JP2806651B2 - Dispersion type electroluminescence device - Google Patents
Dispersion type electroluminescence deviceInfo
- Publication number
- JP2806651B2 JP2806651B2 JP3210318A JP21031891A JP2806651B2 JP 2806651 B2 JP2806651 B2 JP 2806651B2 JP 3210318 A JP3210318 A JP 3210318A JP 21031891 A JP21031891 A JP 21031891A JP 2806651 B2 JP2806651 B2 JP 2806651B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- group
- containing organopolysiloxane
- cyanoalkyl
- coated
- 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.)
- Expired - Fee Related
Links
- 239000006185 dispersion Substances 0.000 title description 11
- 238000005401 electroluminescence Methods 0.000 title description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 36
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 25
- 229920001296 polysiloxane Polymers 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 6
- 150000008282 halocarbons Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 polychlorotrifluoroethylene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004373 Pullulan Substances 0.000 description 3
- 229920001218 Pullulan Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000019423 pullulan Nutrition 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- WKGYMMAZQLFVEB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propanenitrile Chemical compound CO[Si](C)(OC)CCC#N WKGYMMAZQLFVEB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NYZGMENMNUBUFC-UHFFFAOYSA-N P.[S-2].[Zn+2] Chemical compound P.[S-2].[Zn+2] NYZGMENMNUBUFC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 description 1
- CMBXEXDBVNIIKT-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propanenitrile Chemical compound C[Si](C)(Cl)CCC#N CMBXEXDBVNIIKT-UHFFFAOYSA-N 0.000 description 1
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 description 1
- TUBCJNPRMZYENU-UHFFFAOYSA-N 4-[diamino(phenyl)silyl]butanenitrile Chemical compound N#CCCC[Si](N)(N)C1=CC=CC=C1 TUBCJNPRMZYENU-UHFFFAOYSA-N 0.000 description 1
- XMFCIYUZZWZEHI-UHFFFAOYSA-N 4-[methoxy(dimethyl)silyl]butanenitrile Chemical compound CO[Si](C)(C)CCCC#N XMFCIYUZZWZEHI-UHFFFAOYSA-N 0.000 description 1
- PNRYBLONOYAKQG-UHFFFAOYSA-N 5-trimethoxysilylpentanenitrile Chemical compound CO[Si](OC)(OC)CCCCC#N PNRYBLONOYAKQG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YXFLUIRJZBTUIQ-UHFFFAOYSA-N C(#N)CC[SiH2][SiH2][SiH3] Chemical compound C(#N)CC[SiH2][SiH2][SiH3] YXFLUIRJZBTUIQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は分散型エレクトロルミネ
ッセンス素子、特には耐湿性と耐水性を向上させた表面
処理された蛍光体を用いてなる長寿命の分散型エレクト
ロルミネッセンス素子に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion-type electroluminescence device, and more particularly to a long- life dispersion-type electroluminescence device using a surface-treated phosphor having improved moisture resistance and water resistance.
【０００２】[0002]
【従来の技術】エレクトロルミネッセンス素子（以下Ｅ
Ｌ素子と略記する）は近年、平面発光体としての特徴を
いかして各種光源や表示デバイスに適用されており、と
くに分散型のＥＬ素子は比較的大面積なものが低いコス
トで容易に製造できることから液晶表示素子や平面ＴＶ
のバックライトとしての実用化が進められている。2. Description of the Related Art Electroluminescent devices (hereinafter referred to as E)
In recent years, L elements have been applied to various light sources and display devices by taking advantage of the characteristics of a plane light emitter. In particular, a dispersion type EL element having a relatively large area can be easily manufactured at low cost. LCD devices and flat-screen TVs
Is being put to practical use as a backlight.
【０００３】そして、この分散型ＥＬ素子は金属箔また
は金属薄板からなる背面電極、酸化チタンやチタン酸バ
リウムなどの高誘電体粉末を有機誘電体に分散させて薄
膜を形成させた反射絶縁層、蛍光体粉末を有機誘電体に
分散させて薄膜を形成した蛍光体層、および酸化インジ
ウムなどをポリエステルなどの絶縁性フィルム上に蒸着
して形成した透明電極とからなる積層体を、ガラス、ポ
リクロロトリフルオロエチレンなどの透明防湿材料で封
止した構成を有するもので、表面電極と背面電極との間
に交流電場を印加することにより蛍光体が励起されて発
光を与えるものである。[0003] This dispersion-type EL element has a back electrode made of a metal foil or a thin metal plate, a reflective insulating layer formed by dispersing a high dielectric powder such as titanium oxide or barium titanate in an organic dielectric to form a thin film, laminate consisting of a phosphor powder phosphor layer to form a thin film dispersed in an organic dielectrics, and oxidation Lee emissions di <br/> transparent electrode um and was formed by depositing on an insulating film such as a polyester It has a structure in which the body is sealed with a transparent moisture-proof material such as glass or polychlorotrifluoroethylene. By applying an AC electric field between the surface electrode and the back electrode, the phosphor is excited to give light emission Things.
【０００４】しかし、このＥＬ素子は長時間点灯してい
ると経時的に輝度が低下してゆくが、これは素子内の蛍
光体の耐湿性、耐水性が低く、保存ならびに駆動中に素
子に侵入した水分により劣化が進み易いことが原因であ
ると認識されている。そのため、このＥＬ素子について
はその長寿命化の目的で蛍光体粒子を防湿とすべく、こ
れをガラス、チタン酸バリウム、酸化チタン、酸化アル
ミニウムなどで被覆する方法が提案されている（特公昭
39-17874号、特公昭40-28377号、特開平2-32482 号公報
参照）。[0004] However, the luminance of this EL element decreases with time when it is lit for a long time. This is because the phosphor in the element has low moisture resistance and water resistance. It is recognized that deterioration is likely to occur due to invading moisture. For this reason, a method has been proposed for coating the EL element with glass, barium titanate, titanium oxide, aluminum oxide, or the like in order to keep the phosphor particles damp for the purpose of prolonging the life of the EL element.
39-17874, JP-B-40-28377, JP-A-2-32482).
【０００５】しかしながら、この無機物質で蛍光体表面
を被覆する場合には被覆剤懸濁液中に蛍光体を混合して
約200 ℃に熱処理するか、または微結晶化させるために
約600 ℃に高温処理する必要があるが、この熱処理、高
温処理は蛍光体を劣化させるおそれがあり、また金属酸
化物による被覆には逆に導電性低下を招き、ＥＬ素子に
利用した場合に充分な輝度を得ることができなくなると
いうことが多いという不利がある。However, when the phosphor surface is coated with this inorganic substance, the phosphor is mixed in the coating agent suspension and heat-treated at about 200 ° C. or at about 600 ° C. for microcrystallization. It is necessary to perform high-temperature treatment. However, this heat treatment and high-temperature treatment may deteriorate the phosphor, and coating with a metal oxide may cause a decrease in conductivity, and a sufficient luminance may be obtained when used for an EL element. The disadvantage is that it often becomes impossible to obtain.
【０００６】[0006]
【発明が解決しようとする課題】また、この蛍光体の防
湿処理については蛍光体をシランカップリング剤、シリ
コ−ン樹脂などで被覆する方法（特開昭62-195894 号公
報参照）、四フッ化エチレン、三フッ化塩化エチレンな
どのフッ素樹脂で被覆する方法（特開昭63-216291 号公
報参照）、さらには撥水性オイルにより疎水化処理する
方法（特開昭63-271894 号公報参照）なども提案されて
いるが、これらはいずれも誘電率の低い物質による蛍光
体表面処理であることから、蛍光体の耐湿性、耐水性の
向上に効果が期待されるものの、表面処理物質が低誘電
であることから輝度が低下するという問題点があり、こ
れにはまた蛍光体処理表面層と有機誘電体との相溶性が
著しく劣るために、蛍光体を有機誘電体中に均一に分散
させることが難しく、この点からも発光輝度が低下し、
発光効率がわるくなるという欠点もある。Further, regarding the moisture-proof treatment of the phosphor, a method of coating the phosphor with a silane coupling agent, a silicone resin or the like (see Japanese Patent Application Laid-Open No. Sho 62-195894), Coating with a fluororesin such as ethylene fluoride and ethylene trifluoride (see JP-A-63-216291), and a method of hydrophobizing with a water-repellent oil (see JP-A-63-271894). Although these are all phosphor surface treatments with substances having a low dielectric constant, they are expected to improve the moisture resistance and water resistance of the phosphors. There is a problem that the luminance is reduced due to the dielectric, and the compatibility between the phosphor-treated surface layer and the organic dielectric is extremely poor, so that the phosphor is uniformly dispersed in the organic dielectric. Difficult in this regard Et even light emission luminance is lowered,
There is also a disadvantage that the luminous efficiency becomes poor.
【０００７】[0007]
【課題を解決するための手段】本発明はこのような不
利、欠点を解決した分散型ＥＬ素子に関するものであ
り、これは平均組成式SUMMARY OF THE INVENTION The present invention relates to a dispersion-type EL device which solves such disadvantages and disadvantages, and comprises an average composition formula.
【化２】 （式中のR1、R2 は同一または異種の炭素数３〜５のシア
ノアルキル基、R3は水素原子、１価の炭化水素基または
１価のハロゲン化炭化水素基、a, b, c はa=０〜1.8、 b
= ０〜1.8、 c= ０〜1.0 でa+b =0.8〜1.8、a+b+c=1.1
〜1.98である）で示されるシアノアルキル基含有オルガ
ノポリシロキサンにより表面を被覆した蛍光体により蛍
光層を形成してなることを特徴とするものである。Embedded image (Wherein R 1 and R 2 are the same or different cyanoalkyl groups having 3 to 5 carbon atoms, R 3 is a hydrogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, a, b, c is a = 0 to 1.8, b
= 0-1.8, c = 0-1.0, a + b = 0.8-1.8, a + b + c = 1.1
To 1.98), and a phosphor layer formed of a phosphor whose surface is coated with a cyanoalkyl group-containing organopolysiloxane represented by the formula (1):
【０００８】すなわち、本発明者らは蛍光体の耐湿性、
耐水性を向上させ、その輝度低下を防止した分散型ＥＬ
素子を開発すべく種々検討した結果、蛍光体粒子の表面
を前記した式（1)で示されるシアノアルキル基含有オル
ガノポリシロキサンで被覆すると蛍光体の耐湿性、耐水
性が向上されるのでその輝度低下が防止されることを見
出すと共に、このシアノアルキル基含有オルガノポリシ
ロキサンは蛍光層を形成する有機誘電体バインダ−との
相溶性のすぐれたものであるので、この分散型ＥＬ素子
を高輝度、高効率、長寿命のものとすることができると
いうことを確認して本発明を完成させた。以下にこれを
さらに詳述する。That is, the present inventors have studied the moisture resistance of the phosphor,
Dispersion type EL with improved water resistance and prevention of its brightness
As a result of various investigations to develop a device, it was found that when the surface of the phosphor particles is coated with the cyanoalkyl group-containing organopolysiloxane represented by the above formula (1), the moisture resistance and water resistance of the phosphor are improved. In addition to finding that the reduction is prevented, the cyanoalkyl group-containing organopolysiloxane is excellent in compatibility with the organic dielectric binder forming the fluorescent layer , so that the dispersion type EL device has high brightness, The present invention has been completed by confirming that high efficiency and long life can be obtained. This will be described in more detail below.
【０００９】[0009]
【作用】本発明は分散型ＥＬ素子に関するものであり、
これは前記した平均組成式(1)で示されるシアノアルキ
ル基含有オルガノポリシロキサンにより表面を被覆した
蛍光体により蛍光層を形成してなることを特徴とするも
のである。The present invention relates to a dispersion type EL device,
This is characterized in that a phosphor layer is formed of a phosphor whose surface is coated with a cyanoalkyl group-containing organopolysiloxane represented by the above average composition formula (1).
【００１０】本発明の分散型ＥＬ素子の構成は従来公知
のもので、これは前記したように背面電極、反射絶縁
層、蛍光層、透明電極とからなる積層体を透明防湿材料
で封止したものであり、この蛍光体を構成する蛍光体粒
子も硫化亜鉛を母体材料とし、活性剤として銅、マンガ
ン、アルミニウム、臭素、塩素およびヨウ素などを添加
して焼成した公知のものであればよいが、これらは発光
素子としたときの発光特性から平均粒径が10〜80μm の
ものとすることが好ましい。The constitution of the dispersion type EL device of the present invention is conventionally known. As described above, the laminated body composed of the back electrode, the reflective insulating layer, the fluorescent layer and the transparent electrode is sealed with a transparent moisture-proof material. The phosphor particles constituting the phosphor may be any known particles obtained by sintering zinc sulfide as a base material and adding copper, manganese, aluminum, bromine, chlorine and iodine as an activator. It is preferable that these have an average particle diameter of 10 to 80 μm from the light emitting characteristics of a light emitting element.
【００１１】本発明による分散型ＥＬ素子はこの蛍光体
粒子の表面をシアノアルキル基含有オルガノポリシロキ
サンで被覆するのであるが、このシアノアルキル基含有
オルガノポリシロキサンはその平均組成式が[0011] The dispersion type EL device according to the present invention comprises the phosphor
The surface of the particles is coated with a cyanoalkyl group-containing organopolysiloxane, and this cyanoalkyl group-containing organopolysiloxane has an average composition formula of:
【化３】 で示され、このR1、 R2がシアノエチル基、シアノプロピ
ル基、シアノブチル基などの炭素数３〜５の直鎖状また
は分岐状のシアノアルキル基であり、R3が水素原子、メ
チル基、エチル基、プロピル基、ブチル基などのアルキ
ル基、シクロヘキシル基などのシクロアルキル基、フェ
ニル基、トリル基などのアリ−ル基である１価の炭化水
素基またはクロロメチル基、３，３，３−トリフルオロ
プロピル基、１，１，１−トリフルオロヘキシル基など
の１価のハロゲン化炭化水素基で、a、 b、 c がa=０〜1.
8、 b= ０〜1.8 、c=０〜1.0 であるものとされる。Embedded image Wherein R 1 and R 2 are a linear or branched cyanoalkyl group having 3 to 5 carbon atoms such as a cyanoethyl group, a cyanopropyl group or a cyanobutyl group, and R 3 is a hydrogen atom, a methyl group, Monovalent hydrocarbon groups or chloromethyl groups such as alkyl groups such as ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group and tolyl group; -A monovalent halogenated hydrocarbon group such as a trifluoropropyl group or a 1,1,1-trifluorohexyl group, wherein a, b and c are a = 0 to 1.
8, b = 0 to 1.8 and c = 0 to 1.0.
【００１２】なお、この平均組成式(1）で示されるシア
ノアルキル基含有オルガノポリシロキサンにおけるシア
ノアルキル基は１種のみでも、２種類以上の混合物であ
ってもよいが、この含有量はこのa+b が0.8 〜1.8 のも
のとすることがよく、この範囲外であると誘電率が低下
したり、工業的に導入することが難しくなるので好まし
くない。また、上記した式におけるR3で示される水素原
子、１価炭化水素基、１価ハロゲン化炭化水素基の含有
量はそれが大きすぎるとシアノアルキル基量が小さくな
るので、これはc=0.01〜1.0 の範囲とすることがよく、
さらにこのシアノアルキル基、水素原子、１価炭化水
素、１価ハロゲン化炭化水素基の和（式中のa+b+c)は1.
1 〜1.98の範囲とすることがよく、この範囲外ではフイ
ルム成形が不可能となる。The cyanoalkyl group in the cyanoalkyl group-containing organopolysiloxane represented by the average composition formula (1) may be only one type or a mixture of two or more types. The value of + b is preferably 0.8 to 1.8. If the value of + b is out of this range, the dielectric constant is lowered and it is difficult to introduce the compound industrially. Further, if the content of the hydrogen atom, monovalent hydrocarbon group, and monovalent halogenated hydrocarbon group represented by R 3 in the above formula is too large, the amount of cyanoalkyl group becomes small. It is often in the range of ~ 1.0,
Further, the sum of the cyanoalkyl group, the hydrogen atom, the monovalent hydrocarbon and the monovalent halogenated hydrocarbon group (a + b + c in the formula) is 1.
The thickness is preferably in the range of 1 to 1.98, and if it is outside this range, film forming becomes impossible.
【００１３】このシアノアルキル基含有オルガノポリシ
ロキサンはシアノアルキル基含有シランまたはこのシア
ノアルキル基含有シランとシアノアルキル基を含有して
ないシランを加水分解して得られるシロキサンを重合す
るか、またはこれらのシロキサンを付加反応あるいは脱
アルコ−ル反応、脱水反応などのように縮合反応させる
ことによって得ることができる。The cyanoalkyl group-containing organopolysiloxane is prepared by polymerizing a siloxane obtained by hydrolyzing a cyanoalkyl group-containing silane or a silane containing no cyanoalkyl group and a silane containing no cyanoalkyl group. It can be obtained by subjecting a siloxane to a condensation reaction such as an addition reaction, a dealcohol reaction, a dehydration reaction, or the like.
【００１４】このシアノアルキル基含有シランとしては
シアノエチルジメチルクロロシラン、シアノプロピルジ
メチルメトキシシランなどのような一官能性シラン、シ
アノエチルメチルジメトキシシラン、シアノプロピルフ
ェニルジアミノシランなどのような２官能性シラン、シ
アノエチルトリエトキシシラン、シアノブチルトリメト
キシシランなどのような３官能性シランがあげられ、シ
アノアルキル基を含まない物としてはトリメチルクロロ
シラン、トリメチルメトキシシランなどの一官能性シラ
ン、ジメチルジクロロシラン、ジメチルジメトキシシラ
ンなどの２官能性シラン、メチルトリクロロシラン、ト
リメトキシシランなどの３官能性、４官能性シランが例
示されるが、この出発原料としては上記した単量体のほ
かにこれらの単量体から得られるプレポリマ−を使用す
ることもできる。Examples of the cyanoalkyl group-containing silane include monofunctional silanes such as cyanoethyldimethylchlorosilane and cyanopropyldimethylmethoxysilane, bifunctional silanes such as cyanoethylmethyldimethoxysilane and cyanopropylphenyldiaminosilane, and cyanoethyltrisilane. Examples include trifunctional silanes such as ethoxysilane and cyanobutyltrimethoxysilane. Examples of those not containing a cyanoalkyl group include monofunctional silanes such as trimethylchlorosilane and trimethylmethoxysilane, dimethyldichlorosilane and dimethyldimethoxysilane. Examples include trifunctional and tetrafunctional silanes such as difunctional silane, methyltrichlorosilane, and trimethoxysilane. The starting materials include, in addition to the above-mentioned monomers, Obtained from prepolymer - it can also be used.
【００１５】本発明においては上記したように蛍光体粒
子がシアノアルキル基含有オルガノポリシロキサンで被
覆されるのであるが、この被覆方法は一般的な細粒表面
をコ−ティングする方法で行えばよく、したがってこれ
はシアノアルキル基含有オルガノポリシロキサンにアセ
トン、メチルエチルケトン、ジメチルホルムアミドなど
のようなオルガノポリシロキサンを溶解する適当な溶剤
を加え、混合撹拌して均一な溶液としたのち、この混合
溶液中に蛍光体粒子を加えて分散し、得られた分散溶液
をろ過し乾燥後調粒するか、または蛍光体粒子を流動さ
せておいて、これにシアノアルキル基含有オルガノポリ
シロキサンを適当な溶剤に解かした溶液をスプレ−コ−
ティングし、乾燥する方法などが例示されるが、この場
合の被覆膜の厚さは特に限定されるものではないけれど
も通常0.１〜15μm の範囲となるようにすればよい。In the present invention, as described above, the phosphor particles
The particles are coated with a cyanoalkyl group-containing organopolysiloxane. This coating method may be performed by a general method of coating a fine-grained surface. , A suitable solvent for dissolving the organopolysiloxane such as methyl ethyl ketone, dimethylformamide, and the like, and mixing and stirring to form a uniform solution. Then, the phosphor particles are added and dispersed in the mixed solution to obtain a dispersion. The solution is filtered and dried and then granulated, or the phosphor particles are allowed to flow, and a solution obtained by dissolving the cyanoalkyl group-containing organopolysiloxane in a suitable solvent is spray-coated.
For example, a method of coating and drying is used. In this case, the thickness of the coating film is not particularly limited, but may be usually in the range of 0.1 to 15 μm.
【００１６】また、このシアノアルキル基含有オルガノ
ポリシロキサンで被覆した蛍光体粒子を用いてＥＬ素子
を製造するには、このように処理した蛍光体粒子をシア
ノエチルプルラン、シラノエチルポリビニルアルコ−
ル、シアノエチルセルロ−スなどのような高誘電率樹脂
中に分散させて蛍光層を形成させ、これを常法にしたが
ってチタン酸バリウム、酸化チタンなどを主体とする絶
縁層上に積層し、その少なくとも片面を透明電極で挟め
ばよいが、このようにして得られた分散型ＥＬ素子はこ
の蛍光体が耐湿性、耐水性の向上されたものであるの
で、輝度低下がなく、長寿命のものになるという利点が
与えられる。[0016] To manufacture the EL device using the phosphor particles coated with the cyanoalkyl group-containing organopolysiloxane thus treated phosphor particles cyanoethyl pullulan, silanolate ethyl polyvinyl alcohol -
Le, cyanoethyl cellulose - scan dispersed in a high dielectric constant resin, such as to form a fluorescent layer, laminated which barium titanate according to a conventional method, on the insulating layer mainly composed of titanium oxide, at least one surface of it Hasame a transparent electrode, but the thus dispersion-type EL element obtained in the one in which the phosphor is improved in moisture resistance, water resistance
In, no luminance decrease, given the advantage of the intended life.
【００１７】つぎに本発明で使用されるシアノアルキル
基含有オルガノポリシロキサンの合成剤、および実施
例、比較例をあげる。 合成例１，２ ２官能性シランとしてのシアノエチルメチルジメトキシ
シランと３官能性シランとしてのシアノエチルトリエト
キシシランとを表１に示した仕込量で500ml の三ツ口フ
ラスコに入れて撹拌混合し、ついでこれに15％テトラメ
チル水酸化アンモニウム水溶液1.5ml を加えた表１に示
した量の蒸留水を滴下し、90℃で２時間撹拌反応させた
ところ、反応終了後に透明な半固体状のシアノエチル基
含有オルガノポリシロキサンが得られたので、これにつ
いての誘電率、吸湿量をしらべたところ、表１に併記し
たとおりの結果が得られた。比較のために市販のシアノ
エチルプルランについての誘電率および吸湿量をしらべ
たところ、表１に示したとおりの結果が得られた。Next, a synthetic agent for the cyanoalkyl group-containing organopolysiloxane used in the present invention, and Examples and Comparative Examples will be described. Synthetic Examples 1 and 2 Cyanoethylmethyldimethoxysilane as a bifunctional silane and cyanoethyltriethoxysilane as a trifunctional silane were charged into a 500 ml three-necked flask at the charging amounts shown in Table 1 and mixed with stirring. was added dropwise to the amount of distilled water showed a 15% tetramethylammonium hydroxide aqueous ammonium 1.5ml in Table 1 was added, was allowed to stirring for 2 hours reaction at 90 ° C., cyanoethyl group-containing transparent semisolid-like after the completion of the reaction Since the organopolysiloxane was obtained, the dielectric constant and the amount of moisture absorption of the organopolysiloxane were examined . The results were as shown in Table 1 . For comparison, the dielectric constant and moisture absorption of commercially available cyanoethyl pullulan were examined. The results shown in Table 1 were obtained.
【００１８】[0018]
【表１】 [Table 1]
【００１９】実施例１、比較例 合成例１で得たシアノエチル基含有オルガノポリシロキ
サン40g にアセトンを添加し、撹拌溶解して10重量％の
溶液を調製し、これに平均粒子径が32μm であるＥＬ用
硫化亜鉛蛍光体粒子・タイプ727 ＥＬ(ZnS:Cu)［米国シ
ルバニア社製商品名］100gを加えて分散混合し、開口径
５μm のテフロン製フィルタ−を用いて減圧でろ過した
のち、80℃で４時間流動乾燥して表面がシアノエチル基
含有オルガノポリシロキサンで被覆された蛍光体を作製
した。Example 1, Comparative Example Acetone was added to 40 g of the cyanoethyl group-containing organopolysiloxane obtained in Synthesis Example 1 and dissolved by stirring to prepare a 10% by weight solution having an average particle diameter of 32 μm. 100 g of zinc sulfide phosphor particles for EL, type 727 EL (ZnS: Cu) [trade name, manufactured by Sylvania Co., Ltd.] was added, mixed and dispersed, and filtered under reduced pressure using a Teflon filter having an opening diameter of 5 μm. It was fluid-dried at 4 ° C. for 4 hours to prepare a phosphor whose surface was coated with a cyanoethyl group-containing organopolysiloxane.
【００２０】他方、これと別にシアノエチルプルラン・
シアノレジンＣＲ−Ｓタイプ「信越化学工業（株）製商
品名］の30重量％溶液を脱水ジメチルホルムアミドに溶
解して溶液（以下Ａ液と略記する）を作製し、このＡ液
100gに平均粒子径が1.5 μmのチタン酸バリウム50g を
分散してペ−スト状物を作製し、これを背面電極として
の厚みが100 μm であるアルミニウム箔上にスクリ−ン
印刷法で塗布し、120℃で１時間乾燥して厚さが20μm
の絶縁層を形成した。On the other hand, separately from this, cyanoethyl pullulan.
A 30% by weight solution of a cyanoresin CR-S type "trade name of Shin-Etsu Chemical Co., Ltd." is dissolved in dehydrated dimethylformamide to prepare a solution (hereinafter abbreviated as solution A).
A paste was prepared by dispersing 50 g of barium titanate having an average particle size of 1.5 μm in 100 g, and this was coated on a 100 μm-thick aluminum foil as a back electrode by a screen printing method. , Dried at 120 ° C for 1 hour, thickness 20μm
Was formed.
【００２１】ついで、このＡ液100gにシアノエチル基含
有オルガノポリシロキサンで被覆した上記の硫化亜鉛蛍
光体50g を分散して得たペ−スト状物を上記の絶縁層上
にスクリ−ン印刷法で印刷し、120 ℃で１時間乾燥して
蛍光層を形成させた。つぎにこの蛍光層上に透明電極と
してのＰＥＴ−ＩＴＯ膜（日東電工社製）をロ−ルラミ
ネ−タで接着させ、さらに全体にＰＣＴＦＥフィルム
（日東電工社製）で封止して分散型ＥＬ素子を作製した
ところ、このものは100 Ｖ−400Hz の点灯条件で初期輝
度68Cd/m2 を示し、40℃×90％RHの高温多湿下での輝度
半減期は420 時間であった。[0021] Then, the A solution Bae said zinc sulfide phosphor 50g coated with cyanoethyl group-containing organopolysiloxane obtained by dispersing in 100 g - strike-like material on the insulating layer Subscription - in screen printing method Print and dry at 120 ° C for 1 hour
To form a fluorescent layer. Then b the PET-ITO film as a transparent electrode on the fluorescent layer (manufactured by Nitto Denko Corporation) - Ruramine - is bonded with data, distributed sealed yet whole PCTFE film (manufactured by Nitto Denko Corporation) When an EL device was manufactured, the device exhibited an initial luminance of 68 Cd / m 2 under lighting conditions of 100 V-400 Hz, and a luminance half-life under high temperature and high humidity of 40 ° C. × 90% RH was 420 hours. there were.
【００２２】しかし、比較のためにこの蛍光体粒子をシ
アノエチル基含有オルガノポリシロキサンで被覆しなか
ったほかは上記と同じようにして分散型ＥＬ素子を作製
したところ、この素子の初期輝度は61Cd/m2 であった
が、これは半減期が130 時間で寿命の短かいものであっ
た。However, for comparison, a dispersion type EL device was prepared in the same manner as above except that the phosphor particles were not coated with the cyanoethyl group-containing organopolysiloxane.
As a result , the initial luminance of this device was 61 Cd / m 2 , which had a half life of 130 hours and a short life.
【００２３】実施例２ 合成例２で得られたシアノエチル基含有オルガノポリシ
ロキサンを用いたほかは実施例１と同じ方法で分散型Ｅ
Ｌ素子を作製したところ、この素子は初期輝度が62Cd/m
2 であり、40℃×90％RHの高温高湿下での輝度半減期は
450 時間であった。Example 2 A dispersion type E was prepared in the same manner as in Example 1 except that the cyanoethyl group-containing organopolysiloxane obtained in Synthesis Example 2 was used.
When an L element was produced , this element had an initial luminance of 62 Cd / m
2 , and the luminance half-life under high temperature and high humidity of 40 ° C x 90% RH is
450 hours.
【００２４】[0024]
【発明の効果】本発明は分散型ＥＬ素子に関するもので
あり、これは前記したように平均組成式が（１）で示さ
れるシアノアルキル基含有オルガノポリシロキサンによ
り表面を被覆した蛍光体粒子により蛍光層を形成してな
ることを特徴とするものであるが、これによれば蛍光体
の耐湿性、耐水性を向上させることができるので、この
素子は輝度低下を防止することができ、したがって長寿
命で、高輝度の分散型ＥＬ素子を得ることができるとい
う有利性が与えられる。According to the present invention, there is provided a dispersion type EL device, which emits fluorescent light by phosphor particles whose surface is coated with a cyanoalkyl group-containing organopolysiloxane having an average compositional formula of (1) as described above. This is characterized in that a layer is formed. According to this, the moisture resistance and water resistance of the phosphor can be improved, so that this element can prevent a decrease in luminance, and thus can have a long life. The advantage is given that a distributed EL device with high lifetime and high brightness can be obtained.
フロントページの続き (72)発明者 丸山 和政 新潟県中頚城郡頚城村大字西福島28番地 の１ 信越化学工業株式会社 合成技術 研究所内 (56)参考文献 特開 平２−103895（ＪＰ，Ａ) 特開 平１−204393（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H05B 33/14 C09K 11/00Continuation of the front page (72) Inventor Kazumasa Maruyama 28-1, Nishifukushima, Oku-ku, Kutsugi-mura, Nakakushiro-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (56) References JP-A-1-204393 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) H05B 33/14 C09K 11/00
Claims (1)
ノアルキル基、R3は水素原子、１価の炭化水素基または
１価のハロゲン化炭化水素基、a, b, c はa=０〜1.8、b=
０〜1.8、 c= ０〜1.0 でa+b ＝0.8 〜1.8 、a+b+c=1.1
〜1.98である）で示されるシアノアルキル基含有オルガ
ノポリシロキサンにより表面を被覆した蛍光体により蛍
光層を形成してなることを特徴とする分散型エレクトロ
ルミネッセンス素子。(1) An average composition formula: (Wherein R 1 and R 2 are the same or different cyanoalkyl groups having 3 to 5 carbon atoms, R 3 is a hydrogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, a, b, c is a = 0 to 1.8, b =
0 + 1.8, c = 0-1.0 and a + b = 0.8-1.8, a + b + c = 1.1
To 1.98), wherein a phosphor layer is formed of a phosphor whose surface is coated with a cyanoalkyl group-containing organopolysiloxane represented by the formula (1):
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3210318A JP2806651B2 (en) | 1991-07-26 | 1991-07-26 | Dispersion type electroluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3210318A JP2806651B2 (en) | 1991-07-26 | 1991-07-26 | Dispersion type electroluminescence device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0536479A JPH0536479A (en) | 1993-02-12 |
| JP2806651B2 true JP2806651B2 (en) | 1998-09-30 |
Family
ID=16587443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3210318A Expired - Fee Related JP2806651B2 (en) | 1991-07-26 | 1991-07-26 | Dispersion type electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2806651B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5123475B2 (en) * | 2004-09-28 | 2013-01-23 | 京セラ株式会社 | Fluorescent structure, composite, light emitting device, and light emitting device assembly |
| JP2024001371A (en) * | 2020-11-19 | 2024-01-10 | デンカ株式会社 | Phosphor particle, method for producing the same, light-emitting device, and image display device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH086087B2 (en) * | 1988-02-09 | 1996-01-24 | 信越化学工業株式会社 | EL device |
| JPH086088B2 (en) * | 1988-10-11 | 1996-01-24 | 信越化学工業株式会社 | Distributed electroluminescent device |
-
1991
- 1991-07-26 JP JP3210318A patent/JP2806651B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0536479A (en) | 1993-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2756044B2 (en) | Encapsulated electroluminescent phosphor and method of making same | |
| CN1192076C (en) | Electroluminescent phosphor particles encapsulated with an aluminum oxide based multiple oxide coating | |
| JP3187481B2 (en) | Moisture-insensitive zinc sulfide-based luminescent material and method of making same | |
| AU611764B2 (en) | Electroluminescent composition and electroluminescent device therewith | |
| JPH06184530A (en) | Improved electroluminescent device | |
| JP2006124680A (en) | Improved phosphor particulate powder, its production process and el element using the same | |
| JPH09272866A (en) | Electric field-luminescent phosphor and its production | |
| JP4316929B2 (en) | White-emitting electroluminescent phosphor with long lifetime | |
| JP2806651B2 (en) | Dispersion type electroluminescence device | |
| JPH11256150A (en) | Electroluminescent fluorescent substance, its production and el panel | |
| US20030098644A1 (en) | Process for treating previously coated phosphor particles | |
| JPH086088B2 (en) | Distributed electroluminescent device | |
| JPH11106678A (en) | Light-storing pigment | |
| JPH06248261A (en) | Electroluminescent element | |
| JPH048794A (en) | Luminous composition | |
| JP3210655B2 (en) | Electroluminescent lamp | |
| JPH06145656A (en) | Improved electroluminescence device | |
| JPH10298544A (en) | Fluorescent material emitting light in electrical field, and its production | |
| JPH06310276A (en) | Phosphor and dispersed el element using it | |
| JPH04171696A (en) | Distributed el element | |
| JPS6323987A (en) | Electroluminescent phosphor | |
| JP2000136381A (en) | Electroluminescent phosphor and organic dispersion-type electroluminescent element using same | |
| JP4409066B2 (en) | Blue light emitting electroluminescent phosphor and organic dispersion type electroluminescent device using the same | |
| JP2795132B2 (en) | EL device | |
| JPH07326474A (en) | Dispersion type electroluminescent element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080724 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080724 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090724 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090724 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100724 Year of fee payment: 12 |
|
| LAPS | Cancellation because of no payment of annual fees |