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WO2003000821A1 - Procedes de production d'un materiau fluorescent polymere, et element luminescent polymere - Google Patents

Procedes de production d'un materiau fluorescent polymere, et element luminescent polymere Download PDF

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Publication number
WO2003000821A1
WO2003000821A1 PCT/JP2001/005454 JP0105454W WO03000821A1 WO 2003000821 A1 WO2003000821 A1 WO 2003000821A1 JP 0105454 W JP0105454 W JP 0105454W WO 03000821 A1 WO03000821 A1 WO 03000821A1
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WO
WIPO (PCT)
Prior art keywords
acid
group
fluorescent substance
treating
polymeric fluorescent
Prior art date
Application number
PCT/JP2001/005454
Other languages
English (en)
Japanese (ja)
Inventor
Takanobu Noguchi
Masato Ueda
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP37069199A priority Critical patent/JP4482994B2/ja
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to US10/480,332 priority patent/US7297415B2/en
Priority to DE10197254T priority patent/DE10197254T5/de
Priority to PCT/JP2001/005454 priority patent/WO2003000821A1/fr
Publication of WO2003000821A1 publication Critical patent/WO2003000821A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a method for producing a polymer phosphor, and a polymer light-emitting device (hereinafter, may be referred to as a polymer LED) using the polymer phosphor produced by the method.
  • a polymer LED a polymer light-emitting device
  • inorganic electroluminescent elements (hereinafter sometimes referred to as inorganic EL elements) using an inorganic phosphor as a light-emitting material are used in, for example, surface light sources as pack lights and display devices such as flat panel displays. However, a high voltage alternating current was required to emit light.
  • organic EL device 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 in an electrophotographic photoreceptor is laminated.
  • organic EL devices are characterized by low voltage driving, high luminance, and easy emission of many colors.Therefore, the device structure, organic fluorescent dyes, and organic charge transport compounds are more common.
  • Japanese Patent Application Laid-Open No. 3-244630 describes a conjugated polymer having the characteristics that it is itself soluble in a solvent and does not require heat treatment.
  • a polymer luminescent material soluble in a solvent and a luminescent material prepared using the same were prepared. A polymer LED is described.
  • polymer LEDs can easily form an organic layer by coating, they are more advantageous in reducing the area and cost, compared to depositing a low molecular weight phosphor, and have a high molecular weight. Therefore, it is considered that the film has excellent mechanical strength.
  • polymer fluorescent materials used for these polymer LEDs include, in addition to the above-mentioned poly (p-phenylenevinylene), polyfluorene (Japanese Jar Nanole 'ob' 'applied' physics (Jpn. J. Ap.) pl. Ph y s.) Volume 30, L1941 (1991)), polyparaphenylene derivatives (Adv. Materials) Volume 4, Page 36 (1992) Year)) etc. are reported.
  • An object of the present invention is to provide a method for producing a polymer phosphor having a long life when used in a polymer LED, and a long-life polymer LED using the polymer phosphor obtained by the production method. It is in.
  • the present inventors have made intensive studies in view of such circumstances, and as a result, by using a polymer fluorescent substance manufactured by a manufacturing method including a step of treating the polymer fluorescent substance with an acid, a long life and a high life are obtained.
  • the inventors have found that a molecular LED element can be obtained, and have reached the present invention.
  • the present invention provides: (1) a step of treating a polymeric fluorescent substance having fluorescence in a solid state and having a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 8 in terms of polystyrene with an acid; And a method for producing the same. Further, the present invention provides a method of treating a polymeric fluorescent substance having fluorescence in a solid state and having a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 8 in terms of polystyrene with an acid, and Process for producing polymeric fluorescent material Related.
  • the present invention also relates to [3] a step of treating a polymeric fluorescent substance having fluorescence in a solid state and having a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 8 in terms of polystyrene with an acid
  • the present invention relates to a method for producing a polymeric fluorescent substance, which comprises a step of treating with a substance that does not contain an acid and an alkali, and finally a step of treating with a substance that does not contain an acid or an alkali.
  • the present invention also provides [4] a polymer light-emitting device having at least one light-emitting layer containing a polymer fluorescent material between an electrode composed of a pair of anodes and cathodes, at least one of which is transparent or translucent; Further, the present invention relates to a polymer light-emitting device including the polymer phosphor produced by the production method of [1] to [3]. Furthermore, the present invention relates to [5] a planar light source using the polymer light emitting device of [4]. Next, the present invention relates to [6] a segment display device using the polymer light emitting device of the above [4].
  • the present invention relates to [7] a dot matrix display device using the polymer light emitting device of the above [4]. Further, the present invention relates to [8] a liquid crystal display device using the planar light source of the above [4] as a backlight.
  • the method for producing a polymeric fluorescent substance of the present invention includes a polymeric fluorescent substance that has fluorescence in a solid state and has a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 8 in terms of polystyrene (hereinafter referred to as raw material height). (May be referred to as a molecular fluorescent substance) with an acid.
  • the method for producing a polymeric fluorescent substance of the present invention includes a polymeric fluorescent substance that has fluorescence in a solid state and has a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 8 in terms of polystyrene (hereinafter referred to as raw material height). (Which may be referred to as a molecular fluorescent substance) with an acid and an alkali. '' The method for producing a polymeric fluorescent substance of the present invention has fluorescence in a solid state.
  • Polymeric fluorescent substance number average molecular weight of calculation is 1 XI 0 4 ⁇ 1 X 1 0 8 ( hereinafter sometimes referred to as high raw material fluorescent substance) of the process and the end of treatment in the process and an alkali treatment with an acid
  • the method is characterized by including a step of treating with a substance that does not contain an acid or an acid. First, the step of treating with an acid will be described in detail.
  • the acid may be an organic or inorganic substance which is acidic in every sense, such as an organic acid and an inorganic acid.
  • Organic acids are preferred because of their high processing efficiency. Good.
  • Organic acids include alkane carboxylic acids, alkene carboxylic acids, aromatic carboxylic acids, heterocyclic carboxylic acids, aromatic alcohols, alkane sulfonic acids, alkane sulfonic acids, aromatic sulfonic acids, heterocyclic sulfonic acids, alkane sulfonic acids Acid, alkene sulfinic acid, aromatic sulfinic acid, heterocyclic compound sulfinic acid, alkane sulfonic acid, alkene sulfenic acid, aromatic sulfenic acid, heterocyclic compound sulfenic acid, alkane phosphonic acid, alkene phosphonic acid , Aromatic phosphonic acid, heterocyclic compound phosphonic acid, alkanephosphonic acid, alkenephosphenic acid, aromatic phosphenic acid, heterocyclic compound phosphenic acid, alkanephosphinic acid, alkenephosphinic acid, aromatic phosphinic acid, heterocyclic
  • the organic acids include formic acid, acetic acid, propionic acid, oxalic acid, citric acid, tartaric acid, maleic acid, phthalic acid, benzoic acid, 4-pyridinecarboxylic acid, phenol, methanesulfonic acid, and propenesulfonic acid.
  • examples of the inorganic acid include hydrohalic acid, hydroiodic acid, phosphoric acid, hydrogen oxide, nitrogen oxide, and metal oxide.
  • the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, chlorite, nitrite, selenite, arsenite, phosphorous acid, sulfurous acid, periodic acid, chromic acid, and caic acid.
  • sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid are preferred.
  • a single substance of these acids or a mixture of two or more acids can be used.
  • the “step of treating with an acid” refers to a step of bringing a raw material polymeric fluorescent substance into contact with an acid.
  • 1) is preferable from the viewpoint of good contact between the raw polymer fluorescent substance and the acid.
  • the liquid state includes a state in which the raw material polymeric fluorescent substance is dissolved in a solvent.
  • the step of treating with an acid it is preferable to perform stirring, shaking, and the like to increase the efficiency of the treatment. Further, the step of treating with an acid may be included twice or more. Further, when the step of treating with an acid is included twice or more, the type and concentration of the acid used at that time may be changed.
  • the method for producing a 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 that separates phases is used; Examples include a step of purification by reprecipitation, chromatography and the like.
  • the method 1) will be described in more detail.
  • the step of treating the raw material polymeric fluorescent substance with an acid is a step of contacting an acid solution with a solution obtained by dissolving the polymeric fluorescent substance in a solvent.
  • the solvent used for the acid solution may be water or another solvent.
  • those in which the raw material polymeric fluorescent substance in the liquid state and the acid in the liquid state are phase-separated are more preferable because the separation between the polymeric fluorescent substance and the acid is easy.
  • Both the raw polymeric fluorescent substance and the acid are dissolved in a solvent to form a liquid state.
  • a method for phase separation is to dissolve the acid in water to form an aqueous solution of the acid. It is preferable that the polymeric fluorescent substance is dissolved in a solvent that is phase-separated from an aqueous acid solution.
  • the concentration of the aqueous acid solution is not particularly limited, but is adjusted to about 0.1 to 30% by weight.
  • the acid strength of the aqueous acid solution is preferably an acid aqueous solution having a value of 0.1 or more and 5.5 or less, since the high molecular weight fluorescent substance to be treated is expected to be decomposed if too strong.
  • H is not less than 0.5 and not more than 4.5.
  • the water to be used is preferably one containing little impurities such as ions, for example, distilled water, ion-exchanged water, pure water and ultrapure water. Of these, pure water and ultrapure water are preferred, and ultrapure water is particularly preferred. As a specific index of the purity of pure water, there is conductivity, and water having a value of 10 ⁇ S cm or less is preferable, and water having a value of 1 S Z cm or less is more preferable.
  • the solvent that dissolves the polymeric fluorescent substance may be any solvent that dissolves the polymeric fluorescent substance well, and is not particularly limited.
  • Chlorinated solvents such as chlorophonolem, methylene chloride, and dichloroethane, and ethereal solvents such as tetrahydrofuran.
  • aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin and n-butylbenzene.
  • those which phase-separate from an aqueous solution (or water) of an acid are preferable, and chloroform, tetrahydrofuran and toluene are particularly preferable.
  • the temperature for the treatment with an acid is not particularly limited, and the treatment can be carried out at a temperature from room temperature to a temperature lower than the boiling point of the solvent, but is preferably a temperature between room temperature and 50 ° C.
  • the polymeric fluorescent substance is dissolved well in a solvent that dissolves the polymeric fluorescent substance well, and phase-separates from the aqueous acid solution (or water), for example, in the form of the mouth opening. (Contacting with acid). After standing, the aqueous phase of the acid is separated from the phase containing the polymeric fluorescent substance. The phase containing the separated polymeric fluorescent substance is further contacted with an aqueous solution of an acid and the above-mentioned step of treating with the acid is repeated an appropriate number of times.
  • phase containing the polymeric fluorescent substance obtained by the liquid separation is brought into contact with water to remove the acid remaining in the phase containing the polymeric fluorescent substance. Removal of the acid in the phase containing the polymer fluorescent substance is repeated until the pH of the aqueous phase becomes 7, thereby obtaining a solution of the polymer fluorescent substance.
  • a poor solvent for dissolving the polymeric fluorescent substance such as methanol
  • stirring a precipitate of the polymeric fluorescent substance is generated. The precipitate is filtered, washed with ethanol, and dried under reduced pressure to obtain a polymeric fluorescent substance.
  • Examples of the method 3) include a method in which a raw material polymeric fluorescent substance in a liquid state is treated by passing through a power ram 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 or solid-state raw material polymer phosphor.
  • the gaseous acid used here indicates acidity.
  • the method further includes a step of treating with the acid, and further includes a metal contained in the raw material polymeric fluorescent material, such as lithium, sodium, potassium, magnesium, calcium, iron, copper, manganese, aluminum, zinc, nickel, chromium, lead, and the like. Or a base component such as potassium tertiary butoxide is preferably reduced.
  • a metal contained in the raw material polymeric fluorescent material such as lithium, sodium, potassium, magnesium, calcium, iron, copper, manganese, aluminum, zinc, nickel, chromium, lead, and the like.
  • a base component such as potassium tertiary butoxide is preferably reduced.
  • the organic solvent is not particularly limited as long as it can dissolve the crude polymeric fluorescent substance.
  • good solvents for the crude polymeric fluorescent substance include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, and 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 polymer phosphor, usually 0.1% by weight or more can be dissolved in these solvents.
  • alkali used in the production method of the present invention those having a pKa value of 10 or more are preferable.
  • alkali examples include metal alkoxide, metal hydroxide, metal amide compound, metal hydride compound, ammonia, and amines.
  • Metal alkoxides include L i ⁇ CH 3 , Na OCH 3 , KOCH 3 , 'L i OC 2 H 5 , NaOC 2 H 5 , KOC 2 H 5 , L i O (t-C 4 H 9 ),
  • metal hydroxides include LiOH, Na ⁇ H, KOH and the like.
  • the metal amide of compounds is, L i NH 2, NaNH 2 , KNH 2, L i N (i-C 3 H 7) 2, Na N (i- C 3 H 7) 2, KN (i one C 3 H 7 ) 2 and the like, and examples of the metal hydride compound include Li H, Na H and KH.
  • the amines include triethynoleamine, pyridine, 4-dimethylaminopyridine, and diazabicycloundecane.
  • L i O (t—C 4 H 9 ), Na (t-C 4 H 9 ), KO (t-C 4 H 9 ), L i N (i one C 3 H 7) 2, NaN (i -C 3 H 7) 2, KN (i- C 3 H 7) 2, ammonia, Amin are preferred. Further, ammonia and triethynoleamine are more preferable in that the fluorescence intensity becomes stronger, and ammonia is particularly preferable in that they have high volatility and hardly remain after the treatment.
  • 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. Crude polymer fluorescent material In the step of contacting with potassium, contacting the crude polymer fluorescent substance with an alkali in a state of being dissolved in an organic solvent is preferable in terms of 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; and (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.
  • the solvent for dissolving the alkali in the methods (b) and (c) may be an organic solvent or water.
  • the solvent for dissolving the alkali may be a solvent that is uniformly mixed with the dissolved organic solvent or a solvent that is not uniformly mixed.
  • the same organic solvent as that in which the crude polymer fluorescent material is dissolved is preferable.
  • the solution can be agitated and shaken as necessary to improve the contact efficiency between the alkali and the polymeric fluorescent substance.
  • 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.
  • the temperature for contacting with an alkali is usually from 10 ° C. to 200 ° C., preferably from room temperature to less than the boiling point of the solvent. Although it depends on the solvent used, the temperature is practically more preferably 30 ° C. or more and 150 ° C. or less, more preferably 50 ° C. or more and 100 ° C. or less. However, when a highly volatile alkali such as ammonia is used, the treatment is preferably performed at around room temperature.
  • 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.
  • a crude polymer fluorescent substance existing as a solution is not separated as a precipitate, but is brought into contact with an alkaline solution as a solution. After contact with the alkali, it may include neutralization, washing, reprecipitation, drying and other steps as necessary.
  • a step of removing the polymer liquid from the polymer fluorescent substance is performed.
  • it is provided.
  • a neutralization treatment 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 contacting with an alkali once in a good solvent and then re-precipitating it using a poor solvent.
  • highly volatile alcohol such as ammonia
  • drying under reduced pressure or heating in an inert atmosphere may be sufficient.
  • the substance containing no acid or alkali may be an organic substance or an inorganic substance which does not exhibit acidic alkalinity in every sense, and is, for example, a neutral organic solvent, neutral water, or the like. Of water is preferred because of high treatment efficiency.
  • Examples of the neutral organic solvent include alkanes, alkenes, aromatic compounds, heterocyclic compounds, alcohols, ethers, ketones, alkanesulfonic acid esters, alkanecarboxylic acid esters, alkenesulfonic acid esters, and aromatic sulfones. Examples thereof include acid esters, sulfonic acid esters of heterocyclic compounds, and phosphoric acid esters.
  • the neutral organic solvents include hexane, hexene, benzene, toluene, 2-methinolefuran, 2-methinorethiophene, ethanolonole, methanolinole, getylether, t-butylmethylether, acetoneton, and methyl.
  • Examples include isobutyl ketone, methynoleester ethanesulfonate, ethynoleestenolacetate, methynolester propionate, ethyl ethyl 2-buteneate, methyl ethyl toluenesulfonate, ethyl ethyl 2-thiophenesulfonic acid, and trimethyl phosphate. Hexane, tonolene, methanol, ethynoleether, acetone and the like are more preferred.
  • examples of the neutral water include distilled water, ion-exchanged water, a buffer solution having a pH of about 7, and the like. Distilled water, ion-exchanged water, and the like are preferable. In the step of treating with a substance containing no acid or alkali, a single substance or a mixture of two or more of these neutral substances can be used.
  • solid acid or alkali-free substance examples include neutral silica gel, alumina gel, activated carbon, and celite.
  • the “step of treating with a substance that does not contain an acid or alcohol” refers to a high raw material price. This refers to the step of bringing the molecular fluorescent substance into contact with a substance or a substance that does not contain an acid or alcohol.
  • a method of treating a raw material polymeric fluorescent substance with a substance that does not contain acid or alkali for example,
  • 1) is preferable from the viewpoint of good contact between the raw polymer fluorescent substance and the acid.
  • the liquid state includes a state in which the raw material polymeric fluorescent substance is dissolved in a solvent.
  • the step of treating with a substance that does not contain an acid or an alkali it is preferable to perform stirring, shaking, and the like in order to increase the efficiency of the treatment. Further, the step of treating with a substance containing no acid or alkali may be included twice or more. Further, when the step of treating with a substance containing no acid or alkali is included twice or more, the type, concentration, etc. of the substance containing no alkali metal used at that time may be changed.
  • 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.
  • the steps other than the step of treating with a substance containing no acid or alkali include, for example, a step of removing a substance not containing alkali acid; a step of removing the solvent when another solvent is used; When a solvent to be separated is used, a step of separating liquids; a step of reprecipitation, a step of purifying by means of mouth chromatography, and the like can be mentioned.
  • water is preferably used as the substance containing no acid or alkali, and the water has a pH of 6.5 or more and 7.5 or less.
  • the water used has little impurities such as ions, for example, distilled water and ion exchange water. Replacement water, pure water, and ultrapure water are preferred. 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 an electric conductivity, and water having a value of 10 ⁇ S / cm or less is preferable, and water having a value of 1 S / cm or less is more preferable. The following describes the case where water is used.
  • the method 1) will be described in more detail.
  • the step of treating the raw polymer fluorescent substance with a substance containing no acid or alkali is a step of bringing water into contact with a solution obtained by dissolving the polymeric fluorescent substance in a solvent. Is preferred because of high processing efficiency.
  • Both the raw polymer fluorescent material and water are in a liquid state, and the method of separating them is that the raw polymer fluorescent material is dissolved in a solvent that separates from water. preferable.
  • the solvent for dissolving the polymeric fluorescent substance may be any solvent that dissolves the polymeric fluorescent substance well, and is not particularly limited.
  • Chlorinated solvents such as chloroform, methylene chloride and dichloroethane, and ethers such as tetrahydrofuran
  • ethers such as tetrahydrofuran
  • aromatic solvents such as toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. Among these, those which phase-separate with water are preferred, and chloroform, tetrahydrofuran and toluene are particularly preferred.
  • the temperature for the treatment with water is not particularly limited, and the treatment can be carried out at a temperature from room temperature to a temperature lower than the boiling point of the solvent, but is preferably a temperature between room temperature and 50 ° C.
  • the phase containing the separated polymeric fluorescent substance is further contacted with water and the above-mentioned step of treating with a substance containing no alkali is repeated an appropriate number of times. Thereafter, the solution containing the polymer fluorescent substance is dropped into a poor solvent for dissolving the polymer fluorescent substance, such as methanol, with stirring, whereby a precipitate of the polymer fluorescent substance is formed. I do. The precipitate is filtered, washed with ethanol, and dried under reduced pressure to obtain a polymeric fluorescent substance.
  • a poor solvent for dissolving the polymer fluorescent substance such as methanol
  • Examples of the method 2) include a method in which water is mixed with a raw material polymeric fluorescent substance in the form of a solid powder and treated by a stirring repulp type washing operation.
  • a raw material polymeric fluorescent substance in the form of a solid powder according to the present method, it is possible to remove water and other unnecessary components from the raw material polymeric fluorescent substance in the form of a solid powder after treating with water and then filtering.
  • the method 3 there is a method in which a raw material polymeric fluorescent substance in a liquid state is processed by passing through a column filled with a substance not containing an acid or an alkali in a solid state.
  • the order of the step of treating with an acid, the step of treating with an alkali, and the step of treating with a substance that does not include an acid or an alkali is not particularly limited, and is appropriately selected.
  • it is preferable that there is a step of treating with an acid after the step of treating with an acid more preferably a step of treating with an acid, a step of treating with an alkali, and a step of treating with an acid or an alkali. It is preferable to carry out the process in the order of the treatment with a substance that does not contain a force.
  • the raw material polymeric fluorescent substance used in the present invention has fluorescence in a solid state.
  • the raw material polymeric fluorescent substance used in the present invention has fluorescence in a solid state, has a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 8 in terms of polystyrene, and is represented by the following formula (1).
  • a polymeric fluorescent substance comprising at least one kind of the repeating unit shown is preferable.
  • a ri is a divalent group which forms a respective carbon one-carbon bond and two groups P Maise', the number of carbon atoms contained in the main chain is composed of 6 or more 6 0 or less
  • the compound group may have a substituent.
  • k is 0 or 1.
  • the raw material polymeric fluorescent substance used in the present invention has fluorescence in a solid state, has a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 8 in terms of polystyrene, and has the following formula (2): It preferably contains at least one kind of the repeating units represented by the following formulas (3) and (4), and more preferably the repeating units represented by the formulas (2), (3) and (4) And at least one kind of each.
  • a r 2 is a divalent group, respectively two groups adjacent to form a carbon one-carbon bond, the number of carbon atoms contained in the main chain is composed of 6 or more 6 0 or less
  • a r 2 is a plurality of substituents R 3 may be the same or different, and R 3 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, and 7 to 6 carbon atoms.
  • 0 represents an arylalkyl group or a heterocyclic compound group having 4 to 60 carbon atoms, wherein the aryl group, the arylalkyl group and the heterocyclic compound group are It may have a substituent.
  • X one O-, one S-, one CR 6 R 7 -,
  • R 4 , R 5 and R 6 to R 12 each independently represent 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 group selected from the group consisting of a cyano group, wherein the aryl group and the heterocyclic compound group may have a substituent.
  • n is 0 or 1.
  • Ar 3 is a divalent group that forms a carbon-carbon bond with two adjacent groups, and is 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 3 is —Ar 4 and has 1 to 20 carbon atoms.
  • Alkyl group alkoxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 60 carbon atoms, alkylamino group having 1 to 40 carbon atoms, aryl group having 6 to 60 carbon atoms, C6 to C60 aryloxy group, C6 to C60 arylalkyl group, C6 to C60 aryloxy group, C6 to C60 arylamino group, C4 to C60 heterocyclic compound group , And a substituent selected from the group consisting of a cyano group.
  • the Ariru group, ⁇ Li Ruokishi group, ⁇ reel alkyl group, ⁇ reel alkoxy group, Ariruamino group and the heterocyclic I arsenide Gobutsumoto may further have a substituent.
  • a r 3 is plural When it has a substituent, they may be the same or different.
  • Ar 4 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 the heterocyclic compound group may have a substituent.
  • o is an integer from 1 to 4.
  • R 13 and R 14 are each independently a 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. And a group selected from the group consisting of an aryl group and a heterocyclic compound group May have a substituent.
  • p is 0 or 1.
  • Ar 5 is a divalent group that forms a carbon-carbon bond with two adjacent groups, and the number of carbon atoms contained in the main chain part is 6 or more and 60 or less Ariren group, or the number of carbon atoms contained in the main chain shows what is a heterocyclic compound group consisting of 4 or more 6 0 or less.
  • the a r 5 is charcoal in addition one R 1 5 Alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 60 carbon atoms, and phenolic amino group having 1 to 40 carbon atoms ,
  • An aryl group having 6 to 60 carbon atoms, an aryloxy group having 6 to 60 carbon atoms, an arylalkyl group having 6 to 60 carbon atoms, an aryl alkoxy group having 6 to 60 carbon atoms, and 6 to 6 carbon atoms A substituent selected from the group consisting of an arylamino group of 0, a heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group.
  • the aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylamino group and heterocyclic compound group may further have a substituent. If r 5 has a plurality of substituents, they may be the same or different, respectively.
  • 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 The saturated heterocyclic compound group may have a substituent.
  • q is an integer of 1-4.
  • R 16 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, or a heterocyclic compound group having 4 to 60 carbon atoms.
  • a group selected from the group consisting of a cyano group, and the aryl group and the heterocyclic compound group may have a substituent.
  • r is 0 or 1.
  • the total of the repeating units represented by the formulas (2), (3) and (4) is 50 mol of all the repeating units. /. Or more, and the formula (2), Equation (3) and the total of the repeating unit represented by formula (4), 0 is the repeating unit represented by the formula (2). 1 mole 0/0 to 3 0 mole 0/0 or less, the repeating unit represented by the formula (3) is 3 0 mole 0 / o or more I 0 mol%, a polymeric fluorescent substance repeating units of the following 70 mol% on the 30 mol% or more of the formula (4). Most preferably, the repeating unit represented by the formula (2) is at least 0.2 mol% and at most 10 mol% based on the total number of repeating units.
  • Ar 2 , Ar 3 and Ar 5 may be selected so as not to impair the fluorescent properties of the polymeric fluorescent substance. Specific examples include the divalent compounds exemplified in (5) below. Groups.
  • R is selected to have 1 to 4 substituents represented by one X—R 3 in the case of Ar 2
  • Ar 3 is selected a substituent shown by a a r 4 to have one to four
  • a r 5 is 1 to a substituent represented by one R 3 Selected to have four.
  • the remaining R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and a carbon atom having 1 to 20 carbon atoms.
  • alkylamino groups 6 to 60 carbon atoms aryl group, 6 to 60 carbon atoms aryloxy group, 6 to 60 carbon atoms aryl alkyl group, 6 to 60 carbon atoms aryl alkoxy group, carbon Represents a substituent selected from the group consisting of an arylamino group having the number of 6 to 60, a heterocyclic compound group having a carbon number of 4 to 60, and a cyano group, wherein the aryl group, the aryloxy group, the arylalkyl group, the aryl group;
  • the alkoxy group, arylamino group and heterocyclic compound group may further have a substituent.
  • one structural formula has a plurality of Rs, which may be the same or different, and each is independently selected.
  • a r ⁇ has a plurality of substituents, they may be the same or different.
  • Dissolution in solvent I 1 In order to increase the yield, it is preferable to have at least one substituent that is not a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including the substituent is small. .
  • R 6 to R 12 are each independently a group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 60 carbon atoms, a heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. It represents a selected group, and the aryl group and the heterocyclic compound group may further have a substituent.
  • R 3 and 5 include, as an alkyl group having 1 to 20 carbon atoms, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl And a decyl group, a lauryl group and the like, and a pentyl group, a hexyl group, an octyl group and a decyl group are preferred.
  • the aryl groups having 6 to 60 carbon atoms include a phenyl group and a 2- alkoxyphenyl group (CCis indicates that the carbon number is 1 to 12 The same applies to the following.), C i -C 2 alkylphenyl, 1-naphthyl, 2-naphthyl and the like, and C i C ⁇ s alkoxy Preferred are a phenyl group and a C2-C2 alkylphenyl group.
  • examples of the arylalkyl group having 7 to 60 carbon atoms include a phenylenomethynole group, a phenylethyl group, a phenylpropyl group, and a di-C, alkoxyphenyl group.
  • methyl groups C 1 through C 1 2 Anorekokishifue two Ruechinore groups, C I ⁇ C 2 alkoxy phenylpropyl groups, C -C 2 alkylphenyl methylation groups, C 1 through C 1 2 alkylphenyl E chill groups, C !
  • R 3 and A r 4 the heterocyclic compound group having a carbon number of 4-6 0, thienyl group, 2 alkyl chain group, a pyrrolyl group, a furyl group, Pi lysyl group, c ⁇ c such as 2 alkylpyridyl group and the like, thienyl group, c 1 -C 1 2 alkyl chain group, a pyridyl group, C! ⁇ C! Two alkylpyridyl groups are preferred.
  • examples of the cyclic saturated hydrocarbon group having 5 to 16 carbon atoms include a cyclopropynole group, a cyclobutyl group, a cyclopentyl group, a cyclohexynole group, a cycloheptyl group, and a cyclooctyl group And a cyclohexyl group, and a cyclohexyl group are preferred.
  • R! Specific examples of 5 include, as a saturated heterocyclic compound group having 4 to 60 carbon atoms, a tetrahydrofuraninole group, a pyranyl group, a pyrrolidyl group, a pyridyl group, a thiolanyl group, a thianyl group, and the like. And a tetrahydrofuranyl group and a bilanyl group are preferred.
  • alkoxy group having 1 to 20 carbon atoms examples include methoxy, ethoxy, propyloxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, noeroxy, decyloxy, lauryloxy, and the like. And a pentyloxy group, a hexyloxy group, an octyloxy group, and a desyloxy group are preferred.
  • alkylthio group having 1 to 20 carbon atoms examples include a methylthio group, an ethylthio group, a propylthio group, a butynolethio group, a pentylthio group, a hexynolethio group, a heptylthio group, an octylthio group, a nonylthio group, a decylthio group, and a laurylthio group.
  • a pentylthio group, a hexylthio group, an octylthio group and a decylthio group are preferred.
  • alkylsilyl group having 1 to 60 carbon atoms examples include a trimethylsilyl group, a triethylsilyl group, a triprobelsilyl group, a triptylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a triheptylsilyl group, a trioctylsilyl group, and a trinosilyl group.
  • Nylsilinole group tridecylsilyl group, trilaurinoresilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group , Nonyldimethylsilyl group, decyldimethylsilyl group, peryldimethylsilyl group, and the like; tripentylsilyl group, trihexylsilyl group, trioctylsilyl group, tridecylsilyl group, pentyldimethyl Li group, a hexyl dimethyl silyl group, O-lipped Le dimethylsilyl group, decyldimethylsilyl group are preferable.
  • alkylamino group having 1 to 40 carbon atoms examples include a methynoleamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a laurino amino group, and dimethylamino.
  • Examples of the aryl group having 6 to 60 carbon atoms include a phenyl group, and Ci to Ci 2 alkoxyphenyl group 2 has 1 to 12 carbon atoms. The same applies to the following. ), C i ⁇ C 1 2 alkylphenyl group, 1 one naphthyl, 2-naphthyl group and the like, C ⁇ Ji 2 alkoxy phenylalanine group, C I ⁇ C 1 2 Arukirufu Eniru group.
  • a C 1 -C 2 alkoxyphenoxy group and a C 1 -C 12 alkylphenoxy group are preferred.
  • R in a substituted group containing an alkyl chain, they may be any of linear, branched or cyclic or a combination thereof, and examples of non-linear include an isoamyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group, 41 Ci-C! Examples include a 2- alkylcyclyl hexyl group.
  • at least one of the substituents of Ar i, Ar 2 , Ar 3 or Ar 5 must contain a cyclic or branched alkyl chain. Is preferred.
  • k is 0 or 1
  • n is 0 or 1
  • p is 0 or 1
  • r is 0 or 1.
  • R and R 2 in the above formula (1), R 4 and R 5 in the above formula (2), 3 and 4 in the above formula (3), R 16 and 7 in the above formula (4) and the above Re Ri 2 Are independently a hydrogen atom and a carbon number :!
  • R 1 R 2 , R 4 to R 14 , 6 and 7 are a substituent other than a hydrogen atom or a cyano group, as the alkyl group having 1 to 20 carbon atoms, a methynole group, an ethyl group, Propinole, butyl, pentyl, hexyl, heptinole, octyl, nonyl, decyl, lauryl, etc., methyl, ethyl, pentyl, hexyl, heptyl, octyl, etc. Groups are preferred.
  • the Ariru group having 6 to 60 carbon atoms, phenyl group, Ci ⁇ C 1 2 alkoxy phenyl group, C -C 2 alkylphenyl group, 1-naphthyl group, 2-naphthyl group and the like, phenyl group, Ci Ci 2 alkylphenyl groups are preferred.
  • the heterocyclic compound group having 4 to 60 carbon atoms include a chenyl group, a Cj ds alkyl phenyl group, a pyrrolyl group, a furyl group, a pyridyl group, and a C ⁇ to C ⁇ 2 alkylpyridyl group.
  • the terminal group of the polymeric fluorescent substance may be protected with a stable group, since if the polymerization active group remains as it is, the light emission characteristics and life of the device 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 include the substituents described in Chemical Formula 10 of JP-A-9-145478.
  • a method of polymerizing the corresponding monomer by a Suzuki coupling reaction for example, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, F how to more polymerized oxidizing agent such as e C l 3, electrochemically methods oxidative polymerization, a method by decomposition of an intermediate polymer to have a suitable leaving group can be exemplified.
  • the raw material polymeric fluorescent material and the polymeric fluorescent material produced by the method of the present invention are obtained by using the formulas (1), (2), and (3) as long as the fluorescent characteristics and the charge transport characteristics are not impaired.
  • a repeating unit other than the repeating unit represented by the formula (4) may be connected by a non-conjugated unit, or may be a repeating unit. These non-conjugated moieties may be included.
  • the bonding structure include a structure shown in (6) below, a structure obtained by combining a vinylene group shown in (6) below, and a structure obtained by combining two or more of the structures shown in (6) below.
  • R is And Ar is a hydrocarbon group having 6 to 60 carbon atoms.
  • 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. There may be. From the viewpoint of obtaining a polymeric fluorescent substance having a high quantum yield of fluorescence, a random copolymer-block or graft copolymer having block properties is preferable to a complete random copolymer. If the main chain is branched and has three or more terminals, dendrimers are also included.
  • a polymer fluorescent substance having fluorescence in a solid state is preferably used.
  • Examples of good solvents for the polymeric fluorescent substance include chloroform-form, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. 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 1 ⁇ 10 8 in terms of polystyrene, and the degree of polymerization thereof depends on the repeating structure and the ratio thereof. change.
  • the total number of repeating structures is preferably Or 30 to 10,000, more preferably 50 to 5,000.
  • the polymer fluorescent material produced by the method of the present invention is used as a light emitting material for a polymer LED, its purity affects the light emission characteristics. It is preferable to polymerize after purifying by a method such as distillation, sublimation purification, recrystallization and the like. In addition, it is preferable that the polymer fluorescent substance is subjected to purification treatment such as reprecipitation purification, separation by chromatography or the like in the step of producing the raw material polymeric fluorescent substance or in the present invention.
  • 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 anodes and cathodes, at least one of which is transparent or translucent. Is contained 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.
  • the light emitting layer is a layer having a function of emitting light
  • the hole transport layer is a hole transporting layer. It is a layer having a function of transporting
  • the electron transporting layer is a layer having a function of transporting electrons. 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.
  • 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 element include the charge injection layer (hole injection layer). Layer, electron injection layer).
  • the charge injection layer or the insulating layer having a thickness of 2 nm or less Adjacent to the electrode to improve adhesion to the electrode and improve charge injection from the electrode Then, the charge injection layer or the insulating layer having a thickness of 2 nm or less may be provided, and a thin buffer layer may be provided at the interface between the charge transport layer and the light emitting layer in order to improve the adhesion at the interface and prevent mixing. May be inserted.
  • 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.
  • the polymer LED provided with a charge 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.
  • the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer.
  • the electric conductivity of the conductive polymer is 10 to 10.
  • the lower part is more preferable, and the range is more preferably 10 5 SZcm or more and 10 1 S / cm or less.
  • an appropriate amount of ions are doped into the conductive polymer so that the electric conductivity of the conductive polymer is 10 5 S / cm or more and 10 3 S / cm or less.
  • the kind of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer.
  • anions include polystyrenesulfonate, alkylbenzenesulfonate, camphorsulfonate, and the like.
  • cations include lithium, sodium, potassium, tetramethylammonium, and the like. Is exemplified.
  • 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 electrode and the material of the adjacent layer.
  • Polyaniline and its derivatives, polythiophene and its derivatives, polypropyl and its derivatives, and polyphenylene Conductive molecules such as vinylene and its derivatives, poly (vinylenevinylene) and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polymers having an aromatic amine structure in the main chain or side chain, and metal phthalocyanine ( Copper phthalocyanine), carbon and the like.
  • the insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection.
  • the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.
  • As a polymer LED with an insulating layer with a thickness of 2 nm or less an insulating layer with a thickness of 2 nm or less is provided adjacent to the cathode. Polymer LED provided.
  • a film can be formed from a solution by using these organic solvent-soluble polymer phosphors when forming the polymer LED. It is only necessary to remove the solvent by drying after coating the solution. The same method can be applied to the case where a charge transport material and a luminescent material are mixed, which is very advantageous in manufacturing.
  • Examples of the method of forming a film from a solution include a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, Coating methods such as screen printing, flexographic printing, offset printing, and ink jet printing can be used.
  • the thickness of the light-emitting layer is optimally different depending on the material used, and may be selected so that the driving voltage and the luminous efficiency have appropriate values.
  • the thickness is 1 nm to 1 ⁇ m, preferably 2 nm to It is 500 nm, more preferably 5 nm to 200 nm.
  • a light-emitting material other than the polymer fluorescent substance may be mixed and used in the light-emitting layer.
  • 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.
  • the light emitting material known materials can be used.
  • 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.
  • JP-A-57-51781 and JP-A-59-194393 can be used.
  • the hole transport material used may be polyvinyl carbazole or a derivative thereof, borosilane or a derivative thereof, or a polymer having an aromatic amine in a side chain or a main chain.
  • Siloxane derivative, virazoline derivative, thiolamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or its derivative, polythiophene or its derivative, polypyrrole or its derivative, poly (p-phenylenevinylene) or its Derivatives, or poly (2,5-Chenylene vinylene) or derivatives thereof are exemplified.
  • hole transporting material used for the hole transporting layer polybutacarbazole monophosphate 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,
  • Polymeric hole transport materials such as polyaniline 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 can be used.
  • Preferred and more preferred are polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain.
  • a low-molecular-weight hole transport 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 vinylinole monomer by force cation polymerization or radical polymerization.
  • polysilane or a derivative thereof examples include compounds described in Chemikanore Review (Chem. Rev.) Vol. 89, p. 1359 (1989), and British Patent GB 2300196.
  • the synthesis method also uses the methods described in these. Although it can be used, the Kipping method is particularly preferably used.
  • 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.
  • those having an aromatic amine having a hole transporting property in a side chain or a main chain are exemplified.
  • the method of forming the hole transport layer There is no limitation on the method of forming the hole transport layer.
  • a method of forming a film from a mixed solution with a polymer binder is exemplified.
  • 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.
  • 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.
  • the solvent include ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate.
  • polystyrene those which do not extremely inhibit charge transport are preferable, and those which do not strongly absorb visible light are preferably used.
  • a molecular binder examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polychlorovinyl, and polysiloxane.
  • 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. Accordingly, the thickness of the hole transport layer is, for example, 1 nm to 1 m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm. nm.
  • the polymer LED of the present invention has an electron transporting layer
  • known electron transporting materials can be used, such as oxadiazole derivative, anthraquinodimethane or its derivative, benzoquinone or its derivative, naphthoquinone or Derivatives, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, dipheninoresinocyanethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof , Polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and the like.
  • JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-135361, JP-A-209998, JP-A-3-37992 And Japanese Patent Application Laid-Open No. 3-152184 are exemplified.
  • oxadiazole derivatives benzoquinone or its derivatives, anthraquinone or its derivatives, or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinolines or their derivatives, polyquinoxalines or their derivatives, and polyfluorenes or their derivatives More preferably, 2_ (4-biphenylyl) -5- (4-t-butynolepheninole) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.
  • the method for forming the electron transport layer There is no particular limitation on the method for forming the electron transport layer.
  • low molecular electron transport materials vacuum deposition from powder or film formation from a solution or molten state is used.
  • high molecular electron transport materials A method by film formation from a solution or a molten state is exemplified.
  • 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 dissolves the electron transport material and the Z or polymer binder.
  • the solvent examples include chlorinated solvents such as chloroform, methylene 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, and acetic acid.
  • chlorinated solvents such as chloroform, methylene 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
  • acetic acid examples of the solvent
  • Ethyl, butyl acetate, ethylcellsol An ester solvent such as tate is exemplified.
  • microgravure coating method gravure coating method, bar coating method, rono coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method Etc. can be used.
  • polymer binder to be mixed those that do not extremely inhibit charge transport are preferable, and those that do not strongly absorb visible light are preferably used.
  • the polymer binder include poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, and poly (2,5-chenylenevinylene). Or a derivative thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, or the like.
  • 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 ⁇ , preferably 2 nm to 500 nm, and more preferably 5 nm to 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.
  • examples include a glass, plastic, polymer film, and silicon substrate. You.
  • the opposite electrode is preferably transparent or translucent.
  • the anode side is preferably transparent or translucent.
  • a conductive metal oxide film, a translucent metal thin film, or the like is used as the material of the anode.
  • a film formed using a conductive glass made of indium oxide, zinc oxide, tin oxide, or a complex thereof, such as indium tin oxide (ITO) or indium zinc oxide. (Such as NESA), gold, platinum, silver, copper, etc. IT ⁇ , indium-zinc-oxide, and tin oxide are preferred.
  • 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 jam, and preferably from 20 nm to l ⁇ . And more preferably 50 nm to 500 nm.
  • a material having a small work function is preferable.
  • a graphite interlayer compound or the like is used.
  • 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 B thickness of the cathode is a force that can be appropriately selected in consideration of electrical conductivity and durability, for example, from 10 nm to 10 ⁇ m, preferably from 20 nm to 1 ⁇ m, and More preferably, it is 50 nm to 500 nm.
  • a vacuum evaporation method, a sputtering method, a lamination method of thermocompression bonding of a metal thin film, and the like are used as a method for producing the cathode.
  • 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.
  • protect the polymer LED Protective layer may be provided.
  • a polymer compound, a metal oxide, a metal fluoride, a metal boride and the like can be used.
  • 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 and sealed. Is preferably used. If a space is maintained by using a spacer, it is easy to prevent the element from being damaged.
  • a planar anode and a planar cathode may be arranged so as to overlap.
  • 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.
  • both the anode and the cathode may be formed in stripes and arranged orthogonally.
  • a partial color display and a multi-color display can be achieved by a method in which a plurality of types of polymeric fluorescent substances having different emission colors are separately applied, or a method 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 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.
  • planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for backlighting 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.
  • the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using chloroform as a solvent.
  • the polymerization solution was cooled to 50 ° C, and then neutralized by adding acetic acid. After cooling to room temperature, the polymerization solution was poured into 2500 g of ion-exchanged water, and the generated precipitate was collected. The precipitate was washed with methanol and dried under reduced pressure. 7 g of the obtained polymer was dissolved in 1500 g of THF. This solution was poured into 20000 g of methanol, and the generated precipitate was collected. The precipitate was washed with ethanol and dried under reduced pressure to obtain 5 g of a polymer. This polymer is called polymeric fluorescent substance (1).
  • the black-mouthed form solution was washed five times with 200 g of ultrapure water. This black-mouthed form solution was poured into methanol, and the generated precipitate was collected. The precipitate was washed with ethanol, dried under reduced pressure, and pickled to obtain a purified polymeric fluorescent substance (2).
  • Table 1 shows the results of quantifying the metal elements of each of the polymeric fluorescent substances (1) and (2) by means of ICP emission spectrometry.
  • potassium and iron were reduced.
  • a suspension of poly (3,4) ethylenedioxythiophene Z polystyrenesulfonic acid (Bayer, Bytron P TP AI 4083) was placed on a glass substrate with a 150 nm thick ITO film by sputtering. After filtration through a 0.5 ⁇ m membrane filter, a film was formed to a thickness of 7 O nm by spin coating, and dried in a vacuum oven at 120 ° C. for 1 hour. Thereafter, a light emitting layer having a thickness of 70 nm was formed by spin coating using a 0.4 wt% chloroform solution of the polymer fluorescent substance (2).
  • Luminous efficiency at this time 13 is a c DZA, also emission spectrum of the device, was continuously driven at a constant current of 25mA / cm 2 after 1 hour age ring elements under. nitrogen stream had a peak at 548 nm , 2000 cd / m 2 emission luminance was halved in about 60 hours.
  • Example 2 In the same manner as in Example 2, a polymer LED was produced using the polymer phosphor (1) before purification instead of the purified polymer phosphor (2). When a voltage of 3.0 V was applied to the obtained device, a current density of 1.0 mAZcm 2 flowed and yellow EL light emission with a luminance of 110 cd / m was observed. At this time, the light emission efficiency was 11 cd / A, and the light emission spectrum of the device had a peak at 548 nm.
  • Example 2 Life was short.
  • Polymeric fluorescent substance 3 (10 g) synthesized by the above method was dissolved in toluene (1.441). This solution was washed with 1 N hydrochloric acid (1.01) and then separated to collect a toluene layer. The toluene layer was washed with a 2% aqueous ammonia solution (1.11), and further washed twice with pure water (1.01). This toluene solution was poured into methanol (3.01), and the purified precipitate was collected. The precipitate was dried under reduced pressure to obtain purified polymer 4 (9.7 g).
  • a 0.4 wt% chloroform solution of the purified polymeric fluorescent substance 4 was coated on quartz with Thus, a thin film of the purified polymer fluorescent substance 4 was prepared.
  • the ultraviolet-visible absorption spectrum and the fluorescence spectrum of this thin film were measured using an ultraviolet-visible absorption spectrophotometer (Hitachi, Ltd., UV 350) and a fluorescence spectrophotometer (Hitachi, Ltd., 850), respectively.
  • the fluorescence spectrum when excited at 350 nm was used.
  • the relative value of the fluorescence intensity was determined 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 the purified polymeric fluorescent substance 4 was 428 nm, and the relative value of the fluorescent intensity was 5.9.
  • the fluorescent peak wavelength of the resulting polymeric fluorescent substance 3 was 428 nm, and the relative value of the fluorescent intensity was 3.3.
  • 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 devices such as a curved or planar light source as a backlight, a segment type display element, and a dot matrix flat panel display.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un procédé de production d'un matériau fluorescent polymère caractérisé en ce qu'on traite par un acide un matériau fluorescent polymère qui donne une fluorescence à l'état solide et présente un poids moléculaire moyen en nombre de 1 x 104 à 1 x 108 en termes de polystyrène ; un procédé de production d'un matériau fluorescent polymère caractérisé en ce qu'on traite par un acide un matériau fluorescent polymère donnant une fluorescence à l'état solide et présentant un poids moléculaire moyen en nombre de 1 x 104 à 1 x 108 en termes de polystyrène, et en ce qu'on traite le produit obtenu par un agent alcalin ; et un procédé de production d'un matériau fluorescent polymère, caractérisé en ce qu'on traite par un acide un matériau fluorescent polymère donnant une fluorescence à l'état solide et ayant un poids moléculaire moyen en nombre de 1 x 104 et 1 x 108 en termes de polystyrène, en ce qu'on traite le produit obtenu par un agent alcalin, et en ce qu'on traite en définitive le produit résultant par une substance ne contenant ni acide, ni agent alcalin.
PCT/JP2001/005454 1999-12-27 2001-06-26 Procedes de production d'un materiau fluorescent polymere, et element luminescent polymere WO2003000821A1 (fr)

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JP37069199A JP4482994B2 (ja) 1999-12-27 1999-12-27 高分子蛍光体の製造方法および高分子発光素子
US10/480,332 US7297415B2 (en) 1999-12-27 2001-06-26 Processes for producing polymeric fluorescent material and polymeric luminescent element
DE10197254T DE10197254T5 (de) 1999-12-27 2001-06-26 Verfahren zur Herstellung einer polymeren fluoreszierenden Substanz und polymere lichtemittierende Vorrichtung
PCT/JP2001/005454 WO2003000821A1 (fr) 1999-12-27 2001-06-26 Procedes de production d'un materiau fluorescent polymere, et element luminescent polymere

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JP37069199A JP4482994B2 (ja) 1999-12-27 1999-12-27 高分子蛍光体の製造方法および高分子発光素子
PCT/JP2001/005454 WO2003000821A1 (fr) 1999-12-27 2001-06-26 Procedes de production d'un materiau fluorescent polymere, et element luminescent polymere

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EP1682600B1 (fr) * 2003-11-10 2013-01-23 Cambridge Display Technology Limited Polymeres de dibenzosilol, preparation et utilisations associees

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JP4482994B2 (ja) * 1999-12-27 2010-06-16 住友化学株式会社 高分子蛍光体の製造方法および高分子発光素子
JP2003051386A (ja) * 2001-08-06 2003-02-21 Toppan Printing Co Ltd 有機エレクトロルミネッセンス素子
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EP2325225B2 (fr) 2002-10-30 2019-12-11 Sumitomo Chemical Company, Limited Composés de copolymère d'aryle et dispositif électroluminescents à polymère fabriqués à partir de ceux-ci
DE112006002147T5 (de) 2005-08-12 2008-10-23 Sumitomo Chemical Co., Ltd. Polymerverbindung und polymere lichtemittierende Vorrichtung diese verwendend
CN101321801A (zh) 2005-10-07 2008-12-10 住友化学株式会社 共聚物和使用该共聚物的高分子发光元件
KR20080066084A (ko) 2005-11-11 2008-07-15 스미또모 가가꾸 가부시키가이샤 공액 고분자 화합물 및 이를 이용한 고분자 발광 소자
CN101360773B (zh) 2005-11-18 2012-01-04 住友化学株式会社 高分子化合物及用其形成的高分子发光元件
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JP5515542B2 (ja) 2008-10-06 2014-06-11 住友化学株式会社 含窒素複素環構造を含む高分子化合物
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WO2011093428A1 (fr) 2010-01-28 2011-08-04 住友化学株式会社 Composé polymère et dispositif électroluminescent l'utilisant

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EP1682600B1 (fr) * 2003-11-10 2013-01-23 Cambridge Display Technology Limited Polymeres de dibenzosilol, preparation et utilisations associees
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