting polymeric fluorescent substance in a liquid state with an acid in a gaseous state 5) a method of contacting the starting polymeric fluorescent substance in a solid state with an acid in a gaseous state . Among these, 1) is preferable from the viewpoint of good contact property between the polymeric fluorescent substance and an acid. here,
The liquid state includes a state in which the raw polymeric fluorescent substance is dissolved in a solvent.

In the step of treating with an acid, it is preferable to carry out stirring, shaking or the like in order to enhance the efficiency of treatment. Further, the step of treating with an acid may be included twice or more.
Furthermore, when the step of treating with an acid is performed twice or more, the type and concentration of the acid used at that time may be changed.

Further, the method for producing the polymeric fluorescent substance of the present invention may include a step other than the step of treating with an acid, if necessary. The steps other than the step of treating with an acid include, for example, a step of removing an acid; a step of removing a solvent when a solvent is used; a step of separating a liquid when a solvent for phase separation is used; Examples include a step of purifying by precipitation, chromatography and the like. Among these, it is preferable to include a step of removing an acid and a step of purifying in order to remove unnecessary substances.

The method 1) will be described in more detail. As the method 1), the step of treating the starting polymeric fluorescent substance with an acid is a step of contacting a solution of the acid with a solution of the polymeric fluorescent substance in a solvent. It is preferable because it has high efficiency. The solvent used for the acid solution here may be water or another solvent. On the other hand, it is more preferable that the raw material polymeric fluorescent substance in the liquid state and the acid in the liquid state undergo phase separation because the polymeric fluorescent substance and the acid are easily separated.

Both the raw polymeric fluorescent substance and the acid are dissolved in a solvent to be in a liquid state. As a method of phase-separating them, the acid is dissolved in water to form an aqueous solution of the acid. The starting polymeric fluorescent substance is preferably dissolved in a solvent that is phase-separated from the aqueous acid solution.

The concentration of the aqueous acid solution is not particularly limited, but it is adjusted to about 0.1 to 30% by weight before use. As the acid strength of the aqueous acid solution, it is expected that the polymeric fluorescent substance to be treated will decompose if it is too strong,
An acid aqueous solution having a pH of 0.1 or more and 5.5 or less is preferable, and a pH of 0.5 or more and 4.5 or less is more preferable. At this time, the water used is preferably water containing few impurities such as ions, for example, distilled water, ion-exchanged water, pure water, or ultrapure water. Of these, pure water and ultrapure water are preferable, and ultrapure water is particularly preferable. As a specific index of the purity of pure water, there is conductivity, and water having a value of 10 μS / cm or less is preferable, and water having a conductivity of 1 μS / cm or less is more preferable.

The solvent for dissolving the polymeric fluorescent substance is not particularly limited as long as it is a solvent for dissolving the polymeric fluorescent substance well, and is not particularly limited, but is a chlorinated solvent such as chloroform, methylene chloride, dichloroethane, or an ether such as tetrahydrofuran. System solvent, toluene, xylene, mesitylene, tetralin,
Aromatic hydrocarbon solvents such as decalin and n-butylbenzene are exemplified. Among these, those that are phase-separated from the acid aqueous solution (or water) are preferable, and chloroform, tetrahydrofuran, and toluene are particularly preferable. The temperature of the acid treatment is not particularly limited, and the temperature may be from room temperature to a temperature lower than the boiling point of the solvent, preferably room temperature to 50 ° C.

Next, one example of a method of bringing the aqueous solution of an acid into contact with a solution prepared by dissolving the polymeric fluorescent substance in a solvent that causes a phase separation from the aqueous solution of the acid will be specifically described. First,
The raw material polymeric fluorescent substance is dissolved in a solvent that dissolves the polymeric fluorescent substance well and is phase-separated from the aqueous acid solution (or water), for example, chloroform, and the solution is brought into contact with the aqueous acid solution while stirring (acid Process). And after standing still,
The phase of the aqueous acid solution and the phase containing the polymeric fluorescent substance are separated and separated. The phase including the polymeric fluorescent substance that has been separated and separated is further contacted with an aqueous solution of an acid and treated with the above-mentioned acid, and the process is repeated an appropriate number of times. Then, the phase containing the polymeric fluorescent substance obtained by liquid separation is brought into contact with water to remove the acid remaining in the phase containing the polymeric fluorescent substance. A solution of the polymeric fluorescent substance is obtained by repeating the removal of the acid in the phase containing the polymeric fluorescent substance until the pH of the aqueous phase becomes 7. A precipitate of the polymeric fluorescent substance is generated by dropping the solution into a poor solvent for dissolving the polymeric fluorescent substance, for example, into methanol or the like while stirring. The precipitate is filtered, washed with ethanol, and dried under reduced pressure to obtain a polymeric fluorescent substance.

As the method 2), a liquid acid is mixed with a raw material polymer fluorescent substance in the form of a solid powder without a solvent and treated by a stirring repulp type washing operation, and a solid powder is prepared by dissolving the acid in an organic solvent. The method of mixing with the polymeric fluorescent substance (1) and treating with a stirring repulp type washing operation can be mentioned. When the raw material polymeric fluorescent substance in the form of a solid powder is used according to the present method, the acid and other unnecessary components can be removed from the raw material polymeric fluorescent substance in the solid powder state by treating with an acid and then filtering. Furthermore, the acid remaining in the polymeric fluorescent substance can be removed by an agitation repulp type washing operation with an organic solvent, water, or the like.

Examples of the method 3) include a method of treating the starting polymeric fluorescent substance in a liquid state by passing it through a column filled with an acid in a solid state. The methods 4) and 5) are carried out by bringing a gaseous acid into contact with a liquid polymeric material or a solid polymeric fluorescent substance in a solid state. The gaseous acid used here is an organic compound that exhibits acidity. It means an acid in an inorganic gas state. Specifically, it means hydrogen chloride gas, hydrogen bromide gas, hydrogen fluoride gas, gaseous formic acid, gaseous oxalic acid, gaseous trifluoroacetic acid and the like.

Further, including the step of treating with the above-mentioned acid, the metal contained in the raw polymeric fluorescent material, for example, lithium, sodium, potassium, magnesium, calcium, iron, copper, manganese, aluminum, zinc, nickel, chromium. , Lead, or the like; or base components, such as potassium tert-butoxide or the like, are preferably reduced.

Next, the step of treating with alkali will be described in detail. In the production method of the present invention, in order to uniformly treat with alkali, it is preferable that the solvent is sufficiently dissolved, so that it is preferably a good solvent for the crude polymeric fluorescent substance. The organic solvent is not particularly limited as long as it can dissolve the crude polymeric fluorescent substance, but as a good solvent for the crude polymeric fluorescent substance, chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene,
Examples include xylene, mesitylene, tetralin, decalin, n-butylbenzene, dioxane and the like. Although it depends on the structure and molecular weight of the crude polymeric fluorescent substance, usually 0.1% by weight or more can be dissolved in these solvents.

As the alkali used in the production method of the present invention
Preferably has a pKa value of 10 or more.
As the alkali, metal alkoxide, metal hydroxide,
Metal amide compound, metal hydride compound, ammoni
A, amines. As a metal alkoxide
Is LiOCH₃, NaOCH₃, KOCH₃, LiOC₂
H_Five, NaOC₂H_Five, KOC₂H_Five, LiO (t-C
_FourH₉), NaO (t-C_FourH₉), KO (t-C_FourH₉)
Examples of the metal hydroxide include LiOH and Na.
Examples thereof include OH and KOH. Also, metal amide compounds
As a product, LiNH₂, NaNH₂, KNH₂, LiN
(I-C₃H₇)₂, NaN (i-C₃H₇)₂, KN (i-
C₃H₇)₂And metal hydride compounds
Examples thereof include LiH, NaH and KH. Ami
Examples of the amines include triethylamine, pyridine, 4-dimme
Cylaminopyridine, diazabicycloundecane, etc.
Can be mentioned. Among them, in terms of solubility in organic solvents, L
iO (t-C_FourH₉), NaO (t-C_FourH₉), KO (t
-C_FourH₉), LiN (i-C₃H₇)₂, NaN (i-
C₃H ₇)₂, KN (i-C₃H₇)₂, Ammonia, amine
Classes are preferred. In addition, the fluorescence intensity will be stronger
In this respect, ammonia and triethylamine are more preferable,
It is highly volatile and does not easily remain after treatment.
Monia is particularly preferred.

The method for producing the polymeric fluorescent substance of the present invention includes a step of bringing the crude polymeric fluorescent substance into contact with an alkali. This step may be included twice or more. In the step of bringing the crude polymeric fluorescent substance into contact with the alkali, it is preferable in terms of contact efficiency to bring the crude polymeric fluorescent substance into contact with the alkali in a state of being dissolved in an organic solvent. As a method of contacting with an alkali, (a) a method of adding the alkali as it is to a solution in which the crude polymeric fluorescent substance is dissolved; (b) a solution in which the alkali is dissolved in a solvent to dissolve the crude polymeric fluorescent substance Method of adding; (c) to a solution in which an alkali is dissolved,
A method of adding a solution in which the crude polymeric fluorescent substance is dissolved,
(D) A method of dispersing the crude polymeric fluorescent substance in a solvent in which an alkali is dissolved may be used. Method (b), (c)
The solvent for dissolving the alkali may be an organic solvent or water. When the crude polymeric fluorescent substance is dissolved in an organic solvent, the solvent in which the alkali is dissolved may be a solvent that can be uniformly mixed with the dissolved organic solvent, or a solvent that is not uniformly mixed. Among the organic solvents, the same organic solvent as that in which the crude polymeric fluorescent substance is dissolved is preferable.

In the step of contacting with the alkali, the contact efficiency between the alkali and the polymeric fluorescent substance can be improved by stirring and shaking the solution, if necessary.
The time of contact with the alkali is not particularly limited, but usually 30 minutes or more and 20 minutes or more to obtain a sufficient solubility improving effect.
It is not more than an hour, preferably not less than 1 hour and not more than 20 hours.
The temperature for contact with alkali is usually 10 ° C or higher 2
It is preferably 00 ° C. or lower and not lower than room temperature and lower than the boiling point of the solvent. Depending on the solvent used, 30 ° C or higher 150
℃ or less is practical, more preferably 50 ℃ or more 10
0 ° C or lower is more preferable. However, when a highly volatile alkali such as ammonia is used, the treatment at around room temperature is preferable. During the treatment, in order to suppress the alteration of the polymeric fluorescent substance, it is preferable to seal in an inert atmosphere,
Further, it is preferable to block light so that the light of the wavelength absorbed by the polymeric fluorescent substance solution does not hit.

In the present invention, the step of contacting the crude polymeric fluorescent substance with an alkali may be carried out continuously without dividing the step of synthesizing the crude polymeric fluorescent substance. For example, a method may be used in which the crude polymeric fluorescent substance existing as a solution is not separated as a precipitate but is brought into contact with an alkali as a solution. After contacting with alkali, it may include neutralization, washing, reprecipitation, drying and other steps, if necessary.

After the step of contacting with the alkali, it is preferable to provide a step of removing the alkali from the polymeric fluorescent substance. In order to remove the alkali, it is sufficient to carry out a neutralization treatment followed by thorough washing, or sufficient washing with a solvent in which the alkali is well dissolved. Alternatively, the polymeric fluorescent substance obtained by contacting with an alkali may be once dissolved in a good solvent and then reprecipitated with a poor solvent to remove the alkali. In order to remove highly volatile alkali such as ammonia, it may be simply dried under reduced pressure or heated in an inert atmosphere.

The process of treating with a substance containing no acid or alkali will be described in detail. In the present invention, the substance containing no acid or alkali may be an organic or inorganic substance that does not exhibit acidity or alkalinity in any sense, for example, a neutral organic solvent, neutral water, etc. Is preferable because of high treatment efficiency.

Examples of the neutral organic solvent include alkanes, alkenes, aromatic compounds, heterocyclic compounds, alcohols,
Ethers, ketones, alkane sulfonates,
Examples thereof include alkanecarboxylic acid ester, alkenesulfonic acid ester, aromatic sulfonic acid ester, heterocyclic compound sulfonic acid ester, and phosphoric acid ester.

More specifically as the neutral organic solvent, hexane, hexene, benzene, toluene, 2-methylfuran, 2-methylthiophene, ethanol, methanol,
Diethyl ether, t-butyl methyl ether, acetone, methyl isobutyl ketone, ethanesulfonic acid methyl ester, acetic acid ethyl ester, propionic acid methyl ester, 2-butenoic acid ethyl ester, toluenesulfonic acid methyl ester, 2-thiophenesulfonic acid ethyl ester , Phosphoric acid trimethyl ester, etc. can be exemplified,
Hexane, toluene, methanol, diethyl ether,
Acetone and the like are more preferable.

Examples of the neutral water include distilled water, ion-exchanged water, buffer solutions having a pH of about 7, and the like.
Ion-exchanged water is preferred. In the step of treating with a substance containing no acid or alkali, a single substance or a mixture of two or more types of these neutral substances can be used. Examples of the solid substance containing no acid or alkali include neutral silica gel, alumina gel, activated carbon, and Celite.

In the present invention, the "process of treating with a substance containing no acid or alkali" refers to a process of contacting the starting polymeric fluorescent substance with a substance containing no acid or alkali. Examples of the method for treating the starting polymeric fluorescent substance with a substance containing neither acid nor alkali include, for example, 1) a method of bringing the starting polymeric fluorescent substance in a liquid state into contact with a substance containing neither an acid nor an alkaline substance in a liquid state 2) a solid A method of contacting a raw material polymeric fluorescent substance in a liquid state with a substance containing no acid or alkali in a liquid state 3) A method of contacting a raw material polymeric fluorescent substance in a liquid state with a substance containing no solid acid or alkali . Among these, 1) is preferable from the viewpoint of good contact property between the polymeric fluorescent substance and an acid. here,
The liquid state includes a state in which the raw polymeric fluorescent substance is dissolved in a solvent.

In the step of treating with a substance containing no acid or alkali, it is preferable to carry out stirring, shaking or the like in order to enhance the efficiency of treatment. Further, the step of treating with a substance containing no acid or alkali may be included twice or more. Furthermore, when the step of treating with a substance containing no acid or alkali is included twice or more, the type and concentration of the substance containing no acid or alkali used at that time may be changed.

Further, the method for producing a polymeric fluorescent substance of the present invention may include a step other than the step of treating with a substance containing no acid or alkali, if necessary. With the steps other than the step of treating with a substance containing no acid or alkali, for example,
A step of removing a substance containing no acid or an alkali; a step of removing the solvent when another solvent is used; a step of separating the phase when a solvent for phase separation is used; a reprecipitation or a chromatography And the like. Among these, it is preferable to include a step of removing a substance containing no acid or alkali and a step of purifying in order to remove unnecessary substances.

In the above methods 1) and 2), water is preferably used as the substance containing no acid or alkali, and the pH of the water is 6.5 or more and 7.5 or less. At this time, the water used is preferably water containing few impurities such as ions, for example, distilled water, ion-exchanged water, pure water, or ultrapure water. Of these, pure water and ultrapure water are preferable, and ultrapure water is particularly preferable. As a specific index of the purity of pure water, there is conductivity, and water having a value of 10 μS / cm or less is preferable, and water having a conductivity of 1 μS / cm or less is more preferable. Less than,
The case of using water will be described. The method 1) above will be described in more detail. As the method 1), the step of treating the starting polymeric fluorescent substance with a substance containing no acid or alkali is a step of contacting water with a solution prepared by dissolving the polymeric fluorescent substance in a solvent. However, the treatment efficiency is high, which is preferable. On the other hand, it is more preferable that the raw material polymeric fluorescent substance in a liquid state and water are phase-separated because the polymeric fluorescent substance can be easily separated.

Both the raw material polymeric fluorescent substance and water are in a liquid state.
The starting polymeric fluorescent substance is preferably dissolved in a solvent that is phase-separated from water.

The solvent for dissolving the polymeric fluorescent substance may be any solvent which can dissolve the polymeric fluorescent substance well, and is not particularly limited, but is a chlorine-based solvent such as chloroform, methylene chloride, dichloroethane, or an ether such as tetrahydrofuran. System solvent, toluene, xylene, mesitylene, tetralin,
Aromatic hydrocarbon solvents such as decalin and n-butylbenzene are exemplified. Among these, those which are phase-separated from water are preferable, and chloroform, tetrahydrofuran and toluene are particularly preferable. The temperature of the treatment with water is not particularly limited and may be a temperature from room temperature to a temperature lower than the boiling point of the solvent, but a temperature between room temperature and 50 ° C is preferable.

Next, an example of a method for bringing water into contact with a solution prepared by dissolving the polymeric fluorescent substance in a solvent that causes phase separation from the aqueous solution of the acid will be specifically described. First, the polymeric fluorescent substance is well dissolved, and the raw polymeric fluorescent substance is dissolved in a solvent that causes phase separation from water, for example, chloroform, and the solution is water.
Contact them while stirring (step of treating with a substance containing no acid or alkali). Then, after standing still, the water phase and the phase containing the polymeric fluorescent substance are separated and separated. The separated phase containing the polymeric fluorescent substance is further contacted with water and treated with a substance containing no acid or alkali, which is repeated an appropriate number of times. Thereafter, the solution containing the polymeric fluorescent substance is dropped into a poor solvent for the dissolution of the polymeric fluorescent substance, for example, into methanol or the like with stirring to form a precipitate of the polymeric fluorescent substance. . The precipitate is filtered, washed with ethanol, and dried under reduced pressure to obtain a polymeric fluorescent substance.

Examples of the method 2) include a method in which water is mixed with a solid polymer powdery raw material polymer fluorescent material and treated by a stirring repulp type washing operation. In the case of using the raw material polymeric fluorescent substance in the form of a solid powder by this method, after treating with water,
Water and other unnecessary components can be removed from the raw material polymeric fluorescent substance in the form of a solid powder by filtration.

Examples of the method 3) include a method of treating the starting polymeric fluorescent substance in a liquid state by passing it through a column filled with a substance in the solid state containing neither acid nor alkali. The order of the step of treating with the acid, the step of treating with the alkali, and the step of treating with the substance containing no acid or alkali is not particularly limited and may be appropriately selected. In order to sufficiently bring out the purification effect, it is preferable that there is a step of treating with an alkali after the step of treating with an acid, more preferably a step of treating with an acid, a step of treating with an alkali, a substance containing no acid or alkali. It is preferable to carry out in the order of the steps of treatment in.

The starting polymeric fluorescent substance used in the present invention is fluorescent in the solid state and has a polystyrene-reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ . The starting polymeric fluorescent substance used in the present invention has fluorescence in a solid state and has a polystyrene-equivalent number average molecular weight of 1 × 1.
A polymeric fluorescent substance having a molecular weight of 0 ⁴ to 1 × 10 ⁸ and including at least one repeating unit represented by the following formula (1) is preferable.

Embedded image —Ar ₁ — (CR ₁ ═CR ₂ ) _k − (1) (where Ar ₁ is a divalent group that forms a carbon-carbon bond with two adjacent groups, respectively. A group, which is an arylene group having 6 to 60 carbon atoms in the main chain portion, or a heterocyclic compound group having 4 to 60 carbon atoms in the main chain portion The arylene group and the heterocyclic compound group may have a substituent, and R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number 6 Represents a group selected from the group consisting of an aryl group having 60 to 60, a heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group, and the aryl group and heterocyclic compound group may have a substituent, and k is It is 0 or 1.)

Further, the starting polymeric fluorescent substance used in the present invention has fluorescence in a solid state and has a polystyrene-reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ and is represented by the following formula (2). It is preferable that at least one repeating unit represented by the following formulas (3) and (4) is included, and more preferably the repeating units represented by the formulas (2), (3) and (4). Each of them includes at least one type.

[Chemical 3] (Here, Ar ₂ is a divalent group that forms a carbon-carbon bond with two adjacent groups, respectively, and an arylene group in which the number of carbon atoms contained in the main chain is 6 or more and 60 or less. Or a heterocyclic compound group in which the number of carbon atoms contained in the main chain portion is from 4 to 60. Ar ₂ is an alkyl group having 1 to 20 carbon atoms other than —X—R _3. , An alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms
Alkylthio group, C1-60 alkylsilyl group, C1-40 alkylamino group, C6-6
An aryl group of 0, an aryloxy group having 6 to 60 carbon atoms,
Arylalkyl group having 6 to 60 carbon atoms, 6 to 60 carbon atoms
An arylalkoxy group, an arylamino group having 6 to 60 carbon atoms, a heterocyclic compound group having 4 to 60 carbon atoms, and a substituent selected from the group consisting of cyano groups,
The aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylamino group and heterocyclic compound group may further have a substituent. Ar ₂
When has a plurality of substituents, they may be the same or different. R ₃ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms,
Arylalkyl group having 7 to 60 carbon atoms and 4 to 4 carbon atoms
60 represents a group selected from the group consisting of heterocyclic compound groups, and the aryl group, arylalkyl group and heterocyclic compound group may have a substituent. X is -O-, -S
_{-, - CR 6 R 7 -} , - SiR 8 R 9 -, - NR 10 -, - C
O -, - COO -, - SO 2 -, - CR 11 = CR 12 -,
And a group selected from the group consisting of C≡C-. m is 1
Is an integer of ~ 4. R ₄ , R ₅ and R _{6 to} R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heterocyclic compound group having 4 to 20 carbon atoms and a cyano group. A group selected from the group consisting of, wherein the aryl group and the heterocyclic compound group may have a substituent. n is 0 or 1. )

[Chemical 4] (Here, Ar ₃ is a divalent group that forms a carbon-carbon bond with two adjacent groups, respectively, and an arylene group having 6 to 60 carbon atoms in the main chain portion. Or a heterocyclic compound group in which the number of carbon atoms contained in the main chain portion is 4 or more and 60 or less, wherein Ar ₃ is 1 to 20 carbon atoms in addition to -Ar _4.
Alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, C1-C60 alkylsilyl group, C1-C40 alkylamino group, C6-C60 aryl group , An aryloxy group having 6 to 60 carbon atoms, an arylalkyl group having 6 to 60 carbon atoms, and 6 carbon atoms
To an arylalkoxy group having from 60 to 60, an arylamino group having from 6 to 60 carbon atoms, a heterocyclic compound group having from 4 to 60 carbon atoms, and a substituent selected from the group consisting of a cyano group. The aryloxy group, arylalkyl group, arylalkoxy group, arylamino group and heterocyclic compound group may further have a substituent. A
When r ₃ has a plurality of substituents, they may be the same or different. Ar ₄ is
It represents an aryl group having 6 to 60 carbon atoms or a heterocyclic compound group having 4 to 60 carbon atoms, and the aryl group and heterocyclic compound group may have a substituent. o is an integer of 1 to 4. R ₁₃
And R ₁₄ are each independently a hydrogen atom or a carbon number of 1 to 20.
Alkyl group, C6-60 aryl group, C4
To 60 groups represented by the group consisting of a heterocyclic compound group and a cyano group, wherein the aryl group and the heterocyclic compound group may have a substituent. p is 0 or 1. )

[Chemical 5] (Here, Ar ₅ is a divalent group that forms a carbon-carbon bond with two adjacent groups, respectively, and an arylene group in which the number of carbon atoms contained in the main chain portion is 6 or more and 60 or less. Or a heterocyclic compound group in which the number of carbon atoms contained in the main chain portion is 4 or more and 60 or less, wherein Ar ₅ has 1 to 20 carbon atoms in addition to -R _15.
Alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, C1-C60 alkylsilyl group, C1-C40 alkylamino group, C6-C60 aryl group , An aryloxy group having 6 to 60 carbon atoms, an arylalkyl group having 6 to 60 carbon atoms, and 6 carbon atoms
To an arylalkoxy group having from 60 to 60, an arylamino group having from 6 to 60 carbon atoms, a heterocyclic compound group having from 4 to 60 carbon atoms, and a substituent selected from the group consisting of a cyano group. The aryloxy group, arylalkyl group, arylalkoxy group, arylamino group and heterocyclic compound group may further have a substituent. A
When r ₅ has a plurality of substituents, they may be the same or different. R ₁₅ represents an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 5 to 16 carbon atoms or a saturated heterocyclic compound group having 4 to 60 carbon atoms, and the cyclic saturated hydrocarbon group and saturated heterocyclic compound group May have a substituent. q is an integer of 1 to 4. R
₁₆ and R ₁₇ are each independently a hydrogen atom and a carbon number of 1 to 2.
Represents a group selected from the group consisting of an alkyl group having 0, an aryl group having 6 to 60 carbon atoms, a heterocyclic compound group having 4 to 60 carbon atoms and a cyano group, wherein the aryl group and the heterocyclic compound group have a substituent. You may have. r is 0 or 1. ) More preferably, the total of the repeating units represented by formula (2), formula (3) and formula (4) is 50 mol% or more of all repeating units, and formula (2), formula (3) and formula The repeating unit represented by the formula (2) is 0.1 mol% or more and 30 mol% or less with respect to the total of the repeating units represented by (4),
The repeating unit represented by the formula (3) is 30 mol% or more 70
It is a polymeric fluorescent substance in which the content of the repeating unit represented by the formula (4) is 30 mol% or more and 70 mol% or less. Most preferably, the repeating unit represented by formula (2) is 0.2 mol% or more and 10 mol% or less based on the total number of repeating units.

As Ar ₁ , Ar ₂ , Ar ₃ and Ar ₅ ,
It may be selected so as not to impair the fluorescent properties of the polymeric fluorescent substance, and specific examples thereof include the divalent groups exemplified in (5) below.

[0051]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

Here, when R is Ar ₂ , —X—
R ₃ is selected so as to have 1 to 4 substituents, and in the case of Ar ₃ , 1 to 4 substituents represented by —Ar ₄ are represented.
Selected to have 4, and in the case of Ar ₅ ,-
It is selected to have 1 to 4 substituents represented by R ₃ . The remaining R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to carbon atoms.
20 alkylthio group, C 1-60 alkylsilyl group, C 1-40 alkylamino group, C 6-
60 aryl group, C 6-60 aryloxy group, C 6-60 arylalkyl group, C 6-
Represents a substituent selected from the group consisting of an arylalkoxy group having 60, an arylamino group having 6 to 60 carbon atoms, a heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group, wherein the aryl group, aryloxy group and aryl The alkyl group, arylalkoxy group, arylamino group and heterocyclic compound group may further have a substituent. 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 at least one substituent which is not a hydrogen atom, and it is preferable that the repeating unit including the substituent has little symmetry in shape.

[0053] X is -O -, - S -, - CR 6 R 7 -, - S
_{iR 8 R 9 -, - NR} 10 -, - CO -, - COO -, - S
_{O 2 -, - CR 11 =} CR 12 -, and is a group selected from the group consisting of C≡C-, -O -, - S - , - CR 11 =
CR ₁₂ − and C≡C— are preferable, and —O— is more preferable. R ₆ to R ₁₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, a heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Represents a group, and the aryl group and the heterocyclic compound group may further have a substituent.

Specific examples of R ₃ and R ₁₅ include a methyl group, an ethyl group, and an alkyl group having 1 to 20 carbon atoms.
Examples thereof include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a lauryl group, and a pentyl group, a hexyl group, an octyl group and a decyl group are preferable.

Specific examples of R ₃ and Ar ₄ include a phenyl group and a C ₁ to C 6 aryl group having 6 to 60 carbon atoms.
₁₂ alkoxyphenyl groups (C _{1 to} C ₁₂ have 1 to 1 carbon atoms)
12 is shown. The same applies to the following. ), C ₁ ~
Examples thereof include a C ₁₂ alkylphenyl group, a 1-naphthyl group and a 2-naphthyl group, and a C _{1 to} C ₁₂ alkoxyphenyl group and a C _{1 to} C ₁₂ alkylphenyl group are preferable.

R₃, Ar_FourAs a concrete example of,
~ 60 arylalkyl groups include phenylmethyl
Group, phenylethyl group, phenylpropyl group, C₁~ C
₁₂Alkoxyphenylmethyl group, C₁~ C₁₂Alkoxy
Phenylethyl group, C₁~ C₁₂Alkoxyphenyl pro
Pill group, C₁~ C₁₂Alkylphenylmethyl group, C₁~ C
₁₂Alkylphenylethyl group, C₁~ C₁₂Alkylfe
Nylpropyl group, naphthylmethyl group, naphthylethyl group
Group, naphthylpropyl group, etc. are exemplified, and C₁~ C_{1 2}A
Lucoxyphenylmethyl group, C₁~ C₁₂Alkoxyfe
Nylethyl group, C₁~ C₁₂Alkoxyphenylpropyl
Base, C₁~ C₁₂Alkylphenylmethyl group, C₁~ C₁₂A
Rukylphenylethyl group, C₁~ C₁₂Alkylphenyl
A propyl group is preferred.

Specific examples of R ₃ and Ar ₄ include a thienyl group and C ₁ as a heterocyclic compound group having 4 to 60 carbon atoms.
To C ₁₂ alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C _{1 to} C ₁₂ alkyl pyridyl group and the like are exemplified, and thienyl group, C _{1 to} C ₁₂ alkyl thienyl group, pyridyl group, C _{1 to} C ₁₂ alkyl are exemplified. A pyridyl group is preferred.

Specific examples of R ₁₅ include 5 to 16 carbon atoms.
Examples of the cyclic saturated hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group,
Examples thereof include a cycloheptyl group, a cyclooctyl group, a cyclononyl group and a cyclododecyl group, and a cyclohexyl group is preferable.

Specific examples of R ₁₅ include 4 to 60 carbon atoms.
Examples of the saturated heterocyclic compound group include a tetrahydrofuranyl group, a pyranyl group, a pyrrolidyl group, a piperazyl group, a thiolanyl group and a cyanyl group, and a tetrahydrofuranyl group and a pyranyl group are preferable.

R is a hydrogen atom, a cyano group, -X-R ₃ ,
As to the case of a substituent other than the group represented by —Ar ₄ or R ₁₅ , examples of the alkyl group having 1 to 20 carbon atoms include 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 pentyl group, a hexyl group, an octyl group and a decyl group are preferable.

As the alkoxy group having 1 to 20 carbon atoms,
Methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, lauryloxy group and the like, pentyloxy group, hexyloxy group , Octyloxy group and decyloxy group are preferred.

Examples of the alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group and laurylthio group. , A pentylthio group,
Hexylthio group, octylthio group and decylthio group are preferred.

Examples of the alkylsilyl group having 1 to 60 carbon atoms include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, triheptylsilyl group and trioctylsilyl group. , Trinonylsilyl group, tridecylsilyl group, trilaurylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group , Nonyldimethylsilyl group, decyldimethylsilyl group, lauryldimethylsilyl group, and the like.Tripentylsilyl group, trihexylsilyl group, trioctylsilyl group, tridecylsilyl group, pentyldimethylsilyl group, Sill dimethylsilyl group, octyldimethylsilyl group, decyldimethylsilyl group are preferable.

Examples of the alkylamino group having 1 to 40 carbon atoms include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, Decylamino group, laurylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, dilaurylamino group And the like, and a pentylamino group, a hexylamino group, an octylamino group, a decylamino group, a dipentylamino group, a dihexylamino group, a dioctylamino group, and a didecylamino group are preferable.

Examples of the aryl group having 6 to 60 carbon atoms include phenyl group, C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C ₁₂
Indicates that the carbon number is 1 to 12. The same applies to the following. ), A C ₁ -C ₁₂ alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group and the like are exemplified, and a C ₁ -C ₁₂ alkoxyphenyl group and a C ₁ -C ₁₂ alkylphenyl group are preferable.

Examples of the aryloxy group having 6 to 60 carbon atoms include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, a C _{1 to} C ₁₂ alkylphenoxy group, a 1-naphthyloxy group and a 2-naphthyloxy group. And C ₁
To C ₁₂ alkoxyphenoxy group and C _{1 to} C ₁₂ alkylphenoxy group are preferable.

Examples of the arylalkyl group having 6 to 60 carbon atoms include phenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group and C ₁ -C ₁₂ alkylphenyl-C. ₁ -C ₁₂ alkyl group, 1-naphthyl -
Examples are C ₁ -C ₁₂ alkyl groups, 2-naphthyl-C ₁ -C ₁₂ alkyl groups, and C ₁ -C ₁₂ alkoxyphenyl-
C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C
₁ -C ₁₂ alkyl group are preferable.

An arylalkoxy group having 6 to 60 carbon atoms
And then Phenyl-C₁~ C₁₂Alkoxy group, C₁~ C₁₂
Alkoxyphenyl-C₁~ C₁₂Alkoxy group, C₁~ C
₁₂Alkylphenyl-C₁~ C₁₂Alkoxy group, 1-na
Futil-C₁~ C₁₂Alkoxy group, 2-naphthyl-C₁~
C₁₂Examples thereof include alkoxy groups, C₁~ C₁₂Arcoki
Cyphenyl-C₁~ C₁₂Alkoxy group, C₁~ C₁₂Archi
Luphenyl-C₁~ C_{1 2}Alkoxy groups are preferred.

Examples of the arylamino group having 6 to 60 carbon atoms include phenylamino group, diphenylamino group, C ₁ -C
Examples thereof include a ₁₂ alkoxyphenylamino group, a di (C ₁ -C ₁₂ alkoxyphenyl) amino group, a di (C ₁ -C ₁₂ alkylphenyl) amino group, a 1-naphthylamino group, a 2-naphthylamino group, and C ₁ To C ₁₂ alkylphenylamino group and di (C _{1 to} C ₁₂ alkylphenyl) amino group are preferable.

Examples of the heterocyclic compound group having 4 to 60 carbon atoms include thienyl group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C ₁ -C ₁₂ alkylpyridyl group, and the like. A thienyl group, a C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group and a C ₁ -C ₁₂ alkylpyridyl group are preferred.

Among the examples of R, in the substituent containing an alkyl chain, they may be linear, branched or cyclic, or a combination thereof. A 2-ethylhexyl group,
3,7-dimethyloctyl group, cyclohexyl group, 4-
Examples thereof include C _{1 to} C ₁₂ alkylcyclohexyl groups. To increase the solubility of the polymeric fluorescent substance in a solvent,
It is preferable that one or more of the substituents of Ar ₁ , Ar ₂ , Ar ₃ or Ar ₅ include a cyclic or branched alkyl chain.

In the above formula (1), k is 0 or 1, in the above formula (2), n is 0 or 1, and in the above formula (3), p is 0 or 1. In (4), r is 0 or 1. Formula (1) above
R ₁ and R _{2 in} the above, R ₄ and R _{5 in} the above formula (2), R ₁₃ and R _{14 in} the above formula (3), R ₁₆ , R ₁₇ and R _{6 to} R ₁₂ in the above formula (4) are And each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, a heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group,
The aryl group and the heterocyclic compound group may have a substituent.

R ₁ , R ₂ , R _{4 to} R ₁₄ , R ₁₆ and R ₁₇ are
As to the case of a substituent other than a hydrogen atom or a cyano group, examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Examples thereof include a hexyl group, 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.

Examples of the aryl group having 6 to 60 carbon atoms include phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂
Examples thereof include an alkylphenyl group, a 1-naphthyl group and a 2-naphthyl group, and a phenyl group and a C ₁ -C ₁₂ alkylphenyl group are preferable.

Examples of the heterocyclic compound group having 4 to 60 carbon atoms include thienyl group, C _{1 to} C ₁₂ alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C _{1 to} C ₁₂ alkylpyridyl group, and the like. A thienyl group, a C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group and a C ₁ -C ₁₂ alkylpyridyl group are preferred.

If the polymerization active group remains as it is, the terminal group of the polymeric fluorescent substance may be deteriorated in light emission characteristics and life when formed into a device, so that it is protected by a stable group. 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.

As a method for synthesizing the starting polymeric fluorescent substance, when a vinylene group is contained in the main chain, for example, JP-A 5-2 is used.
For example, the method described in JP-A-02355 can be used. That is, polymerization by a Wittig reaction of a dialdehyde compound and a diphosphonium salt compound, polymerization by a Heck reaction of a divinyl compound and a dihalogen compound or a vinyl halogen compound alone, Horner-of a dialdehyde compound and a diphosphite ester compound. Wadswo
Polymerization by rth-Emmons method, polycondensation of compound having two halogenated methyl groups by dehydrohalogenation method, polycondensation of compound having two sulfonium bases by sulfonium salt decomposition method, dialdehyde compound and diacetonitrile compound Examples of the method include polymerization by the Knoevenagel reaction and polymerization by a McMurry reaction of a dialdehyde compound.

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 starting polymeric fluorescent substance and the polymeric fluorescent substance produced by the method of the present invention have the formula (1), the formula (2) and the formula (2) as long as the fluorescent property and the charge transporting property are not impaired. 3)
And a repeating unit other than the repeating unit represented by the formula (4) may be contained. Further, the repeating unit represented by the formula (1), the formula (2), the formula (3) and the formula (4) or another repeating unit may be linked by a non-conjugated unit,
The non-conjugated portion may be contained in the repeating unit. Examples of the bond structure include those shown in (6) below, those shown in (6) below in combination with a vinylene group, and those shown in (6) below, which are a combination of two or more. 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.

[0080]

[Chemical 20]

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 quantum yield of fluorescence, 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 preferably has fluorescence in the solid state. Examples of the good solvent for the polymeric fluorescent substance include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like. Although it depends on the structure and molecular weight of the polymeric fluorescent substance, usually 0.1% by weight or more can be dissolved in these solvents.

The polymeric fluorescent substance produced by the method of the present invention has a molecular weight of 1 × 10 ⁴ to polystyrene equivalent.
It is 1 × 10 ⁸ , and the degree of polymerization thereof varies depending on the repeating structure and the ratio thereof. From the viewpoint of film-forming property, the total number of repeating structures is preferably 30 to 10,000,
More preferably, it is 50 to 5000.

When the polymeric fluorescent substance produced by the method of the present invention is used as a light emitting material of a polymeric LED, its purity affects the emission characteristics. Distillation, sublimation purification,
It is preferable to polymerize after purification by a method such as recrystallization. Further, at the stage of producing the polymeric fluorescent substance or in the present invention, the polymeric fluorescent substance is preferably subjected to purification treatment such as reprecipitation purification and fractionation by chromatography. 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 electrodes composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent, and the polymer phosphor of the present invention is It is contained in the light emitting layer. Further, the polymer L of the present invention
As the ED, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, and an electron between the cathode and the light emitting layer A polymer LED or the like in which a transport layer is provided and a hole transport layer is provided between the anode and the light emitting layer can be used. 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 transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates 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 drive voltage of the element are generally called a charge injection layer (hole injection layer, electron injection layer) in particular.

Further, in order to improve the adhesion to the electrode and the charge injection from the electrode, the charge injection layer or the 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 LED 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 / charge 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 / charge 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

A specific example of the charge injection layer is a layer containing a conductive polymer, which is 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 S / cm or less, and in order to reduce the leak current between the light emitting pixels, 10 ⁻⁵ S / c
m or more and 10 ² S / cm or less are more preferable, and 10 ^-5 S / cm
More preferably, it is not less than 10 cm and not more than 10 ¹ S / cm. Usually, the electric conductivity of the conductive polymer is 10 ^-5 S / cm or more 10
^The conductive polymer is doped with an appropriate amount of ions in order to achieve ³ S / cm or less.

The kinds 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, and polyaniline and its derivative, polythiophene and its derivative, polypyrrole and its derivative, polyphenylenevinylene and its derivative, poly Thienylene 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 (copper phthalocyanine, etc.), carbon, etc. It is illustrated.

The insulating layer having a film 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 having an insulating layer having a thickness of 2 nm or less adjacent to a cathode and a polymer LED having an insulating layer having a thickness of 2 nm or less 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 / luminescent 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 having a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) anode / hole transport layer / light emitting layer / insulating layer having 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 or less / 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 organic 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 or a light emitting material is 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,
A coating method 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 or 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 mixed and used in the light emitting layer. Further, in the polymer LED of the present invention,
A light emitting layer containing a light emitting material other than the polymeric fluorescent substance may be laminated with a light emitting layer containing the polymeric fluorescent substance. As the light emitting material, known materials can be used. Examples of low molecular weight compounds include naphthalene derivatives, anthracene or its derivatives, perylene or its derivatives, polymethine-based, xanthene-based, coumarin-based, cyanine-based dyes, metal complexes of 8-hydroxyquinoline or its derivatives, and aromatic amines. , Tetraphenylcyclopentadiene or its derivative, or tetraphenylbutadiene or its derivative can be used.
Specifically, for example, JP-A-57-51781 and 59
Known ones such as those described in JP-A-194393 can be used.

When the polymer LED of the present invention has a hole-transporting layer, the hole-transporting material used is polyvinylcarbazole or its derivative, polysilane or its derivative, and an aromatic amine in the side chain or main chain. Polysiloxane derivative, pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or its derivative, polythiophene or its derivative, polypyrrole or its derivative, poly (p-phenylenevinylene) or its derivative, or poly (2, 5-thienylene vinylene) or a derivative thereof and the like.

Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359 and JP-A-2-13536 are used.
No. 1, gazette No. 2-209988, gazette No. 3-3799
Examples are those described in JP-A No. 2 and JP-A No. 3-152184.

Among these, as the 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-transporting 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, or a side chain or a main chain is aromatic. It is a polysiloxane derivative having a group amine. 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 its derivative is obtained, for example, from a vinyl monomer by cation 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 in these can be used, but the Kipping method is particularly preferably used.

Since the 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 the 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,
Examples thereof include ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate.

The film formation method from the solution includes spin coating method from solution, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating. 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 differs 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,
The driving voltage of the device becomes high, which is not preferable. 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 oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, 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, polyquinoline or its derivative,
Examples include polyquinoxaline or its derivative, polyfluorene or its derivative, and the like.

Specifically, 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,
Benzoquinone or a derivative thereof, anthraquinone or a derivative thereof, a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and 2- (4-biphenylyl) -5 is preferable. -(4-t-butylphenyl) -1,3
4-Oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

The method for forming the electron transport layer is not particularly limited, but for the low molecular weight electron transport material, the vacuum deposition method from powder or the method by film formation from a solution or a molten state is used as the 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 dissolves 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-based 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 transportation are preferable, and those showing no strong absorption of 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 luminous efficiency have appropriate values, but at least a thickness that does not cause pinholes. Is necessary, and if it is too thick,
The driving voltage of the device becomes high, which is not preferable. 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 forming the polymer LED of the present invention is
Any material that does not change when an electrode is formed and an organic material layer is formed may be used, and examples thereof include glass, plastics, polymer films, and silicon substrates. 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. Such)
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. Further, 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 transmissivity and electric conductivity, and is, for example, 10 n.
m to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.
In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. Layers 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, tin An alloy with one or more of them, graphite, a graphite intercalation compound, or the like is used. Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys,
Examples thereof include lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like. 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, and is 10 n, for example.
m 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. Further, a layer made of a conductive polymer 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 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 period of time, 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. 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 damaged. 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 prevent the element from damaging the element. It is preferable to take any one or more of these measures. In order to obtain planar light emission using the polymer LED of the present invention, planar anodes and cathodes may be arranged so as to overlap each other. Further, in order to obtain a patterned light emission, a method of installing a mask having a patterned window on the surface of the planar light emitting element, and forming the organic layer of the non-light emitting portion to be extremely thick, There is a method of emitting light, a method of forming one or both electrodes of an anode and a cathode in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned ON / OFF independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. 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 applying 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 element can be passively driven, or may be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, 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 illumination light source. Further, if a flexible substrate is used, it can be used as a curved light source or a display device.

[0122]

EXAMPLES Examples will be shown below to explain the present invention in more detail, but the present invention is not limited to these. Here, regarding the number average molecular weight, the polystyrene equivalent number average molecular weight was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

Example 1 <Synthesis of polymeric fluorescent substance (1)> 12 g of 2,5-bis (chloromethyl) -4 ′-(3,7-dimethyloctyloxy) biphenyl and 2-methoxy-5- (2) -Ethylhexyloxy) -p-xylylene dichloride 0.2 g
And were dissolved in 2100 g of dehydrated 1,4-dioxane. After nitrogen bubbling this solution for 20 minutes to replace the inside of the system with nitrogen, the temperature was raised to 95 ° C. in a nitrogen atmosphere. To this liquid, dehydrated 1,4-dioxane was previously added.
210 g of potassium tertiary butoxide 15.
A solution in which 5 g was dissolved was added dropwise in about 10 minutes. After the dropping, the temperature was kept at 97 ° C. for 2.5 hours for polymerization. After polymerization,
After the polymerization liquid was cooled to 50 ° C., acetic acid was added to neutralize it. After cooling to room temperature, this polymerization liquid was poured into 2500 g of ion-exchanged water, and the generated precipitate was collected.
The precipitate was washed with methanol and then dried under reduced pressure.
7 g of the obtained polymer was dissolved in 1500 g of THF. This solution was poured into 2000 g of methanol, and the formed precipitate was recovered. The precipitate was washed with ethanol and then dried under reduced pressure to obtain 5 g of a polymer. This polymer is called polymeric fluorescent substance (1).

<Synthesis of Purified Polymeric Fluorescent Substance 2> Acid Washing Example Polymeric Fluorescent Substance (1) Acid Cleaning Operation 0.4 g of the polymeric fluorescent substance (1) synthesized by the above-mentioned method,
It was dissolved in 200 g of chloroform. The solution was washed with 200 g of a 1% tartaric acid aqueous solution, and then separated to collect a chloroform layer. After repeating this operation 3 times, the chloroform solution was repeatedly washed 5 times with 200 g of ultrapure water. The chloroform solution was poured into methanol and the generated precipitate was collected. The precipitate was washed with ethanol, dried under reduced pressure, and acid-washed to obtain a purified polymeric fluorescent substance (2). Table 1 shows the results of quantifying the metal elements of the polymeric fluorescent substances (1) and (2) by ICP emission spectrometry. In the purified polymeric fluorescent substance (2), potassium and iron were reduced.

[0125]

[Table 1]

Example 2 <Fabrication and Evaluation of Device> Poly (3,4) was formed on a glass substrate having an ITO film with a thickness of 150 nm formed by a sputtering method.
A suspension of ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, Bytron P TP AI 4083) was filtered through a 0.5 μm membrane filter, then spin-coated to form a film with a thickness of 70 nm, and then vacuum oven at 120 ° C. It was dried for 1 hour. Then, a 0.4 wt% chloroform solution of polymeric fluorescent substance (2) was spin-coated to form a light-emitting layer with a thickness of 70 nm. Further, this was dried under reduced pressure at 80 ° C. for 1 hour, and then lithium fluoride was deposited as a cathode at a thickness of about 0.4 nm, calcium was deposited at 40 nm, and aluminum was deposited at 70 nm to prepare a polymer LED device. The degree of vacuum at the time of vapor deposition was 8 × 10 ⁻⁶ Torr or less. When a voltage of 3.0 V was applied to the obtained device, the current density was 2.5.
A current of mA / cm ² was passed, and yellow EL light emission with a brightness of 320 cd / m ² was observed. The luminous efficiency at this time is 13
cd / A, and the emission spectrum of the device is 548
It had a peak at nm. When the device was aged for 1 hour under a nitrogen stream and continuously driven at a constant current of 25 mA / cm ² , the emission luminance of 2000 cd / m ² was reduced by half in about 60 hours.

Comparative Example 1 In the same manner as in Example 2, a polymer LED was produced by using the polymer fluorescent substance (1) before purification in place of the purified polymer fluorescent substance (2). When a voltage of 3.0 V was applied to the obtained device, a current having a current density of 1.0 mA / cm ² flowed, and yellow EL light emission with a luminance of 110 cd / m ² was observed. At this time, the luminous efficiency was 11 cd / A, and the emission spectrum of the device had a peak at 548 nm. After aging the device for 1 hour under nitrogen flow, 25
When continuously driven with a constant current of mA / cm ² , 210
The emission luminance of 0 cd / m ² was halved in about 45 hours, and the life was shorter than that of the device of Example 2.

[0128]

Example 3 <Synthesis of polymeric fluorescent substance 3> 9,9-dioctylfluorene (26.3 g), 9,9-diisopentylfluorene (5.6 g), 2,2'-bipyridyl (2
2 g) was dissolved in 1.6 L of dehydrated THF and purged with nitrogen. Bis (1,5-cyclooctadiene) nickel (0) (40 g) was added thereto, and the mixture was heated with stirring at 60 ° C. for 8 hours. After cooling, the reaction mixture was poured into a mixed solution of methanol (1.2 L) / water (1.2 L) / 25% aqueous ammonia (200 ml), and the deposited precipitate was separated by filtration. The obtained precipitate was dissolved in toluene (1.1 L) after drying, and this was added dropwise to methanol (3.3 L). The deposited precipitate was separated by filtration and dried under reduced pressure to give polymeric fluorescent substance 3 (2
1 g) was obtained.

<Synthesis of Purified Polymeric Fluorescent Material 4> Polymeric fluorescent material 3 (10 g) synthesized by the above method was converted into toluene (1.
It was dissolved in 44 l). This solution was added with 1N hydrochloric acid (1.0
After washing with l), the liquid was separated to collect the toluene layer. This toluene layer was mixed with a 2% aqueous ammonia solution (1.
It was washed with 1 liter) and further washed twice with pure water (1.0 liter). This toluene solution was added to methanol (3.0
1) and the purified precipitate was collected. The precipitate was dried under reduced pressure to obtain purified polymer 4 (9.7 g).

<Evaluation of Fluorescent Properties> A 0.4 wt% chloroform solution of purified polymeric fluorescent substance 4 was spin-coated on quartz to form a thin film of purified polymeric fluorescent substance 4. The UV-visible absorption spectrum and the fluorescence spectrum of this thin film were respectively analyzed by UV-visible absorption spectrophotometer (Hitachi UV3500).
And a fluorescence spectrophotometer (Hitachi 850). For the calculation of fluorescence intensity, the fluorescence spectrum when excited at 350 nm was used. The relative value of the fluorescence intensity was obtained by dividing the area of the fluorescence spectrum plotted by taking the wave number on the horizontal axis by the absorbance at 350 nm. The fluorescence peak wavelength of the purified polymeric fluorescent substance 4 was 428 nm, and the relative value of the fluorescence intensity was 5.9.

[0131]

Comparative Example 2 In the same manner as in Example 3, instead of the purified polymeric fluorescent substance 4, the unpurified polymeric fluorescent substance 3 was used to form a thin film. The fluorescence peak wavelength of the obtained polymeric fluorescent substance 3 was 428 nm, and the relative value of the fluorescence intensity was 3.3.

[0132]

The polymer LED using the polymer phosphor produced by the method of the present invention has a long life. 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, a dot matrix flat panel display, or the like.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G09F 9/35 G09F 9/35 H05B 33/14 H05B 33/14 BF term (reference) 2H091 FA44Z FA45Z FB02 FD06 LA30 3K007 AB00 AB03 AB06 AB18 BA06 CA01 CB01 DA00 DB03 EB00 FA01 4J032 CA03 CA04 CA12 CB12 CF05 CF06 CG02 CG03 5C094 AA37 BA29 BA43 CA19 FB01 5G435 AA14 BB05 BB12 BB15 CC09 EE26 GG25 HH20

Claims (23)

[Claims] 1. A polymer comprising a step of treating a polymeric fluorescent substance which has fluorescence in a solid state and has a polystyrene reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ with an acid. Method for manufacturing phosphor. 2. A step of treating a polymeric fluorescent substance which has fluorescence in a solid state and has a polystyrene reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ with an acid and a step of treating with an alkali. And a method for producing a polymeric fluorescent substance. 3. A step of treating a polymeric fluorescent substance having fluorescence in a solid state and having a polystyrene-reduced number average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁸ with an acid, a step of treating with an alkali, and an acid. A method for producing a polymeric fluorescent substance, which comprises a step of treating with a substance containing no alkali. 4. The method for producing a polymeric fluorescent substance according to claim 1, wherein the metal contained in the polymeric fluorescent substance is reduced by the step of treating with an acid. 5. The method for producing a polymeric fluorescent substance according to claim 2, wherein the metal contained in the polymeric fluorescent substance is reduced by the step of treating with an acid and the step of treating with an alkali. 6. The high-molecular fluorescent substance according to claim 3, wherein the step of treating with an acid, the step of treating with an alkali, and the step of treating with a substance containing no acid or alkali reduce the metal contained in the polymeric fluorescent substance. Method for producing molecular fluorescent substance. 7. The method for producing a polymeric fluorescent substance according to claim 1, wherein the base contained in the polymeric fluorescent substance is reduced by the step of treating with an acid. 8. The method for producing a polymeric fluorescent substance according to claim 2, wherein the base contained in the polymeric fluorescent substance is reduced by the step of treating with an acid and the step of treating with an alkali. 9. The polymeric fluorescent substance according to claim 3, wherein the base contained in the polymeric fluorescent substance is reduced by the step of treating with an acid, the step of treating with an alkali, and the step of treating with a substance containing no acid or alkali. Body manufacturing method. 10. The production method according to claim 1, wherein the acid is an organic acid. 11. The production method according to claim 1, wherein the acid is an inorganic acid. 12. The production method according to claim 1, wherein the alkali is an organic alkali. 13. The production method according to claim 1, wherein the alkali is an inorganic alkali. 14. The step of treating with an acid is a step of bringing an acid solution into contact with a solution prepared by dissolving the polymeric fluorescent substance in a solvent. Production method. 15. The step of treating with an alkali is a step of bringing an alkali solution into contact with a solution prepared by dissolving the polymeric fluorescent substance in a solvent. The manufacturing method described in. 16. The step of treating with a substance containing no acid or alkali is a step of bringing a solution containing no acid or alkali into contact with a solution prepared by dissolving the polymeric fluorescent substance in a solvent. The manufacturing method according to claim 6, 6 or 9. 17. The step of treating with a substance containing no acid or alkali is a step of contacting a solid substance containing no acid or alkali with a solution prepared by dissolving the polymeric fluorescent substance in a solvent. Item 3. The method according to item 3, 6 or 9. 18. The polymeric fluorescent substance contains at least one type of repeating unit represented by the following formula (1).
5. The method for producing the polymeric fluorescent substance according to any one of 5 above. Embedded image —Ar ₁ — (CR ₁ ═CR ₂ ) _k − (1) (wherein Ar ₁ is a divalent group that forms a carbon-carbon bond with two adjacent groups, respectively. A group, which is an arylene group having 6 to 60 carbon atoms in the main chain portion, or a heterocyclic compound group having 4 to 60 carbon atoms in the main chain portion The arylene group and the heterocyclic compound group may have a substituent, and R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number 6 To 60 aryl group, a heterocyclic compound group having 4 to 60 carbon atoms and a cyano group, wherein the aryl group and the heterocyclic compound group may have a substituent, and k is 0 or 1) 19. A polymer light-emitting device having at least one light-emitting layer containing a polymer fluorescent material between a pair of electrodes consisting of an anode and a cathode, at least one of which is transparent or semi-transparent, 16. A polymer light emitting device comprising the polymer fluorescent substance manufactured by the manufacturing method according to claim 16. 20. A planar light source using the polymer light emitting device according to claim 17. 21. A segment display device using the polymer light emitting device according to claim 17. 22. A dot matrix display device comprising the polymer light emitting device according to claim 17. 23. A liquid crystal display device comprising the planar light source according to claim 18 as a backlight.