WO2003064558A1 - Fluorescent compositions comprising diketopyrrolopyrroles - Google Patents
Fluorescent compositions comprising diketopyrrolopyrroles Download PDFInfo
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- WO2003064558A1 WO2003064558A1 PCT/EP2003/000650 EP0300650W WO03064558A1 WO 2003064558 A1 WO2003064558 A1 WO 2003064558A1 EP 0300650 W EP0300650 W EP 0300650W WO 03064558 A1 WO03064558 A1 WO 03064558A1
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Definitions
- Fluorescent compositions comprising diketopyrrolopyrroles
- the present invention relates to fluorescent compositions comprising a guest chromophore and a host chromophore, wherein the absorption spectrum of the guest chromophore overlaps with the fluorescence emission spectrum of the host chromophore, wherein the host chromophore is a diketopyrrolopyrrole having a photoluminescence emission peak at 500 to 720 nm, preferably 500 to 600 nm, most preferred 520 to 580 nm and wherein the guest chromophore is a diketopyrrolopyrrole having an absorption peak at 500 to 720 nm, preferably 500 to 600 nm, most preferred 520 to 580 nm and their use for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, dye lasers and electroluminescent devices.
- a luminescent device comprising a composition according to the
- EL organic electroluminescent
- a vacuum evaporation process e.g. described in Appl. Phys. Lett., 51 , 913 (1987).
- two types of such vacuum evaporation processes are applied according to the constitution of light emitting material: a one-component type process and a two-component type (or "Host-Guest type” or "binary system”) process (e.g. described in J. Appl. Phys., 65, 3610 (1989)).
- the light emitting materials themselves have to emit an intense fluorescence of red, green or blue color.
- a vacuum evaporation process has to give a deposited film of uniform quality, and the film thus formed has to be endowed with appropriate (“carrier") mobility for positive holes and/or electrons i.e. properties of a semiconductor.
- JP-B2 2,749,407 (Pioneer Electron Corp. & Nippon Kayaku Co. Ltd.) describes as a light emitting material N,N'-bis(2,5-di-tert.-butylphenyl)-3,4,9,10-perylenedicarboximide.
- N,N'-bis(2,5-di-tert.-butylphenyl)-3,4,9,10-perylenedicarboximide is as low as 27 cd/m 2 , which is insufficient for commercial applications.
- JP-A2 2,296,891 claims an electroluminescent element comprising a positive electrode, a negative electrode and one organic compound layer or a plurality of organic compound layers held between the positive and negative electrodes, but no hole transporting substance. At least one layer of said organic compound layers is a layer containing a pyrrolopyrrole compound represented by the following formula II"
- Y ⁇ and Y 2 independently from each other represent a substituted or unsubstituted alkyl, cycloalkyl or aryl group
- Y 3 and Y independently represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group
- X represents an oxygen or a sulfur atom
- JP-A2 5,320,633 (Sumitomo) claims an organic EL device having a light emitting layer comprising a light emitting material in an amount of 0.005 to 15 parts by weight of a DPP compound between a pair of electrodes, wherein at least one electrode being transparent or semi-transparent.
- Alq 3 is an essential feature in the claimed EL element or device.
- JP-A2 9003448 (Toyo Ink) claims an organic EL element having between a pair of electrodes a luminous layer containing a DPP compound as electron-transporting material or an organic compound thin film layer including a luminous layer and an electron-injecting layer wherein the electron-injecting layer contains a DPP compound as the electron-transporting material.
- another EL element further comprising a hole-injecting layer is claimed.
- the disadvantage of the claimed EL devices is that according to the examples always Alq 3 and a phenanthrene diamine (as hole-injecting material) have to be used.
- EP-A 499,011 describes electroluminescent devices comprising DPP-compounds. Particularly, in example 1 the DPP-derivative of formula IIP is disclosed.
- EP-A-1087005 relates to fluorescent diketbpyrrolopyrroles ("DPPs") of the formula
- R ⁇ > and R 2 > independently from each other, stand for CrC 25 -alkyl, allyl which can be substituted one to three times with C C 3 alkyl or Ar 3 ., -CR 3' R 4 >-(CH 2 ) m' -Ar 3 ., wherein R 3 . and R 4 .
- Ar 3 > stands for phenyl or 1- or 2-naphthyl which can be substituted one to three times with C Csalkyl, CrC 8 alkoxy, halogen or phenyl, which can be substituted with CrC 8 alkyl or CrC 8 alkoxy one to three times
- m' stands for 0, 1 , 2, 3 or 4, and wherein CrC 25 -alkyl or -CR 3 R 4 -(CH 2 ) m -Ar 3' , preferably CrC 25 -alkyl, can be substituted with a functional group capable of increasing the solubility in water such as a tertiary amino group, -SO 3 " , or PO 4 2" ,
- An and Ar 2 independently from each other, stand for hydrogen or C ⁇ -C alkyl, or phenyl which can be substituted on to three times with C C 3 alkyl
- Ar 3 > stands for phenyl or 1- or 2-naphthyl which can be substituted one to
- R 6 ' and R 7 ' independently from each other, stand for hydrogen, CrC ⁇ alkyl, -NR 8 R 9 ' , -OR 10 ' , -S(O) n R 8 , -Se(O) n R 8 ' , or phenyl, which can be substituted one to three times with C C 8 alkyl or C C 8 alkoxy, but do not stand simultaneously for hydrogen, wherein R 8 .
- R 10 stands for C 6 -C 24 -aryl, or a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein Ph, the aryl and heterocyclic radical can be substituted one to three times with C ⁇ -C 8 alkyl, CrC 8 alkoxy, or halogen, or R 8 > and R g - stand for -C(O)R 10 ', wherein Rn> can be CrC 2 5-alkyl, C 5 -C ⁇ 2 -cycloalkyl, R 10 ', -OR 12' or -NR 13 .R ⁇ 4'
- the DPP compounds can be used for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, or for the preparation of polymeric ink particles, toners, dye lasers and electroluminescent devices.
- EP-A-1087006 relates to an electroluminescent device comprising in this order (a) an anode, (b) a hole transporting layer, (c) a light-emitting layer, (d) optionally an electron transporting layer and (e) a cathode and a light-emitting substance, wherein the light-emitting substance is a diketopyrrolopyrrole ("DPP") represented by formula P.
- DPP diketopyrrolopyrrole
- luminescent devices which are high in the efficiency of electrical energy utilisation and high in luminance, can be obtained if specific combinations of DPP compounds are used as light emitting substances.
- the present invention relates to compositions comprising a guest chromophore and a host chromophore, wherein the absorption spectrum of the guest chromophore overlaps with the fluorescence emission spectrum of the host chromophore, wherein the host chromophore is a diketopyrrolopyrrole having a photoluminescence emission peak at 500 to 720 nm, preferably 500 to 600 nm, most preferred 520 to 580 nm and wherein the guest chromophore is a diketopyrrolopyrrole having an absorption peak at 500 to 720 nm, preferably 500 to 600 nm, most preferred 520 to 580 nm
- compositions comprising a diketopyrrolopyrrole (“DPP”) represented by formula I
- R 1 , R 2 , R 3 and R 4 independently from each other stand for C 1 -C 25 -alkyl, which can be substituted by fluorine, chlorine or bromine, C 5 -C 12 -cycloalkyl or C 5 -C 12 -cycloalkyl which can be condensed one or two times by phenyl which can be substituted one to three times with C C 4 -alkyl, halogen, nitro or cyano, silyl, A 5 or -CR 11 R 12 -(CH 2 ) m -A 5 , wherein R 11 and R 12 independently from each other stand for hydrogen, fluorine, chlorine, bromine, cyano or C C 4 alkyl, which can be substituted by fluorine, chlorine or bromine, or phenyl which can be substituted one to three times with C 1 -C 3 alkyl, A 5 stands for phenyl or 1- or 2-naphthyl which can be substituted one to three times with C C 8
- R 8 and R 9 independently from each other stand for hydrogen, CrC 25 -alkyl, C 5 -C 12 - cycloalkyl, -CR 11 R 12 -(CH 2 ) m -A 5 , C 6 -C 24 -aryl, in particular A 1 , or a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, and R 16 and R 17 independently from each other stand for hydrogen and C 6 -C 24 - aryl, in particular phenyl; an electroluminescent device comprising the above-mentioned composition and the use of the composition for coloring a high molecular weight organic material, i.e. the use of the composition for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, dye
- the present invention provides red or orange fluorescent compositions with a high heat stability, a good solubility in polymers, hydrocarbon based fuels, lubricants etc., a high light stability, and the ability to be used in plastics, especially polyamides, without decomposition and loss of lightfastness, and in paints and with a high electroluminescent (EL) emission intensity.
- EL electroluminescent
- R 1 , R 2 , R 3 and R 4 independently from each other stand for CrC 25 -alkyl, preferably C C 8 alkyl, in particular n-butyl, tert.-butyl and neopentyl, C 5 -C 12 cycloalkyl or C 5 -C 12 -cycloalkyl which can be condensed one or two times by phenyl which can be substituted one to three times with CrC 4 -alkyl, halogen and cyano, in particular cyclohexyl, which can be substituted one to three times with C ⁇ -C 8 alkyl and/or C r C 8 alkoxy, in particular 2,6-di-isopropylcyclohexyl, or
- R 1 and R 2 are independently of each other C C 8 alkyl
- R 11 is hydrogen
- R 12 is hydrogen
- a 5 is or wherein R 5 ,
- R 6 and R 7 are independently of each other hydrogen, C ⁇ -C 4 -alkyl, or halogen, in particular Br,
- R 6 is CrC- 4 -alkyl, phenyl or Br and R 5 and R 7 are hydrogen; R 5 is C C 4 -alkyl and R 6 and R 7 are hydrogen; or R 6 is hydrogen and R 5 and R 7 are C r C 4 -alkyl are most preferred.
- R 3 and R 4 are independently of each other CrCo-alkyl or -CR 11 R 12 -A 5 , wherein R 11 is hydrogen, R 12 is methyl or phenyl, in particular hydrogen and A 5 is
- R 5 , R 6 and R 7 are independently of each other hydrogen, C C 4
- the weight ratio of the DPP compound of the formula I to the DPP compound of the formula II is in general 50:50 to 99.99:0.01 , preferably 90:10 to 99.99:0.01 , more preferably 95:5 to 99.9:0.1 , most preferably 98:2 to 99.9:0.1.
- the DPP compounds of the formula I and II are distinguished by the substituents A 1 and A 2 and A 3 and A 4 , respectively.
- a 1 and A 2 independently from each other stand for
- R , R , R , n and R >15 have the above-mentioned meanings.
- a 1 and A 2 independently from each other can stand for
- n is an integer of 1 to 4, in particular 1 or 2
- R 5 and R 6 independently from each other can stand for hydrogen, C C 8 alkyl or C C 8 alkoxy and R 15 is C 6 -C 24 aryl, such as phenyl, 1- naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, terphenyl, pyrenyl, 2- or 9-fluorenyl or anthracenyl, preferably C 6 -C 12 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, which may be unsubstituted or substituted by CrC 8 alkyl or CrC 8 alkoxy, wherein groups of the following formula are preferred:
- R 5 , R 6 and R 7 independently from each other stand for hydrogen, C r C 8 -alkyl, C C 8 - alkoxy, -OCR 11 R 12 -(CH 2 ) m -A 5 , cyano, chloro, -OR 10 , or phenyl, which can be substituted one to three times with C Csalkyl or C ⁇ -C 8 alkoxy, wherein R 10 stands for C 6 -C 24 -aryl, such as phenyl, 1-naphthyl or 2-naphthyl, R 11 and R 12 are hydrogen or C ⁇ -C 4 -alkyl, m is 0 or 1 , A 5 is phenyl, 1-naphthyl or 2-naphthyl, wherein groups of the following formula are preferred:
- R 5 is C Cs-alkyl
- DPP compounds of the formula I are preferred, wherein R 1 and R 2 are C C 25 - alkyl, in particular C 1 -C 25 -alkyl, wherein all or part of the hydrogen atoms are replaced by fluorine atoms, a group -CR 11 R 12 -A 5 , wherein R 11 is hydrogen or C 1-4 -alkyl, in particular methyl, R 12 is CF 3 or F, and A 5 is phenyl, or a group -CR 11 R 12 -A 5 , wherein R 11 is hydrogen,
- R 12 is C 1-4 -alkyl, in particular methyl, A 5 is a group , wherein R 6 is fluorine, chlorine, bromine, preferably cyano or nitro.
- CrC 25 -alkyl, which are substituted by fluorine comprises linear or branched C 1 -C 25 -alkyl groups wherein all or a part of the hydrogen atoms are replaced by fluorine atoms.
- Examples of such groups are -CH 2 F, -CHF 2 , -CF 3 , FH 2 CCH 2 -, FH 2 CCHF-, F 2 HCCH 2 -, F 2 HCCHF-, F 3 CCH 2 -, F 2 HCCF 2 -, F 3 CCHF-, F 3 CCF 2 -, CF 3 CF 2 CF 2 -, CF 3 CF 2 CF 2 -, or F 3 C(CF 2 ) 3 CF 2 ..
- DPP compounds of the formula I are the following compounds:
- R 5 , R b , R , R , R and R have the above-defined meanings.
- R° and R b are preferably hydrogen
- R 8 is preferably d-C ⁇ alkyl or phenyl
- R 16 and R 17 are preferably hydrogen or phenyl.
- R 5 and R 6 are preferably hydrogen and R 8 is preferably C C 6 alkyl or phenyl.
- R 5 , R 6 , R 7 independently from each other stand for hydrogen, CrC 8 -alkyl, C r C 8 - alkoxy, -OCR 11 R 12 -(CH 2 ) m -A 5 , cyano, chloro, -OR 10 , or phenyl, which can be substituted one to three times with C ⁇ -C 8 alkyl or C C 8 alkoxy, wherein R 10 stands for C 6 -C 24 -aryl, such as phenyl, 1-naphthyl or 2-naphthyl, R 11 and R 12 are hydrogen or CrC 4 -alkyl, m is 0 or 1 , A 5 is phenyl, 1 -naphthyl or 2-naphthyl, R 8 and R 9 independently from each other stand for hydrogen, CrC 8 -alkyl, C 5 -C 12 -cycloalkyl, in particular cyclohexyl, -CR 11 R 12
- R 8 and R 9 are independently of each other a group of the formula
- R 21 , R 22 and R 23 are independently of each other hydrogen, C C 8 alkyl, a hydroxyl group, a mercapto group, C r C 8 alkoxy, CrC 8 alkylthio, halogen, halo-C C 8 alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group.
- R 21 , R 22 and R 23 are independently of each other hydrogen, CrC 8 alkyl, C C 8 alkoxy or C 1 -C 8 alkylthio.
- Particularly preferred DPP compounds of the formula II are the following compounds:
- compositions comprise compounds A-2 and B-1 , A-2 and B-3, A-2 and B-7, A-11 and B-1 or A-11 and B-7.
- inventive DPP compounds of formula I or II can be synthesized according to or in analogy to methods well known in the art, such as described, for example, in US 4,579,949, EP-A 353,184, EP-A-133,156, EP-A-1 , 087,005 and EP- A-1 ,087,006.
- halogen means fluorine, chlorine, bromine and iodine.
- C C ⁇ alkyl is typically linear or branched - where possible - methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n- hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl, preferably CrC 8
- aldehyde group, ketone group, ester group, carbamoyl group and amino group include those substituted by an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group or the like, wherein the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may be unsubstituted or substituted.
- sil group means a silicon compound group such as trimethylsilyl.
- siloxanyl group means a silicon compound group linking through intermediation of an ether linkage, such as trimethylsiloxanyl and the like.
- Examples of CrC 8 alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n- heptoxy, n-octoxy, 1 ,1 ,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably CrC 4 alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy.
- alkylthio group means the same groups as the alkoxy groups, except that the oxygen atom of ether linkage is replaced by a sulfur atom.
- aryl group is typically C 6 -C 24 aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 4- biphenyl, phenanthryl, terphenyl, pyrenyl, 2- or 9-fluorenyl or anthracenyl, preferably C 6 - C ⁇ 2 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, which may be unsubstituted or substituted.
- cycloalkyl group is typically C 5 -C 12 cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, may be unsubstituted or substituted.
- cycloalkenyl group means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted.
- the cycloalkyl group in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with CrC 4 -alkyl , halogen and cyano. Examples of such condensed cyclohexyl groups
- R 26 are independently of each other C C 4 -alkyl , halogen and cyano, in particular hydrogen.
- heterocyclic radical is a ring with five to seven ring atoms, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic radical with five to 18 atoms having at least six conjugated ⁇ -electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindoly
- the above-mentioned substituents can be substituted by a CrC 8 alkyl, a hydroxyl group, a mercapto group, CrC 8 alkoxy, C C 8 alkylthio, halogen, halo-CrC 8 alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group,
- the present invention relates further to an electroluminescent device having the composition according to the present invention between an anode and a cathode and emitting light by the action of electrical energy.
- Typical constitutions of latest organic electroluminescent devices are: (i) an anode/a hole transporting layer/an electron transporting layer/a cathode, in which the compositions are used either as positive-hole transport composition, which is exploited to form the light emitting and hole transporting layers, or as electron transport compositions, which can be exploited to form the light-emitting and electron transporting layers, and (ii) an anode/a hole transporting layer/a light-emitting layer/an electron transporting layer/a cathode, in which the compositions form the light-emitting layer regardless of whether they exhibit positive-hole or electron transport properties in this constitution, and (iii) an anode/a hole injection layer /a hole transporting layer/a light-emitting layer/an electron transporting layer/a cathode, and (iv) an anode/a hole transporting layer/a light-emitting layer/ a positive hole inhibiting layer / an electron transporting layer/a cathode, and
- Thin film type electroluminescent devices usually consist essentially of a pair of electrodes and at least one charge transporting layer in between.
- a hole transporting layer (next to the anode) and an electron transporting layer (next to the cathode) are present.
- Either one of them contains - depending on its properties as hole-transporting or electron-transporting material - an inorganic or organic fluorescence substance as light-emitting material. It is also common, that a light-emitting material is used as an additional layer between the hole-transporting and the electron-transporting layer.
- a hole injection layer can be constructed between a anode and a hole transporting layer and/or a positive hole inhibiting layer can be constructed between a light emitting layer and a electron transporting layer to maximise hole and electron population in the light emitting layer, reaching large efficiency in charge recombination and intensive light emission.
- the devices can be prepared in several ways. Usually, vacuum evaporation is used for the preparation.
- the organic layers are laminated in the above order on a commercially available indium-tin-oxide ("ITO") glass substrate held at room temperature, which works as the anode in the above constitutions.
- ITO indium-tin-oxide
- the membrane thickness is preferably in the range of 1 to 10,000 nm, more preferably 1 to 5,000 nm, more preferably 1 to 1 ,000 nm, more preferably 1 to 500 nm.
- the cathode metal such as a Mg/Ag alloy or a binary Li-AI system of ca. 200 nm is laminated on the top of the organic layers.
- the vacuum during the deposition is preferably less than 0.1333 Pa (1x 10 "3 Torr), more preferably less than 1.333x 10 "3 Pa (1x 10 "5 Torr), more preferably less than 1.333x 10 "4 Pa (1x 10 '6 Torr).
- anode materials which possess high work function such as metals like gold, silver, copper, aluminum, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungsten and the like, metallic alloys such as magnesium/copper, magnesium/silver, magnesium/aluminum, aluminum/indium and the like, semiconductors such as Si, Ge, GaAs and the like, metallic oxides such as indium-tin-oxide ("ITO"), ZnO and the like, metallic compounds such as Cul and the like, and furthermore, electroconducting polymers such polyacetylene, polyaniline, polythiophene, polypyrrole, polyparaphenylene and the like, preferably ITO, most preferably ITO on glass as substrate can be used.
- metallic alloys such as magnesium/copper, magnesium/silver, magnesium/aluminum, aluminum/indium and the like, semiconductors such as Si, Ge, GaAs and the like, metallic oxides
- metals, metallic alloys, metallic oxides and metallic compounds can be transformed into electrodes, for example, by means of the sputtering method.
- the electrode can be formed also by the vacuum deposition method.
- the electrode can be formed, furthermore, by the chemical plating method (see for example, Handbook of Electrochemistry, pp 383-387, Mazuren, 1985).
- an electrode can be made by forming it into a film by means of anodic oxidation polymerization method onto a substrate which is previously provided with an electroconducting coating.
- the thickness of an electrode to be formed on a substrate is not limited to a particular value, but, when the substrate is used as a light emitting plane, the thickness of the electrode is preferably within the range of from 1 nm to 100 nm, more preferably, within the range of from 5 to 50 nm so as to ensure transparency.
- ITO is used on a substrate having an ITO film thickness in the range of from 10 nm (100 A) to 1 ⁇ (10000 A), preferably from 20 nm (200 A) to 500 nm (5000 A).
- the sheet resistance of the ITO film is chosen in the range of not more than 100 ⁇ /cm 2 , preferably not more than 50 ⁇ /cm 2 .
- Such anodes are commercially available from Japanese manufacturers, such as Geomatech Co.Ltd., Sanyo Vacuum Co. Ltd., Nippon Sheet Glass Co. Ltd.
- an electronconducting or electrically insulating material can be used as substrate either an electronconducting or electrically insulating material.
- a light emitting layer or a positive hole transporting layer is directly formed thereupon, while in case of using an electrically insulating substrate, an electrode is firstly formed thereupon and then a light emitting layer or a positive hole transporting layer is superposed.
- the substrate may be either transparent, semi-transparent or opaque. However, in case of using a substrate as an indicating plane, the substrate must be transparent or semi- transparent.
- Transparent electrically insulating substrates are, for example, inorganic compounds such as glass, quartz and the like, organic polymeric compounds such as polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate, polyvinylchloride, polyvinylalcohol, polyvinylacetate and the like.
- inorganic compounds such as glass, quartz and the like
- organic polymeric compounds such as polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate, polyvinylchloride, polyvinylalcohol, polyvinylacetate and the like.
- semi-transparent electrically insulating substrates examples include inorganic compounds such as alumina, YSZ (yttrium stabilized zirconia) and the like, organic polymeric compounds such as polyethylene, polypropylene, polystyrene, epoxy resins and the like. Each of these substrates can be transformed into a semi-transparent electroconducting substrate by providing it with an electrode according to one of the abovementioned methods.
- opaque electroconducting substrates are metals such as aluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper, silver, gold, platinum and the like, various elctroplated metals, metallic alloys such as bronze, stainless steel and the like, semiconductors such as Si, Ge, GaAs, and the like, electroconducting polymers such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyparaphenylene and the like.
- a substrate can be obtained by forming one of the above listed substrate materials to a desired dimension. It is preferred that the substrate has a smooth surface. Even if it has a rough surface, it will not cause any problem for practical use, provided that it has round unevenness having a curvature of not less than 20 ⁇ m. As for the thickness of the substrate, there is no restriction as far as it ensures sufficient mechanical strength.
- cathode materials which possess low work function such as alkali metals, earth alkaline metals, group 13 elements, silver, and copper as well as alloys or mixtures thereof such as sodium, lithium, potassium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-copper alloy, magnesium-aluminum alloy, magnesium- indium alloy, aluminum, aluminum-aluminum oxide alloy, aluminum-lithium alloy, indium, calcium, and materials exemplified in EP-A 499,011 such as electroconducting polymers e.g. polypyrrole, polythiophene, polyaniline, polyacetylene etc., preferably Mg/Ag alloys, or Li-AI compositions can be used.
- electroconducting polymers e.g. polypyrrole, polythiophene, polyaniline, polyacetylene etc., preferably Mg/Ag alloys, or Li-AI compositions can be used.
- a magnesium-silver alloy or a mixture of magnesium and silver, or a lithium-aluminum alloy or a mixture of lithium and aluminum can be used in a film thickness in the range of from 10 nm (100 A) to 1 ⁇ m (10000 A), preferably from 20 nm (200 A) to 500 nm (5000 A).
- Such cathodes can be deposited on the foregoing electron transporting layer by known vacuum deposition techniques described above.
- a light-emitting layer can be used between the hole transporting layer and the electron transporting layer.
- the light-emitting layer is prepared by forming a thin film on the hole transporting layer.
- the vacuum deposition method As methods for forming said thin film, there are, for example, the vacuum deposition method, the spin-coating method, the casting method, the Langmuir-Blodgett ("LB") method and the like.
- the vacuum deposition method, the spin-coating method and the casting method are particularly preferred in view of ease of operation and cost.
- the conditions under which the vacuum deposition is carried out are usually strongly dependent on the properties, shape and crystalline state of the compound(s).
- optimum conditions are usually as follows: temperature of the heating boat: 100 to 400°C; substrate temperature: -100 to 350°C; pressures .33x10 4 Pa (1x10 2 Torr) to 1.33x10 "4 Pa (1x10 6 Torr) and deposition rate: 1 pm to 6 nm/sec
- the thickness of the light emitting layer is one of the factors determining its light emission properties. For example, if a light emitting layer is not sufficiently thick, a short circuit can occur quite easily between two electrodes sandwiching said light emitting layer, and therefor, no EL emission is obtained. On the other hand, if the light emitting layer is excessively thick, a large potential drop occurs inside the light emitting layer because of its high electrical resistance, so that the threshold voltage for EL emission increases. Accordingly, the thickness of the organic light emitting layer is limited to the range of from 5 nm to 5 ⁇ m, preferably to the range of from 10 nm to 500 nm.
- the coating can be carried out using a solution prepared by dissolving the composition in a concentration of from 0.0001 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyltetrahydrofurane, N,N- dimethylformamide, dichloromethane, dimethylsulfoxide and the like. If the concentration exceeds 90% by weight, the solution usually is so viscous that it no longer permits forming a smooth and homogenous film. On the other hand, if the concentration is less than 0.0001 % by weight, the efficiency of forming a film is too low to be economical.
- a preferred concentration of the composition is within the range of from 0.01 to 80% by weight.
- a polymer binder may be used, provided that it is soluble in the solvent in which the composition is dissolved.
- polymer binders are polycarbonate, polyvinylalcohol, polymethacrylate, polymethylmethacrylate, polyester, polyvinylacetate, epoxy resin and the like.
- the fluidity of the solution is usually so low that it is impossible to form a light emitting layer excellent in homogeneity.
- the content of the composition is substantially smaller than that of the polymer binder, the electrical resistance of said layer is very large, so that it does not emit light unless a high voltage is applied thereto.
- the preferred ratio of the polymer binder to the composition is chosen within the range of from 10:1 to 1 :50 by weight, and the solid content composed of both components in the solution is preferably within the range of from 0.01 to 80% by weight, and more preferably, within the range of 0.1 to 60% by weight.
- organic hole transporting compounds such as polyvinyl carbazole
- Q ⁇ and Q 2 each represent a hydrogen atom or a methyl group; a compound disclosed in J. Appl. Phys. 65(9) (1989) 3610: a stilbene based compound
- T and Ti stand for an organic radical; a hydrazone based compound
- R ⁇ N R x z wherein Rx, Ry and Rz stand for an organic radical, and the like can be used.
- Compounds to be used as a positive hole transporting material are not restricted to the above listed compounds. Any compound having a property of transporting positive holes can be used as a positive hole transporting material such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivative, pyrazolone derivatives, phenylene diamine derivatives, arylamine derivatives, amino substituted chalcone derivatives, oxazole derivatives, stilbenylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, copolymers of aniline derivatives, electro-conductive oligomers, particularly thiophene oligomers, porphyrin compounds, aromatic tertiary amine compounds, stilbenyl amine compounds etc.
- aromatic tertiary amine compounds such as N,N,N',N'-tetraphenyl-4,4'- diaminobiphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)- 4,4'-diaminobiphenyl (TPD), 2,2'- bis(di-p-torylaminophenyl)propane, 1 ,1 '-bis(4-di-torylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenyl- methane, N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'- tetraphenyl-4,4'-d
- a positive hole transporting layer can be formed by preparing an organic film containing at least one positive hole transporting material on the anode.
- the positive hole transporting layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, the LB method and the like. Of these methods, the vacuum deposition method, the spin-coating method and the casting method are particularly preferred in view of ease and cost.
- the conditions for deposition may be chosen in the same manner as described for the formation of a light emitting layer (see above). If it is desired to form a positive hole transporting layer comprising more than one positive hole transporting material, the coevaporation method can be employed using the desired compounds.
- the layer can be formed under the conditions described for the formation of the light emitting layer (see above).
- a smoother and more homogeneous positive hole transporting layer can be formed by using a solution containing a binder and at least one positive hole transporting material.
- the coating using such a solution can be performed in the same manner as described for the light emitting layer.
- Any polymer binder may be used, provided that it is soluble in the solvent in which the at least one positive hole transporting material is dissolved. Examples of appropriate polymer binders and of appropriate and preferred concentrations are given above when describing the formation of a light emitting layer.
- the thickness of the positive hole transporting layer is preferably chosen in the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, more preferably from 2 to 50 nm.
- organic hole transporting compounds such as metal-free phthalocyanine (H 2 Pc), copper-phthalocyanine (Cu-Pc) and their derivatives as described, for example, in JP64-7635 can be used.
- H 2 Pc metal-free phthalocyanine
- Cu-Pc copper-phthalocyanine
- JP64-7635 organic hole transporting compounds
- some of the aromatic amines defined as hole transporting materials above, which have a lower ionisation potential than the hole transporting layer, can be used.
- a hole injection layer can be formed by preparing an organic film containing at least one hole injection material between the anode layer and hole transporting layer.
- the hole injection layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, the LB method and the like.
- the thickness of the layer is preferably from 5 nm to 5 ⁇ m, and more preferably from 10 nm to 100 nm.
- the electron transporting materials should have a high electron injection efficiency (from the cathode) and a high electron mobility.
- the following materials can be exemplified for electron transporting materials: tris(8-hydroxyquinolinato)-aluminum(lll) and its derivatives, bis(10- hydroxybenzo[h]quinolinolato)beryllium(ll) and its derivatives, oxadiazole derivatives, such as 2-(4-biphenyl)-5-(4-tert.-butylphenyl)-1 ,3,4-oxadiazole and its dimer systems, such as 1 ,3- bis(4-tert.-butylphenyl-1 ,3,4)oxadiazolyl)biphenylene and 1 ,3-bis(4-tert.-butylphenyl-1 ,3,4- oxadiazolyl)phenylene, dioxazole derivatives, triazole derivatives, coumarine derivatives, imidazo
- An electron transporting layer can be formed by preparing an organic film containing at least one electron transporting material on the hole transporting layer or on the light-emitting layer.
- the electron transporting layer can be formed by the vacuum deposition method, the spin- coating method, the casting method, the LB method and the like.
- the positive hole inhibiting materials for a positive hole inhibiting layer have high electron injection/transporting efficiency from the electron transporting layer to the light emission layer and also have higher ionisation potential than the light emitting layer to prevent the flowing out of positive holes from the light emitting layer to avoid a drop in luminescence efficiency.
- phenanthroline derivatives e.g. bathocuproine (BCP)
- BCP bathocuproine
- the positive hole inhibiting layer can be formed by preparing an organic film containing at least one positive hole inhibiting material between the electron transporting layer and the light-emitting layer.
- the positive hole inhibiting layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, the LB method and the like.
- the thickness of the layer preferably is chosen within the range of from 5 nm to 2 ⁇ m, and more preferably, within the range of from 10 nm to 100 nm.
- a smoother and more homogeneous electron transporting layer can be formed by using a solution containing a binder and at least one electron transporting material.
- the thickness of an electron transporting layer is preferably chosen in the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, more preferably from 2 to 50 nm.
- the light-emitting compositions have a fluorescence emission maximum in the range of from 500 to 780, preferably from 520 to 750, more preferred from 540 to 700 nm. Further, the inventive compounds preferably exhibit an absorption maximum in the range of 450 to 580 nm.
- the light-emitting compositions usually exhibit a fluorescence quantum yield ("FQY") in the range of from 1 > FQY > 0.3 (measured in aerated toluene or DMF). Further, in general, the inventive compositions exhibit a molar absorption coefficient in the range of from 5000 to 100000.
- FQY fluorescence quantum yield
- Another embodiment of the present invention relates to a method of coloring high molecular weight organic materials (having a molecular weight usually in the range of from 10 3 to 10 7 g/mol; comprising biopolymers, and plastic materials, including fibres) by incorporating therein the inventive composition by methods known in the art.
- inventive compositions can be used, as described for the DPP compounds of formula I' in EP-A-1087005, for the preparation of inks, for printing inks in printing processes, for flexographic printing, screen printing, packaging printing, security ink printing, intaglio printing or offset printing, for pre-press stages and for textile printing, for office, home applications or graphics applications, such as for paper goods, for example, for ballpoint pens, felt tips, fiber tips, card, wood, (wood) stains, metal, inking pads or inks for impact printing processes (with impact-pressure ink ribbons), for the preparation of colorants, for coating materials, for industrial or commercial use, for textile decoration and industrial marking, for roller coatings or powder coatings or for automotive finishes, for high-solids (low-solvent), water-containing or metallic coating materials or for pigmented formulations for aqueous paints, for the preparation of pigmented plastics for coatings, fibers, platters or mold carriers, for the preparation of non-impact-printing material for digital printing, for the thermal wax
- Another preferred embodiment concerns the use of the inventive compositions for color changing media.
- inventive compounds are useful for EL materials for the above category (i) and, in addition, for the above mention technique (ii). This is because the invented combinations of compounds can exhibit strong photoluminescence as well as electrolunimescence.
- Technique (ii) is, for example, known from US-B-5,126,214, wherein EL blue with a maximum wavelength of ca. 470-480 nm is converted to green and red using coumarin, 4- (dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran, pyridine, rhodamine 6G, phenoxazone or other dyes.
- Particularly preferred high molecular weight organic materials are, for example, cellulose ethers and esters, e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetic resins (polymerization or condensation resins) such as aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyester, ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone and silicone resins as well as their possible mixtures with one another.
- cellulose ethers and esters e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate
- natural resins or synthetic resins polymerization or condensation resins
- aminoplasts in particular urea/formalde
- organic materials in dissolved form as film formers, for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
- film formers for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
- Said high molecular weight organic materials may be obtained singly or in admixture, for example in the form of granules, plastic materials, melts or in the form of solutions, in particular for the preparation of spinning solutions, paint systems, coating materials, inks or printing inks.
- the inventive compositions are used for the mass coloration of polyvinyl chloride, polyamides and, especially, polyolefins such as polyethylene and polypropylene as well as for the preparation of paint systems, including powder coatings, inks, printing inks, color filters and coating colors.
- preferred binders for paint systems are alkyd/melamine resin paints, acryl/melamine resin paints, cellulose acetate/cellulose butyrate paints and two-pack system lacquers based on acrylic resins which are crosslinkable with polyisocyanate.
- inventive compositions can be added in any desired amount to the material to be coloured, depending on the end use requirements.
- composition comprising
- customary additives such as rheology improvers, dispersants, fillers, paint auxiliaries, siccatives, plasticizers, UV-stabilizers, and/or additional pigments or corresponding precursors in effective amounts, such as e.g. from 0 to 50% by weight, based on the total weight of (a) and (b).
- inventive fluorescent DPP compounds of formula I may advantageously be used in admixture with fillers, transparent and opaque white, colored and/or black pigments as well as customary luster pigments in the desired amount.
- the corresponding high molecular weight organic materials such as binders, synthetic resin dispersions etc. and the inventive compositions are usually dispersed or dissolved together, if desired together with customary additives such as dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments or pigment precursors, in a common solvent or mixture of solvents.
- customary additives such as dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments or pigment precursors, in a common solvent or mixture of solvents. This can be achieved by dispersing or dissolving the individual components by themselves, or also several components together, and only then bringing all components together, or by adding everything together at once.
- a further embodiment of the present invention relates to a method of using the inventive compositions for the preparation of dispersions and the corresponding dispersions, and paint systems, coating materials, color filters, inks and printing inks comprising the inventive compositions.
- a particularly preferred embodiment relates to the use of the inventive compositions for the preparation of fluorescent tracers for e.g. leak detection of fluids such as lubricants, cooling systems etc., as well as to fluorescent tracers or lubricants comprising the inventive compositions.
- the inventive compositions are mixed with the high molecular weight organic materials using roll mills, mixing apparatus or grinding apparatus.
- the pigmented material is subsequently brought into the desired final form by conventional processes, such as calandering, compression molding, extrusion, spreading, casting or injection molding.
- the high molecular weight organic materials and the inventive compositions are generally dissolved or dispersed in a common organic solvent or solvent mixture.
- additives such as fillers, other pigments, siccatives or plasticizers
- the present invention additionally relates to inks comprising a coloristically effective amount of the pigment dispersion of the inventive compositions.
- the weight ratio of the pigment dispersion to the ink in general is chosen in the range of from 0.001 to 75% by weight, preferably from 0.01 to 50% by weight, based on the overall weight of the ink.
- the color filters can be coated for example using inks, especially printing inks, which can comprise pigment dispersions comprising the inventive compositions or can be prepared for example by mixing a pigment dispersion comprising an inventive composition with chemically, thermally or photolytically structurable high molecular weight organic material (so-called resist).
- the subsequent preparation can be carried out, for example, in analogy to EP-A 654 711 by application to a substrate, such as a LCD (liquid crystal display), subsequent photostructuring and development.
- pigment dispersions comprising an inventive composition which possess non-aqueous solvents or dispersion media for polymers.
- the present invention relates, moreover, to toners comprising a pigment dispersion containing an inventive composition or a high molecular weight organic material pigmented with an inventive composition in a coloristically effective amount.
- the present invention additionally relates to colorants, colored plastics, polymeric ink particles, or non-impact-printing material comprising an inventive composition, preferably in the form of a dispersion, or a high molecular weight organic material pigmented with an inventive composition in a coloristically effective amount.
- a coloristically effective amount of the pigment dispersion according to this invention comprising an inventive composition denotes in general from 0.0001 to 99.99% by weight, preferably from 0.001 to 50% by weight and, with particular preference, from 0.01 to 50% by weight, based on the overall weight of the material pigmented therewith.
- inventive compositions can be applied to colour polyamides, because they do not decompose during the incorporation into the polyamides. Further, they exhibit an exceptionally good lightfastness, a superior heat stability, especially in plastics.
- the organic EL device of the present invention has significant industrial values since it can be adapted for a flat panel display of an on-wall television set, a flat light-emitting device, a light source for a copying machine or a printer, a light source for a liquid crystal display or counter, a display signboard and a signal light.
- the compositions of the present invention can be used in the fields of an organic EL device, an electrophotographic photoreceptor, a photoelectric converter, a solar cell, an image sensor, and the like.
- a glass substrate manufactured by Asahi Glass Co., a product prepared by electron beam vapor deposition method
- the substrate thus obtained is subjected to ultrasonic washing with acetone for 15 minutes and then to ultrasonic washing with Semikoklin 56 for 15 minutes, and then washing with ultra-pure water.
- the substrate is subjected to ultrasonic washing with isopropyl alcohol for 15 minutes, dipped in hot methanol for 15 minutes, and then dried.
- the substrate thus obtained is subjected to an UV-ozone treatment for one hour and placed in a vacuum vapour deposition apparatus, and the apparatus is evacuated until the inner pressure reached 1 x 10 s Pa or less. Then, according to the resistance heating method, N,N'-diphenyl-N,N'-(3-methylphenyl)- 1 ,1'-diphenyl-4,4'-diamine (TPD) is vapor-deposited as a positive hole transporting material up to a thickness of 50 nm, to form a positive hole transporting layer.
- TPD N,N'-diphenyl-N,N'-(3-methylphenyl)- 1 ,1'-diphenyl-4,4'-diamine
- a Alq 3 layer is vapor-deposited to form an electron transporting layer having a thickness of 50 nm.
- a Mg-Ag alloy (10:1) is vapor-deposited to form a cathode having a thickness of 150 nm, whereby an element having a size of 5 x 5 mm square is prepared.
- Table 1 The luminescent peak wavelength and emission intensity of the luminescent element thus obtained is summarized in Table 1.
- Example 6 is repeated, except that the emitting material of example 6 is replaced by the emitting materials as described in table 1.
- Example 2 was repeated except that 4-phenyl-1 -(1 -bromoethyl)benzene was used instead of 1-bromoethylbenzene.
- Example 24-26 Example 6 is repeated, except that the emitting material of example 6 is replaced by the emitting materials as described in table 2. Table 2
- Example 8 is repeated, except that the compound below (A-3; Example 81 of EP-A-1087006) is used as the light emitting material.
- the maximum luminance is 5260 Cd/m 2 .
- Example 6 is repeated, except that A-1 (Example 93 of EP-A-1087006) is used as the light emitting material.
- the maximum luminance thereof is 2600 Cd/m 2 .
- composition of the present invention comprising a DPP of the formula I and a DPP of the formula II, can provide a luminescent element which is high in the efficiency of electrical energy utilisation and is characterized by a much higher luminance than the individual DPP compounds of formula I and II.
- Example 28 Fluorescence spectrophotometer F-4500 (Hitachi, Ltd.).
- the film When the film is irradiated by blue light with 470 nm, the film emits red light, the peak of which locates at 597 nm.
- the composition comprising the host and the guest is found to be applicable to CCM converting effectively blue light into red light.
Abstract
Description
Claims
Priority Applications (8)
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AU2003239272A AU2003239272A1 (en) | 2002-02-01 | 2003-01-23 | Fluorescent compositions comprising diketopyrrolopyrroles |
CA002469269A CA2469269A1 (en) | 2002-02-01 | 2003-01-23 | Fluorescent compositions comprising diketopyrrolopyrroles |
JP2003564157A JP2005526152A (en) | 2002-02-01 | 2003-01-23 | Fluorescent composition containing diketopyrrolopyrrole |
MXPA04006662A MXPA04006662A (en) | 2002-02-01 | 2003-01-23 | Fluorescent compositions comprising diketopyrrolopyrroles. |
BR0307402-1A BR0307402A (en) | 2002-02-01 | 2003-01-23 | Fluorescent compositions comprising diketopyrrolopyrols |
EP03734603A EP1478713A1 (en) | 2002-02-01 | 2003-01-23 | Fluorescent compositions comprising diketopyrrolopyrroles |
KR10-2004-7011640A KR20040086312A (en) | 2002-02-01 | 2003-01-23 | Fluorescent compositions comprising diketopyrrolopyrroles |
US10/501,573 US20050008892A1 (en) | 2002-02-01 | 2003-01-23 | Fluorescent compositions comprising diketopyrrolopyrroles |
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WO2007003520A1 (en) * | 2005-07-05 | 2007-01-11 | Ciba Specialty Chemicals Holding Inc. | Fluorescent diketopyrrolopyrroles and derivatives |
WO2008000664A1 (en) * | 2006-06-30 | 2008-01-03 | Ciba Holding Inc. | Diketopyrrolopyrrole polymers as organic semiconductors |
JP2008523023A (en) * | 2004-12-09 | 2008-07-03 | チバ ホールディング インコーポレーテッド | Fluorescent diketopyrrolopyrrole |
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WO2013028441A3 (en) * | 2011-08-19 | 2013-06-06 | University Of Washington | New poly(heteroarylene vinylene)s based on diketopyrrolopyrrole |
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Also Published As
Publication number | Publication date |
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CN1625589A (en) | 2005-06-08 |
WO2003064558A8 (en) | 2004-06-03 |
TWI275626B (en) | 2007-03-11 |
JP2005526152A (en) | 2005-09-02 |
US20050008892A1 (en) | 2005-01-13 |
AU2003239272A1 (en) | 2003-09-02 |
MXPA04006662A (en) | 2004-10-04 |
TW200302866A (en) | 2003-08-16 |
CA2469269A1 (en) | 2003-08-07 |
EP1478713A1 (en) | 2004-11-24 |
BR0307402A (en) | 2004-12-28 |
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