CA2185878A1 - Electroluminescent devices - Google Patents
Electroluminescent devicesInfo
- Publication number
- CA2185878A1 CA2185878A1 CA002185878A CA2185878A CA2185878A1 CA 2185878 A1 CA2185878 A1 CA 2185878A1 CA 002185878 A CA002185878 A CA 002185878A CA 2185878 A CA2185878 A CA 2185878A CA 2185878 A1 CA2185878 A1 CA 2185878A1
- Authority
- CA
- Canada
- Prior art keywords
- butyl
- tert
- phenol
- bis
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
An electroluminescent device which contains at least 2 electrodes, the base electrode and the top electrode, a light-emitting layer, and a stabiliser which is effective against atmospheric oxidation, thermal oxidation, ozone and UV radia-tion, wherein the electroluminescent device may contain at least one further layer selected from the sequence comprising the hole-injecting layer, the hole-transporting layer, and the electron-injecting layer.
Description
Le A 31 307-Forei~n Countries / KM/m/S-P 21~ ~ ~ 7 8 Electroluminescent devices An electroluminescent (EL) device is characterised in that it emits light with aflow of current when an electrical voltage is applied. Devices of this type havelong been known in the art under the description "light-emitting diodes" (LEDs =light emitting diodes). The emission of light occurs due to the recombination ofpositive charges ("holes") and negative charges ("electrons") with the radiation of light.
Inorganic semiconductors such as gallium arsenide are mainly used nowadays for the development of light-emitting components for electronics or photo-electronics.
Point source display elements can be produced based on substances of this type.
Large-surface devices are not possible.
In addition to semiconductor light-emitting diodes, electroluminescent devices based on vapour-deposited low molecular weight organic compounds are known (US-P 4 539 507, US-P 4 769 262, US-P 5 077 142, EP-A 406 762). Only LEDs of small dimensions can be produced with these materials also - due to the production process. Moreover, these electroluminescent devices only have very short lifetimes.
Polymers such as poly-(p-phenylenes) and poly-(p-phenylenevinylenes (PPV)) have also been described as electroluminescent polymers: G. Leising et al., Adv.Mater. 4 (1992) No. l; Friend et al., J. Chem. Soc., Chem. Commun. 32 (1992);
Saito et al., Polymer, 1990, Vol. 31, 1137; Friend et al., Physical Review B, Vol.
42, No. 18, 11670, or WO 90/13148. Other examples of PPV in electroluminescent displays are described in EP-A 443 861, and in WO-A-9203490 and 92003491.
EP-A 0 294 061 discloses an optical modulator based on polyacetylene.
Heeger et al. have proposed soluble, conjugated PPV derivatives for the production of flexible polymer LEDs (WO 92/16023).
Organic EL devices generally contain one or more layers of organic charge-transport compounds. The basic structure within the sequence of layers is as follows:
Le A 31 307-Forei~n Countries ~ 7 8 support, substrate 2 base electrode 3 hole-injecting layer 4 hole-transporting layer light-emitting layer 6 electron-transporting layer 7 electron-injecting layer 8 top electrode ~ - -9 contacts cladding, encapsulation.
This structure constitutes the most general case, and can be simplified by omitting individual layers so that one layer assumes a plurality of functions. In the simplest case, an EL device consists of two electrodes, between which there is an organic layer which performs all the functions - including that of the emission of 15 light. Systems of this type based on poly(p-phenylene vinylene) are described in the Application WO 90/13148, for example.
A common feature of all these EL devices which are based on low molecular weight compounds is that they do not have a satisfactory operating lifetime.
During operation, organic light-emitting diodes become very hot (> 100C), and 20 this results in a change in the layers (up to their destruction), so that a reduction of their performance or a complete loss of function then occurs. In these LED
displays based on organic materials, the long-term stability of the luminous layer is a problem.
It has now been found that the long-term stability of the electroluminescent device 25 can be significantly increased by additive substances.
The present invention relates to electroluminescent devices which comprises at least 2 electrodes, the base electrode 2 and the top electrode 8, a light-emitting layer 5, and a stabiliser which is effective against atmospheric oxidation, thermal oxidation, ozone and UV radiation, wherein the electroluminescent device may 30 contain at least one further layer selected from the sequence comprising the hole-injecting layer 3, the hole-transporting layer 6, and the electron-injecting layer 7.
Le A 31 307-Forei~n Countries 2 ~ 7 8 The stabilisers may be added to one or more of layers 3-7. The stabilisers are preferably introduced into the light-emitting layer 5.
The amounts of stabilisers added are between 0.1 and 10 % by weight, with respect to the weight of the layers to which the stabilisers are added. 0.2 to 3 %
S by weight of stabiliser is preferably used.
The stabilisers are usually deposited from solution, together with the remaininglayer constituents of layers 3-7. The stabilisers may also be deposited on their own as an additional intermediate layer from solution or may be vacuum-deposited as a pure compound.
10 In the case of UV absorbers, the stabilisers may also be deposited as an uppermost additional layer on the support or substrate 1. For this purpose, the UV absorbers are used in admixture with a binder, such as polystyrene, polyurethane, polyvinyl acetate, polyacrylate, polycarbonate, polyolefines or polysulphone, which facili-tates bonding to 1. High stabilities are preferably obtained by using the stabilisers in cro~linking systems such as those described in EP-A-637 899.
Examples of suitable stabilisers include UV stabilisers such as those listed in Table I (the number of the compound is given in brackets in each case).
Le A 31 307-Forei~n Countries ~ 7 8 Table 1 (1) Rl = H, R2 = CH~ R1 OH
(2) Rl = H, R2 = n-C~Hl7 ~CO_~
(3) Rl = OH, R2 = CH~ W ~OR2 (4) R = H, R = n-Cl2H~
Inorganic semiconductors such as gallium arsenide are mainly used nowadays for the development of light-emitting components for electronics or photo-electronics.
Point source display elements can be produced based on substances of this type.
Large-surface devices are not possible.
In addition to semiconductor light-emitting diodes, electroluminescent devices based on vapour-deposited low molecular weight organic compounds are known (US-P 4 539 507, US-P 4 769 262, US-P 5 077 142, EP-A 406 762). Only LEDs of small dimensions can be produced with these materials also - due to the production process. Moreover, these electroluminescent devices only have very short lifetimes.
Polymers such as poly-(p-phenylenes) and poly-(p-phenylenevinylenes (PPV)) have also been described as electroluminescent polymers: G. Leising et al., Adv.Mater. 4 (1992) No. l; Friend et al., J. Chem. Soc., Chem. Commun. 32 (1992);
Saito et al., Polymer, 1990, Vol. 31, 1137; Friend et al., Physical Review B, Vol.
42, No. 18, 11670, or WO 90/13148. Other examples of PPV in electroluminescent displays are described in EP-A 443 861, and in WO-A-9203490 and 92003491.
EP-A 0 294 061 discloses an optical modulator based on polyacetylene.
Heeger et al. have proposed soluble, conjugated PPV derivatives for the production of flexible polymer LEDs (WO 92/16023).
Organic EL devices generally contain one or more layers of organic charge-transport compounds. The basic structure within the sequence of layers is as follows:
Le A 31 307-Forei~n Countries ~ 7 8 support, substrate 2 base electrode 3 hole-injecting layer 4 hole-transporting layer light-emitting layer 6 electron-transporting layer 7 electron-injecting layer 8 top electrode ~ - -9 contacts cladding, encapsulation.
This structure constitutes the most general case, and can be simplified by omitting individual layers so that one layer assumes a plurality of functions. In the simplest case, an EL device consists of two electrodes, between which there is an organic layer which performs all the functions - including that of the emission of 15 light. Systems of this type based on poly(p-phenylene vinylene) are described in the Application WO 90/13148, for example.
A common feature of all these EL devices which are based on low molecular weight compounds is that they do not have a satisfactory operating lifetime.
During operation, organic light-emitting diodes become very hot (> 100C), and 20 this results in a change in the layers (up to their destruction), so that a reduction of their performance or a complete loss of function then occurs. In these LED
displays based on organic materials, the long-term stability of the luminous layer is a problem.
It has now been found that the long-term stability of the electroluminescent device 25 can be significantly increased by additive substances.
The present invention relates to electroluminescent devices which comprises at least 2 electrodes, the base electrode 2 and the top electrode 8, a light-emitting layer 5, and a stabiliser which is effective against atmospheric oxidation, thermal oxidation, ozone and UV radiation, wherein the electroluminescent device may 30 contain at least one further layer selected from the sequence comprising the hole-injecting layer 3, the hole-transporting layer 6, and the electron-injecting layer 7.
Le A 31 307-Forei~n Countries 2 ~ 7 8 The stabilisers may be added to one or more of layers 3-7. The stabilisers are preferably introduced into the light-emitting layer 5.
The amounts of stabilisers added are between 0.1 and 10 % by weight, with respect to the weight of the layers to which the stabilisers are added. 0.2 to 3 %
S by weight of stabiliser is preferably used.
The stabilisers are usually deposited from solution, together with the remaininglayer constituents of layers 3-7. The stabilisers may also be deposited on their own as an additional intermediate layer from solution or may be vacuum-deposited as a pure compound.
10 In the case of UV absorbers, the stabilisers may also be deposited as an uppermost additional layer on the support or substrate 1. For this purpose, the UV absorbers are used in admixture with a binder, such as polystyrene, polyurethane, polyvinyl acetate, polyacrylate, polycarbonate, polyolefines or polysulphone, which facili-tates bonding to 1. High stabilities are preferably obtained by using the stabilisers in cro~linking systems such as those described in EP-A-637 899.
Examples of suitable stabilisers include UV stabilisers such as those listed in Table I (the number of the compound is given in brackets in each case).
Le A 31 307-Forei~n Countries ~ 7 8 Table 1 (1) Rl = H, R2 = CH~ R1 OH
(2) Rl = H, R2 = n-C~Hl7 ~CO_~
(3) Rl = OH, R2 = CH~ W ~OR2 (4) R = H, R = n-Cl2H~
(5) Rl = COOH, R2 = CH~
(6) Rl = H, R2 = CH~ R3 = H
(7) Rl = H, R2 = tert.-butyl, Q R2 R3 = tert.-butyl R1 N~ /~( (8) Rl = Cl, R2 =.CH
R3 = tert.-butyl ~Q
R3 = tert.-butyl ~Q
(9) R3 = H, R2 = tert.-butyl, OH R3 R = tert.-butyl (10) R3 = Cl, R2 = tert.-amyl, R = tert.-amyl (I 1) OH
~CO-O~
(12) ~co--O~n-C8H17 OH
(13) R=C2H5 /=\
\\ //
C = C
(14) R = CH2--CHn C4Hg ~; CO OR
C2Hs ~
(15) R = tert.-butyl R
~NH--CO--CO--NH~
(16) R = H C2Hs OC2Hs Le A 31 307-Forei~n Countries 2 1 8 5 8 7 ~
In addition, antioxidants and light stabilisers, e.g. those based on sterically hindered phenols, may be used as stabilisers (see Table 2).
Table 2 (1) 2,6-di-tert.-butyl-phenol 5 (2) 2,6-di-tert.-butyl-4-methyl-phenol (3) 2,4,6-tri-tert.-butyl-phenol (4) 2,6-di-tert.-butyl-4-nonyl-phenol (5) 6-tert.-butyl-2,4-dimethyl-phenol (6) 2,4-dimethyl-6-nonyl-phenol (7) 2,4-dimethyl-6-(1-phenyl-ethyl)-phenol (8) 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol (9) 2,6-di-octadecyl-4-methyl-phenol ( 10) (5 -tert.-butyl-4-hydroxy-3 -methyl-benzyl)-malonic acid-di-n-octadecyl ester (11) 2,6-di-tert.-butyl-4-methoxy-phenol, 3,5-di-tert.-butyl-4-hydroxy-anisole 15 (12) 2,5-di-tert.-butyl-hydroquinone (DBH) (13) 2,5-bis-(1,1-dimethyl-propyl)-hydroquinone OH
H3C ~, CH3 (14) tocopherols H C ~
>~ CH3 H3C (CH2CH2CH2CH-) 3CH3 DL-a-tocopherol OH OH
(15) nordihydro-guaiaretic acid (NDGA) ~OH HO~
H3C--CH3--f H CH3 20 (16) a- and ,~-naphthol ( 17) 6,7-dihydroxy-4-methyl-coumarin ( 18) 5 ,7-dihydroxy-4-methyl-coumarin monohydrate (19) 1,3,5-trihydroxy-benzene, phloroglucinol Le A 31 307-Forei~n Countries ~ 1 ~ 5 8 7 8 (20) 3,4,5-tri-hydroxy-benzoic acid propyl ester= propyl gallate, PG
(21) 3,4,5-tri-hydroxy-benzoic acid octyl ester= octyl gallate, OG
(22) 3,4,5-tri-hydroxy-benzoic acid dodecyl ester = dodecyl gallate, lauryl gallate, LG
(23) 2,4,5-trihydroxy-butyrophenone = THBP
(24) 2,2'-methylene-bis-(4-ethyl-6-tert.-butyl-phenol) (25) 1,1-bis-(2-hydroxy-3,5-dimethyl-phenyl)-butane (26) 1,1 '-methylene-bis-(naphthol-2) (27) 2,2-bis-(4-hydroxy-phenyl)-propane = bisphenol A
(28) mixture of tert.-butylated 2,2-bis-(4-hydroxy-phenyl)-propanes (29) bis-3,3-bis-(4-hydroxy-3-tert.-butyl-phenyl)-butanoic acid glycol ester =
DTB glycol ester -(30) 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (31) 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (32) 4,4'-methylene-bis-(2-tert.-butyl-6-methyl-phenol) (33) 4,4'-methylene-bis-(2,6-di-tert.-butyl-phenol) (34) 4,4'-methylene-bis-(2,5-di-tert.-butyl-phenol) (35) 1,1-bis-(4-hydroxy-phenyl)-cyclohexane (36) 1,1-bis-(3-cyclohexyl-4-hydroxy-phenyl)-cyclohexane (37) 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-benzene:
OH
(H3C)3C ~C(CH3)3 R= 1~
CH3 f H2 R~R
H3C ~ CH3 (38) catechol (39) 4-tert.-butyl-catechol = TBC; 1,2-dihydroxy-4-tert.-butylbenzene (40) hydroquinone 25 (41) 4-methoxyphenol, hydroquinone monomethyl ether (42) 4-benzyloxyphenol, hydroquinone monobenzyl ether (43) mixtures of 3-tert.-butyl-4-hydroxy-anisole Le A 31 307-Forei~n Countries 218 ~ ~ 7 8 OH OH
3-isomer 2-isomer OH
(44) styrenated phenols I~CH g~ )n CH3 n = 1, 2, 3, mostly in the 2-, 4-, 6-position (45) 3,5-di-tert.-butyl-4-hydroxy-benzyl alcohol (46) 2,6-di-tert.-butyl-4-methoxy-phenol (47) octadecyl-3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate (48) pentaerythrityl-tetrakis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate]
(49) 1,6-bis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionyloxy]-n-hexane (50) 2,2-bis-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-malonic acid di-n-octyl ester (51) 2,2'-methylene-bis-(4,6-dimethyl-phenol) (52) 2,2'-methylene-bis-(6-tert.-butyl-4-methyl-phenol) R - -C(CHs)3 (53) 2,2'-methylene-bis-(4-methyl-6-nonyl-phenol) (54) 2,2 '-methylene-bis-[4-methyl-6-(1 -methyl-cyclohexyl)-phenol ]
(55) 2,2 '-methylene-bis[4-methyl-(6-a-methyl-benzyl)-phenol]
15 Furthermore, antiozonants can be used as stabilisers, e.g. those from the benzo-furan series, those from the enol series, those based on phenylenediamines, such as N-phenyl-1 or 2-naphthylamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, or N,N'-bis-(1-ethyl-3-methylpentyl)-p-phenylene- diamine. Examples of these are listed in Table 3: ~
20 Table 3:
(1) N,N'-di-sec-butyl-p-phenylenediamine = DBPPD
(2) N,N'-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine Le A 31 307-Foreign Countries 2 1 ~ S 8 7 8 (3) N,N'-bis-(1-ethyl-3-methyl-pentyl)-p-phenylenediamine (4) N,N'-bis-(1-methyl-heptyl)-p-phenylenediamine (5) N,N'-dicyclohexyl-p-phenylenediamine (6) N,N'-diphenyl-p-phenylenediamine = DPPD
5 (7) N,N'-di-(naphthyl-2)-p-phenylenediamine (8) N-isopropyl-N'-phenyl-p-phenylenediamine (9) N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine (10) N-(1 -methyl-heptyl)-N ' -phenyl-p-phenylenediamine ~ ~~
(11) N-cyclohexyl-N '-phenyl-p-phenylenediamine 10 (12) 4-(p-toluene-sulphonamido)-diphenylamine (13) N,N'-dimethyl-N,N'-di-sec.-butyl-p-phenylenediamine (14) diphenylamine (15) 4-isopropoxy-diphenylamine (16) N-phenyl-l-naphthylamine 15 (17) N-phenyl-2-naphthylamine (18) octylated diphenylamine, predominantly 4-octyl-diphenylamine (19) 4-n-butylamino-phenol (20) 4-butyrylamino-phenol (21) 4-nonanoylamino-phenol 20 (22) 4-dodecanoylamino-phenol (23) 4-octadecanoyl-amino-phenol (24) di-(4-methoxy-phenyl)-amine (25) 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol (26) 2,4 '-diamino-diphenylmethane 25 (27) 4,4 '-diamino-diphenylmethane (28) N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane (29) 1,2-di-(phenylamino)-ethane (30) 1,2-di-[(2-methyl-phenyl)-amino]-ethane (31) 1,3-di-(phenylamino)-propane 30 (32) (o-tolyl)-biguanide (33) the condensation product of aniline and acetaldehyde, (34) aniline-aldol-condensate (35) the product from aniline and butyraldehyde (36) (polymeric) 2,2,4-trimethyl- 1,2-dihydroquinoline 35 (37) aniline-acetone condensate (38) 6-ethoxy-2,2,4-trimethyl- 1,3 -dihydroquinoline = ethoxyquin Le A 31 307-Forei~n Countries 2 ~ ~ 5 ~ 7 8 ._ 9 CH3 R, =-OC2H3 R1 ~ R2 = -CH3 ~ N J<
(39) 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline (40) 2,2,4-trimethyl-6-phenyl- 1 ,2-dihydroquinoline (41) 1-aminonaphthalene-aldol condensate N =CH--CH3--CH--CH3 ~$ OH
(42) the product of 2-phenylamino-naphthalene and acetone (43) diphenylamine-acetone condensate, compounds of 5,5-dimethyl-acridine, etc.
H
10 (44) N,N'-diisopropyl-p-phenylenediamine Sulphur compounds are also suitable as stabilisers. Examples are given in Table 4 Table 4:
(1) 3,3'-thiodipropionic acid (2) 3,3 '-thio-bis-(propionic acid dodecyl ester), dilauryl dithiopropionate /s CH2 l H2 CO CO
OR OR
Le A 31 307-Forei~n Countries ~ 1 ~3 5 ~ 7 8 where R=
(3) -Cl2H25 (4) ~CI4H2s S) -Cl6H27 OH
5 (6) ~3~CH~
OH
~,C(CH3)3 (7) ~J
(8) ~OH
C(CH3)3 C(CH3)3 g) ~OH
,~OH
(10) ~
10 (Il) R = H
~CO-O~
(12) ~co--O~n-C8H17 OH
(13) R=C2H5 /=\
\\ //
C = C
(14) R = CH2--CHn C4Hg ~; CO OR
C2Hs ~
(15) R = tert.-butyl R
~NH--CO--CO--NH~
(16) R = H C2Hs OC2Hs Le A 31 307-Forei~n Countries 2 1 8 5 8 7 ~
In addition, antioxidants and light stabilisers, e.g. those based on sterically hindered phenols, may be used as stabilisers (see Table 2).
Table 2 (1) 2,6-di-tert.-butyl-phenol 5 (2) 2,6-di-tert.-butyl-4-methyl-phenol (3) 2,4,6-tri-tert.-butyl-phenol (4) 2,6-di-tert.-butyl-4-nonyl-phenol (5) 6-tert.-butyl-2,4-dimethyl-phenol (6) 2,4-dimethyl-6-nonyl-phenol (7) 2,4-dimethyl-6-(1-phenyl-ethyl)-phenol (8) 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol (9) 2,6-di-octadecyl-4-methyl-phenol ( 10) (5 -tert.-butyl-4-hydroxy-3 -methyl-benzyl)-malonic acid-di-n-octadecyl ester (11) 2,6-di-tert.-butyl-4-methoxy-phenol, 3,5-di-tert.-butyl-4-hydroxy-anisole 15 (12) 2,5-di-tert.-butyl-hydroquinone (DBH) (13) 2,5-bis-(1,1-dimethyl-propyl)-hydroquinone OH
H3C ~, CH3 (14) tocopherols H C ~
>~ CH3 H3C (CH2CH2CH2CH-) 3CH3 DL-a-tocopherol OH OH
(15) nordihydro-guaiaretic acid (NDGA) ~OH HO~
H3C--CH3--f H CH3 20 (16) a- and ,~-naphthol ( 17) 6,7-dihydroxy-4-methyl-coumarin ( 18) 5 ,7-dihydroxy-4-methyl-coumarin monohydrate (19) 1,3,5-trihydroxy-benzene, phloroglucinol Le A 31 307-Forei~n Countries ~ 1 ~ 5 8 7 8 (20) 3,4,5-tri-hydroxy-benzoic acid propyl ester= propyl gallate, PG
(21) 3,4,5-tri-hydroxy-benzoic acid octyl ester= octyl gallate, OG
(22) 3,4,5-tri-hydroxy-benzoic acid dodecyl ester = dodecyl gallate, lauryl gallate, LG
(23) 2,4,5-trihydroxy-butyrophenone = THBP
(24) 2,2'-methylene-bis-(4-ethyl-6-tert.-butyl-phenol) (25) 1,1-bis-(2-hydroxy-3,5-dimethyl-phenyl)-butane (26) 1,1 '-methylene-bis-(naphthol-2) (27) 2,2-bis-(4-hydroxy-phenyl)-propane = bisphenol A
(28) mixture of tert.-butylated 2,2-bis-(4-hydroxy-phenyl)-propanes (29) bis-3,3-bis-(4-hydroxy-3-tert.-butyl-phenyl)-butanoic acid glycol ester =
DTB glycol ester -(30) 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (31) 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (32) 4,4'-methylene-bis-(2-tert.-butyl-6-methyl-phenol) (33) 4,4'-methylene-bis-(2,6-di-tert.-butyl-phenol) (34) 4,4'-methylene-bis-(2,5-di-tert.-butyl-phenol) (35) 1,1-bis-(4-hydroxy-phenyl)-cyclohexane (36) 1,1-bis-(3-cyclohexyl-4-hydroxy-phenyl)-cyclohexane (37) 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-benzene:
OH
(H3C)3C ~C(CH3)3 R= 1~
CH3 f H2 R~R
H3C ~ CH3 (38) catechol (39) 4-tert.-butyl-catechol = TBC; 1,2-dihydroxy-4-tert.-butylbenzene (40) hydroquinone 25 (41) 4-methoxyphenol, hydroquinone monomethyl ether (42) 4-benzyloxyphenol, hydroquinone monobenzyl ether (43) mixtures of 3-tert.-butyl-4-hydroxy-anisole Le A 31 307-Forei~n Countries 218 ~ ~ 7 8 OH OH
3-isomer 2-isomer OH
(44) styrenated phenols I~CH g~ )n CH3 n = 1, 2, 3, mostly in the 2-, 4-, 6-position (45) 3,5-di-tert.-butyl-4-hydroxy-benzyl alcohol (46) 2,6-di-tert.-butyl-4-methoxy-phenol (47) octadecyl-3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate (48) pentaerythrityl-tetrakis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate]
(49) 1,6-bis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionyloxy]-n-hexane (50) 2,2-bis-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-malonic acid di-n-octyl ester (51) 2,2'-methylene-bis-(4,6-dimethyl-phenol) (52) 2,2'-methylene-bis-(6-tert.-butyl-4-methyl-phenol) R - -C(CHs)3 (53) 2,2'-methylene-bis-(4-methyl-6-nonyl-phenol) (54) 2,2 '-methylene-bis-[4-methyl-6-(1 -methyl-cyclohexyl)-phenol ]
(55) 2,2 '-methylene-bis[4-methyl-(6-a-methyl-benzyl)-phenol]
15 Furthermore, antiozonants can be used as stabilisers, e.g. those from the benzo-furan series, those from the enol series, those based on phenylenediamines, such as N-phenyl-1 or 2-naphthylamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, or N,N'-bis-(1-ethyl-3-methylpentyl)-p-phenylene- diamine. Examples of these are listed in Table 3: ~
20 Table 3:
(1) N,N'-di-sec-butyl-p-phenylenediamine = DBPPD
(2) N,N'-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine Le A 31 307-Foreign Countries 2 1 ~ S 8 7 8 (3) N,N'-bis-(1-ethyl-3-methyl-pentyl)-p-phenylenediamine (4) N,N'-bis-(1-methyl-heptyl)-p-phenylenediamine (5) N,N'-dicyclohexyl-p-phenylenediamine (6) N,N'-diphenyl-p-phenylenediamine = DPPD
5 (7) N,N'-di-(naphthyl-2)-p-phenylenediamine (8) N-isopropyl-N'-phenyl-p-phenylenediamine (9) N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine (10) N-(1 -methyl-heptyl)-N ' -phenyl-p-phenylenediamine ~ ~~
(11) N-cyclohexyl-N '-phenyl-p-phenylenediamine 10 (12) 4-(p-toluene-sulphonamido)-diphenylamine (13) N,N'-dimethyl-N,N'-di-sec.-butyl-p-phenylenediamine (14) diphenylamine (15) 4-isopropoxy-diphenylamine (16) N-phenyl-l-naphthylamine 15 (17) N-phenyl-2-naphthylamine (18) octylated diphenylamine, predominantly 4-octyl-diphenylamine (19) 4-n-butylamino-phenol (20) 4-butyrylamino-phenol (21) 4-nonanoylamino-phenol 20 (22) 4-dodecanoylamino-phenol (23) 4-octadecanoyl-amino-phenol (24) di-(4-methoxy-phenyl)-amine (25) 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol (26) 2,4 '-diamino-diphenylmethane 25 (27) 4,4 '-diamino-diphenylmethane (28) N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane (29) 1,2-di-(phenylamino)-ethane (30) 1,2-di-[(2-methyl-phenyl)-amino]-ethane (31) 1,3-di-(phenylamino)-propane 30 (32) (o-tolyl)-biguanide (33) the condensation product of aniline and acetaldehyde, (34) aniline-aldol-condensate (35) the product from aniline and butyraldehyde (36) (polymeric) 2,2,4-trimethyl- 1,2-dihydroquinoline 35 (37) aniline-acetone condensate (38) 6-ethoxy-2,2,4-trimethyl- 1,3 -dihydroquinoline = ethoxyquin Le A 31 307-Forei~n Countries 2 ~ ~ 5 ~ 7 8 ._ 9 CH3 R, =-OC2H3 R1 ~ R2 = -CH3 ~ N J<
(39) 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline (40) 2,2,4-trimethyl-6-phenyl- 1 ,2-dihydroquinoline (41) 1-aminonaphthalene-aldol condensate N =CH--CH3--CH--CH3 ~$ OH
(42) the product of 2-phenylamino-naphthalene and acetone (43) diphenylamine-acetone condensate, compounds of 5,5-dimethyl-acridine, etc.
H
10 (44) N,N'-diisopropyl-p-phenylenediamine Sulphur compounds are also suitable as stabilisers. Examples are given in Table 4 Table 4:
(1) 3,3'-thiodipropionic acid (2) 3,3 '-thio-bis-(propionic acid dodecyl ester), dilauryl dithiopropionate /s CH2 l H2 CO CO
OR OR
Le A 31 307-Forei~n Countries ~ 1 ~3 5 ~ 7 8 where R=
(3) -Cl2H25 (4) ~CI4H2s S) -Cl6H27 OH
5 (6) ~3~CH~
OH
~,C(CH3)3 (7) ~J
(8) ~OH
C(CH3)3 C(CH3)3 g) ~OH
,~OH
(10) ~
10 (Il) R = H
(12) R-Zn-R ~ ~S-- = R
N
N
(13) phenothiazine and its alkyl derivatives ~ Le A 31 307-Foreign Countries 21~ S 8 7 8 H R = H, alkyl R~ S~\R
(14) nickel-(N,N'-dibutyl-dithiocarbamate) ~R ~ Me; Ni - - -N C--S ~Me ~/ S J
(1 5) N,N'-diethylthiourea 5 (16) N,N'-dibutylthiourea (17) bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid-bis-(3-thiapentadecyl) ester '\ ,R2 R2 R, C~CH3)3 R~ = HO ~CH2-C(CH3)3 R2 = -CO-O-(CH2)2-S-c12H25 Phosphorus compounds are also suitable as stabilisers. Examples are given in 10 Table 5:
Le A 31 307-Forei~n Countries 218 S ~ 7 8 Table 5:
(1) triphenylphosphine (2) diethyl phosphite (3) triphenyl phosphite 5 (4) tris-nonylphenyl phosphite (5) tris-(mono-dinonylphenyl)-phosphite (6) tridecyl phosphite - - -(7) tri-isodecyl phosphite (8) tri-dodecyl phosphite C~,CH3)3 C(CH3)3 C(C H3)3~ 0 C(CH3)3 (10) the condensation product of 4,4'-thio-bis-(2-tert.-butyl-5-methyl-phenol) ( 1 1 ) octyl-diphenyl phosphite (12) isooctyl-diphenyl phosphite (13) decyl-diphenyl phosphite 15 (14) isodecyl-diphenyl phosphite (15) didecyl-phenyl phosphite (16) diisodecyl-phenyl phosphite (17) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid diethyl ester (18) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid di-n-octadecyl ester 20 Examples of various zinc, barium and calcium thiophosphates include 0-Alkyl (1) ZntS l=s)2 0-Alkyl Le A 31 307-Foreign Countries 21 ~ ~ 8 7 8 (2) ,~ ~ P
C(CH3)3 C(CH3)3 Examples of further stabilisers may comprise boric acid esters and other organo-boron compounds, e.g.
B ( O CH C5H1, )3 t~)3 C(CH3)3 CH3 ~OB(OC4Hg)2 C(CH3)3 Ph, ~o~, ` IB'O (Ph=phenyl) Ph Low molecular weight silicon compounds may also be used, such as C4Hg\ ~0--C - (C~)2 si o Le A 31 307-Forei~n Countries 21~ ~ 8 7 8 f H3 Cl H3 CH Si O--Si--OC H
H3C Si O--fi CH3 (C4Hg)2N ~ j N(C4Hg)2 or organopolysiloxanes such as R R R
si o--si--o--si--o R R R
o 5 where R = -CH3, -Ph, -H oder -(CH2)3O-CH2 CH--CH2 ~ CH3 ~ CH3 or X--~iO ~i X
\ CH3 /n CH3 where n= 1-10 and X = -cH2o-(cH2)3-o(cH2)3-oH
-(CH2)4-OH
-OC H
Sterically hindered amines may also be used, e g those based on 2,6-tetramethyl-piperidine, such as Le A 31 307-Forei~n Countries 2 1~ ~ 8 7 8 H3C ) \ O--CO--(CH2)4 HN ~<
H3C ~J H
H H
CH3~<CHCH3>~CH3 ~N~N (CH2)6 N~
\ N~N n NH--C(CH3)2--CH2--C(CH3)2 CH3 ~ CH3 CH~ OC (CH2)8 CO ~H3 r "~CH3 CH3>L~
--~(CH2)2 OlCI (CH2)2--ICIO~CH2)2~0lCI--(CH2)2--lCI--5 The stabilisers may be used on their own or as a mixture.
W absorbers, sterically hindered phenols or sterically hindered amines are prefer-ably used as stabilisers.
Charge transport compounds according to the invention are understood to be all compounds which transport charges (holes and/or electrons) in any manner. These 10 also expressly comprise those compounds which are constituents of the emitter Le A 31 307-Forei .n Countries 2~8~878 layer and which therefore constitute photoluminescent materials, such as fluorescent dyes, for example.
A multiplicity of organic compounds which transport charges (holes and/or elec-trons) is described in the literature. Low molecular weight substances which are5 vapour-deposited under high vacuum, for example, are predominantly used. Theseare mostly tertiary aryl amines or compounds containing oxadiazole groups. A
good survey of these classes of substances and their use is given in the publi- ~ ~
cations EP-A-387 715, and in US-P 4 539 507, 4 720 432 and 4 769 292. In principle, all substances can be used which are known as photoconductors from 10 electrophotography.
Glass or plastics material, e.g. a sheet of polyethylene terephthalate, is used as a transparent support.
The following are examples of suitable electrode materials:
a) metal oxides, e.g. indium-tin oxide (ITO), tin oxide (NESA), etc.
15 b) semi-transparent metal films, e.g. Au, Pt, Ag, Cu, etc.
c) conductive polymer films such as polyanilines, polythiophenes, etc.
Metal oxide and semi-transparent metal film electrodes are deposited as a thin layer by techniques such as vacuum-metallising, sputtering, platinising, etc.
One of the electrodes is generally transparent in the visible region of the spectrum.
20 The thickness of the transparent electrode is 50 A to about several llm, preferably loo A to 5000 A.
The electroluminescent substance is deposited directly as a thin film on the transparent electrode or on a charge-transporting layer which may optionally be present. The thickness of the film is 30 A to 10 ~,~m, preferably 50 A to I ~Lm.
25 After drying the EL layer, it is provided with a counterelectrode. The latter consists of a conductive substance which may be transparent.
Le A 31 307-Forei~n Countries 2 ~ g S 8 7 8 The device according to the invention is placed in contact with the two electrodes by means of two electrical leads (e.g. metal wires).
When a DC voltage within the range up to 100 volts is applied, the devices emit light with a wavelength of 400 to 700 nm. They exhibit photoluminescence within the range from 400 to 700 nm.
The electroluminescent layer contains photoluminescent materials such as those which are described in EP-443 861, WO 9203 490 and WO 92 003 491, for example. They may also optionally contain customary additives such as inert binders, charge-transporting substances, or mixtures of inert binders and charge-10 transporting substances. Charge-transporting substances increase the intensity of electroluminescence and reduce the operating voltages.
Soluble transparent polymers are preferably used as inert binders, such as poly-carbonates, polystyrene and copolymers of polystyrene such as SAN, poly-sulphones, polyacrylates, polyvinyl carbazole, vinyl acetate and vinyl alcohol 15 copolymers, and copolymeric polyolefines, etc., for example. These inert binders are also suitable as binders for the stabilisers.
Le A 31 307-Forei~n Countries - 18- 218~878 Example Production of electroluminescent devices of polymers, with the addition of addi-tives to increase their storage- and operational stability.
ITO-coated glass (manufactured by Balzers) was cut into substrates of size 5 20 x 30 mm2 and cleaned. In the course of this procedure, the following steps were performed in succession~
1. rinsing for 15 minutes with distilled water and falterol in an ultrasonic bath, 2. rinsing for 2 x 15 minutes with fresh distilled water each time in an ultra-sonic bath, 3. rinsing for 15 minutes with ethanol in an ultrasonic bath, 4. rinsing for 2 x 15 minutes with fresh acetone each time in an ultrasonicbath, 5. drying on lint-free lens cloths.
15 A 1 % solution in dichloroethane was prepared of the polyether of formula A.
0.5 % by weight, with respect to the amount of electroluminescent polymer, of the additive TINIJVIN 622LD (Ciba-Geigy) was added to the solution. The solution was then filtered (0.2 llm filter, supplied by Sartorius). The filtered solution was distributed on the ITO layer using a lacquer centrifuge operating at 100 rpm. The 20 thickness of the dry film was 120 nm. The Ra value of the surface was 5 nm (Alpha-Step 200 stylus profilometer supplied by Tencor Inst.). In parallel with this, a control specimen was produced without the additive. The polymeric layersproduced in this manner were then vacuum-metallised with Al electrodes. For thispurpose, isolated Al spots with a diameter of 3 mm were vacuum-evaporated on to 25 the polymer surface with the aid of a perforated mask. During the vacuum-evaporation process, the prevailing pressure in the vacuum-evaporation apparatus(Leybold) was less than 10-' mbar.
Le A 31 307-Forei~n Countries - 21~5~7~
(1 5) N,N'-diethylthiourea 5 (16) N,N'-dibutylthiourea (17) bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid-bis-(3-thiapentadecyl) ester '\ ,R2 R2 R, C~CH3)3 R~ = HO ~CH2-C(CH3)3 R2 = -CO-O-(CH2)2-S-c12H25 Phosphorus compounds are also suitable as stabilisers. Examples are given in 10 Table 5:
Le A 31 307-Forei~n Countries 218 S ~ 7 8 Table 5:
(1) triphenylphosphine (2) diethyl phosphite (3) triphenyl phosphite 5 (4) tris-nonylphenyl phosphite (5) tris-(mono-dinonylphenyl)-phosphite (6) tridecyl phosphite - - -(7) tri-isodecyl phosphite (8) tri-dodecyl phosphite C~,CH3)3 C(CH3)3 C(C H3)3~ 0 C(CH3)3 (10) the condensation product of 4,4'-thio-bis-(2-tert.-butyl-5-methyl-phenol) ( 1 1 ) octyl-diphenyl phosphite (12) isooctyl-diphenyl phosphite (13) decyl-diphenyl phosphite 15 (14) isodecyl-diphenyl phosphite (15) didecyl-phenyl phosphite (16) diisodecyl-phenyl phosphite (17) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid diethyl ester (18) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid di-n-octadecyl ester 20 Examples of various zinc, barium and calcium thiophosphates include 0-Alkyl (1) ZntS l=s)2 0-Alkyl Le A 31 307-Foreign Countries 21 ~ ~ 8 7 8 (2) ,~ ~ P
C(CH3)3 C(CH3)3 Examples of further stabilisers may comprise boric acid esters and other organo-boron compounds, e.g.
B ( O CH C5H1, )3 t~)3 C(CH3)3 CH3 ~OB(OC4Hg)2 C(CH3)3 Ph, ~o~, ` IB'O (Ph=phenyl) Ph Low molecular weight silicon compounds may also be used, such as C4Hg\ ~0--C - (C~)2 si o Le A 31 307-Forei~n Countries 21~ ~ 8 7 8 f H3 Cl H3 CH Si O--Si--OC H
H3C Si O--fi CH3 (C4Hg)2N ~ j N(C4Hg)2 or organopolysiloxanes such as R R R
si o--si--o--si--o R R R
o 5 where R = -CH3, -Ph, -H oder -(CH2)3O-CH2 CH--CH2 ~ CH3 ~ CH3 or X--~iO ~i X
\ CH3 /n CH3 where n= 1-10 and X = -cH2o-(cH2)3-o(cH2)3-oH
-(CH2)4-OH
-OC H
Sterically hindered amines may also be used, e g those based on 2,6-tetramethyl-piperidine, such as Le A 31 307-Forei~n Countries 2 1~ ~ 8 7 8 H3C ) \ O--CO--(CH2)4 HN ~<
H3C ~J H
H H
CH3~<CHCH3>~CH3 ~N~N (CH2)6 N~
\ N~N n NH--C(CH3)2--CH2--C(CH3)2 CH3 ~ CH3 CH~ OC (CH2)8 CO ~H3 r "~CH3 CH3>L~
--~(CH2)2 OlCI (CH2)2--ICIO~CH2)2~0lCI--(CH2)2--lCI--5 The stabilisers may be used on their own or as a mixture.
W absorbers, sterically hindered phenols or sterically hindered amines are prefer-ably used as stabilisers.
Charge transport compounds according to the invention are understood to be all compounds which transport charges (holes and/or electrons) in any manner. These 10 also expressly comprise those compounds which are constituents of the emitter Le A 31 307-Forei .n Countries 2~8~878 layer and which therefore constitute photoluminescent materials, such as fluorescent dyes, for example.
A multiplicity of organic compounds which transport charges (holes and/or elec-trons) is described in the literature. Low molecular weight substances which are5 vapour-deposited under high vacuum, for example, are predominantly used. Theseare mostly tertiary aryl amines or compounds containing oxadiazole groups. A
good survey of these classes of substances and their use is given in the publi- ~ ~
cations EP-A-387 715, and in US-P 4 539 507, 4 720 432 and 4 769 292. In principle, all substances can be used which are known as photoconductors from 10 electrophotography.
Glass or plastics material, e.g. a sheet of polyethylene terephthalate, is used as a transparent support.
The following are examples of suitable electrode materials:
a) metal oxides, e.g. indium-tin oxide (ITO), tin oxide (NESA), etc.
15 b) semi-transparent metal films, e.g. Au, Pt, Ag, Cu, etc.
c) conductive polymer films such as polyanilines, polythiophenes, etc.
Metal oxide and semi-transparent metal film electrodes are deposited as a thin layer by techniques such as vacuum-metallising, sputtering, platinising, etc.
One of the electrodes is generally transparent in the visible region of the spectrum.
20 The thickness of the transparent electrode is 50 A to about several llm, preferably loo A to 5000 A.
The electroluminescent substance is deposited directly as a thin film on the transparent electrode or on a charge-transporting layer which may optionally be present. The thickness of the film is 30 A to 10 ~,~m, preferably 50 A to I ~Lm.
25 After drying the EL layer, it is provided with a counterelectrode. The latter consists of a conductive substance which may be transparent.
Le A 31 307-Forei~n Countries 2 ~ g S 8 7 8 The device according to the invention is placed in contact with the two electrodes by means of two electrical leads (e.g. metal wires).
When a DC voltage within the range up to 100 volts is applied, the devices emit light with a wavelength of 400 to 700 nm. They exhibit photoluminescence within the range from 400 to 700 nm.
The electroluminescent layer contains photoluminescent materials such as those which are described in EP-443 861, WO 9203 490 and WO 92 003 491, for example. They may also optionally contain customary additives such as inert binders, charge-transporting substances, or mixtures of inert binders and charge-10 transporting substances. Charge-transporting substances increase the intensity of electroluminescence and reduce the operating voltages.
Soluble transparent polymers are preferably used as inert binders, such as poly-carbonates, polystyrene and copolymers of polystyrene such as SAN, poly-sulphones, polyacrylates, polyvinyl carbazole, vinyl acetate and vinyl alcohol 15 copolymers, and copolymeric polyolefines, etc., for example. These inert binders are also suitable as binders for the stabilisers.
Le A 31 307-Forei~n Countries - 18- 218~878 Example Production of electroluminescent devices of polymers, with the addition of addi-tives to increase their storage- and operational stability.
ITO-coated glass (manufactured by Balzers) was cut into substrates of size 5 20 x 30 mm2 and cleaned. In the course of this procedure, the following steps were performed in succession~
1. rinsing for 15 minutes with distilled water and falterol in an ultrasonic bath, 2. rinsing for 2 x 15 minutes with fresh distilled water each time in an ultra-sonic bath, 3. rinsing for 15 minutes with ethanol in an ultrasonic bath, 4. rinsing for 2 x 15 minutes with fresh acetone each time in an ultrasonicbath, 5. drying on lint-free lens cloths.
15 A 1 % solution in dichloroethane was prepared of the polyether of formula A.
0.5 % by weight, with respect to the amount of electroluminescent polymer, of the additive TINIJVIN 622LD (Ciba-Geigy) was added to the solution. The solution was then filtered (0.2 llm filter, supplied by Sartorius). The filtered solution was distributed on the ITO layer using a lacquer centrifuge operating at 100 rpm. The 20 thickness of the dry film was 120 nm. The Ra value of the surface was 5 nm (Alpha-Step 200 stylus profilometer supplied by Tencor Inst.). In parallel with this, a control specimen was produced without the additive. The polymeric layersproduced in this manner were then vacuum-metallised with Al electrodes. For thispurpose, isolated Al spots with a diameter of 3 mm were vacuum-evaporated on to 25 the polymer surface with the aid of a perforated mask. During the vacuum-evaporation process, the prevailing pressure in the vacuum-evaporation apparatus(Leybold) was less than 10-' mbar.
Le A 31 307-Forei~n Countries - 21~5~7~
Polyether of formula A:
--(-CH2--)6--O~CH=CH--~CH=CH
--n The ITO layer and the Al electrode were connected via electrical leads to a voltage source. When the voltage was increased, a current flows through the 5 polymer layer. Electroluminescence was detectable above a voltage of 5 volts.
The colour of the electroluminescence was blue-green.
Comparison of the electroluminescent devices:
dark storage period before use: 14 days applied voltage: 17 volts.
10 TINUVIN 622LD:
CH CH
f ~ CH3 CH3 ~ ~
--O~(cH~)2-olcl (CH2)2--Iclo~cH2)~olcl--(CH2)2 ICI--Le A 31 307-Forei~n Countries 2 1~ ~ ~ 7 8 A~ter 1000 seconds of operation Al`ter 2000 seconds of operation Device ~tructure Current EL Efficiency Current EL Efficiency (mA) intensity (arbitrary (mA) intensity (arbitrary (arbitrary units) (arbitrary units) units) units) ITO/polyether A/AI 50 S.OOE-10 IE-I I 50 4.00E-10 8E-12 (control specimen) without stabiliser ITO/polyether A + 2 6.00E-08 3E-08 2.2 8.00E-08 4E-08 0.5 %
TINUVIN
Al = aluminium
--(-CH2--)6--O~CH=CH--~CH=CH
--n The ITO layer and the Al electrode were connected via electrical leads to a voltage source. When the voltage was increased, a current flows through the 5 polymer layer. Electroluminescence was detectable above a voltage of 5 volts.
The colour of the electroluminescence was blue-green.
Comparison of the electroluminescent devices:
dark storage period before use: 14 days applied voltage: 17 volts.
10 TINUVIN 622LD:
CH CH
f ~ CH3 CH3 ~ ~
--O~(cH~)2-olcl (CH2)2--Iclo~cH2)~olcl--(CH2)2 ICI--Le A 31 307-Forei~n Countries 2 1~ ~ ~ 7 8 A~ter 1000 seconds of operation Al`ter 2000 seconds of operation Device ~tructure Current EL Efficiency Current EL Efficiency (mA) intensity (arbitrary (mA) intensity (arbitrary (arbitrary units) (arbitrary units) units) units) ITO/polyether A/AI 50 S.OOE-10 IE-I I 50 4.00E-10 8E-12 (control specimen) without stabiliser ITO/polyether A + 2 6.00E-08 3E-08 2.2 8.00E-08 4E-08 0.5 %
TINUVIN
Al = aluminium
Claims (6)
1. An electroluminescent device which contains at least 2 electrodes, the base electrode and the top electrode, a light-emitting layer, and a stabiliser which is effective against atmospheric oxidation, thermal oxidation, ozone and UV radiation, wherein the electroluminescent device may contain at least one further layer selected from the sequence comprising the hole-injecting layer, the hole-transporting layer, and the electron-injecting layer.
2. An electroluminescent device according to claim 1, wherein the stabiliser is introduced into the light-emitting layer.
3. An electroluminescent device according to claim 1, wherein the stabiliser is added in amounts of 0.1 to 10 % by weight with respect to the weight of the layers to which the stabiliser is added.
4. An electroluminescent device according to claim 3, wherein the stabiliser is added in amounts of 0.2 to 3 % by weight.
5. An electroluminescent device according to claim 1, wherein the stabiliser is selected from the series comprising UV stabilisers, antioxidants and light stabilisers, antiozonants, sulphur compounds, phosphorus compounds, zinc, barium and calcium thiophosphates, boric acid esters, low molecular weight silicon compounds, organopolysiloxanes and sterically hindered amines.
6. An electroluminescent device according to claim 5, wherein the following stabilisers are used:
Table 1 Table 2 (1) 2,6-di-tert.-butyl-phenol (2) 2,6-di-tert.-butyl-4-methyl-phenol (3) 2,4,6-tri-tert.-butyl-phenol (4) 2,6-di-tert.-butyl-4-nonyl-phenol (5) 6-tert.-butyl-2,4-dimethyl-phenol (6) 2,4-dimethyl-6-nonyl-phenol (7) 2,4-dimethyl-6-(1-phenyl-ethyl)-phenol (8) 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol (9) 2,6-di-octadecyl-4-methyl-phenol (10) (5-tert.-butyl-4-hydroxy-3-methyl-benzyl)-malonic acid-di-n-octadecyl ester(11) 2,6-di-tert.-butyl-4-methoxy-phenol, 3,5-di-tert.-butyl-4-hydroxy-anisole (12) 2,5-di-tert.-butyl-hydroquinone (DBH) (13) 2,5-bis-(1,1-dimethyl-propyl)-hydroquinone (14) tocopherols (15) nordihydro-guaiaretic acid (NDGA) (16) .alpha.- and .beta.-naphthol (17) 6,7-dihydroxy-4-methyl-coumarin (18) 5,7-dihydroxy-4-methyl-coumarin monohydrate (19) 1,3,5-trihydroxy-benzene, phloroglucinol (20) 3,4,5-tri-hydroxy-benzoic acid propyl ester = propyl gallate, PG
(21) 3,4,5-tri-hydroxy-benzoic acid octyl ester = octyl gallate, OG
(22) 3,4,5-tri-hydroxy-benzoic acid dodecyl ester = dodecyl gallate, lauryl gallate, LG
(23) 2,4,5-trihydroxy-butyrophenone = THBP
(24) 2,2'-methylene-bis-(4-ethyl-6-tert.-butyl-phenol) (25) 1,1-bis-(2-hydroxy-3,5-dimethyl-phenyl)-butane (26) 1,1'-methylene-bis-(naphthol-2) (27) 2,2-bis-(4-hydroxy-phenyl)-propane = bisphenol A
(28) mixture of tert.-butylated 2,2-bis-(4-hydroxy-phenyl)-propanes (29) bis-3,3-bis-(4-hydroxy-3-tert.-butyl-phenyl)-butanoic acid glycol ester =
DTB glycol ester (30) 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (31) 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (32) 4,4'-methylene-bis-(2-tert.-butyl-6-methyl-phenol) (33) 4,4'-methylene-bis-(2,6-di-tert.-butyl-phenol) (34) 4,4'-methylene-bis-(2,5-di-tert.-butyl-phenol) (35) 1,1-bis-(4-hydroxy-phenyl)-cyclohexane (36) 1,1-bis-(3-cyclohexyl-4-hydroxy-phenyl)-cyclohexane (37) 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-benzene:
(38) catechol (39) 4-tert.-butyl-catechol = TBC; 1,2-dihydroxy-4-tert.-butylbenzene (40) hydroquinone (41) 4-methoxyphenol, hydroquinone monomethyl ether (42) 4-benzyloxyphenol, hydroquinone monobenzyl ether (43) mixtures of 3-tert.-butyl-4-hydroxy-anisole 3-isomer 2-isomer (44) styrenated phenols (45) 3,5-di-tert.-butyl-4-hydroxy-benzyl alcohol (46) 2,6-di-tert.-butyl-4-methoxy-phenol (47) octadecyl-3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate (48) pentaerythrityl-tetrakis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate]
(49) 1,6-bis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionyloxy]-n-hexane (50) 2,2-bis-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-malonic acid-di n-octyl ester(51) 2,2'-methylene-bis-(4,6-dimethyl-phenol) (52) 2,2'-methylene-bis-(6-tert.-butyl-4-methyl-phenol) R = -C(CH3)3 (53) 2,2'-methylene-bis-(4-methyl-6-nonyl-phenol) (54) 2,2'-methylene-bis-[4-methyl-6-(1-methyl-cyclohexyl)-phenol]
(55) 2,2'-methylene-bis[4-methyl-(6-.alpha.-methyl-benzyl)-phenol]
Table 3:
(1) N,N'-di-sec.-butyl-p-phenylenediamine = DBPPD
(2) N,N'-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine (3) N,N'-bis-(1-ethyl-3-methyl-pentyl)-p-phenylenediamine (4) N,N'-bis-(1-methyl-heptyl)-p-phenylenediamine (5) N,N'-dicyclohexyl-p-phenylenediamine (6) N,N'-diphenyl-p-phenylenediamine = DPPD
(7) N,N'-di-(naphthyl-2)-p-phenylenediamine (8) N-isopropyl-N'-phenyl-p-phenylenediamine (9) N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine (10) N-(1-methyl-heptyl)-N'-phenyl-p-phenylenediamine (11) N-cyclohexyl-N'-phenyl-p-phenylenediamine (12) 4-(p-toluene-sulphonamido)-diphenylamine (13) N,N'-dimethyl-N,N'-di-sec.-butyl-p-phenylenediamine (14) diphenylamine (15) 4-isopropoxy-diphenylamine (16) N-phenyl-1-naphthylamine (17) N-phenyl-2-naphthylamine (18) octylated diphenylamine, predominantly 4-octyl-diphenylamine (19) 4-n-butylamino-phenol (20) 4-butyrylamino-phenol (21) 4-nonanoylamino-phenol (22) 4-dodecanoylamino-phenol (23) 4-octadecanoyl-amino-phenol (24) di-(4-methoxy-phenyl)-amine (25) 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol (26) 2,4'-diamino-diphenylmethane (27) 4,4'-diamino-diphenylmethane (28) N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane (29) 1,2-di-(phenylamino)-ethane (30) 1,2-di-[(2-methyl-phenyl)-amino]-ethane (31) 1,3-di-(phenylamino)-propane (32) (o-tolyl)-biguanide (33) the condensation product of aniline and acetaldehyde, (34) aniline-aldol-condensate (35) the product from aniline and butyraldehyde (36) (polymeric) 2,2,4-trimethyl-1,2-dihydroquinoline (37) aniline-acetone condensate (38) 6-ethoxy-2,2,4-trimethyl-1,3-dihydroquinoline = ethoxyquin (39) 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline (40) 2,2,4-trimethyl-6-phenyl-1,2-dihydroquinoline (41) 1-aminonaphthalene-aldol condensate (42) the product of 2-phenylamino-naphthalene and acetone (43) diphenylamine-acetone condensate, compounds of 5,5-dimethyl-acridine, etc.
(44) N,N'-diisopropyl-p-phenylenediamine Table 5:
(1) triphenylphosphine (2) diethyl phosphite (3) triphenyl phosphite (4) tris-nonylphenyl phosphite (5) tris-(mono-dinonylphenyl)-phosphite (6) tridecyl phosphite (7) tri-isodecyl phosphite (8) tri-dodecyl phosphite (9) (10) the condensation product of 4,4'-thio-bis-(2-tert.-butyl-5-methyl-phenol) (11) octyl-diphenyl phosphite (12) isooctyl-diphenyl phosphite (13) decyl-diphenyl phosphite (14) isodecyl-diphenyl phosphite (15) didecyl-phenyl phosphite (16) diisodecyl-phenyl phosphite (17) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid diethyl ester (18) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid di-n-octadecyl ester Zinc, barium and calcium thiophosphates, e.g. of formula (1) (2) boric acid esters of formula (Ph-phenyl) low molecular weight silicon compounds organopolysiloxanes of formula where R= -CH3, -Ph, -H or -(CH2)3O-CH2 or where n = 1-10 and X = -CH2O-(CH2)3-O(CH2)3-OH
-(CH2)4-OH
-OC2H5, or sterically hindered based on 2,6-tetramethyl-piperidine
Table 1 Table 2 (1) 2,6-di-tert.-butyl-phenol (2) 2,6-di-tert.-butyl-4-methyl-phenol (3) 2,4,6-tri-tert.-butyl-phenol (4) 2,6-di-tert.-butyl-4-nonyl-phenol (5) 6-tert.-butyl-2,4-dimethyl-phenol (6) 2,4-dimethyl-6-nonyl-phenol (7) 2,4-dimethyl-6-(1-phenyl-ethyl)-phenol (8) 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol (9) 2,6-di-octadecyl-4-methyl-phenol (10) (5-tert.-butyl-4-hydroxy-3-methyl-benzyl)-malonic acid-di-n-octadecyl ester(11) 2,6-di-tert.-butyl-4-methoxy-phenol, 3,5-di-tert.-butyl-4-hydroxy-anisole (12) 2,5-di-tert.-butyl-hydroquinone (DBH) (13) 2,5-bis-(1,1-dimethyl-propyl)-hydroquinone (14) tocopherols (15) nordihydro-guaiaretic acid (NDGA) (16) .alpha.- and .beta.-naphthol (17) 6,7-dihydroxy-4-methyl-coumarin (18) 5,7-dihydroxy-4-methyl-coumarin monohydrate (19) 1,3,5-trihydroxy-benzene, phloroglucinol (20) 3,4,5-tri-hydroxy-benzoic acid propyl ester = propyl gallate, PG
(21) 3,4,5-tri-hydroxy-benzoic acid octyl ester = octyl gallate, OG
(22) 3,4,5-tri-hydroxy-benzoic acid dodecyl ester = dodecyl gallate, lauryl gallate, LG
(23) 2,4,5-trihydroxy-butyrophenone = THBP
(24) 2,2'-methylene-bis-(4-ethyl-6-tert.-butyl-phenol) (25) 1,1-bis-(2-hydroxy-3,5-dimethyl-phenyl)-butane (26) 1,1'-methylene-bis-(naphthol-2) (27) 2,2-bis-(4-hydroxy-phenyl)-propane = bisphenol A
(28) mixture of tert.-butylated 2,2-bis-(4-hydroxy-phenyl)-propanes (29) bis-3,3-bis-(4-hydroxy-3-tert.-butyl-phenyl)-butanoic acid glycol ester =
DTB glycol ester (30) 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (31) 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butane (32) 4,4'-methylene-bis-(2-tert.-butyl-6-methyl-phenol) (33) 4,4'-methylene-bis-(2,6-di-tert.-butyl-phenol) (34) 4,4'-methylene-bis-(2,5-di-tert.-butyl-phenol) (35) 1,1-bis-(4-hydroxy-phenyl)-cyclohexane (36) 1,1-bis-(3-cyclohexyl-4-hydroxy-phenyl)-cyclohexane (37) 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-benzene:
(38) catechol (39) 4-tert.-butyl-catechol = TBC; 1,2-dihydroxy-4-tert.-butylbenzene (40) hydroquinone (41) 4-methoxyphenol, hydroquinone monomethyl ether (42) 4-benzyloxyphenol, hydroquinone monobenzyl ether (43) mixtures of 3-tert.-butyl-4-hydroxy-anisole 3-isomer 2-isomer (44) styrenated phenols (45) 3,5-di-tert.-butyl-4-hydroxy-benzyl alcohol (46) 2,6-di-tert.-butyl-4-methoxy-phenol (47) octadecyl-3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate (48) pentaerythrityl-tetrakis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate]
(49) 1,6-bis-[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionyloxy]-n-hexane (50) 2,2-bis-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-malonic acid-di n-octyl ester(51) 2,2'-methylene-bis-(4,6-dimethyl-phenol) (52) 2,2'-methylene-bis-(6-tert.-butyl-4-methyl-phenol) R = -C(CH3)3 (53) 2,2'-methylene-bis-(4-methyl-6-nonyl-phenol) (54) 2,2'-methylene-bis-[4-methyl-6-(1-methyl-cyclohexyl)-phenol]
(55) 2,2'-methylene-bis[4-methyl-(6-.alpha.-methyl-benzyl)-phenol]
Table 3:
(1) N,N'-di-sec.-butyl-p-phenylenediamine = DBPPD
(2) N,N'-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine (3) N,N'-bis-(1-ethyl-3-methyl-pentyl)-p-phenylenediamine (4) N,N'-bis-(1-methyl-heptyl)-p-phenylenediamine (5) N,N'-dicyclohexyl-p-phenylenediamine (6) N,N'-diphenyl-p-phenylenediamine = DPPD
(7) N,N'-di-(naphthyl-2)-p-phenylenediamine (8) N-isopropyl-N'-phenyl-p-phenylenediamine (9) N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine (10) N-(1-methyl-heptyl)-N'-phenyl-p-phenylenediamine (11) N-cyclohexyl-N'-phenyl-p-phenylenediamine (12) 4-(p-toluene-sulphonamido)-diphenylamine (13) N,N'-dimethyl-N,N'-di-sec.-butyl-p-phenylenediamine (14) diphenylamine (15) 4-isopropoxy-diphenylamine (16) N-phenyl-1-naphthylamine (17) N-phenyl-2-naphthylamine (18) octylated diphenylamine, predominantly 4-octyl-diphenylamine (19) 4-n-butylamino-phenol (20) 4-butyrylamino-phenol (21) 4-nonanoylamino-phenol (22) 4-dodecanoylamino-phenol (23) 4-octadecanoyl-amino-phenol (24) di-(4-methoxy-phenyl)-amine (25) 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol (26) 2,4'-diamino-diphenylmethane (27) 4,4'-diamino-diphenylmethane (28) N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane (29) 1,2-di-(phenylamino)-ethane (30) 1,2-di-[(2-methyl-phenyl)-amino]-ethane (31) 1,3-di-(phenylamino)-propane (32) (o-tolyl)-biguanide (33) the condensation product of aniline and acetaldehyde, (34) aniline-aldol-condensate (35) the product from aniline and butyraldehyde (36) (polymeric) 2,2,4-trimethyl-1,2-dihydroquinoline (37) aniline-acetone condensate (38) 6-ethoxy-2,2,4-trimethyl-1,3-dihydroquinoline = ethoxyquin (39) 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline (40) 2,2,4-trimethyl-6-phenyl-1,2-dihydroquinoline (41) 1-aminonaphthalene-aldol condensate (42) the product of 2-phenylamino-naphthalene and acetone (43) diphenylamine-acetone condensate, compounds of 5,5-dimethyl-acridine, etc.
(44) N,N'-diisopropyl-p-phenylenediamine Table 5:
(1) triphenylphosphine (2) diethyl phosphite (3) triphenyl phosphite (4) tris-nonylphenyl phosphite (5) tris-(mono-dinonylphenyl)-phosphite (6) tridecyl phosphite (7) tri-isodecyl phosphite (8) tri-dodecyl phosphite (9) (10) the condensation product of 4,4'-thio-bis-(2-tert.-butyl-5-methyl-phenol) (11) octyl-diphenyl phosphite (12) isooctyl-diphenyl phosphite (13) decyl-diphenyl phosphite (14) isodecyl-diphenyl phosphite (15) didecyl-phenyl phosphite (16) diisodecyl-phenyl phosphite (17) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid diethyl ester (18) 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid di-n-octadecyl ester Zinc, barium and calcium thiophosphates, e.g. of formula (1) (2) boric acid esters of formula (Ph-phenyl) low molecular weight silicon compounds organopolysiloxanes of formula where R= -CH3, -Ph, -H or -(CH2)3O-CH2 or where n = 1-10 and X = -CH2O-(CH2)3-O(CH2)3-OH
-(CH2)4-OH
-OC2H5, or sterically hindered based on 2,6-tetramethyl-piperidine
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19535063.4 | 1995-09-21 | ||
| DE19535063A DE19535063A1 (en) | 1995-09-21 | 1995-09-21 | Electroluminescent devices |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2185878A1 true CA2185878A1 (en) | 1997-03-22 |
Family
ID=7772756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002185878A Abandoned CA2185878A1 (en) | 1995-09-21 | 1996-09-18 | Electroluminescent devices |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0764712A3 (en) |
| JP (1) | JPH09125054A (en) |
| KR (1) | KR970019759A (en) |
| CN (1) | CN1159131A (en) |
| CA (1) | CA2185878A1 (en) |
| DE (1) | DE19535063A1 (en) |
| TW (1) | TW325638B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6888174B2 (en) | 2002-03-25 | 2005-05-03 | Patent-Treuhand-Gesellschaft Fur Elektrische Gluhlampen Mbh | Opto-electronic semiconductor component |
| US7541096B2 (en) | 2002-06-06 | 2009-06-02 | Ciba Specialty Chemicals Corporation | Electroluminescent device |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100269015B1 (en) * | 1997-07-08 | 2000-11-01 | 최재준 | Semiconductor lead frame picker sending apparatus |
| TW572990B (en) | 2000-03-16 | 2004-01-21 | Sumitomo Chemical Co | Polymeric fluorescent substance, polymeric fluorescent substance solution and polymer light-emitting device using the same substance |
| JP2001351785A (en) * | 2000-06-09 | 2001-12-21 | Sumitomo Chem Co Ltd | Organic electroluminescent element |
| ITRM20010471A1 (en) * | 2001-08-02 | 2003-02-03 | Enea Ente Nuove Tec | LUMINESCENCE STABILIZATION FROM ORGANIC MATERIALS WITH PHENOLIC ORIGIN COMPOSTIDES. |
| KR100542995B1 (en) | 2003-07-29 | 2006-01-20 | 삼성에스디아이 주식회사 | Organic electroluminescent dispaly device comprising ultraviolet light stabilizer |
| JP5874860B1 (en) * | 2015-03-24 | 2016-03-02 | 三菱化学株式会社 | Composition for organic electroluminescent device and method for producing organic electroluminescent device |
| JP6724294B2 (en) * | 2015-05-08 | 2020-07-15 | 三菱ケミカル株式会社 | Composition for organic electroluminescent device, organic electroluminescent device, display device and lighting device |
| CN112993177B (en) * | 2021-02-05 | 2022-07-26 | 华南理工大学 | Blue-light perovskite light-emitting diode and preparation method thereof |
| CN116600613B (en) * | 2023-07-17 | 2023-09-26 | 四川京龙光电科技有限公司 | Perovskite flexible display device preparation method and flexible display device |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104555A (en) * | 1977-01-27 | 1978-08-01 | Atkins & Merrill, Inc. | High temperature encapsulated electroluminescent lamp |
| JPS5867690A (en) * | 1981-10-19 | 1983-04-22 | Sumitomo Chem Co Ltd | Acetylenecarbamide derivative and antioxidant containing said derivative as active component |
| DE3856117D1 (en) * | 1987-10-30 | 1998-02-26 | Nippon Kasei Chem | Pastes for producing a luminescent layer or an insulating layer of a dispersion electroluminescent device and a dispersion electroluminescent device |
| US5330866A (en) * | 1991-02-18 | 1994-07-19 | Minolta Camera Kabushiki Kaisha | Photosensitive member comprising an amino compound |
| DE4235197A1 (en) * | 1991-10-22 | 1993-04-29 | Ciba Geigy Ag | New complexes comprising zinc di:thiophosphate and sterically hindered amine ligand - used as stabiliser and antioxidant in lubricating oil, hydraulic fluid, metal working fluid or organic polymer |
| JPH05127402A (en) * | 1991-11-07 | 1993-05-25 | Ricoh Co Ltd | Electrophotographic sensitive body |
| CA2163010A1 (en) * | 1994-03-16 | 1995-09-21 | Takashi Uemura | Organic electroluminescent element |
| US5681664A (en) * | 1994-08-04 | 1997-10-28 | Toyo Ink Manufacturing Co., Ltd. | Hole-transporting material and use thereof |
| US5629389A (en) * | 1995-06-06 | 1997-05-13 | Hewlett-Packard Company | Polymer-based electroluminescent device with improved stability |
-
1995
- 1995-09-21 DE DE19535063A patent/DE19535063A1/en not_active Withdrawn
-
1996
- 1996-09-09 EP EP96114371A patent/EP0764712A3/en not_active Withdrawn
- 1996-09-13 TW TW085111175A patent/TW325638B/en active
- 1996-09-17 JP JP8266752A patent/JPH09125054A/en active Pending
- 1996-09-18 CA CA002185878A patent/CA2185878A1/en not_active Abandoned
- 1996-09-20 CN CN96122547A patent/CN1159131A/en active Pending
- 1996-09-20 KR KR1019960041206A patent/KR970019759A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6888174B2 (en) | 2002-03-25 | 2005-05-03 | Patent-Treuhand-Gesellschaft Fur Elektrische Gluhlampen Mbh | Opto-electronic semiconductor component |
| US7541096B2 (en) | 2002-06-06 | 2009-06-02 | Ciba Specialty Chemicals Corporation | Electroluminescent device |
Also Published As
| Publication number | Publication date |
|---|---|
| TW325638B (en) | 1998-01-21 |
| CN1159131A (en) | 1997-09-10 |
| EP0764712A2 (en) | 1997-03-26 |
| KR970019759A (en) | 1997-04-30 |
| DE19535063A1 (en) | 1997-03-27 |
| EP0764712A3 (en) | 1997-08-20 |
| JPH09125054A (en) | 1997-05-13 |
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