WO2002102925A1 - Polymeric fluorescent material, process for producing the same, and polymeric luminescent element - Google Patents

Abstract

A process for producing a polymeric fluorescent material characterized by comprising a step in which a crude polymeric fluorescent material which fluoresces in a solid state, has a number-average molecular weight of 104 to 108 in terms of polystyrene, and comprises one or more kinds of repeating units represented by the following formula (1) is brought into contact with an alkali: -Ar1-(CR1=CR2)n- (1) (wherein Ar1 represents an arylene or heterocyclic compound group which optionally has one or more substituents; R1 and R2 each independently represents hydrogen or a group selected from the group consisting of alkyl, aryl, heterocyclic compound, and cyano groups, provided that the aryl and heterocyclic compound groups may be optionally substituted; and n is 0 or 1).

Description

 Description Polymer fluorescent substance, manufacturing method thereof and polymer light emitting device

 The present invention relates to a method for producing a polymer phosphor and a polymer light-emitting device using the same (hereinafter, may be referred to as a polymer LED). '

Background art

 Unlike high-molecular-weight luminescent materials (polymer fluorescent materials), which are soluble in solvents and can form light-emitting layers in light-emitting elements by a coating method, various studies have been made on them. For example, poly (p-phenylene vinylene) (hereinafter sometimes referred to as PPV) (WO 901 3148 published specification, JP-A-3-244630, Ryo Pride 'Physics' Letters (Ap pl. Physs) Lett. Vol. 58, pp. 1 982 (1991), etc., Polyfluorene (Japanese / Giannano / Love / Applied / Physics) (Jpn. J. Ap 1. Phy s.) No. 30 Vol., L1941 (1991)) and polyparaphenylene derivatives (Advanced Materials (Ad v. Mater.) Vol. 4, page 36 (1992)).

 In order to take advantage of the characteristics of a polymer fluorescent substance that is soluble in a solvent and can form a light-emitting layer by a coating method, a polymer fluorescent substance having even higher solubility has been demanded.

Disclosure of the invention

 An object of the present invention is to provide a polymer phosphor excellent in solubility, a method for producing the polymer phosphor, and a high-performance polymer LED that can be driven with low voltage and high efficiency by using the polymer phosphor. It is in.

 The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, by contacting a specific polymer fluorescent substance with an alkali, the solubility of the polymer fluorescent substance in an organic solvent has been improved, and the polymer fluorescent substance has been improved. The present inventors have found that a high-performance polymer LED that can be driven at a low voltage and with high efficiency can be obtained by using a body, and have led to the present invention.

That is, the present invention 1) having fluorescence in the solid state, the number average molecular weight in terms of polystyrene is 1 0 ⁴ to 1 0 ^8, and alkali crude polymeric fluorescent substance containing a repeating unit represented by the following formula (1) one or more The present invention relates to a method for producing a polymeric fluorescent substance, which includes a step of contacting the polymeric fluorescent substance.

-Ar!-(CR ₁ = CR ₂ ) _n — (1) where A ri is an arylene group or a heterocyclic compound group, and is unsubstituted or has one or more substituents. Is also good. 1 ₁及Pi 1 ₂ each independently represent a hydrogen atom, an alkyl group, Ariru group, a group selected from the group consisting of heterocyclic compound group and Shiano group. The aryl group and the heterocyclic compound group may further have a substituent. n is 0 or 1.

 Further, the present invention relates to 2) a polymeric fluorescent substance that can be produced by the production method of 1) above.

 The present invention also provides 3) a polymer light-emitting device having at least a light-emitting layer between a pair of anodes and cathodes, at least one of which is transparent or translucent, wherein the light-emitting layer is as described in 2) above. The present invention relates to a polymer light emitting device including a molecular phosphor.

 Furthermore, the present invention relates to 4) a planar light source using the polymer light-emitting device of the above 3). Next, the present invention relates to 5) a segment display device using the polymer light-emitting device of the above 3). Next, the present invention relates to 6) a dot matrix display device using the polymer light emitting device of the above 3). Further, the present invention relates to 7) a liquid crystal display device using the polymer light-emitting device according to 3) as a backlight. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the method for producing the polymer phosphor of the present invention and the polymer LED using the same will be described in detail.

The method for producing a polymeric fluorescent substance of the present invention has fluorescence in a solid state, a polystyrene equivalent number average molecular weight of 10 ⁴ to 10 ⁸ , and one type of a repeating unit represented by the following formula (1). The method is characterized in that it includes a step of contacting the crude polymer fluorescent material containing the above with an aluminum alloy. -Ar!-(CR ^ CRs) _n- (1) The organic solvent that can be used in the production method of the present invention is not particularly limited as long as it can dissolve the crude polymer fluorescent substance. In order to perform the treatment, it is preferable that the solvent is sufficiently dissolved. Therefore, it is preferable that the solvent be a good solvent for the crude polymer fluorescent substance.

 Examples of good solvents for the crude polymer fluorescent substance include chloroform-form, dichloromethane, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, η-butylbenzene, dioxane and the like. Depending on the structure and molecular weight of the crude polymer phosphor, these solvents can usually be dissolved in an amount of 0.1% by weight or more.

The alkali used in the production method of the present invention, _sigma> 1 & value preferably der shall of 10 or more.

 Examples of the alkali include metal alkoxide, metal hydroxide, metal amide compound, metal hydride compound, ammonia, and amines.

As the metal _{alkoxide, L i OCH 3, Na OCH} 3, KOCH 3, L i 〇_C _{2 H 5, Na OC 2 H} 5, KOC 2 H 5, L i O (t -C 4 H 9), N a O (t-C ₄ H ₉ ), KO (t-C ₄ H ₉ ) and the like, and the metal hydroxides include LiOH, NaOH, KOH and the like. Further, as a metal amide _{compound, L i NH 2, NaNH 2} , KNH 2, L i N (i- C 3 H 7) 2, N a N (i- C 3 H 7) 2, KN (i C ₃ H ₇ ) _{2 and the} like; and metal hydride compounds include Li H, NaH, KH and the like. Examples of the amines include triethylamine, pyridine, 4-dimethylaminopyridine, diazabisic oral decane, and the like.

Among them, in terms of solubility in organic solvents, L i O (t_C ₄ H ₉ ), Na O (t-C ₄ H ₉ ), KO (t-C ₄ H ₉ ), L i N (t C _{3 H 7) 2, Na N} (i one _{C 3 H 7) 2, KN} (i one C ₃ H _{7) 2,} ammonia, Amin are preferred.

Further, ammonia and triethylamine are more preferable in that the fluorescence intensity becomes stronger, and ammonia is particularly preferable because it has high volatility and hardly remains after the treatment. preferable.

 The method for producing a 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 polymer fluorescent substance into contact with the alkali, the crude polymer fluorescent substance dissolved in an organic solvent is preferably brought into contact with an alkali in view of the contact efficiency.

 Examples of the method of contacting with an alkali include: (a) a method in which an alkali is directly added to a solution in which a crude polymer fluorescent substance is dissolved; (b) a solution in which an alkali is dissolved in a solvent to dissolve a coarse polymeric fluorescent substance (C) a method in which a solution in which a crude polymer fluorescent substance is dissolved is added to a solution in which the polymer is dissolved, and (d) a method in which the crude polymer fluorescent substance is dissolved in a solvent in which the polymer is dissolved. And a method of dispersing the body.

 In the methods (b) and (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 solvent is dissolved may be a solvent that is uniformly mixed with the dissolved organic solvent, or may be a solvent that is not uniformly mixed. Among the organic solvents, the same organic solvent as that in which the crude polymer fluorescent material is dissolved is preferred.

 In the step of bringing into contact with the alkali, the contact efficiency between the alkali and the polymeric fluorescent substance can be improved by stirring and shaking the solution as necessary.

 The time for contact with the alkali is not particularly limited, but is usually 30 minutes or more and 20 hours or less, preferably 1 hour or more and 20 hours or less in order to obtain a sufficient solubility improving effect. Further, the temperature for contacting with anorecali is usually from 10 ° C. to 200 ° C., and preferably from room temperature to less than the boiling point of the solvent. Although it depends on the solvent used, it is practically more preferable that the temperature is 30 ° C. or more and 150 ° C. or less, and it is more preferable that the temperature is 50 ° C. or more and 100 ° C. or less. However, when using a highly volatile solvent such as ammonia, treatment at around room temperature is preferred. During the treatment, it is preferable to seal in an inert atmosphere in order to suppress the deterioration of the polymer fluorescent substance, and it is preferable to shield the light so that light of a wavelength absorbed by the polymer fluorescent substance solution is not irradiated. .

In the present invention, the step of bringing the crude high molecular weight phosphor into contact with an alkali may be performed continuously without separating the step of synthesizing the coarse high molecular weight phosphor. For example, a crude polymer fluorescent substance that exists as a solution is not separated as a precipitate, And the like.

 The production method of the present invention may include, as necessary, neutralization, washing, reprecipitation, drying, and other steps in addition to the step of bringing into contact with an alkali.

 After the step of contacting the polymer phosphor, it is preferable to provide a step of removing the polymer phosphor from the polymer phosphor. In order to remove the alkali, it is necessary to carry out a neutralization treatment and then to wash sufficiently, or to wash sufficiently using a solvent that can dissolve the alcohol well.

 The alkali can also be removed by dissolving the polymeric fluorescent substance obtained by bringing it into contact with an alkali and reprecipitating it with a solvent and a poor solvent. In order to remove highly volatile alcohol such as ammonia, drying under reduced pressure or heating in an inert atmosphere may be used.

At the time of drying, it is sufficient that the remaining solvent is sufficiently removed. In order to prevent deterioration of the polymer phosphor, it is preferable to dry the polymer phosphor in a light-shielded atmosphere under an inert atmosphere. Further, it is preferable to dry at a temperature at which the polymeric fluorescent substance does not thermally deteriorate. : Polymeric fluorescent substance of the present invention are typically, a molecular weight of 10 ⁴ to polystyrene standards

It is 0 ^u , and the total number of those repeating structures varies depending on the repeating structures, their ratio, and the processing method after combining. In general, the total number of the repeating structures is preferably from 20 to 10,000, more preferably from 30 to 10,000, and particularly preferably from 50 to 5,000, from the viewpoint of film formability.

 When the polymer fluorescent substance of the present invention is used as a light emitting material for a polymer LED, its purity affects the light emitting properties.Therefore, after polymerization or alkali treatment, purification treatment such as reprecipitation purification, separation by chromatographic method, etc. should be performed. Is preferred.

 Next, the crude polymer phosphor will be described.

The crude polymer fluorescent substance has fluorescence in a solid state, has a number average molecular weight of 10 ⁴ to 10 ⁸ in terms of polystyrene, and contains at least one kind of the repeating unit represented by the above formula (1). the total amount of the repeating units is not more than 100 Mo ^ ^% 10 mole _^0/0 or more of the total repeating units, in order to obtain a sufficient effect of contacting with the alkali is not less than 30 mol% to 100 mol _^0/0 or less Is more preferable, and it is further preferable that it is 50 mol% or more and 100 mol% or less.

In the above formula (1), Ar i is an arylene group or a heterocyclic compound group. The arylene group usually has 6 to 60 carbon atoms in the main chain, and the heterocyclic compound group usually has 4 or more carbon atoms in the main chain. It consists of 60 or less. Note that "number of carbon atoms contained in the main chain portion" also Alpha _{gamma iota} can have a substituent group, the number of carbon atoms of Alpha _{gamma iota} is that no such include the number of carbon atoms of the substituent means.

 Ar ;! may be selected so as not to impair the fluorescent properties of the polymeric fluorescent substance, and specific examples include the following divalent groups.

TZS0 / I0df / X3d

lZSO / lOdf / X3 «I

Here, R is independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an aryl group. Alkenyl group It represents a group selected from the group consisting of a reelalkynyl group, an arylamino group, a heterocyclic compound group and a cyano group. In the above example, one structural formula has a plurality of Rs, but they may be the same or different groups, and each is independently selected. When Ar has a plurality of substituents, they may be the same or different. In order to increase the solubility in a solvent, the compound preferably has at least one substituent that is not a hydrogen atom, and preferably has low symmetry in the shape of the repeating unit including the substituent.

 R force The case where the substituent is other than a hydrogen atom or a cyano group will be described.

 The alkyl group may be straight-chain, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl, i-propyl, butyl, i Monobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl, etc. And a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and a 3,7-dimethinoleoctyl group are preferred.

 The alkoxy group may be straight-chain, branched or cyclic, and usually has about 1 to 20 carbon atoms.Specifically, methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, otatyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyl And a pentoxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group.

The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methylthio, ethylthio, propylthio, i-propylthio, butylthio, i —Butylthio, t-butyl ^^ thio, pentylthio, hexylthio, cyclohexylthio, heptylthio, otatinolethio, 2-ethylhexylthio, nonylthio, decylthio, 3,71 Dimethyl otatyl thio group, lauryl thio group, etc., pentyl thio group, Hexylthio, octylthio, 2-ethylhexylthio, decylthio, and 3,7-dimethylotatylthio are preferred.

 The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. Specifically, methylsilyl group, ethylsilyl group, propylsilyl group, i- propylsilyl group, butylsilyl group , I-butylsilyl, t-butylsilyl, pentylsilyl, hexylsilyl, cyclohexylsilyl, heptylsilyl, octylsilyl, 2-ethylhexylsilyl, nonylsilyl, decylsilyl, 3,7- Dimethyloctylsilyl group, laurylsilinole group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, i-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilinole group, pentyl dimethylinosilyl group, Hexyldimethylsilinole group, Hepti Dimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethinoleoctyl monodimethylsilyl group, lauryldimethylsilyl group, etc. Pentylsilyl group, hexylsilyl group, octylsilyl group, 2-ethylhexynolesilyl group, decylsilyl group, 3,71-dimethyloctylsilyl group, pentinoresmethynolesilyl group, hexyldimethylsilyl group, octyldimethyl Preferred are silyl, 2-ethylhexyldimethylsilyl, decyldimethylsilyl, and 3,7-dimethyloctyl-dimethylsilyl.

The alkylamino group may be linear, branched or cyclic, may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. Specifically, a methylamino group, a dimethylamino group, Ethylamino, acetylamino, propylamino, i-propylamino, butylamino, i-butylamino, t-butylamino, pentylamino, hexinoleamino, cyclohexylamino, heptylamino, octylamino, 21-ethyl Hexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, etc., pentylamino group, hexylamino group, octylamino group, 2-ethylhexylamino group, decylamino group, 3, 7—Dimethyl Tachiruamino group is preferred. Ariru group has a carbon number of usually 6-6 0 degree, specifically, phenyl group, ^c i ~ ^c i 2 alkoxy phenylalanine group ^(c i to ^c i 2 is the number 1 to 1 2 carbon atoms the same is true. below indicate that.), C i~C 1 ₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group and the like, Ji ^ ~ Ji ₂ alkoxy phenylalanine groups, C i C i ₂ alkylphenyl group are preferable.

Ariruokishi group has a carbon number of usually 6-6 0 degree, specifically, Fuweno alkoxy group, C i~C ₂ alkoxy phenoxyethanol group, C i~C 1 ₂ alkylphenoxy groups, 1- Examples include a naphthyloxy group and a 2-naphthyloxy group;

A C ₁₂ alkoxy phenoxy group and a C i C jL ₂ alkyl phenoxy group are preferred. § reel alkyl group has a carbon number of usually 7-6 0 degree, specifically, Hue sulfonyl one C丄～〇 ₁ 2 alkyl group, C E ~ C丄2 § Honoré Koki Schiff enyl one C. 1 to C ₁ 2 alkyl group, C E ~ i ₂ Arukirufue two Lou C ~! _2- alkyl group, 1-naphthyl-C 1 ~ 2 ₁ alkyl group, 2-naphthyl-C-! Such as _2-alkyl group is represented example, C i~C 1 ₂ Arukokishifue two Lou C I～C 1 ₂ alkyl group, C! Le Shi preferred is ~ C ₁ 2 alkyl Fe two Lou C丄~ C i ₂ alkyl groups ,.

§ reel alkoxy group has a carbon number of usually 7-6 0 degree, specifically, full Eniru C丄~ Ji _{1 2} alkoxy, C -C 2 alkoxy phenylalanine one C-C _{1 2} alkoxy group, C to 〇i ₂ alkylphenyl C to C ₁₂ alkoxy group,

1- Nafuchiru C丄~ Ji _{1 2} alkoxy group, 2-Nafuchiru C etc. -C _{1 2} an alkoxy group and the like, C I～C 1 ₂ Arukokishifue two Lou C I～C 1 2 Anorekokishi group, C -C _{A 2-} alkylphenyl C ₁ -〇 ₁₂ alkoxy group is preferred.

Ariruamino group has a carbon number of usually 6-6 0 C., Fueniruamino group, Jifueniruamino group, C i~C 1 ₂ alkoxy phenylalanine § amino group, di (C! ~ C! ₂ alkoxy phenylpropyl) amino group, di (C丄_1-2 alkylphenyl) amino groups, 1 _ Nafuchiruamino group, such as 2-Nafuchiruamino group and the like,

C! ₂ alkylphenyl § amino group, di (C ~ C i ₂ alkylphenyl) amino group are preferable.

Heterocyclic compound group has a carbon number of usually 4-6 0 degree, specifically, thienyl group, C 1~◦] L ₂ alkyl chain group, a pyrrolyl group, a furyl group, a pyridyl group, C! ~ CJ 2 such alkyl pyridyl group are exemplified, thienyl group, C ~ CJ ₂ Al Kirucheniru group, a pyridyl group, a C丄~ C i ₂ alkyl pyridyl group are preferable.

Among the examples of R, in the substituent containing an alkyl chain, they may be linear, branched, or cyclic, or a combination thereof. When the substituent is not linear, for example, isoamyl group, 2-ethyl Hexyl group, 3,7-dimethyloctyl group, hexyl hexyl group, 41. Examples thereof include _2- alkylcyclohexyl group and the like. In order to enhance the solubility of the polymeric fluorescent substance in the solvent, it is preferable that at least one of the substituents of Ari contains a cyclic or branched alkyl chain.

 Further, a plurality of Rs may be linked to form a ring. Further, when R is a group containing an alkyl chain, the alkyl chain may be interrupted by a group containing a hetero atom. Here, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the group containing a hetero atom include the following groups.

I ³ ^ 3 Ο

 -0- -S--N--B--Si- -C-

O 0 0 0

 II II II II

 -C-O- — O— C— — N— C— -C-N-

R ₃ R ₃

Here, examples of R ₃ include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, and a heterocyclic compound group having 4 to 60 carbon atoms. Further, among the examples of R, when a aryl group / heterocyclic compound group is contained in a part thereof, they may further have one or more substituents.

In the above formula (1), n is 0 or 1. In the above formula (1), R ₂ represents a group independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a heterocyclic compound group and a cyano group.

The case where R i and R ₂ are substituents other than a hydrogen atom or a cyano group will be described.

The alkyl group may be straight-chain, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl, i-propyl, Butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl A pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and a 3,7-dimethyloctyl group.

Ariru group has a carbon number of usually 6-6 0 degree, specifically, Fuyuniru group, C I～C丄₂ alkoxy phenylalanine group, C ~ Ji ₂ alkylphenyl group, 1 one naphthyl group, Examples thereof include a 2-naphthyl group and the like, with preference given to C 1 -C 2 i-alkoxyphenyl groups and C i -C 2 -alkylphenyl groups.

The heterocyclic compound group usually has about 4 to 60 carbon atoms, and specifically includes a phenyl group. ~ Ji ₂ alkyl chain group, a pyrrolyl group, a furyl group, a pyridyl group, ^c. 1 to C 1 ₂ alkyl pyridyl group are exemplified, thienyl group, C I～C 2 Al Kirucheniru group, a pyridyl group, C ~ C i _Two alkylpyridyl groups are preferred.

 In addition, the terminal group of the crude polymer fluorescent substance may be protected with a stable group, since if the polymerization active group remains as it is, the light-emitting characteristics and life of the element may be reduced. . Those having a conjugate bond continuous with the conjugate 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 of JP-A-9-145478.

 The polymeric fluorescent substance obtained by the production method of the present invention also has substantially the same repeating units as the crude polymeric fluorescent substance used in the production.

As a method for synthesizing the crude polymer fluorescent substance, when a main chain has a vinylene group, for example, a method described in Japanese Patent Application Laid-Open No. H5-220355 may be mentioned. That is, polymerization of a dialdehyde compound and a diphosphonium salt compound by a Wittig reaction, polymerization of a divinyl compound and a dihalogen compound or Heck reaction of a vinylamine compound alone, and polymerization of a dialdehyde compound and a diphosphorous acid. Polymerization with ester compound by Horner-W adsworth-Emmons method, polycondensation of compound having two methyl groups by hydrogen dehydrohalogenation method, polymerization of compound having two sulfonium salt groups Polycondensation by sulfonium salt decomposition method, dialdehyde compound Examples include methods such as polymerization of a compound and a diacetonitrile compound by a Kn oevenagel reaction, and methods such as polymerization of a dialdehyde compound by a McMurry reaction.

When the main chain does not have a vinylene group, for example, a method of polymerizing the corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, Fe method of polymerizing Ri by the oxidizing agent, such as C l _3, electrochemically methods oxidative polymerization, a method by decomposition of an intermediate polymer that have a suitable leaving group can be exemplified.

 When the polymer fluorescent substance of the present invention is used as a light emitting material for a polymer LED, its purity affects the emission characteristics. Therefore, the monomer before polymerization of the crude polymer fluorescent substance is distilled, sublimated, purified and recrystallized. It is preferable to polymerize after purifying by such a method.

 Note that the crude polymer fluorescent material has a formula within a range that does not impair the fluorescence characteristics and the charge transport characteristics.

A repeating unit other than the repeating unit represented by (1) may be included. Further, the repeating unit represented by the formula (1) and other repeating units may be connected by a non-conjugated portion, or the repeating unit may include the non-conjugated portion. Examples of the bonding structure containing the non-conjugated moiety include the following, a combination of the following and a vinylene group, and a combination of two or more of the following. Here, R is a group selected from the same substituents as described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

 o o o o

 II II II II

 -c-o- one o-c— — N-C one — C-N-

R R

-C≡C-I

Further, the crude polymer 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. Good. From the viewpoint of obtaining a polymer fluorescent substance having a high quantum yield of fluorescence, a random copolymer-block or graft copolymer having a block property is preferable to a complete random copolymer. If the main chain is branched and has three or more terminal groups, ゃ dendrimers are also included.

 When used as a light emitting material for a polymer LED, light emission from a thin film is used, and therefore, a crude polymer fluorescent material having fluorescence in a solid state is preferably used. Examples of good solvents for the crude polymer fluorescent substance include chloroform form, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, decalin, n-butylbenzene, dioxane and the like. Although it depends on the structure and molecular weight of the polymeric fluorescent substance, usually, it is possible to dissolve it in these solvents in an amount of 0.1% by weight or more.

 Next, the polymer LED of the present invention will be described.

 The structure of the polymer LED of the present invention has a light emitting layer between a pair of anodes and cathodes, at least one of which is transparent or translucent. A molecular phosphor is included in the light emitting layer.

 The polymer LED of the present invention includes a polymer LED having an electron transport layer between a cathode and a light-emitting layer, a polymer LED having a hole transport layer between an anode and a light-emitting layer, and a cathode. Polymer LED in which an electron transporting layer is provided between the light emitting layer and the anode, and a hole transporting layer is provided between the anode and the light emitting layer.

 For example, the following structures a) to d) are specifically exemplified.

a) Anode Z light emitting layer / cathode

b) Anode / hole transport layer Z light-emitting layer / cathode

c) Anode Z Light-emitting layer Z Electron transport layer Z Cathode

d) Anode / hole transport layer Z light-emitting layer electron transport layer / cathode

(Here, Z indicates that the respective layers are stacked adjacent to each other. The same applies hereinafter.) Here, the light emitting layer is a layer having a function of emitting light, and the hole transport layer is A layer having a function of transporting electrons. An electron transporting layer has a function of transporting electrons. Layer. Note that the electron transport layer and the hole transport layer are collectively called a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently. Among the charge transport layers provided adjacent to the electrodes, those having the function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the device are particularly suitable for the charge injection layer (hole injection layer). Layer, electron injection layer).

 Further, the above-described charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode in order to improve adhesion to the electrode and improve charge injection from the electrode. A thin buffer layer may be inserted at the interface between the charge transport layer and the light-emitting layer for the purpose of improvement and prevention of mixing.

 The order and number of layers to be stacked 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 a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to a cathode, and a charge injection layer adjacent to an anode. Polymer LED provided.

 For example, the following structures e) to p) are specifically mentioned.

e) Anode Z charge injection layer / emission layer Z cathode

f) Anode Z light emitting layer / charge injection layer / cathode

g) Anode Z charge injection layer Z light emitting layer Z charge injection layer / cathode

h) anode Z charge injection layer Z hole transport layer Z light emitting layer Z cathode

 i) Anode / Hole transport layer Z Light emitting layer Z Charge injection layer / Cathode

j) anode Z charge injection layer Z hole transport layer Z light emitting layer / charge injection layer / cathode

k) Anode / charge injection layer / emission layer Z electron transport layer

 1) Anode Z light emitting layer Z electron transport layer Z charge injection layer / cathode

m) Anode / charge injection layer / emission layer Z electron transport layer / charge injection layer / cathode

n) anode Z charge injection layer Z hole transport layer Z light emitting layer Z electron transport layer / cathode

o) Anode / hole transport layer Z light-emitting layer z electron transport layer / charge injection layer / cathode

P) Anode / Charge injection layer / Hole transport layer Z Emitting layer Z Electron transport layer / Charge injection layer Negative cathode Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer. Between the anode material and the hole transport material contained in the hole transport layer. A layer containing a material having an ionization potential of, and a layer provided between the cathode and the electron transport layer and containing a material having an electron affinity of an intermediate value between the P pole material and the electron transport material contained in the electron transport layer And the like.

When the charge injection layer is a layer containing a conductive polymer, the conductive polymer preferably has an electric conductivity of 10 to ⁵ SZcm or more and 10 ³ S / cm or less. 10 0 to make it smaller. S / cm or more 10 ² SZcm hereinafter more preferably, 10- ⁵ SZcm or more and 10 ¹ S / cm or less is more preferred. Normally in order to electrically conductivity 10- ⁵ S / cm or more 10 ³ S / cm or less under the conducting polymer, a suitable amount of ions are doped into the conducting polymer.

 The kind of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrenesulfonate, alkylbenzenesulfonate, camphorsulfonate, and the like.Examples of cations include lithium, sodium, potassium, and tetrabutylammonium. And the like.

 The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

 The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer.Polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylenevinylene and its Derivatives, polyphenylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), carbon And the like. The insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. S Polymer LEDs with an insulation layer of 2 nm or less in thickness include polymer LEDs with an insulation layer of 2 nm or less adjacent to the cathode, and insulation of 2 nm or less adjacent to the anode. A polymer LED having a layer is exemplified.

 Specifically, for example, the following structures q) to ab) are mentioned.

q) Anode Z Insulation layer with a thickness of 2 nm or less r) Anode / Emitting layer / Insulating layer with thickness less than 2 nm / Cathode

 s) Anode Z Insulating layer with thickness less than 2 nm Z Emitting layer Z Insulating layer with thickness less than 2 nm / cathode t) Anode / Insulating layer with thickness less than 2 nm / hole transport layer Z emitting layer Z cathode

 u) Anode Z Hole transport layer Z Luminescent layer / insulating layer 2 nm or less in thickness Z Cathode

 V) Anode / Insulation layer with a thickness of 2 nm or less / Hole transport layer Z Luminescent layer Z Absolute with a thickness of 2 nm or less w) Anode / Insulation layer with a thickness of 2 nm or less Z Luminescent layer / Electron transport layer Z Cathode

 x) Anode emission layer Z Electron transport layer / Insulation layer with thickness of 2 nm or less Z cathode

y) Anode Z Insulation layer / light-emitting layer with a thickness of 2 nm or less Z Electron transport layer Z Insulation layer with a thickness of 2 nm or less Z cathode

 z) Anode Z Insulation layer / Hole transport layer / Emitting layer with thickness less than 2 nm / Electron transport layer Z Electron transport layer / Z cathode aa) Anode / Hole transport layer Z Emitting layer / Electron transport layer / Insulation layer with thickness less than 2 nm A cathode) Anode Z Insulation layer with a thickness of 2 nm or less Z Hole transport layer Z Emission layer / Electron transport layer / Insulation layer with a thickness of 2 nm or less Z Cathode

 When forming a polymer LED, by using these organic solvent-soluble polymer fluorescent materials obtained by the manufacturing method of the present invention and forming a film from a solution, the solution is applied and dried to form a solvent. The same method can be applied to the case where a charge transporting material or a luminescent material is mixed, which is very advantageous in manufacturing. Spin coating, casting, microgravure coating, gravure coating, percoating, roll coating, wire coating, dip coating, spray coating, screen printing, etc. It is possible to use a coating method such as flexographic printing, offset printing, and ink jet printing.

 The optimum value of the thickness of the light emitting layer differs depending on the material used, and may be selected so that the driving voltage and the light emitting efficiency have appropriate values. For example, the thickness is 1 nm to 1 μm, and preferably 2 η π ! 5500 nm, more preferably 5 nm n200 nm.

In the polymer LED of the present invention, a light-emitting material other than the above-described polymer fluorescent substance obtained by the production method of the present invention may be mixed and used in the light-emitting layer. In addition, the invention of the present application In the molecular LED, a light emitting layer containing a light emitting material other than the polymer fluorescent substance may be laminated with the light emitting layer containing the polymer fluorescent substance.

 As the light emitting material, known materials can be used. Examples of low molecular compounds include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, and cyanine-based dyes, metal complexes of 8-hydroxyquinoline or derivatives thereof, and aromatics. For example, amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.

 Specifically, known materials such as those described in JP-A-57-51781 and JP-A-59-194393 can be used.

 When the polymer LED of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and an aromatic amine in a side chain or a main chain. Polysiloxane derivative, virazoline derivative, arylamine derivative, stilbene derivative, triphenylenoresamine derivative, polyaniline or its derivative, polythiophene or its derivative, polypyrrole or its derivative, poly (p-phenylenevinylene) Is exemplified by a derivative thereof, or poly (2,5-Chenylene vinylene) or a derivative thereof.

 Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-209988, Examples thereof include those described in JP-A-3-37992 and JP-A-3-152184.

Among these, as a hole transporting material used for the hole transporting layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, or a polyaniline. A high molecular weight hole transporting material such as phosphorus or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, or poly (2,5-chenylenevinylene) or a derivative thereof is preferable. More preferably, polybulcarpazole or its derivative, polysilane or its derivative, side chain or main chain A polysiloxane derivative having an aromatic amine in the chain. In the case of a low molecular weight hole transporting material, it is preferable to use it by dispersing it in a high molecular binder.

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

 As polysilane or a derivative thereof, Chemical 'Review (Chem. Rev.), Vol. 89, pp. 139 (1989), British Patent No. GB 2 301 196 Compounds described in this document are exemplified. The method described in these methods can be used for the synthesis method, but the Kibbing method is particularly preferably used.

 Since the siloxane skeleton structure has little hole-transport property, those having the structure of the above-described low-molecular-weight hole-transport material in a side chain or a main chain are preferably used as the polysiloxane or a derivative thereof. Particularly, those having an aromatic amine having a hole transporting property in a side chain or a main chain are exemplified.

 There is no limitation on the method of forming the hole transport layer. For the low molecular weight hole transport material, a method of forming a film from a mixed solution with a polymer binder is exemplified. In the case of a polymer hole transporting material, a method of forming a film from a solution is exemplified.

 The solvent used for film formation from a solution is not particularly limited as long as it dissolves the hole transport material. Examples of the solvent include chlorinated solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, and ketones such as acetone and methyl ethyl ketone. Examples of the solvent include ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate.

 Solution coating methods include spin coating, casting, microgravure coating, gravure coating, percoating, roll coating, wire bar coating, dip coating, spray coating, and screen coating from solution. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

As the polymer binder to be mixed, those which do not extremely inhibit charge transport are preferable, and those which do not strongly absorb visible light are preferably used. Examples of the polymer binder include polycarbonate, polyatarylate, and polymethyl atalay. , Polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

 The optimal value of the thickness of the hole transport layer depends on the material used, and may be selected so that the driving voltage and the luminous efficiency are at appropriate values, but at least a thickness that does not cause pinholes is necessary. If the thickness is too large, the driving voltage of the device becomes high, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 im, 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, any known electron transporting material can be used, such as oxadiazole derivative, anthraquinodimethane or its derivative, benzoquinone or its derivative, naphthoquinone or its derivative. Derivative, anthraquinone or its derivative, tetracyanoanthraquinodimethane or its derivative, fluorenone derivative, diphenyldicyanoethylene or its derivative, diphenoquinone derivative, or metal complex of 8-hydroxyquinoline or its derivative, polyquinoline or Derivatives thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof and the like are exemplified. Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-135351, JP-A-2-209998, JP-A-3-37992 And Japanese Patent Publication No. 3-152184.

 Of these, oxadiazole derivatives, benzoquinone or its derivatives, anthraquinone or its derivatives, or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, and polyfluorene or its derivatives are preferred. 2- (4-biphenylyl) -5- (4-t-butylphenyl) 1,1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolino-mono) aluminum, and polyquinoline are more preferred.

There is no particular limitation on the film formation method of the electron transport layer. For low molecular weight electron transport materials, a vacuum deposition method from powder or a film formation method from a solution or a molten state is used. For the electron transport material, a method by film formation 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 in combination. The solvent used for film formation from a solution is not particularly limited as long as it can dissolve the electron transport material and / or the polymer binder. Examples of the solvent include chlorinated solvents such as chlorophonolem, dimethyl chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, and acetic acid. Ester solvents such as butyl and ethyl cellosolve acetate are exemplified.

 Spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire-coating, dip coating, spray coating, screen coating, etc. An application method such as an ink-jet printing method, a flexographic printing method, an offset printing method, and an ink-jet printing method can be used.

'As the polymer binder to be mixed, those which do not extremely inhibit charge transport are preferable, and those which do not strongly absorb visible light are preferably used. Poly ( _{と し て -vinylcarbazole)} is used as the _polymer binder. , Polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (ρ-phenylenevinylene) or a derivative thereof, poly (2,5-chenylenevinylene) or a derivative thereof, polycarbonate, polyatarylate, polymethylacrylic Rate, polyethylene methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

 The optimum value of the thickness of the electron transporting layer depends on the material used, and may be selected so that the driving voltage and the luminous efficiency are appropriate. However, at least a thickness that does not cause pinholes is necessary. Yes, too thick is not desirable because the driving voltage of the device is high. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 im, preferably 2 nm to 500 nm, and more preferably 5 ηπ! ~ 200 nm.

The substrate on which the polymer LED of the present invention is formed may be any substrate as long as it does not change when an electrode is formed and an organic layer is formed. For example, glass, plastic, polymer And a silicon substrate. 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 translucent. As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, it is made using conductive glass consisting of indium oxide, zinc oxide, tin oxide, and their composites, such as indium tin oxide (ITO), aluminum oxide, oxide, and oxide. Films (eg, NESA), gold, platinum, silver, copper, etc., are used, and ITO, indium oxide, zinc oxide, and tin oxide are preferred. Examples of the manufacturing method include a vacuum evaporation method, a sputtering method, an ion plating method, and a plating method. An organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode. The thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, from 10 nm to 10 μιη, preferably from 20 nm to 1 μm. And more preferably 50 nm to 500 nm.

 In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness made of a metal oxide, a metal fluoride, an organic insulating material, or the like is formed on the anode. Even if a layer of nm or less is 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, metals such as lithium, sodium, potassium, norebium, cesium, beryllium, magnesium, calcium, strontium, barium, anorenium, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc.合金 Alloys of two or more of them, or one or more of them, and one or more of gold, silver, platinum, copper, manganese, titanium, copanoleto, nickele, tungsten, and tin, graphs Aite or a graphite interlayer compound is used. Examples of alloys include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, etc. . The cathode may have a laminated structure of two or more layers. The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, for example, 10 11 111 to 10 μπι, preferably 2 O nm to l / im, More preferably, it is 50 nm to 500 nm.

 As a method for producing the cathode, a vacuum evaporation method, a sputtering method, a lamination method of thermocompression bonding of a metal thin film, and the like are used. 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 having an average thickness of 2 nm or less may be provided between the cathode and the organic material layer. After fabrication, a protective layer for protecting the polymer LED may be attached. In order to use the polymer LED stably for a long period of time, it is preferable to attach a protective layer and Z or a protective cover to protect the element from the outside.

 As the protective layer, a polymer compound, a metal oxide, a metal fluoride, a metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate whose surface has been subjected to a low water permeability treatment, or the like can be used, and the cover is bonded to the element substrate with a heat effect resin or a photocurable resin to seal the cover. Is preferably used. If the space is maintained using a spacer, it is easy to prevent the element from being damaged. By enclosing an inert gas such as nitrogen or argon in the space, it is possible to prevent oxidation of the cathode, and by installing a desiccant such as an oxidation slurry in the space. It becomes easy to suppress the moisture adsorbed in the manufacturing process from damaging the element. It is preferable to take one or more of these measures.

In order to obtain planar light emission using the polymer LED of the present invention, a planar anode and a planar cathode may be arranged so as to overlap. Further, in order to obtain patterned light emission, a method in which a mask having a patterned window provided on the surface of the planar light emitting element is provided. There is a method of emitting light, a method of forming one or both of an anode and a cathode in a pattern. By forming a pattern using one of these methods and arranging several electrodes so that they can be turned on and off independently, a segment-type display element that can display numbers, letters, simple symbols, etc. can be obtained. . Further, in order to form a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. A method of applying different types of polymer phosphors with different emission colors, a color filter Depending on the method using one or a fluorescence conversion filter, partial color display and multi-color display can be realized. The dot matrix element can be driven passively or may be driven actively 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 packing in a liquid crystal display device or a planar illumination light source. Also, if a flexible substrate is used, it can be used as a curved light source or display device.

 Hereinafter, examples will be shown in order to explain the present invention in further detail, but the present invention is not limited to these.

 Here, the number average molecular weight was determined by gel permeation chromatography (GPC) using the form of solvent as a solvent, and the number average molecular weight in terms of polystyrene was determined.

Example 1

 <Synthesis of polymeric fluorescent substance 1>

 2-Methoxy-5- (2-ethylhexyloxy) -p-xylene dichloride 0.166 g and 4- (3,7-dimethyloctyloxy) phenyl _p-xylylene dichloride 9.7 7 g was dissolved in 180 g of dried 1,4-dioxane, and the reaction solution was heated to 95 ° C. after degassing by bubbling with nitrogen for 15 minutes. To this solution, a solution of 7.4 g of t-butoxycalide / 100 g of dried 1,4-dioxane was added dropwise in 5 minutes. After the temperature of the solution was further raised to 97 ° C., a solution of 5.6 g of t_butoxy potassium / 100 g of dried 1,4-dioxane was added dropwise. The reaction was allowed to proceed at 97 to 98 ° C for 2 hours. After the reaction, the mixture was cooled to 50 ° C, and neutralized by adding a mixed solution of acetic acidΊ0 g / 1,4-dioxane 7.0 g. After allowing to cool to room temperature, the reaction solution was poured into stirred methanol. Next, the step of separating the deposited precipitate by filtration and washing with methanol was repeated twice. The obtained precipitate was dried under reduced pressure at 50 ° C for 8 hours to obtain a polymer.

Next, this polymer is dissolved in tetrahydrofuran, and this is poured into methanol. And purified by reprecipitation. After washing the precipitate with methanol, 50. It was dried under reduced pressure at C for 8 hours to obtain 4.41 g of a polymer.

<Alkali treatment>

 0.93 g of the polymer was dissolved in 32 g of dry 1,4-dioxane, bubbled with nitrogen for 15 minutes, degassed, and the solution was heated to 90 ° C. To this solution, a solution of 1.3 g of t-butoxy potassium and 20 g of dried 1,4-dioxane was added dropwise over 5 minutes. The temperature of the solution was further increased to 93 ° C, and stirring was continued for 9 hours.

 Thereafter, the mixture was cooled to 50 ° C. and neutralized by adding a mixed solution of 1.1 g / l of acetic acid and 1.1 g of 4-dioxane. After allowing to cool to room temperature, the reaction solution was poured into stirred ion-exchanged water. Next, the deposited precipitate was separated by filtration and washed with methanol. This was dried under reduced pressure at 50 ° C for 4 hours to obtain 0.888 g of a polymer.

 This was dissolved in tetrahydrofuran, poured into methanol, and purified by reprecipitation. The precipitate was washed with methanol and dried under reduced pressure at 50 ° C for 5.5 hours to obtain 85 g of a polymer. This polymer is referred to as polymeric fluorescent substance 1.

The polystyrene equivalent number average molecular weight of polymeric fluorescent substance 1, 1. 6 X 1 0 ⁵ der ivy. The 0.4% toluene solution of polymeric fluorescent substance 1 became a homogeneous solution when heated, and did not become entrapped even at room temperature.

Comparative Example 1

 In the first embodiment, the crude polymer fluorescent substance before the initial processing is referred to as polymer fluorescent substance 2. The number average molecular weight in terms of polystyrene of the polymeric fluorescent substance 2 is 4.3 X 1

0. Met. The 0.4% toluene solution of polymeric fluorescent substance 2 became a homogeneous solution when heated, but gelled when returned to room temperature.

Example 2

 <Preparation and evaluation of device>

A glass substrate on which an IT〇 film with a thickness of 150 nm was applied by sputtering was spin-coated with a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Baytron, Baytron) by spin coating. Deposited to a thickness of nm and 120 on a hot plate. Dry at C for 5 minutes. Next, a film having a thickness of 100 nm was formed by spin coating using a polymer solution of 0.4 wt% of a polymeric fluorescent substance 1 in a pore form. Sa After drying at 80 ° C for 1 hour under reduced pressure, 0.4 nm of lithium fluoride as a cathode buffer layer, 25 nm of calcium as a cathode, and then 40 nm of aluminum were deposited. A polymer LED was fabricated. The degree of vacuum in vapor deposition, to base Te was 1~8 X 10- ⁶ T orr. By applying a voltage to the obtained device, EL light emission from polymeric fluorescent substance 1 was obtained. The luminescence starting voltage was about 3 V, and the luminous efficiency was up to about 6.8 cd / A.

Example 3

Synthesis of fluorescent polymer 3>

Under an inert atmosphere, 9,9-dioctylfluorene-1,2,7-bis (ethylenpolonate) (900 mg, 1.641 mmo 1), 2,7-dibromo-1,9,9-dioctylfluorene ( 914 mg, 1.723 mm o 1) and a 1 iquat 336 (66 O mg) were dissolved in toluene (30 ml), and an aqueous solution (30 ml) of potassium carbonate (680 mg, 4.923 mm o 1) was added thereto. Was. Further, tetrakis (triphenylphosphine) palladium (57 mg, 0.0492 mmo 1) was added, and the mixture was heated under reflux for 20 hours. After allowing to cool, liquid separation was performed, and the organic layer was washed with water. The organic layer was dropped into methanol (300 ml), and the deposited precipitate was separated by filtration. The polymer was purified by silica gel chromatography (toluene) to obtain a polymer. The yield was 863 mg. The polystyrene-equivalent number average molecular weight of the polymer was 1.3 × 10 ⁴ .

<Alkali treatment>

 Next, 50 mg of the obtained polymer was dissolved in toluene to obtain a 4 g solution. This solution and 2 ml of 25% aqueous ammonia were mixed in a closed vessel, and the mixture was stirred at room temperature for 3 hours. After standing and separating into toluene and water, the liquid was separated and the toluene portion was recovered. This solution was added to 100 ml of methanol and stirred, and the resulting precipitate was separated by filtration. This was washed with methanol, and dried under reduced pressure at 50 for 2 hours to obtain 38 mg of a polymer. This polymer is referred to as polymeric fluorescent substance 3. Polymeric fluorescent substance 3 was soluble in solvents such as toluene and black-mouthed form.

Solubility>

Store 1.5% toluene solution of polymeric fluorescent substance 3 in refrigerator (about 10 ° C) overnight It turned into a soft gel, but soon returned to room temperature and became a homogeneous solution.

<Fluorescence properties>

 A 0.4% chloroform solution of polymeric fluorescent substance 3 was spin-coated on a quartz plate to form a thin film of polymeric fluorescent substance 3. The ultraviolet-visible absorption spectrum and the fluorescence spectrum of this thin film were measured using an ultraviolet-visible absorption spectrophotometer (Hitachi Ltd. UV3500) and a fluorescence spectrophotometer (Hitachi Ltd. 850), respectively. The fluorescence spectrum when excited at 350 nm was used to calculate the fluorescence intensity. The relative value of the fluorescence intensity was obtained by dividing the area of the fluorescence spectrum plotted with the wave number on the horizontal axis by the absorbance at 350 nm.

 The fluorescent peak wavelength of polymeric fluorescent substance 3 was 428η, and the relative value of the fluorescent intensity was 3.1.

Comparative Example 2

 In the third embodiment, the crude polymer fluorescent material before the initial processing is referred to as a polymer fluorescent material 4. Using this polymeric fluorescent substance 4, the UV-visible absorption peak and the fluorescent spectrum were measured in the same manner as in Example 3, and the relative value of the fluorescent intensity was obtained.

 The fluorescent peak wavelength of polymeric fluorescent substance 4 was 426 nm, and the relative value of the fluorescent intensity was 0.26.

 When a 1.5% toluene solution of polymeric fluorescent substance 4 was stored in a refrigerator (approximately 10 ° C) overnight, it became gel-like, and did not immediately become a homogeneous solution even after returning to room temperature. Industrial applicability

 The polymeric fluorescent substance obtained by the production method of the present invention has excellent solubility in an organic solvent and can be suitably used as a polymeric LED or a dye for laser. The polymer LED using the polymer phosphor obtained by the manufacturing method has low voltage and high luminous efficiency. Therefore, the polymer LED has a curved or planar light source as a backlight, a segment type display element, and a dot matrix flat panel.

 'It can be used preferably for devices such as Ray.

Claims

Claim 4

1. It has fluorescence in the solid state and has a polystyrene equivalent number average molecular weight of 10

0 is ^8, producing how the polymeric fluorescent substance, characterized in that the crude polymer fluorescent body comprising repeating units of one or more comprising the step of contacting with alkali represented by the following formula (1)

-Ar!-(CR ₁ = CR ₂ ) _n- (1) (where, A ri is an arylene group or a heterocyclic compound group, and may be unsubstituted or have one or more substituents. ,! ^ And! ^ Each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a heterocyclic compound group and a cyano group, and the aryl group and the heterocyclic compound group are And may further have a substituent, and n is 0 or 1.).

 2. The method according to claim 1, which is an alkali metal alkoxide, ammonia or an amine.

 3. The method according to claim 1, wherein the temperature at which the crude polymer fluorescent substance is brought into contact with the aluminum alloy is 10 ° C. or more and 200 ° C. or less.

 4. A polymer phosphor that can be produced by the production method according to any one of claims 1 to 3.

 5. A polymer light-emitting device having at least a light-emitting layer between electrodes consisting of a pair of anodes and cathodes, at least one of which is transparent or translucent, wherein the light-emitting layer is the polymer phosphor according to claim 4. A polymer light emitting device comprising:

 6. The polymer light emitting device according to claim 5, wherein a layer made of an electron transporting compound is provided between the cathode and the light emitting layer, adjacent to the light emitting layer.

 7. The polymer light emitting device according to claim 5, wherein a layer made of a hole transporting compound is provided between the anode and the light emitting layer, adjacent to the light emitting layer.

8. a layer comprising an electron transporting compound adjacent to the light emitting layer between the cathode and the light emitting layer; and a hole transporting layer adjacent to the light emitting layer between the anode and the light emitting layer. Consisting of compounds 6. The polymer light emitting device according to claim 5, wherein a layer is provided.

 9. A planar light source characterized by using the polymer light-emitting device according to any one of claims 5 to 8.

 10. A segment display device using the polymer light-emitting device according to any one of claims 5 to 8.

 11. A dot matrix display device characterized by using the polymer light emitting device according to any one of claims 5 to 8.

 12. A liquid crystal display device comprising the polymer light-emitting device according to any one of claims 5 to 8 as a pack light.