Disclosed is a practical, organic, blue-emitting EL device having a long life and having high luminous efficiency and good thermal stability. The device comprises organic compound layers, of which at least one is an organic blue-emitting layer, as sandwiched between a pair of electrodes, and is characterized in that the organic blue-emitting layer comprises an organic host compound having a fluorescence quantum efficiency of not smaller than 0.3 in a solid state and a fluorescent substance, and the organic host compound and the fluorescent substance are selected such that the device retains a monomeric blue-emitting ability, and that all the organic compound layers have a glass transition temperature of not lower than 75xc2x0 C., while the organic compound layers adjacent to the organic blue-emitting layer have a glass transition temperature of not lower than 105xc2x0 C.

The present invention relates to an organic electroluminescent (EL) device, and more precisely, to a blue-emitting, organic EL device having a long life and having high luminous efficiency and good thermal stability.
As being self-luminescent, EL devices have high visibility. In addition, they have high impact resistance as being completely solid devices. Therefore, the use of EL devices in various displays as light emitters is being widely noticed.
EL devices are grouped into inorganic EL devices in which are used inorganic compounds as light-emitting materials, and organic EL devices in which are used light-emitting organic compounds. Of those, organic EL devices have been being much studied and expected as light emitters in the coming generations, since they require a greatly reduced level of voltage, they can be easily small-sized, they consume small electric power, they can emit light in a mode of plane emission, and they can easily emit three primary colors.
Known are various structures of organic EL devices having a basic constitution of positive electrode/organic light-emitting layer/negative electrode and optionally provided with a hole injection and transportation layer and an electron injection layer, such as positive electrode/hole transportation layer/organic light-emitting layer/negative electrode, and positive electrode/hole transportation layer/organic light-emitting layer/electron injection layer/negative electrode, etc.
For such organic EL devices, for example, metal complexes of phenolato-substituted 8-hydroxyquinolines have been disclosed as blue-emitting materials (see Japanese Patent Application Laid-Open No. 5-198378). However, these are problematic in that their luminous efficiency is low to be at most 0.2 lumen(lm)/W or so. The reason is because the fluorescence quantum efficiency of the host compounds is low to be at most 0.07 or so. Doping of fluorescent substances into the host compounds is effective in prolonging the life of the doped host compounds, but is not in improving their luminous efficiency.
As luminous materials (host materials) for organic EL devices capable of emitting blue at high efficiency, distyrylarylene compounds have been disclosed (see Japanese Patent Application Laid-Open No. 2-247278). In addition, it has been disclosed that the doping of organic host compounds with fluorescent substances produces the improvement in the luminous efficiency of the doped organic host compounds while prolonging their life (see International Patent Application Laid-Open No. 94/06157).
Many of those blue-emitting compounds generally have a low glass transition temperature (Tg), since xcfx80-electrons are distributed in narrow regions therein and since they have a low molecular weight. Therefore, organic EL devices comprising those compounds are problematic in that their thermal stability is poor. Organic EL devices for outdoor applications or applications in vehicles require high-temperature storage stability generally at 75xc2x0 C. or so. However, conventional organic EL devices are problematic in those applications in that, when they are kept at high temperatures of 75xc2x0 C. or so, the color to be emitted by them varies and their luminous efficiency is lowered. For these reasons, the applications of organic EL devices are inevitably limited.
Given that situation, various studies have been made in order to improve the thermal stability of organic EL devices. One example is to modify luminous materials to have dimer or oligomer structures, thereby making the materials have an elevated glass transition temperature. For this, referred to is Japanese Patent Application Laid-Open No. 8-12600, which discloses compounds (phenylanthracene derivatives) having a glass transition temperature of 181xc2x0 C. In this publication, they tried to improve the efficiency of their devices and to prolong the life thereof by mixing the hole transportation layer and the light-emitting layer. However, the devices disclosed have a luminous efficiency of at most 0.6 lm/W, which is lower than 1 lm/W, and the capacity of the devices is not satisfactory.
As has been mentioned hereinabove, no blue-emitting, organic EL devices having a long life, high efficiency and good thermal stability, which are all indispensable in their practical use, is unknown.
Given this situation, the object of the invention is to provide a practical, blue-emitting, organic EL device having a long life and having high luminous efficiency and good thermal stability.
We, the present inventors have assiduously studied in order to obtain an organic EL device having those favorable properties, and, as a result, have found that an organic EL device, in which the organic blue-emitting layer comprises an organic host compound having a specific fluorescence quantum efficiency and a fluorescent substance, and the organic host compound and the fluorescent substance are selected such that the device retains a monomeric blue-emitting ability, and in which the organic compound layers constituting the device have a specific glass transition temperature, meets the requirements. The invention has been attained on the basis of these findings.
Specifically, the invention provides an organic EL device comprising organic compound layers, of which at least one is an organic blue-emitting layer, as sandwiched between a pair of electrodes, which is characterized in that (1) the organic blue-emitting layer comprises an organic host compound having a fluorescence quantum efficiency of not smaller than 0.3 in a solid state, and a fluorescent substance, and the organic host compound and the fluorescent substance are selected such that the device retains a monomeric blue-emitting ability, and (2) all the organic compound layers have a glass transition temperature of not lower than 75xc2x0 C., while the organic compound layers adjacent to the organic blue-emitting layer have a glass transition temperature of not lower than 105xc2x0 C.
The organic EL device of the invention has an organic blue-emitting layer comprising an organic host compound and a fluorescent substance.
The organic host compound which is one component constituting the organic blue-emitting layer is not specifically defined, provided that its function is such that holes and electrons are injected thereinto and are transported therethrough to be recombined together to give off fluorescence, that its fluorescence quantum efficiency is not smaller than 0.3, and that it forms, along with the fluorescent substance, the organic blue-emitting layer having a glass transition temperature of not lower than 75xc2x0 C. Therefore, various compounds are employable herein.
For example, the organic host compound may be selected from distyrylarylene derivatives of a general formula (I):
In formula (I), k, m and n each are 0 or 1, and (k+m+n)xe2x89xa71. In the formula, R1 to R12 each independently represent a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an aryloxy group having from 6 to 18 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group, a halogen atom, or a group of:
The alkyl group having from 1 to 6 carbon atoms includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl group, a neopentyl group, an n-hexyl group, and an i-hexyl group. The alkoxy group having from 1 to 6 carbon atoms includes, for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butyloxy group, an i-butyloxy group, a sec-butyloxy group, an i-pentyloxy group, a t-pentyloxy group, and an n-hexyloxy group. The aryloxy group having from 6 to 18 carbon atoms includes, for example, a phenoxy group, and a naphthyloxy group. The aryl group having from 6 to 20 carbon atoms includes, for example, a phenyl group, and a naphthyl group. The amino group is represented by xe2x80x94NH2; the alkylamino group is by xe2x80x94NHR or xe2x80x94NR2 (where R indicates an alkyl group having from 1 to 6 carbon atoms); and the arylamino group is by xe2x80x94NHAr or xe2x80x94NAr2 (where Ar indicates an aryl group having from 6 to 20 carbon atoms).
The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Where k=1 and m=n=0 in formula (I), the substituents in at least one combination of R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10, and R11 and R12 are bonded to each other to form a saturated or unsaturated, 5-membered or 6-membered ring. In that case, the substituents maybe bonded via a hetero atom (N, O, S) to form the ring. As specific examples where R1 and R2, R9 and R10, and R5 and R6 each are bonded to each other to form an unsaturated 6-membered ring, mentioned are compounds of the following formula:
As specific examples where R7 and R8 are bonded to each other via a hetero atom O to form a saturated 5-membered ring, R11 and R12 are bonded to each other via a hetero atom N to form a saturated 5-membered ring, and R3 and R4, and R9 and R10 each are bonded to each other to form a saturated 6-membered ring, mentioned are compounds of the following formula:
Where k=m=1 and n=0 in formula (I), the compounds are represented by the following formula:
wherein R3xe2x80x2, R4xe2x80x2, R9xe2x80x2 and R10xe2x80x2 each independently represent a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an aryloxy group having from 6 to 18 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group, a halogen atom, or a group of:
and R1 to R12 have the same meanings as above.
In those, R1 and R2, R3 and R4, R3xe2x80x2 and R4xe2x80x2, R5 and R6, R7 and R8, R9 and R10, R9xe2x80x2 and R10xe2x80x2, and R11 and R12 each may be or may not be bonded to each other to form a saturated or unsaturated, 5-membered or 6-membered ring. Optionally, they may be bonded to each other via a hetero atom (N, O, S) to form the ring.
R2 and R3, R4 and R3xe2x80x2, R4xe2x80x2 and R5, R8 and R9, R10 and R9xe2x80x2, and R10xe2x80x2 and R11 each may be or may not be bonded to each other to form a saturated or unsaturated, 5-membered or 6-membered ring. Optionally, they may be bonded to each other via a hetero atom (N, O, S) to form the ring.
As specific examples where R2 and R3, R10 and R9xe2x80x2, and R4xe2x80x2 and R5 each are bonded to each other to form a saturated 5-membered ring, mentioned are compounds of the following formula:
As those where R4 and R3xe2x80x2, and R10 and R9xe2x80x2 each are bonded to each other to form a saturated 6-membered ring, mentioned are compounds of the following formula:
As those where R10 is a group of:
and R9xe2x80x2 is a hydrogen atom to give a 5-membered ring, mentioned are compounds of the following formula:
Where k=m=n=1 in formula (I), the compounds are represented by the following formula:
wherein R3xe2x80x3, R4xe2x80x3, R9xe2x80x3 and R10xe2x80x3 each independently represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an aryloxy group having f rom 6 to 18 carbon atoms, an aryl group having f rom 6 to 20 carbon atoms, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group, a halogen atom, or a group of:
and R1 to R12, R3xe2x80x2, R4xe2x80x2, R9xe2x80x2 and R10xe2x80x2 have the same meanings as above.
In those, R1 and R2, R3 and R4, R3xe2x80x2 and R4xe2x80x2, R3xe2x80x3 and R4xe2x80x3, R5 and R6, R7 and R8, R9 and R10, R9xe2x80x2 and R10xe2x80x2, R9xe2x80x3 and R10xe2x80x3, and R11 and R12 each may be or may not be bonded to each other to form a saturated or unsaturated, 5-membered or 6-membered ring. Optionally, they may be bonded to each other via a hetero atom (N, O, S) to form the ring.
R2 and R3, R4 and R3xe2x80x2, R4xe2x80x2 and R3xe2x80x3, R4xe2x80x3 and R5, R8 and R9, R10 and R9xe2x80x2, R10xe2x80x2 and R9xe2x80x3, and R10xe2x80x3 and R11 each may be or may not be bonded to each other to form a saturated or unsaturated, 5-membered or 6-membered ring. Optionally, they may be bonded to each other via a hetero atom (N, O, S) to form the ring.
As specific examples where R8, R9, R10xe2x80x3 and R11 each are a group of:
to form an unsaturated 5-membered ring, and R3xe2x80x2 and R4xe2x80x2 together form a saturated 5-membered ring via a hetero atom N, mentioned are compounds of the following formula:
X and Y each independently represent an aryl group having from 6 to 20 carbon atoms, such as a substituted or unsubstituted phenyl, naphthyl, biphenyl, terphenyl, anthraryl, phenathryl, pyrenyl or perylenyl group.
The substituent includes, for example, an alkyl group having from 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl group, a neopentyl group, an n-hexyl group, an i-hexyl group; an alkoxy group having from 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butyloxy group, an i-butyloxy group, a sec-butyloxy group, an i-pentyloxy group, a t-pentyloxy group, an n-hexyloxy group; an aryloxy group having from 6 to 18 carbon atoms, such as a phenoxy group, a naphthyloxy group; a phenyl group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a hydroxyl group; and a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom. The group of X and Y may be substituted with one or more of those substituents.
X and Y and optionally their substituents may be bonded together to form a substituted or unsubstituted, saturated 5-membered, or saturated 6-membered ring. As specific examples of the styryl compounds where X and Y form a saturated, 5-membered or 6-membered ring, mentioned are the following compounds where X and Y form a saturated 5-membered ring, k=m=1 and n=0:
As those where X and Y form a saturated 6-membered ring, mentioned are the following compounds:
In the invention, the organic blue-emitting layer must indispensably have a glass transition temperature of not lower than 75xc2x0 C. Therefore, the organic host compounds to be in the layer are preferably selected from those of the following general formula (II) in which the central polyphenylene skeletons are all bonded to the adjacent ones at their para-positions:
wherein R1 to R12, R3xe2x80x2, R4xe2x80x2, R9xe2x80x2, R10xe2x80x2, R3xe2x80x3, R4xe2x80x3, R9xe2x80x3, R10xe2x80x3, X, Y, k, m and n have the same meanings as above.
The styryl compounds of formula (I) can be produced by various known methods. For producing these, for example, mentioned are the following three methods.
Method 1
A phosphonate of a general formula (a):
wherein k, m and n each are 0 or 1, and (k+m+n)xe2x89xa71;
R1 to R12, R3xe2x80x2, R4xe2x80x2, R9xe2x80x2, R10xe2x80x2, R31xe2x80x3, R4xe2x80x3, R9xe2x80x3 and R10xe2x80x3 have the same meanings as above; and R represents an alkyl group having from 1 to 4 carbon atoms, or a phenyl group,
is condensed with a carbonyl group of a general formula (b):
wherein X and Y have the same meanings as above, in the presence of a base through Wittig reaction or Wittig-Horner reaction to give styryl compounds of formula (I).
Method 2
A dialdehyde compound of a general formula (c):
wherein k, m and n each are 0 or 1, and (k+m+n)xe2x89xa71;
and R1 to R12, R3xe2x80x2, R4xe2x80x2, R9xe2x80x2, R10xe2x80x2, R31xe2x80x3, R4xe2x80x3, R9xe2x80x3 and R10xe2x80x3 have the same meanings as above,
is condensed with a phosphonate of a general formula (d):
wherein R, X and Y have the same meanings as above, in the presence of a base through Wittig reaction or Wittig-Horner reaction to give styryl compounds of formula (I).
As the reaction solvent for that condensation, preferred are hydrocarbons, alcohols, and ethers. Specific examples of the solvent are methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, dioxane, tetrahydrofuran(THF), toluene, and xylene. Also preferably employed are dimethylsulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Especially preferred are tetrahydrofuran and dimethylsulfoxide.
As the condensing agent, preferred are sodium hydroxide, potassium hydroxide, sodium amide, sodium hydride, n-butyl lithium, and even alcoholates such as sodium methylate, potassium t-butoxide, etc. Especially preferred are n-butyl lithium and potassium t-butoxide.
The reaction temperature varies, depending on the starting compounds to be reacted, and therefore cannot be defined indiscriminately. In general, however, it may be widely from 0xc2x0 C. to about 100xc2x0 C. Especially preferably, the reaction temperature falls between 0xc2x0 C. and room temperature.
Method 3
A bromide of a general formula (e):
wherein X, Y, R1, R2, R7, R8, and also R5, R6, R11 and R12 have the same meanings as above,
is reacted with Mg to give a Grignard reagent, which is coupled with a dibromoarylene compound of a general formula (f):
wherein k, m and n each are 0 or 1, and (k+m+n)xe2x89xa71;
and R3, R4, R9, R10, R3xe2x80x2, R4xe2x80x2, R9xe2x80x2, R10xe2x80x2, R3xe2x80x3, R4xe2x80x3, R9xe2x80x3 and R10xe2x80x3 have the same meanings as above,
in the presence of a metal catalyst to give styryl compounds of formula (I).
As the metal catalyst for the coupling, employable is a transition metal complex catalyst. Preferred are nickel catalysts and palladium catalysts, which include, for example, NiCl2 (dppp) (Tokyo Kasei), [NiCl2(PPh3)2], and also PdCl2 (dppf), and Pd(PPh3)4.
As the reaction solvent, employable is any of dewatered diethyl ether, THF, di-n-propyl ether, di-n-butyl ether, di-i-propyl ether, diethylene glycol dimethyl ether (diglyme), dioxane, dimethoxyethane (DME), etc.
Preferred are diethyl ether and THF.
Specific examples (1) to (61) of the styryl compounds for use in the invention are mentioned below, which, however, are not intended to restrict the scope of the invention.
In the invention, one or more of those organic host compounds may be used either singly or as combined.
The fluorescent substance which is the other component constituting the organic blue-emitting layer is doped into the organic light-emitting layer in order to improve the efficiency of the organic EL device and to prolong the life thereof. The fluorescent substance is not specifically defined, provided that it can emit light in response to the recombination of holes and electrons, and may be any known fluorescent dye. However, it is important that the fluorescent substance is so selected that its energy gap is smaller than the energy gap of the organic host compound. The fluorescent substance includes, for example, stilbene derivatives, tristyrylarylene derivatives, and distyrylarylene derivatives (see Japanese Patent Application Laid-Open No. 5-129438). In the invention, one or more such fluorescent substances can be used either singly or as combined.
The organic host compound and the fluorescent substance are suitably selected and combined to give the organic blue-emitting layer, in which the efficient energy transfer from the organic host compound to the fluorescent substance is realized to attain the improvement in the efficiency of the organic EL device and the prolongation of the life thereof. In that preferred case, it has been found that the profile of the EL spectrum quite agrees with that of the fluorescence spectrum of the fluorescent substance within a range of xc2x110 nm with respect to the fluorescence peak wavelengths and the individual peak wavelengths of the vibronic structure. The fluorescence spectrum of the fluorescent substance is measured in a solution of the fluorescent substance as dissolved in a non-polar solvent such as toluene. When the profile of the EL spectrum quite agrees with that of the fluorescence spectrum of the fluorescent substance, it is herein referred that the EL device has xe2x80x9cmonomeric light-emitting abilityxe2x80x9d.
In the organic EL device of the invention having the monomeric light-emitting ability, it is meant that the initial state of EL corresponds to the excited monomeric state of the fluorescent substance in the organic light-emitting layer.
In order to improve the luminous efficiency of the organic EL device, it is effective to increase the fluorescence quantum efficiency of the organic host compound in the device. In the invention, therefore, that quantum efficiency must be not smaller than 0.3. The fluorescence quantum efficiency of the organic host compound is measured in a thin film of the substance, and is different from that as measured in its solution.
The organic EL device of the invention must retain a monomeric blue-emitting ability. Therefore, the organic host compound and the fluorescent substance are selected such that the interaction between the organic host compound and the fluorescent substance is absent and the interaction between the organic host compound and the adjacent compound layers is absent. As for blue-emitting organic host compounds, the interaction between the organic host compound and the fluorescent substance existing in the emitting layer and the interaction between the organic host compound and the adjacent organic compound layers are often large in many cases, in those cases the state having energy smaller than the energy of an excited state of the fluorescent substance is formed (an exciplex) . As a result, in those cases, the energy of the excited state of the fluorescent substance is transferred to the state having smaller energy, whereby the EL device gives a broad emission spectrum which, being different from the fluorescence spectrum of the monomeric emission from the fluorescent substance, has peaks at longer wavelengths. Even if the EL devices of those cases could produce monomeric emission in the initial stage of their driving, the light as emitted by them will often become different from monomeric one while the devices are continuously driven for long. Such EL devices that could not retain the ability of monomeric emission shall have an extremely short life.
Therefore, in the organic EL device of the invention, it is extremely important to select the combination of the organic host compound and the fluorescent substance so that the device can retain the ability of monomeric emission.
In addition, all the organic compound layers constituting the organic EL device of the invention must have a glass transition temperature of not lower than 75xc2x0 C., in order to make the device have good heat resistance. Moreover, in order to further improve the storage stability of the device at 75xc2x0 C., the stability of the interfaces between the organic light-emitting layer and the adjacent organic compound layers is an important factor. Therefore, the organic compound layers adjacent to the organic light-emitting layer must have a glass transition temperature of not lower than 105xc2x0 C. If satisfying those requirements, the organic EL device is free from the change in the color to be emitted by it and from the reduction in the efficiency of the device, while maintaining its good properties for long, even though stored in a high-temperature atmosphere at 75xc2x0 C.
The layer constitution of the organic EL device of the invention is not specifically defined, and may be any desired one. Basically, however, the organic blue-emitting layer is sandwiched between a pair of electrodes (positive electrode and negative electrode), in which are optionally provided a hole injection and transportation layer and an electron injection layer. Those are formed on a transparent substrate, through which the light emitted is seen. Examples of the organic EL device having that layer constitution are mentioned below.
(1) Positive electrode/organic light-emitting layer/negative electrode
(2) Positive electrode/hole injection layer/organic light-emitting layer/negative electrode
(3) Positive electrode/organic light-emitting layer/electron injection layer/negative electrode
(4) Positive electrode/hole injection layer/organic light-emitting layer/electron injection layer/negative electrode
(5) Positive electrode/hole injection layer/hole transportation layer/organic light-emitting layer/electron injection layer/negative electrode
In these structures, the organic compound layers such as the hole injection layer, the hole transportation layers and the electron injection layer are not specifically defined, provided that they satisfy the requirements for their glass transition temperature.
The organic EL device of the invention is optionally provided with a hole injection and transportation layer, which functions to inject holes thereinto from the positive electrode and to transport them into the light-emitting layer. Preferably, the hole injection and transportation layer has a hole mobility of not smaller than 10xe2x88x926 cm2/Vxc2x7s in an electric field of from 104 to 106 V/cm. If desired, the organic EL device may be provided with a laminate of a hole injection layer and a hole transportation layer.
The material to be in the hole injection and transportation layer may be selected from, for example, compounds of a general formula (III):
In formula (III), Q1 and Q2 each represent a group having a nitrogen atom and at least three carbon rings (of which at least one is an aromatic ring such as a phenyl group), and these maybe the same or different; G represents a cycloalkylene group, an arylene group, or a linking group comprising a carbon-carbon bond.
In the organic EL device of the invention, the hole injection layer and the hole transportation layer that are directly adjacent to the organic light-emitting layer must have a glass transition temperature of not lower than 105xc2x0 C. Therefore, the materials of those layers are preferably selected from oligomer amines of the compounds of formula (III) comprising three or more arylamines as bonded in a linear or branched manner.
The compounds of that type are, for example, represented by the following general formula (IV):
wherein R13 to R17 each represent an alkyl group, an alkoxy group or a phenyl group, and may be the same or different, the phenyl substituent being optionally condensed with the group on which it is substituted to give a naphthyl group.
Specific examples of the compounds are mentioned below.
The layers may comprise one or more of those compounds either singly or as combined.
The organic EL device of the present invention is optionally provided with an electron injection layer (electron injection and transportation layer), which functions to transfer the electrons as injected thereinto from the negative electrode to the organic light-emitting layer, and may comprise any known conventional electron-transmitting compound. For example, the material to be in the layer is preferably selected from metal complexes of 8-hydroxyquinoline or its derivatives, or oxadiazole derivatives.
As examples of metal complexes of 8-hydroxyquinoline or its derivatives, mentioned are metal chelate oxanoid compounds containing chelates of oxine (generally, 8-quinolinol or 8-hydroxyquinoline), etc. Compounds of that type all have a glass transition temperature of not lower than 105xc2x0 C.
The electron injection layer may comprise one or more of those compounds either singly or as combined.
Preferably, the organic EL device of the invention having the constitution mentioned above is supported by a substrate, and the substrate in this use is not specifically defined. Any ordinary substrate for conventional organic EL devices is employable herein. For example, employed is any of glass or transparent plastics.
The positive electrode constituting the organic EL device of the invention is to inject holes into the device. For this, preferred are electrode materials having a large work function (not smaller than 4 eV), such as metals, alloys, electroconductive compounds and their mixtures. Specific examples of such preferred electrode materials are metals such as Au, and electroconductive transparent materials such as CuI, ITO (indium tin oxide), SnO2, ZnO, etc. The positive electrode can be formed, for example, through vacuum vapor deposition or sputtering of such an electrode material to give a thin film. For light emission through the electrode, it is preferred that the electrode has a transmittance, relative to the light emitted, of not smaller than 10%, and that the sheet resistance of the electrode is not larger than hundreds of ohms per square (xcexa9/xe2x96xa1).
The thickness of the electrode film may be generally between 10 nm and 1 xcexcm, preferably between 50 and 200 nm, depending on the material of the electrode.
The negative electrode constituting the organic EL device of the invention is to inject electrons into the device. For this, preferred are electrode materials having a small work function (not larger than 4 eV), such as metals, alloys, electroconductive compounds and their mixtures. Specific examples of such preferred electrode materials are sodium, sodium/potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver alloys, aluminium/lithium alloys, Al/Al2O3 mixtures, indium, rare earth metals, etc. The negative electrode can be formed, for example, through vacuum vapor deposition or sputtering of such an electrode material to give a thin film. For light emission through the electrode, it is preferred that the electrode has a transmittance, relative to the light emitted, of not smaller than 10%, and that the sheet resistance of the electrode is not larger than hundreds of ohms per square (xcexa9/xe2x96xa1). The thickness of the electrode film may be generally between 10 nm and 1 xcexcm, preferably between 50 and 200 nm, depending on the material of the electrode.
Now, preferred embodiments of producing the organic EL device of the invention are referred to hereinunder. First, a thin film of a desired electrode material, for example, a positive electrode material is formed on a suitable substrate through vapor deposition or sputtering to have a thickness of from 50 to 200 nm. This is formed a positive electrode on the substrate. Next, thin films of a hole injection layer, a hole transportation layer, an organic blue-emitting layer, and an electron injection layer are formed on the positive electrode.
To form those thin films, for example, employable is any of spin-coating, casting or vapor deposition. Preferred is vacuum vapor deposition, through which uniform films with few pin holes are easy to obtain. For the vapor deposition to form those thin films, the condition varies, depending on the type of the compound to be vaporized for the deposition, and the intended crystal structure and association structure of the molecular film to be deposited, but is preferably such that the boat heating temperature falls between 50 and 400xc2x0 C., the vacuum degree falls between 10xe2x88x926 and 10xe2x88x923 Pa, the deposition rate falls between 0.01 and 50 nm/sec, the substrate temperature falls between xe2x88x9250 and 300xc2x0 C., and the film thickness falls between 5 nm and 5 xcexcm.
After the formation of those layers, a thin film of a negative electrode material is formed thereover, for example, through vapor deposition or sputtering to be a negative electrode having a film thickness of from 10 nm to 1 xcexcm, preferably from 50 to 200 nm. Thus is produced the intended organic EL device. To produce the device, the order of forming the electrodes and the layers may be reversed.
Where a direct current voltage is applied to the organic EL device thus produced in that manner, a voltage of from 3 to 40 V or so may be applied thereto with its positive electrode being charged to be plus (+) and its negative electrode to be minus (xe2x88x92), whereby the device emits blue. Even if the same voltage is applied to the device in the reversed manner relative to the polarity of the electrodes, the device emits no light. Where an alternating current is applied to the device, the device emits light only when its positive electrode is charged to be plus (+) and its negative electrode to be minus (xe2x88x92). The wave mode of the alternating current to be applied to the device may be any desired one.
Now, the invention is described in more detail with reference to the following Examples, which, however, are not intended to restrict the scope of the invention.


In each horizontal period, by switching ON switches respectively provided for three data signal lines for R, G and B in a group at the same time only in a predetermined period, the data signal lines in the group are preliminary charged to a predetermined potential at the same time before a data signal supply period. In a subsequent data signal supply period, respective switches of data signal lines for R, G and B are switched ON sequentially, to sequentially supply respective data for R, G and B to pixels on a scanning signal line as selected are supplied via data signal lines. As a result, in a display device driven by time-division based on a group of sequentially provided data signal lines, it is possible to suppress up-throw potential fluctuations when display.

Known methods of driving a display device provided with a pixel section in which a plurality of pixels are arranged two-dimensionally in a matrix form at respective intersections between a plurality of scanning signal lines and a plurality of data signal lines include the SSD (Source Shared Driving) method. In this driving method, a plurality of data signal lines in a group are driven by a common data output circuit. For example, data signal lines for R, G and B are provided respectively, and the data signal lines for R, G and B which form a set of colors in each group are driven by a data output circuit in a data signal line driving circuit provided in each group in common among R, G and B. By this data output circuit, data is output to data signal lines for R, G and B in this order for each group. Here, in order to ensure the time for writing data signals from each data signal line to a pixel while increasing the driving speed, the data signal lines in the same color of respective groups are driven at the same time. According to the foregoing driving method, to meet a demand for higher resolution of a display device in which a large number of data signal lines are closely packed together, it is possible to reduce a size of the data signal line driving circuit without reducing the driving speed.
FIG. 9 illustrates an example structure of a display panel 1 of the liquid crystal display device adopting the SSD method. This display panel 1 is driven by a scanning signal line driving circuit (not shown) and a data signal line driving circuit 17, and includes a plurality of scanning signal lines GL and a plurality of data signal lines (source bus lines) RSL, GSL and BSL arranged in a matrix form. In FIG. 9, the scanning signal lines GL are designated as GL1, GL2 and GLn in this order from the side of the data signal line driving circuit 17 (from the top of the sheet of FIG. 9). A plurality of data signal lines are divided into groups of data signal lines RSL, GSL and BSL, some of the groups of the data signal lines are shown in FIG. 9 and indicated from the left end, as data signal lines RSLn−1, GSLn−1 and BSLn−1 in the n−1th group, data signal lines RSLn, GSLn and BSLn in the nth group, and data signal lines RSLn+1, GSLn+1 and BSLn+1 in the n+1th group.
Pixels PIX are provided at respective intersections between the scanning signal lines GL and the data signal lines RSL, GSL and BSL two-dimensionally to form a pixel section 11. Each pixel PIX includes a TFT 12, a liquid crystal capacitance 13 and an auxiliary capacitance 14, and the liquid crystal capacitance 13 and the auxiliary capacitance 14 are connected to the data signal line RSL, GSL or BSL via the TFT 12. The gate of each TFT 12 is connected to the scanning signal line GL. Incidentally, the electrode on the side of the TFT 12 of the liquid crystal capacitance 13 serves as a common electrode. Furthermore, the electrode of the auxiliary capacitance 14 facing the electrode of the TFT 12 is connected to an auxiliary capacitance line CsL.
The respective ends of the data signal lines RSL, GSL, BSL on the side of the data signal line driving circuit 17 (on the upstream side in the direction of supplying data signal) are connected to analog switches ASW. As shown in FIG. 9, analog switches ASWRn−1 , ASWGn−1 and ASWBn−1 are provided corresponding to RSLn−1, GSLn−1 and BSLn−1, analog switches ASWRn, ASWGn and ASWBn are provided corresponding to data signal lines RSLn, GSLn and BSLn, and analog switches ASWBn+1 are provided corresponding to data signal lines RSLn+1, GSLn+1 and BSLn+1.
The analog switch ASWR connected to the data signal line RSL for R is switched ON/OFF by a switching signal Ron, the analog switch ASWG connected to the data signal line GSL for G is switched ON/OFF by a switching signal Gon, and the analog switch ASWB connected to the data signal line BSL for B is switched ON/OFF by a switching signal Bon. A control circuit 18 is provided for outputting these switching signals Ron, Gon and Bon.
Here, respective terminals of the analog switches ASWR, ASWG and ASWB in the same group of data signal lines on the opposite side of the data signal lines (on the upstream side in the direction of supplying a data signal) are mutually connected by a common wiring 15. In FIG. 9, the corresponding group numbers are given as subscripts to the common wirings 15. These common wirings 15 are connected to respective data output circuits DOAn−1, DOAn and DOAn+1 provided for each group in the data signal line driving circuit 17. Namely, each of these data output circuits DOAn−1, DOAn and DOAn+1 is used in common among all the data signal lines in the same group. In FIG. 9, the analog switches ASWRn−1, ASWGn−1 and WSBn−1 are connected to the data output circuit DoAn−1 which outputs data DATAn−1, the analog switches ASWRn, ASWGn and ASWBn are connected to the data output circuit DoAn which outputs data DATAn, and the analog switches ASWRn+1, ASWGn+1 and ASWBn+1 are connected to the data output circuit DOAn+1 which outputs data DATAn+1.
The respective analog switches ASW in the same group are switched ON/OFF so that the ON period transits in the order of R, G and B, for example, and the ON/OFF of the supply of the data from the common data output circuit DOA to the data signal lines changes among R, G and B. As described, a data switching section 16 made up of three data switches is provided for each group of data signal lines. In FIG. 9, the corresponding group number is given as a subscript to the data switching section 16.
Next, the method of driving the liquid crystal display device will be explained. Specifically, the supply of a data signal in a certain horizontal period, i.e., to a data signal line for one scanning period will be explained. FIG. 10 shows a timing chart. In the data switching sections 16 shown in FIG. 10, switching signals Ron, Gon and Bon are supplied by time-division, and in synchronous with the supply of these signals, the data DATAn is input as the DATAn(R), DATAn(D) and DATAn(B). In the certain horizontal period 1H, a scanning signal line GLi is selected, and the ON period of the switching signal transits in each group of data signal lines in the order of Ron→Gon→Bon, thereby outputting data to the data signal lines in the order of DATAn(R)→DATAn(D)→DATAn(B).
Here, adopted is the method of driving liquid crystal, called "1H inversion driving", wherein the data DATA is selected in each horizontal period, for example, from the positive-polarity potential range of 6 V to 10.5 V and the negative-polarity potential range of 1.5 V to 6 V. Generally, a liquid crystal material for use in the liquid crystal display device alternates a voltage to be applied to a liquid crystal material. In the conventional driving method, one of the potentials to be supplied to the liquid crystal material is set the potential of the data DATA, and the other potential is set around 6 V. In the certain horizontal period (1H), the data DATA having the positive-polarity potential (6 V to 10.5 V) is supplied, and in the subsequent horizontal period (1H), the DATA having the negative-polarity potential (1.5 V to 6 V) is supplied. In the next frame, the data DATA whose polarity is inversed is supplied, and the AC driving of the liquid crystal is performed. In FIG. 10, in a certain frame, the negative-polarity data DATA is supplied to the data signal line in the previous horizontal period, and in the subject horizontal period, the positive-polarity DATA is supplied.
FIG. 11 illustrates an example structure of a display panel 2 of another liquid crystal display device in which driving is performed by the SSD method. The members having the same reference numerals as those of the liquid crystal panel 1 shown in FIG. 9 are designated as the same reference numerals. In FIG. 11, the adjoining odd-numbered data signal line OSL and the even-numbered data signal line ESL form a pair. The terminal of the data signal line OSL on the side of the data signal line driving circuit 27 (upstream side in the direction of supplying data signal) is connected to the analog switch ASWO, and the terminal of the data signal line ESL on the side of the data signal line driving circuit 27 (on the upstream side in the direction of supplying data) is connected to the analog switch ASWE. The analog switch ASWO is switched ON/OFF by the switching signal ODDon, and the analog switch ASWE is switched ON/OFF by the switching signal EVENon.
Here, respective terminals of the analog switches ASWO and ASWE in the same group of data signal lines on the opposite side of the data signal lines (on the upstream side in the direction of supplying data signal) are connected via the common wiring 25. This common wiring 25 is connected to the data output circuit DOB provided in the data signal line driving circuit 27 for each group. Namely, each data output circuit DOB is used in common among all the data signal lines in the same group. This data output circuit DOB outputs the data DATA. The analog switches ASW in the same group are switched ON/OFF so that the ON period transits in the order of ASWO to ASWE, for example, and whether the data is supplied or not supplied from the common data output circuit to the data signal line is switched between the odd-numbered data signal line and the even-numbered data signal line. As described, a data switching section 26 made up of two data switches is provided for each group of data signal lines.
FIG. 12 shows a timing chart of driving the liquid device adopting the 1H inversion driving. In the data switching sections 26 shown in FIG. 12, switching signals ODDon, EVENon are supplied by time-division from the control circuit 28. In synchronous with the supply of these switching signals ODDon and EVENon, the data DATAn in the nth group is input as DATAn (ODD) and DATAn(EVEN). In the certain horizontal period 1H, the gate signal line GLi is selected, and in this period, the ON period of the switching signal in each group of the data signal lines transits in the order of ODDon to EVENon, and the data is output to the data signal line in the order of DATAn(ODD) to DATAn(EVEN).
The following documents are listed for the relevant prior art documents.    (Document 1)
Japanese Unexamined Patent Publication No. 11-338438/1999 (Tokukaihei 11-338438), published on Dec. 10, 1999.    (Document 2)
Japanese Unexamined Patent Publication No. 10-39278/1998 (Tokukaihei 10-39278), published on Feb. 13, 1998.    (Document 3)
U.S. Patent Application Publication No. US 2001/0020929 A1).
The timing chart of FIG. 10 will be explained in more details. When the switching signals Ron, Gon and Bon are sent by time-division, and the data DATAn(R), DATAn(D) and DATAn(B) are supplied to the data signal lines RSLn, GSLn and BSLn, first, the data DATAn(R) is supplied to the data signal line RSLn by the switching signal Ron, and the data signal line RSLn is stably charged to the potential of the data DATAn(R). By the switching signals Gon and Bon, the analog switches ASWGn and ASWBn are set in the OFF state, and the data signal lines GSLn and BSLn are set in the floating state, and the data signal lines RSLn, GSLn and BSLn are subjected to capacitive coupling. Therefore, for example, with a sudden increase in potential of the data signal line RSLn, the respective potentials of the adjacent data signal line BSLn−1 and GSLn in the floating state, and the potential of the data signal line BSLn are subjected to fluctuations. In FIG. 10, the foregoing potential fluctuations are not shown.
Next, the switching signal Ron is not supplied, and the switching signal Gon is supplied to supply the data DATAn(G) to the data signal line GSLn. This data signal line GSLn is stably charged to the potential of the data DATAn(G); however, the analog switch ASWRn is switched in the OFF state by the switching signal Ron, and the data signal line RSLn is set in the floating state. Therefore, the potential of the data signal line RSLn changes by ΔV1, and this change in potential is referred to as up-throw potential fluctuations ΔV1. The respective potentials of the adjacent data signal line BSLn−1 and BSLn are also subjected to fluctuations at the same time. The foregoing potential fluctuations are not shown in FIG. 10.
Next, the switching signal Gon is not supplied, and the switching signal Bon is supplied to supply the data DATAn(B) to the data signal line BSLn. The data signal line BSLn is stably charged to the potential of the data DATAn(B). By the switching signals Ron and Gon, the analog switches ASWRn and ASWRn are set in the OFF state, and the data signal lines RSLn and GSLn are set in the floating state, and the data signal lines RSLn, GSLn and BSLn are subjected to capacitive coupling. Therefore, the data signal line RSLn is subjected to further up-throw potential fluctuations from the state where the data DATAn(R) is supplied to the data signal line RSLn from ΔV1 to ΔV2, due to the potentials of the data signal line BSLn−1 and the potential of the data signal line GSLn. Similarly, the potential of the data signal line GSLn is subjected to the up-throw potential fluctuations by ΔV3 due to the potentials of the data signal line RSLn−1 and the potential of the data signal line BSLn from the state where the data DATAn(G) is supplied to the data signal line GSLn.
As described, when data are sequentially supplied to the data signal lines by time division, only the most currently charged data DATAn(B) is charged without being affected by up-throw potential fluctuations due to capacitive coupling, and upon completing the function of the scanning signal for controlling the charge of the pixel in one horizontal period, the color in the potential of the pixel as charged is displayed in the display section. Here, as explained above, the up-throw potential fluctuations ΔV due to the capacitive coupling are accumulated corresponding to respective data signal lines by the order of the supply period of the switching signal Ron→Gon→Bon. Therefore, for example, when an attempt is made to display in an intermediate tone (gray), by setting the data DATAn(R), DATAn(G) and DATAn(B) to the same potential, the respective potentials of VRSLn, VGSLn and VBSLn of the final data signal lines RSLn, GSLn and BSLn hold the relationship of VRSLn>VGSLn>VBSLn. Here, in the case where the liquid crystal display is in a normally while mode, it is displayed in dark bluish gray. In response to the foregoing problem, the prior art document 1 adopts the means of altering the order of switching the switches in recognizing the importance in the wavelength dependency of a liquid crystal material.
In the driving method shown in the timing chart of FIG. 12, when the data signal is supplied to the data signal line ESLn, the data signal line OSLn after having the data DATAn (ODD) supplied are subjected to up-throw potential fluctuations by ΔV11.
As described, the conventional driving methods wherein the potential of the data signal line is changed significantly in the positive direction and the negative direction at each horizontal period by the 1H inversion driving present the problem in that up-throw potential fluctuations ΔV become large, resulting in poor display quality due to changes in color.
Furthermore, when supplying negative-polarity data to the data signal lines RSLn, GSLn and BSLn, down-throw potential fluctuations occur in a direction opposite to the positive-polarity.
The foregoing up-throw potential fluctuations ΔV are noticeable in a display device wherein a large number of data signal lines are closely packed together, and electrostatic capacitive coupling between the data signal lines is strong, such as a liquid crystal display device adopting the SSD method.

Display device and method of driving the same


A method for modifying asphalt comprises blowing an oxygen-containing gas through a base asphalt at a high gas flow rate while simultaneously agitating the base asphalt at a high shear rate and at an elevated temperature for a period of time that is effective to substantially improve at least two paving properties of the base asphalt. In preferred embodiments, modified asphalts are produced having both substantially improved rutting resistance and substantially improved fatigue resistance as compared to the base asphalt.

1. Field of the Invention
This invention generally relates to methods for making modified asphalt materials.
2. Description of the Related Art
Conventional air-blowing of asphalt materials involves passing an oxidizing gas through the asphalt in a molten condition. In general, the effect of such conventional air-blowing is to partially oxidize the asphalt, resulting in decreased penetration and increased viscosity and softening point. However, for paving applications, such conventional air-blowing generally has a negative effect on the fatigue resistance and the low temperature properties.
The disclosures of the following references are hereby incorporated by reference in their entireties: U.S. Pat. Nos. 1,782,186; 2,179,208; 2,370,007; 2,450,756; 3,126,329; 3,462,359; 4,338,137; 4,440,579; 4,456,523; 4,456,524; 5,284,509; 5,336,705; 5,342,866; and 6,087,419. The following EPO patent documents are also hereby incorporated by reference in their entireties: EP 0 459 811 B1 and EP 0 618 274 A1.

Methods and systems for modifying asphalts


Disclosed herein are methods and compositions for insertion of transgene sequences encoding proteins that is aberrantly expressed in disease or disorder such as a lysosomal storage disease.

An especially attractive application of gene therapy involves the treatment of disorders that are either caused by an insufficiency of a secreted gene product or that are treatable by secretion of a therapeutic protein. Such disorders are potentially addressable via delivery of a therapeutic transgene to a modest number of cells, provided that each recipient cell expresses a high level of the therapeutic gene product. In such a scenario, relief from the need for gene delivery to a large number of cells can enable the successful development of gene therapies for otherwise intractable indications. Such applications would require permanent, safe, and very high levels of transgene expression. Thus the development of a safe harbor which exhibits these properties would provide substantial utility in the field of gene therapy.
Hemophilias such as hemophilia A and hemophilia B, are genetic disorders of the blood-clotting system, characterized by bleeding into joints and soft tissues, and by excessive bleeding into any site experiencing trauma or undergoing surgery. Hemophilia A is clinically indistinguishable from hemophilia B, but factor VIII (FVIII or F8) is deficient or absent in hemophilia A while factor IX (FIX or F.IX) is deficient or absent in patients with hemophilia B. The F8 gene encodes a plasma glycoprotein that circulates in association with von Wilebrand's factor in its inactive form. Upon surface injury, the intrinsic clotting cascade initiates and factor VIII is released from the complex and becomes activated. The activated form acts with Factor IX to activate Factor X to become the activated Xa, eventually leading to change of fibrinogen to fibrin and clot induction. See, Levinson, et al. (1990) Genomics 7(1):1-11. 40-50% of hemophilia A patients have a chromosomal inversion involving F8 intron 22 (also known as IVS22). The inversion is caused by an intra-chromosomal recombination event between a 9.6 kb sequence within the intron 22 of the F8 gene and one of the two closely related inversely orientated sequences located about 300 kb distal to the F8 gene, resulting in an inversion of exons 1 to 22 with respect to exons 23 to 26. See, Textbook of Hemophilia, Lee, et al. (eds) 2005, Blackwell Publishing. Other hemophilia A patients have defects in F8 including active site mutations, and nonsense and missense mutations. For its part, Factor IX (F.IX) encodes one of the serine proteases involved with the coagulation system, and it has been shown that restoration of even 3% of normal circulating levels of wild type Factor IX protein can prevent spontaneous bleeding. Additional hemophilias are associated with aberrant expression of other clotting factors. For example, Factor VII deficiency is an autosomal recessive trait occurring in approximately 1 in 300,000 to 500,000 people and is associated with inadequate Factor VII levels in the patient. Similarly, Factor X deficiency is also an autosomal recessive trait occurring in 1 in every 500,000 to 1 million people, and is caused by genetic variants of the FX gene. Factor X deficiency can have varying degrees of severity in the patient population.
Current treatments for Hemophilia B rely on chronic, repeated intravenous infusions of purified recombinant Factor IX and suffer from a number of drawbacks. This includes the need for repeated intravenous infusions, is associated with inhibitor formation, and is prophylactic rather than curative.
Gene therapy for patients with Hemophilia A or B, involving the introduction of plasmid and other vectors (e.g., AAV) encoding a functional F8 or F.IX proteins have been described. See, e.g., U.S. Pat. Nos. 6,936,243; 7,238,346; and 6,200,560; Shi, et al. (2007) J Thromb Haemost. (2):352-61; Lee, et al. (2004) Pharm. Res. 7:1229-1232; Graham, et al. (2008) Genet Vaccines Ther. 6:9; Manno, et al. (2003) Blood 101(8):2963-72; Manno, et al. (2006) Nature Medicine 12(3):342-7; Nathwani, et al. (2011) Molecular Therapy 19(5):876-85; Nathwani, et al. (2011) N Engl J Med. 365(25):2357-65. However, in these protocols, the formation of inhibitory anti-factor VIII or IX (anti-F8 or anti-F.IX) antibodies and antibodies against the delivery vehicle remains a major complication of F8 and F.IX replacement-based treatment for hemophilia. See, e.g., Scott & Lozier (2012) Br J Haematol. 156(3):295-302.
Lysosomal storage diseases (LSDs) are a group of rare metabolic monogenic diseases characterized by the lack of functional individual lysosomal proteins normally involved in the breakdown of waste lipids, glycoproteins and mucopolysaccharides. These diseases are characterized by a buildup of these compounds in the cell since it is unable to process them for recycling due to the mis-functioning of a specific enzyme. The most common examples are Gaucher's (glucocerebrosidase deficiency—gene name: GBA), Fabry's (α galactosidase deficiency—GLA), Hunter's (iduronate-2-sulfatase deficiency-IDS), Hurler's (alpha-L iduronidase deficiency—IDUA), and Niemann-Pick's (sphingomyelin phosphodiesterase 1 deficiency—SMPD1) diseases. When grouped all together, LSDs have an incidence in the population of about 1 in 7000 births. These diseases have devastating effects on those afflicted with them. They are usually first diagnosed in babies who may have characteristic facial and body growth patterns and may have moderate to severe mental retardation. Treatment options include enzyme replacement therapy (ERT) where the missing enzyme is given to the patient, usually through intravenous injection in large doses. Such treatment is only to treat the symptoms and is not curative, thus the patient must be given repeated dosing of these proteins for the rest of their lives, and potentially may develop neutralizing antibodies to the injected protein. Often these proteins have a short serum half-life, and so the patient must also endure frequent infusions of the protein. For example, Gaucher's disease patients receiving the Cerezyme® product (imiglucerase) must have infusions three times per week. Production and purification of the enzymes is also problematic, and so the treatments are very costly (>$100,000 per year per patient).
Various methods and compositions for targeted cleavage of genomic DNA have been described. Such targeted cleavage events can be used, for example, to induce targeted mutagenesis, induce targeted deletions of cellular DNA sequences, and facilitate targeted recombination at a predetermined chromosomal locus. See, e.g., U.S. Pat. Nos. 8,623,618; 8,034,598; 8,586,526; 6,534,261; 6,599,692; 6,503,717; 6,689,558; 7,067,317; 7,262,054; 7,888,121; 7,972,854; 7,914,796; 7,951,925; 8,110,379; 8,409,861; U.S. Patent Publication Nos. 2003/0232410; 2005/0208489; 2005/0026157; 2006/0063231; 2008/0159996; 2010/00218264; 2012/0017290; 2011/0265198; 2013/0137104; 2013/0122591; 2013/0177983; and 2013/0177960 and U.S. Pat. No. 9,873,894, the disclosures of which are incorporated by reference in their entireties for all purposes. These methods often involve the use of engineered cleavage systems to induce a double strand break (DSB) or a nick in a target DNA sequence such that repair of the break by an error born process such as non-homologous end joining (NHEJ) or repair using a repair template (homology directed repair or HDR) can result in the knock out of a gene or the insertion of a sequence of interest (targeted integration). This technique can also be used to introduce site specific changes in the genome sequence through use of a donor oligonucleotide, including the introduction of specific deletions of genomic regions, or of specific point mutations or localized alterations (also known as gene correction). Cleavage can occur through the use of specific nucleases such as engineered zinc finger nucleases (ZFN), transcription-activator like effector nucleases (TALENs), or using the CRISPR/Cas system with an engineered crRNA/tracr RNA ('single guide RNA') to guide specific cleavage. Further, targeted nucleases are being developed based on the Argonaute system (e.g., from T. thermophilus, known as 'TtAgo', see Swarts, et al. (2014) Nature 507(7491):258-261), which also may have the potential for uses in genome editing and gene therapy.
This nuclease-mediated targeted transgene insertion approach offers the prospect of improved transgene expression, increased safety and expressional durability, as compared to classic integration approaches, since it allows exact transgene positioning for a minimal risk of gene silencing or activation of nearby oncogenes.
Targeted integration of a transgene may be into its cognate locus, for example, insertion of a wild type transgene into the endogenous locus to correct a mutant gene. Alternatively, the transgene may be inserted into a non-cognate locus, for example a "safe harbor" locus. Several safe harbor loci have been described, including CCR5, HPRT, AAVS1, Rosa and albumin. See, e.g., U.S. Pat. Nos. 7,951,925 and 8,110,379; U.S. Patent Publication Nos. 2008/0159996; 2010/00218264; 2012/0017290; 2011/0265198; 2013/0137104; 2013/0122591; 2013/0177983 and 2013/0177960 and U.S. Pat. No. 9,873,894. For example, U.S. Patent Publication No. 2011/0027235 relates to targeted integration of functional proteins into isolated stem cells and U.S. Patent Publication No. 2012/0128635 describes methods of treating hemophilia B. In addition, U.S. Patent Publication Nos. 2014/0017212 and 2014/0112896 describe methods of treating lysosomal storage diseases. See also Li, et al. (2011) Nature 475 (7355):217-221 and Anguela, et al. (2013) Blood 122:3283-3287.
However, there remains a need for additional compositions and methods of providing therapeutic proteins to a subject with a disease or disorder in which one or more proteins are lacking, deficient and/or aberrantly expressed.

This patent is subject to a terminal disclaimer.

Methods and compositions for genome engineering


A kill-switch control circuit for use with a light-duty combustion engine determines whether to execute a controlled shut down method or an immediate shut down method in response to kill-switch activation. The selection of a shut down method is made, at least in part, by using engine speed readings and by counting engine revolutions. The controlled shut down method utilizes ignition timing delay and/or spark ratio techniques to quickly bring the engine to a stop, yet does so in a controlled manner that avoids backfiring and other undesirable effects. Conversely, the immediate shut down method abruptly stops sending a current to the spark plug.

Internal combustion engines commonly have kill-switches incorporated into their ignition systems so that manual or automatic activation of the kill-switch results in an immediate shut down of the engine. Various types of kill-switches and accompanying circuitry have been utilized across a variety of applications, including light-duty combustion engines. The term 'light-duty combustion engine' used herein broadly includes all types of non-automotive combustion engines, including two- and four-stroke engines used with hand-held power tools, lawn and garden equipment, lawnmowers, weed trimmers, edgers, chain saws, snowblowers, personal watercraft, boats, snowmobiles, motorcycles, all-terrain-vehicles, etc.
Under certain operating conditions, activation of some kill-switches can result in an engine backfiring or emitting a flame from an exhaust pipe outlet. This is because many engines currently operate on leaner air/fuel mixtures or utilize catalytic converters in order to improve their emission characteristics. This can result in the engine having 'hot spots', which generally include any high temperature area of the engine capable of causing an unintended combustion of air/fuel charges. Hot spots are commonly located in the combustion chamber and exhaust system and can unintentionally ignite air/fuel charges, thereby causing the engine to backfire or to emit a flame. One factor that can contribute to air/fuel charge build up, and hence unintentional combustion, is when an engine operating at high speeds is suddenly shut off via activation of a kill-switch.
For example, a typical hand-held trimmer operating at an engine speed of 10,000 rpm can take approximately 2.5 sec to come to a complete stop after the kill-switch has been activated and the ignition system has stopped sending an ignition pulse to the spark plug. During that time, a considerable amount of air/fuel mixture passes through the combustion chamber and enters the exhaust system, at which point it can build up and be ignited by one or more hot spots. As previously mentioned, such an ignition can result in the engine backfiring, producing a loud noise commonly called an "after boom", and/or discharging a blue flame.
Some applications address this issue by using a solenoid that shuts off fuel in response to kill-switch activation. For example, a typical lawn tractor operating at an engine speed of 3,600 rpm can take five seconds or so to come to a complete stop after a kill-switch has been activated. During this time, the solenoid blocks excess fuel from entering the muffler and thereby prevents backfiring.

Engine kill-switch control circuit and method of operating the same


A system and method is provided for securely duplicating digital documents of disparate types, such that there is a cryptographically secure link between the duplicate and the original. The system also provides each document with a serial number that is both sequential with all other copied documents and cryptographically linked with the document itself, and which includes verifiable proof against tampering and modification. The system further produces copies of documents in a canonical format suitable for indexing and searching using automated processing tools.

1. Field of the Invention
The present invention relates generally to systems and methods for authenticating electronic data, and specifically to the searchability of digitally notarized electronic documents.
2. Description of Related Art
Traditionally, a paper document is validated through a notarization process, in which a Notary Public embosses a notary stamp (notary seal) on the document and signs and dates the notary seal on the document. However, with the advent of the digital age, many documents are being moved to digital form without retaining a paper copy of the document. Therefore, in order to validate the electronic document, a print-out of the document must be obtained in a format appropriate for the document. However, computer forensics has highlighted the differences between native electronic files and their paper or TIFF renditions. Such differences include certain document properties (often referred to as metadata), comments appended to business documents (e.g., notes to word processing files and PowerPoint presentations) and formulae and hidden columns in spreadsheets.
Therefore, over the past decade, a new digital notarization process has emerged to provide digital time stamping and notarization of electronic documents over the Internet. The Digital Notary® Service provided by Surety, Inc. allows users to notarize, timestamp and validate digital data of any type using client software provided to the user. Surety's Digital Notary® Service accomplishes digital notarization through a one-way hashing function that produces a digital fingerprint of the document. The digital fingerprint is transmitted over the Internet to Surety's Notary Server for notarization. After the fingerprint is notarized, the Notary Server returns a Notary Record (i.e., a small data record) to the user that contains the equivalent of a Notary Public's seal, date and signature on a paper document.
Although Surety's Digital Notary® Service provides the ability to validate digital documents, the Digital Notary® Service does not provide any medium for searching or otherwise organizing notarized digital documents. Most applications are automatically linked to some type of searching functionality. However, if there are multiple documents created using multiple applications, it can be inefficient and costly to pull up each application separately for each document to search through the documents.
In addition, some documents, such as TIFF images, must be converted to a searchable format prior to beginning the search process. The typical OCR drivers used to convert TIFF images to searchable text not only change the format of the original file, but also provide an unacceptable level of accuracy in terms of creating the searchable text component. For example, twenty thousand pages scanned at a 97 percent accuracy level will contain approximately 1.2 million errors, and it is nearly impossible to achieve a 97 percent accuracy level with non-e-mail types of business documents (e.g., spreadsheets). In these cases, the searchable text version of the TIFF image cannot be considered a valid copy of the document. Therefore, there is a need for a process that securely converts files of any format into accurate, searchable, readable and printable files capable of being digitally notarized and validated.

System and method for securely duplicating digital documents


Embodiments describe a semi-transparent or transparent module antenna assembly disposed on a transparent portion of a user wearable device (e.g., a head wearable display or a smartwatch). Embodiments describe semi-transparent or transparent antenna assemblies disposed on portions of a wearable computing device not in direct contact with the user when the device is worn to increase the antenna's efficiency for receiving radio signals and to decrease the radiation absorbed by the user's body. Furthermore, the antenna is disposed on a transparent or semi-transparent surface to further increase the antenna's efficiency. For some embodiments utilized by head wearable displays, the portion of the device including the semi-transparent or transparent antenna assembly may be the optical system, which includes a transparent portion (e.g., a prism) for displaying CGI to a user; in other embodiments, the head wearable display including the semi-transparent or transparent antenna assembly is the lens.

A wearable computing device is a device including a housing worn by a user. For example, a head wearable display is a display device worn on or about the head of a user. The size and form factor of wearable computing devices is minimized for reasons including user comfort, aesthetics, and cost. Antenna assemblies may be used by wearable computing devices for cellular connectivity, WiFi connectivity, Global Positioning System (GPS) services, and other applications. A solution to add these assemblies while minimizing the increase to the size and form factor of wearable computing devices is desired.

Transparent module antenna for wearable devices


A natural language processing method, comprising: receiving multiple input words; and reducing the multiple words into one or more subject word data structures according to sets stored in a database, wherein one of the subject word data structures includes a first input word and a second input words among the input words, wherein one of the sets includes a compatible relation between the first input word and the second input word, wherein the compatible relation between the first input word and the second word includes a compatible property for denoting an intensity representing occurrences of the first input word and the second word in a training corpus.

Traditional natural language analysis tools (e.g. parser, Chinese word segmentation) emphasize grammar. However, grammars of some languages (e.g. Chinese) are quite loose. Spoken languages on the Internet have a lot of omissions, changes of order and ungrammatical sentences. Parsing systems trained with regular academic trainings have difficulties to deal with them. It must consider a lot of semantic information to correctly parse and to understand the semantics. Even the basic Chinese segmentation system may make many inexplicable errors. For example: "yi tai da bing xiang; hai yao ji zhang cai you?" (Segmentation errors are caused by two proper nouns "tai da" and "zhang cai".)
Voice inputs and outputs of natural languages already became important input and output interfaces of modern electronics, which are one of human-machine interfaces for controlling computers. Hence, there exists a need of a method for accurately judging semantic meanings of sentences, in order to correctly select words according to inputted syllables, to parse ungrammatical verbal languages for accurately machine translations or to output execution results in natural language.

Natural language processing method and computing apparatus thereof


A lid device for a wide-mouthed container comprises a metallic lid body having an inner margin defining an opening of a predetermined shape, a resinous rim member extending along and anchored to the inner margin of the lid body, and a closure film attached to the rim member to close the opening of the lid body. The lid body is fittable to an open mouth of the container. For opening, the closure film may be peeled off the rim member or torn along the rim member.

1. Field of the Invention
This invention relates generally to lids for containers. More particularly, the present invention relates to a lid device of the type which comprises a metallic lid body fittable to an open mouth of a wide-mouthed container and having an inner margin defining an opening, and a closure film attached to the lid body for closing the opening. The invention also relates to a method for making such a lid device.
2. Description of the Prior Art
In general, a lid device of the above-described type is made by forming a metallic plate of e.g. aluminum or tin into a predetermined shape to provide a lid body with an opening, and directly attaching a closure film ( e.g. aluminum foil or resin film) to the lid body for closing the opening. In use, the closure film is peeled off the closure film to provide access into the container.
Typically, the closure film is attached to the lid body by utilizing the heat sealing method, as disclosed in U.S. Patent to Bloeck et al or Japanese Utility Model Application Laid-open No. 62-108229 (Inventors: Susumu TAKADA et al.). Specifically, according to the known heat sealing method, a bonding layer of thermally meltable adhesive or thermoplastic resin is preliminarily formed on the lid body and/or the closure film, and a hot plate is pressed against the closure film overlapped on the lid body to cause thermal fusion of the bonding layer.
The heat sealing method provides uniform attachment of the film over the entire circumference thereof as long as the lid body has a strictly flat attachment surface. In reality, however, it is difficult to make the attachment surface of the lid body strictly flat because the lid body is subjected to various forces at the time of forming from a metallic plate. Thus, the hot plate for heat sealing may pressed unevenly circumferentially of the film, which results in uneven attachment of the film. In an extreme case, the film may be left non-attached at one or more circumferential positions, which causes unexpected gas entry and/or leakage at the non-attached positions.

Lid device for wide-mouthed container and method for making the same


A jack handle which limits the torque that can be applied to a jack so as to prevent overload and injury. The jack handle has a reduced cross-sectional portion between the handle and the jack engaging portion so that the handle will break off at the reduced cross-sectional portion, thus, preventing overloading of the jack. A portion of the handle which does not break off is provided with a jack engaging portion so that the broken portion of the jack can be removed and the second jack engaging portion can be inserted into the jack to lower it.

1. Field of the Invention
This invention relates in general to an improved jack handle which prevents overloading of the jack. Generally, truck and van jacks require extension handles for operating the jack.
2. Description of Related Art
It is dangerous if such jacks are overloaded and it is desirable to provide means for limiting the operating input torque so that if the jack is misused, such as overloaded the jack will not be destroyed. Bottle-type jacks such as used on many trucks and vans typically will not stand more than about 50 foot pounds of torque. A drive mechanism of the jack brakes above that level of torque. When this occurs, the jack is left under the vehicle with no way to lower the jack and remove it and this presents the user with the dangerous problem of how to remove the jack. See also U.S. Pat. Nos. 3,602,065, 3,921,471 and 3,707,885.

Jack handle with means for limiting the torque which can be applied to a jack


A variable inductor includes a conductor and an electroconductive member. The conductor has a coil and a pair of terminals electrically connected with the coil. The electroconductive member is movable closer to and farther away from the coil. The inductance between the terminals becomes smaller as the distance between the coil and the electroconductive member becomes shorter. Conversely, the inductance between the terminals becomes larger as the distance between the coil and the electroconductive member becomes longer.

1. Field of the Invention
The present invention relates to a variable inductor incorporated e.g. in radio communications equipment.
2. Description of the Related Art
In the technical field of radio communications equipment such as mobile phones, there is an increasing requirement for smaller high-frequency circuits or RF circuits due to increase in the number of parts incorporated in the equipment for advanced features. In response to such a requirement, a variety of parts needed for building the circuitry are a focus of miniaturization using technologies called MEMS (micro-electromechanical systems). Inductors are a category of such parts. Inductors are an electronic part to be incorporated in electric circuits or electronic circuits, for use of an inductance provided by them, and sometimes there is a need for the inductance to be variable.
FIG. 30 and FIG. 31 show a primary configuration of an inductor X4 which is a conventional variable inductor whose inductance is variable. FIG. 30 is a plan view of the inductor X4 whereas FIG. 31 is a sectional view taken in lines XXXI—XXXI in FIG. 31.
The inductor X4 includes a substrate 91, a conductor 92 and a ferrite core 93. The conductor 92, which is formed on the substrate 91 using such technologies as thin-film formation and patterning technology, has an electroconductive coil 92a and a pair of terminals 92b. The ferrite core 93 has a high magnetic permeability and faces the coil 92a. Further, the ferrite core 93 is movable toward and away from the substrate 91 or the coil 92a within a predetermined range of movement. Such a variable inductor is disclosed in e.g. the following Patent Document 1.
Patent Document 1: JP-A-H08-204139
In the inductor X4, the ferrite core 93 is brought closer to the coil 92a in order to increase the inductance (self inductance) between the pair of terminals 92b in the inductor X4. When the ferrite core 93 is moved away from the coil 92a, the inductance is decreased. The coil's self inductance is known to be proportional to magnetic permeability in which the coil is placed. The closer is the distance between the ferrite core 93 and the coil 92a, higher is the net magnetic permeability in the environment around the coil 92a (and therefore higher is the net density of the magnetic flux generated around the coil 92a in association with an electric current flowing through the coil 92a), and so the inductance is higher.
However, in the inductor X4 whose inductance is varied by an advancing/retracting movement of a magnetically highly permeable member (the ferrite core 93) with respect to the coil 92a, the inductance can only be varied within a relatively small range of 10% approx, as mentioned in the Patent Document 1. Therefore, the inductor X4 is sometimes unable to vary its inductance as much as desired.


A metallic ring is located on a multilayer ceramic substrate. An optical semiconductor laser is located on the multilayer ceramic substrate, inside the metallic ring. A metallic cap with a window is joined to the metallic ring. The metallic cap covers the optical semiconductor laser. An external heat sink is joined to an external side surface of the metallic cap. These features make it possible to improve high-frequency characteristics, producibility, and heat dissipation.

Conventional semiconductor packages for optical communication include metal packages and CAN packages. A metal package is a combination of a multilayer ceramic substrate and a metallic box. A CAN package has a metal plate, a metallic rod passed through an open hole in the metal plate and hermetically sealed and insulated with glass, and a welded cap with a window.
The metal package has an excellent high-frequency characteristic because of use of the multilayer ceramic substrate. The metal package, however, has a complicated structure and a large number of parts and is high in cost. Also, because of its box form, parts can be mounted only from the opening side (upper side) before the package is closed.
In the case of the CAN package, parts can be mounted from all directions onto the upper surface of the metal plate, and the metal plate and the cap can be joined to each other in an instance by electric welding. The CAN package therefore has high producibility. However, since the lead for supplying a signal is fixed by glass sealing on the metal plate, it is difficult to achieve impedance matching thereat and the CAN package is inferior in high-frequency characteristic.
A semiconductor package has been proposed which has an optical semiconductor element mounted in a recess in an upper surface of a multilayer ceramic substrate and covered with a metallic cap with a window (see, for example, Patent Literature 1)


A vibration damping laminate includes a magnetic layer and an uncoated constraining layer joined by a viscoelastic layer, wherein the modulus of elasticity of the viscoelastic layer is substantially less than that of either of the other two layers. The laminate is magnetically attached to an associated source of vibrations by the magnetic layer, and substantially all vibrational damping is effected by the viscoelastic layer.

This application relates to the vibration damping materials for minimizing vibrations in structural members, and relates in particular to vibration damping laminates.
Structural vibration can occur in a wide variety of structural members. Common deleterious results of such vibration can be mechanical failure of the structural element and/or the generation of acoustic noise. One method commonly employed to reduce such vibration involves the addition of damping material to a vibrating structure. This is referred to as add-on damping, and typically consists of a piece of metal or the like applied to the vibrating structure by means of a pressure-sensitive adhesive. Such add-on damping typically works on the principal of constrained layer damping, which is commonly a three-layer construction consisting of the vibrating source, a viscoelastic layer, such as the pressure-sensitive adhesive, and a constraining layer, such as the piece of metal. The vibrating source provides the unwanted vibrational energy, which causes the outer constraining layer or a piece of metal to shear the viscoelastic layer, causing friction (heat) between the polymer chains of the viscoelastic layer, thereby dissipating the energy. Thus, the viscoelastic layer has two purposes: adhesion of the constraining layer to the vibrating source and vibration reduction.
However, when such an add-on damping material is utilized, pressure is needed during attachment of the damping material to the vibrating source to ensure cold temperature adhesion.
It is known to provide a three-layer damping material, including a constraining layer, a viscoelastic adhesive layer and a magnetic layer, such an arrangement being disclosed, for example, in U.S. Pat. No. 5,300,355 to Mifune et al. In that arrangement, the magnetic layer is formed of a composite which includes, in addition to a magnetic powder, a polymeric material and an adhesive resin. Thus, the composite magnetic layer achieves both a magnetic and an adhesive attachment of the damping laminate to the vibrating source. Furthermore, the material is designed so that the modulus of elasticity of the magnetic layer is equal to or less than that of the adhesive layer so that most of the vibrational damping is effected in the magnetic layer.
Japanese patent publication no. 3-47750, referred in U.S. Pat. No. 5,300,355, discloses a similar arrangement, wherein the metal layer is primed and coated with a rust preventive coating.

Material Sciences Corporation, Engineered Materials and Solutions Group, Inc.


An information display and control device of an air purifying respirator comprises: a blower motor; a pulse width modulation drive unit controlling rotation of the blower motor; a temperature sensor; an air flow sensor; an oxygen sensor; a voltage detection unit for a battery; a differential pressure sensor detecting a differential pressure value of a filter; a switch input unit for a user to input predetermined temperature, air flow, and oxygen amount and operation commands; a controller executing a diagnostic mode, calibrating the oxygen sensor, calculating a detected value of the voltage detection unit to determine whether the voltage is low, comparing the detected value of the differential pressure sensor with a reference to determine whether the filter is absent or clogged, and comparing the detected value of the oxygen sensor with a reference to determine whether oxygen is insufficient or excessive; and an alarm output unit outputting an alarm.

1. Field of the Invention
The present invention relates to an information display and control device of a powered air purifying respirator including a filter device for filtering off a toxic substance contained in air and a blower device for suctioning and supplying the filtered air to the air purifying respirator.
2. Description of the Related Art
A powered air purifying respirator system includes a filter device for filtering off a toxic substance contained in air and a blower device for suctioning and supplying the filtered air to an air purifying respirator. The blower device is configured to uniformly supply air to the air purifying respirator. The blower device detects clogging of a filter due to external foreign matter to correct air flow. A user may periodically inspect air flow using an air flow display device provided together with the blower device when the user buys the blower device.
Generally, a worker puts the blower device on the back of the worker using a belt. The worker puts the air purifying respirator and the blower device on, and connects the air purifying respirator to the blower using a hose. The powered air purifying respirator system is configured to detect discharge of a battery during operation, clogging of the filter due to abnormality of the filter, or the change of air flow due to foreign matter and to transmit the detected result to sensory organs of the user in the form of a sound or others so that the worker can rapidly take proper measures.
In conventional inspection of air flow, whether the blower device is operated at an air flow level required by a manufacturer is simply displayed using a separately manufactured air flow display device. In conventional correction of air flow, the change in current and the number of rotations of a motor due to pressure at the filter and the air purifying respirator is detected to correct air flow. Alternatively, an air flow sensor may be mounted to correct air flow.
In such a conventional art, however, an error may be generated due to change of air temperature and atmospheric pressure, and different amounts of air may be generated at a correction step of correcting clogging of the filter due to the pressure difference between the air flow display device and the air purifying respirator.
Also, the manufacturer detects the change of air flow in a state in which an outlet of the blower device is fully closed using a hand to inspect whether an alarm is given with respect to low air flow. However, it is not possible to display a clogging rate of the filter.
For reference, a portable air supply apparatus is disclosed in Korean Patent Application Publication No. 10-2005-0074391 (published on Jul. 18, 2005).

Information display and control device of powered air purifying respirator


The present invention relates to an amorphous alloy and a method for manufacturing thereof. The amorphous alloy according to the present invention includes has a chemical formula of Feioo-a-b-c-d-e-f-gCraMobCcBaYeMflg. Here, the M is at least one selected from a group consisting of Al, Co, N1 and Ni, and the I is at least one selected from a group consisting of Mn, P, S, and O as impurities. The a, b, c, d, e, f, and g are satisfied with the compositions of 16.0 wt %≦a<22.0 wt %, 15.0 wt %<b≦27.0 wt %, 2.0 wt %≦c<3.5 wt %, 1.0 wt %<d≦1.5 wt %, 1.0 wt %<e≦3.5 wt %, 0.25 wt %<f≦3.0 wt %, and 0.01 wt %≦g<0.5 wt %, respectively.

(a) Field of the Invention
The present invention relates to an amorphous alloy and a manufacturing method there of, and more specifically to an amorphous alloy with good strength and high corrosion resistance and a manufacturing method thereof.
(b) Description of the Related Art
A fuel cell has been spotlighted as an alternative energy source due to global warming, pollution, and depletion of oil resources. The fuel cell is an electric generator. In the fuel cell, reactants continuously flow into the system while products are continuously discharged from the system. At the same time, electric energy is generated. That is, oxygen and hydrogen are continuously supplied to the fuel cell and a chemical reaction occurs, thereby generating electrical energy.
Various types of fuel cells have been developed. The fuel cells can be classified as high temperature fuel cells and low temperature fuel cells depending on electrolytes in a unit cell and operational temperature. The high temperature fuel cells include molten carbonate fuel cells, solid oxide fuel cells, and so on. The low temperature fuel cells include phosphoric acid fuel cells, polymer electrolyte fuel cells, alkaline fuel cells, and so on.
In particular, a polymer electrolyte membrane fuel cell (hereinafter referred to as a "PEMFC"), one of the solid polymer electrolyte fuel cells (hereinafter referred to as a "SPEFC") that is a low temperature fuel cell, is compact and light-weight, and has an advantage to be capable of operating at a low temperature. The PEMFC generates electric power from hydrogen and oxygen through a polymer membrane consisting of a membrane electrode assembly (hereinafter referred to as an "MEA"). The MEA is made by combining the polymer membrane with electrodes located on each side thereof.
Each electrode support is made of carbon cloth supporting electrode materials such as carbon black including platinum catalysts. A plurality of the MEAs with a thickness of several tens to several hundreds of micrometers are filled between multi-functional bipolar plates in order to obtain sufficient electric power. Therefore, several tens to several hundreds of unit cells are serially connected to each other and form a fuel cell stack.
The bipolar plates of the PEMFC are exposed to severe operating conditions in which current and stress are applied and corrosion occurs. Therefore, materials for the bipolar plates are required to have properties of gas impermeability, high strength, corrosion resistance, and good electrical conductivity. Currently used bipolar plates mainly made of a carbon do not have such properties. In particular, thin metallic bipolar plates with high strength and low cost are required since bulk graphite bipolar plates are weak.
Therefore, research relating to bipolar plates made of graphite composites and stainless steels as a replacing material of the bipolar plates has been undertaken. In addition, as a method of manufacturing bipolar plates, research relating to a thermal nitriding surface treatment, TiN coating on stainless steel, thin PVD (physical vapor deposition) coatings, etc., has been pursued.
However, there is a problem in that metallic ions are dissolved and the MEA is poisoned if the electrons are lost in the bipolar plates. Furthermore, metallic oxides grow in a cathode since the metallic bipolar plates obtain electrons and then a recovery reaction occurs. Therefore, there is a problem in that electrical resistance of the surface increases while performance of the fuel cell is deteriorated. Materials with high strength and corrosion resistance have been seriously required in other circumstances in addition to materials for the fuel cells.

Amorphous alloy and manufacturing method thereof

Korea Institute of Science and Technology


Apparatus for cancelling magnetic fields for cancelling a leakage magnetic field from a static magnetic field generation assembly are disposed outside the static magnetic field generation assembly. A magnetic shield made of a magnetic substance is disposed between the static magnetic field generating assembly and the cancelling magnetic field apparatus. The cancelling magnetic field generation apparatus is of a cryostatless type.

1. Field of the Invention
This invention relates to a static magnetic field generating system. More particularly, it relates to a static magnetic field generating system which can be used suitably in combination with a nuclear magnetic resonance imaging (MRI) apparatus.
2. Description of the Related Art
Magnetic field generation means include a super-conducting magnet (SCM), a resistive magnet (RM), a permanent magnet (PM) and their hybrid magnet systems. These magnet systems generate magnetic fields inside a magnetic field generation space in accordance with their intended applications, but the magnetic flux leaks outside the required space depending on the intensity of the magnetic fields generated and the shape and size of each magnet system. This leakage magnetic field exerts an adverse influence on other instruments and appliances (e.g. electron beam application appliances such as color television, X-CT, magnetic tape application appliances, etc), people bearing a pace maker, a magnetic card, and so forth. A typical example of the adverse influences can be observed in a magnet used for a nuclear magnetic resonance imaging (MRI) apparatus. Recently, the field intensity has been increased in MRI apparatus to improve sensitivity, and a magnetic field as high as from 0.5 to 2.0 T (Tesla) has been employed. Particularly, the number of MRI apparatuses using 1.5 T has increased. In the MRI magnet 1 shown in FIG. 1, a human body 14, an NMR signal detection coil 13, a gradient magnetic field coil system 7 and a system 9 for improving a field homogeneity are accommodated in a magnetic field generation space 16. Therefore, this room temperature magnetic field generation space 16 has a large diameter of 800 to 1,000 mm. To generate a high magnetic field, the magnet becomes inevitably a superconducting magnetic system. In FIG. 1, a cylindrical superconducting magnet (SCM) is shown split longitudinally, and its internal structure is shown. A magnetic field Ho in a Z direction is generated in the internal cylindrical magnetic field space 16 by causing a permanent current Ip to flow through the superconducting coil group 1. To detect nuclear magnetic resonance (NMR) signals with a high sensitivity, the magnetic field Ho must be homogeneous over a wide range. Therefore, the superconducting coil group 1 is so designed as to attain .+-.5 ppm/40 cm dsv (diameter spherical volume), for example, and is finely adjusted by the shim system 9. The superconducting coil group 1 is positioned in a vessel 2 filled with liquid He, and this vessel 2 is encompassed by aluminum cylinders 3 and 4 kept at temperatures of 80 K. and 20 K., respectively, in order to reduce evaporation of liquid He. The cylinders 3 and 4 can be kept at the low temperatures by means of contact with a refrigerator 10. The inside of the magnet is kept at a vacuum in the order of 10.sup.-6 Torrs to reduce evaporation of liquid He.
In FIG. 1, reference numeral 5 denotes a magnet outer cylinder, 6 is a inner cylindrical bore, 11 is an 80 K. contact, 12 is a 20 K. contact, and 15 is a patient table.
FIG. 2 shows a closed loop which is formed when the lines of magnetic force of the cylindrical magnetic space 16 of the cylindrical superconducting magnet 17 described with reference to FIG. 1 leave one of the apertures of the space 16, pass through a loop in an external space as shown in the drawing, and then return to the other aperture of the space 16.
It can be understood from FIG. 2 that if the magnetic shield does not exist, a wide range is magnetically contaminated. When the diameter of the apertures of the magnet 17 is about 1.0 m and the field intensity inside the space 16 is 1.5 T (Tesla), for example, the contour line of the magnetic field 5 mT (5 Gauss), which is said to be a safe line for people bearing a pace maker, is shown in FIG. 3.
In other words, the surface of a Z axis ellipsoid of revolution which is .+-.12 to 13 m in the Z direction in the magnetic field generating direction of the magnet 17 and .+-.9 to 10 m in Y (vertical) and X (horizontal) directions is the contour line 20 of 5 mT. If the magnetic field generator is used without magnetic shielding, therefore, an extremely wide range must be kept off-limits, and various magnetosensitive appliances, as described above, cannot be used.
Therefore, a magnetic shield must be utilized.
Conventionally, the following magnetic shields have been employed.

Hitachi Instrument Engineering Co., Ltd.