text:
|Publication number
|Publication type
|Application number
|PCT number
|Publication date
|Feb 1, 2011
|Filing date
|Oct 15, 2007
|Priority date
|Nov 8, 2006
|Fee status
|Also published as
|Publication number
|Noriyuki Kokeguchi
|Original Assignee
|Konica Minolta Holdings, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (12), Non-Patent Citations (1), Classifications (6), Legal Events (2)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a U.S. national stage of application No. PCT/JP2007/070061, filed on 15 Oct. 2007. Priority under 35 U.S.C. �119(a) and 35 U.S.C. �365(b) is claimed from Japanese Application No. 2006-302596, filed 8 Nov. 2006, the disclosure of which is also incorporated herein by reference.
The present invention relates to an electrochromic display element employing silver dissolution and deposition.
In recent years, with enhancement of operation speed of personal computers, widespread use of network infrastructure, and realization of mass storage of data, as well as cost reduction of data storage, there are increasing occasions in which information of documents and images, having been conventionally provided in the form of printed paper matter, is received and viewed as more convenient electronic information.
As viewing methods for such electronic information, there are mainly used those which are of light emitting types such as conventional liquid crystal display devices and CRTs, or organic EL display devices, which have recently been marketed. Especially, however, when electronic information is composed of items of document information, it is necessary to stare at these viewing devices for a relatively long time, which is certainly not viewer-friendly. It is commonly known that light emitting type display devices have disadvantages such as eye fatigue due to flicker, inconvenience of portability, limited reading posture, necessity to look closely at still images, and high power consumption due to the use of these devices for long-time reading.
As display devices to overcome these disadvantages, there are known memory effect reflective display devices, which utilize external light, resulting in consuming no electrical power to retain images. However, these devices do not exhibit adequate performance due to the following reasons.
Namely, a system, employing a polarizing plate such as a reflective type liquid crystal, creates a problem in white display due to its low reflectance of approximately 40%, and most of the production methods of constituent members are neither simple nor easy. Further, polymer dispersion type liquid crystals require a high operating voltage and exhibit poor contrast of resultant images due to the utilization of a refractive index difference between the used organic compounds. Still further, polymer network type liquid crystals have problems such that high operating voltages result and complicated TFT circuits are required to enhance memory capability. Yet further, display elements employing electrophoresis require a high operating voltage of at least 10 V and tend to exhibit low operation life due to electrophoretic particle aggregation. In contrast, although being drivable at a low voltage of at most 3 V, electrochromic display elements have the disadvantage of exhibiting poor color quality of black or colors (such as yellow, magenta, cyan, blue, green, and red), as well as having the disadvantage that each display cell requires a complicated film structure such as a vapor deposition film to ensure memory capability.
As a display system to overcome any of the disadvantages in each of the systems described above, there is known an electrode deposition (hereinafter referred to simply as ED) system employing dissolution and deposition of a metal or metallic salt. The ED system is drivable at a low voltage of at most 3 V, and features advantages such as a simple cell structure and excellence in black and white contract, as well as in black image quality, resulting in disclosure of a variety of systems (for example, refer to Patent Documents 1-3).
The present inventor has made detailed investigation in the technologies disclosed in each of the Patent Documents described above, and found that these conventional technologies have problems of exhibiting color change of white color during white display after accumulated repeating driving operation. In addition, it is known that an onium cation is applied for an electrolytic capacitor (for example, refer to Patent Documents 4-5). However, its application to a display element was not described or suggested.
Patent Document 1: U.S. Pat. No. 4,240,716 specification
Patent Document 2: Japanese Patent Publication No. 3428603
Patent Document 3: Unexamined Japanese Patent Application Publication No. 2003-241227
Patent Document 4: Japanese Patent Publication No. 2701874
Patent Document 5: Unexamined Japanese Patent Application Publication No. 2005-5357
In view of the above problems, the present invention was achieved. An object of the present invention is to provide a display element exhibiting a decreased color change in white display after repeated driving operation of the display element.
The object of the present invention was achieved employing the following constitutions.
(In Formula, X and Y each represent an alkyl group having to 4 carbon atoms, and they may be the same or different. "k" and "i" each represent 0 or a positive integer of 1 to 4; and "m" and "n" each represent a positive integer of 3 to 7. "A" represents an acid component.)
R7—S—R8 Formula (1)
(In Formula, R7 and R8 each represent a substituted or unsubstituted hydrocarbon group, provided that an aromatic ring is not included when a ring containing a sulfur atom is formed.)
(In Formula, M is a hydrogen atom, a metal atom or a quaternary ammonium. Z represents a nitrogen containing heterocylic group. "n" represents an integer of 0 to 5. R9 represents: a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, a arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a carbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, a carboxyl group, a carbonyl group, a sulfonyl group, an amino group, a hydroxyl group, or a heterocyclic group. When "n" is two or more, plural R s may be the same or different, and further, they may be joined to form a ring resulting in forming a condensed ring.)
According to the present invention, it was achieved to provide a display element which exhibits a decreased color change in white display after repeated driving operation of the display element.
The best mode to carry out the present invention will now be detailed.
In view of the above problems, the present inventor conducted diligent investigations and realized the following: a display element having opposed electrodes and an electrolyte layer incorporating silver or a compound containing silver in its chemical structure between the opposed electrodes; and by carrying out driving operation for the opposed electrodes to induce silver dissolution and deposition, wherein the aforesaid electrolyte contains a compound represented by Formula (A); and a compound represented by Formula (1) or Formula (2). It was found that the display element can realize a decreased color change in white display even after repeated driving operation of the display element.
In the constitution of the display element according to the present invention, the compound represented by Formula (A) has an effect of increasing an ion conductivity of the electrolyte, thereby improving the speed of whitening or blackening of the display element. Known compounds capable to increase such speed are, for example: an imidazolium derivative, a pyridinium derivative, an ammonium derivative and a pyrrolidinuim derivative. It was found that these compounds may interact with silver ions in the electrolyte, the composition of which is peculiar to the ED method of the present invention, and the stability of the compound itself may be insufficient resulting in insufficient reliability of the display after repeated driving of the display element. It was revealed that the compound represented by Formula (A) of the present invention will not interact with silver ions and it can achieve both properties at the same time: speed of blackening and whitening; and display reliability of the display element.
The present invention will now be detailed.
The display element of the present invention is an ED system display element having an electrolyte, incorporating silver or a compound containing silver in its chemical structure, between opposed electrodes, and carrying out driving operation for the opposed electrodes to induce silver dissolution and deposition.
The display element of the present invention has an electrolyte between a pair of electrodes. "Electrolyte" of the present invention generally refers to a compound which dissolves in a solvent such as water and the solution exhibits an ionic conductivity (hereafter it is called as "an electrolyte in a narrow definition"). However, in the description of the present invention, a mixture of an electrolyte in a narrow definition and other metal or compound (regardless of electrolytic or non-electrolytic) may be also called as an electrolyte (such a mixture is called as "an electrolyte in a broad definition".)
(Silver, or Compound Containing Silver in Chemical Structure)
A compound containing silver, or a compound containing silver in their chemical structure, according to the present invention, is common designations of a compound such as silver oxide, silver sulfide, metallic silver, colloidal silver particles, sliver halide, silver complex compound, or a silver ion. The phase states such as a solid state, a state solubilized to liquid, a gas state, and charge state types such as neutral, anionic or cationic are not particularly considered.
(Basic Structure of the Display Element)
In the display element of the present invention, each ED display portion has corresponding paired counter electrodes. An electrode 1 of the paired counter electrodes positioned nearer to the ED is provided with a transparent electrode such as ITO electrode, while the other electrode 2 is provide with a metal electrode such as silver electrode.
An electrolyte is sandwiched between electrode 1 and electrode 2, and the electrolyte contains silver or a compound having silver in the molecule. By applying voltage having a positive and a negative polarity to the counter electrodes, an oxidation-reduction reaction takes place on electrode 1 and electrode 2. Thereby a black silver image of reduced state and a transparent silver of oxidized state will be reversibly interchanged.
[Compound Represented by Formula (A)]
The compound represented by Formula (A) of the present invention will be described.
In Formula (A), when X and Y each represent an alkyl group having 1-4 carbon atoms, and they may be the same or different. k and i each represent 0 or a positive integer of 1 to 4; and m and n each represent a positive integer of 3 to 7.
In Formula (A), when X and Y are equal to 5 or larger, and k and i are equal to 5 or larger, or n and m are equal to 8 or larger, ionic conductivity of the spiroammonium salt is decreased to give an unwanted effect.
Examples of cations of spiroammonium salts in Formula (A) are as follows: spiro-(1,1′)-biazacyclobutyl ion, azacyclopentane-1-spiro-1′-azacyclobutyl ion, azacyclohexane-1-spiro-1′-azacyclobutyl ion, azacycloheptane-1-spiro-1′-azacyclobutyl ion, azacyclooctane-1-spiro-1′-azacyclobutyl ion, spiro-(1,1′)-biazacyclopentyl ion, azacyclohexane-1-spiro-1′-azacyclopentyl ion, azacycloheptane-1-spiro-1′-azacyclopentyl ion, azacyclooctatane-1-spiro-1′-azacyclopentyl ion, spiro-(1,1′)-biazacyclohexyl ion, azacycloheptane-1-spiro-1′-azacyclohexyl ion, azacyclooctane-1-spiro-1′-azacyclohexyl ion, spiro-(1,1′)-biazacycloheptyl ion, azacyclooctane-1-spiro-1′-azacycloheptyl ion, spiro-(1,1′)-biazacyclooctyl ion.
In Formula (A), A represents an acid component. Examples of A are: a perchloric acid ion (ClO4 −), a fluorine ion (F−), a chlorine ion (Cl−), a bromine ion (Br−), an iodine ion (I−), a hexafluorophosphoric acid ion (PF6 −), a hexafluoroantimonic acid ion (SbF6 −), a tetrafluoroboric acid ion (BF4 −), a trifluoromethanesulfonic acid ion (CF3SO3 −), a trifluoroacetic acid ion (CF3CO2 −), a bistrifluoromethanesulfonylimide ion ((CF3SO2)2N−), a perfluorobutanesulfonic acid ion (C4F9SO3 −), a tristrifluoromethanesulfonylmethyde ion ((CF3SO2)3C−), a dicyanamide ion ((CN)2N−), p-toluenesulfonic acid, a borate compound such as bis[oxalate(2-)]borate. Among them, the ions containing no halogen atoms, such as a dicyanamide ion ((CN)2N−), p-toluenesulfonic acid and bis[oxalate(2-)]borate are preferable.
Spiroammonium salts represented by Formula (A) of the present invention can be produced by the following method.
At first, an azacycloalkane is allowed to react with a dibromoalkane which is substituted with two bromine atoms at two terminal positions in isopropylalcohol under the presence of sodium carbonate to obtain a spiroammonium bromide. Then, the obtained bromide is subjected to electrodialytic desalination in water or alcohol to obtain a spiroammonium hydroxide. The obtained spiroammonium hydroxide solution is neutralized by adding an equal amount of an acid component corresponding to "A" in Formula (1). Then water is eliminated under reduced pressure and the targeted spiroammonium salt can be obtained. Also, these compounds are available as commercial products, for example, SBP—BF4 (produced by Japan Carlit Co., Ltd.) can be cited.
An added amount of a compound represented by Formula (A) to the electrolyte solution is preferably from 0.1 weight % to 10 weight %. When it is 0.1 weight % or more, the improved effect of the present invention can be achieved. When it is 10 weight % or less, it can be prevented from precipitating out in the electrolyte solution at low temperature and it can be stably incorporated in the electrolyte solution.
(Porous White Scattering Layer)
The display element of the present invention may incorporate a porous white scattering layer from the viewpoint of enhancing display contrast and white display reflectance.
The porous white scattering layers which can be applied to the present invention are formed by coating and drying an aqueous mixture of aqueous polymers substantially insoluble in the electrolyte solvents and white pigment.
Examples of white pigments which can be used in the present invention include: titanium dioxide (anatase or rutile type), barium sulfate, calcium carbonate, aluminum oxide, zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, alkaline earth metallic salts, talc, kaolin, zeolite, acid clay, glass, and organic compounds such as polyethylene, polystyrene, acryl resins, ionomers, ethylene-vinyl acetate copolymeric resins, benzoguanamine resins, urea-formaldehyde resins, melamine-formaldehyde resins, or polyamide resins. These substances may be uses individually or in combination, or in the form in which voids, capable of varying the refractive index, are contained in the particles.
In the present invention, titanium dioxide, zinc oxide and zinc hydroxide are preferably employed among the-above described white particles. Further, titanium oxide may be titanium oxide which has been subjected to a surface treatment employing an inorganic oxide (such as Al2O3, AlO(OH), or SiO2), or titanium oxide which has been subjected to a treatment employing an organic compound such as trimethylolethane, triethanolamine acetic acid salts, or trimethylcyclosilane, in addition to the above surface treatment.
Among these white particles, it is preferable to use titanium oxide or zinc oxide in view of minimization of coloration at high temperature and reflectance of elements due to refractive index.
Listed as an aqueous polymer which is substantially insoluble in electrolyte solvent according to the present invention may be water-soluble polymer and polymer which dispersed in water based solvent.
As polymers applicable to the present invention, there can be listed, for example, protein such as gelatin, or gelatin derivatives; cellulose derivatives; natural compounds including polysaccharides such as starch, gum arabic, dextran, pullulan, carrageenan; and synthetic polymers such as polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, acrylamide polymers, or derivatives thereof. The gelatin derivatives include acetyl gelatin and phthalic gelatin. The polyvinyl alcohol derivatives include terminal alkyl group-modified polyvinyl alcohol and terminal mercapto group-modified polyvinyl alcohol. The cellulose derivatives include hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.
In addition, there are also usable those described in Research Disclosure and on pages 71-75 of Unexamined Japanese Patent Application Publication (hereinafter referred to as JP-A) No. 64-13546; highly water-absorbing polymers, described in U.S. Pat. No. 4,960,681 and JP-A No. 62-245260, that is, homopolymers of vinyl monomers containing —COOM or —SO3 M (wherein M is a hydrogen atom or an alkali metal), or copolymers of these monomers or copolymers of the same with other monomers (for example, sodium methacrylate, ammonium methacrylate, or potassium acrylate). These binders may be used in combinations of at least 2 types.
In the present invention, preferably employed may be gelatin and derivatives thereof, or polyvinyl alcohol and derivatives thereof.
Listed as polymers dispersed in water based solvents may be latexes such as natural rubber latex, styrene butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, heat curable resins which are prepared by dispersing, in water based solvents, polyisocyanate based, epoxy based, acryl based, silicone based, polyurethane based, urea based, phenol based, formaldehyde based, epoxy-polyamide based, melamine based, or alkyd based resins, or vinyl based resins. Of these polymers, it is preferable to employ water based polyurethane resins described in JP-A No. 10-76621.
"Being substantially insoluble in electrolyte solvents", as described in the present invention, is defined as a state in which the dissolved amount per kg of the electrolyte solvents is 0-10 g in the temperature range of −20 to 120� C. It is possible to determine the above dissolved amount employing the methods known in the art, such as a weight measuring method, or a component quantitative method utilizing liquid chromatogram and gas chromatogram.
In the present invention, a preferred embodiment of the aqueous mixture of water based compounds and white pigments is dispersed in water with the dispersion methods known in the art. The mixing ratio of water based compounds/titanium oxide is preferably in the range of 1-0.01 in terms of volume ratio, but is more preferably in the range of 0.3-0.05.
In the present invention, a media on which the aqueous mixture of the water based compounds and white pigments is coated may be located anywhere as long as they are located on the structural components between the counter electrodes of the display element. However, it is preferable that they are provided on at least one of the above counter electrodes. Examples of media providing methods include a coating system, a liquid spraying system, a spraying method via a gas phase, such as a system which jets liquid droplets employing vibration of a piezoelectric element such as a piezoelectric system ink-jet head, a BUBBLE JET (registered trade name) ink-jet head which ejects liquid droplets employing a thermal head utilizing bumping, and a spray system in which liquid is sprayed via air or liquid pressure.
An appropriate coating system may be selected from any of the coating systems known in the art, and examples thereof include an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, an impregnation coater, a reverse roller coater, a transfer roller coater, a curtain coater, a double roller coater, a slide hopper coater, a gravure coater, a kiss roller coater, a bead coater, a cast coater, a spray coater, a calender coater, and an extrusion coater.
Methods to dry the aqueous mixture of water based compounds and white pigments provided on the medium are not particularly limited as long as they facilitate water evaporation. Examples thereof include heating employing a heating source, a heating method employing infrared radiation, and a heating method utilizing electromagnetic induction. Further, water evaporation may be performed under reduced pressure.
The term "porous" referred to in the present invention is of a penetrating state capable of inducing silver dissolution and deposition reaction and enabling ion species to move between electrodes, wherein a porous white scattering substance is formed by coating and drying the dispersion on an electrode, and an electrolyte liquid incorporating silver or a compound containing silver in its chemical structure is applied on the scattering substance, followed by being sandwiched with opposed electrodes to produce a potential difference between the opposed electrodes.
In the display element of the present invention, during coating and drying of the aforesaid water based dispersion or after drying thereof, the above water based dispersion is preferably hardened using a hardener.
As examples of hardeners used in the present invention, there are listed, for example, hardeners described in column 41 of U.S. Pat. No. 4,678,739, ibid. No. 4,791,042, and JP-A Nos. 59-116655, 62-245261, 61-18942, 61-249054, 61-245153, and 4-218044. More specifically, there are exemplified aldehyde based hardeners (e.g. formaldehyde), aziridine based hardeners, epoxy based hardeners, vinyl sulfone based hardeners (e.g., N,N′-ethylene-bis(vinylsulfonylacetamido)ethane), N-methylol based hardeners (e.g., dimethylol urea), boric acid, metaboric acid, or polymer hardeners (compounds described, for example, in JP-A No. 62-234157). When gelatin is used as a polymer, of these hardeners, a vinyl sulfone based hardener and a chlorotriazine based hardener are preferably used individually or in combination. Further, when a polyvinyl alcohol is used, a boron-containing compound such as boric acid or metaboric acid is preferably used.
There are used 0.001-1 g of, preferably 0.005-0.5 g of these hardeners per 1 g of the water based compound. Further, to enhance film strength, it is optionally possible to carry out heat treatment or moisture controlling during hardening reaction.
[Compounds Represented by Formula (1) and Formula (2)]
The display element of the present invention is characterized in containing in the electrolyte a compound represented by Formula (A) and further at least one compound represented by the aforesaid Formula (1) or Formula (2).
In Formula (1), R7 and R8 each represent a substituted or unsubstituted hydrocarbon group which includes a straight chain or a branched chain. The hydrocarbon group may contain one or more nitrogen atoms, oxygen atoms, phosphor atoms, sulfur atoms, or halogen atoms. When the hydrocarbon group forms a ring which contains a sulfur atom as a ring member, the ring is not an aromatic ring. Further, the atoms adjacent to the sulfur atom are preferably carbon atoms.
Examples of groups which may be substituted in the hydrocarbon groups are as follows: an amino group, a guanidino group, a quaternary ammonium group, a hydroxyl group, a halogenated compound, a carboxylic acid group, a carboxylate group, an amide group, a sulfinic acid group, a sulfonic acid group, the sulfate group, a phosphonic acid group, a phosphate group, a nitro group and a cyano group.
In order to produce dissolution and deposition of silver, generally, it is required to solubilize silver in an electrolyte. The common method is, for example, to incorporate a compound which has a chemical species that interacts with silver to form a coordination bond or a weak covalent bond with silver, and resulting in changing silver or the compound containing silver in the molecule into a soluble compound. Known chemical species described above are: a halogen atom, a mercapto group, a carboxyl group and an imino group. In the present invention, a thioether group effectively works as a silver dissolving agent with showing only a small effect to the other coexisting compounds and having a specific feature of high solubility in the solvent.
Specific examples of the compound represented by Formula (1) will now be listed, but the present invention is not limited to the exemplified compounds.
1-29: NaO3SCH2CH2CH2SCH2CH2SCH2CH2CH2SO3Na
1-31: H2N(NH)CSCH2CH2SC(NH)NH2.2HBr
1-32: H2N(NH)CSCH2CH2OCH2CH2OCH2CH2SC(NH)NH2.2HCl
1-33: H2N(NH)CNHCH2CH2SCH2CH2SCH2CH2NHC(NH)NH2.2HBr
1-34: [(CH3)3NCH2CH2SCH2CH2SCH2CH2N(CH3)3]2+.2Cl−
Of these exemplified compounds, the exemplified compound 1-2 is specifically preferable from the viewpoint of sufficiently producing the targeted effects of the present invention.
Then, the compound represented by Formula (2) will now be described.
In above Formula (2), M represents a hydrogen atom, a metallic atom, or a quaternary ammonium. Z represents a nitrogen-containing heterocycle, and n represents an integer of 0-5. R9 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a carbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, a carboxyl group, a carbonyl group, a sulfonyl group, an amino group, a hydroxy group, or a heterocyclic group. When n represents at least 2, R9 each may be the same or different and each may be joined to form a condensed ring.
The metallic atom represented by M in Formula (2) includes, for example, Li, Na, K, Mg, Ca, Zn, and Ag. The quaternary ammonium includes, for example, NH4, N(CH3)4, N(C4H9)4, N(CH3)3C12H25, N(CH3)3C16H33, and N(CH3)3CH2C6H5.
The nitrogen-containing heterocycle represented by Z in Formula (2) includes, for example, a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, an indole ring, an oxazole ring, a benzoxazole ring, a benzimidazole ring, a benzothiazole ring, a benzoselenazole ring, and a naphthoxazole ring. Among them, a triazole ring is preferable.
The halogen atom represented by R9 in Formula (2) includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented thereby includes, for example, a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group, a dodecyl group, a hydroxyethyl group, a methoxyethyl group, a trifluoromethyl group, and a benzyl group. The aryl group includes, for example, a phenyl group and a naphthyl group. The alkylcarbonamide group includes, for example, an acetylamino group, a propionylamino group, and a butyroylamino group. The arylcarbonamide group includes, for example, a benzoylamino group. The alkylsulfonamide group includes, for example, a methanesulfonylamino group and an ethanesulfonylamino group. The arylsulfonamide group includes, for example, a benzenesulfonylamino group and a toluenesulfonylamino group. The aryloxy group includes, for example, a phenoxy group. The alkylthio group includes, for example, a methylthio group, an ethylthio group, and a butylthio group. The arylthio group includes, for example, a phenylthio group and a tolylthio group. The alkylcarbamoyl group includes, for example, a methylcarbamoyl group, a dimethylcarbamoyl group, an ethylcarbamoyl group, a diethylcarbamoyl group, a dibutylcarbamoyl group, a piperidylcarbamoyl group, and a morpholylcarbamoyl group. The arylcarbamoyl group includes, for example, a phenylcarbamoyl group, a methylphenylcarbamoyl group, an ethylphenylcarbamoyl group, and a benzylphenylcarbamoyl group. The alkylsulfamoyl group includes, for example, a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfamoyl group, a diethylsulfamoyl group, a dibutylsulfamoyl group, a piperidylsulfamoyl group, and a morpholylsulfamoyl group. The arylsulfamoyl group includes, for example, a phenylsulfamoyl group, a methylphenylsulfamoyl group, an ethylphenylsulfamoyl group, and a benzylphenylsulfamoyl group. The alkylsulfonyl group includes, for example, a methanesulfonyl group and an ethanesulfonyl group. The arylsulfonyl group includes, for example, a phenylsulfonyl group, a 4-chlorophenylsulfonyl group, and a p-toluenesulfonyl group. The alkoxycarbonyl group includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. The aryloxycarbonyl group includes, for example, a phenoxycarbonyl group. The alkylcarbonyl group includes, for example, an acetyl group, a propionyl group, and a butyroyl group. The arylcarbonyl group includes, for example, a benzoyl group and an alkylbenzoyl group. The acyloxy group includes, for example, an acetyloxy group, a propionyloxy group, and a butyroyloxy group. The heterocyclic group includes, for example, an oxazole ring, a thiazole ring, a triazole ring, a selenazole ring, a tetrasol ring, an oxadiazole ring, a thiadiazole ring, a thiazin ring, triazine ring, a benzoxazole ring, a benzothiazole ring, an indolenine ring, a benzoselenazole ring, a naphthothiazole ring, a triazaindolizine ring, a diazaindolizine ring, and a tetraazaindolizine ring. These substituents may further have a substituent.
Specific examples, which are preferable, of the compound represented by Formula (2) will now be listed that by no means limit the scope of the present invention.
Of these exemplified compounds, the exemplified compounds 2-12 and 2-18 are specifically preferable from the viewpoint of sufficiently producing the targeted effects.
In the display element of the present invention, the condition specified by the following expression (1) is satisfied, provided that [X] is the molar concentration of a halogen ion and halogen atom contained in an electrolyte and is expressed in mol/kg; and [Ag] is the total molar concentration of silver and a compound containing the silver in its chemical structure, contained in the electrode and is expressed in mol/kg.
0≦[X]/[Ag]≦0.01. Expression (1)
The halogen atom referred to in the present invention refers to an iodine atom, a chlorine atom, a bromine atom, or a fluorine atom. When [X]/[Ag] is more than 0.01, X−→X2 is induced during oxidation-reduction reaction of silver, and then X2 dissolves blackened silver by readily undergoing cross-oxidation with the blackened silver, which becomes one of the factors decreasing memory capability. Therefore, the molar concentration of a halogen atom is preferably as low as possible with respect to that of silver. In the present invention, the relationship of 0≦[X]/[Ag]≦0.001 is more preferable. When halogen ions are added, with regard to the halogen species, the sum of the molar concentration of each of the halogen species is preferably [I]<[Br]<[Cl]<[F] from the viewpoint of enhancing memory capability.
(Solvent in Electrolyte)
To the electrolyte of the present invention, any solvents may be used together with the electrolyte to the extent that the targeted effects of the present invention are not adversely affected. Specifically, there can be listed tetramethylurea, sulfolane, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, 2-(N-methyl)-2-pyrrolidinone, hexamethylphospholtriamide, N-methylpropioneamide, N,N-dimethylacetamide, N-methylacetamide, N,N-dimetylformamide, N-metylformamide, butylonitrile, propionitrile, acetonitrile, acetylacetone, 4-methyl-2-pentanone, 2-butanol, 1-butanol, 2-propanol, 1-propanol, ethanol, methanol, acetic anhydride, ethyl acetate, ethyl propionate, dimethoxyethane, diethoxyfuran, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol monobutyl ether, and water. Of these solvents, at least one type of solvent, featuring a freezing point of at most −20� C. and a boiling point of at least 120� C., is preferably contained.
Solvents employable in the present invention include compounds described in J. A. Riddick, W. B. Bunger, T. K. Sakano, "Organic Solvents", 4th ed., John Wiley & Sons (1986); Y. Marcus, "Ion Solvation", John Wiley & Sons (1985); C. Reichardt, "Solvents and Solvent Effects in Chemistry", 2nd ed., VCH (1988); and G. J. Janz, R. P. T. Tomkins, "Nonaquaeous Electrolytes Handbook", Vol. 1.., Academic Press (1972).
In the present invention, the electrolyte solvent may be a single kind of solvent or a solvent mixture. However, a mixed solvent containing ethylene carbonate is preferable. The amount of ethylene carbonate added is preferably from 10% by weight -90% by weight based on the total electrolyte solvent weight. A specifically preferable electrolyte solvent is a mixed solvent of propylene carbonate/ethylene carbonate at a weight ratio of 7/3-3/7. When the propylene carbonate ratio is more than 7/3, poor ion conductivity is exhibited, resulting in decreased response speed. When the ratio is less than 3/7, an electrolyte tends to be deposited at low temperatures.
(Electrolyte-Silver Salt)
In the display element of the present invention, there can be used silver salt compounds known in the art such as silver iodide, silver chloride, silver bromide, silver oxide, silver sulfide, silver citrate, silver acetate, silver behenate, silver p-toluenesulfonate, silver salts of mercapto compounds, and silver complexes of iminodiacetic acids. Of these, it is preferable to use, as silver salts, compounds without a nitrogen atom exhibiting coordination capability with a halogen, carboxylic acid, or silver, and for example, silver p-toluenesulfonate is preferable.
The concentration of silver ions contained in the electrolyte of the present invention is preferably in the range of 0.2 mol/kg≦[Ag]≦2.0 mol/kg. When the silver ion concentration is less than 0.2 mol/kg, a diluted silver solution is formed to lower the driving rate, while when it exceeds 2 mol/kg, solubility is degraded, which tends to result in inconvenience of deposition during low temperature storage.
In the display element of the present invention, in addition to the components described above, various constituent layers may be provided, if appropriate.
(Porous Electrode Incorporating Metal Oxide)
Further, in the display element of the present invention, a porous electrode incorporating a metal oxide can also be used.
In the display element of the present invention, it was found that when, of the opposed electrodes, the electrode on the side of no image observation was protected with a porous electrode incorporating a metal oxide, oxidation-reduction reaction of silver or a compound containing silver in its chemical structure on the side of no image observation occurred on or within the porous electrode incorporating the metal oxide. Accordingly, the option of selecting the type of the electrode on the side of no image observation can be broadened and the durability thereof can be enhanced.
A metal oxide constituting the porous electrode of the present invention includes, for example, titanium oxide, silicon oxide, zinc oxide, tin oxide, Sn-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide, or a mixture thereof.
The porous electrode is formed via bonding or contacting of plural particles of any of the above metal oxide. The average particle diameter of the metal oxide fine particles is preferably 5 nm-10 μm, more preferably 20 nm-1 μm. Further, the specific surface area of the metal oxide particles is preferably 1�10−3-1�102 m2/g, more preferably 1�10−2-10 m2/g. Still further, any appropriate shape such as the amorphous, acicular, or spherical one is employable as the shape of the metal oxide particles.
As the forming or bonding method of metal oxide particles, a sol-gel method and a firing method known in the art are employable, including, methods described, for example, in 1) Journal of the Ceramic Society of Japan, 102, 2, P 200 (1994), 2) Yogyo Kyokai Shi, 90, 4, p 157, and 3) J. of Non-Cryst. Solids, 82, 400 (1986). Further, there can be used a method in which titanium oxide dendrimer particles prepared using a gas phase method are coated on a substrate via dispersion on a solution and then a solvent is removed by drying at a temperature of about 120—about 150� C. to obtain a porous electrode. The metal oxide particles are preferably in the state of being bonded, and further in the state where a resistance of at least 0.1 g, preferably at least 1 g, is exhibited, based on measurement using a continuous weight surface measurement system (e.g., a scratch tester).
The term "porous" referred to in the present invention is of a penetrating state where a porous electrode is arranged and then a potential difference is produced between opposed electrodes, which enables induction of silver dissolution and deposition reaction and enables ion species to move in the porous electrode.
(Electron Insulating Layer)
In the display element of the present invention, an electron insulating layer can be provided.
It is only necessary for an electron insulating layer applicable to the present invention to be a layer exhibiting ion conductivity as well as electron insulating properties. There are listed, for example, a solid electrolyte film in the form of film of a polymer with a polar group or a salt; a pseudo-solid electrolyte film composed of a porous film, exhibiting high electron insulating properties, in the voids of which an electrolyte is held; a polymer porous film having voids; and a porous body of an inorganic material such as a silicon-containing compound featuring a low specific dielectric constant.
As a forming method of a porous film, there can be used any appropriate method known in the art such as a firing method (fusing method) (utilizing pores created among particles prepared by partially fusing polymer fine particles or inorganic particles via addition of a binder); an extraction method (in which a constituent layer is formed using an organic or inorganic substance soluble in a solvent and a binder insoluble in the solvent, followed by dissolving the organic or inorganic substance with the solvent to obtain fine pores); a foaming method of allowing a high molecular weight polymer to foam by heating or degassing; a phase conversion method of allowing a mixture of polymers to be phase-separated by use of a good solvent and a poor solvent; and a radiation exposure method of forming pores via exposure of various kinds of radiations.
Specifically, there can be listed the electron insulating layers described in JP-A Nos. 10-30181, 2003-107626; Examined Japanese Patent Application Publication No. 7-95403; and Japanese Patent Publication Nos. 2635715, 2849523, 2987474, 3066426, 3464513, 3483644, 3535942, and 3062203.
(Electrolyte Materials)
In the display element of the present invention, the electrolyte can appropriately incorporate any of the following compounds when the electrolyte is liquid. Examples of the compounds include a potassium compound such as KCl, KI, or KBr; a lithium compound such as LiBF4, LiClO4, LiPF6, or LiCF3SO3; and a tetraalkylammonium compound such as tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetraethylammonium borofluoride, tetrabutylammonium borofluoride, or tetrabutylammonium halide. Further, there can preferably be used the fused salt electrolyte compositions described in Paragraph Nos. [0062]-[0081] of JP-A No. 2003-187881. Still further, there can also be used a compound which forms an oxidation-reduction pair such as I−/I3 −, Br−/Br3 −, or quinone/hydroquinone.
Further, when being solid, a solid electrolyte can incorporate any of the following compounds exhibiting electron or ion conductivity.
Examples of the compounds include a fluorinated vinyl based polymer containing perfluorosulfonic acid; polythiophene; polyaniline; polypyrrole; a triphenylamine; a polyvinylcarbazole; a polymethylphenylsilane; a calcogenide such as Cu2S, Ag2S, Cu2Se, or AgCrSe2; a fluorine-containing compound such as CaF2, PbF2, SrF2, LaF3, TlSn2F5, or CeF3; a lithium salt such as Li2SO4, Li4SiO4, Li3PO4; and a compound such as ZrO2, CaO, Cd2O3, HfO2, Y2O3, Nb2O5, WO3, Bi2O3, AgBr, AgI, CuCl, CuBr, CuBr, CuI, LiI, LiBr, LiCl, LiAlCl4, LiAlF4, AgSBr, C5H5NHAg5I6, Rb4 Cu16I7Cl13, Rb3Cu7Cl10, LiN, Li5NI12, or Li6NBr3.
Still further, a gel-like electrolyte can also be used as a supporting electrolyte. When an electrolyte is nonaqueous, there can be used the oil gelling agents described in Paragraph Nos. [0057]-[0059] of JP-A No. 11-185836.
(Thickeners to be Added to the Electrolyte)
In the display element of the present invention, there can be used a thickener for the electrolyte, including gelatin, gum arabic, poly(vinyl alcohol), hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, poly(vinylpyrrolidone), poly(alkylene glycol), casein, starch, poly(acrylic acid), poly(methylmethacrylic acid), poly(vinyl chloride), poly(methacrylic acid), copoly(styrene-maleic anhydride), copoly(styrene-acrylonitrile), copoly(styrene-butadiene), a poly(vinyl acetal) (e.g., poly(vinyl formal) and poly(vinyl butyral)), a poly(ester), a poly(urethane), a phenoxy resin, poly(vinylidene chloride), a poly(epoxide), a poly(carbonate), poly(vinyl acetate), a cellulose ester, and a poly(amide); and including, as a transparent hydrophobic binder, polyvinylbutyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, poly(acrylic acid), and polyurethane.
These thickeners may be used in combinations of at least 2 types. There are further listed the compounds described on pages 71-75 of JP-A No. 64-13546. Of these, a compound preferably used includes a polyvinyl alcohol, a polyvinylpyrrolidone, a hydroxypropyl cellulose, and a polyalkylene glycol, from the viewpoint of enhancement of compatibility with various types of additives and of dispersion stability of white particles.
(Other Additives)
The constituent layers of the display element of the present invention include auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cutting layer, and a backing layer. These auxiliary layers may incorporate, as appropriate, chemical sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, high boiling point solvents, antifoggants, stabilizers, development inhibitors, bleach accelerators, fixing accelerators, color mixing inhibitors, formalin scavengers, toning agents, hardeners, surfactants, thickeners, plasticizers, lubricants, UV absorbents, anti-irradiation dyes, filter light absorbing dyes, fungicides, polymer latexes, heavy metals, antistatic agents, and matting agents.
The additives described above are detailed in Research Disclosure (hereinafter referred to simply as RD), Vol. 176, Item/17643 (December 1978), RD, Vol. 184, Item/18431 (August 1979), RD, Vol. 187, Item/18716 (November 1979), and RD, Vol. 308, Item/308119 (December 1989).
Types of compounds shown in three of these RD articles are listed below with the described portions thereof.
Page & Class
Page & Class
Page & Class
648 upper
648 upper
649 upper
651 left
650 right
Active Agent
650 right
650 right
Matting Agent
650 right
A metallocene derivative can be used in a constitution layer of the display element of the present invention. A ferrocene derivative is preferably used as an example of a metallocene derivative. Specific examples of a ferrocene derivative are: ferrocene, methylferrocene, dimethylferrocene, ethylferrocene, propylferrocene, n-butylferrocene, t-butylferrocene, and 1,1-dicarboxylferrocene. A metallocene derivative can be used singly or used as a mixture of two or more metallocene derivatives.
(Layer Structure)
The constituent layers between the opposed electrodes in the display element of the present invention will now further be described.
As a constituent layer according to the display element of the present invention, a constituent layer incorporating a positive hole transport material can be provided. The positive hole transport material includes, for example, an aromatic amine, a triphenylene derivative, an oligothiophene compound, a polypyrrole, a polyacetylene derivative, a polyphenylene vinylene derivative, a polythienylene vinylene derivative, a polythiophene derivative, a polyaniline derivative, a polytoluidine derivative, CuI, CuSCN, CuInSe2, Cu(In,Ga)Se, CuGaSe2, Cu2O, CuS, CuGaS2, CuInS2, CuAlSe2, GaP, NiO, CoO, FeO, Bi2O3, MoO2, and Cr2O3.
As a substrate usable in the present invention, there are also preferably used a synthetic plastic film including a polyolefin such as polyethylene or polypropylene, a polycarbonate, cellulose acetate, polyethylene terephthalate, polyethylene dinaphthalene dicarboxylate, a polystyrene naphthalate, polyvinyl chloride, polyimide, a polyvinyl acetal, and polystyrene. A syndiotactic structure polystyrene is also preferable. These can be prepared via the methods described, for example, in each of JP-A Nos. 62-117708, 1-46912, and 1-178505. Further, there are exemplified metal substrates such as stainless steel; paper supports such as baryta paper or resin coated paper; supports prepared by arranging a reflection layer on any of the above plastic films; and those which are described in JP-A No. 62-253195 (pages 29-31) as supports. There can also preferably be used those described on page 28 of RD No. 17643; from the right column of page 647 to the left column of page 648 of RD No. 18716; and on page 879 of RD No. 307105. As these substrates, there can be used those heat-treated at a temperature of at most Tg so that core-set curl is decreased, as described in U.S. Pat. No. 4,141,735. Further, any of these supports may be surface-treated to enhance adhesion of the support to other constituent layers.
In the present invention, there may be employed, as surface treatment, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment. Further, the supports described on pages 44-149 of Kochi Gijutsu (Known Techniques), No. 5 (issued on Mar. 22, 1991, published by Aztech Corp.) may be used. Still further, there are listed those described on page 1009 of RD, No. 308119, and in "Supports" of Product Licensing Index, Vol. 92, Page 108. In addition, glass substrates, and epoxy resins kneaded with glass powder are employable.
In the display element of the present invention, at least one of the opposed electrodes is preferably a metal electrode. For the metal electrode, there can be used a metal known in the art such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, or bismuth, and alloys thereof. For the metal electrode, preferable are metals exhibiting a work function close to the oxidation-reduction potential of silver in an electrolyte. Of these, a silver electrode or an electrode having a silver content of at least 80% is advantageous to maintain a reduced state of silver, which is also superior in anti-staining of the electrode. As preparation methods of the electrode, there can be used conventional ones such as a vapor deposition method, a printing method, an ink-jet method, a spin coating method, and a CVD method.
Further, in the display element of the present invention, at least one of the opposed electrodes is preferably a transparent electrode. The transparent electrode is not specifically limited if being transparent and electrically conductive. Examples thereof include Indium Tin Oxide (ITO: indium tin oxide), Indium Zinc Oxide (IZO: indium zinc oxide), fluorine-doped tin oxide (FTO), indium oxide, zinc oxide, platinum, gold, silver, rhodium, copper, chromium, carbon, aluminum, silicon, amorphous silicon, and BSO (Bismuth Silicon Oxide). To form an electrode in such a manner, for example, mask deposition via a method of sputtering an ITO film on a substrate, or patterning via a photolithographic method after formation of the entire ITO film may be carried out. The surface resistance value is preferably at most 100 Ω/□, more preferably at most 10 Ω/□. The thickness of the transparent electrode is not specifically limited, but is commonly 0.1-20 μm.
(Other Components of Display Element)
For the display element of the present invention, any appropriate sealing agent, columnar structure substance, and spacer particle are employable, if appropriate.
The sealing agent, functioning to enclose the content in order not to leak out, is also referred to as an enclosing agent. As the sealing agent, there are employable curable type resins including thermally curable, light curable, moisture curable, or anaerobically curable resins such as epoxy resins, urethane resins, acrylic resins, vinyl acetate reins, ene-thiol resins, silicone resins, or modified polymer resins.
The columnar structure substance provides strong self-holding force (strength) between the substrates, including, for example, columnar structure substances such as cylindrical, square pole, elliptically cylindrical, and trapezoidally cylindrical substances, wherein these substances are arranged so as to form a predetermined pattern such as a grid at regular intervals. A stripe arrangement at predetermined intervals may be also employed. The columnar structure substance is not arranged at random, but preferably arranged in such a manner as to appropriately hold the distance between the substrates, and not to inhibit displaying images, wherein the columnar structure substance is arranged at regular intervals, in a pattern in which the intervals are gradually varied, or in a predetermined pattern repeated at regular intervals. When the ratio of the display area of the display element occupied by the columnar structure substance is in the range of 1% -40%, the display element exhibits practically adequate strength.
A spacer may be placed between a pair of the substrates to uniformly hold the gap thereof. As the spacer, spherical objects of resins or inorganic oxides are exemplified. Further, an adhesive spacer, the surface of which is coated with a thermoplastic resin, may suitably be used. To uniformly hold the gap between the substrates, the columnar structure substance may be provided by itself, and both of the spacer and the columnar structure substance may be also provided. Further, instead of the columnar structure substance, the spacer may be used by itself as a space-holding member. When a columnar structure is formed, the diameter of the spacer is equivalent to at most the height of the columnar structure substance, but is preferably equal to the height thereof. When no columnar structure substance is formed, the diameter of the spacer is equivalent to the cell gap thickness.
(Screen Printing)
In the present invention, a sealing agent, a columnar structure substance, and an electrode pattern may be formed via a screen printing method. In the screen printing method, the electrode surface of a substrate is covered with a screen having a predetermined pattern, followed by placing a printing material (being a composition, to form the columnar structure substance, such as radiation curable resins) on the screen. Subsequently, a squeegee is moved at a predetermined pressure, angle, and rate, whereby the printing material is transferred onto the substrate via the screen pattern. Then, the transferred material is thermally cured and dried.
When the columnar structure substance is formed via the screen printing method, resin materials to be used are not limited to the radiation curable resins. For example, thermally curable resins or thermoplastic resins such as epoxy resins or acrylic resins may be also used. Examples of the thermoplastic resins include polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polymethacrylate resins, polyacrylate resins, polystyrene resins, polyamide resins, polyethylene resins, polypropylene resins, fluorine resins, polyurethane resins, polyacrylonitrile resins, polyvinyl ether resins, polyvinyl ketone resins, polyether resins, polyvinyl pyrrolidone resins, saturated polyester resins, polycarbonate resins, and chlorinated polyether resins. These resin materials are preferably used in a paste form prepared by dissolving corresponding resins in appropriate solvents.
After the columnar structure substance has been formed on the substrate as described above, a spacer is provided on at least one of the substrates, as appropriate, and then a pair of the substrates are stacked to form an empty cell, wherein the electrode-forming surfaces are faced each other. A display cell is obtained by bonding a pair of the stacked substrates via heat application under pressure applied from both sides thereof. To prepare a display element, an electrolyte composition is injected between the substrates, for example, via a vacuum injection method. Alternatively, in the bonding process of the substrates, a liquid crystal component may be enclosed just before bonding of the substrates, after the electrolyte component has been dripped on one of the substrates.
(Driving Method of Display Element)
In the display element of the present invention, it is preferable to perform a driving operation such that blackened silver is deposited by applying a voltage of at least the deposition overpotential and the deposition of blackened silver is continued by applying a voltage of at most the deposition overpotential. Performance of such a driving operation results in reduced writing energy, reduced load of the drive circuit, and enhanced writing speed as an image screen. Existence of overpotential in electrode reaction is generally known in the electrochemistry field. The overpotential is detailed, for example, on page 121 of "Denshi-ido no Kagaku/Denkikagaku Nyumon (Chemistry of Electron Transfer/Introduction to Electrochemistry)" (1996, published by Asakura Shoten). The display element of the present invention is also regarded as electrode reaction of an electrode with silver in an electrolyte so that existence of an overpotential in silver dissolution and deposition is readily understood. Since the magnitude of an overpotential is controlled by an exchange current density, from the fact that after formation of blackened silver, deposition of blackened silver can be continued via application of a voltage of at most a deposition overpotential, it is presumed that the surface of blackened silver has less excess energy, resulting in easy electron injection.
The driving operation for the display element of the present invention is either a simple matrix drive or an active matrix drive. In the present invention, the simple matrix drive refers to a driving method, in which current is successively applied to a circuit formed by vertically crossing of an anode line containing plural anodes to a facing cathode line containing plural cathodes. The use of the simple matrix drive has the advantage that the circuit structure and the driving IC can be simplified to reduce the production cost. The active matrix drive refers to a driving method, in which scanning lines, data lines, and current supplying lines are formed on a grid, and driving is carried out via TFT circuits positioned in each of the grids. The active matrix drive is advantageous in gradation and memory functions since a switching function is allocated to each pixel. The circuit described, for example, in FIG. 5 of JP-A 2004-29327 is employable.
(Commercial Applications)
The display element of the present invention is applied to fields including electronically published books, ID cards, public use, transportation, broadcasting, financial clearance, and distribution and logistics. Specific examples include door keys, student ID cards, employee ID cards, membership cards, convenience store cards, department store cards, vending machine cards, gas station cards, subway and railroad cards, bus cards, cashing cards, credit cards, highway cards, driver's license cards, hospital consultation cards, electronic medical charts, health insurance cards, basic resident registers, passports, and electronic books.
The present invention will now specifically be described with reference to examples, but the scope of the present invention is not limited to them. Incidentally, "part" or "%" to be shown in the examples represents "part by weight" or "% by weight" unless otherwise specified.
<<Preparation of Display Element>>
(Preparation of Display Element 1)
(Preparation of Electrolyte Liquid 1)
To 2.5 g of dimethyl sulfoxide was added 90 mg of sodium iodide, 50 mg of example compound (2-19), 75 mg of silver iodide, and 0.1 g of ethylmethylimidazolium-bistrifluoromethanesulfonimide. After the mixture was completely dissolved, 150 mg of polyvinylpyrrolidone (average molecular weight of 15,000) was added and the mixture was stirred for 1 hour with heating at 120� C. to obtain electrolyte liquid 1.
(Preparation of Electrode 1)
An ITO (Indium Tin Oxide) film having a pitch of 145 μm and a width of 130 μm was formed on a glass substrate of a size of 2 cm�4 cm with a thickness of 1.5 mm using a commonly known method to obtain a transparent electrode (electrode 1).
(Preparation of Electrode 2)
A silver-palladium electrode (electrode 2) having an electrode thickness of 0.8 μm, a pitch of 145 μm and a distance between the electrodes of 130 μm was formed on a glass substrate of a size of 2 cm�4 cm with a thickness of 1.5 mm using a commonly known method to obtain electrode 2.
(Preparation of Electrode 3)
An isopropanol mixture liquid was prepared by ultrasonic dispersion of 20 weight % of titanium oxide with isopropanol containing 2 weight % of polyvinyl alcohol (having an average polymerization degree of 3500 and a saponification degree of 87%). Thus prepared isopropanol mixture liquid was applied with a thickness of 100 μm on electrode 2 on the edge of which was coated with an olefinic sealing agent containing 10 volume % of glass beads having an average particle size of 40 μm. Then the coated isopropanol mixture liquid was dried at 15� C. for 30 minutes so as to evaporate the solvent, and was further dried at 15� C. for 30 minutes to obtain electrode 3.
(Preparation of Display Element)
Electrode 3 and electrode 1 were bonded together in such a manner that the striped form electrodes crossed at a right angle, then followed by heat pressing to prepare an empty cell. Electrolyte liquid 1 was vacuum injected into the empty cell, and the injection inlet was sealed with an epoxy-based ultraviolet curable resin to prepare Display Element 1.
(Preparation of Display Element 2)
Display Elements 2 was prepared in the same manner as in preparation of Display Element 1 except that example compound (2-19) in electrolyte liquid 1 was exchanged with example compound (1-2).
(Preparation of Display Element 3)
Display Elements 3 was prepared in the same manner as in preparation of Display Element 1 except that ethylmethylimidazolium-bistrifluoromethanesulfonimide in electrolyte liquid 1 was exchanged with the same amount of azacyclopentane-1-spiro-1′-azacyclobutyl-p-toluenesulfonic acid.
(Preparation of Display Element 4)
Display Elements 4 was prepared in the same manner as in preparation of Display Element 1 except that ethylmethylimidazolium-bistrifluoromethanesulfonimide in electrolyte liquid 1 was exchanged with the same amount of azacyclohexane-1-spiro-1′-azacyclobutyl-p-toluenesulfonic acid.
(Preparation of Display Element 5)
Display Elements 5 was prepared in the same manner as in preparation of Display Element 4 except that example compound (2-19) in the electrolyte liquid was exchanged with example compound (1-2).
(Preparation of Display Element 6)
Display Elements 6 was prepared in the same manner as in preparation of Display Element 1 except that ethylmethylimidazolium-bistrifluoromethanesulfonimide in electrolyte liquid 1 was exchanged with the same amount of spiro-(1,1′)-biazacyclobutyl-p-toluenesulfonic acid.
(Preparation of Display Element 7)
Display Elements 7 was prepared in the same manner as in preparation of Display Element 3 except that dimethyl sulfoxide, silver iodide and example compound (2-19) in electrolyte liquid 1 were each respectively exchanged with the same amount of propylene carbonate, silver p-toluenesulfonate and example compound (2-12).
(Preparation of Display Element 8)
Display Elements 8 was prepared in the same manner as in preparation of Display Element 7 except that azacyclohexane-1-spiro-1′-azacyclobutyl-p-toluenesulfonic acid in the electrolyte liquid was exchanged with the same amount of spiro-(1,1′)-biazacyclobutyl-p-toluenesulfonic acid.
(Preparation of Display Elements 9-16)
Display Elements 9-16 were prepared in the same manner as in preparation of Display Element 8 except that the amount of sodium iodide in the electrolyte liquid were each respectively changed to 0 mg, 5.28 mg, 7.2 mg, 46 mg, 0.53 mg, 0.72 mg, 0.47 mg, and 0.23 mg.
<Evaluation of Display Elements>
(Resistance of Color Change)
The driving condition for each of display elements thus prepared were determined so as to exhibit L* value of 65 using spectrophotometer CM-3700d (produced by Konica Minolta Sensing, Inc.). Then the obtained driving condition was applied to display elements to produce white color state. L* value, a* value and b* value of the produced white color state were measured. They were denoted as L1, a1 and b1 respectively. Display elements were subjected to 1000 times of repeated change of whitening-blackening using the same driving condition. Then L* value, a* value and b* value of the produced white color state were measured to give L2, a2 and b2.
From each of the measured values, the evaluation value for color change were calculated by the equation:
ΔE=[(L 2 −L 1)2+(a 2 −a 1)2+(b 2 −b 1)2]1/2.
The relative value of ΔE for each display element was determined by setting ΔE for Display Element 1 to be 1. The obtained results were shown in Table 1. The smaller the ΔE, the color change under repeated driving condition is small and the property of display element is indicated to be good.
Resistance of
Color Change
ΔE value
From the results shown in Table 1, the display elements having the constitution of the present invention have a reduced color change an superior to others after repeated driving.
The similar superior effects were obtained from the display elements prepared by changing example compound (1-2) used in Example 1 to example compounds (1-3) or (1-4), and also example compound (2-19) was changed to example compounds (2-18) or (2-17).
|Cited Patent
|Filing date
|Publication date
|Dec 15, 1978
|Dec 23, 1980
|Bell Telephone Laboratories, Incorporated
|Electrodeposition display device
|Apr 5, 1995
|Nov 24, 1998
|Hoechst Aktiengesellschaft
|Spiro compounds and their use as electroluminescence materials
|Jun 30, 2000
|Apr 2, 2002
|Heterocyclic aromatic anion salts, and their uses as ionic conducting materials
|Mar 25, 2004
|Sep 29, 2005
|Eastman Kodak Company
|Electroluminescent device with anthracene derivative host
|Feb 14, 2006
|Jun 19, 2008
|Daikin Industries, Ltd
|Electrolytic Solution
|Oct 19, 2009
|Apr 22, 2010
|Konica Minolta Holdings, Inc.
|Display element
|Title not available
|Title not available
|Title not available
|Title not available
|Nov 18, 2005
|Jun 15, 2006
|Konica Minolta Holdings, Inc.
|Display element
|Jan 13, 2006
|Aug 10, 2006
|Konica Minolta Holdings, Inc.
|Display element
|International Search Report for International Application No. PCT/JP2007/070061 mailed Nov. 20, 2007 with English Translation.
|U.S. Classification
|359/270, 204/468, 359/267
|International Classification
|Cooperative Classification
|European Classification
|May 7, 2009
Owner name: KONICA MINOLTA HOLDINGS, INC., JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KOKEGUCHI, NORIYUKI;REEL/FRAME:022654/0894
Effective date: 20090309
|Jul 2, 2014
|Fee payment
Year of fee payment: 4


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Recruitment Consultant
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Oaklands Global is hiring… Oaklands Global is market leading recruitment consultancy specialising in the Aviation & Aerospace Industry. Due to continued expansion, we are looking for ambitious and self-motivated Recruitment Consultants to join our expanding team, based in Tunbridge Wells, Kent. At Oaklands Global we strongly believe in personal development and a structured career path. We understand that continuous support and learning is vital to making a successful recruiter and we provide all employees with professional in-house and external training. Duties: •Managing and developing an established portfolio of international clients. •Business development through lead generation and cold/warm calls. •Identifying and developing new sales opportunities. •Sourcing and head-hunting candidates through database searches & networking. •Qualifying candidate's suitability for a variety of specialist roles throughout the industry. •Developing a good understanding of the Aviation and Aerospace industries. •Managing offers, negotiating packages and finalising placements. •Establish yourself as a specialist in our sector. Desired Skills and Experience: •Candidates must have at least 1 year's successful sales or telesales experience and demonstrate a strong desire to succeed. •Excellent written and verbal communication skills are essential and so is a good team working ethic. •Relationship management and business development skills are essential. •Aviation, Aerospace or Technical Recruitment experience is advantageous All opportunities are permanent and candidates must be within a commutable distance of Tunbridge Wells, Kent or willing to relocate. We offer a vibrant office environment, competitive starting salaries, very generous commission structures and a variety of other target driven benefits
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CEU's Dondra Nance talks to some of the participants at TRiO day. Last week, CEU's TRiO office invited the community to a one-day program featuring information and activities provided by the TRiO program. Many toured the multimedia room featuring information tables about local, regional and national TRiO programs. TRIO DayTRIO DayTRIO Day
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Conference Speakers
ISACA Keynote Speakers
Dr. Christos Dimitriadis, INTRALOT Group Director of Information Security
ISACA International President 2015-2016, Ph.D., CISA, CISM, CRISC
Abstract: In this keynote, Christos will present an overview of the Cyber Threat landscape and present ISACA CSX, the new Cyber Security Program of ISACA. Christos will also discuss how several professions are impacted by the emerging Cyber Threats internationally, as well as the response at a policy level in several jurisdictions.
BIO: International President Christos K. Dimitriadis, Ph.D., CISA, CISM, CRISC , is group director of Information Security for INTRALOT (Greece) He has served ISACA as international vice president for three terms, has been a member of the Board of Directors for four terms, chaired the Knowledge Board, the External Relations Committee, the COBIT for Security Task Force, and has been a member of the Relations Board, Academic Relations Committee, Journal Editorial Committee and Business Model for Information Security Workgroup.
Rosemary Amato, CISA, CMA, CPA
ISACA International Vice President, Deloitte Netherlands
Abstract: How do you start tackling risk concerns that may become evident when you use Big Data? Key Concepts surrounding an understanding of Big Data will be presented. Should an advanced data visualization tool be used or not used with Big Data? Qlik will be discussed with a case study of an implementation to showcase how to recognize risks within your Big Data.
BIO: International Vice President Rosemary M. Amato, CISA, CMA, CPA, is a Director within the Dutch member firm of Deloitte, based in Amsterdam. Her current role is that of Program Director for Global Client Intelligence. Her previous roles included being the Global Enterprise Risk Services Knowledge Management leader and a client service practitioner for 12 years serving Consumer Business, Manufacturing and Life Sciences clients in the areas of IT Audit, Internal Audit, Security and Privacy controls, GRC and other Risk offerings. She has been a member of ISACA's Knowledge Board, and previously co-chaired their Knowledge Management and Education Committee. She also served on the first ISACA Knowledge Management Task Force team. She is a CISA, as well as a CPA, CMA and a Six Sigma Green Belt.
Expert Speakers (in alphabetical order)
with Mr. Antal Lajos, Partner, Enterprise Risk Services - Cyber Risk Services, Deloitte Hungary
Abstract: IT audit has always been an engagement that professionals treated as a commodity, the service providers delivering the IT audits followed similar workplans, steplines and delivered results in similar ways to address the client`s IT systems. We are all aware of the so called low-hanging-fruits that mean the password policies, log systems, the segregation of duty restrictions and the list goes on. Honestly, this approach ticks the boxes and looks like something of value on a board meeting agenda, but does not address real challenges and issues. This approach does not take into account the organizations size, industry, vulnerable points and the constantly changing cyber risk landscape. This approach no longer –if it ever – delivers true value to the client organizations and does not help them develop their IT security strategy in a way that reduces/mitigates risk and builds a strong and effective IT security system. Lajos Antal has over 20 years of IT security experience and in addition to the penetration, vulnerability tests, his team delivers IT audits on regular basis. He will speak about how the security industry evolved in the past few years and what he sees as the challenges of IT auditors. Lajos will speak about how the security industry evolved in the past few years and what he sees as the challenges of IT auditors.
BIO: Lajos Antal, Partner, Enterprise Risk Services - Cyber Risk Services, Deloitte Hungary is head of the Hungarian Deloitte Cyber Risk Services team. Lajos has over 18 years Big4 Security Consulting experience. He led and performed high number of security penetration tests primarily for clients across Europe. He also led many large scale IT security risk assessment project. Lajos has in depth knowledge of open systems security and is a specialist of IBM mainframe security. In addition, Lajos is also an experienced forensic&fraud examiner and has led and completed several fraud related investigations – from the stage of forensic data collection, imaging to giving the witness testimonies at courts to support clients` legal claims - with his team.
with Ms. Athena Bourka, Expert in Network & Information Security, ENISA
Abstract: The presentation will present the main privacy risks associated with big data and will explore relevant technologies that can support the protection of personal data in the big data era.
BIO: Athena Bourka, received from NTUA her PhD on information security in 2002. For the period 2004-2013 was employed in the Auditors Department of the Hellenic Data Protection Authority (HDPA). During that time she was seconded twice as a National Expert on IT privacy and security to the European Data Protection Supervisor (EDPS). In January 2014 she joined the European Network and Information Security Agency's (ENISA) team on privacy and trust.
with Dejan Cvetkovic, Chief Technology Officer of Microsoft, Central and East Europe.
Abstract: In a mobile-first, cloud-first world, trust is more important than ever. At Microsoft, we believe that organizations won't use technology they don't trust. That is why we want to show you a customer case study and the values, principles and specific Finance Compliance Program that Microsoft implements as cloud service provider so as to assist Financial Institution customers to meet their compliance and security needs. Microsoft cloud services are designed, developed, and operated to help ensure customer data is secure. We also provide an appropriate level of transparency into our practices and actions. As your partner, we want to provide the level of assurance that you need to be able to trust the use of cloud computing services, so that you can focus more on your core business.
BIO: Dejan Cvetkovic is the Chief Technology Officer of Microsoft, Central and East Europe. Having gained an education in Serbia he then built his career within Microsoft Canada in a wide variety of positions, ranging from software development to business development. Some of the innovative projects where he led teams and developed solutions include the very first e-banking for HSBC and e-government for Western Canada back in mid 90s. In 2003, Dejan was appointed as a first General Manager for the newly formed country team of Microsoft Serbia and Montenegro. In 2008 Dejan assumed the role of Microsoft public sector business director for Central and East Europe, multicountry region, where he has brought together a strong and ambitious team of professionals that forged relationships with a network of 1000+ local partners and generated a list of clients that reads as the Who's Who of Central and East Europe business and technology, but also includes educational institutions, humanitarian projects and international organizations. Dejan also held a position of the President of the American Chamber of Commerce in Serbia striving for simplicity in laws, regulations and procedures in order to accelerate the attraction of the Foreign Direct Investments. In his current role, Dejan works with the Government officials, policy makers and influencers to help paint the technology vision of the countries in CEE.
with Dr. Vasilis Katos, Professor, Bournemouth University, United Kingdom
Abstract: The unprecedented rise of cyber crime is a direct consequence of the wide adoption of personal digital devices such as smartphones and tablets used for both personal and business purposes. When a cyber crime is committed, first responders and forensic analysts are faced with a number of challenges when conducting digital investigations. On the other hand, the wealth of information that can be found online and in a digital form may potentially work in the investigators favour. In this talk, the challenges resulting from the increased systems complexity will be outlined and strategies for identification of a cyber offender and their modus operandi will be presented.
BIO: Professor Vasilis Katos is Head of Computing at Bournemouth University. Prior to this post he was Associate Professor at Democritus University of Thrace in Greece and Principal Lecturer and course tutor for the MSc in Forensic IT at the University of Portsmouth in the UK.
with Mr. Jim Manico, founder of Manicode Security and Global Board Member for the OWASP foundation
Abstract: This talk with discuss the OWASP Application Security Verification Standard 3.0 standard which was just released in October 2015. The OWASP Application Security Verification Standard (ASVS) Project provides a basis for testing web application technical security controls. The primary aim of the OWASP Application Security Verification Standard (ASVS) Project is to normalize the range in the coverage and level of rigor available in the market when it comes to performing Web application security verification using a commercially-workable open standard. The standard provides a basis for testing application technical security controls, as well as any technical security controls in the environment, that are relied on to protect against vulnerabilities such as Cross-Site Scripting (XSS) and SQL injection. This standard can be used to establish a level of confidence in the security of Web applications.
BIO: Jim Manico is the founder of Manicode Security where he trains software developers on secure coding and security engineering. He is also the founder of Brakeman Security, Inc. and is a investor/advisor for Signal Sciences. Jim is a frequent speaker on secure software practices and is a member of the JavaOne rockstar speaker community. Jim is also a Global Board Member for the OWASP foundation where he helps drive the strategic vision for the organization. He is the author of "Iron-Clad Java: Building Secure Web Applications" from McGraw-Hill.
with Mr. Artemios Miropoulos, Managing Director, Linkage Inc. Greece
Abstract: Two stories of Leadership from Ancient Greece that link to modern corporate and social reality and surface different traits and behaviors such as prejudice, judgement, data management and interpretation.
BIO: Artemios Miropoulos, Leaders Developing Leaders - Managing Partner Linkage Greece. After a career that reached senior positions in multinational organizations, Artemios Miropoulos is now a co-owner of Linkage in Greece, US most highly respected Leadership Development company. He is working with senior and middle management teams of large domestic and international corporations as a workshop facilitator, an executive coach and a public speaker. He has studied Mechanical Engineering, Marketing and HR and Performance Management in Greece and abroad. He lives in Athens with his wife Julie and their three daughters.
with Mr. Nikolaos Tsalis, Researcher, INFOSEC Laboratory, Athens University of Economics & Business
Abstract: Browsers enable the user to surf over the Internet and access web sites that may include social media, email service, etc. However, such an activity incorporates various web threats (e.g. tracking, malicious content, etc.) that may imperil the user's data and any sensitive information involved. Therefore, web browsers offer pre-installed security controls to protect users from these threats. Third-party browser software (i.e. add-ons) is also available that enhances these pre-installed security controls, or substitutes them. This presentation will talk about which are the current web threats, along with the security mechanisms that are available for protection. In addition, there will be an evaluation presented regarding the aforementioned defences, so as to clear out whether the provided security is adequate or not.
BIO: Nick Tsalis is a PhD candidate at the AUEB. He participated in Greek projects as an analyst and penetration tester, funded by various agencies such as the Ministry of Finance, General Secretariat of Information Systems and General Secretariat for Digital Plan.
with Mr. Christos Vidakis, CISA, CISSP, CISM, ISO 27001, Senior Manager, Risk Consulting and Forensic Technology, KPMG Greece
Abstract: The e-World is changing, the Cyber battlefield is not an exception. Whilst Cyber Security is on top of many board agendas, organizations struggle to properly assess, measure and communicate to what extent their business is resilient against cyber-attacks in order to develop a strategy on "how to balance their efforts" and "where to invest" for the new Cyber battlefield. Christos Vidakis will present a "positive" approach to managing Cyber risks, leveraging KPMG's Cyber Threat Intelligence model to set organizations free from fear, uncertainty and doubt, free to challenge, to invest and to change.
BIO: Christos Vidakis, CISA, CISSP, CISM, ISO 27001 LA is a Senior Manager, Risk Consulting and Forensic Technology in KPMG Greece. He has more than twelve years of information systems security, auditing and technology experience, with special emphasis on cyber security and continuous security testing engagements. Christos also directs the Forensic technology practice, guiding clients from discovery preparedness diagnostic to timely, accurate and effectively response to IT fraud incidents, suspected security breaches and assisting in taking preventative measures for the future. He has conducted tens of international electronically stored information (ESI) collections and analysis and he can demonstrate deep experience in both proactive and reactive data analytics fraud analysis, digital evidence collection and analysis as also incident response. Christos has directed and managed the technology integration aspects of financial statement audits, has designed and implemented information security management systems, and has performed and managed a number of security assessments and system implementations such as SSAE 16/ISAE3402, SOC, PCI/DSS, SOX 404 and ISO 27001.
Cybersecurity Workshop
Dr. Konstantinos Papapanagiotou,
Information Security Services Sales Manager at OTE, OWASP Greek Chapter Leader,
ISACA Cyber Security Nexus Liaison for Greece
BIO: Dr. Konstantinos Papapanagiotou is Information Security Services Sales Manager at OTE. In the past he has led teams of consultants, helping large organizations in Greece, Cyprus, Balkans and the Middle East improve their security posture. He has more than 12 years of experience in the field of information security both as a corporate consultant and as a researcher. Konstantinos holds a BSc and PhD in Information Security from the University of Athens and an MSc in Information Security with distinction from Royal Holloway. He is also leading the OWASP Greek Chapter and is an ISACA CyberSecurity Nexus Liaison for Greece.
Conference Chairman
Professor, Athens University of Economics and Business
BIO: Dr. Dimitris Gritzalisis a Professor of ICT Security and the Director of the Information Security and Critical Infrastructure Protection Research Group (www.cis.aueb.gr) with the Dept. of Informatics of the Athens University of Economics and Business, Greece. He holds a B.Sc. (Mathematics, Univ. of Patras), a M.Sc. (Computer Science, City University of New York), and a Ph.D. (Critical Information Systems Security, Univ. of the Aegean).


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Putin visits international jazz festival in Crimea's KoktebelSociety & Culture August 21, 2:31
Militants launch shell on exhibition complex near Damascus - televisionWorld August 20, 15:27
Cardinal Parolin: Dialogue of Roman Catholic and Orthodox Churches to help them feel unitySociety & Culture August 20, 8:27
Polina Dibrova, mother of three, wins Mrs. Russia 2017 beauty pageantSociety & Culture August 20, 4:41
Russian emergencies ministry plane returns from firefighting mission in ArmeniaWorld August 20, 4:39
East Ukraine conflict claimed nearly 3,000 civilian lives — ICRCWorld August 20, 1:56
Renowned Russian filmmaker Andrei Konchalovsky turns 80Society & Culture August 20, 0:48
One of seven injured in Surgut stabbing spree in critical condition — authoritiesSociety & Culture August 19, 23:51
Netanyahu expects to meet with Putin in Sochi on August 23 — Israeli premier's officeRussian Politics & Diplomacy August 19, 22:47
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BANGALORE, February 5 (Itar-Tass) – Russia and India concluded a contract for the adaptation of the Russian-Indian missile BrahMos to the fighter Su-30. The contract was signed last December, Director of the Federal Service for Military-Technical Cooperation Alexander Fomin told reporters on Tuesday.
"We signed a contract for the adaptation of BrahMos to the Sukhoi fighters last December and are currently in the active stage of fulfilling this idea of our Indian partners," Fomin said.
In reply to ARMS-TASS, whether the signing of the contract means that an opportunity of this adaptation was proved, Fomin said, "I did not say so. I said that the contract was signed for the adaptation of the missile to the fighter. In the fulfilment of this contract it will become clear whether the adaptation is feasible and whether BrahMos will be suitable for this fighter. I cannot promise it instead of designers and developers and cannot resolve this issue."
Fomin also noted that Russia mainly offers "the consultative participation in this contract," whereas India will do the bulk of the works. If this comes down to the trials, "Russia will participate in them," Fomin said. "This is very difficult to adapt the new weapon to the fighter. The results should satisfy the developer of the missile and the developer of the fighter. In general, the missile will be perfect," Fomin remarked.
Alexander Fomin heads the Russian delegation at the aerospace show Aero India-2013, which is being held in the Indian city Bangalore on February 6-10.
India is quite interested in the fulfilment of the idea to arm the fighters Su-30MKI with the missiles BrahMos. India has put into service ground-based and sea-based models of this missile. Meanwhile, the Sukhoi Company explained to ARMS-TASS that this is quite problematic. The point is that the missile BrahMos was not initially developed for the deployment of the aircraft and its weight dimension characteristics exceed the indicators of any other airborne missile. "To say the least, the wing of the warplane will have to be reinforced or the missile will have to be converted," a Sukhoi specialist said.


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Shop policies
Last updated on February 25, 2014
Welcome to my store! I create and sell original paintings here. My art is very whimsical and is sure to bring a smile to animal lovers!
Accepted payment methods
PayPal is the only payment method accepted.
Items will be shipped within 3-5 business days of order or sooner.
Refunds and Exchanges
Not saying it can't happen, but it would be a rare occurrence if you received the wrong item. If this were to happen, please return in original packaging and the correct item will be sent to you immediately. Otherwise there are no refunds or returns on original art purchased from this seller.
Additional policies and FAQs
Items are packaged with care and shipped through USPS (local post office) with delivery confirmation.


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Balatonfüred at Lake Balaton in Hungary
...konyhán innen - kerten túl...: Vegyes savanyúság
Spongebob Squarepants Bunting Banner INSTANT DOWNLOAD Printable
Vaszary villa - Balatonfüred, Hungary
Hungary, Balatonfüred
Horváth Villa - Balatonfüred
Balatonfüred- Rózsa kapuk
További ötletek
raised flower beds - love the idea of not straining my back to get fresh veggies
weathered granite hot tub . Freshwater Stone. Wherever this is, I'm going.
amazing beehives! Hey Leslie, you think Luke could build these for your bees?
Martha Stewart's peony garden is creative inspiration for us. Get more photo about Home Decor related with by looking at photos gallery at the bottom of this page. We are want to say thanks if you like to share this post to another people via your facebook, pinterest, google plus …
Sharpen your shears. We have some sculpting to do!
Dry river bed landscape. I'd like 2 do something like this sometime in my back yard.
Free-flowing boxwood hedges wow love the simplicity of wild grass with a strong hedge .. BEAUTIFUL ! (1) by KarlGercens.com, via Flickr
Boxwoods and spring bulbs.
Маленькие одинокие дома одиноких людей • НОВОСТИ В ФОТОГРАФИЯХ


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The Joke O' Lantern is a furniture item that is sold at Rare & Scare in Moshi Monsters.
In the witching hour, why not give a grinful grin? As monsters say, "Trick or Eat?"
- From 2009 to 2011, Cap'n Buck returned from Halloween Island with the Joke O'Lantern, making it available at the Cloudy Cloth Clipper.
- In 2012 the item was sold at Yukea around Halloween time.
- The Joke O' Lantern was obtainable on the release of Rare & Scare in 2013.
- It can also be obtained via secret codes from Series 1 and 2 of the Halloween figures.


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Home > Volunteer
There are many opportunities to get involved at PCMS! Your help is needed!
Volunteer Opportunities
Fall Opportunities
picture day, Tues, 8/22
CV Classic
football parents - game day snacks
football parents - chain gang volunteers
work in front office
school store
Peachtree Charter Middle School conforms with the open enrollment requirements pursuant to O.C.G.A 20-2-2066 (admission, enrollment, and withdrawal of students) and SBOE Rule 160-4-9-.05 (Charter Schools Petition Process).


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Chilly nights are coming!
ONLY $179.00 / ton (while supplies last)
Don't wait until it's cold, pick up your pellets now!
Not valid with any other discounts or sales.
Feel free to contact us anytime with comments or questions. Our trained staff is ready and waiting to help you. Use this form to contact us and we'll be in touch soon.


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In the old days of the Net, there were no SEO Professionals, automated systems, or all that high innovation things. Those were the days of IBM (or "It's Best done By hand) and Organic Search Engine Optimization.
The only difference between Organic Search Engine Optimization and also the SEO we now know is that Organic Search Engine Optimization is a hands-on procedure vs. the present automatic procedures of page entry and modification that identifies "modern-day" Search Engine Optimization. Organic SEO focuses on promoting websites on the Natural search engine results likewise understood as organic results in contrast with sponsored links (Pay-Per-Click/PPC).
Organic SEO is based upon a clear understanding of essential concepts, consisting of:
• Online search engine and just how they work
Undoubtedly, you can not exercise Organic Search Engine Optimization if you do not also recognize just how the initial 2 letters of SEO (i.e., Internet search engine) functions. An internet search engine is a web site that provides the visitor a list of recommended sites to go to, based on a certain key phrase or keyword phrases. The rank of a website is statistically established by exactly what is termed as "keyword density" or the proportion of key phrases to the overall variety of words of material in a website. Incoming web links and their importance is one more variable that identifies your positions. The collector of this statistical data is exactly what is called a "spider" or "crawler crawler", which is a program whose function is to count the variety of times a key words appears in a website via a process called "crawling".
• Seo
You cannot have Organic SEO without the Search Engine Optimization component, which stands exactly what Seo. SEO's major goal is straightforward: bring as numerous site visitors to your website as possible by applying impact on the search engine to position your site as near the top of the list as feasible. As a result of having more site visitors, it is hoped that your web site will certainly generate service for you. This outcome is every Organic SEO practitioner's clear action of success.
• Viral Advertising and marketing
Viral Advertising and marketing is a technique to significantly increase the number of sites site visitors to your internet site from a small base that you have created from your preliminary Organic SEO strategy. This approach is absolutely an useful component of the collection of a professional of Organic SEO.
• Optimized Domain
One of the simplest principles to recognize, yet likewise one that is not as simple to implement. Obtaining a keyword-rich domain name is every Organic Search Engine Optimization professional's desire since it brings so much weight in the significance range. You will certainly be able to smoothly cruise on without much of an issue in the rankings if you domain name is specifically what you are offering. The trouble, of course, is that there is a really high possibility that the "good" domain names currently belong site to a person, and this makes an Organic Search Engine Optimization expert life more difficult.
• Key phrase Research
Because it plays a major function in establishing your optimization strategy, this is the very first action on the listing of to-dos for an Organic Search Engine Optimization expert. Considering that it takes months for any optimization method to take effect, an Organic SEO specialist's efforts will certainly be lost if he makes the error of maximizing a website based upon keywords that are not as prominent as he assumed.
Due to the fact that it needs a deep understanding of the fundamentals that those making use of automated systems take for approved, becoming an Organic SEO specialist is not a simple job at all. There is a major advantage, however, of Organic SEO vs. the "lazy man's" Search Engine Optimization: A clear understanding of the concepts permits you to assess SEO situations more accurately and create methods that are a lot more proper as well as responsive to your site's demands.
The only difference between Organic SEO as well as the Search Engine Optimization we currently recognize is that Organic Search Engine Optimization is a hand-operated procedure vs. the present automatic processes of page entry and also change that characterizes "modern" Search Engine Optimization. Organic Search Engine Optimization focuses on promoting internet sites on the All-natural search engine outcomes likewise understood as natural outcomes in comparison with funded links (Pay-Per-Click/PPC). Clearly, you could not practice Organic SEO if you do not even understand just how the very first two letters of Search Engine Optimization (i.e., Look Engine) works. You can't have Organic Search Engine Optimization without the SEO component, which stands exactly what Search Engine Optimization. Viral Marketing my review here is a method to exponentially raise the number of site visitors to your website from a little base that you have developed from your first Organic Search Engine Optimization technique.
Recognizing Organic SEO
In the old days of the Net, there were no SEO Professionals, automated systems, or all that high innovation things. Those were the days of IBM (or "It's Best done By hand) and Organic Search Engine Optimization.


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Here's another criticism on creepy treehouses.
Are Institutional Portals and VLEs Really "Creepy Treehouses"? @ UK Web Focus
I particularly found the following quotation from a commenter (Phil Wilson) insightful concerning what makes treehouses creepy:
"The creepy treehouse (which has been around for years and years, and started with video games I think) is, classically, about an inauthentic experience of some kind created by adults, designed for children and which normally singularly fails to achieve what it set out to - that is to provide an experience the children are already used to and enjoy (and to therefore become popular). It's the uncanny valley of using software - you know *something* is wrong, but you can't put your finger on it."
Uncanny valley is a metaphor within a metaphor, usually used concerning animation, where animated characters that become too realistic are deemed creepy by viewers, as particularly happened with the Polar Express. See http://www.wwnorton.com/college/film/movies2/ch/04/essay_uncanny_valley.aspx for more.
Does it really matter how much your startup raises? - "How much money does it take to get a startup off the ground?" Entrepreneurs and venture capitalists are faced with this question all the time, and the on...
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