CN102138364A - Conjugated high-molecular-weight copolymer, color conversion film using same, and multicolor light-emitting organic EL device - Google Patents
Conjugated high-molecular-weight copolymer, color conversion film using same, and multicolor light-emitting organic EL device Download PDFInfo
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Abstract
Disclosed is a green light-emitting color conversion film which can be produced by a low-cost wet process and is capable of maintaining a sufficient converted light intensity for a long time without having an increased thickness. The color conversion film contains a conjugated high-molecular-weight compound represented by general formula (1). Also disclosed is a multicolor light-emitting organic EL device which comprises: a pair of electrodes, at least one of which is a transparent electrode; an organic EL layer interposed between the pair of electrodes; and a color conversion film containing a conjugated high-molecular-weight compound.
Description
Technical field
The present invention relates to the color conversion film that a kind of use has fluorescence or phosphorescence under the solid film state conjugated polymer copolymer can utilize coating process to form and have high look conversion efficiency.The invention still further relates to the multicolor luminous organic EL device that uses this color conversion film to form.
Background technology
In recent years, the research towards practicability of organic EL is being carried out actively.Organic EL is in order to realize high current density under low-voltage, expectation realizes high luminosity and luminous efficiency.Particularly expectation can realize the practicability of the multicolor organic display of high-accuracy polychrome or panchromatic demonstration.As an example of the method for the multicolor of OLED display or panchromaticization, the method (filter method) of multiple filter of the light transmission of the particular wavelength region of making is arranged.Under the situation of using the filter method, the employed organic EL of demand can carry out multicolor luminous, sends so-called " white light " of the three primary colors (red (R), green (G), blue (B)) that balancedly comprise light.
In order to obtain multicolor luminous organic EL, Japanese kokai publication hei 3-230584 communique and TOHKEMY 2000-243563 communique have proposed to use a plurality of luminescent layers of comprising luminescent pigment of the same race not, have encouraged the method (with reference to patent documentation 1 and 2) of their luminescent pigment simultaneously.Perhaps, in No. 5683823 specification of United States Patent (USP), proposed to use the luminescent layer that comprises main body luminescent material (host emitting material) and object luminescent material (guest emitting material) in addition, made the excitation of main body luminescent material also luminous, made energy move and make the luminous method of object luminescent material (with reference to patent documentation 3) to guest materials simultaneously by the main body luminescent material.
But, any mode that excitation or the energy between multiple luminescent material shifted when these multicolor luminous organic ELs relied on multiple luminescent material.In such element, reported the process of following driving time or the variation of electrical current, the balance of the luminous intensity between luminescent material changes, and may cause resulting form and aspect to change.
As other method that is used to obtain multicolor luminous organic EL, TOHKEMY 2002-75643 communique and TOHKEMY 2003-217859 communique have proposed to use the monochromatic luminous organic EL and the look converter technique (with reference to patent documentation 4 and 5) of color conversion film.The color conversion film that in this motion, uses be contain the light that absorbs the short wavelength and be converted to the long wavelength light one or more look conversion materials the layer.
But, when using single look conversion material to form color conversion film, be known as the phenomenon of concentration quenching." concentration quenching " is meant by the energy of look conversion material absorbing and do not follow luminous and lost phenomenon intermolecular in moving repeatedly.In order to suppress this phenomenon, proposed to make look conversion material in some medium, to dissolve in the TOHKEMY 2000-230172 communique or disperseed, make the color conversion film (with reference to patent documentation 6) of the medium decentralized that concentration reduces.In the color conversion film of medium decentralized, follow the reduction of the concentration of look conversion material, can suppress the contact each other of look conversion material.
At this, if reduce the concentration of look conversion material, because the reduction of the absorbance of the light that should absorb, so can not get sufficient conversion luminous intensity.For this problem, the thickness that increases color conversion film is kept the look conversion efficiency to improve absorbance.Like this, when using thick color conversion film (about thickness 10 μ m), big step difference, high-accuracyization difficulty, moisture or solvent residual etc. problem in film can take place.If there is big step difference, forming on the color conversion film under the situation of organic EL in hope, can be at the broken string of step difference generating electrodes pattern.In addition, under the residual situation, when making up with organic EL, residual moisture or solvent can make organic EL layer rotten, thereby produce display defect in film for moisture or solvent.
In addition, in the color conversion film of above-mentioned such medium decentralized, as time passes, look conversion material spreads in medium and moves mutual aggegation, and its result causes the phenomenon of concentration quenching through regular meeting.Therefore, in such color conversion film, be difficult to keep for a long time high look conversion efficiency.
Therefore, for the color conversion film of realizing not increasing thickness, can keeping sufficient conversion luminous intensity for a long time, wish that (a) has suitable absorption and luminescent spectrum, (b) and have high fluorescent quantum yield and (c) be difficult to cause the material that concentrates cancellation when reducing thickness.In the prior art, almost the material of not finding to absorb ultraviolet light or blue light and converting green light expeditiously to, and, useful for the multicolor luminous organic EL device that uses color conversion film, can absorb blue light and convert the material of green light expeditiously to especially rare.In order to realize color conversion film or to use the multicolor luminous organic EL device of this color conversion film, urgently wish to occur such material.
In addition,, wish to adopt wet process, for example adopt the coating process that uses the solution that is dissolved in the look coversion material in the appropriate solvent in order to make color conversion film with low cost.For this reason, it is soluble needing look conversion material.In addition, from technology point of view, hope can easily be suitable for the viscosity adjustment of operative installations.In order to reach this purpose, wish to use soluble choice of Solvent scope wide and by changing the look conversion material that macromolecular material that molecular weight carries out the viscosity adjustment of solution easily constitutes.
In the prior art, as the color conversion film that uses macromolecular material, TOHKEMY 2000-26852 communique has proposed to contain has the color conversion film (refer to Patent Document 7) of polyarylene vinylene as the macromolecular material of repetitive.TOHKEMY 2006-169265 communique has proposed to contain has the color conversion film (refer to Patent Document 8) of fluorenes as the macromolecular material of repetitive.
In addition, as Appl.Phys.Lett., 61,2793 (1992) and Nature, 365, record in 628 (1992) because the inferior ethene derivatives of poly (arylene ether) has higher fluorescent quantum yield and high solubility, has been carried out extensive studies (with reference to non-patent literature 1,2) as the candidate of the luminescent material of macromolecule EL element.
In the color conversion film that uses macromolecular material, also require to have high fluorescent quantum yield.But the fluorescent quantum yield under the solid film state of the inferior ethene derivatives of the poly (arylene ether) of report is about 10～40% up to now, is not enough to use as color conversion film.In addition, the illuminant colour of the inferior ethene derivatives of these poly (arylene ether)s is a yellow green～orange, can not use as the look coversion material that is used to convert to green light.
In addition, in a single day the color conversion film that is made of the inferior ethene derivatives of poly (arylene ether) exposes at high temperature, will gather or associate between the molecule of the inferior ethene derivatives of poly (arylene ether), and its result causes concentration quenching, the problem that the fluorescent quantum yield reduces occurs.In other words, there is the shortcoming that so-called thermal endurance is low, can not use in the color conversion film that is made of the inferior ethene derivatives of poly (arylene ether) under the high temperature atmosphere.
Technical literature formerly
Patent documentation
Patent documentation 1: Japanese kokai publication hei 3-230584 communique
Patent documentation 2: TOHKEMY 2000-243563 communique
Patent documentation 3: No. 5683823 specification of United States Patent (USP)
Patent documentation 4: TOHKEMY 2002-75643 communique
Patent documentation 5: TOHKEMY 2003-217859 communique
Patent documentation 6: TOHKEMY 2000-230172 communique
Patent documentation 7: TOHKEMY 2000-26852 communique
Patent documentation 8: TOHKEMY 2006-169265 communique
Patent documentation 9: Japanese kokai publication hei 10-36487 communique
Non-patent literature
Non-patent literature 1:Applied Physics Letters, (1992), 61 volumes, No. 23, p.2793
Non-patent literature 2:Nature, (1992) 365 volumes, p.628
Summary of the invention
The problem that invention will solve
The green emitting color conversion film that one object of the present invention is to provide a kind of does not increase thickness, can keep sufficient conversion luminous intensity for a long time and can make with wet process cheaply.In addition, another object of the present invention is to provide the multicolor luminous organic EL device that uses this color conversion film.More specifically, the object of the present invention is to provide the variation of a kind of process of not following driving time or electrical current and the form and aspect that cause change and demonstrate the multicolor luminous organic EL device of the characteristics of luminescence steady in a long-term.
The means of dealing with problems
Through further investigation, found that: the conjugated polymer compound that in the inferior ethene derivatives of specific poly (arylene ether), imports the repetitive of specific fluorene skeleton, under the solid film state, has excellent fluorescent quantum yield, the film of this conjugated polymer compound has sufficient look conversion efficiency when using as the color conversion film of green, thereby has finished the present invention.
The color conversion film of first execution mode of the present invention is characterised in that, contains the conjugated polymer compound, and this conjugated polymer compound has the structure shown in the general formula (1), and has the glow peak wavelength from 490nm to 560nm under the solid film state,
(in the formula, Ar represents arlydene or divalent heterocyclic radical, R
1And R
2Represent hydrogen atom, alkyl, alkoxyl, alkylthio group, alkyl silicyl, alkyl amino, aryl, aryloxy group, aralkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, 1 valency heterocyclic radical, amino, nitro, halogen or cyano group respectively independently, and n and m are 1～10000 integer independently respectively).
Here, the conjugated polymer compound can have the structure shown in the general formula (2).
(in the formula, R
1, R
2, R
3And R
4Represent hydrogen atom, alkyl, alkoxyl, alkylthio group, alkyl silicyl, alkyl amino, aryl, aryloxy group, aralkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, 1 valency heterocyclic radical, amino, nitro, halogen or cyano group respectively independently, and n and m are 1～10000 integer independently respectively.)
And the conjugated polymer compound can have the weight average molecular weight more than 1000, below 500,000.In addition, the color conversion film of present embodiment can form by coating process.
The multicolor luminous organic EL device of second execution mode of the present invention is characterised in that, have the pair of electrodes that at least one side is a transparency electrode, the organic EL layer of this pair of electrodes clamping and the color conversion film of first execution mode, this color conversion film has the following thickness of 2 μ m.Here, preferred color conversion film and transparency electrode are provided with in contacted mode.
The invention effect
In the present invention,, the fluorescent quantum yield under the solid film state can be improved, the look conversion efficiency that is enough to as the color conversion film use can be accessed by in the inferior ethene derivatives of poly (arylene ether), importing the repetitive of fluorene skeleton.In addition, the importing of fluorene skeleton can make glow peak wavelength hypsochromic shift moving, makes the illuminant colour of the inferior ethene derivatives of poly (arylene ether) of common demonstration yellow green-orange luminescence become green, can be with acting on the look coversion material that obtains green light.In addition, the importing of fluorene skeleton can suppress to follow the gathering or the association of temperature rising, the stable on heating effect of the color conversion film that can also be improved.
Thus, color conversion film of the present invention although be made of homogenous material, can not increase thickness and keep high look conversion efficiency.In addition, color conversion film of the present invention can be by selecting to dissolve in the macromolecular material of solvent, formed by coating process cheaply.In addition, form and aspect can not take place along with the variation of the process of driving time or electrical current and change in the multicolor luminous organic EL device that uses color conversion film of the present invention to form, and can show the characteristics of luminescence steady in a long-term.
Description of drawings
Figure 1A is the figure of a configuration example of expression multicolor luminous organic EL device of the present invention.
Figure 1B is the figure of a configuration example of expression multicolor luminous organic EL device of the present invention.
Fig. 1 C is the figure of a configuration example of expression multicolor luminous organic EL device of the present invention.
Fig. 1 D is the figure of a configuration example of expression multicolor luminous organic EL device of the present invention.
Fig. 2 is the absorption spectrum of color conversion film of expression embodiment 1 and the figure of fluorescence spectrum.
Embodiment
The color conversion film of first execution mode of the present invention is characterised in that, contains with the inferior ethene skeleton of arlydene and the fluorene skeleton conjugated polymer compound as repetitive.Particularly, the material shown in the conjugated polymer compound preferred formula (1).
In general formula (1), Ar represents arlydene or divalent heterocyclic radical.Arlydene among the present invention is for removing 2 atomic groups behind the hydrogen atom from monocyclic aromatic hydrocarbon or fused-ring aromatic hydrocarbon.Preferred monocyclic aromatic hydrocarbon contains the benzene etc. that replaces or do not have replacement.Preferred fused-ring aromatic hydrocarbon is that contained carbon number is generally aromatic compound about 6～60 in 2 to 5 phenyl ring condensations and the ring.Particularly, the fused-ring aromatic hydrocarbon comprises naphthalene, anthracene, phenanthrene, Bi, perylene, aphthacene, pentacene, bends (chrysene), coronene etc.Preferred fused-ring aromatic hydrocarbon comprises naphthalene and anthracene.
In addition, in general formula (1), R
1And R
2Represent hydrogen atom, alkyl, alkoxyl, alkylthio group, alkyl silicyl, alkyl amino, aryl, aryloxy group, aralkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, 1 valency heterocyclic radical, amino, nitro, halogen or cyano group respectively independently, and n and m independently are 1～10000 integer respectively.
In the conjugated polymer compound shown in the general formula (1), preferred Ar is replacement or does not have 1 of replacement, the conjugated polymer compound shown in the general formula of 4-arlydene (2).
In general formula (2), R
1, R
2, R
3And R
4Represent hydrogen atom, alkyl, alkoxyl, alkylthio group, alkyl silicyl, alkyl amino, aryl, aryloxy group, aralkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, 1 valency heterocyclic radical, amino, nitro, halogen or cyano group respectively independently, and n and m are 1～10000 integer independently respectively.
In the conjugated polymer compound of general formula (1) and (2), the arrangement of the repetitive of the inferior ethene skeleton of arlydene and the repetitive of fluorene skeleton can for random, block or alternately arrange any.Perhaps the conjugated polymer compound can also have the structure of their centre, for example has the random copolymerization structure of block.From the viewpoint of the conjugated polymer compound that obtains having high fluorescent quantum yield, to compare with complete random copolymerization, preferred block or alternately arrange is more preferably alternately arranged.Have the conjugated polymer compound of alternately arranging and have the structure (in the formula, n is 1～10000 integer) of general formula (1 ') or (2 ').
Alkyl among the present invention can be any of straight chain, side chain or ring-type, and has 1～20 carbon atom usually.Particularly, alkyl among the present invention comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, cyclohexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyl octyl group, dodecyl etc.Preferred alkyl comprises amyl group, hexyl, octyl group, 2-ethylhexyl, decyl, 3,7-dimethyl octyl group etc.
Alkoxyl among the present invention can be any of straight chain, side chain or ring-type, and has 1～20 carbon atom usually.Particularly, alkoxyl among the present invention comprises methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, amoxy, own oxygen base, cyclohexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy, dodecyloxy etc.Preferred alkoxyl comprises amoxy, own oxygen base, octyloxy, 2-ethyl hexyl oxy, last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy etc.
Alkylthio group among the present invention can be any of straight chain, side chain or ring-type, and has 1～20 carbon atom usually.Particularly, alkylthio group among the present invention comprises methyl mercapto, ethylmercapto group, positive rosickyite base, different rosickyite base, positive butylthio, isobutyl sulfenyl, uncle's butylthio, penta sulfenyl, own sulfenyl, hexamethylene sulfenyl, heptan sulfenyl, hot sulfenyl, the own sulfenyl of 2-ethyl, ninth of the ten Heavenly Stems sulfenyl, last of the ten Heavenly stems sulfenyl, 3,7-dimethyl-octa sulfenyl, dodecane sulfenyl etc.Preferred alkylthio group comprises penta sulfenyl, own sulfenyl, hot sulfenyl, the own sulfenyl of 2-ethyl, last of the ten Heavenly stems sulfenyl, 3,7-dimethyl-octa sulfenyl etc.
Alkyl silicyl among the present invention can be any of monoalkyl silicyl, two alkyl silicyl or trialkylsilkl, and has 1～20 carbon atom usually.Alkyl in the alkyl silicyl among the present invention can be any of straight chain, side chain or ring-type.Particularly, alkyl silicyl among the present invention comprises the methyl silicane base, the ethyl silicane base, the n-pro-pyl silicyl, the isopropyl silicyl, the normal-butyl silicyl, the isobutyl group silicyl, tert-butyl group silicyl, the amyl group silicyl, the hexyl silicyl, the cyclohexyl silicyl, the heptyl silicyl, the octyl group silicyl, 2-ethylhexyl silicyl, the nonyl silicyl, the decyl silicyl, 3,7-dimethyl octyl group silicyl, the dodecyl silicyl, dimetylsilyl, the diethylsilane base, the di silicyl, the diisopropyl silicyl, the di-n-butyl silicyl, the diisobutyl silicyl, the di-t-butyl silicyl, the diamyl silicyl, the dihexyl silicyl, the dicyclohexyl silicyl, the diheptyl silicyl, the dioctyl silicyl, two (2-ethylhexyl) silicyl, the dinonyl silicyl, the didecyl silicyl, two (3,7-dimethyl octyl group) silicyl, the dilauryl silicyl, trimethyl silyl, triethylsilyl, three n-pro-pyl silicyls, the triisopropyl silicyl, three normal-butyl silicyls, tri-iso-butylsilyl, the tri-tert silicyl, three amyl group silicyls, three hexyl silicyls, the thricyclohexyl silicyl, three heptyl silicyls, the trioctylphosphine silicyl, three (2-ethylhexyl) silicyl, three nonyl silicyls, three decyl silicyls, three (3,7-dimethyl octyl group) silicyl, three lauryl silicyls etc.Preferred alkyl silicyl comprises amyl group silicyl, hexyl silicyl, octyl group silicyl, 2-ethylhexyl silicyl, decyl silicyl, 3,7-dimethyl octyl group silicyl etc.
Alkyl amino among the present invention can be any of alkyl monosubstituted amino or two alkyl aminos, and has 1～20 carbon atom usually.Alkyl in the alkyl amino among the present invention can be any of straight chain, side chain or ring-type.Particularly, alkyl amino among the present invention comprises methylamino, dimethylamino, ethylamino, diethylamino, n-pro-pyl amino, isopropyl amino, normal-butyl amino, isobutylamino, tert-butyl group amino, amyl group amino, hexyl amino, cyclohexyl amino, heptyl amino, octyl group amino, 2-ethylhexyl amino, nonyl amino, decyl amino, 3,7-dimethyl octyl group amino, dodecyl amino etc.Preferred alkyl amino comprises amyl group amino, hexyl amino, octyl group amino, 2-ethylhexyl amino, decyl amino, 3,7-dimethyl octyl group amino etc.
Aryl among the present invention has 6～60 carbon atoms usually.Particularly, the aryl among the present invention comprises phenyl, C
1～C
12Alkoxyl phenyl (C
1～C
12The expression carbon number is 1～12, down with), C
1～C
12Alkyl phenyl, 1-naphthyl, 2-naphthyl etc.Preferred aryl groups comprises C
1～C
12Alkoxyl phenyl, C
1～C
12Alkyl phenyl.
Aryloxy group among the present invention has 6～60 carbon atoms usually.Particularly, the aryloxy group among the present invention comprises phenoxy group, C
1～C
12Alkoxyl phenoxy group, C
1～C
12Alkyl phenoxy, 1-naphthoxy, 2-naphthoxy etc.Preferred aryloxy group comprises C
1～C
12Alkoxyl phenoxy group, C
1～C
12Alkyl phenoxy.
Aralkyl among the present invention has 7～60 carbon atoms usually.Particularly, the alkylaryl among the present invention comprises phenyl-C
1～C
12Alkyl, C
1～C
12Alkoxyl phenyl-C
1～C
12Alkyl, C
1～C
12Alkyl phenyl-C
1～C
12Alkyl, 1-naphthyl-C
1～C
12Alkyl, 2-naphthyl-C
1～C
12Alkyl etc.Preferred aralkyl comprises C
1～C
12Alkoxyl phenyl-C
1～C
12Alkyl, C
1～C
12Alkyl phenyl-C
1～C
12Alkyl.
Alkoxy aryl among the present invention has 7～60 carbon atoms usually.Particularly, the alkoxy aryl among the present invention comprises phenyl-C
1～C
12Alkoxyl, C
1～C
12Alkoxyl phenyl-C
1～C
12Alkoxyl, C
1～C
12Alkyl phenyl-C
1～C
12Alkoxyl, 1-naphthyl-C
1～C
12Alkoxyl, 2-naphthyl-C
1～C
12Alkoxyl etc.The preferred aryl groups alkoxyl comprises C
1～C
12Alkoxyl phenyl-C
1～C
12Alkoxyl, C
1～C
12Alkyl phenyl-C
1～C
12Alkoxyl.
Arylamino among the present invention has 6～60 carbon atoms usually.Arylamino among the present invention can be single arylamino or two arylamino.Particularly, the arylamino among the present invention comprises phenyl amino, diphenyl amino, C
1～C
12Alkyl phenyl amino, two (C
1～C
12Alkyl phenyl) amino, C
1～C
12Alkoxyl phenyl amino, two (C
1～C
12Alkoxyl phenyl) amino, two (C
1～C
12Alkyl phenyl) amino, 1-naphthyl amino, 2-naphthyl amino etc.Preferred aryl groups amino comprises C
1～C
12Alkyl phenyl amino, two (C
1～C
12Alkyl phenyl) amino.
Aryl alkenyl among the present invention has 8～60 carbon atoms usually.Particularly, the aryl alkenyl among the present invention comprises phenyl-C
2～C
12Thiazolinyl, C
1～C
12Alkoxyl phenyl-C
2～C
12Thiazolinyl, C
1～C
12Thiazolinyl phenyl-C
2～C
12Thiazolinyl, 1-naphthyl-C
1～C
12Thiazolinyl, 2-naphthyl-C
2～C
12Thiazolinyl etc.The preferred aryl groups thiazolinyl comprises C
1～C
12Alkoxyl phenyl-C
2～C
12Thiazolinyl, C
1～C
12Alkyl phenyl-C
2～C
12Thiazolinyl.
Aromatic yl polysulfide yl among the present invention has 8～60 carbon atoms usually.Particularly, the aromatic yl polysulfide yl among the present invention comprises phenyl-C
2～C
12Alkynyl, C
1～C
12Alkoxyl phenyl-C
2～C
12Alkynyl, C
1～C
12Thiazolinyl phenyl-C
2～C
12Alkynyl, 1-naphthyl-C
1～C
12Alkynyl, 2-naphthyl-C
2～C
12Alkynyl etc.The preferred aryl groups alkynyl comprises C
1～C
12Alkoxyl phenyl-C
2～C
12Alkynyl, C
1～C
12Alkyl phenyl-C
2～C
12Alkynyl.
" 1 valency heterocyclic radical " among the present invention is meant from replacing or not having the heterocyclic compound of replacement and remove the remaining atomic group of 1 hydrogen atom.1 valency heterocyclic radical among the present invention has 4～60 carbon atoms usually.Particularly, 1 valency heterocyclic radical among the present invention comprises thienyl, C
1～C
12Alkylthrophene base, pyrrole radicals, furyl, pyridine radicals, C
1～C
12Alkylpyridyl etc.Preferred 1 valency heterocyclic radical comprises thienyl, C
1～C
12Alkylthrophene base, pyridine radicals, C
1～C
12Alkylpyridyl etc.
Employed conjugated polymer compound in the color conversion film of the present invention absorbs the light from light source, and issues out the long green light of spike with 490～580nm at the solid film state.Employed conjugated polymer compound preferably has 1000～500,000, more preferably has the weight average molecular weight in 5000～200,000 scopes in the color conversion film of the present invention.In order to improve the durability of color conversion film, the composition of preferred low polymerization degree is few.Preferably not contain the degree of polymerization (that is the n in n in general formula (1) and (2) and m and general formula (1 ') and (2 ')) be the composition below 5 to employed conjugated polymer compound in the color conversion film of the present invention.
(American DyeSource inc. 108GE) is illustrated in (n is 1～10000 integer in the formula) in the following chemical formula (3) to the object lesson of the conjugated polymer copolymer shown in the general formula (1).
-Me＝-CH
3
-2EH＝-CH
2CH(C
2H
5)C
4H
9
Conjugated polymer compound shown in general formula (1) or (2) for example can prepare (referring to Patent Document 9) according to the method that Japanese kokai publication hei 10-36487 communique is put down in writing.Perhaps the conjugated polymer compound shown in general formula (1) or (2) can also obtain from organic material manufacturers such as American Dye Sourceinc..
Even if having the organic fluorescence materials of high fluorescent quantum yield under thin solution state, in case form solid film, owing to the concentration quenching effect based on intermolecular strong interaction, the fluorescent quantum yield can reduce usually significantly.Give one example, at present the inferior vinyl compound of the poly (arylene ether) of report shows the fluorescent quantum yield about 80～90% under thin solution state, and is about 10～40% at fluorescent quantum yield under the solid film state.Therefore, the inferior vinyl compound of the poly (arylene ether) of report is not enough to use as color conversion film at present.
But we find that the conjugated polymer compound shown in the general formula (1) has 70～80% high fluorescent quantum yield under the solid film state, for being enough for the use of color conversion film.
Below, can improve the reason of the fluorescent quantum yield of solid film state for the repetitive of the fluorene skeleton that imports in the conjugated polymer compound shown in the general formula (1) and study.
Do not have a mind to be limited to certain theory, can think that first effect that imports fluorene skeleton is to give for the macromolecule chain rigidity.In the prior art, point out that the fluorescent quantum yield of macromolecular material is relevant with the macromolecule chain rigidity.That is, exist the material of macromolecular chain to have the tendency of high fluorescent quantum yield with high rigidity.On the contrary, exist the material of macromolecular chain to have the tendency of low fluorescent quantum yield with softness and bendability.Known fluorene skeleton is the high skeleton of rigidity, imports fluorene skeleton and has the effect of macromolecular chain being given rigidity.Can think by in the repetitive of the inferior ethene skeleton of arlydene, importing the repetitive of fluorene skeleton, give macromolecular chain, thereby the fluorescent quantum yield of solid film state increases with high rigidity.
Second effect that imports fluorene skeleton is that the luminescent spectrum hypsochromic shift is moving.Compare with the conjugated polymer compound that only constitutes by the repetitive of the inferior ethene skeleton of arlydene, the luminescent spectrum hypsochromic shift is moving, thereby the conjugated polymer compound of the present invention with formula (1) or (2) can use as the look coversion material that is used to obtain green light.The emission wavelength of the inferior vinyl compound of arlydene is generally about 590～650nm, is equivalent to yellow green-orange illuminant colour.Therefore be not suitable for using as the look coversion material of green emitting.Yet, by importing the repetitive of fluorene skeleton, the glow peak wavelength of conjugated polymer compound exhibits of the present invention after the hypsochromic shift about 490～550nm is moving with formula (1) or (2) can be as the look coversion material use that is used to obtain green light.The conjugated polymer compound that is made of the repetitive of fluorene skeleton only has glow peak in short wavelength's blue-light-emitting zone more.Though detailed luminescence mechanism is still indeterminate, but can think because the inferior ethene skeleton of arlydene that has the fluorene skeleton of glow peak in the short wavelength zone and have glow peak in the long wavelength zone exists in a part, thereby glow peak moves to the wavelength region may in the middle of both.
The 3rd effect that imports fluorene skeleton is to improve the thermal endurance of color conversion film.Usually, in case give the macromolecule membrane heat, the motion of the molecule in the film will become acutely, because molecule is interior or intermolecular interaction, forms aggregation or association body.Compare with non-gathering or non-associated molecule, aggregation or association body have little optical band gap.Therefore,, move to the association body, cause luminous from the association body owing to absorb the energy that incident light obtained if form such association body.Its result causes the variation of emission wavelength and/or the reduction of luminous efficiency." stable on heating raising " among the present invention is meant the rising of the temperature that the reduction of the variation of such emission wavelength or luminous efficiency begins to take place.Import the conjugated polymer compound of the present invention of the repetitive of fluorene skeleton, compare, observe 50～100 ℃ stable on heating raising with the macromolecular compound that only constitutes by the repetitive of arlydene ethenylidene.Can think that the importing of repetitive of fluorene skeleton gives macromolecular chain with high rigidity, and limit high molecular warm-up movement.Its result can think that the association of conjugated polymer compound is suppressed, and the thermal endurance of color conversion film is improved.
Color conversion film of the present invention have 2000nm (2 μ m) following, be preferably 100～2000nm, the thickness of 400～1000nm more preferably.In color conversion film of the present invention,, therefore, in thin like this thickness, also has sufficient color conversion film efficient even because above-mentioned conjugated polymer compound also shows high fluorescent quantum yield under the solid film state.
The color conversion film of present embodiment can be by making for the solution of suitable transparent supporting mass coating conjugated polymer compound.Perhaps also can be as described later, for suitable transparent supporting mass, the solution that is coated with the conjugated polymer compound that also contains other key elements is made color conversion film.As can be used as the material that transparent supporting mass uses, can be the such inorganic material of glass, also can be cellulose esters such as diacetyl cellulose, tri acetyl cellulose (TAC), propiono cellulose, bytyry cellulose, celluloid; Polyamide; Merlon; Polyester such as PETG, PEN, polybutylene terephthalate (PBT); Polystyrene; Polyolefin such as polyethylene, polypropylene, polymethylpentene; Acrylic resins such as polymethyl methacrylate; Merlon; Polysulfones; Polyether sulfone; Polyether-ketone; Polyetherimide; Polyoxyethylene; The macromolecular material of norbornene resin etc.When using macromolecular material, transparent supporting mass can be rigidity also can be flexible.Transparent supporting mass preferably has transmissivity more than 80% for visible light, more preferably has the transmissivity more than 86%.
The color conversion film of present embodiment also can contain the solution of conjugated polymer compound by coating on temporary transient supporting mass, filming of obtaining is peeled off from temporary transient supporting mass, thereby form with the form of independent film.Be coated with employed solution and also can contain other key elements described later.In addition, as temporary transient supporting mass, except above-mentioned transparent supporting mass, also can use opaque supporting masses such as metal, pottery.
Color conversion film of the present invention can contain the oxygen absorbent that can not cause dysgenic amount to its look conversion characteristics.Conjugated polymer compound with general formula (1) or (2), under the condition that oxygen exists, can be oxidized during by rayed, may cause the reduction of fluorescent quantum yield.For this problem, in the present invention, can prevent the reduction of the fluorescent quantum yield of color conversion film by containing the oxidation that oxygen absorbent prevents the conjugated polymer compound.The oxygen absorbent that can use in the present invention for example comprises metals such as iron, aluminium, lithium, sodium, zinc, barium, inorganic compounds such as cuprous oxide, frerrous chloride, organic compounds such as hydroquinones, aniline.
Color conversion film of the present invention can be provided with the oxygen barrier film of blocking the oxygen in the atmosphere in its surface.The oxygen barrier film preferably can make the light after the conversion fully see through.By utilizing the oxygen in the oxygen barrier film blocking-up atmosphere to invade in this color conversion film, can prevent the oxidation of conjugated polymer compound, prevent the reduction of the fluorescent quantum yield of color conversion film.Operable oxygen barrier film for example comprises plastic films such as Merlon, PETG, nylon; Inorganic material films such as aluminium foil, silicon oxide film, silicon nitride film; Or with film laminations such as above-mentioned plastic film and aluminium, silica or silicon nitrides and the composite membrane that obtains.
The multicolor luminous organic EL device of second embodiment of the invention comprises the color conversion film of the organic EL and first execution mode, this organic EL is characterised in that containing at least one side is the pair of electrodes of transparency electrode and the organic EL layer of this pair of electrodes clamping.
The illustration structure of expression multicolor luminous organic EL device of the present invention among Figure 1A～Fig. 1 D.The device of Figure 1A has the structure of transparency carrier 10/ color conversion film 20/ organic EL 30a, and here, organic EL 30a comprises transparency electrode 31, organic EL layer 32 and reflecting electrode 33.The device of Figure 1A has color conversion film 20 and transparency electrode 31 contacted structures, is the device in the so-called bottom-emission mode of transparency carrier 10 side radiating lights.The device of Figure 1B has the structure of substrate 11/ organic EL 30b/ color conversion film 20.Here, organic EL 30b and element 30a comprise transparency electrode 31, organic EL layer 32 and reflecting electrode 33 equally, but its laminated layer sequence is opposite.The device of Figure 1B has color conversion film 20 and transparency electrode 31 contacted structures, is the device in the so-called top light emitting mode of the opposition side radiating light of substrate 11.
In the device of Figure 1A and Figure 1B, the side in the pair of electrodes is a transparency electrode 31, and the light that organic EL layer 32 is sent (EL light) directly or by the reflection of reflecting electrode 33 is emitted to the direction of transparency electrode 31, reenters and is mapped to color conversion film 20.The part of EL light is absorbed by the conjugated polymer compound, is radiated as the light (light of luminescence generated by light, PL light) with different wave length distribution.Then, because the EL light and the PL light that are not absorbed by color conversion film 20, organic EL device plays a role as sending out heterogeneous light.
On the other hand, the device of Fig. 1 C has the structure in transparency carrier 10/ organic EL 30a/ color conversion film 20/ reflector 40, and here, organic EL 30c comprises the 1st transparency electrode 31a, organic EL layer 32 and the 2nd transparency electrode 31b.The device of Fig. 1 C is the device of bottom-emission mode.The device of Fig. 1 D has the structure of substrate 11/ reflector 40/ color conversion film, 20/ organic EL 30c.The device of Fig. 1 D is the device of top light emitting mode.
In the device of Fig. 1 C and Fig. 1 D, the both sides of pair of electrodes are transparency electrode 31 (a, b), the part of the EL light that sends at organic EL layer 32 is not emitted to outside (being the direction of transparency carrier 10 in Fig. 1 C, is the direction of the 2nd transparency electrode 31b) in Fig. 1 D via color conversion film 20.In the EL light, absorbed by color conversion film 20, be converted to PL light towards the part of the light of the direction of color conversion film 20.In addition, the light by color conversion film 20 40 is reflected in the reflector, incides color conversion film 20 once more, is subjected to the Wavelength distribution conversion, emits to the outside by organic EL 30c again.
In any device of Figure 1A～Fig. 1 D, all be provided with color conversion film 20 and the contacted mode of transparency electrode 31 (comprising the 1st and the 2nd transparency electrode 31a, 31b).Such setting can make the distance minimization of organic EL layer 32 and color conversion film 20, improves the incident efficient of EL light to color conversion film 20, and very effective for reducing view angle dependency.
About adopting above-mentioned which kind of structure, depend on purposes, the desired form and aspect of device of needed device etc.Below describe about each inscape of multicolor luminous organic EL device of the present invention respectively.
On the other hand, employed substrate 11 in the top emission type structure of Figure 1B and Fig. 1 D owing to do not require the transparency, except can using above-mentioned transparency carrier 10 employed materials, can also use metal or pottery etc.
Transparency electrode 31 (comprising the 1st and the 2nd transparency electrode 31a, 31b), preferably the light for wavelength 400～800nm have more than 50%, the more preferably transmissivity more than 85%.Transparency electrode 31 can be used ITO (In-Sn oxide), Sn oxide, In oxide, IZO (In-Zn oxide), Zn oxide, Zn-Al oxide, Zn-Ga oxide or add alloy such as F, Sb for these oxides and the conductive clear metal oxide that forms forms.Transparency electrode 31 uses vapour deposition method, sputtering method or chemical vapor deposition (CVD) method to form, and preferably uses sputtering method to form.In addition, when the transparency electrode 31 that need constitute by a plurality of partial electrodes as described later, also can on whole surface, be formed uniformly the conductive clear metal oxide, be etched with afterwards and obtain required pattern, form the transparency electrode 31 that constitutes by a plurality of partial electrodes.
The transparency electrode 31 that is formed by above-mentioned material is suitable as the anode use.On the other hand, when using transparency electrode 31 as negative electrode, preferably with organic EL layer 32 cathode buffer layer is set at the interface, improve electron injection efficiency.As the material of cathode buffer layer, can use alkali metal such as Li, Na, K or Cs, alkaline-earth metal such as Ba, Sr or contain their alloy, rare earth metal, or the fluoride of these metals etc., but be not limited to these.The thickness of cathode buffer layer can be considered suitably selection such as the driving voltage and the transparency, but is preferably below the 10nm under the common situation.
(1) anode/organic luminous layer/negative electrode
(2) anode/hole injection layer/organic luminous layer/negative electrode
(3) anode/organic luminous layer/electron injecting layer/negative electrode
(4) anode/hole injection layer/organic luminous layer/electron injecting layer/negative electrode
(5) anode/hole transmission layer/organic luminous layer/electron injecting layer/negative electrode
(6) anode/hole injection layer/hole transmission layer/organic luminous layer/electron injecting layer/negative electrode
(7) anode/hole injection layer/hole transmission layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode
In above-mentioned layer structure, anode and negative electrode are respectively any of transparency electrode 31 (comprising the 1st and the 2nd transparency electrode 31a, 31b) or reflecting electrode 33.
As the material of each layer that constitutes organic EL layer 32, use material known.For example, as the material that is used to obtain organic luminous layer luminous from the blueness to the blue-green, for example preferably use the material of the fluorescent whitening agent, metal-chelating oxygen compound, styryl benzene-like compounds etc. of benzothiazoles, benzimidazole, Benzooxazole kind etc.
Material as electron transfer layer, can use 2-(4-xenyl)-5-(right-tert-butyl-phenyl)-1,3, the oxyquinoline complex of the oxadiazole derivative of this sample of 4-oxadiazole (PBD), triazole derivative, pyrrolotriazine derivatives, phenyl quinoxaline, aluminium (three (oxine) aluminium (Alq for example
3)) etc.As the material of electron injecting layer, except the material of above-mentioned electron transfer layer, can also use the oxyquinoline complex of the aluminium that is doped with alkali metal or alkaline-earth metal.
Material as hole transmission layer, can use to comprise TPD, N N '-two (1-naphthyl)-N, N '-diphenylbenzidine (α-NPD), 4,4 ', the 4 " well known materials of the triaryl amine material of three (N-3-tolyl-N-phenyl amino) triphenylamine (m-MTDATA) etc.As the material of hole injection layer, can use phthalocyanines (copper phthalocyanine etc.) or indanthrene (indanthrene) compounds etc.
Reflecting electrode 33 preferred metal, amorphous alloy or the crystallite alloys of high reflectance of using form.The metal of high reflectance comprises Al, Ag, Mo, W, Ni, Cr etc.The amorphous alloy of high reflectance comprises NiP, NiB, CrP and CrB etc.The crystallite alloy of high reflectance comprises NiAl etc.Reflecting electrode 33 can be used as negative electrode and uses, and also can be used as anode and uses.When reflecting electrode 33 uses as negative electrode, can be at reflecting electrode 33 interface with organic EL layer 32, above-mentioned cathode buffer layer is set improves electron injection efficiency for organic EL layer 32.Perhaps, when reflecting electrode 33 uses as negative electrode, can add alkaline-earth metal such as alkali metal, calcium, magnesium, strontium such as the little material lithium of work function, sodium, potassium and carry out alloying for above-mentioned high-reflectivity metal, amorphous alloy or crystallite alloy, improve electron injection efficiency.When reflecting electrode 33 uses as anode, also can the layer of above-mentioned conductive clear metal oxide be set at the interface of reflecting electrode 33 with organic EL layer 32, improve hole injection efficiency for organic EL layer 32.
Reflecting electrode 33 can adopt known any means in this technology such as evaporation (resistance heating or electron beam heating), sputter, ion plating, laser ablation to form according to employed material.When the reflecting electrode 33 that need constitute by a plurality of partial electrodes as described later, also can use the mask of giving required form to form the reflecting electrode 33 that constitutes by a plurality of partial electrodes.
In Figure 1A～Fig. 1 D, represent, in order (to form a plurality of independently illuminating parts among a～c) at organic EL 30, pair of electrodes is formed by a plurality of parts of parallel striated respectively, the example that forms in the mode of the striped that forms side's electrode and the striped that forms the opposing party's electrode (preferred quadrature) intersected with each other.Therefore, these organic ELs can carry out matrix driving, that is, when applying voltage on the specific striped of the special stripe of side's electrode and the opposing party's electrode, at these striped cross sections, organic EL layer 32 is luminous.Perhaps, side's electrode design can be become not have the plane electrode of the homogeneous of candy strip, the opposing party's electrode design is become patterning on corresponding to a plurality of partial electrodes of each illuminating part.At this moment, design a plurality of switch elements, and connect, can carry out so-called driven with active matrix on 1 pair 1 ground of above-mentioned partial electrode corresponding to each illuminating part corresponding to each illuminating part.Perhaps when the organic EL device of whole uniformly light-emitting of needs, also pair of electrodes can be designed to the plane electrode of homogeneous respectively.
In multicolor luminous organic EL device of the present invention, by kind that changes the conjugated polymer copolymer that constitutes color conversion film 20 or the thickness of adjusting color conversion film 20, the absorption light quantity that can regulate EL light in the color conversion film 20.Regulate the radiation light quantity of the absorption light quantity of EL light and PL light except utilizing these methods, by the configuration of the color conversion film 20 shown in suitable selection Figure 1A～Fig. 1 D, multicolor luminous organic EL device of the present invention can send the light of any form and aspect that comprise white light.
Multicolor luminous organic EL device of the present invention, pair of electrodes forms as one separately, can be with acting on the area source (backlight) of making display (monochromatic or and with the polychrome of colored filter).Perhaps as mentioned above, form pair of electrodes in the mode that can carry out matrix driving, can be as monochrome display or and with the multicolor display of colored filter.
Embodiment
＜embodiment 1 〉
As transparent glass substrate, use is through 1737 glass of the Corning company production of 50 * 50 * 0.7mm of pure water cleaning and drying.With the conjugated polymer compound of chemical formula (3) (9, the inferior ethene alternate copolymer of 9-dioctyl fluorene/MEH-phenylene, American Dye Sourceinc.; 108GE) be dissolved in the mesitylene solvent, obtain the coating fluid that concentration is 1wt%.Above-mentioned glass substrate is installed on the spin coater, drips coating fluid, make the substrate rotation, form uniform film.At this moment, make substrate with rotary speed 800rpm rotation 3 minutes.The weight average molecular weight of the conjugated polymer compound of the present embodiment that records with the GPC method counts 100,000 with polystyrene conversion.
For the color conversion film of embodiment 1, measuring absorption spectrum and excitation wavelength is fluorescence (PL) spectrum of 470nm.Absorption spectrum that obtains and PL spectral representation are in Fig. 2.
As shown in Figure 2, the maximum absorption wavelength of the color conversion film of embodiment 1 is 450nm, and the maximum emission wavelength of PL light is positioned at 550nm.This shows that this color conversion film has good spectral characteristic as the color conversion film that obtains green light when the organic EL with blue-light-emitting is used as backlight.
Use integrating sphere to measure the PL quantum yield (excitation wavelength 470nm) of the color conversion film of embodiment 1.In addition, in order to compare, the conjugated polymer compound of also having measured chemical formula (3) is at solution state (solvent: the PL quantum yield mesitylene).The gained result is as shown in table 1.
[table 1]
The PL quantum yield of the conjugated polymer compound of chemical formula (3)
(excitation wavelength 470nm)
| PL quantum yield (%) | |
| Solid film (embodiment 1) | 72 |
| Solution | 80 |
As shown in Table 1, the color conversion film of embodiment 1 demonstrates 72% this high PL quantum yield.On the other hand, the PL quantum yield of solution state is 80%.Because the effect of concentration quenching, mostly the PL quantum yield of the solid film of conjugated polymer compound be reduced to solution state the PL quantum yield about 60～30%.But, in the conjugated polymer compound of Shi Yonging, follow being reduced in 10% of film formed PL quantum yield in the present embodiment.This shows that the conjugated polymer compound that is used to form color conversion film of the present invention has the effect of excellent inhibition concentration quenching.
In addition, use the color conversion film of baking oven heating embodiment 1, the relation of research heating condition and PL quantum yield.Its result pining for 150 ℃ add through 30 minutes, does not observe the decline of PL quantum yield.
(comparative example 1)
Except using the inferior ethene of poly (arylene ether) to replace repeating the step of embodiment 1 the conjugated polymer compound of chemical formula (3), make color conversion film.The weight average molecular weight of the inferior ethene of poly (arylene ether) that uses in this comparative example that uses the GPC method to record counts 120,000 with polystyrene conversion.
The color conversion film of comparative example 1 shows the maximum emission wavelength of 590nm and 45% PL quantum yield (excitation wavelength 470nm).In addition, the color conversion film of comparative example 1 through 30 minutes with 100 ℃ of heating, the PL quantum yield has dropped to 25%.
As known from the above, be in the color conversion film of the embodiment 1 in the scope of the invention, by containing the conjugated polymer compound that has imported fluorene skeleton, has the inhibition that can realize concentration quenching simultaneously, glow peak wavelength hypsochromic shift is moving and the performance of the practicality of high-fire resistance.
(embodiment 2)
As substrate 11, prepare 1737 glass that the process pure water cleans and the Corning company of 50 * 50 * 0.7mm of drying produces.Substrate 11 conveyances to sputter equipment, are used the DC magnetron sputtering method, form the CrB film of thickness 200nm.From sputter equipment, take out the substrate that film forming finishes, use photoetching process to form 4 striated electrodes, obtain reflecting electrode 33.The striated electrode that obtains has the live width of 2mm respectively, with the arranged spaced of 2mm.In utilizing photolithographic patterning, use commercially available photoresist AZ-1500 (AZ ElectronicMaterials) and commercially available etching solution Cr-01N (Kanto Kagaku K. K.).
The board carrying that will be formed with reflecting electrode 33 is to vacuum deposition apparatus.Mask with the wide striated peristome of 2mm at first, in the zone of the 25 * 25mm of portion of substrate center and only is set on reflecting electrode.Then,, pile up the Li film of thickness 1.5nm, obtain cathode buffer layer at the upper surface of reflecting electrode 33 by this mask.
Then, do not destroy vacuum, mask is replaced by the mask that has peristome in the zone of the 25 * 25mm of portion of substrate center.By this mask, pile up electron transfer layer/luminescent layer/hole transmission layer/hole injection layer in turn 4 layers, obtain organic EL layer 32.Each layer is respectively with the 0.1nm/ evaporation rate accumulation of second.Use Alq
3Forming thickness is the electron transfer layer of 20nm, use 4,4 '-two (2,2 '-diphenylacetylene) to form thickness be the luminescent layer of 30nm to biphenyl (DPVBi), use 4,4 '-(α-NPD) the formation thickness is the hole transmission layer of 10nm to two [N-(1-naphthyl)-N-phenyl amino] biphenyl, and uses copper phthalocyanine (CuPc) to form the hole injection layer of thickness as 100nm.
In addition, do not destroy vacuum, the substrate that will be formed with organic EL layer 32 moves to relative sputter equipment.And the striated peristome of the wide 2mm of setting and reflecting electrode 33 quadratures is with the mask of 2mm arranged spaced.By this mask, piling up thickness is indium-tin-oxide (ITO) of 200nm, obtains transparency electrode 31.
Then, will be formed with the board carrying of transparency electrode 31 to the ink discharge device that is arranged in the glove box.In glove box, import drying nitrogen (dew point＜-40 ℃) in advance.The conjugated polymer compound solution that uses among the embodiment 1 is injected ink discharge device.Use this ink discharge device, in the zone of the 25 * 25mm of portion of substrate center and only making thickness on transparency electrode 31 is the color conversion film 20 of 600nm, obtains the structure shown in Figure 1B.
At last, on the substrate that is formed with color conversion film 20, the zone that sticks on the width 3mm on four limits is coated with the glass for sealing substrate of 40 * 40 * 0.7mm of ultraviolet-curing adhesive, with the sealing structure of color conversion film below 20, obtains multicolor luminous organic EL device.
In order to compare, except not forming color conversion film 20, repeat above-mentioned steps, obtain monochromatic luminous organic EL device.Giving 10mA/cm
2The condition of current density under, drive the monochromatic luminous organic EL device of gained, send (x, blue light y)=(0.13,0.20) in the cie color coordinate.Brightness-current efficiency of this moment is 6.2cd/A.
Then, giving 10mA/cm
2The condition of current density under, drive the multicolor luminous organic EL device of present embodiment, send (x, green light y)=(0.30,0.66) in the cie color coordinate.Brightness-current efficiency of this moment is 4.0cd/A.Hence one can see that, and the thickness of present embodiment is that the color conversion film 20 of 600nm can fully absorb the blue light that is sent by luminescent layer, radiates high-intensity green light.
Then, the multicolor luminous organic EL device that obtains light test continuously.By current density is fixed on 0.3A/cm
2Constant current drive to implement test.In the multicolor luminous organic EL device of present embodiment, through 100 hours Continuous Drive, the form and aspect of not observing along with the driving time process changed.Therefore, the multicolor luminous organic EL device of present embodiment can send very stable green light as can be known.
Symbol description
10: transparency carrier; 11: substrate; 20: color conversion film; 30 (a～c): organic EL; 31 (a, b): transparency electrode; 32: organic EL layer; 33: reflecting electrode; 40: the reflecting layer.
Claims (6)
1. color conversion film is characterized in that:
Contain the conjugated polymer compound, this conjugated polymer compound has the structure shown in the general formula (1), and has the glow peak wavelength from 490nm to 560nm under the solid film state,
In the formula, Ar represents arlydene or divalent heterocyclic radical, R
1And R
2Represent hydrogen atom, alkyl, alkoxyl, alkylthio group, alkyl silicyl, alkyl amino, aryl, aryloxy group, aralkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, 1 valency heterocyclic radical, amino, nitro, halogen or cyano group respectively independently, and n and m are 1～10000 integer independently respectively.
2. color conversion film as claimed in claim 1 is characterized in that:
Described conjugated polymer compound has the structure shown in the general formula (2),
In the formula, R
1, R
2, R
3And R
4Represent hydrogen atom, alkyl, alkoxyl, alkylthio group, alkyl silicyl, alkyl amino, aryl, aryloxy group, aralkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, 1 valency heterocyclic radical, amino, nitro, halogen or cyano group respectively independently, and n and m are 1～10000 integer independently respectively.
3. color conversion film as claimed in claim 1 is characterized in that:
Described conjugated polymer compound has the weight average molecular weight more than 1000, below 500,000.
4. color conversion film as claimed in claim 1 is characterized in that:
It is formed by coating process.
5. multicolor luminous organic EL device is characterized in that:
Have each described color conversion film in the organic EL layer of pair of electrodes that at least one side is a transparency electrode, this pair of electrodes clamping and the claim 1 to 3, wherein, this color conversion film has the following thickness of 2 μ m.
6. multicolor luminous organic EL device as claimed in claim 5 is characterized in that:
Described color conversion film and described transparency electrode are provided with in contacted mode.
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| JP2008245913 | 2008-09-25 | ||
| PCT/JP2009/065204 WO2010024439A1 (en) | 2008-09-01 | 2009-08-31 | Conjugated high-molecular-weight copolymer, color conversion film using same, and multicolor light-emitting organic el device |
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| WO2013118671A1 (en) * | 2012-02-10 | 2013-08-15 | 日本ゼオン株式会社 | Organic electroluminsecent light source device |
| KR102491605B1 (en) * | 2017-12-27 | 2023-01-20 | 엘지디스플레이 주식회사 | Lighting device |
| KR102531874B1 (en) * | 2018-11-12 | 2023-05-12 | 주식회사 엘지화학 | Color conversion film, back light unit and display apparatus comprising same |
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| JP2005276749A (en) * | 2004-03-26 | 2005-10-06 | Sanyo Electric Co Ltd | Organic electroluminescent element |
| JP2006321910A (en) * | 2005-05-19 | 2006-11-30 | Mie Univ | Organic el hybrid material and method for producing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021196278A1 (en) * | 2020-03-30 | 2021-10-07 | 深圳市华星光电半导体显示技术有限公司 | Color conversion thin film manufacturing method, color conversion thin film and display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110069769A (en) | 2011-06-23 |
| TW201014896A (en) | 2010-04-16 |
| JPWO2010024439A1 (en) | 2012-01-26 |
| WO2010024439A1 (en) | 2010-03-04 |
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