CA1041344A - High surface area carrier - Google Patents
High surface area carrierInfo
- Publication number
- CA1041344A CA1041344A CA225,837A CA225837A CA1041344A CA 1041344 A CA1041344 A CA 1041344A CA 225837 A CA225837 A CA 225837A CA 1041344 A CA1041344 A CA 1041344A
- Authority
- CA
- Canada
- Prior art keywords
- surface area
- carrier
- carrier materials
- less
- electrostatographic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/107—Developers with toner particles characterised by carrier particles having magnetic components
- G03G9/1075—Structural characteristics of the carrier particles, e.g. shape or crystallographic structure
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/107—Developers with toner particles characterised by carrier particles having magnetic components
- G03G9/108—Ferrite carrier, e.g. magnetite
- G03G9/1085—Ferrite carrier, e.g. magnetite with non-ferrous metal oxide, e.g. MgO-Fe2O3
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
- G03G9/1132—Macromolecular components of coatings
- G03G9/1133—Macromolecular components of coatings obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
- G03G9/1138—Non-macromolecular organic components of coatings
Abstract
HIGH SURFACE AREA CARRIER
ABSTRACT OF THE DISCLOSURE
Classified high surface area carrier materials and an electrostatic imaging process using same. The electrostato-graphic imaging process comprising the steps of providing an electrostatographic imaging member having a recording surface, forming an electrostatic latent image on said recording surface, and contacting said electrostatic latent image with a developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classified high surface area carrier materials having a specific surface area of at least about 150 cm2/gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 microns, whereby at least a portion of said finely divided toner particles are attracted to and deposited on said recording surface in conformance with said electrostatic latent image.
ABSTRACT OF THE DISCLOSURE
Classified high surface area carrier materials and an electrostatic imaging process using same. The electrostato-graphic imaging process comprising the steps of providing an electrostatographic imaging member having a recording surface, forming an electrostatic latent image on said recording surface, and contacting said electrostatic latent image with a developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classified high surface area carrier materials having a specific surface area of at least about 150 cm2/gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 microns, whereby at least a portion of said finely divided toner particles are attracted to and deposited on said recording surface in conformance with said electrostatic latent image.
Description
~.o~344 1 ::
BACKGROUND OE` THE INVENTION
This invention relates in general to electrostato-graphic imaging systems, and, in particular, to improved developer materials and their use.
The formation and development of images on the surface of photoconductive materials by electrostatic means is well known.
The basic electrostatographic process, as taught by C. F. Carlson in U. S. Patent 2,297,691, involves placing a uniform electrostatic charge on a photoconductive insulating layer, exposing the layer to a light and shadow image to dissipate the charge on the areas of the layer exposed to the light and developing the resulting electrostatic latent image by depositing on the image a finely-divided electroscopic material referred to in the art as "toner".
The toner will normally be attracted to those areas of the layer , . . .
".
which retain a charge, thereby forming a toner image corresponding to the electrostatic latent image. This powder image may then be transferred to a support surface such as paper. The transferred image may subsequently be permanently affixed to the support surface as by heat. Instead of latent image formation by uniformly charging the photoconductive layer and then exposing the layer to a light and shadow image, one may form the latent image by directly charging the layer in image configuration. The powder .
image may be fixed to the photoconductive layer if elimination , . , 1 of the powder image transfer step is desired. Other suitable :, , .
' fixing means such as solvent or overcoating treatment may be substituted for the foregoing heat fixing step.
~i, .
Many methods are known for applying the electroscopic - particles to the electrostatic latent image to be developed. One !~i'` development method, as disclosed by E. N. Wise in U. S. Patent - ........... .
i 2,618,552 is Xnown as "cascade" development. In this method, . .
.'."; .
~ . . - . : . . : . ~ ; :
10413~4 developer material comprising relatively large carrier particles having finely-divided toner particles electrostatically clinging to the surface of the carrier particles is conveyed to and rolled or cascaded across the electrostatic latent image-bearing surface.
The composition of the toner par-ticle is so chosen as to have a triboelectric polarity opposite that of the carrier particles.
In order to develop a negatively charged electrostatic latent image, an electroscopic powder and carrier combination should be selected in which the powder i5 triboelectrically positive in relation to the carrier. Conversely, to develop a positively charged electro-static latent image, the electroscopic powder and carrier should be selected in which the powder is triboelectrically negative in relation to the carrier. This triboelectric relationship between the powder and carrier depends on their relative positions in a triboelectric series in which the materials are arranyed in such a way that each material is charged with a positive electrical charge when contacted with any material below it in the series and . , .
with a negative electrical charge whèn contacted with any material above it in the series. As the mixture cascades or rolls across the image~bearing surface, the toner particles are electrostatically deposited and secured to the charged portions of the latent image and are not deposited on the uncharged or background portions of the image. Most of the toner particles accidentally deposited in ~ ~ .
the background are removed by the rolling carrier, due apparently, to the greater electrostatic attraction between the toner and the carrier than between the toner and the discharged background. The ~` carrier particles and unused toner particles are then recycled.
This technique is extremely good for the development of line copy ~ images. The cascade development process is the most widely used ;? commercial electrostatographid development technique. A general ,, purpose office copying machine incorporating this technique is ~':
~s:~
BACKGROUND OE` THE INVENTION
This invention relates in general to electrostato-graphic imaging systems, and, in particular, to improved developer materials and their use.
The formation and development of images on the surface of photoconductive materials by electrostatic means is well known.
The basic electrostatographic process, as taught by C. F. Carlson in U. S. Patent 2,297,691, involves placing a uniform electrostatic charge on a photoconductive insulating layer, exposing the layer to a light and shadow image to dissipate the charge on the areas of the layer exposed to the light and developing the resulting electrostatic latent image by depositing on the image a finely-divided electroscopic material referred to in the art as "toner".
The toner will normally be attracted to those areas of the layer , . . .
".
which retain a charge, thereby forming a toner image corresponding to the electrostatic latent image. This powder image may then be transferred to a support surface such as paper. The transferred image may subsequently be permanently affixed to the support surface as by heat. Instead of latent image formation by uniformly charging the photoconductive layer and then exposing the layer to a light and shadow image, one may form the latent image by directly charging the layer in image configuration. The powder .
image may be fixed to the photoconductive layer if elimination , . , 1 of the powder image transfer step is desired. Other suitable :, , .
' fixing means such as solvent or overcoating treatment may be substituted for the foregoing heat fixing step.
~i, .
Many methods are known for applying the electroscopic - particles to the electrostatic latent image to be developed. One !~i'` development method, as disclosed by E. N. Wise in U. S. Patent - ........... .
i 2,618,552 is Xnown as "cascade" development. In this method, . .
.'."; .
~ . . - . : . . : . ~ ; :
10413~4 developer material comprising relatively large carrier particles having finely-divided toner particles electrostatically clinging to the surface of the carrier particles is conveyed to and rolled or cascaded across the electrostatic latent image-bearing surface.
The composition of the toner par-ticle is so chosen as to have a triboelectric polarity opposite that of the carrier particles.
In order to develop a negatively charged electrostatic latent image, an electroscopic powder and carrier combination should be selected in which the powder i5 triboelectrically positive in relation to the carrier. Conversely, to develop a positively charged electro-static latent image, the electroscopic powder and carrier should be selected in which the powder is triboelectrically negative in relation to the carrier. This triboelectric relationship between the powder and carrier depends on their relative positions in a triboelectric series in which the materials are arranyed in such a way that each material is charged with a positive electrical charge when contacted with any material below it in the series and . , .
with a negative electrical charge whèn contacted with any material above it in the series. As the mixture cascades or rolls across the image~bearing surface, the toner particles are electrostatically deposited and secured to the charged portions of the latent image and are not deposited on the uncharged or background portions of the image. Most of the toner particles accidentally deposited in ~ ~ .
the background are removed by the rolling carrier, due apparently, to the greater electrostatic attraction between the toner and the carrier than between the toner and the discharged background. The ~` carrier particles and unused toner particles are then recycled.
This technique is extremely good for the development of line copy ~ images. The cascade development process is the most widely used ;? commercial electrostatographid development technique. A general ,, purpose office copying machine incorporating this technique is ~':
~s:~
-2-. ~ .
44 ~:
described in U. S. Patent 3,099,943.
Another technique for developing electrostatic images is the "magnetic brush" process as disclosed, for example, in U. S. patent 2,874,063. In this method a developer material con-, .
taining toner and magnetic carrier particles is carried by amagnet. The magnetic field of the magnet causes alignment of the magnetic carriers in a brush-like configuration. This "magnetic brush" is engaged with an electrostatic latent image-bearing surface and the toner particles are drawn from the brush to the electrostatic image by electrostatic attraction. Many other methods such as "touchdown" development as disclosed by C. R. Mayo in U.S. Patent 2,895,847 are known for applying electroscopic particles to the electrostatic latent image to be developed. The development processes as mentioned above together with numerous variations are well known to the art through various patents and publications and through the widespread availability and utiliza-tion of electrostatographic imaging equipment.
In automatic electrostatographic equipment, it is con-ventional to employ an electrostatographic plate in the form of a cylindrical drum which is continuously rotated through a cycle of sequential operations including charging, exposure, developing, transfer and cleaning. The plate is usually charged with corona with positive polarity by means of a corona generating device of the type disclosed by L. E. Walkup in U. S. patent 2,777,957 which is connected to a suitable source of high potential. After forming a powder image on the electrostatic image during the development step, the powder image is electrostatically transferred to a support surface by means of a corona generating device such as the corona device mentioned above. In automatic equipment employing a rotating drum, a support surface to which a powdered image is to be transferred is moved through the equipment at the same rate as .. .
44 ~:
described in U. S. Patent 3,099,943.
Another technique for developing electrostatic images is the "magnetic brush" process as disclosed, for example, in U. S. patent 2,874,063. In this method a developer material con-, .
taining toner and magnetic carrier particles is carried by amagnet. The magnetic field of the magnet causes alignment of the magnetic carriers in a brush-like configuration. This "magnetic brush" is engaged with an electrostatic latent image-bearing surface and the toner particles are drawn from the brush to the electrostatic image by electrostatic attraction. Many other methods such as "touchdown" development as disclosed by C. R. Mayo in U.S. Patent 2,895,847 are known for applying electroscopic particles to the electrostatic latent image to be developed. The development processes as mentioned above together with numerous variations are well known to the art through various patents and publications and through the widespread availability and utiliza-tion of electrostatographic imaging equipment.
In automatic electrostatographic equipment, it is con-ventional to employ an electrostatographic plate in the form of a cylindrical drum which is continuously rotated through a cycle of sequential operations including charging, exposure, developing, transfer and cleaning. The plate is usually charged with corona with positive polarity by means of a corona generating device of the type disclosed by L. E. Walkup in U. S. patent 2,777,957 which is connected to a suitable source of high potential. After forming a powder image on the electrostatic image during the development step, the powder image is electrostatically transferred to a support surface by means of a corona generating device such as the corona device mentioned above. In automatic equipment employing a rotating drum, a support surface to which a powdered image is to be transferred is moved through the equipment at the same rate as .. .
-3-3g~
the periphery of the drum and contac'ts the drum in the transfer position interposed between the drum surface and the corona generating device. Transfer is effected by the corona generating device which imparts an electrostatic charge to attract the powder image from the drum to the support surface. The polarity of charge required to effect image transfer is dependent upon the visual form of the original copy relative to the reproduction and , the electroscopic characteristics of a developing material emp~oyed to effect development. For example, where a positive reproduction is to be made of a positive original, it is conventional to employ a positive polarity corona to effect transfer of a negatively charged toner image to the support surface. When a p,ositive reproduction from a negative original is desired, it is conven-tional to employ a positively charged developing material which is repelled by the charged areas on the plate to the discharge areas thereon to form a positive image which may be transferred by ~ .
negative polarity corona. In either case, a residual powder image ~` and occasionally carrier particles remain on the plate after trans-fer. Before the plate may be reused for a subsequent cycle, it is necessa-ry that the residual image and carrier particles, if any, be removed to prevent ghost images from forming on subsequent copies. In the positive-to-positive reproduction process described above, the residual developer powder as well as any carrier particles present are tightly retained on the plate surface by a phenomenon that is not fully understood but believed caused by an electric charge. The charge is substantially neutralized by means of a corona generating device prior to contact of the residual powder with a cleaning device. The neutralization of a charge enhances the cleaning efficiency of the cleaning device.
~,~{ :, ....
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, ~
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Typical electrostatographic cleaning devices include the "web" type cleaning apparatus as disclosed, for example, by W. P~ Graff, Jr. et al in U. S. Patent 3,186,838. In the Graff, Jr. et al patent, removal of the residual powder and carrier particles on the plate is effected by rubbing a web of fibrous material against the imaging plate surface. These inexpensive and disposable webs of fibrous material are advanced into pressure and rubbing or wiping contact with the imaging surface and are gradually advanced to present a clean surface to the plate whereby substantially complete removal of the residual powder and carrier particles from the plate is effected.
While ordinarily capable of producing good ~uality image, conventional developing systems suffer serious deficiencies in certain areas. In the reproduction of high contrast copies such as letters, tracings and the like, it is desirable to select the electroscopic powder and carrier materials so that their mutual electrification being governed in most cases by the distance between their relative positions in the triboelectric series. However, when otherwise compatible electroscopic powder and carrier materials are removed from each other in the triboelectric series by too great a distance, the resulting images are very faint because the attractive forces between the carrier and toner particles compete with the attractive forces between the electrostatic latent image and the toner particles. Although the image density described in the immediately preceding sentence may be improved by increasing the toner concentration in the developer mixture, undesirably high background toner deposition as well as increased toner impaction and agglomeration is encountered when the toner concentration in the ` developer mixture is excessive. The initial electrostatographic plate charge may be increased to improve the density of the deposited powder image, but the plate charge would ordinarily have to be excessively high in order to attract the electroscopic powder away from the carrier particle. Excessively high electrostato~raphic , :lV~ 4~
plate charges are not only undesirable because of the high power consumption necessary to maintain the electrostatographic plate at high potentials, but also because the high potential causes the carrier particles to adhere to the electrostatographic plate surface rather than merely roll across and off the electro-statographic plate surface. Print deletion and massive carry-over of carrier particles often occur when carrier particles adhere to reusable elec-trostatographic imaging surfaces. Massive carrier carry-over problems are particularly acute when the developer is employed in solid area coverage machines where excessive quantities of toner particles are removed from carrier particles thereby leaving many carrier particles substantially bare of toner particles. Further, adherence of carrier particles to reusable electrostatographic imaging surfaces promotes the formakion of undesirable scratches on the surfaces during image transfer and surface cleaning operations. It is therefore, apparent that many materials which o~therwise have suitable properties for employment as carrier particles are unsuitable because they possess unsatisfactory triboelectric properties.
In addition, uniform triboelectric surface characteristics of many carrier surfaces are difficult to achieve with mass produc-tion techniques. Quality images are in some instances almost impossible to obtain in high speed automatic machines when carriers having non-uniform triboelectric properties are employed. Although it may be possible to alter the triboelectric value of an insula-:`:
ting carrier material by blending the carrier material with , another insulating material having a triboelectric value remote from the triboelectric value of the original carrier material, relatively larger quantities of additional material is necessary to alter the triboelectric value of the original carrier material.
; The addition of large quantities of material to the original ',,'''':
~:
~L041344 carrier material to change t~ triboelectric properties thereof requires a major manufacturing operation and often undesirably alters the original physical characteristics of the carrier material. Further, it is highly desirable to control the triboelectric properties of carrier surfaces to accommodate the use of desirable toner compositions while retaining the other desirable physical characteristics of the carrier. The alteration of the triboelectric properties of a carrier by applying a surface coating thereon is a particularly desiràble -technique. With this technique, not only is it possible to control the triboelectric properties of a carrier made from materials having desirable physical characteristics, it is -also possible to employ materials previously not suitable as a carrier. Thus, for example, a carrier having desirable physical properties with the exception of hardness, can be coated with a material having desirable har~dness as well as other physical properties rendering the resultant product more useful as a carrier. Thus, there is a continuing need for a better electxostatographio carrier and an improved method for obtaining the same. i In accordance with one aspect of this invention there 1s provided an electrostatographic imaging process comprising the steps of providing an electrostatographic imaging member having a recording surface, forming an electrostatic latent image on said recording surface, and contacting said electrostatic latent image with a developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classified high surface area carrier materials having a specific surface area of at least about 150 cm2/gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distri-bution wherein the carrier particles have an average particle .. . . .
34~
diameter of less than about 100 microns, ~Ihereby at least a portion of said finely-divided toner particles are attracted to and deposited on said recording surface in conformance with said electrostatic latent image.
In accordance with another aspect of this invention there is provided an electrostatographic developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classi~ied hign surface area carrier materials having a specific surface area of at least about 150 cm /gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 microns.
In accordance with another aspect of this invention there is provided cLassified high surface area carrier materials ~omprising carrier materials having a specific surface area of at least about 150 cm2 /gram, a particle size ~oluma distribution geometric standard deviation of less than about ~-1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 micron~.
More specifically, the improved developer materials o~
this invention provide satisfactory results when the carrier materials have a specific surface area of at least about 150 cmZ/gram. However, it is preferred that the carrier materials have a specific surface area of at least about 165 cm2/gram -~
because developer life is improved such as to provide increased .,~ . .
' copy quantity with the developer material in a high speed electrostatographic reproduction apparatus while maintaining low background levels and sustaining solid area development :, . .
-~ den~ity. Optimum results are obtained when ~le carrier .. .
, .
~ - 8 -. . .
'.. . . . .
1~4~34~ ~
~ materials of this invention have a specific surface area of ;. at least about 175 cm2/gram. .
It has been found that the area ratios of carrier to toner material in a high speed magnetic brush development ~.
. .
system were such that the toner concentration could not be sufficiently reduced to enable a charge level for minimal ;-deposit of toner material in background areas of an electro~
static latent image during development thereof while retain~
ing suffi~iont toner ~ .
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concentration to provide satisfactory solid area density. By providing the carrier materials of this invention having a minimum specific surface area this problem has been overcome.
Thus, this invention now enables the use of a developer mixture having a lower toner concentration per unit surface area of carrier to provide a higher net electrical charge level. It has been found that in the electrostatic copying process that where any given carrier material is employed to provide a tribo-electric charge to toner materials by contact charge trnasfer, the area of carrier triboelectric charging surface is critically ' important. The carrier charging surface area has been foùnd to relate to the amount of toner ma~erial that, for a given toner material, can be charged to a useful triboelectric potential or level. Therefore, in accordance with this invention, it has been found that the triboelectric charging capacity of a carrier material is surface area dependent and accordingly, this invention may be employed to design optimum carrier materials for any given ~, .
electrostatographic development system.
In addition, the classified high surface area carrier materials of this invention have a particle size volume distribu-tion geometric standard deviation of less than about 1.3 and a particle size distribution wherein the particles have an average particle diameter of less than about 100 microns. The term geometric standard deviation as employed herein is defined as the deviation encountered in a particle size analysis approximately measured as the ratio of the particle diameter which is greater than that of 84 percent of the sample to that of the particle diameter which is greater than that of 50 percent of the sample.
This value represents the median or average particle size . . .
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distribution by weight or volume of the carrier particles and has an important reflection on copy quality obtained in an electro-statographic development system. Another measure of the geometric standard deviation of the classified carrier materials of this invention is the deviation encountered in a particle size analysis approximately measured as the ratio of the particle diameter which is greater than that of 50 percent of the sample to that of the particle diameter which is greater than that of 16 percent of the sample. The 50 percent value represents the median or average particle size b~ volume of the carrier particles and has an important reflection on the measure of the useful lifetime of the developer. In both cases, the values obtained for the volume average particle diameter and the geometric standard deviation are determined by size analysis performed by a sieve analysis employ-ing all U. S. Standard sieves from 325 mesh to 70 mesh.
It has been found that the classified carrier materials of this invention provide satisfactory results when the particle size volume distribution geometric standard,deviation thereof is less than about 1.3 and the volume average particle diameter is less than about 100 microns. Improved results are obtained with, and it is preferred, that the particle size volume distribution geometric standard deviation thereo~ be less than about 1.2 and the volume average particle diameter is less than about 90 microns.
Optimum results are obtained when the volume distribution geometric standard deviation of the classified carrier materials of this invention is less than about 1.15 and the volume average particle diameter is less than about 85 microns.
Any suitable particle classification method may be employed to obtain the high surface area carrier materials of this invention. Typical particle classification methods include '."'' -, --10--. .
,;:. .: . : : - : : , . ::
:, . ., . , ", : :: :: , .~L04~3~
air classification, screening, cyclone separation, elutriation, centrification, and combinations thereof. The preferred method of obtaining the high surface area carrier materials of this invention is by screening or selving~
Any suitable coated or uncoated electrostatographic carrier bead material may be employed as the high surface area carrier material of this invention. Typical cascade development process carriers include sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, potassium chlorate, granular zircon, granular silicon, methyl methacrylate, glass and silicon dioxide. Typical magnetic brush development process carriers include nickel, steel, ' iron, ferrites, and the like. The car~iers may be employed with . or without a coating. Many of the foregoing and other typical carriers are described by L. E. Walkup et al in U. S. patent 2,638,41~ and E. N. Wise in U. S. patent 2,618,552. An ultimate ~, coated carrier particle diameter between about 30 microns to about 1,000 microns is preferred because the carrier particles ` then possess sufficient density and inertia to avoid adherence ~1 to the electrostatic images during the cascade development process.
For magnetic brush development, the carrier particles generally .... , \
have an average diameter between about 30 microns and about 250 microns. -Generally speaking, satisfactory results are obtained ,, , '~ when about 1 part toner is used with about 10 to 200 parts by ~,...
:~ weight of carrier.
.,!:, i The high surface area carrier materials of this inven-'';;:
~ tion may be coated with any suitable coating material. Typical ....
electrostatographic carrier particle coating materials include .~ . .
vinyl chloride-vinyl acetate copolymers, styrene-acrylate-' organosilicon terpolymers, natural resins such as caoutchouc, ~t-' :,."' ':
,.. .
" .
, '~ , , , , . .. ~, , . .. .. .. ........ . . -3LO~L3~4 colophony, copal, dammar, Drangon's Blood, jalap, storax;
thermoplastic resins including the polyolefins such as poly-ethylene, polypropylene, chlorinated polyethylene, and chloro-sulfonated polyethylene; polyvinyls and polyvinylidenes such as polystyrene, polymethylstyrene, polym~ethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, poly-vinyl butyral, polyvinyl chloride, polyvinyl carbazole, poly-vinyl ethers, and polyvinyl ketones; fluorocarbons such as poly-tetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride;
and polychlorotrifluoroethylene; polyamides such as polycapro-lactam and polyhexamethylene adipamide; polyesters such as polyethylene terephthalate; polyurethanes; polysulfides, poly-carbonates; thermosetting resins includiny phenolic resins such as phenol-formalidehyde, phenol-furfural and resorcinol formal-dehyde; amino resins such as urea-formaldehyde and melamineformal-dehyde; polyester resins; epoxy resins; and the like. Many of the foregoing and other typical carrier coating materials are described by L. E. walkup in U. S. patent 2,618,551; B. B. Jacknow et al in U. S. patent 3,526,533; and R. J. Hagenbach et al in U. S. patents 3,533,835 and 3,658,500.
When the high surface area carrier materials of this invention are coated, any suitable electrostatographic carrier coating thickness may be employed. However, a carrier coating having a thickness at least sufficient to form a thin continuous film on the carrier particle is preferred because the carrier coating will then possess sufficient thickness to resis~abrasion and prevent pinholes which adversely affect the triboelectric .:
properties of the coated carrier particles. ~enerally, for cascade and magnetic brush development, the carrier coating may comprise from about 0.1 percent to about 10.0 percent by weight :.
., .
.;. -: :.. . -based on the weight of the coated carrier particles. Preferably~
the carrier coating should comprise from about .3 percent to about 1.5 percent by weight based on the weight of the coated carrier particles because maximum durabil;ty, toner impaction resistance, and copy quality are achieved. To achieve further variation in the properties of the coated composite carrier particles, well-known additives such as plasticizers, reactive and non-reactive polymers, dyes, pigments, wetting agents and mixtures thereof may be mixed with the coating materials.
When the high surface area carrier materials of this invention are coated, the carrier coating composition may be applied to the carrier cores by any conventional method such as spra~ing, dipping, fluidized bed coating, tumbling, brushing and the like. The coating compositions may be applied as a powder, a dispersion, solution, emulsion or hot melt~ When applied as a solution, any suitable solvent may be employed.
Solvents having relatively low boiling points are preferred because less energy and time is required to remove the solvent subsequent to application of the coating to the carrier cores.
If desired, the coating may comprise resin monomers which are polymerized in situ on the surface of the cores or plastisols gelled in situ to a non-flowable state on the surface of the cores. Surprisingly, it has been found that for a given inefficient coating process, carrier core materials having the specific surface areas designated in this invention results in increased effective area, that is, triboelectric charging coated area per unit weight. Thus, increased carrier active area increases the net toner material triboelectric charge level for a given toner concentration by weight in a developer mixture. Therefore, where it is preferred to operate an ~13-~,. . .
104~344 electrostatographic development system at a minimum toner concentration as to provide solid area coverage and at a toner concentration high enough to minimize toner deposits in background areas of a developed electrostatic latent image resulting from toner particles having a low or weak triboelectric charge, these objectives may be attained by employing the high surface area carrier materials of this invention. In accordance with this invention, the aforementioned objectives are attained by operating at a decreased toner concentration providing lower background deposits and enabling longer developer life.
Any suitable pigmented or dyed electroscopic toner material may be employed with the high surface carriers of this invention. Typical toner materials include: gum sandarac, rosin, cumaroneindene resin, asphaltum, gilsonite, phenol-formaldehyde resins, methacrylic resins, polystyrene resins, polypropylene resins, epoxy resins, polyethylene resins, and mixtures thereof.
The particulat toner material to be employed obviously depends upon the separation of the toner particles from the high surface area carrier beads in the triboelectric series. Among the patents describing electroscopic toner compositions are U. S. Patent 2,659,670 to Copley; U. S. Patent 2,753,308 to Landrigan; U. S.
patent 3,079,342 to Insalaco; U. S. Patent Reissue 25,136 to Carlson and U. S. Patent 2,788,288 to Rheinfrank et al. These toners generally have an average particle diameter between about 1 and about 30 microns.
"..
Any suitable toner concentration may be employed with ~;1 the high surface area carriers of this invention. Typical toner ~. .
`~ concentrations for cascade and magnetic brush development systems 3;; include about 1 part toner with ahout 10 to about ~00 parts by ;ij weight of carrier.
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the periphery of the drum and contac'ts the drum in the transfer position interposed between the drum surface and the corona generating device. Transfer is effected by the corona generating device which imparts an electrostatic charge to attract the powder image from the drum to the support surface. The polarity of charge required to effect image transfer is dependent upon the visual form of the original copy relative to the reproduction and , the electroscopic characteristics of a developing material emp~oyed to effect development. For example, where a positive reproduction is to be made of a positive original, it is conventional to employ a positive polarity corona to effect transfer of a negatively charged toner image to the support surface. When a p,ositive reproduction from a negative original is desired, it is conven-tional to employ a positively charged developing material which is repelled by the charged areas on the plate to the discharge areas thereon to form a positive image which may be transferred by ~ .
negative polarity corona. In either case, a residual powder image ~` and occasionally carrier particles remain on the plate after trans-fer. Before the plate may be reused for a subsequent cycle, it is necessa-ry that the residual image and carrier particles, if any, be removed to prevent ghost images from forming on subsequent copies. In the positive-to-positive reproduction process described above, the residual developer powder as well as any carrier particles present are tightly retained on the plate surface by a phenomenon that is not fully understood but believed caused by an electric charge. The charge is substantially neutralized by means of a corona generating device prior to contact of the residual powder with a cleaning device. The neutralization of a charge enhances the cleaning efficiency of the cleaning device.
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Typical electrostatographic cleaning devices include the "web" type cleaning apparatus as disclosed, for example, by W. P~ Graff, Jr. et al in U. S. Patent 3,186,838. In the Graff, Jr. et al patent, removal of the residual powder and carrier particles on the plate is effected by rubbing a web of fibrous material against the imaging plate surface. These inexpensive and disposable webs of fibrous material are advanced into pressure and rubbing or wiping contact with the imaging surface and are gradually advanced to present a clean surface to the plate whereby substantially complete removal of the residual powder and carrier particles from the plate is effected.
While ordinarily capable of producing good ~uality image, conventional developing systems suffer serious deficiencies in certain areas. In the reproduction of high contrast copies such as letters, tracings and the like, it is desirable to select the electroscopic powder and carrier materials so that their mutual electrification being governed in most cases by the distance between their relative positions in the triboelectric series. However, when otherwise compatible electroscopic powder and carrier materials are removed from each other in the triboelectric series by too great a distance, the resulting images are very faint because the attractive forces between the carrier and toner particles compete with the attractive forces between the electrostatic latent image and the toner particles. Although the image density described in the immediately preceding sentence may be improved by increasing the toner concentration in the developer mixture, undesirably high background toner deposition as well as increased toner impaction and agglomeration is encountered when the toner concentration in the ` developer mixture is excessive. The initial electrostatographic plate charge may be increased to improve the density of the deposited powder image, but the plate charge would ordinarily have to be excessively high in order to attract the electroscopic powder away from the carrier particle. Excessively high electrostato~raphic , :lV~ 4~
plate charges are not only undesirable because of the high power consumption necessary to maintain the electrostatographic plate at high potentials, but also because the high potential causes the carrier particles to adhere to the electrostatographic plate surface rather than merely roll across and off the electro-statographic plate surface. Print deletion and massive carry-over of carrier particles often occur when carrier particles adhere to reusable elec-trostatographic imaging surfaces. Massive carrier carry-over problems are particularly acute when the developer is employed in solid area coverage machines where excessive quantities of toner particles are removed from carrier particles thereby leaving many carrier particles substantially bare of toner particles. Further, adherence of carrier particles to reusable electrostatographic imaging surfaces promotes the formakion of undesirable scratches on the surfaces during image transfer and surface cleaning operations. It is therefore, apparent that many materials which o~therwise have suitable properties for employment as carrier particles are unsuitable because they possess unsatisfactory triboelectric properties.
In addition, uniform triboelectric surface characteristics of many carrier surfaces are difficult to achieve with mass produc-tion techniques. Quality images are in some instances almost impossible to obtain in high speed automatic machines when carriers having non-uniform triboelectric properties are employed. Although it may be possible to alter the triboelectric value of an insula-:`:
ting carrier material by blending the carrier material with , another insulating material having a triboelectric value remote from the triboelectric value of the original carrier material, relatively larger quantities of additional material is necessary to alter the triboelectric value of the original carrier material.
; The addition of large quantities of material to the original ',,'''':
~:
~L041344 carrier material to change t~ triboelectric properties thereof requires a major manufacturing operation and often undesirably alters the original physical characteristics of the carrier material. Further, it is highly desirable to control the triboelectric properties of carrier surfaces to accommodate the use of desirable toner compositions while retaining the other desirable physical characteristics of the carrier. The alteration of the triboelectric properties of a carrier by applying a surface coating thereon is a particularly desiràble -technique. With this technique, not only is it possible to control the triboelectric properties of a carrier made from materials having desirable physical characteristics, it is -also possible to employ materials previously not suitable as a carrier. Thus, for example, a carrier having desirable physical properties with the exception of hardness, can be coated with a material having desirable har~dness as well as other physical properties rendering the resultant product more useful as a carrier. Thus, there is a continuing need for a better electxostatographio carrier and an improved method for obtaining the same. i In accordance with one aspect of this invention there 1s provided an electrostatographic imaging process comprising the steps of providing an electrostatographic imaging member having a recording surface, forming an electrostatic latent image on said recording surface, and contacting said electrostatic latent image with a developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classified high surface area carrier materials having a specific surface area of at least about 150 cm2/gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distri-bution wherein the carrier particles have an average particle .. . . .
34~
diameter of less than about 100 microns, ~Ihereby at least a portion of said finely-divided toner particles are attracted to and deposited on said recording surface in conformance with said electrostatic latent image.
In accordance with another aspect of this invention there is provided an electrostatographic developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classi~ied hign surface area carrier materials having a specific surface area of at least about 150 cm /gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 microns.
In accordance with another aspect of this invention there is provided cLassified high surface area carrier materials ~omprising carrier materials having a specific surface area of at least about 150 cm2 /gram, a particle size ~oluma distribution geometric standard deviation of less than about ~-1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 micron~.
More specifically, the improved developer materials o~
this invention provide satisfactory results when the carrier materials have a specific surface area of at least about 150 cmZ/gram. However, it is preferred that the carrier materials have a specific surface area of at least about 165 cm2/gram -~
because developer life is improved such as to provide increased .,~ . .
' copy quantity with the developer material in a high speed electrostatographic reproduction apparatus while maintaining low background levels and sustaining solid area development :, . .
-~ den~ity. Optimum results are obtained when ~le carrier .. .
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~ materials of this invention have a specific surface area of ;. at least about 175 cm2/gram. .
It has been found that the area ratios of carrier to toner material in a high speed magnetic brush development ~.
. .
system were such that the toner concentration could not be sufficiently reduced to enable a charge level for minimal ;-deposit of toner material in background areas of an electro~
static latent image during development thereof while retain~
ing suffi~iont toner ~ .
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concentration to provide satisfactory solid area density. By providing the carrier materials of this invention having a minimum specific surface area this problem has been overcome.
Thus, this invention now enables the use of a developer mixture having a lower toner concentration per unit surface area of carrier to provide a higher net electrical charge level. It has been found that in the electrostatic copying process that where any given carrier material is employed to provide a tribo-electric charge to toner materials by contact charge trnasfer, the area of carrier triboelectric charging surface is critically ' important. The carrier charging surface area has been foùnd to relate to the amount of toner ma~erial that, for a given toner material, can be charged to a useful triboelectric potential or level. Therefore, in accordance with this invention, it has been found that the triboelectric charging capacity of a carrier material is surface area dependent and accordingly, this invention may be employed to design optimum carrier materials for any given ~, .
electrostatographic development system.
In addition, the classified high surface area carrier materials of this invention have a particle size volume distribu-tion geometric standard deviation of less than about 1.3 and a particle size distribution wherein the particles have an average particle diameter of less than about 100 microns. The term geometric standard deviation as employed herein is defined as the deviation encountered in a particle size analysis approximately measured as the ratio of the particle diameter which is greater than that of 84 percent of the sample to that of the particle diameter which is greater than that of 50 percent of the sample.
This value represents the median or average particle size . . .
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distribution by weight or volume of the carrier particles and has an important reflection on copy quality obtained in an electro-statographic development system. Another measure of the geometric standard deviation of the classified carrier materials of this invention is the deviation encountered in a particle size analysis approximately measured as the ratio of the particle diameter which is greater than that of 50 percent of the sample to that of the particle diameter which is greater than that of 16 percent of the sample. The 50 percent value represents the median or average particle size b~ volume of the carrier particles and has an important reflection on the measure of the useful lifetime of the developer. In both cases, the values obtained for the volume average particle diameter and the geometric standard deviation are determined by size analysis performed by a sieve analysis employ-ing all U. S. Standard sieves from 325 mesh to 70 mesh.
It has been found that the classified carrier materials of this invention provide satisfactory results when the particle size volume distribution geometric standard,deviation thereof is less than about 1.3 and the volume average particle diameter is less than about 100 microns. Improved results are obtained with, and it is preferred, that the particle size volume distribution geometric standard deviation thereo~ be less than about 1.2 and the volume average particle diameter is less than about 90 microns.
Optimum results are obtained when the volume distribution geometric standard deviation of the classified carrier materials of this invention is less than about 1.15 and the volume average particle diameter is less than about 85 microns.
Any suitable particle classification method may be employed to obtain the high surface area carrier materials of this invention. Typical particle classification methods include '."'' -, --10--. .
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air classification, screening, cyclone separation, elutriation, centrification, and combinations thereof. The preferred method of obtaining the high surface area carrier materials of this invention is by screening or selving~
Any suitable coated or uncoated electrostatographic carrier bead material may be employed as the high surface area carrier material of this invention. Typical cascade development process carriers include sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, potassium chlorate, granular zircon, granular silicon, methyl methacrylate, glass and silicon dioxide. Typical magnetic brush development process carriers include nickel, steel, ' iron, ferrites, and the like. The car~iers may be employed with . or without a coating. Many of the foregoing and other typical carriers are described by L. E. Walkup et al in U. S. patent 2,638,41~ and E. N. Wise in U. S. patent 2,618,552. An ultimate ~, coated carrier particle diameter between about 30 microns to about 1,000 microns is preferred because the carrier particles ` then possess sufficient density and inertia to avoid adherence ~1 to the electrostatic images during the cascade development process.
For magnetic brush development, the carrier particles generally .... , \
have an average diameter between about 30 microns and about 250 microns. -Generally speaking, satisfactory results are obtained ,, , '~ when about 1 part toner is used with about 10 to 200 parts by ~,...
:~ weight of carrier.
.,!:, i The high surface area carrier materials of this inven-'';;:
~ tion may be coated with any suitable coating material. Typical ....
electrostatographic carrier particle coating materials include .~ . .
vinyl chloride-vinyl acetate copolymers, styrene-acrylate-' organosilicon terpolymers, natural resins such as caoutchouc, ~t-' :,."' ':
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, '~ , , , , . .. ~, , . .. .. .. ........ . . -3LO~L3~4 colophony, copal, dammar, Drangon's Blood, jalap, storax;
thermoplastic resins including the polyolefins such as poly-ethylene, polypropylene, chlorinated polyethylene, and chloro-sulfonated polyethylene; polyvinyls and polyvinylidenes such as polystyrene, polymethylstyrene, polym~ethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, poly-vinyl butyral, polyvinyl chloride, polyvinyl carbazole, poly-vinyl ethers, and polyvinyl ketones; fluorocarbons such as poly-tetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride;
and polychlorotrifluoroethylene; polyamides such as polycapro-lactam and polyhexamethylene adipamide; polyesters such as polyethylene terephthalate; polyurethanes; polysulfides, poly-carbonates; thermosetting resins includiny phenolic resins such as phenol-formalidehyde, phenol-furfural and resorcinol formal-dehyde; amino resins such as urea-formaldehyde and melamineformal-dehyde; polyester resins; epoxy resins; and the like. Many of the foregoing and other typical carrier coating materials are described by L. E. walkup in U. S. patent 2,618,551; B. B. Jacknow et al in U. S. patent 3,526,533; and R. J. Hagenbach et al in U. S. patents 3,533,835 and 3,658,500.
When the high surface area carrier materials of this invention are coated, any suitable electrostatographic carrier coating thickness may be employed. However, a carrier coating having a thickness at least sufficient to form a thin continuous film on the carrier particle is preferred because the carrier coating will then possess sufficient thickness to resis~abrasion and prevent pinholes which adversely affect the triboelectric .:
properties of the coated carrier particles. ~enerally, for cascade and magnetic brush development, the carrier coating may comprise from about 0.1 percent to about 10.0 percent by weight :.
., .
.;. -: :.. . -based on the weight of the coated carrier particles. Preferably~
the carrier coating should comprise from about .3 percent to about 1.5 percent by weight based on the weight of the coated carrier particles because maximum durabil;ty, toner impaction resistance, and copy quality are achieved. To achieve further variation in the properties of the coated composite carrier particles, well-known additives such as plasticizers, reactive and non-reactive polymers, dyes, pigments, wetting agents and mixtures thereof may be mixed with the coating materials.
When the high surface area carrier materials of this invention are coated, the carrier coating composition may be applied to the carrier cores by any conventional method such as spra~ing, dipping, fluidized bed coating, tumbling, brushing and the like. The coating compositions may be applied as a powder, a dispersion, solution, emulsion or hot melt~ When applied as a solution, any suitable solvent may be employed.
Solvents having relatively low boiling points are preferred because less energy and time is required to remove the solvent subsequent to application of the coating to the carrier cores.
If desired, the coating may comprise resin monomers which are polymerized in situ on the surface of the cores or plastisols gelled in situ to a non-flowable state on the surface of the cores. Surprisingly, it has been found that for a given inefficient coating process, carrier core materials having the specific surface areas designated in this invention results in increased effective area, that is, triboelectric charging coated area per unit weight. Thus, increased carrier active area increases the net toner material triboelectric charge level for a given toner concentration by weight in a developer mixture. Therefore, where it is preferred to operate an ~13-~,. . .
104~344 electrostatographic development system at a minimum toner concentration as to provide solid area coverage and at a toner concentration high enough to minimize toner deposits in background areas of a developed electrostatic latent image resulting from toner particles having a low or weak triboelectric charge, these objectives may be attained by employing the high surface area carrier materials of this invention. In accordance with this invention, the aforementioned objectives are attained by operating at a decreased toner concentration providing lower background deposits and enabling longer developer life.
Any suitable pigmented or dyed electroscopic toner material may be employed with the high surface carriers of this invention. Typical toner materials include: gum sandarac, rosin, cumaroneindene resin, asphaltum, gilsonite, phenol-formaldehyde resins, methacrylic resins, polystyrene resins, polypropylene resins, epoxy resins, polyethylene resins, and mixtures thereof.
The particulat toner material to be employed obviously depends upon the separation of the toner particles from the high surface area carrier beads in the triboelectric series. Among the patents describing electroscopic toner compositions are U. S. Patent 2,659,670 to Copley; U. S. Patent 2,753,308 to Landrigan; U. S.
patent 3,079,342 to Insalaco; U. S. Patent Reissue 25,136 to Carlson and U. S. Patent 2,788,288 to Rheinfrank et al. These toners generally have an average particle diameter between about 1 and about 30 microns.
"..
Any suitable toner concentration may be employed with ~;1 the high surface area carriers of this invention. Typical toner ~. .
`~ concentrations for cascade and magnetic brush development systems 3;; include about 1 part toner with ahout 10 to about ~00 parts by ;ij weight of carrier.
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10~13~4 Any suitable colorant such as a pigment or dye may be employed to color the toner particles. Toner colorants are well known and include, for example, carbon black, nigrosine dye, aniline blue, Calco Oil Blue, chrorne yellow, ultra-marine blue, Quinoline Yellow, methylene blue chloride, Mona-stral Blue, Malachite Greene Ozalate, lampblack, Rose Bengal, Monastral Red, Sudan Black B~, and mixtures thereof. The pigment or dye should be present in the toner in a quantity sufficient to render it highly colored so that it will form a c:Learly visible image on a recording member. Preferably, the pigment is employed in an amount from about 3 percent to about 20 percent, b~ weight, based on the total weight of the colored ,, .
toner because hiyh quality images are obtained. If the toner cPlorant empLoyed is a dye, substantially smaller quantities of colorant may be used.
Any suitable organic or inorganic photoconductive !,' . .
material may be employed as the recording surface with the high surface area carriers of this invention. Typical inorganic photoconductor materials include: sulfur, selenium, zinc sulfide, zinc oxide, zinc cadmium sulfide, zinc magnesium oxide, cadmium selenide, zinc silicate, calcium strontium sulfide, cadmium sulfide, mercuric iodide, mercuric oxide, mercuric sulfide, indium trisulfide, gallium selenide, arsenic disulfide, arsenic . . .
trisulfide, arsenic triselenide, antimony trisulfide, cadmium sulfo-selenide and mixtures thereof. Typical organic photo-conductors include: guinacridone pigments, phthalocyanine pigments, triphenylamine, 2,4-bix(4,4'-diethylamino-phenol) -1, 3,4,-oxadiazol, ~-isopropylcarbazol, triphenylpyrrol, 4,5-diphenyl-imidazolidinone, 4,5-diphenyl-imidazolidinethione, 4,5-bix-(4'-amino-phenyl)-imidazolidinone, 1,5-dicyanonaphthalene, ,'',"' :. .:
;;,..
:
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1,4-dicyanonaphthalene, aminophthalodinitrile, nitropht'halodi-nitrile, 1,2,5,6-tetraazacyclooctatetraene-(2,4,6,8), 2-mercaptobenzothiazole-2-phenyl-4-disphenylideneoxazolone, 6-hydroxy-2,3-ditp-methoxyphenyl)-benzo~Eurane, ~-dimethylamino-benzylidene-benzhydrazide, 3-benzylidene-aminocarbazole, poly-vinyl carbazole, (2-nitro-benzylidene)-p-bromoaniline, 2,4-diphenylquinazoline, 1,2,4-triazine, 5-diphenyl-3-methyl-pyrazoline,2-(4'dimethylamino phenyl)-benzoxazole, 3-amine-carbazole, and mixtures thereof. Representative patents in which photoconductive materials are disclosed include U. S.
Patents 2,803,542 to Ullrich, U. S. Patent 2,970,906 to BiXby, U. S. Patent 3,121,006 to Middleton, U. S. Patent 3,121,007 to Middleton, and U. S. patent 3,151,982 to Corrsin.
The following example9 further define, describe and compare methods of preparing the carrier materials of the present :, invention and of utilizing them to develop electrostatic latent "., .
images. parts and percentages are byweight unless otherwise indicated.
i.~
EXAMPLE I
, A control developer mixture is prepared by mixing about . :.
' 1 part of toner material comprising a styrene-n-butyl methacrylate ,' copolymer, polyvinyl butyral, and carbon black produced by the method disclosed in Example I of U. S. patent ~o. 3,079,3~2 having an average particle size of about'10 to about 20 microns with ~` about 100 parts of a carrier core material comprising nickel-, zinc ferrite coated with about 0.6% by weight, based on the ~:-~'' weight of the core material, of a carrier coating composition '~ comprising styrene, a methacrylate ester, and an organosilicon ~;' compound as disclosed in U~ S. Patent 3,526,533. The coated ferrite carrier material is determined by seive analysis to have a particle size distribution as follows:
:
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U. S. Seive /O by Weight 70 mesh ~ 210u) 0 80 mesh ( 177u) 100 mesh ( 149u) .1 120 mesh ( 125u) .1 1~0 mesh ( 105u) - 7.2 170 mesh ( 88u) 30.4 200 mesh ( 7~u) 30.7 230 mesh ( 63u) 25.5 270 mesh ( 54u) 5.7 325 mesh ( 44u) 0.2 pan ' .
By calculation, the coated ferrite carrier material i9 deter-mined to have a specific surface area of about 128 cm2/gram.
The developer mixture is used to develop a selenium photoconduc-tor recording surface bearing an electrostatic latent image by the "magnetic brush" development method described in U. S. Patent No. 2,874,063. The magnetic field of the magnet causes alignment of the carrier and toner into a brush-like configuration. The magnetic brush is brought into developing configuration with the electrostatic imagebearing surface and toner particles are drawn from the carrier particles to the latent image by electrostatic ~- attraction. The resultant copies of a standard image test ,. .
pattern are of good quality up to about 25,000 copies when the image background level is found to exceed the maximum value of 0.010 which is deemed acceptable.
,~ -EXAMPLE II
:.
A developer mixutre is prepared by mixing about 1 part of the toner material employed in Example I with about 100 parts ':
:, , ~ - ~ .. ... . . ... ..
, ,, . . . ~ . . , , - .
4~3~4 of the carrier material employed in Example I except that the carrier material was determined by seive analysis to have the ., following particle size distribution:
" ~
U. S. Seive% By_Wei~ht :~; .
70 Mesh ( 210u) 0 80 Mesh ( 177u) 0 100 Mesh ( 149u) 0.8 120 Mesh ( 125u) 5.9 140 Mesh ( 105u) 21.4 170 Mesh ( 88u) 40.3 200 Mesh ( 74u) 28.5 230 Mesh ( 63u) 1.4 270 Mesh ( 54u) 1.4 325 Mesh ( 44u) Ø3 pan ;,:.
. By calculation, the coated ferrite càrrier material is determined '. to have a specific surface area of about 151 cm2/gram. The developer is used to develop a selenium photoconductor recording ; surace bearing an electrostatic latent image under substantially the same conditions as in Example I. It is found that the resultant copies of the standard image test pattern are of good : quality up to about 70,000 copies when the image background level . is found to be about the maximum value of 0.010 deemed acceptable.
EXAMPLE III
: A developer mixture is prepared by mixing about 1 part of the toner material employed in Example I with about 100 parts : ~ .
.. of the carrier material employed in Example I except that the carrier material was determined by seive analysis to have the ~,~ following particle size distribution:
. ........... .
3q~
U. S. Seive /O By Weight 70 Mesh ( 210u) 0 80 Mesh ( 177u) 0 . 100 Mesh ( 149u) 0 120 Mesh ( 125u) 0.16 .: 140 Mesh ( 105u~ 13.8 ~ 170 Mesh ( 88u) 35.1 i:
200 Mesh ( 74u) 40O9 230 Mesh ( 63u) 7.59 : 270 Mesh ( 54u) 1.86 325 Mesh ( 44u) .53 pan 0.06 i , : By calculation, the coated ferrite carrier material is determined , . . .
to have a specific surface area of about 160 cm2/sram. The '~ developer is used to develop a selenium photoconductor recording surface bearing an electrostatic la'tent image under substantially ~' the same conditions as in Example I. It is found that the ;., resultant copies of the standard image test pattern are good ~: quality up to about 100,000 copies when the image background level ,. is found to be about the maximum value of 0.010 deemed acceptable.
~,, EXAMPLE IV
A developer mixture is prepared by mixing about 1 part of the toner material employed in Example I with about 100 parts '~ of the carrier material employed in Example I except that the carrier material was determined by seive analysis to have the following particle size distribution:
~, .
.
... . .
,.` --19-,,".. ..
... . . . . . . .
U. S. Seive % By Wei~ht 70 Mesh ( 210u~ o 80 Mesh ~ 177u) 0 100 Mesh ~ 149u) 0 120 Mesh ~ 125u) 0 140 Mesh ( 105u) 5.7 170 Mesh (88u) 44.7 200 Mesh (74u) 34.9 230 Mesh (63u) 10.9 270 Mesh ~54u) 3.7 325 Mesh ~44u) .13 pan .
,; .
: By calculation, the coated ferrite carrier material is determined to have a specific surface area of about 168 cm2/gram. The ~! developer is used to develop a selenium photoconductor recording surface bearing an electrostatic latent image under substantially the same conditions as in Example I. It is found that the . resultant copies of the standard image test pattern are good , . .
- quality up to about 130,000 copies when the image backgroun~
` level is found to be about the maximum value of 0.010 deemed ~; acceptable.
- EXAMPLE V
:. .
A developer mixture is prepared by mixing about 1 part . ..-., x~l of the toner material employed in Example I with about 100 parts i~ of the carrier material employed in Example I except that the :
carrier material was determined by seive analysis to have the following particle size distribution:
, ....
,. ..
.
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. . .
~ 20-~ . ~
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. - . .. .. ... . . .: . : ~ ~ :-. .. .
3~
U. S. Seive % By Weight 70 Mesh ( 210u) o 80 Mesh ( 177u) .2 . . .
lOO Mesh ( 149u~ 1.7 120 Mesh ( 125u~ 4.5 140 Mesh ( 105u) 7.5 170 Mesh ( 88u) 10.3 200 Mesh ( 74u) 62.4 230 Mesh ( 63u) 2.6 270 Mesh ( 54u) 5.1 , .
325 Mesh ( 44u) 5.1 Pan .51 .:
,................ . .
This distribution was reconstructed artificially and does not satisfy a log-normal plot for a geometric standard deviation !;
calculation. By calculation, the coated ferrite carrier material is determined to have a specific surface area of about 177 cm2/gram.
:
The developer is used to develop a selenium photoconductor record-ing surface bearing an electrostatic latent image under substan-,. , :
` tially the same conditions as in Example I. It is found that the , resultant copies of the standard image test pattern are good , quality up ta about 150,000 copies when the image background level is found to be about .008 and still well within the maximum value ,, .
of 0.010 deemed acceptable. The test was terminated at this copy count level.
s~ Thus, the high surface area carrier materials of this invention are characterized as providing improved copy quality ;::
experienced in reduced toner deposits in background areas. In addition, the high surface area carrier materials of this inven-tion are further characterized as resulting in improved machine .:
. . .
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performance with longer systems life, that is, these carrier materials provide substantially improved triboelectric charging properties of the developer mixtures for substantially longer periods of time thereby increasing the developer life of the developer mixtures and decreasing the time intervals between replacement of the developer materials. Further still, the high surface area carrier materials of this invention may be charac-terized as providing dense toner images and are particularly useful in magnetic brush development systems. Thus, by providing the developer materials of this invention, substantial improvements in systems life due to intrinsic developer life result upon the classification and use of carrier materials having the specified surace areas.
Although specific materials and conditions are set forth in the above examples of making and using the developer materials of this invention, these are merely intended as illustrations of the present invention. These and other high surface area~carrier materials, toner materials, substitutents, and processes, such as those listed above, may be substituted for those in the Examples with similar results.
.:
~ Other modifications of the present invention will occur ,:
to those skilled in the art upon a reading of the present disclosure.
~These are intended to be included within the scope of this ~ .
~ invention.
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.:
.. .. .
10~13~4 Any suitable colorant such as a pigment or dye may be employed to color the toner particles. Toner colorants are well known and include, for example, carbon black, nigrosine dye, aniline blue, Calco Oil Blue, chrorne yellow, ultra-marine blue, Quinoline Yellow, methylene blue chloride, Mona-stral Blue, Malachite Greene Ozalate, lampblack, Rose Bengal, Monastral Red, Sudan Black B~, and mixtures thereof. The pigment or dye should be present in the toner in a quantity sufficient to render it highly colored so that it will form a c:Learly visible image on a recording member. Preferably, the pigment is employed in an amount from about 3 percent to about 20 percent, b~ weight, based on the total weight of the colored ,, .
toner because hiyh quality images are obtained. If the toner cPlorant empLoyed is a dye, substantially smaller quantities of colorant may be used.
Any suitable organic or inorganic photoconductive !,' . .
material may be employed as the recording surface with the high surface area carriers of this invention. Typical inorganic photoconductor materials include: sulfur, selenium, zinc sulfide, zinc oxide, zinc cadmium sulfide, zinc magnesium oxide, cadmium selenide, zinc silicate, calcium strontium sulfide, cadmium sulfide, mercuric iodide, mercuric oxide, mercuric sulfide, indium trisulfide, gallium selenide, arsenic disulfide, arsenic . . .
trisulfide, arsenic triselenide, antimony trisulfide, cadmium sulfo-selenide and mixtures thereof. Typical organic photo-conductors include: guinacridone pigments, phthalocyanine pigments, triphenylamine, 2,4-bix(4,4'-diethylamino-phenol) -1, 3,4,-oxadiazol, ~-isopropylcarbazol, triphenylpyrrol, 4,5-diphenyl-imidazolidinone, 4,5-diphenyl-imidazolidinethione, 4,5-bix-(4'-amino-phenyl)-imidazolidinone, 1,5-dicyanonaphthalene, ,'',"' :. .:
;;,..
:
;,. ` , ,~;
~: ;. , . . . . -3~
1,4-dicyanonaphthalene, aminophthalodinitrile, nitropht'halodi-nitrile, 1,2,5,6-tetraazacyclooctatetraene-(2,4,6,8), 2-mercaptobenzothiazole-2-phenyl-4-disphenylideneoxazolone, 6-hydroxy-2,3-ditp-methoxyphenyl)-benzo~Eurane, ~-dimethylamino-benzylidene-benzhydrazide, 3-benzylidene-aminocarbazole, poly-vinyl carbazole, (2-nitro-benzylidene)-p-bromoaniline, 2,4-diphenylquinazoline, 1,2,4-triazine, 5-diphenyl-3-methyl-pyrazoline,2-(4'dimethylamino phenyl)-benzoxazole, 3-amine-carbazole, and mixtures thereof. Representative patents in which photoconductive materials are disclosed include U. S.
Patents 2,803,542 to Ullrich, U. S. Patent 2,970,906 to BiXby, U. S. Patent 3,121,006 to Middleton, U. S. Patent 3,121,007 to Middleton, and U. S. patent 3,151,982 to Corrsin.
The following example9 further define, describe and compare methods of preparing the carrier materials of the present :, invention and of utilizing them to develop electrostatic latent "., .
images. parts and percentages are byweight unless otherwise indicated.
i.~
EXAMPLE I
, A control developer mixture is prepared by mixing about . :.
' 1 part of toner material comprising a styrene-n-butyl methacrylate ,' copolymer, polyvinyl butyral, and carbon black produced by the method disclosed in Example I of U. S. patent ~o. 3,079,3~2 having an average particle size of about'10 to about 20 microns with ~` about 100 parts of a carrier core material comprising nickel-, zinc ferrite coated with about 0.6% by weight, based on the ~:-~'' weight of the core material, of a carrier coating composition '~ comprising styrene, a methacrylate ester, and an organosilicon ~;' compound as disclosed in U~ S. Patent 3,526,533. The coated ferrite carrier material is determined by seive analysis to have a particle size distribution as follows:
:
~ . .
,,, ~
~ -16-:;i:
.;.,; ,,~ . . . . , ~ .
., : ~ . . ~ . .
~4~4~
U. S. Seive /O by Weight 70 mesh ~ 210u) 0 80 mesh ( 177u) 100 mesh ( 149u) .1 120 mesh ( 125u) .1 1~0 mesh ( 105u) - 7.2 170 mesh ( 88u) 30.4 200 mesh ( 7~u) 30.7 230 mesh ( 63u) 25.5 270 mesh ( 54u) 5.7 325 mesh ( 44u) 0.2 pan ' .
By calculation, the coated ferrite carrier material i9 deter-mined to have a specific surface area of about 128 cm2/gram.
The developer mixture is used to develop a selenium photoconduc-tor recording surface bearing an electrostatic latent image by the "magnetic brush" development method described in U. S. Patent No. 2,874,063. The magnetic field of the magnet causes alignment of the carrier and toner into a brush-like configuration. The magnetic brush is brought into developing configuration with the electrostatic imagebearing surface and toner particles are drawn from the carrier particles to the latent image by electrostatic ~- attraction. The resultant copies of a standard image test ,. .
pattern are of good quality up to about 25,000 copies when the image background level is found to exceed the maximum value of 0.010 which is deemed acceptable.
,~ -EXAMPLE II
:.
A developer mixutre is prepared by mixing about 1 part of the toner material employed in Example I with about 100 parts ':
:, , ~ - ~ .. ... . . ... ..
, ,, . . . ~ . . , , - .
4~3~4 of the carrier material employed in Example I except that the carrier material was determined by seive analysis to have the ., following particle size distribution:
" ~
U. S. Seive% By_Wei~ht :~; .
70 Mesh ( 210u) 0 80 Mesh ( 177u) 0 100 Mesh ( 149u) 0.8 120 Mesh ( 125u) 5.9 140 Mesh ( 105u) 21.4 170 Mesh ( 88u) 40.3 200 Mesh ( 74u) 28.5 230 Mesh ( 63u) 1.4 270 Mesh ( 54u) 1.4 325 Mesh ( 44u) Ø3 pan ;,:.
. By calculation, the coated ferrite càrrier material is determined '. to have a specific surface area of about 151 cm2/gram. The developer is used to develop a selenium photoconductor recording ; surace bearing an electrostatic latent image under substantially the same conditions as in Example I. It is found that the resultant copies of the standard image test pattern are of good : quality up to about 70,000 copies when the image background level . is found to be about the maximum value of 0.010 deemed acceptable.
EXAMPLE III
: A developer mixture is prepared by mixing about 1 part of the toner material employed in Example I with about 100 parts : ~ .
.. of the carrier material employed in Example I except that the carrier material was determined by seive analysis to have the ~,~ following particle size distribution:
. ........... .
3q~
U. S. Seive /O By Weight 70 Mesh ( 210u) 0 80 Mesh ( 177u) 0 . 100 Mesh ( 149u) 0 120 Mesh ( 125u) 0.16 .: 140 Mesh ( 105u~ 13.8 ~ 170 Mesh ( 88u) 35.1 i:
200 Mesh ( 74u) 40O9 230 Mesh ( 63u) 7.59 : 270 Mesh ( 54u) 1.86 325 Mesh ( 44u) .53 pan 0.06 i , : By calculation, the coated ferrite carrier material is determined , . . .
to have a specific surface area of about 160 cm2/sram. The '~ developer is used to develop a selenium photoconductor recording surface bearing an electrostatic la'tent image under substantially ~' the same conditions as in Example I. It is found that the ;., resultant copies of the standard image test pattern are good ~: quality up to about 100,000 copies when the image background level ,. is found to be about the maximum value of 0.010 deemed acceptable.
~,, EXAMPLE IV
A developer mixture is prepared by mixing about 1 part of the toner material employed in Example I with about 100 parts '~ of the carrier material employed in Example I except that the carrier material was determined by seive analysis to have the following particle size distribution:
~, .
.
... . .
,.` --19-,,".. ..
... . . . . . . .
U. S. Seive % By Wei~ht 70 Mesh ( 210u~ o 80 Mesh ~ 177u) 0 100 Mesh ~ 149u) 0 120 Mesh ~ 125u) 0 140 Mesh ( 105u) 5.7 170 Mesh (88u) 44.7 200 Mesh (74u) 34.9 230 Mesh (63u) 10.9 270 Mesh ~54u) 3.7 325 Mesh ~44u) .13 pan .
,; .
: By calculation, the coated ferrite carrier material is determined to have a specific surface area of about 168 cm2/gram. The ~! developer is used to develop a selenium photoconductor recording surface bearing an electrostatic latent image under substantially the same conditions as in Example I. It is found that the . resultant copies of the standard image test pattern are good , . .
- quality up to about 130,000 copies when the image backgroun~
` level is found to be about the maximum value of 0.010 deemed ~; acceptable.
- EXAMPLE V
:. .
A developer mixture is prepared by mixing about 1 part . ..-., x~l of the toner material employed in Example I with about 100 parts i~ of the carrier material employed in Example I except that the :
carrier material was determined by seive analysis to have the following particle size distribution:
, ....
,. ..
.
~,,~, .
. . .
~ 20-~ . ~
~:,, ~..
. - . .. .. ... . . .: . : ~ ~ :-. .. .
3~
U. S. Seive % By Weight 70 Mesh ( 210u) o 80 Mesh ( 177u) .2 . . .
lOO Mesh ( 149u~ 1.7 120 Mesh ( 125u~ 4.5 140 Mesh ( 105u) 7.5 170 Mesh ( 88u) 10.3 200 Mesh ( 74u) 62.4 230 Mesh ( 63u) 2.6 270 Mesh ( 54u) 5.1 , .
325 Mesh ( 44u) 5.1 Pan .51 .:
,................ . .
This distribution was reconstructed artificially and does not satisfy a log-normal plot for a geometric standard deviation !;
calculation. By calculation, the coated ferrite carrier material is determined to have a specific surface area of about 177 cm2/gram.
:
The developer is used to develop a selenium photoconductor record-ing surface bearing an electrostatic latent image under substan-,. , :
` tially the same conditions as in Example I. It is found that the , resultant copies of the standard image test pattern are good , quality up ta about 150,000 copies when the image background level is found to be about .008 and still well within the maximum value ,, .
of 0.010 deemed acceptable. The test was terminated at this copy count level.
s~ Thus, the high surface area carrier materials of this invention are characterized as providing improved copy quality ;::
experienced in reduced toner deposits in background areas. In addition, the high surface area carrier materials of this inven-tion are further characterized as resulting in improved machine .:
. . .
.'.', ,:
,i,".
~L041;~49~
performance with longer systems life, that is, these carrier materials provide substantially improved triboelectric charging properties of the developer mixtures for substantially longer periods of time thereby increasing the developer life of the developer mixtures and decreasing the time intervals between replacement of the developer materials. Further still, the high surface area carrier materials of this invention may be charac-terized as providing dense toner images and are particularly useful in magnetic brush development systems. Thus, by providing the developer materials of this invention, substantial improvements in systems life due to intrinsic developer life result upon the classification and use of carrier materials having the specified surace areas.
Although specific materials and conditions are set forth in the above examples of making and using the developer materials of this invention, these are merely intended as illustrations of the present invention. These and other high surface area~carrier materials, toner materials, substitutents, and processes, such as those listed above, may be substituted for those in the Examples with similar results.
.:
~ Other modifications of the present invention will occur ,:
to those skilled in the art upon a reading of the present disclosure.
~These are intended to be included within the scope of this ~ .
~ invention.
''''~ .
.
$
~'''.`
:i,' .~. "
.:
.. .. .
Claims (24)
1. An electrostatographic imaging process comprising the steps of providing an electrostatographic imaging member having a recording surface, forming an electrostatic latent image on said recording surface, and contacting said electro-static latent image with a developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classified high surface area carrier materials having a specific surface area of at least about 150 cm2/gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 microns, whereby at least a portion of said finely-divided toner particles are attracted to and deposited on said recording surface in conformance with said electrostatic latent image.
2. An electrostatographic imaging process according to Claim 1 wherein said carrier materials have a specific surface area of at least about 165 cm2/gram.
3. An electrostatographic imaging process according to Claim 1 wherein said carrier materials have a specific surface of at least about 175 cm2/gram.
4. An electrostatographic imaging process according to Claim 1 wherein said carrier materials have a particle size volume distribution geometric standard deviation of less than about 1.2 and a volume average particle diameter of less than about 90 microns.
5. An electrostatographic imaging process according to Claim 1 wherein said carrier materials have a volume distri-bution geometric standard deviation of less than about 1.15 and a volume average particle diameter of less than about 85 microns.
6. An electrostatographic imaging process according to Claim 1 wherein said carrier materials are overcoated with a thin continuous film of a coating material.
7. An electrostatographic imaging process according to Claim 6 wherein said coating material comprises from about 0.1% to about 10.0% by weight based on the weight of the coated carrier particles.
8. An electrostatographic imaging process according to Claim 1 wherein said carrier material comprises nickel-zine ferrite coated with a thin continuous film of a coating composi-tion comprising styrene, a methacrylate ester, and an organosilicon compound.
9. Classified high surface area carrier materials comprising carrier materials having a specific surface area of at least about 150 cm2/gram, a particle size volume dis-tribution geometric standard deviation of less than about 1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 microns.
10. Classified high surface area carrier materials in accordance with Claim 9 wherein said carrier materials have a specific surface area of at least about 165 cm2/gram.
11. Classified high surface area carrier materials in accordance with Claim 9 wherein said carrier materials have a specific surface area of at least about 175 cm2/gram.
12. Classified high surface area carrier materials in accordance with Claim 9 wherein said carrier materials have a particle size volume distribution geometric standard deviation of less than about 1.2 and a volume average particle diameter of less than about 90 microns.
13. Classified high surface area carrier materials in accordance with Claim 9 wherein said carrier materials have a volume distribution geometric standard deviation of less than about 1.15 and a volume average particle diameter of less than about 85 microns.
14. Classified high surface area carrier materials in accordance with Claim 9 wherein said carrier materials are overcoated with a thin continuous film of a coating material.
15. Classified high surface area carrier materials in accordance with Claim 14 wherein said coating material com-prises from about 0.1% to about 10.0% by weight based on the weight of the coated carrier particles.
16. Classified high surface area carrier materials in accordance with Claim 9 wherein said carrier material com-prises nickel-zinc ferrite coated with a thin continuous film of a coating composition comprising styrene, a methacrylate ester, and an organosilicon compound.
17. An electrostatographic developer mixture comprising finely-divided toner particles electrostatically clinging to the surface of classified high surface area carrier materials having a specific surface area of at least about 150 cm2/gram, a particle size volume distribution geometric standard deviation of less than about 1.3, and a particle size distribution wherein the carrier particles have an average particle diameter of less than about 100 microns.
18. An electrostatographic developer mixture according to Claim 17 wherein said carrier materials have a specific surface area of at least about 165 cm2/gram.
19. An electrostatographic developer mixture according to Claim 17 wherein said carrier materials have a specific surface area of at least about 175 cm2/gram.
20. An electrostatographic developer mixture according to Claim 17 wherein said carrier materials have a particle size volume distribution geometric standard deviation of less than about 1.2 and a volume average particle diameter of less than about 90 microns.
21. An electrostatographic developer mixture according to Claim 17 wherein said carrier materials have a volume distri-bution geometric standard deviation of less than about 1.15 and a volume average particle diameter of less than about 85 microns.
22. An electrostatographic developer mixture according to Claim 17 wherein said carrier materials are overcoated with a thin continuous film of a coating material.
23. An electrostatographic developer mixture according to Claim 14 wherein said coating material comprises from about 0.1% to about 10.0% by weight based on the weight of the coated carrier particles.
24. An electrostatographic developer mixture according to Claim 17 wherein said carrier material comprises nickel-zinc ferrite coated with a thin continuous film of a coating composition comprising styrene, a methacrylate ester, and an organosilicon compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/474,623 US4040969A (en) | 1974-05-30 | 1974-05-30 | High surface area carrier |
| US05/474,489 US4126454A (en) | 1974-05-30 | 1974-05-30 | Imaging process utilizing classified high surface area carrier materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1041344A true CA1041344A (en) | 1978-10-31 |
Family
ID=27044473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA225,837A Expired CA1041344A (en) | 1974-05-30 | 1975-04-25 | High surface area carrier |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5913023B2 (en) |
| BR (1) | BR7503081A (en) |
| CA (1) | CA1041344A (en) |
| DE (1) | DE2520214C2 (en) |
| ES (1) | ES438084A1 (en) |
| FR (1) | FR2273308B1 (en) |
| GB (1) | GB1497732A (en) |
| IT (1) | IT1038561B (en) |
| NL (1) | NL7506484A (en) |
| SE (1) | SE406653B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4214160A (en) * | 1976-03-04 | 1980-07-22 | Finnigan Corporation | Mass spectrometer system and method for control of ion energy for different masses |
| US4297427A (en) * | 1978-01-26 | 1981-10-27 | Xerox Corporation | Polyblend coated carrier materials |
| CA1147192A (en) * | 1978-04-06 | 1983-05-31 | John L. Webb | Electrostatographic developer including toner of diameter between 3 and 15 microns and carrier of diameter between 15 and 65 microns |
| DE2840717C3 (en) * | 1978-09-19 | 1981-12-17 | Addressograph-Multigraph Corp., Los Angeles, Calif. | Carrier for the development of electrostatic images |
| DE3043040A1 (en) * | 1979-11-14 | 1981-05-21 | Canon K.K., Tokyo | METHOD FOR DEVELOPING ELECTRIC LATEN IMAGES, AND A DEVICE FOR CARRYING OUT THIS METHOD |
| JPS5684402A (en) * | 1979-12-14 | 1981-07-09 | Nippon Teppun Kk | Iron powder as core materials for resin-coated carrier |
| JPS5840557A (en) * | 1981-09-03 | 1983-03-09 | Canon Inc | Electrophotographic developer |
| JPS58123553A (en) * | 1982-01-19 | 1983-07-22 | Hitachi Metals Ltd | Electrophotographic developing carrier |
| JPS5938755A (en) * | 1982-08-30 | 1984-03-02 | Konishiroku Photo Ind Co Ltd | Electrostatic charge image developing carrier |
| JPS60258559A (en) * | 1984-06-06 | 1985-12-20 | Ricoh Co Ltd | Electrostatic latent image developer |
| JPH0619593B2 (en) * | 1984-07-30 | 1994-03-16 | 三田工業株式会社 | Two-component magnetic developer |
| JPH0680465B2 (en) * | 1984-11-27 | 1994-10-12 | 三田工業株式会社 | Magnetic brush development method |
| JPS63277413A (en) * | 1987-05-06 | 1988-11-15 | Kyoshin Eng:Kk | Sealing device for covered cord penetrating partition wall |
| US5512402A (en) * | 1993-05-20 | 1996-04-30 | Canon Kabushiki Kaisha | Carrier for electrophotography, two-component type developer, and image forming method |
| DE69425624T2 (en) * | 1993-10-15 | 2001-04-26 | Canon Kk | Carrier material for electrophotography, developer of the two-component type, and imaging process |
| EP0689100B1 (en) | 1994-06-22 | 2000-10-11 | Canon Kabushiki Kaisha | Carrier for electrophotography, two component type developer, and image forming method |
| CA2151988C (en) | 1994-06-22 | 2001-12-18 | Kenji Okado | Carrier for electrophotography, two component-type developer and image forming method |
| DE60120556T2 (en) | 2000-05-23 | 2007-06-06 | Ricoh Co., Ltd. | Two-component developer, a container filled with this developer, and image forming apparatus |
| GB201103854D0 (en) | 2011-03-07 | 2011-04-20 | Micromass Ltd | Dynamic resolution correction of quadrupole mass analyser |
| KR20210008386A (en) * | 2018-06-21 | 2021-01-21 | 쌩-고벵 글래스 프랑스 | Manufacturing method of composite plate glass with polarization selective coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL297491A (en) * | 1962-09-06 | 1900-01-01 |
-
1975
- 1975-04-25 CA CA225,837A patent/CA1041344A/en not_active Expired
- 1975-05-02 GB GB18406/75A patent/GB1497732A/en not_active Expired
- 1975-05-06 DE DE2520214A patent/DE2520214C2/en not_active Expired
- 1975-05-19 BR BR3929/75A patent/BR7503081A/en unknown
- 1975-05-23 JP JP50061814A patent/JPS5913023B2/en not_active Expired
- 1975-05-23 FR FR7516181A patent/FR2273308B1/fr not_active Expired
- 1975-05-27 SE SE7506043A patent/SE406653B/en not_active IP Right Cessation
- 1975-05-28 IT IT23855/75A patent/IT1038561B/en active
- 1975-05-30 NL NL7506484A patent/NL7506484A/en not_active Application Discontinuation
- 1975-05-30 ES ES438084A patent/ES438084A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2273308B1 (en) | 1978-09-22 |
| ES438084A1 (en) | 1977-06-16 |
| JPS5913023B2 (en) | 1984-03-27 |
| BR7503081A (en) | 1976-04-20 |
| SE406653B (en) | 1979-02-19 |
| JPS513238A (en) | 1976-01-12 |
| GB1497732A (en) | 1978-01-12 |
| SE7506043L (en) | 1975-12-01 |
| DE2520214A1 (en) | 1975-12-11 |
| DE2520214C2 (en) | 1984-01-05 |
| AU8149475A (en) | 1976-11-25 |
| NL7506484A (en) | 1975-12-02 |
| FR2273308A1 (en) | 1975-12-26 |
| IT1038561B (en) | 1979-11-30 |
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