|Publication number||US3567450 A|
|Publication date||Mar 2, 1971|
|Filing date||Feb 20, 1968|
|Priority date||Feb 20, 1968|
|Also published as||DE1908343A1, DE1908343B2|
|Publication number||US 3567450 A, US 3567450A, US-A-3567450, US3567450 A, US3567450A|
|Inventors||Brantly Thomas B, Contois Lawrence E, Fox Charles J|
|Original Assignee||Eastman Kodak Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (272), Classifications (16)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,567,450 PHOTOCONDUCTIVE ELEMENTS CON- TAINING SUBSTITUTED TRllARYL- AMINE PHOTOCONDUCTORS Thomas B. Brantly, Lawrence E. Contois, and Charles J. Fox, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y. No Drawing. Filed Feb. 20, 1968, Ser. No. 706,800 Int. Cl. 603g 5/06, 13/22 US. Cl. 96--1.5 17 Claims ABSTRACT OF THE DISCLOSURE Triarylamines having at least one of the aryl radicals substituted by either a vinyl radical or a vinylene radical having at least one active hydrogen-containing group are good organic photoconductors in electrophotographic systems.
This invention relates to electrophotography, and in particular to photoconductive compositions and elements.
The process of xerography, as disclosed by Carlson in US. 2,297,691, employs an electrophotographic element comprising a support material bearing a coating of a normally insulating material whose electrical resistance Varies with the amount of incident actinic radiation it receives during an imagewise exposure. The element, commonly termed a photoconductive element, is first given a uniform surface charge, generally in the dark after a suitable period of dark adaptation. It is then exposed to a pattern of actinic radiation which has the effect of differentially reducing the potential of the surface charge in accordance with the relative energy contained in various parts of the radiation pattern. The differential surface charge or electrostatic latent image remaining on the electrophotographic element is then made visible by contacting the surface with a suitable electroscopic marking material. Such marking material or toner, whether contained in an insulating liquid or on a dry carrier, can be deposited on the exposed surface in accordance with either the charge pattern or the discharge pattern as desired. The deposited marking material can then be either permanently fixed to the surface of the sensitve element by known means such as heat, pressure, solvent vapor, or the like, or transferred to a second element to which it can similarly be fixed. Likewise, the electrostatic latent image can be transferred to a second element and developed there.
Various photoconductive insulating materials have been employed in the manufacture of electrophotographic elements. For example, vapors of selenium and vapors of selenium alloys deposited on a suitable support and particles of photoconductive zinc oxide held in a resinous, film-forming binder have found wide application in present-day document copying applications.
Since the introduction of electrophotography, a great many organic compounds have also been screened for their photoconductive properties. As a result, a very large number of organic compounds are known to possess some degree of photoconductivity. Many organic compounds have revealed a useful level of photoconduction and have been incorporated into photoconductive compositions. Optically clear organic photoconductor-containing elements having desirable electrophotographic properties can be especially useful in electrophotography. Such electrophotographic elements can be exposed through a transparent base if desired, thereby providing unusual flexibility in equipment design. Such compositions, when coated as a film or layer on a suitable support also yield an element which is reusable; that is, it can be used to form subsequent images after residual toner from prior images 3,567,450 Patented Mar. 2, 1971 has been removed by transfer and/or cleaning. Thus far, the selection of organic compounds for incorporation into photoconductive compositions to form electrophotographic layers has proceeded on a compound by compound basis. Nothing has yet been discovered from the large number of different photoconductive substances tested which permits effective prediction and therefore selection of particular compounds exhibiting the desired electrophotographic properties.
It is, therefore, an object of this invention to provide photoconductive elements for use in electrophotography containing a novel class of organic photoconductors having enhanced photosensitivity when electrically charged.
It is also an object to provide electrophotographic elements having a layer of a novel photoconductive composition which can be positively or negatively charged.
It is another object to provide novel transparent electro photographic elements having high speed characteristics.
It is a further object of this invention to provide novel electrophotographic elements useful for producing images electrophotographically by reflex or birefiex processes.
These and other objects of this invention are accomplished with electrophotographic elements having coated thereon organic photoconductive compositions containing a triarylamine photoconductor wherein at least one of the aryl radicals is substituted by either a vinyl radical or a vinylene radical having at least one active hydrogencontaining group. The phrase vinylene radical includes substituted as well as unsubstituted vinylene radicals and also includes those radicals having at least one and as many as three repeating units of vinylene groups such as tCH=CH+ wherein n is an integer of from one to three. Groups which contain active hydrogen are well known in the art, the definition of this term being set forth in several textbooks such as Advanced Organic Chemistry, R. C. Fuson, pp. 154157, John Wiley & Sons, 1950'. The term active hydrogen-containing group as used herein includes those compounds encompassed by the discussion in the textbook cited above and in addition includes those compounds which contain groups which are hydrolyzable to active hydrogen-containing groups. Typical active hydrogen-containing groups substituted on the vinylene radical of the triarylamine according to this invention include:
(a) carboxy radicals,
(b) hydroxy radicals,
(c) ethynyl radicals including substituted ethynyl radicals such as hydroxy ethynyl radicals, aryl ethynyl radicals and alkyl ethynyl radicals,
(d) ester radicals (e.g.,
0 ll -ooR wherein R is alkyl or aryl) including cyclic ester radicals 0 ll -COR wherein R is a cyclic alkylene radical connected to a vinylene combination such as is found in coumarin de rivatives, (e) carboxylic acid anhydride radicals, (f) semicarbazono radicals, (g) cyano radicals, (h) acyl halide radicals (e.g.,
(i) amido radicals (e.g.,
o R H -C-N wherein R is a hydrogen atom, an alkyl group or an aryl group).
Other active hydrogen-containing groups include substituted and unsubstited al kylidyne oximido radicals.
The preferred photoconductors of this invention are represented by the following structure:
Ar;- :0 X 1.4 (I. i.
(a) Ar and Ar are each a phenyl radical including a substituted phenyl radical such as a halophenyl radical, an al kyl phenyl radical or an aminophenyl radical;
(b) Ar is an arylene radical including a substituted arylene radical such as a phenylene radical or a naphthylene radical,
(c) R and R are each hydrogen, a phenyl radical including a substituted phenyl radical or a lower alkyl radical preferably having 1-8 carbon atoms;
(d) X is either (1) an active hydrogen-containing group such as a carboxy radical, an acyl halide radical, an amido radical, a carboxylic acid anhydride radical, an ester radical, a cyano radical, a hydroxy radical, a semicarbazone radical, an ethynyl radical, or a methylidyne oximido radical or (2) hydrogen, provided that when X is hydrogen R and R are also hydrogen; and
(e) n is an integer of one to three.
The vinyl or vinylene radical can be substituted in any position on the arylene nucleus. However, when Ar is phenylene, particularly good results are obtained if the substitution occurs in the para position.
The organic photoconductors of this invention exhibit substantial improvements in speed over comparable photoconductors which do not have both an active hydrogencontaining group (including groups hydrolyzable to active hydrogen-containing groups) and a vinyl or vinylene group. Also, those compounds having an unsubstituted vinyl radical show improvements in electrical speed as organic photoconductors when compared to similar compounds which lack such a group. Thus, a compound according to the above formula when n is zero and X is an active hydrogen-containing group would not exhibit the higher speeds attainable when compared to a compound where n is 1, 2, or 3. Furthermore, if X is a group other than an active hydrogen-containing group or hydrogen (and n is 1, 2 or 3), the photoconductivity of the resulting compound is generally lower than that attainable if such groups are present. Finally, if X is a group other than an active hydrogen-containing group or hydrogen and n in the above formula is zero, the resultant speeds attainable from such compounds when used as organic photoconductors are somewhat lower than those attainable from comparable compounds according to this invention.
Those compounds in which Ar; and Ar in the above formula are phenyl radicals generally have improved photo-conducting properties over those which are substituted by one or two alkyl or benzyl radicals. Thus, pdiphenyl amino-cinnamic acid and methyl p-diphenylaminocinnamate display improved electrical speeds over p-(N-methyl, N-phenylamino)cinnamic acid, methyl p- (N-imethyl, N-phenylamino)cinnamate or methyl p-dibenzylaminocinnamate. Also, ethyl p-diphenylaminophenylvinylacrylate has enhanced electrical speed properties compared to ethyl p-dimethylaminophenylvinylacrylate.
Some typical photoconductors of this invention are:
Table I (I) 4- (p-diphenylaminophenyl) -3-buten1-yne (II) p-diphenylaminostyrene (III) ethyl p-diphenylaminocinnamate (IV) methyl p-diphenylaminocinnamate (V) p-diphenylaminocinnamoyl chloride (VI) p-diphenylaminocinnamic acid N,N-diphenylamide (VII) p-diphenylaminocinnamic acid anhydride (VIII) 3-(p-diphenylaminophenyl)-2-butenoic acid (IX) bis (p-diphenylaminobenzal)succinic acid (X) 4-N,N-bis(p-bromophenyl)aminocinnaimic acid (XI) 1-(4-diphenylamino)naphthacrylic acid (XII) p-diphenylaminocinnamic acid (XIII) p-diphenylaminocinnamonitrile (XIV) 7-diphenylamino coumarin (XV) p-diphenylaminophenylvinylacrylic acid (XVI) p-diphenylaminobenzyl p-diphenylaminocin namate (XVII) 7- (p-diphenylaminostyryl) coumarin (XVIII) p-diphenylaminocinnamyl alcohol (XIX) 4-diphenylaminocinnamaldehyde semicarbazone (XX) O-p-diphenylaminocinnamoyl p'-diphenylaminobenzaldehyde oxime (XXI) p-diphenylaminocinnamaldehyde oxime, and
(XXII) 1,3-bis (p-diphenylaminophenyl)-2-propen-1-ol These compounds can be prepared by the methods set forth in a copending application filed concurrently herewith entitled Novel Substituted Triarylamines, Serial Number 706,799, filed Feb. 20, 1968.
:Electrophotographic elements of the invention can be prepared with these photoconducting compounds in the usual manner, i.e., by blending a dispersion or solution of a photoconductive compound together with a binder, when necessary or desirable, and coating or forming a self-supporting layer with the photoconductor-containing materials. Mixtures of the photoconductors described herein can be employed. Likewise, other photoconductors known in the art can be combined with the present photoconductors. In addition, supplemental materials useful for changing the spectral sensitivity or electrophotosensitivity of the element can be added to the composition of the element when it is desirable to produce the characteristic effect of such materials.
Sensitizing compounds useful with the photoconductive compounds of the present invention can include a wide variety of substances such as pyrylium, thiapyrylium, and selenapyrylium salts of US. Patent 3,250,615, issued May 10, 1966; fluorenes, such as 7,12-dioxo-l3-dibenzo(a,h) fluorene, 5,10 dioxo-4a,11-diazabenzo(b)fluorene, 3,13- dioxo-7-oxadibenzo-('b,g)fluorene, trinitrofluorenone, tetranitrofiuorenone and the like; aromatic nitro compounds of US. Patent 2,610,120; anthro-nes of US. Patent 2,670,- 285; quinones of US. Patent 2,670,286; benzophenones of US. Patent 2,670,287; thiazoles of US. Patent 2,732, 301; mineral acids; carboxylic acids, such as maleic acid, dichloroacetic acid, and salicylic acid; sulfonic and phosphoric acids; and various dyes such as triphenylmethane, diarylmethane, thiazine, azine, oxazine, Xanthene, phthalein, acridine, azo, anthraquinone dyes and many other suitable sensitizing dyes. The preferred sensitizers for use with the compounds of this invention are pyrylium and thiapyrylium salts, fluorenes, carboxylic acids, and triphenylmethane dyes.
Where a sensitizing compound is to be used within a photoconductive layer as disclosed herein it is conventional practice to mix a suitable amount of the sensitizing compounds with the coating composition so that, after thorough mixing, the sensitizing compound is uniformly distributed throughout the desired layer of the coated element. In preparing the photoconducting layers, no sensitizing compound is needed for the layer to exhibit photoconductivity. The lower limit of sensitizer required in a particular photoconductive layer is, therefore, zero. However, since relatively minor amounts of sensitizing compound give substantial improvement in the electrophotographic speed of such layers, the use of some sensitizer is preferred. The amount of sensitizer that can be added to a photoconductor-incorporating layer to give effective increases in speed can vary widely. The optimum concentration in any given case will vary with the specific photoconductor and sensitizing compound used. In general, substantial speed gains can be obtained where an appropriate sensitizer is added in a concentration range from about 0.0001 to about percent by weight based on the weight of the film-forming coating composition.
Generally, a sensitizer is added to the coating composi-' tion in an amount by weight from about 0.005 to about 5.0 percent by Weight of the total coating composition.
Preferred binders for use in preparing the present photoconductive layers are film-forming polymeric binders having fairly high dielectric strength which are good electrically insulating film-forming vehicles. Materials of this type comprise styrene-butadiene copolymers; silicone resins; styrene-alkyd resins; silicone-alkyd resins; soya-alkyd resins; poly(vinyl chloride); poly(vinylidene chloride); vinylidene chloride-acrylonitrile copolymers; poly(vinyl acetate); vinyl acetate-vinyl chloride copolymers; poly(vinyl acetals), such as poly(vinyl butyral); polyacrylic and methacrylic esters, such as poly(methylmethacrylate), poly(n-butylmethacrylate) poly (isobutyl methacrylate), etc.; polystyrene; nitrated polystyrene; polymethylstyrene; isobutylene polymers; polyesters, such as poly(ethylenealkaryloxyalkylene terephthalate); phenol-formaldehyde resins; ketone resins; polyamides; polycarbo-nates; polythiocarbonates; poly(ethylene-glycol-cobishydroxyethoxy-phenyl propane terephthalate); nuclear substituted vinyl haloarylates such as poly(vinyl metabromobenzoate-co-vinyl acetate); etc. Methods of making resins of this type have been described in the prior art, for example, styrene-alkyd resins can be prepared according to the method described in U.S. Patents 2,361,019 and 2,258,423. Suitable resins of the type contemplated for use in the photoconductive layers of the invention are sold under such trade names as Vitel PE101, Cymac, Piccopale 100, Saran F220 and Lexan 105. Other types of binders which can be used in the photoconductive layers of the invention include such materials as paraffin, mineral waxes, etc.
Solvents of choice for preparing coating compositions of the present invention can include a number of solvents such as benzene, toluene, acetone, Z-butanone, chlorinated hydrocarbons, e.g., methylene chloride, ethylene chloride, etc., ethers, e.g., tetrahydrofuran, or mixtures of these solvents etc.
In preparing the coating composition useful results are obtained where the photoconductor substance is present in an amount equal to at least about 1 weight percent of the coating composition. The upper limit in the amount of photoconductor substance present can be widely varied in accordance with usual practice. In those cases where a binder is employed, it is normally required that the photoconductor substance be present in an amount from about 1 weight percent of the coating composition to about 99 weight percent of the coating composition. A preferred Weight range for the photoconductor substance in the coating composition is from about 10 weight percent to about 60 weight percent.
Coating thicknesses of the photoconductive composition on a support can vary widely. Normally, a coating in the range of about 0.001 inch to about 0.01 inch before drying is useful for the practice of this invention. The preferred range of coating thickness was found to be in the range from about 0.002 inch to about 0.006 inch before drying although useful results can be obtained outside of this range.
Suitable supporting materials for coating the photoconductive layers of the present invention can include any of a wide variety of electrically conducting supports, for example, paper (at a relative humidity above 20 percent); aluminum-paper laminates; metal foils such as aluminum foil, zinc foil, etc.; metal plates, such as aluminum, copper, zinc, brass, and galvanized plates; vapor deposited metal layers such as silver, nickel, or aluminum and the like. Metal (e.g., nickel, etc.) conducting layers deposited by high vacuum deposition techniques can be coated at low coverages so as to be substantially transparent to facilitate image exposure through the support. An especially useful conducting support can be prepared by coating a support material such as poly(ethylene terephthalate) with a layer containing a semiconductor dispersed in a resin. Suitable conducting layers both with and without insulating barrier layers are described in US. Patent 3,245,833. Other suitable conducting layers are described in U.S. Patent 3,120,- 028. Likewise, a suitable conducting coating can be prepared from the sodium salt of a carboxyester lactone of maleic anhydride and a vinyl acetate polymer. Such kinds of conducting layers and methods for their optimum preparation and use are disclosed in US. 3,007,901 and 3,267,807.
The elements of the present invention can be employed in any of the well-known electrophotographic processes which require photoconductive layers. One such process is the aforementioned xerographic process. As previously explained, in a process of this type the electrophotographic element is given a blank electrostatic charge by placing the same under a corona discharge which serves to give a uniform charge to the surface of the photoconductive layer. This charge is retained by the layer owing to the substantial insulating property of the layer, i.e., the low conductivity of the layer in the dark. The electrostatic charge formed on the surface of the photoconducting layer is then selectively dissipated from the surface of the layer by exposure to light through an image-bearing transparency by a conventional exposure operation such as, for example, by contact-printing techniques, or by lens projection of an image, etc., to form a latent image in the photoconducting layer. By exposure of the surface in this manner, a charge pattern is created by virtue of the fact that light causes the charge to be conducted away in pro portion to the intensity of the illumination in a particular area. The charge pattern remaining after exposure is then developed, i.e., rendered visible, by treatment with a medium comprising electrostatically attractable particles having optical density. The developing electrostatically attractable particles can be in the form of a dust, e.g., powder, pigment in a resinous carrier, i.e., toner, or a liquid developer may be used in which the developing particles are carried in an electrically insulating liquid carrier. Methods of development of this type are widely known and have been described in the patent literature in such patents, for example, as US. Patent 2,297,691 and in Australian Patent 212,315. In processes of electrophotographic reproduction such as in xerography, by selecting a developing particle which has as one of its components, a low-melting resin, it is possible to treat the developed photoconductive material with heat to cause the powder to adhere permanently to the surface of the photoconductive layer. In other cases, a transfer of the image formed on the photoconductive layer can be made to a second support, which would then become the final print. Techniques of the type indicated are well known in the art and have been described in a number of US. and foreign patents, such as US. Patents 2,297,691 and 2,551,582, and in RCA Review, vol. 15, (1954) pages 469484.
The present invention is not limited to any particular mode of use of the new electrophotographic materials, and the exposure technique, the charging method, the transfer (if any), the developing method, and the fixing method as Well as the materials used in these methods can be selected and adapted to the requirements of any particular technique.
Electrophotographic materials according to the present invention can be applied to reproduction techniques wherein different kinds of radiations, i.e., electromagnetic radiations as well as nuclear radiations, can be used. For this reason, it is pointed out herein that although materials according to the invention are mainly intended for use in connection with methods comprising an exposure, the term electrophotography wherever appearing in the description and the claims, is to be interpreted broadly and understood to comprise both xerography and xeroradiography.
The following examples are included for a further understanding of the invention.
EXAMPLE 1 Organic photoconductors of the type described herein are separately incorporated into a coating dope having the following composition:
Organic photoconductor: 0.5 g. Polymeric binder: 1.05 g. Sensitizer: 0.02 g.
Methylene chloride: 11.7 mi.
The resulting compositions are coated at a wet thickness of 0.004 inch on a conducting layer comprising the sodium salt of a carboxyester lactone, such as described in US 3,120,028, which in turn is coated on a cellulose acetate film base. The coating blocks are maintained at a temperature of 90 F. These electrophotographic elements are charged under a positive or negative corona source until the surface potentials, as measured by an electrometer probe, reach between about 500 and 600 volts. They are then subjected to exposure from behind a stepped density gray scale to a 3000 K. tungsten source. The exposure causes reduction of the surface potentials of the elements under each step of the gray scale from their initial potential, V0, to some lower potential, V Whose exact value depends on the actual amount of exposure in meter-candleseconds received by the areas. The results of the measure ments are plotted on a graph of surface potential V vs. log exposure for each step. The speed is the numerical expression of 10 multiplied by the reciprocal of the exposure in meter-candle-seconds required to reduce the 500 to 600 volt charged surface potentials to 100 volts above volt. The reduction of the surface potential to 100* volts or below is significant in that it represents a requirement for suitable broad area development of a latent image. This speed at 100 volts is a measure of the ability to produce and hence forth to develop or otherwise utilize the latent image, higher speeds requiring less illumination to produce a latent image. When the photoconductor is absent from the coating, the surface potential does not drop to, or below, 100 volts and no speed value can be assigned. This is also the case when a compound is present in the composition but is ineffective as a photoconductcr. The speeds of the various photoconductive compositions are shown in Table 11 below. The sensitizers used are referred to below as follows:
(E) 2,6-'( 4-e-thylphenyl -4- (4-amyloxyphenyl thiapyrylium perchlorate (F) 2,4-bis 4-ethoxyphenyl) -6- (4-n-amyloxystyryl)pyrylium fluoborate (G) 2,4-bis 4-ethylphenyl -6- (4-styryistyryl) pyryliurn perchlorate (H) .2,6-bis (4-ethoxyphenyl) -4- (4-n-amyloxy-phenyl) thiapyrylium perchlorate The data in the following Table II represents the positive speeds at 100 volts of various compositions prepared as described above containing severai of the organic photoconductors set forth in Table I. The binder employed is poly(vinyl meta-bromobenzoate-co-vinyl acetate).
TABLE II Speed at volts sensitizer Photoconduetor F G H The latent electrostatic images in each instance developed with conventional electrophotographic liquid developers (e.g., U.S. Patent 2,907,674) to form sharp dense images.
EXAMPLE 2 Example 1 is repeated except that the binder employed is a film-forming polycarbonate resin sold commercially as Lexan by General Electric Co. The photoconductor employed in the photoconductive composition is p-diphenylaminocinnamoyl chloride (Compound V). The positive speed at 100 volts for compositions containing sensitizer F is 260 and for sensitizer G the speed is 220.
EXAMPLE 3 In order to show the efiicacy of the vinylene moiety in the photoconductors of this invention, two closely related compounds are tested for their electrophotographic speeds at 100 volts positive. The first compound, p-diphenylaminocinnamic acid (Compound XII) has a vinylene moiety While the second, 4-carboxytriphenylamine, is the same as compound XII but lacks a vinylene moiety. Two photoconductive compositions are prepared and tested according to Example 1 except the following composition is used:
Photoconductor: 0.15 g. Binder Vitel 101 0.50 g. Sensitizer F: 0002 g. Dichlorornethane: 5.0 ml.
1 A polyester of te'rephthalie acid and a mixture of ethylene glycol (1 part by weight) and 2, 2-bis[ l-(B-hyrlroxyethoxy) phenyl1propane (9 parts by weight).
The speed of 4-carboxytriphenylamine is 50. The speed of Compound XII is 160.
EXAMPLE 4 This example demonstrates the increases in speed attainable with a photoconducting compound having both a vinylene moiety and an active hydrogen-containing group such as compound XII as opposed to a photoconducting compound having neither moiety present such as triphenylamine. Thus, photoconducting compositions containing the above photo-conductors are prepared and tested according to Example 1 except the following composition is used:
Photoconductor: 1.0 g.
Binder, poly(vinyl meta-bromo-henzoate-co-vinyl acetate): 1.0 g.
Sensitizer G: 0.02 g.
Dichloromethane: 11.7 ml.
The positive 100 volt speed of the composition containing triphenylamine is 130. The positive 100 volt speed of the composition containing compound XI-I is 630.
EXAMPLE 6 EXAMPLE 7 The 100 volt positive speed of p-diphenplaminocinnamonitrile is determined according to Example 1 using the following composition:
Photoconductor: 0.15 g. Vitel 101: 0.50 g. Sensitizer G: 0.002 g. Dichloromethane: 5.0 ml.
The resultant speed is 110.
EXAMPLE 8 Coating dopes prepared in the manner set forth in Example 1 containing the compounds in Table I are coated in the manner described in Example 1. In a darkened room, the surface of each of the photoconductive layers so prepared is charged to a potential of about +600 volts under a corona charger. The layer is then covered with a transparent sheet bearing a pattern of opaque and light transmitting areas and exposed to the radiation from an incandescent lamp with an illumination intensity of about 75 meter-candles for 12 seconds. The resulting electrostatic latent image is developed in the usual manner by cascading over the surface of the layer a mixture of negatively charged black thermoplastic toner particles and glass beads. A good reproduction of the pattern results in each instance.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinbefore and as defined in the appended claims.
1. An electrophotographic element comprising a conductive support having coated thereon a photoconductive composition comprising a photoconductor having the structure:
an ethynyl radical, an acyl halide radical, a cyano radical, a carboxylic acid anhydride radical, a hydroxy radical, a semicarbazono radical, an oximido radical and an amido radical; and
(e) n is an integer of 1 to 3.
2. A photoconductive element as defined by claim 1 wherein the photoconductive composition contains a sensitizer for said photoconductor.
3. An electrophotographic element as defined in claim 1 wherein the photoconductive composition is sensitized with a compound selected from the group consisting of:
(a) a pyrylium salt,
(b) a thiapyrylium salt,
(0) a selenapyrylium salt,
(d) a fiuorenone, and
(e) a triphenylmethane dye.
4. An electrophotographic element as defined in claim 4 wherein a binder is utilized for the photoconductor, said binder being a polymer of a nuclear substituted vinyl haloarylate.
5. An electrophotographic element as defined in claim 4 wherein a poly(ethylenealkaryloxykylene terephthalate) binder is utilized for the photoconductor.
6. An electrophotographic element comprising an electrically conductive support having coated thereon a photoconductive composition comprising a polymeric binder and a photoconductor selected from the group consisting of: I
(a) ethyl p-diphenylaminocinnamate,
(b) methyl p-diphenplaminocinnamate,
(c) p-diphenylaminocinnamoyl chloride,
((1) p-diphenylaminocinnamic acid N,N diphenylamide,
(e) p-diphenylaminocinnamic acid,
(f) p-diphenylaminocinnamic acid anhydride,
(g) 3-(p-diphenylaminophenyl)-2-butenoic acid,
(h) 4-N,N-bis (p-bromophenyl)aminocinnamic acid,
(i) bis (p-diphenylaminobenzal)succinic acid,
(j) l-(4-diphenylamino)naphthacrylic acid,
(m) p-diphenylaminophenylvinylacrylic acid, and
(n) 7-diphenylamino coumarin.
7. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition comprising:
(a) about 10 to 60% by weight based on said photoconductive composition of methyl p-diphenylaminocinnamate as a photoconductor, and
(b) a film-forming polymeric binder for said photoconductor.
8. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition comprising:
(a) about 10 to 60% by weight based on said photoconductive composition of p-diphenylaminocinnamic acid anhydride as a photoconductor, and
(b) a film-forming polymeric binder for said photoconductor.
9. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition comprising:
(a) about 10' to 60% by weight based on said photoconductive composition of 3-(p-diphenylarninophenyl)-2-butenoic acid as a photoconductor, and
(b) a film-forming polymeric binder for said photoconductor.
10. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition comprising:
(a) about 10 to 60% by weight based on said photoconductive composition of p-diphenylaminocinnamic acid as a photoconductor, and
(b) a film-forming polymeric binder for said photoconductor.
11. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition compris- (a) about 10 to 60% by weight based on said photoconductive composition of ethyl p-diphenylamino cinamate as a photoconductor, and
(b) a film-forming polymeric binder for said photoconductor.
12. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition comprismg:
(a) about 10 to 60% by Weight based on said photoconductive composition of methyl p-diphenylaminocinnamate as a photoconductor,
(b) about 0.005 to 5.0% by weight based on said photoconductive composition of a pyrylium salt as a sensitizer, and
(c) poly(vinyl meta-bromobenzoate-co-vinyl acetate) as a binder for said photoconductor.
13. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition comprismg:
(a) about 10 to 60% by weight based on said photoconductive composition of p-diphenylarninocinnamic acid anhydride as a photoconductor,
(b) about 0.005 to 5.0% by weight based on said photoconductive composition of a pyrylium salt as a sensitizer, and
(c) poly(viny1 metabromobenzoate-co-vinyl acetate) as a binder for said photoconductor.
14. A photoconductive element for use in electrophotography comprising a conductive support having coated thereon a photoconductive composition comprismg:
(a) about 10 to 60% by weight based on said photoconductive composition of 3-(p-diphenylaminopheny1)-2-butenoic acid as a photoconductor,
(b) about 0.005 to 5.0% by weight based on said photoconductive composition of a pyrylium salt as a sensitizer, and
(c) poly(vinyl meta-bromobenzoate-co-vinyl acetate) as a binder for said photoconductor.
a coated thereon a photoconductive composition compris- (a) about 10 to 60% by weight based on said photoconductive composition of ethyl p-diphenylaminocinnamate as a photoconductor,
(c) poly(vinyl meta-bromobenzoate-co-vinyl acetate) as a binder for said photoconductor.
17. In an electrophotographic process wherein an electrostatic charge pattern is formed on an electrophotographic element, the improvement characterized in that the charge pattern is formed on the electrophotographic element of claim 4.
References Cited UNITED STATES PATENTS 2,766,233 10/ 1956 Kartinos 260-240 3,180,730 4/1965 Klupfel 961 3,221,041 11/1965 Roland 260-465 3,265,496 8/1966 FOX 96-1 3,387,973 6/1968 FOX et al. 96-1.5
GEORGE F. LESMES, Primary Examiner J. C. COOPER, III, Assistant Examiner US. Cl. X.R.
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4105447 *||Jul 14, 1975||Aug 8, 1978||Eastman Kodak Company||Photoconductive insulating compositions including polyaryl hydrocarbon photoconductors|
|US4222902 *||Nov 3, 1978||Sep 16, 1980||Minnesota Mining And Manufacturing Company||Semiconductive and sensitized photoconductive compositions|
|US4299897 *||Feb 15, 1980||Nov 10, 1981||Xerox Corporation||Aromatic amino charge transport layer in electrophotography|
|US4402573 *||Jun 18, 1981||Sep 6, 1983||International Business Machines Corporation||Materials for electrochromic display devices|
|US4581311 *||May 7, 1985||Apr 8, 1986||Fuji Photo Film Co., Ltd.||Photoconductive composition with vinylidene chloride-acrylonitrile copolymer additive|
|US4937165 *||Apr 3, 1989||Jun 26, 1990||Xerox Corporation||Photoconductive imaging members with N,N-bis(biarylyl)aniline charge transport polymers|
|US4959288 *||Apr 3, 1989||Sep 25, 1990||Xerox Corporation||Photoconductive imaging members with diaryl biarylylamine copolymer charge transport layers|
|US5061569 *||Jul 26, 1990||Oct 29, 1991||Eastman Kodak Company||Electroluminescent device with organic electroluminescent medium|
|US5121029 *||Jan 5, 1990||Jun 9, 1992||Idemitsu Kosan Co., Ltd.||Electroluminescence device having an organic electroluminescent element|
|US5294869 *||Dec 30, 1991||Mar 15, 1994||Eastman Kodak Company||Organic electroluminescent multicolor image display device|
|US5409783 *||Feb 24, 1994||Apr 25, 1995||Eastman Kodak Company||Red-emitting organic electroluminescent device|
|US5443922 *||Oct 28, 1992||Aug 22, 1995||Konica Corporation||Organic thin film electroluminescence element|
|US5468583 *||Dec 28, 1994||Nov 21, 1995||Eastman Kodak Company||Cyclic bis-dicarboximide electron transport compounds for electrophotography|
|US5484922 *||Feb 14, 1994||Jan 16, 1996||Eastman Kodak Company||Internal junction organic electroluminescent device with a novel composition|
|US5488137 *||Mar 22, 1994||Jan 30, 1996||Ricoh Company, Ltd.||Acrylic acid ester derivative having a triphenyl amine skeleton|
|US5500568 *||Jul 22, 1993||Mar 19, 1996||Idemitsu Kosan Co., Ltd.||Organic El device|
|US5552678 *||Sep 23, 1994||Sep 3, 1996||Eastman Kodak Company||AC drive scheme for organic led|
|US5554450 *||Mar 8, 1995||Sep 10, 1996||Eastman Kodak Company||Organic electroluminescent devices with high thermal stability|
|US5585483 *||Oct 20, 1995||Dec 17, 1996||Fuji Electric., Ltd.||Metal-free phythalocyanine, process for preparing the same, and electrophotographic photoconductor using the same|
|US5591555 *||Jan 10, 1995||Jan 7, 1997||Fuji Electric Co., Ltd.||Electrophotographic photoconductor including a metal-free phthalocyanine|
|US5824800 *||Jun 21, 1996||Oct 20, 1998||Fuji Electric Co., Ltd.||Process for preparing a metal-free phthalocyanine|
|US5834100 *||Jun 25, 1996||Nov 10, 1998||Northwestern University||Organic light-emitting dioddes and methods for assembly and emission control|
|US5935721 *||Mar 20, 1998||Aug 10, 1999||Eastman Kodak Company||Organic electroluminescent elements for stable electroluminescent|
|US5972247 *||Mar 20, 1998||Oct 26, 1999||Eastman Kodak Company||Organic electroluminescent elements for stable blue electroluminescent devices|
|US6020078 *||Dec 18, 1998||Feb 1, 2000||Eastman Kodak Company||Green organic electroluminescent devices|
|US6127004 *||Jan 29, 1999||Oct 3, 2000||Eastman Kodak Company||Forming an amorphous fluorocarbon layer in electroluminescent devices|
|US6208077||Nov 5, 1998||Mar 27, 2001||Eastman Kodak Company||Organic electroluminescent device with a non-conductive fluorocarbon polymer layer|
|US6399221||Nov 6, 1998||Jun 4, 2002||Northwestern University||Organic light-emitting diodes and methods for assembly and emission control|
|US6428912||Sep 30, 1998||Aug 6, 2002||Agere Systems Guardian Corp.||Electron transport material and light emitting diode that contains the electron transport material|
|US6444333 *||Oct 12, 1999||Sep 3, 2002||Fuji Photo Film Co., Ltd.||Organic luminescent device material, organic luminescent device using the same, and tetraarylmethane compound|
|US6610455||Jan 30, 2002||Aug 26, 2003||Eastman Kodak Company||Making electroluminscent display devices|
|US6765349 *||Sep 30, 2002||Jul 20, 2004||Eastman Kodak Company||High work function metal alloy cathode used in organic electroluminescent devices|
|US6770502 *||Apr 4, 2002||Aug 3, 2004||Eastman Kodak Company||Method of manufacturing a top-emitting OLED display device with desiccant structures|
|US6835953||Apr 8, 2003||Dec 28, 2004||Eastman Kodak Company||Desiccant structures for OLED displays|
|US6872472||Feb 15, 2002||Mar 29, 2005||Eastman Kodak Company||Providing an organic electroluminescent device having stacked electroluminescent units|
|US6890627||Aug 2, 2002||May 10, 2005||Eastman Kodak Company||Laser thermal transfer from a donor element containing a hole-transporting layer|
|US6939625||Mar 15, 2002||Sep 6, 2005||Nôrthwestern University||Organic light-emitting diodes and methods for assembly and enhanced charge injection|
|US6939660||Aug 2, 2002||Sep 6, 2005||Eastman Kodak Company||Laser thermal transfer donor including a separate dopant layer|
|US7094121||Jul 1, 2003||Aug 22, 2006||Northwestern University||Organic light-emitting diodes and methods for assembly and emission control|
|US7221332||Dec 19, 2003||May 22, 2007||Eastman Kodak Company||3D stereo OLED display|
|US7390601||Jun 16, 2005||Jun 24, 2008||Xerox Corporation||Imaging member comprising modified binder|
|US7449268||May 27, 2005||Nov 11, 2008||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US7544450||Mar 19, 2008||Jun 9, 2009||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US7576059 *||Jan 30, 2001||Aug 18, 2009||Novo Nordisk A/S||Peptide derivatives|
|US7718825 *||Mar 28, 2006||May 18, 2010||Xerox Corporation||Arylamine process|
|US7820780||Jun 5, 2009||Oct 26, 2010||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US7911133||May 10, 2007||Mar 22, 2011||Global Oled Technology Llc||Electroluminescent device having improved light output|
|US7931975||Nov 7, 2008||Apr 26, 2011||Global Oled Technology Llc||Electroluminescent device containing a flouranthene compound|
|US7947974||Mar 25, 2008||May 24, 2011||Global Oled Technology Llc||OLED device with hole-transport and electron-transport materials|
|US7968215||Dec 9, 2008||Jun 28, 2011||Global Oled Technology Llc||OLED device with cyclobutene electron injection materials|
|US7969088||May 4, 2009||Jun 28, 2011||Northwestern University||Method of using silicon molecular components for controlling charge migration and light emission of organic light-emitting diodes|
|US7990058||May 13, 2010||Aug 2, 2011||Global Oled Technology Llc||Top-emitting OLED device with light-scattering layer and color-conversion|
|US8016631||Nov 16, 2007||Sep 13, 2011||Global Oled Technology Llc||Desiccant sealing arrangement for OLED devices|
|US8034465||Jun 20, 2007||Oct 11, 2011||Global Oled Technology Llc||Phosphorescent oled having double exciton-blocking layers|
|US8053094||Jul 2, 2009||Nov 8, 2011||Northwestern University||Organic light-emitting diodes and methods for assembly and enhanced charge injection|
|US8057916||Apr 20, 2005||Nov 15, 2011||Global Oled Technology, Llc.||OLED device with improved performance|
|US8076009||Oct 26, 2007||Dec 13, 2011||Global Oled Technology, Llc.||OLED device with fluoranthene electron transport materials|
|US8088500||Nov 12, 2008||Jan 3, 2012||Global Oled Technology Llc||OLED device with fluoranthene electron injection materials|
|US8102114||Feb 27, 2009||Jan 24, 2012||Global Oled Technology, Llc.||Method of manufacturing an inverted bottom-emitting OLED device|
|US8129039||Oct 26, 2007||Mar 6, 2012||Global Oled Technology, Llc||Phosphorescent OLED device with certain fluoranthene host|
|US8147989||Feb 27, 2009||Apr 3, 2012||Global Oled Technology Llc||OLED device with stabilized green light-emitting layer|
|US8202674||Oct 11, 2010||Jun 19, 2012||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US8206842||Apr 6, 2009||Jun 26, 2012||Global Oled Technology Llc||Organic element for electroluminescent devices|
|US8216697||Feb 13, 2009||Jul 10, 2012||Global Oled Technology Llc||OLED with fluoranthene-macrocyclic materials|
|US8247088||Aug 28, 2008||Aug 21, 2012||Global Oled Technology Llc||Emitting complex for electroluminescent devices|
|US8253126||Oct 31, 2006||Aug 28, 2012||Lg Chem. Ltd.||Organic electronic device|
|US8258693||Jun 22, 2011||Sep 4, 2012||Global Oled Technology Llc||Top-emitting OLED device with integrated light-scattering and color-conversion layer|
|US8268457||Dec 5, 2008||Sep 18, 2012||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device and material for organic electroluminescent device|
|US8324800||Jun 12, 2008||Dec 4, 2012||Global Oled Technology Llc||Phosphorescent OLED device with mixed hosts|
|US8420229||Oct 26, 2007||Apr 16, 2013||Global OLED Technologies LLC||OLED device with certain fluoranthene light-emitting dopants|
|US8431242||Oct 26, 2007||Apr 30, 2013||Global Oled Technology, Llc.||OLED device with certain fluoranthene host|
|US8628862||Sep 10, 2008||Jan 14, 2014||Basf Se||Electroluminescent device|
|US8680693||Jan 17, 2007||Mar 25, 2014||Lg Chem. Ltd.||OLED having stacked organic light-emitting units|
|US8795855||Jan 30, 2007||Aug 5, 2014||Global Oled Technology Llc||OLEDs having high efficiency and excellent lifetime|
|US8877350||Dec 11, 2007||Nov 4, 2014||Global Oled Technology Llc||White OLED with two blue light-emitting layers|
|US8900722||Nov 29, 2007||Dec 2, 2014||Global Oled Technology Llc||OLED device employing alkali metal cluster compounds|
|US8956738||Oct 5, 2009||Feb 17, 2015||Global Oled Technology Llc||Organic element for low voltage electroluminescent devices|
|US9040170||Nov 29, 2005||May 26, 2015||Global Oled Technology Llc||Electroluminescent device with quinazoline complex emitter|
|US9118020||Dec 9, 2009||Aug 25, 2015||Global Oled Technology Llc||Electroluminescent devices including organic eil layer|
|US9620721||Feb 7, 2014||Apr 11, 2017||Global Oled Technology Llc||OLEDs having high efficiency and excellent lifetime|
|US9666826||Apr 27, 2006||May 30, 2017||Global Oled Technology Llc||Electroluminescent device including an anthracene derivative|
|US20010016643 *||Jan 30, 2001||Aug 23, 2001||Ib Jonassen||Peptide derivatives|
|US20030162053 *||Mar 15, 2002||Aug 28, 2003||Marks Tobin J.||Organic light - emitting diodes and methods for assembly and enhanced charge injection|
|US20030203551 *||Apr 8, 2003||Oct 30, 2003||Cok Ronald S.||Desiccant structures for OLED displays|
|US20040029039 *||Aug 2, 2002||Feb 12, 2004||Eastman Kodak Company||Laser thermal transfer donor including a separate dopant layer|
|US20040043138 *||Aug 21, 2002||Mar 4, 2004||Ramesh Jagannathan||Solid state lighting using compressed fluid coatings|
|US20040043140 *||Nov 20, 2002||Mar 4, 2004||Ramesh Jagannathan||Solid state lighting using compressed fluid coatings|
|US20040061435 *||Sep 30, 2002||Apr 1, 2004||Eastman Kodak Company||High work function metal alloy cathode used in organic electroluminescent devices|
|US20040092195 *||Jul 1, 2003||May 13, 2004||Marks Tobin J.||Organic light-emitting diodes and methods for assembly and emission control|
|US20040108806 *||Nov 18, 2003||Jun 10, 2004||Eastman Kodak Company||OLED displays with fiber-optic faceplates|
|US20050029933 *||Sep 2, 2004||Feb 10, 2005||Eastman Kodak Compamy||Cascaded organic electroluminescent devices with color filters|
|US20060240278 *||Apr 20, 2005||Oct 26, 2006||Eastman Kodak Company||OLED device with improved performance|
|US20060269855 *||May 27, 2005||Nov 30, 2006||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US20060286470 *||Jun 16, 2005||Dec 21, 2006||Xerox Corporation||Imaging member|
|US20070048545 *||Aug 31, 2005||Mar 1, 2007||Eastman Kodak Company||Electron-transporting layer for white OLED device|
|US20070102698 *||Oct 31, 2006||May 10, 2007||Kang Min S||Organic electronic device|
|US20070122655 *||Nov 29, 2005||May 31, 2007||Eastman Kodak Company||Electroluminescent device with quinazoline complex emitter|
|US20070122657 *||Nov 30, 2005||May 31, 2007||Eastman Kodak Company||Electroluminescent device containing a phenanthroline derivative|
|US20070171525 *||Feb 22, 2007||Jul 26, 2007||Miller Michael E||3d stereo oled display|
|US20070207345 *||Dec 20, 2006||Sep 6, 2007||Eastman Kodak Company||Electroluminescent device including gallium complexes|
|US20070232830 *||Mar 28, 2006||Oct 4, 2007||Xerox Corporation||Arylamine process|
|US20070247066 *||Apr 6, 2004||Oct 25, 2007||Idemitsu Kosan Co., Ltd.||Electrode Substrate and Its Manufacturing Method|
|US20070252522 *||Apr 27, 2006||Nov 1, 2007||Eastman Kodak Company||Electroluminescent device including an anthracene derivative|
|US20080171275 *||Mar 19, 2008||Jul 17, 2008||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US20080176099 *||Jan 18, 2007||Jul 24, 2008||Hatwar Tukaram K||White oled device with improved functions|
|US20080182129 *||Jan 30, 2007||Jul 31, 2008||Klubek Kevin P||Oleds having high efficiency and excellent lifetime|
|US20080278067 *||May 10, 2007||Nov 13, 2008||Yuan-Sheng Tyan||Electroluminescent device having improved light output|
|US20080284317 *||May 17, 2007||Nov 20, 2008||Liang-Sheng Liao||Hybrid oled having improved efficiency|
|US20080284318 *||May 17, 2007||Nov 20, 2008||Deaton Joseph C||Hybrid fluorescent/phosphorescent oleds|
|US20080315753 *||Jun 20, 2007||Dec 25, 2008||Liang-Sheng Liao||Phosphorescent oled having double exciton-blocking layers|
|US20090004365 *||Sep 8, 2008||Jan 1, 2009||Liang-Sheng Liao||Contaminant-scavenging layer on oled anodes|
|US20090004485 *||Jun 27, 2007||Jan 1, 2009||Shiying Zheng||6-member ring structure used in electroluminescent devices|
|US20090009101 *||Jan 17, 2007||Jan 8, 2009||Kang Min-Soo||Oled Having Stacked Organic Light-Emitting Units|
|US20090053557 *||Aug 23, 2007||Feb 26, 2009||Spindler Jeffrey P||Stabilized white-emitting oled device|
|US20090053559 *||Aug 20, 2007||Feb 26, 2009||Spindler Jeffrey P||High-performance broadband oled device|
|US20090091242 *||Oct 5, 2007||Apr 9, 2009||Liang-Sheng Liao||Hole-injecting layer in oleds|
|US20090108734 *||Oct 26, 2007||Apr 30, 2009||Begley William J||Oled device with certain fluoranthene light-emitting dopants|
|US20090108735 *||Oct 26, 2007||Apr 30, 2009||Begley William J||Oled device with fluoranthene electron transport materials|
|US20090108736 *||Oct 26, 2007||Apr 30, 2009||Begley William J||Phosphorescent oled device with certain fluoranthene host|
|US20090110957 *||Oct 26, 2007||Apr 30, 2009||Begley William J||Oled device with certain fluoranthene host|
|US20090130941 *||Nov 16, 2007||May 21, 2009||Boroson Michael L||Desiccant sealing arrangement for oled devices|
|US20090146552 *||Dec 11, 2007||Jun 11, 2009||Spindler Jeffrey P||White oled with two blue light-emitting layers|
|US20090162612 *||Dec 19, 2007||Jun 25, 2009||Hatwar Tukaram K||Oled device having two electron-transport layers|
|US20090167167 *||Dec 5, 2008||Jul 2, 2009||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device and material for organic electroluminescent device|
|US20090191427 *||Jan 30, 2008||Jul 30, 2009||Liang-Sheng Liao||Phosphorescent oled having double hole-blocking layers|
|US20090234092 *||Jun 5, 2009||Sep 17, 2009||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US20090242877 *||Mar 25, 2008||Oct 1, 2009||Eastman Kodak Company||Oled device with hole-transport and electron-transport materials|
|US20090284137 *||May 4, 2009||Nov 19, 2009||Northwestern University||Organic light-emitting diodes and methods for assembly and emission control|
|US20090284145 *||Jul 2, 2009||Nov 19, 2009||Marks Tobin J||Organic Light-Emitting Diodes and Methods for Assembly and Enhanced Charge Injection|
|US20090309487 *||Jun 12, 2008||Dec 17, 2009||Royster Jr Tommie L||Phosphorescent oled device with mixed hosts|
|US20100019671 *||Oct 5, 2009||Jan 28, 2010||Eastman Kodak Company||Organic element for low voltage electroluminescent devices|
|US20100052516 *||Aug 28, 2008||Mar 4, 2010||Xiaofan Ren||Emitting complex for electroluminescent devices|
|US20100084647 *||Dec 9, 2009||Apr 8, 2010||Kondakova Marina E||Electroluminescent devices including organic eil layer|
|US20100117063 *||Oct 31, 2006||May 13, 2010||Kang Min Soo||Organic electronic device|
|US20100117519 *||Nov 7, 2008||May 13, 2010||Begley William J||Electroluminescent device containing a flouranthene compound|
|US20100117520 *||Nov 12, 2008||May 13, 2010||Begley William J||Oled device with fluoranthene electron injection materials|
|US20100141122 *||Dec 9, 2008||Jun 10, 2010||Begley William J||Oled device with cyclobutene electron injection materials|
|US20100207513 *||Feb 13, 2009||Aug 19, 2010||Begley William J||Oled with fluoranthene-macrocyclic materials|
|US20100219429 *||May 13, 2010||Sep 2, 2010||Cok Ronald S||Top-emitting oled device with light-scattering layer and color-conversion|
|US20100219747 *||Feb 27, 2009||Sep 2, 2010||Tutt Lee W||Inverted bottom-emitting oled device|
|US20100219748 *||Feb 27, 2009||Sep 2, 2010||Kondakova Marina E||Oled device with stabilized green light-emitting layer|
|US20100244677 *||Mar 31, 2009||Sep 30, 2010||Begley William J||Oled device containing a silyl-fluoranthene derivative|
|US20100277060 *||Sep 10, 2008||Nov 4, 2010||Basf Se||Electroluminescent device|
|US20100307791 *||Jun 9, 2009||Dec 9, 2010||The Government Of The United States Of America, As Represented By The Secretary Of The Navy||Electrically Conductive Polymers|
|US20110024770 *||Oct 12, 2010||Feb 3, 2011||Tutt Lee W||Inverted Bottom-Emitting OLED Device|
|US20110028724 *||Oct 11, 2010||Feb 3, 2011||Xerox Corporation||Polymers of napthalene tetracarboxylic diimide dimers|
|US20140008640 *||Sep 9, 2013||Jan 9, 2014||Idemitsu Kosan, Co.||Asymmetric monoanthracene derivative, material for organic electroluminescent device and organic electroluminescent device utilizing the same|
|CN101891642A *||Jul 7, 2010||Nov 24, 2010||中国科学院上海微系统与信息技术研究所||Fluorescent compound and application thereof to detection of trace nitrobenzene substances|
|CN101891642B||Jul 7, 2010||Sep 17, 2014||中国科学院上海微系统与信息技术研究所||Fluorescent compound and application thereof to detection of trace nitrobenzene substances|
|DE102010006280A1||Jan 30, 2010||Aug 4, 2011||Merck Patent GmbH, 64293||Farbkonvertierung|
|DE102010055901A1||Dec 23, 2010||Jun 28, 2012||Merck Patent Gmbh||Organische Elektrolumineszenzvorrichtung|
|DE102011117422A1||Oct 28, 2011||May 2, 2013||Merck Patent Gmbh||Hyperverzweigte Polymere, Verfahren zu deren Herstellung sowie deren Verwendung in elektronischen Vorrichtungen|
|DE102016003104A1||Mar 15, 2016||Sep 21, 2017||Merck Patent Gmbh||Behälter umfassend eine Formulierung enthaltend mindestens einen organischen Halbleiter|
|EP0373582A1 *||Dec 12, 1989||Jun 20, 1990||Idemitsu Kosan Company Limited||Electroluminescence device|
|EP0534510A1||Aug 1, 1992||Mar 31, 1993||Eastman Kodak Company||Improved blue emitting internal junction organic electroluminescent device|
|EP0616020A1||Mar 14, 1990||Sep 21, 1994||Idemitsu Kosan Company Limited||Aromatic dimethylidyne compounds and process for preparation thereof|
|EP0786925A2||Jan 13, 1997||Jul 30, 1997||Eastman Kodak Company||White light-emitting electroluminescent devices|
|EP0903964A1||Sep 7, 1998||Mar 24, 1999||Eastman Kodak Company||Organic electroluminescent device with inorganic electron transporting layer|
|EP1367677A2||May 16, 2003||Dec 3, 2003||Eastman Kodak Company||Lighting apparatus with flexible oled area illumination light source and fixture|
|EP2161272A1||Sep 5, 2008||Mar 10, 2010||Basf Se||Phenanthrolines|
|EP2229039A1||Jun 16, 2004||Sep 15, 2010||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device and display using same|
|EP2239352A2||Sep 16, 2005||Oct 13, 2010||Global OLED Technology LLC||Delivering particulate material to a vaporization zone|
|EP2262032A2||Apr 4, 2000||Dec 15, 2010||Idemitsu Kosan Co., Ltd.||Organic electroluminescence device and its manufacturing method|
|EP2270117A2||Dec 22, 1999||Jan 5, 2011||Idemitsu Kosan Co., Ltd.||Organic electroluminescence device|
|EP2276089A2||Jul 13, 2005||Jan 19, 2011||Global OLED Technology LLC||Method for reducing moisture contamination in a top-emitting oled using a dessicant|
|EP2355198A1||May 8, 2006||Aug 10, 2011||Global OLED Technology LLC||OLED electron-injecting layer|
|EP2371810A1||Dec 20, 2005||Oct 5, 2011||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescent device using same|
|EP2448374A2||Nov 30, 2004||May 2, 2012||Idemitsu Kosan Co., Ltd.||Asymmetric monoanthracene derivative, material for organic electroluminescent device and organic electroluminescent device utilizing the same|
|EP2498317A2||Jul 23, 2008||Sep 12, 2012||Global OLED Technology LLC||Preventing stress transfer in OLED display components|
|EP2518045A1||Oct 26, 2007||Oct 31, 2012||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescent element using the same|
|EP2568515A1||Oct 16, 2008||Mar 13, 2013||Global OLED Technology LLC||OLED device with fluoranthene electron transport materials|
|EP2713415A1||Dec 22, 2009||Apr 2, 2014||Idemitsu Kosan Co., Ltd||Material for organic electroluminescent element, and organic electroluminescent element|
|EP2752866A1||Aug 8, 2003||Jul 9, 2014||Global OLED Technology LLC||Color organic light emitting diode display with improved lifetime|
|EP2910619A1||Dec 13, 2004||Aug 26, 2015||Idemitsu Kosan Co., Ltd||Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device|
|EP3101647A1||Dec 2, 2003||Dec 7, 2016||Global OLED Technology LLC||A color oled display with improved power efficiency|
|EP3101691A1||Dec 2, 2003||Dec 7, 2016||Global OLED Technology LLC||A color oled display with improved power efficiency|
|WO2000041443A1||Dec 22, 1999||Jul 13, 2000||Idemitsu Kosan Co., Ltd.||Organic electroluminescence device|
|WO2006034028A2||Sep 16, 2005||Mar 30, 2006||Eastman Kodak Company||Delivering particulate material to a vaporization source|
|WO2006073054A1||Dec 20, 2005||Jul 13, 2006||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescent device using same|
|WO2007007553A1||Jun 28, 2006||Jan 18, 2007||Idemitsu Kosan Co., Ltd.||Biphenyl derivatives, organic electroluminescent materials, and organic electroluminescent devices made by using the same|
|WO2007017995A1||Jun 30, 2006||Feb 15, 2007||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescence device making use of the same|
|WO2007029410A1||Jul 5, 2006||Mar 15, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent element using polyarylamine|
|WO2007032161A1||Aug 8, 2006||Mar 22, 2007||Idemitsu Kosan Co., Ltd.||Asymmetric fluorene derivative and organic electroluminescent element containing the same|
|WO2007032162A1||Aug 8, 2006||Mar 22, 2007||Idemitsu Kosan Co., Ltd.||Pyrene derivative and organic electroluminescence device making use of the same|
|WO2007052759A1||Nov 2, 2006||May 10, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent element|
|WO2007058044A1||Oct 18, 2006||May 24, 2007||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescent element employing the same|
|WO2007058127A1||Nov 10, 2006||May 24, 2007||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescent element using the same|
|WO2007058172A1||Nov 14, 2006||May 24, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device|
|WO2007060795A1||Oct 17, 2006||May 31, 2007||Idemitsu Kosan Co., Ltd.||Amine compound and organic electroluminescent element employing the same|
|WO2007061063A1||Nov 24, 2006||May 31, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device|
|WO2007063993A1||Dec 1, 2006||Jun 7, 2007||Idemitsu Kosan Co., Ltd.||Nitrogenous heterocyclic derivative and organic electroluminescence device making use of the same|
|WO2007077766A1||Dec 22, 2006||Jul 12, 2007||Idemitsu Kosan Co., Ltd.||Material for organic electroluminescent device and organic electroluminescent device|
|WO2007080704A1||Nov 15, 2006||Jul 19, 2007||Idemitsu Kosan Co., Ltd.||Aromatic amine derivatives and organic electroluminescent devices made by using the same|
|WO2007097178A1||Feb 2, 2007||Aug 30, 2007||Idemitsu Kosan Co., Ltd.||Material for organic electroluminescent device, method for producing same and organic electroluminescent device|
|WO2007099983A1||Feb 28, 2007||Sep 7, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device using fluoranthene derivative and indenoperylene derivative|
|WO2007100010A1||Feb 28, 2007||Sep 7, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device|
|WO2007102361A1||Feb 28, 2007||Sep 13, 2007||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescent device using same|
|WO2007105448A1||Feb 22, 2007||Sep 20, 2007||Idemitsu Kosan Co., Ltd.||Naphthacene derivative and organic electroluminescent device using same|
|WO2007111262A1||Mar 23, 2007||Oct 4, 2007||Idemitsu Kosan Co., Ltd.||Nitrogen-containing heterocyclic derivative and organic electroluminescent device using same|
|WO2007111263A1||Mar 23, 2007||Oct 4, 2007||Idemitsu Kosan Co., Ltd.||Nitrogen-containing heterocyclic derivative and organic electroluminescent device using same|
|WO2007114358A1||Mar 30, 2007||Oct 11, 2007||Idemitsu Kosan Co., Ltd.||Benzanthracene derivative and organic electroluminescent device using the same|
|WO2007116750A1||Mar 27, 2007||Oct 18, 2007||Idemitsu Kosan Co., Ltd.||Material for organic electroluminescent device and organic electroluminescent device using the same|
|WO2007116828A1||Mar 30, 2007||Oct 18, 2007||Idemitsu Kosan Co., Ltd.||Bisanthracene derivative and organic electroluminescent device using the same|
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|WO2007132704A1||May 9, 2007||Nov 22, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescence element|
|WO2007138906A1||May 21, 2007||Dec 6, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device and full color light-emitting device|
|WO2007148660A1||Jun 19, 2007||Dec 27, 2007||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device employing heterocycle-containing arylamine derivative|
|WO2008001551A1||May 10, 2007||Jan 3, 2008||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative, and organic electroluminescence device using the same|
|WO2008015949A1||Jul 26, 2007||Feb 7, 2008||Idemitsu Kosan Co., Ltd.||Organic electroluminescence device|
|WO2008023549A1||Aug 1, 2007||Feb 28, 2008||Idemitsu Kosan Co., Ltd.||Aromatic amine derivatives and organic electroluminescent devices made by using the same|
|WO2008023623A1||Aug 15, 2007||Feb 28, 2008||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device|
|WO2008023759A1||Aug 23, 2007||Feb 28, 2008||Idemitsu Kosan Co., Ltd.||Aromatic amine derivatives and organic electroluminescence devices using the same|
|WO2008056652A1||Nov 6, 2007||May 15, 2008||Idemitsu Kosan Co., Ltd.||Organic el material-containing solution, method for synthesizing organic el material, compound synthesized by the synthesizing method, method for forming thin film of organic el material, thin film of organic el material, and organic el device|
|WO2008056722A1||Nov 8, 2007||May 15, 2008||Idemitsu Kosan Co., Ltd.||Organic el material-containing solution, method for forming thin film of organic el material, thin film of organic el material, and organic el device|
|WO2008056723A1||Nov 8, 2007||May 15, 2008||Idemitsu Kosan Co., Ltd.||Organic el material-containing solution, method for forming thin film of organic el material, thin film of organic el material, and organic el device|
|WO2008059713A1||Oct 30, 2007||May 22, 2008||Idemitsu Kosan Co., Ltd.||Fluoranthene compound, organic electroluminescent device using the fluoranthene compound, and organic electroluminescent material-containing solution|
|WO2008062636A1||Oct 26, 2007||May 29, 2008||Idemitsu Kosan Co., Ltd.||Aromatic amine derivative and organic electroluminescent element using the same|
|WO2008081823A1||Dec 26, 2007||Jul 10, 2008||Idemitsu Kosan Co., Ltd.||Solution containing organic el material, method for synthesis of organic el material, compound synthesized by the synthesis method, method for formation of thin film of organic el material, thin film of organic el material, organic el element|
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|WO2008126802A1||Apr 4, 2008||Oct 23, 2008||Idemitsu Kosan Co., Ltd.||Organic electroluminescent element|
|WO2009011327A1||Jul 14, 2008||Jan 22, 2009||Idemitsu Kosan Co., Ltd.||Organic electroluminescent device material and organic electroluminescent device|
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|WO2009066778A1||Nov 21, 2008||May 28, 2009||Idemitsu Kosan Co., Ltd.||Organic el element and solution containing organic el material|
|WO2009069717A1||Nov 27, 2008||Jun 4, 2009||Idemitsu Kosan Co., Ltd.||Azaindenofluorenedione derivative, organic electroluminescent device material, and organic electroluminescent device|
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|WO2010074087A1||Dec 22, 2009||Jul 1, 2010||Idemitsu Kosan Co.,Ltd.||Material for organic electroluminescent element, and organic electroluminescent element|
|WO2010074181A1||Dec 24, 2009||Jul 1, 2010||Idemitsu Kosan Co.,Ltd.||Organic electroluminescence element and compound|
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|WO2011015265A2||Jul 7, 2010||Feb 10, 2011||Merck Patent Gmbh||Electronic devices comprising multi cyclic hydrocarbons|
|WO2011032686A1||Sep 15, 2010||Mar 24, 2011||Merck Patent Gmbh||Formulas for producing electronic devices|
|WO2011046182A1||Oct 14, 2010||Apr 21, 2011||出光興産株式会社||Fluorene-containing aromatic compound, material for organic electroluminescent element, and organic electroluminescent element using same|
|WO2011076314A1||Nov 11, 2010||Jun 30, 2011||Merck Patent Gmbh||Electroluminescent formulations|
|WO2011076323A1||Nov 24, 2010||Jun 30, 2011||Merck Patent Gmbh||Formulations comprising phase-separated functional materials|
|WO2011076326A1||Nov 24, 2010||Jun 30, 2011||Merck Patent Gmbh||Electroluminescent functional surfactants|
|WO2011091946A1||Jan 3, 2011||Aug 4, 2011||Merck Patent Gmbh||Organic electroluminescent device comprising an integrated layer for colour conversion|
|WO2011110275A2||Feb 15, 2011||Sep 15, 2011||Merck Patent Gmbh||Radiative fibers|
|WO2011110277A1||Feb 15, 2011||Sep 15, 2011||Merck Patent Gmbh||Fibers in therapy and cosmetics|
|WO2011137922A1||Nov 26, 2010||Nov 10, 2011||Merck Patent Gmbh||Formulations and electronic devices|
|WO2011147522A1||Apr 28, 2011||Dec 1, 2011||Merck Patent Gmbh||Compositions comprising quantum dots|
|WO2012013270A1||Jun 24, 2011||Feb 2, 2012||Merck Patent Gmbh||Nanocrystals in devices|
|WO2012013272A1||Jun 28, 2011||Feb 2, 2012||Merck Patent Gmbh||Quantum dots and hosts|
|WO2012014841A1||Jul 25, 2011||Feb 2, 2012||出光興産株式会社||Organic electroluminescence element|
|WO2012084114A1||Nov 24, 2011||Jun 28, 2012||Merck Patent Gmbh||Organic electroluminescent device|
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|WO2012126566A1||Feb 28, 2012||Sep 27, 2012||Merck Patent Gmbh||Organic ionic functional materials|
|WO2012152366A1||Apr 18, 2012||Nov 15, 2012||Merck Patent Gmbh||Organic ionic compounds, compositions and electronic devices|
|WO2012157211A1||May 9, 2012||Nov 22, 2012||Sony Corporation||Organic el multi-color light-emitting device|
|WO2012163464A1||May 5, 2012||Dec 6, 2012||Merck Patent Gmbh||Hybrid ambipolar tfts|
|WO2013013754A1||Jun 28, 2012||Jan 31, 2013||Merck Patent Gmbh||Copolymers with functionalized side chains|
|WO2013035275A1||Aug 29, 2012||Mar 14, 2013||出光興産株式会社||Nitrogen-containing heteroaromatic ring compound|
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|WO2013060411A1||Oct 1, 2012||May 2, 2013||Merck Patent Gmbh||Hyperbranched polymers, methods for producing same, and use of same in electronic devices|
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|WO2015014427A1||Jun 26, 2014||Feb 5, 2015||Merck Patent Gmbh||Electro-optical device and the use thereof|
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|WO2016034262A1||Aug 4, 2015||Mar 10, 2016||Merck Patent Gmbh||Formulations and electronic devices|
|WO2016107663A1||Dec 2, 2015||Jul 7, 2016||Merck Patent Gmbh||Formulations and electronic devices|
|WO2016155866A1||Mar 4, 2016||Oct 6, 2016||Merck Patent Gmbh||Formulation of an organic functional material comprising a siloxane solvent|
|WO2016198141A1||May 13, 2016||Dec 15, 2016||Merck Patent Gmbh||Esters containing non-aromatic cycles as solvents for oled formulations|
|WO2017036572A1||Jul 29, 2016||Mar 9, 2017||Merck Patent Gmbh||Formulation of an organic functional material comprising an epoxy group containing solvent|
|WO2017097391A1||Nov 11, 2016||Jun 15, 2017||Merck Patent Gmbh||Formulations containing ketones comprising non-aromatic cycles|
|WO2017102048A1||Nov 15, 2016||Jun 22, 2017||Merck Patent Gmbh||Esters containing aromatic groups as solvents for organic electronic formulations|
|WO2017102049A1||Nov 17, 2016||Jun 22, 2017||Merck Patent Gmbh||Formulations containing a mixture of at least two different solvents|
|WO2017102052A1||Nov 18, 2016||Jun 22, 2017||Merck Patent Gmbh||Formulations containing a solid solvent|
|WO2017140404A1||Jan 17, 2017||Aug 24, 2017||Merck Patent Gmbh||Formulation of an organic functional material|
|WO2017157783A1||Mar 10, 2017||Sep 21, 2017||Merck Patent Gmbh||Receptacle comprising a formulation containing at least one organic semiconductor|
|U.S. Classification||430/73, 564/431, 558/401, 562/456, 430/96, 560/48, 562/457, 564/168, 564/265, 558/402, 564/163, 558/408, 564/36|