JPH11241069A - Liquid crystalline charge transport material - Google Patents
Liquid crystalline charge transport materialInfo
- Publication number
- JPH11241069A JPH11241069A JP10218148A JP21814898A JPH11241069A JP H11241069 A JPH11241069 A JP H11241069A JP 10218148 A JP10218148 A JP 10218148A JP 21814898 A JP21814898 A JP 21814898A JP H11241069 A JPH11241069 A JP H11241069A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- charge transport
- charge
- aromatic ring
- charge transporting
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 121
- 239000007788 liquid Substances 0.000 title claims description 19
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 52
- 238000005401 electroluminescence Methods 0.000 claims abstract description 17
- 239000002178 crystalline material Substances 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 125000005647 linker group Chemical group 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 23
- 239000000975 dye Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 14
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 12
- 230000005684 electric field Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- -1 acrylate ester Chemical class 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- WHJKVPBAKQHFPP-UHFFFAOYSA-N 2-dodecoxy-6-(4-octylphenyl)naphthalene Chemical compound C1=CC2=CC(OCCCCCCCCCCCC)=CC=C2C=C1C1=CC=C(CCCCCCCC)C=C1 WHJKVPBAKQHFPP-UHFFFAOYSA-N 0.000 description 1
- VESMRDNBVZOIEN-UHFFFAOYSA-N 9h-carbazole-1,2-diamine Chemical class C1=CC=C2C3=CC=C(N)C(N)=C3NC2=C1 VESMRDNBVZOIEN-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000005264 High molar mass liquid crystal Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Chemical class CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-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
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- MDYOLVRUBBJPFM-UHFFFAOYSA-N tropolone Chemical group OC1=CC=CC=CC1=O MDYOLVRUBBJPFM-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
- Electroluminescent Light Sources (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、少なくとも蛍光性
を有し、且つ電荷輸送性を有する液晶材料又は電荷輸送
性を有する液晶材料と蛍光性材料からなり、エレクトロ
ルミネッセンス発光が偏光性を有するような液晶性電荷
輸送材料、及び該材料を用いて形成された偏光発光が容
易に生じるエレクトロルミネッセンス素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal material having at least a fluorescent property and a charge transporting property, or a liquid crystal material having a charge transporting property and a fluorescent material, so that the electroluminescence emission has a polarizing property. The present invention relates to a novel liquid crystal charge transporting material and an electroluminescent element formed using the material, which easily emits polarized light.
【０００２】[0002]
【従来の技術】従来、電荷輸送材料としては、電荷を輸
送するサイトとなる電荷輸送性分子を、ポリカーボネー
ト樹脂等のマトリックス材料中に溶解或いは分散させた
材料や、ポリビニルカルバゾール等の如くポリマー主鎖
に電荷輸送性分子構造をペンダントさせた材料が知られ
ている。これらの材料は、複写機やプリンタ等の感光体
の材料として広く使用されている。2. Description of the Related Art Conventionally, as a charge transporting material, a material in which a charge transporting molecule serving as a site for transporting a charge is dissolved or dispersed in a matrix material such as a polycarbonate resin, or a polymer main chain such as polyvinyl carbazole is used. There is known a material in which a charge transporting molecular structure is pendant. These materials are widely used as materials for photoconductors such as copiers and printers.
【０００３】又、エレクトロルミネッセンス材料として
は無機系及び有機系の材料がある。無機系材料として
は、高電界によって加速されたキャリアの運動によって
励起発光するものとして、ＺｎＳ、ＺｎＳｅ、ＺｎＳ：
Ｍｎ等があり、固体内に作った電子のポテンシャルエネ
ルギー差を利用してキャリアを注入発光させるものとし
てＧａＮ、ＳｉＣ、ＣａＡｓ等があり、薄膜型エレクト
ロルミネッセンスディスプレイ、平面ランプ等に使用さ
れている。[0003] As the electroluminescence material, there are inorganic and organic materials. As the inorganic material, ZnS, ZnSe, and ZnS that excite and emit light by the motion of carriers accelerated by a high electric field include:
There are Mn and the like, and GaN, SiC, CaAs and the like are used for injecting and emitting carriers by utilizing the potential energy difference of electrons created in a solid, and are used for thin-film electroluminescence displays, flat lamps and the like.
【０００４】一方、有機系では、キヤリヤ注入型が高い
変換効率を示す電気−光変換系として注目されている。
発光色は青色から赤色まで任意の可視領域の波長の高輝
度発光が実現でき、しかも１０Ｖ以下の印加電圧で十分
な輝度が得られる。有機系材料の問題点の１つに耐久性
の限界が挙げられる。しかしながら、材料選択の無限の
可能性という他の材料系にない優位性が利用できること
から、材料設計、作成方法等によって耐久性の限界は克
服されつつある。有機系材料を使用した素子としては、
低分子量色素を真空蒸着法で薄膜に形成し積層型素子と
した有機薄膜系とπ共役高分子を用いたもの、非π共役
型高分子に電子輸送性色素分子や正孔輸送性色素分子を
分散した薄膜系とがある。On the other hand, among organic systems, a carrier injection type has attracted attention as an electro-optical conversion system exhibiting high conversion efficiency.
As for the emission color, high luminance light emission of any wavelength in the visible region from blue to red can be realized, and sufficient luminance can be obtained with an applied voltage of 10 V or less. One of the problems of organic materials is the limitation of durability. However, the limit of durability is being overcome by material design, production methods, and the like, because the unlimited possibility of material selection, which is an advantage not found in other material systems, can be used. As elements using organic materials,
An organic thin film system using a π-conjugated polymer with a low molecular weight dye formed into a thin film by a vacuum deposition method as a stacked element, and a π-conjugated polymer, and an electron transporting dye molecule or a hole transporting dye molecule on a non-π conjugated polymer. There is a dispersed thin film system.
【０００５】[0005]
【発明が解決しようとする課題】上記従来の電荷輸送材
料において、分散型の電荷輸送材料の場合には、電荷輸
送分子がマトリックスであるポリマーに高い溶解性を有
することが電荷輸送性能を向上させるためには望ましい
が、実際にはマトリックス中における電荷輸送分子を高
濃度にすると電荷輸送分子がマトリックスにおいて結晶
化し、電荷輸送分子の濃度は、種類によって異なるが、
一般的には２０〜５０重量％の濃度が限界である。その
結果、全体の５０重量％以上が電荷輸送性のないマトリ
ックスが占めることになり、成膜した場合に十分な電荷
輸送性や十分な応答速度が、マトリックスによって制限
されるという問題がある。In the above-mentioned conventional charge transporting material, in the case of a dispersion type charge transporting material, the charge transporting molecule has high solubility in a polymer as a matrix to improve the charge transporting performance. Although it is desirable to increase the concentration of the charge transport molecules in the matrix, the charge transport molecules crystallize in the matrix in practice, and the concentration of the charge transport molecules differs depending on the type.
Generally, a concentration of 20 to 50% by weight is the limit. As a result, 50% by weight or more of the entire matrix is occupied by the matrix having no charge transporting property, and there is a problem in that a sufficient charge transporting property and a sufficient response speed when the film is formed are limited by the matrix.
【０００６】一方、前記ペンダント型の電荷輸送性ポリ
マーの場合には、電荷輸送性を有するペンダントの占め
る割合が高いが、成膜した膜の機械的強度、環境安定
性、耐久性、成膜性の点で実用上の問題が多い。又、こ
の種の電荷輸送材料は、電荷輸送性ペンダントが局所的
に近接配置をとるために、このような局所近接部分が電
荷をホッピングする際に安定サイトとなり、一種のトラ
ップとして作用するために、電荷の移動度を低下させる
という問題がある。On the other hand, in the case of the pendant type charge transporting polymer, although the proportion of the pendant having the charge transporting property is high, the mechanical strength, environmental stability, durability and film forming property of the formed film are high. There are many practical problems in this respect. In addition, since this kind of charge transporting material has a locally close arrangement of the charge transporting pendant, such a locally adjacent portion becomes a stable site when hopping charges, and acts as a kind of trap. In addition, there is a problem that the mobility of charges is reduced.
【０００７】又、上記いずれの材料においても、上記の
如きアモルファス材料の電気特性からみた特徴は、結晶
性材料とは異なり、ホッピングサイトが空間的にばかり
でなく、エネルギー的にも揺らぎを有するという問題が
存在する。そのために電荷輸送サイトの濃度に大きく依
存し、その移動度は一般に１０-6〜１０-5ｃｍ2／ｖｓ
程度で、分子性結晶の０．１〜１ｃｍ2／ｖｓに比較し
て著しく小さい。更には電荷の輸送特性に対して強い温
度依存性や電界強度依存性があるという問題がある。こ
の点は結晶性の電荷輸送材料と大きく異なる点である。[0007] In any of the above materials, the characteristic of the above-mentioned amorphous material in terms of the electrical characteristics is that, unlike the crystalline material, the hopping site has fluctuations not only in space but also in energy. The problem exists. Therefore, the mobility largely depends on the concentration of the charge transport site, and the mobility is generally 10 −6 to 10 −5 cm 2 / vs.
On the order of 0.1 to 1 cm 2 / vs for molecular crystals. Further, there is a problem that the charge transport characteristics have strong temperature dependence and electric field intensity dependence. This point is significantly different from a crystalline charge transport material.
【０００８】又、大面積の電荷輸送性層が必要とされる
用途においては、大面積に均一な電荷輸送性膜が均一に
形成し得るという点で多結晶の電荷輸送性材料が期待さ
れているが、多結晶材料はミクロ的には本質的に不均一
な材料であって、例えば、粒子界面に形成される欠陥を
抑制する必要がある等の問題がある。In applications where a large-area charge transporting layer is required, a polycrystalline charge-transporting material is expected in that a uniform charge-transporting film can be uniformly formed over a large area. However, the polycrystalline material is essentially a non-uniform material microscopically, and has problems such as the need to suppress defects formed at the grain boundaries.
【０００９】従って本発明の目的は、上記従来技術の問
題を解決し、構造柔軟性と大面積にわたる均一性を有す
るアモルファス材料の利点と、分子配向性を有する結晶
性材料の利点を同時に有し、高品位の電荷輸送性、薄層
形成性、各種耐久性等に優れた新規な電荷輸送材料を用
いた電気−光変換材料を提供することである。更に、電
荷輸送材料自身に蛍光性を持たせることで、蛍光材料を
導入することによる液晶分子の並びの阻害、電荷輸送性
の低下、又は液晶性の変化を防ぐことができる新規な電
荷輸送材料を提供することである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and simultaneously have the advantages of an amorphous material having structural flexibility and uniformity over a large area, and the advantage of a crystalline material having molecular orientation. Another object of the present invention is to provide an electro-optical conversion material using a novel charge transporting material which is excellent in high quality charge transporting property, thin layer forming property, various durability and the like. Furthermore, by imparting fluorescence to the charge transport material itself, a novel charge transport material capable of preventing the arrangement of liquid crystal molecules, reducing the charge transport property, or preventing a change in liquid crystal property due to the introduction of the fluorescent material. It is to provide.
【００１０】[0010]
【課題を解決するための手段】上記目的は以下の本発明
によって達成される。即ち、本発明は、少なくとも蛍光
性を有し、且つ電荷輸送性を有する液晶材料又は電荷輸
送性を有する液晶材料と蛍光性材料とからなり、エレク
トロルミネッセンス発光が偏光性を有することを特徴と
する液晶性電荷輸送材料、及び該材料を用いた偏光発光
が容易に生じるエレクトロルミネッセンス素子である。The above object is achieved by the present invention described below. That is, the present invention is characterized by comprising at least a fluorescent material and a liquid crystal material having a charge transporting property or a liquid crystal material having a charge transporting property and a fluorescent material, wherein the electroluminescence emission has a polarizing property. A liquid crystal charge transport material, and an electroluminescent device that easily emits polarized light using the material.
【００１１】本発明の液晶性電荷輸送材料は、その分子
構造により自己配向性を有するため、これをホッピング
サイトとする電荷輸送は、前述の分子分散系材料とは異
なり、ホッピングサイトの空間的且つエネルギー的な分
散が抑制され、分子性結晶にみられるバンドライクな輸
送特性が実現する。このために従来の分子分散系材料に
比べて極めて大きな移動度が実現でき、更にその温度・
電界の依存性がないという特徴があらわれる。又、上記
の自己配向性を有する液晶性分子に蛍光材料を導入する
ことによって、自己配向性が蛍光材料の添加によって阻
害されることのない液晶性電荷輸送材料となる。Since the liquid crystalline charge transporting material of the present invention has self-orientation due to its molecular structure, the charge transport using this as a hopping site is different from the above-mentioned molecular dispersion material in terms of spatial and hopping of the hopping site. Energetic dispersion is suppressed, and band-like transport characteristics found in molecular crystals are realized. For this reason, extremely high mobility can be realized as compared with the conventional molecular dispersion material,
There is a characteristic that there is no dependence on the electric field. Further, by introducing a fluorescent material into the liquid crystal molecules having the self-orientation property, a liquid crystal charge transporting material in which the self-orientation property is not hindered by the addition of the fluorescent material is obtained.
【００１２】[0012]
【発明の実施の形態】次に実施の形態を挙げて本発明を
更に詳細に説明する。本発明の液晶性電荷輸送材料は、
電気光学スイッチング、ディスプレイデバイス、光セン
サ、エレクトロルミネッセンス素子等の用途に有用であ
る。又、本発明の液晶性電荷輸送材料は、電荷輸送性に
優れ、蛍光性も併せ持つからエレクトロルミネッセンス
素子の電荷輸送層として使用することができる。BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments. The liquid crystalline charge transport material of the present invention,
It is useful for applications such as electro-optic switching, display devices, optical sensors, and electroluminescent elements. Further, the liquid crystalline charge transporting material of the present invention has excellent charge transporting properties and also has fluorescence, so that it can be used as a charge transporting layer of an electroluminescence device.
【００１３】この材料系から得られる発光は分子配向性
を有することから、特定の方向に配向させることによっ
て偏光したエレクトロルミネッセンスが得られる。本発
明の液晶材料は、電荷輸送性と蛍光性とを併せ有するた
め、例えば、エレクトロルミネッセンス素子として使用
する場合、通常のエレクトロルミネッセンス素子がエレ
クトロン輸送性、ホール輸送性、蛍光性を有する材料を
用いて、エレクトロン輸送層、ホール輸送層、及び発光
層からなる２層又は３層で構成する必要があるのに対し
て、該液晶性材料単独で偏光性を有するエレクトロルミ
ネッセンス素子が形成可能なため素子形成の工程が簡略
化される。セル厚が通常のエレクトロルミネッセンス素
子と比較するとかなり厚いが、電極を含むデバイス形状
のデザイン検討及び／又はドーピングによるバルクの改
質等により液晶の電導性を調節することによって改善可
能であると考えられる。この材料系から得られる偏光は
光発振液晶ディスプレイを含む新しい電子デバイスに使
われる可能性を示している。[0013] Since the light emission obtained from this material system has molecular orientation, polarized electroluminescence can be obtained by orienting it in a specific direction. Since the liquid crystal material of the present invention has both charge transporting property and fluorescent property, for example, when used as an electroluminescent element, a normal electroluminescent element uses a material having electron transporting property, hole transporting property, and fluorescent property. In contrast, the liquid crystal material alone needs to be composed of two or three layers including an electron transport layer, a hole transport layer, and a light emitting layer, but the liquid crystal material alone can form a polarizable electroluminescent element. The formation process is simplified. Although the cell thickness is considerably thicker than that of a normal electroluminescent element, it is considered that the cell thickness can be improved by adjusting the conductivity of the liquid crystal by studying the design of the device shape including the electrodes and / or modifying the bulk by doping. . The polarized light obtained from this material system shows potential for use in new electronic devices, including light-oscillating liquid crystal displays.
【００１４】又、通常の２層又は３層構成のエレクトロ
ルミネッセンス素子では、各層を形成する材料に素材や
構造が大きく異なるものを用いているため、エレクトロ
ン輸送層やホール輸送層と発光層との間で形成される界
面でのエレクトロンやホールの受け渡しがうまく行われ
ずに、発光の効率が落ちる場合があるが、本発明の液晶
性電荷輸送材料を用いたエレクトロルミネッセンス素子
は、同一の材料を各層の区別なく用いることができるた
め、発光の効率の低下を極力抑えることが可能となる。Further, in the usual two-layer or three-layer electroluminescence device, since the materials forming the respective layers are greatly different from each other in the material and structure, the electron transport layer or the hole transport layer and the light emitting layer are not used. Although the efficiency of light emission may be reduced due to poor transfer of electrons and holes at the interface formed between the layers, the electroluminescent device using the liquid crystalline charge transport material of the present invention may use the same material for each layer. Can be used without distinction between them, and it is possible to minimize a decrease in light emission efficiency.
【００１５】偏光したエレクトロルミネッセンスについ
ては、Jpn.J.Appl. Phys.,34(1995)L712に記載の導電性
高分子であるポリ（２，５−ジノニロキシ−ｐ−フェニ
レンビフェニレン）を用い、ラビング処理することによ
って得られたものがあるが、液晶分子による単層型（電
荷輸送部と発光部とが同じ）で偏光したエレクトロルミ
ネッセンスについては報告されていない。For polarized electroluminescence, rubbing is carried out using poly (2,5-dinonyloxy-p-phenylene biphenylene) which is a conductive polymer described in Jpn. J. Appl. Phys., 34 (1995) L712. There is a material obtained by the treatment, but no report has been made on electroluminescence polarized in a single layer type (the charge transport portion and the light emitting portion are the same) by liquid crystal molecules.
【００１６】本発明の液晶性電荷輸送材料のうちで好ま
しい材料としては、前記基準を満たすとともに、（６π
電子系芳香環）ｌ、（１０π電子系芳香環）ｍ、又は
（１４π電子系芳香環）ｎ（ｌ＋ｍ＋ｎ＝１〜４、ｌ、
ｍ、ｎは夫々０〜４の整数を表す）を少なくともコアの
一部に有し、且つ液晶性を有する電荷輸送材料、６π電
子系芳香環、１０π電子系芳香環又は１４π電子系芳香
環がそれぞれ又は相互に炭素−炭素二重結合又は炭素−
炭素三重結合を有する連結基で連結されている電荷輸送
材料が挙げられる。尚、芳香環の連結数は移動度の観点
から制限される。液晶については特に制限はなく、棒状
分子が望ましく、スメクチック液晶、ネマチック液晶、
強誘電性液晶、反強誘電性液晶が使用できる。Among the liquid crystalline charge transporting materials of the present invention, preferred materials are those satisfying the above criteria and satisfying (6π
(Electron-based aromatic ring) l, (10π-electron-based aromatic ring) m, or (14π-electron-based aromatic ring) n (l + m + n = 1 to 4, l,
m and n each represent an integer of 0 to 4) in at least a part of the core, and a charge transporting material having liquid crystallinity, a 6π electron aromatic ring, a 10π electron aromatic ring, or a 14π electron aromatic ring. A carbon-carbon double bond or carbon-
Charge transport materials linked by a linking group having a carbon triple bond may be mentioned. The number of aromatic rings connected is limited from the viewpoint of mobility. There is no particular limitation on the liquid crystal, rod-like molecules are desirable, smectic liquid crystal, nematic liquid crystal,
Ferroelectric liquid crystals and antiferroelectric liquid crystals can be used.
【００１７】６π電子系芳香環としては、例えば、ベン
ゼン環、ピリジン環、ピリミジン環、ピリダジン環、ピ
ラジン環、トロポロン環、１０π電子系芳香環として
は、例えば、ナフタレン環、アズレン環、ベンゾフラン
環、インドール環、インダゾール環、ベンゾチアゾール
環、ベンゾオキサゾール環、ベンゾイミダゾール環、キ
ノリン環、イソキノリン環、キナゾリン環、キノキサリ
ン環、１４π電子系芳香環としては、例えば、フェナン
トレン環、アントラセン環等が挙げられる。The 6π-electron aromatic ring includes, for example, a benzene ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a tropolone ring, and the 10π-electron aromatic ring includes, for example, a naphthalene ring, an azulene ring, a benzofuran ring, Examples of the indole ring, indazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, and 14π electron aromatic ring include a phenanthrene ring and an anthracene ring.
【００１８】本発明の好ましい液晶性電荷輸送材料は、
棒状分子であり、且つ骨格部に下記に示される構造を有
する材料である。The preferred liquid crystalline charge transporting material of the present invention is:
The material is a rod-shaped molecule and has the following structure in the skeleton.
【化１】 Embedded image
【００１９】但し、上記式中のＲ1及びＲ2は、それぞれ
置換又は置換されていないアルキル基、置換又は置換さ
れていないアルコキシ基、置換又は置換されていないア
ルコキシカルボニル基或いは置換又は置換されていない
アルキルカルボニル基を、Ｒ3はトリフルオロメチル
基、アルキル基、ニトロ基、ハロゲン原子又は水素原子
を、ＸはＣＨ又はＮを示す。However, R 1 and R 2 in the above formula each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or substituted group. R 3 represents a trifluoromethyl group, an alkyl group, a nitro group, a halogen atom or a hydrogen atom, and X represents CH or N.
【００２０】上記電荷輸送材料には発光性材料を併用す
ることができる。発光材料としては、蛍光量子収率の高
い色素材料を利用する。例えば、ジフェニルエチレン誘
導体、トリフェニルアミン誘導体、ジアミノカルバゾー
ル誘導体、ビススチリル誘導体、ベンゾチアゾール誘導
体、ベンゾキサゾール誘導体、芳香族ジアミン誘導体、
キナクリドン系化合物、ペリレン系化合物、オキサジア
ゾール誘導体、クマリン系化合物、アントラキノン誘導
体又はＤＣＭ−１等のレーザー発振用色素等が挙げられ
る。これらの色素は、本発明の電荷輸送材料の液晶性を
壊さない程度に、好ましくは本発明の電荷輸送材料１０
０重量部に対して約０．０１〜３０重量％程度添加す
る。A light emitting material can be used in combination with the charge transporting material. As the light emitting material, a dye material having a high fluorescence quantum yield is used. For example, diphenylethylene derivative, triphenylamine derivative, diaminocarbazole derivative, bisstyryl derivative, benzothiazole derivative, benzoxazole derivative, aromatic diamine derivative,
Examples include quinacridone-based compounds, perylene-based compounds, oxadiazole derivatives, coumarin-based compounds, anthraquinone derivatives, and laser oscillation dyes such as DCM-1. These dyes are preferably used to such an extent that the liquid crystallinity of the charge transporting material of the present invention is not destroyed.
About 0.01 to 30% by weight is added to 0 parts by weight.
【００２１】発光のメカニズムとしては、おそらく色素
分子が注入キャリアの再結合中心として働いていると考
えられる。このことは、クマリン系色素（3-(2-Benzoth
iazolyl)-7-(dicthylamino)2H-1-benzopyran-2-one、株
式会社日本感光色素研究所製）を１モル％ドープした後
述の実施例１の場合に、電子キャリアの輸送性が悪くな
ることに示される。この時の負電荷の移動度は１０-5ｃ
ｍ／Ｖｓまで下がり、電子に対するトラップレベルの形
成を意味していると思われる。As a mechanism of light emission, it is considered that the dye molecule probably functions as a recombination center of the injected carrier. This means that coumarin dyes (3- (2-Benzoth
In the case of Example 1 described below where 1 mol% of (iazolyl) -7- (dicthylamino) 2H-1-benzopyran-2-one (manufactured by Japan Photographic Dye Laboratories Co., Ltd.) is doped, the transportability of electron carriers becomes poor. Is shown. At this time, the mobility of the negative charge is 10 −5 c.
m / Vs, which seems to indicate the formation of a trap level for electrons.
【００２２】本発明で使用される液晶性電荷輸送材料
は、又、加工性を容易にするために有機高分子マトリッ
クス中に包含させて使用することができる。この時、該
液晶性化合物が有機高分子膜中で膜の厚さ方向に連続的
に繋がっている構造を付与することで、膜形成性を有す
ると同時に、マトリックスによる電荷輸送性や応答速度
の制限が起こりにくい電荷輸送材料が得られる。The liquid crystalline charge transporting material used in the present invention can be used by being incorporated in an organic polymer matrix to facilitate processability. At this time, by providing a structure in which the liquid crystalline compound is continuously connected in the thickness direction of the film in the organic polymer film, the film has a film forming property, and at the same time, has a charge transport property and a response speed due to the matrix. A charge transport material that is less likely to be restricted is obtained.
【００２３】この時使用される高分子マトリックスとし
ては、セルロースアセテート系樹脂、ニトロセルロース
系樹脂、スチレン系（共）重合体、（メタ）アクリル酸
エステル系（共）重合体、ポリビニールブチラール系樹
脂、アミノアルキッド系樹脂、ポリエステル系樹脂、ポ
リウレタン系樹脂、ポリアミド系樹脂、可溶性ポリイミ
ド系樹脂、可溶性ポリアミドイミド系樹脂、可溶性ポリ
エステルイミド系樹脂、ポリビニルアルコール系樹脂、
カゼイン、ヒドロキシエチルセルロース、スチレン−マ
レイン酸エステル系共重合体等が挙げられる。The polymer matrix used at this time includes a cellulose acetate resin, a nitrocellulose resin, a styrene (co) polymer, a (meth) acrylate ester (co) polymer, and a polyvinyl butyral resin. , Amino alkyd resin, polyester resin, polyurethane resin, polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, polyvinyl alcohol resin,
Casein, hydroxyethylcellulose, styrene-maleic acid ester-based copolymer and the like can be mentioned.
【００２４】上記高分子マトリックス中に前記液晶化合
物を包含させる方法としては、多孔質高分子膜中に液晶
化合物を強制的に含浸させ、膜の両面を封止する方法、
高分子マトリックスと液晶化合物とを共通溶剤中に溶解
し、得られた溶液を適当な基板上に塗布し、適当な方法
で脱溶剤して膜を形成する方法、高分子マトリックスの
溶液中に液晶化合物を乳化分散させた分散液を適当な基
材上に塗布し、適当な方法で成膜する方法、高分子を形
成するモノマー或いはプレポリマー等のポリマープレカ
ーサー中に液晶化合物を相溶させ、上記プレカーサーを
重合させるとともに、液晶性化合物を相分離させる方法
等、従来公知の方法が挙げられる。The method of incorporating the liquid crystal compound into the polymer matrix includes a method of forcibly impregnating the liquid crystal compound in a porous polymer film and sealing both surfaces of the film.
A method in which a polymer matrix and a liquid crystal compound are dissolved in a common solvent, the obtained solution is applied on an appropriate substrate, and the solvent is removed by an appropriate method to form a film. A method in which a dispersion obtained by emulsifying and dispersing the compound is applied on a suitable base material, and a liquid crystal compound is dissolved in a polymer precursor such as a monomer or a prepolymer which forms a polymer by forming a film by a suitable method. Conventionally known methods such as a method of polymerizing a precursor and a phase separation of a liquid crystal compound can be used.
【００２５】本発明で使用される液晶性電荷輸送材料
は、該液晶性化合物を主鎖及び／又は側鎖に含む高分子
液晶として用いることができる。これらは一般に融点以
下の温度でも溶融状態における分子配向がそのまま固定
される場合が多く、高い光導電性を保持したまま成形性
及び膜形成性を付与することができる。The liquid crystal charge transporting material used in the present invention can be used as a polymer liquid crystal containing the liquid crystal compound in a main chain and / or a side chain. In many cases, the molecular orientation in the molten state is generally fixed as it is even at a temperature equal to or lower than the melting point, and moldability and film-formability can be imparted while maintaining high photoconductivity.
【００２６】以上の如き本発明の液晶性電荷輸送材料
は、特にエレクトロルミネッセンス素子の用途に有用で
ある。図１〜４は、本発明の電荷輸送材料のエレクトロ
ルミネッセンス素子への応用を代表例として説明する図
である。素子の最も簡単な構造は図１に示したように、
発光層及び電荷輸送層を一層として陰極と陽極で挟んだ
ものであり、本発明の液晶性電荷輸送材料のような、電
荷輸送性と蛍光性とを併せ持つ場合のみ、この層構成で
のエレクトロルミネッセンス素子の作製が可能となる。
この時、強い発光を得るためには、電子注入の役割を果
たす陰極材料は仕事関数の小さいもの、陽極材料は逆に
仕事関数の値が陰極と同じ値又はより大きなものを選択
することが好ましい。The liquid crystalline charge transporting material of the present invention as described above is particularly useful for electroluminescent devices. FIGS. 1 to 4 are diagrams illustrating the application of the charge transport material of the present invention to an electroluminescent device as a typical example. The simplest structure of the device is shown in FIG.
The light emitting layer and the charge transport layer are sandwiched between a cathode and an anode as a single layer. Only when the liquid crystal charge transport material of the present invention has both charge transportability and fluorescence, electroluminescence in this layer configuration An element can be manufactured.
At this time, in order to obtain strong light emission, it is preferable that the cathode material that plays the role of electron injection has a small work function, and that the anode material has the same or larger work function value as the cathode. .
【００２７】陽極材料としては、一般的に、例えば、Ｉ
ＴＯ、酸化インジウム、酸化錫（アンチモン、砒素、又
はフッ素ドープ）、Ｃｄ2ＳｎＯ4、酸化亜鉛、沃化銅、
又はアルカリ金属又はアルカリ土類金属を基本とするナ
トリウム、カリウム、マグネシウム、リチウム、ナトリ
ウム−カリウム合金、マグネシウム−インジウム合金、
マグネシウム−銀合金、アルミニウム、金、銀、ガリウ
ム、インジウム、銅等、更に陽極に使用した材料と同一
のものが挙げられる。As the anode material, generally, for example, I
TO, indium oxide, tin oxide (doped with antimony, arsenic, or fluorine), Cd 2 SnO 4 , zinc oxide, copper iodide,
Or sodium, potassium, magnesium, lithium, sodium-potassium alloy, magnesium-indium alloy, based on alkali metal or alkaline earth metal,
Magnesium-silver alloys, aluminum, gold, silver, gallium, indium, copper, etc., and the same materials as those used for the anode can also be used.
【００２８】発光層及び電荷輸送層に用いる材料は、電
荷輸送材料と発光材料とからなる。電荷輸送材料は、電
子及び正孔両輸送性材料又は両輸送性材料の混合物、若
しくは電子輸送性材料と正孔輸送性材料の混合物が好ま
しいが、電極界面での発光を利用する場合には一方の輸
送性材料だけでもよい。又、液晶自身が蛍光を持つ場合
には、発光材料は特に必要としないが併用してもよい。
液晶のコア部分が固体状態で強い蛍光を持つ有機色素類
から構成される場合の多くが上記条件に該当する。The materials used for the light emitting layer and the charge transport layer consist of a charge transport material and a light emitting material. The charge transporting material is preferably an electron and hole transporting material or a mixture of both transporting materials, or a mixture of an electron transporting material and a hole transporting material. May be used alone. When the liquid crystal itself has fluorescence, a light emitting material is not particularly required, but may be used in combination.
In many cases, the above condition is satisfied when the core portion of the liquid crystal is composed of organic dyes having strong fluorescence in a solid state.
【００２９】又、図３及び４に示したような層構成とし
た場合には、発光層（発光材料）の厚みは電子又は正孔
の移動を妨げない程度とする。発光層の膜厚は、好まし
くは０．２〜１５μｍとし、材料中へのスペーサ粒子の
散布、或いはセルの周囲に設ける封止剤で膜厚を調整す
ることができる。In the case of the layer structure as shown in FIGS. 3 and 4, the thickness of the light emitting layer (light emitting material) is set to such an extent that the movement of electrons or holes is not hindered. The thickness of the light emitting layer is preferably 0.2 to 15 μm, and the thickness can be adjusted by dispersing spacer particles in the material or by using a sealant provided around the cell.
【００３０】[0030]
【実施例】次に実施例を挙げて、本発明を更に具体的に
説明するが、本発明はこれらの実施例に限定されない。 実施例１ 真空成膜によりＩＴＯ電極（表面抵抗：１００〜２００
Ω／□）を設けたガラス基板を、ＩＴＯ電極が対向する
ように、スペーサー粒子によってギャップ（約２μｍ）
を設け、張り合わせたセルを作成した。ＩＴＯ電極の片
面にはポリイミド（約６００Å）を塗布し、ラビング処
理を行っている。そのセルに、ナフタレン系液晶（2-4'
-octylphenyl)-6-dodecyloxynaphthalene,Crystal-79.3
℃-SmX1-100.4℃-SmX2-121.3℃-Iso.）に対して発光材
料（3-(2-Benzothiazolyl)-7-(dicthylamino)2H-1-benz
opyran-2-one、株式会社日本感光色素研究所製）を１モ
ル％の割合で混合し、１２５℃の条件下で注入した。液
晶が配向していることを確認しながら、暗所中、上記セ
ルに９０℃、２１０Ｖの直流電界をかけたところ発光色
素の蛍光波長に由来する発光が見られ、偏光子と平行方
向に偏光が確認された。Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 An ITO electrode (surface resistance: 100 to 200) was formed by vacuum film formation.
Ω / □) is placed on the glass substrate with spacer particles so that the ITO electrode faces the gap (about 2 μm).
Was provided to create a bonded cell. One side of the ITO electrode is coated with polyimide (about 600 °) and rubbed. A naphthalene-based liquid crystal (2-4 '
-octylphenyl) -6-dodecyloxynaphthalene, Crystal-79.3
℃ -SmX1-100.4 ℃ -SmX2-121.3 ℃ -Iso.) And the luminescent material (3- (2-Benzothiazolyl) -7- (dicthylamino) 2H-1-benz
opyran-2-one, manufactured by Japan Photographic Dye Laboratories, Inc.) was mixed at a ratio of 1 mol% and injected at 125 ° C. When a DC electric field of 90 ° C. and 210 V was applied to the cell in a dark place while confirming that the liquid crystal was oriented, light emission derived from the fluorescent wavelength of the luminescent dye was observed, and the light was polarized in the direction parallel to the polarizer. Was confirmed.
【００３１】実施例２ 液晶材料として上記ナフタレン系液晶（2-4'-octylphen
yl)-6-dodecyloxynaphthalene,Crystal-79.3℃-SmX1-10
0.4℃-SmX2-121.3℃-Iso.）に対して発光材料（2,3,6,
7,10,11-hexahydro-1H,5H-cyclopenta[3,4][1]benzopyr
ano[6,7,8-ij]quinolizin-12(9H)-one、株式会社日本感
光色素研究所製）を１モル％の割合で混合し、実施例１
と同様にセルを作成し、２５０Ｖの直流電界をかけたと
ころ、発光色素の蛍光波長に由来する発光が見られ、偏
光子と平行方向に偏光が確認された。Example 2 The above-mentioned naphthalene liquid crystal (2-4'-octylphen) was used as a liquid crystal material.
yl) -6-dodecyloxynaphthalene, Crystal-79.3 ℃ -SmX1-10
0.4 ° C-SmX2-121.3 ° C-Iso.) To the luminescent material (2,3,6,
7,10,11-hexahydro-1H, 5H-cyclopenta [3,4] [1] benzopyr
Example 1 was mixed with ano [6,7,8-ij] quinolizin-12 (9H) -one, manufactured by Japan Photographic Dye Laboratories at a ratio of 1 mol%.
A cell was prepared in the same manner as described above, and a DC electric field of 250 V was applied. As a result, light emission derived from the fluorescence wavelength of the luminescent dye was observed, and polarized light was confirmed in the direction parallel to the polarizer.
【００３２】実施例３ 液晶材料として上記ナフタレン系液晶（2-4'-octylphen
yl)-6-dodecyloxynaphthalene,Crystal-79.3℃-SmX1-10
0.4℃-SmX2-121.3℃-Iso.）に対して発光材料（perylen
e)を１モル％の割合で混合し、実施例１と同様にセルを
作成し、２５０Ｖの直流電界をかけたところ、発光色素
の蛍光波長に由来する発光が見られ、偏光子と平行方向
に偏光が確認された。Example 3 The above-mentioned naphthalene-based liquid crystal (2-4'-octylphen) was used as a liquid crystal material.
yl) -6-dodecyloxynaphthalene, Crystal-79.3 ℃ -SmX1-10
0.4 ° C-SmX2-121.3 ° C-Iso.)
e) was mixed at a ratio of 1 mol%, and a cell was prepared in the same manner as in Example 1. When a DC electric field of 250 V was applied, light emission derived from the fluorescence wavelength of the luminescent dye was observed. The polarization was confirmed.
【００３３】実施例４ 液晶材料としてビフェニル系液晶（4-hexyloxy-4'-octa
noylbiphenyl,Crystal-123℃-SmA-142.5℃-Iso.）に対
して発光材料（3-(2-Benzothiazolyl)-7-(dicthylamin
o)2H-1-benzopyran-2-one、株式会社日本感光色素研究
所製）を１モル％の割合で混合し、実施例１と同様にセ
ルを作成し、１００Ｖの直流電界をかけたところ発光色
素の蛍光波長に由来する発光が見られ、偏光子と平行方
向に偏光が確認された。Example 4 A biphenyl liquid crystal (4-hexyloxy-4'-octa) was used as a liquid crystal material.
noylbiphenyl, Crystal-123 ℃ -SmA-142.5 ℃ -Iso.) and luminescent material (3- (2-Benzothiazolyl) -7- (dicthylamin
o) 2H-1-benzopyran-2-one (produced by Japan Photographic Dye Laboratories Co., Ltd.) was mixed at a ratio of 1 mol%, a cell was prepared in the same manner as in Example 1, and a DC electric field of 100 V was applied. Light emission derived from the fluorescence wavelength of the luminescent dye was observed, and polarized light was confirmed in the direction parallel to the polarizer.
【００３４】実施例５ 液晶材料としてビフェニル系液晶（4-hexyloxy-4'-buta
noylbiphenyl,Crystal-109℃-SmE相-116℃-SmA-149.6℃
-Iso.）に対して発光材料（3-(2-Benzothiazolyl)-7-(d
icthylamino)2H-1-benzopyran-2-one、株式会社日本感
光色素研究所製）を１モル％の割合で混合し、実施例１
と同様にセルを作成し、１００Ｖの直流電界をかけたと
ころ発光色素の蛍光波長に由来する発光が見られ、偏光
子と平行方向に偏光が確認された。Example 5 A biphenyl liquid crystal (4-hexyloxy-4'-buta) was used as a liquid crystal material.
noylbiphenyl, Crystal-109 ℃ -SmE phase-116 ℃ -SmA-149.6 ℃
-Iso.) To the luminescent material (3- (2-Benzothiazolyl) -7- (d
icthylamino) 2H-1-benzopyran-2-one (manufactured by Japan Photographic Dye Laboratories Co., Ltd.) at a ratio of 1 mol%.
A cell was prepared in the same manner as described above, and when a DC electric field of 100 V was applied, light emission derived from the fluorescence wavelength of the luminescent dye was observed, and polarized light was confirmed in the direction parallel to the polarizer.
【００３５】実施例６ 液晶材料としてビフェニル系液晶（4-heptyloxy-4'-dod
ecylbiphenyl,Crystal-106℃-SmA-130℃-Iso.）に対し
て発光材料（3-(2-Benzothiazolyl)-7-(dicthylamino)2
H-1-benzopyran-2-one、株式会社日本感光色素研究所
製）を１モル％の割合で混合し、実施例１と同様にセル
を作成し、１０５℃、５０Ｖの直流電界をかけたところ
発光色素の蛍光波長に由来する発光が見られ、偏光子と
平行方向に偏光が確認された。Example 6 A biphenyl liquid crystal (4-heptyloxy-4'-dod) was used as a liquid crystal material.
ecylbiphenyl, Crystal-106 ℃ -SmA-130 ℃ -Iso.) and luminescent material (3- (2-Benzothiazolyl) -7- (dicthylamino) 2
H-1-benzopyran-2-one (manufactured by Japan Photosensitive Dye Laboratories, Inc.) was mixed at a ratio of 1 mol% to prepare a cell in the same manner as in Example 1, and a DC electric field of 105 ° C. and 50 V was applied. However, light emission derived from the fluorescent wavelength of the luminescent dye was observed, and polarized light was confirmed in the direction parallel to the polarizer.
【００３６】実施例７ 液晶材料としてベンゾチアゾール系液晶（2-(4'-heptyl
oxyphenyl)-6-dodecylbenzothiazole、Crystal-90℃-SmA
-100℃-Iso.）を用い、発光材料は使用せずに、実施例
１と同様にセルを作成し、２５０Ｖの直流電界をかけた
ところ液晶に由来する発光が見られ、偏光子と平行方向
に偏光が確認された。Example 7 A benzothiazole liquid crystal (2- (4'-heptyl) was used as a liquid crystal material.
(oxyphenyl) -6-dodecylbenzothiazole, Crystal-90 ℃ -SmA
-100 ° C.-Iso.), Without using a light-emitting material, and forming a cell in the same manner as in Example 1. When a DC electric field of 250 V was applied, light emission derived from the liquid crystal was observed, and the light was parallel to the polarizer. Polarization was confirmed in the direction.
【００３７】実施例８ 液晶材料としてビフェニル系液晶（4-heptyloxy-4'-dod
ecylbiphenyl,Crystal-106℃-SmA-130℃-Iso.）を用
い、発光材料は使用せずに、実施例１と同様にセルを作
成し、１０６℃、５０Ｖの直流電界をかけたところ液晶
に由来する発光が見られ、偏光子と平行方向に偏光が確
認された。Example 8 A biphenyl liquid crystal (4-heptyloxy-4'-dod) was used as a liquid crystal material.
Using ecylbiphenyl, Crystal-106 ° C-SmA-130 ° C-Iso.), without using a light emitting material, a cell was prepared in the same manner as in Example 1, and a DC electric field of 106 ° C and 50 V was applied. Emitted light was observed, and polarized light was confirmed in the direction parallel to the polarizer.
【００３８】[0038]
【発明の効果】以上の如き本発明によれば、液晶性を有
するとともに、電荷輸送性及び蛍光性を有する新規液晶
性化合物が提供される。該新規液晶性化合物は従来の用
途に加えて、電荷輸送性を利用した光センサ、エレクト
ロルミネッセンス素子、光導電体、空間変調素子、薄膜
トランジスター、その他のセンサー等の材料として有用
である。特に本発明の液晶性化合物は、エレクトロルミ
ネッセンス素子の材料として使用した場合、蛍光材料を
導入することによる電荷輸送性の低下、液晶性の変化を
防いで、偏光性を有する発光を容易に得ることができ
る。According to the present invention as described above, a novel liquid crystalline compound having a liquid crystallinity, a charge transporting property and a fluorescent property is provided. The novel liquid crystalline compounds are useful as materials for photosensors utilizing charge transport properties, electroluminescent elements, photoconductors, spatial modulation elements, thin film transistors, other sensors, and the like, in addition to conventional uses. In particular, when the liquid crystal compound of the present invention is used as a material for an electroluminescence device, it is possible to easily obtain a light emission having a polarization property by preventing a decrease in charge transport property and a change in liquid crystal property by introducing a fluorescent material. Can be.
【図１】 エレクトロルミネッセンス素子の模式図FIG. 1 is a schematic diagram of an electroluminescence device.
【図２】 エレクトロルミネッセンス素子の模式図（電
極パターン例）FIG. 2 is a schematic view of an electroluminescence element (example of an electrode pattern).
【図３】 エレクトロルミネッセンス素子の模式図FIG. 3 is a schematic diagram of an electroluminescence element.
【図４】 エレクトロルミネッセンス素子の模式図FIG. 4 is a schematic diagram of an electroluminescent element.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｇ０３Ｇ 5/06 ３１１ Ｇ０３Ｇ 5/06 ３１１ ──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. 6 Identification code FI // G03G 5/06 311 G03G 5/06 311
Claims (9)
性を有する液晶材料又は電荷輸送性を有する液晶材料と
蛍光性材料とからなり、エレクトロルミネッセンス発光
が偏光性を有することを特徴とする液晶性電荷輸送材
料。1. A liquid crystal comprising at least a fluorescent material and a liquid crystal material having a charge transporting property, or a liquid crystal material having a charge transporting property and a fluorescent material, wherein the electroluminescence emission has a polarizing property. Charge transport material.
に記載の材料。2. The charge transport material is a rod-like molecule.
The material described in the above.
む高分子材料。3. A polymer material containing the liquid crystalline material according to claim 1.
請求項３に記載の高分子材料。4. The polymer material according to claim 3, wherein a liquid crystalline material is contained in a main chain and / or a side chain.
系芳香環）ｍ又は（１４π電子系芳香環）ｎ（ｌ＋ｍ＋
ｎ＝１〜４、ｌ、ｍ、ｎは夫々０〜４の整数を表す）を
少なくともコアの一部に有する請求項１又は２に記載の
液晶性電荷輸送材料。5. (6π-electron aromatic ring) l, (10π-electron aromatic ring) m or (14π-electron aromatic ring) n (l + m +
3. The liquid crystalline charge transport material according to claim 1, wherein n = 1 to 4, 1, m, and n each represent an integer of 0 to 4) in at least a part of the core.
又は１４π電子系芳香環がそれぞれ又は相互に炭素−炭
素二重結合又は炭素−炭素三重結合を有する連結基で連
結されている請求項５に記載の液晶性電荷輸送材料。6. The 6π-electron aromatic ring, the 10π-electron aromatic ring, or the 14π-electron aromatic ring are connected to each other or to each other by a linking group having a carbon-carbon double bond or a carbon-carbon triple bond. 6. The liquid crystalline charge transport material according to 5.
１種を駆動経路に有することを特徴とするエレクトロル
ミネッセンス素子。7. An electroluminescent device comprising at least one of the materials according to claim 1 in a drive path.
記載の材料の少なくとも１種からなることを特徴とする
エレクトロルミネッセンス素子。8. An electroluminescent device, wherein the charge transport portion and the light emitting portion are made of at least one of the materials according to claim 1.
１種を駆動経路に有し、且つ電荷輸送部と発光部とが単
層構造であることを特徴とするエレクトロルミネッセン
ス素子。9. An electroluminescent device having at least one of the materials according to claim 1 in a drive path, and wherein the charge transport portion and the light emitting portion have a single-layer structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10218148A JPH11241069A (en) | 1997-12-22 | 1998-07-31 | Liquid crystalline charge transport material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-352847 | 1997-12-22 | ||
| JP35284797 | 1997-12-22 | ||
| JP10218148A JPH11241069A (en) | 1997-12-22 | 1998-07-31 | Liquid crystalline charge transport material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11241069A true JPH11241069A (en) | 1999-09-07 |
Family
ID=26522419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10218148A Pending JPH11241069A (en) | 1997-12-22 | 1998-07-31 | Liquid crystalline charge transport material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11241069A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002164177A (en) * | 1999-11-29 | 2002-06-07 | Canon Inc | Liquid crystal element |
| JP2002169154A (en) * | 2000-12-04 | 2002-06-14 | Sony Corp | Liquid crystal display |
| KR100495700B1 (en) * | 2002-08-30 | 2005-06-14 | 최종선 | Fabricating Process of Polarized Organic Electroluminescent Devices |
| JP2005258178A (en) * | 2004-03-12 | 2005-09-22 | Seiko Epson Corp | Display element and electronic equipment |
| US8879024B2 (en) | 2008-09-10 | 2014-11-04 | Merck Patent Gmbh | Liquid crystal display with a fluorescent backlight emitting polarised light |
| KR20200057713A (en) | 2017-09-20 | 2020-05-26 | 니폰 가야꾸 가부시끼가이샤 | Optical system and display |
-
1998
- 1998-07-31 JP JP10218148A patent/JPH11241069A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002164177A (en) * | 1999-11-29 | 2002-06-07 | Canon Inc | Liquid crystal element |
| JP4717198B2 (en) * | 1999-11-29 | 2011-07-06 | キヤノン株式会社 | Organic electroluminescence device |
| JP2002169154A (en) * | 2000-12-04 | 2002-06-14 | Sony Corp | Liquid crystal display |
| KR100495700B1 (en) * | 2002-08-30 | 2005-06-14 | 최종선 | Fabricating Process of Polarized Organic Electroluminescent Devices |
| JP2005258178A (en) * | 2004-03-12 | 2005-09-22 | Seiko Epson Corp | Display element and electronic equipment |
| US8879024B2 (en) | 2008-09-10 | 2014-11-04 | Merck Patent Gmbh | Liquid crystal display with a fluorescent backlight emitting polarised light |
| KR20200057713A (en) | 2017-09-20 | 2020-05-26 | 니폰 가야꾸 가부시끼가이샤 | Optical system and display |
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