CA1074166A - Developer containing a resin and diazo colorant c-1-solvent yellow 29 - Google Patents
Developer containing a resin and diazo colorant c-1-solvent yellow 29Info
- Publication number
- CA1074166A CA1074166A CA253,564A CA253564A CA1074166A CA 1074166 A CA1074166 A CA 1074166A CA 253564 A CA253564 A CA 253564A CA 1074166 A CA1074166 A CA 1074166A
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- Canada
- Prior art keywords
- toner
- carrier
- developer
- yellow
- coated steel
- 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.)
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Classifications
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- 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
- G03G9/09—Colouring agents for toner particles
- G03G9/0906—Organic dyes
- G03G9/091—Azo dyes
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
YELLOW DEVELOPER
ABSTRACT OF THE DISCLOSURE
A novel yellow electrostatographic colorant is disclosed. This colorant may be employed as an electro-statographic toner or developer material. Electrophotographic processes are disclosed employing this colorant. When employed as an electrophotographic developing material, this colorant is found to possess superior triboelectric properties among others which result in superior electro-photographic machine life than known yellow colorants.
ABSTRACT OF THE DISCLOSURE
A novel yellow electrostatographic colorant is disclosed. This colorant may be employed as an electro-statographic toner or developer material. Electrophotographic processes are disclosed employing this colorant. When employed as an electrophotographic developing material, this colorant is found to possess superior triboelectric properties among others which result in superior electro-photographic machine life than known yellow colorants.
Description
~74~66 BACKGROUND OF THE INVENTION
_ This invention relates to imaging ~ystems, and more particularly, to improved xerographic developing materials, thair manufacture, and use.
Electrostatography, that branch of the imaging art which relates to the formation and utilization of latent electrostatic charge patterns to record and reproduce patterns in visible form is well known in the art.
When a photoconductor is employed to form these electrostatic latent images by first charging and then selectively exposing the photoconductive layer, this imaging method is referred to as electrophotography and more commonly known as xerography, the basic techniques of which are disclosed in U. S. Patent 2,297,691. The latent electro-static images thus formed may be developed or rendered visible by deposition of a finely divided electroscopic material referred to in the art as tonerO The image thus obtained may be utilized in a number of ways t for example, the image may be fused or fixed in place or transferred and then fixed to a second surface.
Electrography, the other broad general branch of electrostatography, generally divided into two broad sectors which are referred to as xeroprinting and electro-graphic or TESI recording, does not employ a photoresponsive medium, the c:harging and selective discharging thereof to form its latent electxostatic image. Xeroprinting, the electrostatis~ analog of ordinary printing is more fully described in U. S. Patent 2,576,047 to Schaffert. TESI
imaging or transfer of electxostatic images, more fully described in U. S. Patent 2,285,814, involves the formation ~ ,.
, ~7~66 o an electrostatic charge pattern conforming to a desired reproduction on a uniform insulating lay~r by means of an electrical dischaxge between two or more electrodes on opposite sides of the insulating medium. The lines of force generated by the latent electrostatic image are employed to control the deposition of the toner material to form an image.
Various developers both powder and liquid and developing systems are well known to those skilled in the art including cascade development as disclosed in U. S. Patent 2,618,552 to E. N. Wise; magnetic brush development as generally described in U. S. Patent 2,874,063; powder cloud development as generally described in U. S. Patent 2,784,109; touchdown development descri~ed in U. S. Patent 3,166,432; and liquid development as described in U. S. Patent 2,877,133 among others. These development systems, though they enjoy widespread use for black and white reproductions may also be employed in other colors and combinations of colors for example, a trichromatic color system of either the additive or subtractive color formation types. In full color systems at least three different colors must be employed to synthesize any other desired color which involves generally the formation of at least ~hree color separation images and their combination in registration with each other to form a color reproduction of the original. Thus, in any o the electrostatographic recoxding systems at least three diferent latent electro-static images must be foxmed, developed with different color toners and combined to orm the final image. For example, in color xerography an electrostatic latent image resulting from exposure to a first primary color may be formed on the ~7~6 photoconductive layer and developed with a toner complementary to the primary color. In a s:imilar fashion, succeeding developments of electrostatic latent images corre~ponding to primary colors are accomplished with complementary toners.
When exposing through color separation negatives, the toner is the complament of the radiation of exposure.
In a three color electrophotographic system which amploys superimposed color images it is necessary that the toners be quite transparent except for the underlying one so as not to ob~cure the different colored toner images below it and that each toner have sufficient color saturation at the same time and brightness to satisfy the colorimetric requirements for three color synthesis of natural color images. As can be àppreciated, these requirements are virtually diametrically opposed and are further complicated by the additional requirement that when all the toners are com~ined, they must produce a deep black. It has been found that in order to produce deep blacks in a color system it is required to superpose four different colored images including a black registered image. Additional problems generally arise when inorganic pigments are used as the coloring material either in printing inks or electrophotographic toners since it is difficult to achieve proper color balance and saturation while at the same time keeping the colors transparent. When employing inorganic pigments, the range of colors available is relatively narrow and these pigments are found to impart opacity to the materials to which they are added even in relatively small amounts.
Bartoszawicz et al in U. S. Patent 3,345,293 teaches colored electrophotographic toners comprising .. .. . . , . . , : .. .
~74~66 substantially transparent resin particles containing organic dye pigments. These materials are stated to be advantageous in their use over prior art materials in that they are more resistant to bleeding of color upon toner fusing and they are specifically adaptable for use in three color electro-photographic processes since their colors are yellow, cyan, magenta and their mixtures in pairs produce blue, red and green while the three toners together produce a black.
Notwithstanding the apparent advantages of the Bartoszewicz et al toners, there are nevertheless disadvantages connected with these specific toners, specifically in the case of the yellow toner when employed in an automatic electrophoto-graphic machine. The yellow colorant as ad~anced by Bartoszewicz et al consists essentiall~ of from about .92 to about 1.08 parts by weight of 3,3'-dichloro, 4'-bis (2"-acetyl-2l'-azo-o-acetotoluidide)biphenyl per 10 parts by weight of a substantially transparent resin. The problem in employing this colorant residas in its inability to disperse substantially uniformly in transparent resin materials and more significantly the undersirable triboelectric properties which result from its use causing poor images of low contrast and low machine life. It is found that the triboelectric properties of the resulting toner material are not maintained under conditions where the toner is exposed to mechanical abrasion, high temperatures, and high ambient humidity conditions, all of which are common in electrophotographic machines~ This results in a number of problems includin~ poor transfers from the drum surface to the cop~ sheet as well as maintaining ~37~ 6 cleanliness of the drum. More specifically, it is Eound that in electrophotographic machine use this toner imp~cts on its carrier further degrading the already existing undesirable triboelectric relationship and thereby adversely effecting machine performance.
SUMMARY OF THE INVENTION
In accordance with one aspect of this invention there is provided an electrostatographic material for developing electrostatic latent images comprising a resin material and a colorant, said colorant sa~isfying the formula:
o7 C~3 CH3 ~
C~ll C6Hll .. . :
In accordance with anothèr aspect of-this invention there is provided an electrostatographic imaging process comprising establishing an electrostatic latent image on a surface and contacting said surface with an electrostatographic material-comprising a resin material and a colorant, the colorant having the formula indicated above.
In accordance with another aspect of this invention there is provided a color electrophotographic imaging process comprising charging a photoconductive member, exposing said photoconductive member to an original to be reproduced through a filter of one color thereby selectively discharging said photoconductive member, developing the electros*atic image formed thereby with a developer of a complementary color, said developer being one member of the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethyl-. . ~' - 6 - ~
. . . ~ .
~74~66 quinacridone identi~ied in the Colour Index as C.I. Pigment Red 122, magenta toner and a nickel berry carrier; azo dye C.I.
21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductor for a second time and selectively exposing said photoconductor to the same image through a filter of another primary color, developing the latent electrostatic image formed thereby with a developer of a complementary color, said developer being another member selected from the group consisting of copper tetra-4-~octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethyl-quinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I.
21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductive member for a third time, exposing said photoconductor to the same imAge through a filter of the remaining primary color and developing the latent electrostatic image with a complementary developer, said developer being the remaining developer of the group con-sisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethylquinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I. 2I230 Solvent Yellow 29 yellow toner and a methyl te:rpolymer coated steel carrier.
The colorant having the formula previously noted, classified in the Colour Index as C.I. Solvent Yellow 29, C.I.
21230, is combined with an appropriate electrophotographic resin, for example, a styrene-n-butyl-methacrylate resin to form a toner and then combined with a conventional carrier for example, methyl terpolymer coated steel carrier to provide a highly desirable yellow developer ~or use in color electro-. . ~ ~. . - . .
~079~ 6 photography. These are hereinafter referred to as Solvent Yellow 29 developers and Yellow 29 toners and are distinctly different and superior to those yellow colorants taught by Bartoszewicz et al and other conventional yellow developers since they are ~ound to be transparent while other known colorants are opaque. These developers unlike other yellow developers are readily dispersible and have desirable solubility properties in electrostatographic resins. The most significant property of these developers, however, is their superior triboelectric properties or tribo which allow these developers to be employed very successfully in electrophotographic developing applications. When employed in an automatic electrophotographic imaging device where developer is employed, it is found that the machine tends to impact the toner and the carrier for both prior art yellow colorants and Solvent Yellow 29 ~olorants; however, where as in the case of prior art yellow colorants the triboelectric property tends to degrade ~74166 and consequently machine performance is severel~ curtailed, Solvent Yellow 29 developers maintain their triboelectric properties and in some cases have been found to improve upon continued impaction, thus providing superior machine life and performance.
It has been found that upon continuous use in a conventional àutomatic electrophotographic imaging device, for example, a Xerox 720 Copier under controlled conditions that a benzidine yellow toner as taught by Bartoszewicz et al displayed a machine life of 1400 prints, two conventionally employed black toners have useful lives of 4200 and 9000 prints whereas a Solvent Yellow 29 toner composition exhibited a useful life in excess of 25,000 prints with no apparent adverse effects. It is, therefore, demonstrated that prior art colorants including the yellow colorant of Bartoszewicz et al when combined with suitable resins to optimize their respective performances and employed in the same machine under identical conditions do not in any way begin to compare with the useful life and performance of the toner compositions of the instant invention. Further upon extended use in machine testing, conventional black toners tend to drop tribo-electrically in steps until they reach a final failure level after which imaging is difficult if not impossible. These steps are not evident in prior art yellow toner life studies such as the Bartoszewicz et al yellow toner, since these toners exhibit a steady and extreme drop in tribo, resulting in shortened m,achine life and poor machine performance.
Yellow 29 toner compositions, much the same as diarylide yellow compositions, exhibit very stable tribo values within a well defined range with acceptable copy quality and ~074~66 operational characteristics over a test run o~ over 25,000 prints. In addition, the impac:tion rating exhibited by this yellow toner and a developer is actually less than generated by conventionally employed blac:k developers over an equilvalent test period. From the table below, Table I, developer compositions employing Solvent Yellow 29 colorants, it can be seen that developer compositions employing Solvent Yellow 29 colorants are capable of achieving at least 25,000 print cycles o~ acceptable copy quality and development characteristics.
Impaction was not found to be a problem so that this parameter ic not at all reported. In addition, it may seem that Solvent Yellow 29 pigment itself when employed as reci~ed above exhibits high triboelectric characteristics far superior -to tho~e found in the prior art as may be seen by the following table.
TABLE I
TONER OF EXAMPLE I Carrier-Methylterpolymer coated steel beads, 100 ~ particle size Toner Conc. Tribo Tribo Background Prints (%)(Uc/qm) Product Densit~ Avera~e _
_ This invention relates to imaging ~ystems, and more particularly, to improved xerographic developing materials, thair manufacture, and use.
Electrostatography, that branch of the imaging art which relates to the formation and utilization of latent electrostatic charge patterns to record and reproduce patterns in visible form is well known in the art.
When a photoconductor is employed to form these electrostatic latent images by first charging and then selectively exposing the photoconductive layer, this imaging method is referred to as electrophotography and more commonly known as xerography, the basic techniques of which are disclosed in U. S. Patent 2,297,691. The latent electro-static images thus formed may be developed or rendered visible by deposition of a finely divided electroscopic material referred to in the art as tonerO The image thus obtained may be utilized in a number of ways t for example, the image may be fused or fixed in place or transferred and then fixed to a second surface.
Electrography, the other broad general branch of electrostatography, generally divided into two broad sectors which are referred to as xeroprinting and electro-graphic or TESI recording, does not employ a photoresponsive medium, the c:harging and selective discharging thereof to form its latent electxostatic image. Xeroprinting, the electrostatis~ analog of ordinary printing is more fully described in U. S. Patent 2,576,047 to Schaffert. TESI
imaging or transfer of electxostatic images, more fully described in U. S. Patent 2,285,814, involves the formation ~ ,.
, ~7~66 o an electrostatic charge pattern conforming to a desired reproduction on a uniform insulating lay~r by means of an electrical dischaxge between two or more electrodes on opposite sides of the insulating medium. The lines of force generated by the latent electrostatic image are employed to control the deposition of the toner material to form an image.
Various developers both powder and liquid and developing systems are well known to those skilled in the art including cascade development as disclosed in U. S. Patent 2,618,552 to E. N. Wise; magnetic brush development as generally described in U. S. Patent 2,874,063; powder cloud development as generally described in U. S. Patent 2,784,109; touchdown development descri~ed in U. S. Patent 3,166,432; and liquid development as described in U. S. Patent 2,877,133 among others. These development systems, though they enjoy widespread use for black and white reproductions may also be employed in other colors and combinations of colors for example, a trichromatic color system of either the additive or subtractive color formation types. In full color systems at least three different colors must be employed to synthesize any other desired color which involves generally the formation of at least ~hree color separation images and their combination in registration with each other to form a color reproduction of the original. Thus, in any o the electrostatographic recoxding systems at least three diferent latent electro-static images must be foxmed, developed with different color toners and combined to orm the final image. For example, in color xerography an electrostatic latent image resulting from exposure to a first primary color may be formed on the ~7~6 photoconductive layer and developed with a toner complementary to the primary color. In a s:imilar fashion, succeeding developments of electrostatic latent images corre~ponding to primary colors are accomplished with complementary toners.
When exposing through color separation negatives, the toner is the complament of the radiation of exposure.
In a three color electrophotographic system which amploys superimposed color images it is necessary that the toners be quite transparent except for the underlying one so as not to ob~cure the different colored toner images below it and that each toner have sufficient color saturation at the same time and brightness to satisfy the colorimetric requirements for three color synthesis of natural color images. As can be àppreciated, these requirements are virtually diametrically opposed and are further complicated by the additional requirement that when all the toners are com~ined, they must produce a deep black. It has been found that in order to produce deep blacks in a color system it is required to superpose four different colored images including a black registered image. Additional problems generally arise when inorganic pigments are used as the coloring material either in printing inks or electrophotographic toners since it is difficult to achieve proper color balance and saturation while at the same time keeping the colors transparent. When employing inorganic pigments, the range of colors available is relatively narrow and these pigments are found to impart opacity to the materials to which they are added even in relatively small amounts.
Bartoszawicz et al in U. S. Patent 3,345,293 teaches colored electrophotographic toners comprising .. .. . . , . . , : .. .
~74~66 substantially transparent resin particles containing organic dye pigments. These materials are stated to be advantageous in their use over prior art materials in that they are more resistant to bleeding of color upon toner fusing and they are specifically adaptable for use in three color electro-photographic processes since their colors are yellow, cyan, magenta and their mixtures in pairs produce blue, red and green while the three toners together produce a black.
Notwithstanding the apparent advantages of the Bartoszewicz et al toners, there are nevertheless disadvantages connected with these specific toners, specifically in the case of the yellow toner when employed in an automatic electrophoto-graphic machine. The yellow colorant as ad~anced by Bartoszewicz et al consists essentiall~ of from about .92 to about 1.08 parts by weight of 3,3'-dichloro, 4'-bis (2"-acetyl-2l'-azo-o-acetotoluidide)biphenyl per 10 parts by weight of a substantially transparent resin. The problem in employing this colorant residas in its inability to disperse substantially uniformly in transparent resin materials and more significantly the undersirable triboelectric properties which result from its use causing poor images of low contrast and low machine life. It is found that the triboelectric properties of the resulting toner material are not maintained under conditions where the toner is exposed to mechanical abrasion, high temperatures, and high ambient humidity conditions, all of which are common in electrophotographic machines~ This results in a number of problems includin~ poor transfers from the drum surface to the cop~ sheet as well as maintaining ~37~ 6 cleanliness of the drum. More specifically, it is Eound that in electrophotographic machine use this toner imp~cts on its carrier further degrading the already existing undesirable triboelectric relationship and thereby adversely effecting machine performance.
SUMMARY OF THE INVENTION
In accordance with one aspect of this invention there is provided an electrostatographic material for developing electrostatic latent images comprising a resin material and a colorant, said colorant sa~isfying the formula:
o7 C~3 CH3 ~
C~ll C6Hll .. . :
In accordance with anothèr aspect of-this invention there is provided an electrostatographic imaging process comprising establishing an electrostatic latent image on a surface and contacting said surface with an electrostatographic material-comprising a resin material and a colorant, the colorant having the formula indicated above.
In accordance with another aspect of this invention there is provided a color electrophotographic imaging process comprising charging a photoconductive member, exposing said photoconductive member to an original to be reproduced through a filter of one color thereby selectively discharging said photoconductive member, developing the electros*atic image formed thereby with a developer of a complementary color, said developer being one member of the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethyl-. . ~' - 6 - ~
. . . ~ .
~74~66 quinacridone identi~ied in the Colour Index as C.I. Pigment Red 122, magenta toner and a nickel berry carrier; azo dye C.I.
21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductor for a second time and selectively exposing said photoconductor to the same image through a filter of another primary color, developing the latent electrostatic image formed thereby with a developer of a complementary color, said developer being another member selected from the group consisting of copper tetra-4-~octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethyl-quinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I.
21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductive member for a third time, exposing said photoconductor to the same imAge through a filter of the remaining primary color and developing the latent electrostatic image with a complementary developer, said developer being the remaining developer of the group con-sisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethylquinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I. 2I230 Solvent Yellow 29 yellow toner and a methyl te:rpolymer coated steel carrier.
The colorant having the formula previously noted, classified in the Colour Index as C.I. Solvent Yellow 29, C.I.
21230, is combined with an appropriate electrophotographic resin, for example, a styrene-n-butyl-methacrylate resin to form a toner and then combined with a conventional carrier for example, methyl terpolymer coated steel carrier to provide a highly desirable yellow developer ~or use in color electro-. . ~ ~. . - . .
~079~ 6 photography. These are hereinafter referred to as Solvent Yellow 29 developers and Yellow 29 toners and are distinctly different and superior to those yellow colorants taught by Bartoszewicz et al and other conventional yellow developers since they are ~ound to be transparent while other known colorants are opaque. These developers unlike other yellow developers are readily dispersible and have desirable solubility properties in electrostatographic resins. The most significant property of these developers, however, is their superior triboelectric properties or tribo which allow these developers to be employed very successfully in electrophotographic developing applications. When employed in an automatic electrophotographic imaging device where developer is employed, it is found that the machine tends to impact the toner and the carrier for both prior art yellow colorants and Solvent Yellow 29 ~olorants; however, where as in the case of prior art yellow colorants the triboelectric property tends to degrade ~74166 and consequently machine performance is severel~ curtailed, Solvent Yellow 29 developers maintain their triboelectric properties and in some cases have been found to improve upon continued impaction, thus providing superior machine life and performance.
It has been found that upon continuous use in a conventional àutomatic electrophotographic imaging device, for example, a Xerox 720 Copier under controlled conditions that a benzidine yellow toner as taught by Bartoszewicz et al displayed a machine life of 1400 prints, two conventionally employed black toners have useful lives of 4200 and 9000 prints whereas a Solvent Yellow 29 toner composition exhibited a useful life in excess of 25,000 prints with no apparent adverse effects. It is, therefore, demonstrated that prior art colorants including the yellow colorant of Bartoszewicz et al when combined with suitable resins to optimize their respective performances and employed in the same machine under identical conditions do not in any way begin to compare with the useful life and performance of the toner compositions of the instant invention. Further upon extended use in machine testing, conventional black toners tend to drop tribo-electrically in steps until they reach a final failure level after which imaging is difficult if not impossible. These steps are not evident in prior art yellow toner life studies such as the Bartoszewicz et al yellow toner, since these toners exhibit a steady and extreme drop in tribo, resulting in shortened m,achine life and poor machine performance.
Yellow 29 toner compositions, much the same as diarylide yellow compositions, exhibit very stable tribo values within a well defined range with acceptable copy quality and ~074~66 operational characteristics over a test run o~ over 25,000 prints. In addition, the impac:tion rating exhibited by this yellow toner and a developer is actually less than generated by conventionally employed blac:k developers over an equilvalent test period. From the table below, Table I, developer compositions employing Solvent Yellow 29 colorants, it can be seen that developer compositions employing Solvent Yellow 29 colorants are capable of achieving at least 25,000 print cycles o~ acceptable copy quality and development characteristics.
Impaction was not found to be a problem so that this parameter ic not at all reported. In addition, it may seem that Solvent Yellow 29 pigment itself when employed as reci~ed above exhibits high triboelectric characteristics far superior -to tho~e found in the prior art as may be seen by the following table.
TABLE I
TONER OF EXAMPLE I Carrier-Methylterpolymer coated steel beads, 100 ~ particle size Toner Conc. Tribo Tribo Background Prints (%)(Uc/qm) Product Densit~ Avera~e _
2~% RHInitial 2.43 12.42 30.181.16 .010 500 3.09 12.22 37.76 .92 .01~
l.OK 3.09 12.65 39.72 .87 .010 1.5R 3.07 12.50 38.38 .94 .010 2.OK 2.78 13.42 37.31 .93 .010 2.5R 2.81 13.11 36.83 .97 .010
l.OK 3.09 12.65 39.72 .87 .010 1.5R 3.07 12.50 38.38 .94 .010 2.OK 2.78 13.42 37.31 .93 .010 2.5R 2.81 13.11 36.83 .97 .010
3.OK 2.'71 14.48 39.25 .94 .010 3.5K 2.49 14.64 36.45 .89 .010
4.OK 2.';1 14~06 35.66 .81 .010 4.5K 2.04 15.81 32.26 .84 .010
5.OK 2.;26 15.12 34.17 .84 .010 5.5K 2.:37 14.57 34.53 .89 .010
6.OK 2.59 13.29 34.42 .92 .010 ~9~74~66 TABLE I (Continued) Toner Conc.Tribo Tribo Background Prints (%)(~c/qm) Product Density Average 6.5K 2.4013.98 33.55 .82 .010
7.OK 2.5312.50 31.63 1.06 .010 7.5K 2.3213.16 30.53 1.02 .010
8.5K 2.3514.66 34.46 1.04 .010
9.5R 2-.8714.83 42.56 .88 .010 lO.OK 2.2614.90 33.67 .98 .010 ll.OK 2.2513.99 31.49 .92 .010 12.OK 2.0311.54 23.42 .85 .010 13.OK 2.0612.42 25.59 .93 .010 13.5K 1.9511.00 21.45 .85 .010 14.OK 2.2411.14 24.96 1.34 .010 15.OK 2.2112.94 27.94 1.01 .010 16.OK 2.0512.33 2~.28 .92 .010 16.5K 1.9711.89 23.28 .84 .010 17.OK 2.2412.50 28.00 1.11 .010 - 18.OK 2.0914.75 30.83 .66 .010 l9.OK 2.0615.14 31.18 .72 .010 8~/o RH
19.5~ 2.2410.42 23.35 .98 .010 20.0K 2.178.71 18.90 1.05 .010 2a.5K 2.2710.42 23.35 .98 .010 21~ OK 1.59lD.93 17.38 .86 .010 21.5K 2.117.89 16.66 1.04 .010 22.OK 2.028.40 16.97 1.04 .010 22.5K 2 .139. 36 19.93 .94` .010 23. OK 1. 828.45 15.36 .82 - .010 24.OK 1.549.58 14.76 .54 .010 25.OK 1.6110.26 16.51 .94 .010 26.OK 1.727.91 13.61 .92 .010 Structurally the Solvent Yellow 29 yellow colorants satisfying the following formula: --C6Hll C6Hll .
differ from the diarylide yellow colorants listed in the Colour ::
Index as C. I. 21090 Pigment Yellow 12 and disclosed in Canadian Patent No. 986~767~ issued April 6~ 1976~ Warren E.
Solodar, satisfying the formula:
~741~6 IH3 l H3 COH Cl Cl HOC
~MEI-OC~C--N=~N=~--C-CO ~
and from the benzidine yellow colorants as disclosed by Bartoszewicz et al listed in the Colour Index as C.I. 21095 Pigment Yellow 14 and satisfying the following formula:
c~3 CH3 CH3 1 0H C1 C1 C_OH H3C
~lHOC- ~ _ I_CO~I~
Any suitable resin material may be used for the toner compositions of the present invention. As previously stated, substantially transparent resins are preferred when the toner is to be used in a three color electrophotographic system. Although any substantially transparent resin material may be utilized as the resin component of this toner, it is preferable that resins having other desirable properties be utilized in this invention. Thus, for example, it is desirable that a resin be used which is a non-tacky solid at room temperature so as to facilitate handling and use in the most common electrophotographic processes. Thermal plastics are Idesirable with melting points significantly above room temperature, but below that of which ordinary paper tends to char so that once the toner images form ~ ~ 7 ~ ~ 6 thereon or transfer to a paper copy sheet it may be employed and fixed to paper copy sheets by other techniques, such as, subjecting the paper copy sheet bearing the powder image to vapors of a solvent for the resin as generally described in U. S. Patent 2,776,907. The resins selected should desirably have good triboelectric properties and have sufficient insulating properties to hold charge so that they may be employed in a number of development systems.
While any suitable transparent resin possessing the properties as above described may be employed in the system of the present invention, particularly good results are obtained with the use o~ vinyl resins and polymeric esterification products of a dicarboxylic acid and a diol comprising a diphenol. Any suitable vinyl resin may be employed in the toners of the present system including homo-polymers or copolymers of two or more vinyl monomers.
Typical such vinyl monomeric units include: styrene;
p-chlorostyrene; vinyl naphthalene; ethylenically unsaturated mono-olefins such as ethylene, propylene, butyIene, isobutylene and the like; vinyl esters such as vinyl chloride, vinyl bromide, ~inyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and the like; esters of alphamethylane aliphatic monocarboxylic acids such as methyl acrylate, ethyl acrylate, n-butylacrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl-alpha~chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like; acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl isobutyl .. ,. . . ~ .
74~6 ether, vinyl ethyl ether, and the like; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and the like; vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride and the like; and N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene and the like; and mixtures thereof.
It is generally found that toner resins containing a relatively high percentage of styrene are preferred since greater image definition and density is obtained with their use. The styrene resin employed may be a homopolymer of styrene or styrene homologs or copolymers of styrene with other monomeric groups containing a single methylene group attached to a carbon atom by a double bond. Any of the above typical monomeric units may be copolymerized with styrene by addition polymerization. Styrene resins may also be formed by the polymerization of mixtures of two or more unsaturated monomeric materials with a styrene monomer.
The addition polymerization technique employed embraces known polymerization techniques such as free radical, anionic and cationic polymerization processes. Any of these vinyl resins may he blended with one or more other resins if desired, preferably other vinyl resins which insure good t:riboelectric stability and uniform resistance against physi.cal degradation. However, non-vinyl type thermoplastic: resins may also be employed including rosin modified phenol formaldehyde resins, oil modified epoxy resins, polyurethane resins, cellulosic resins, polyether resins and mixtures thereof.
~IL074~6 Polymeric esterification products of a dicarboxylic acid and a diol comprising a diphenol may also be used as a preferred resin material for the toner compositions of the instant invention. The diphenol reactant has the general ormula:
X X' H(OR')n10 ~ R ~ O(OR")n2H
wharein R represents substituted and unsubstituted alkylene radicals having from 2 to 12 carbon atoms, alkylidene radicals having from 1 to 12 carbon atoms and cycloalkylidene radicals having from 3 to 12 carbon atoms; R' and R" represent substi-tuted and unsubstituted alkylene radicals having from 2 to 12 carbon atoms, alkylene arylene radicals having from 8 to 12 carbon atoms, and arylene radicals; X and X' represent hydrogen or an alkyl radical having from 1 to 4 carbon atoms;
and nl and n2 are each at least 1 and the average sum of n and n2 is less than 21. Diphenols wherein R represents an alkylidene radical having from 2 to 4 carbon atoms are preferred because greater blocking resistance; increased definition of xerographic characters and more complete transfer of toner images are achieved. Optimum results are obtained with diols in which R' is an isopropylidene radical and R' and R'l are selected from the group consisting of propylene and butylene radicals because tha resins formed from these diols possess higher agglomeration resistance and penetrate extremely rapidly into paper receiving sheets under fusing conditions.
Dicarboxylic acids having from 3 to 5 carbon atoms are ~L~74~66 preferred because the resulting toner resin possesses greater resistance to film formation on reusable imaging surfaces and resist the formation of fines under machine operation conditions~ Optimum results are obtained with alpha unsaturated dicarboxylic acids including fumaric acid, maleic acid or maleic acid anhydride because maximum resistance to physical degradation of the tonar as well as rapid melting properties are achieved. Any suitable-diphenol which satisfies the above formula may be employed.
Typical such dipenols include: 2,2-bis(4-beta hydroxyl ethoxy phenyl)-propane, 2,2-bis(4-hydroxy isopropoxy phenyl) propane, 2,2-bis(4-beta hydroxy ethoxy phenyl) pentane, 2,2-bis(4-beta hydroxy ethoxy phenyl)-butane, 2,2-bis(4-hydroxy-propoxy-phenyl)-propane, 2,2-bis(4-hydroxy -propoxy-phenyl) propane, 1,1-bis(4-hydroxyl-ethoxy-phenyl) -butane, 1,1-bis(4-hydroxyl isopropoxy-phenyl) heptane, 2,2-bis~3-methyl-4-beta-hydroxy ethoxy-phenyl) propane, 1,1-bis(4-beta hydroxy ethoxy phenyl)-cyclohexane, 2,2'-bis ~4-beta hydroxy ethoxy phenyl)-norbornane, 2,2'-bis(4-beta hydroxy ethoxy phenyl) norbornane, 2,2-bis(4-beta hydroxy styryl oxyphenyl) propane, the polyoxyethylene ether of isopropylidene diphenol in which both phenolic hydroxyl groups are oxyethylated and the average number of oxy~thylene groups per mole is 2.6, the polyoxypropylene ether of 2-butylidene cliphenol in which both the phenolic hydroxy groups are oxyalkylated and the average number of oxypropylene groups per mo]e is 2.5, and the like. Diphenols wherein R represents zm alkylidene radical having from 2 to 4 carbon atoms and R' and R" represent an alkylene radical ~ 7~6~
having from 3 to 4 carbon atoms are preferred because greater blocking resistance, increased deinition of xerographic characters and more complete transfer of toner images are achieved. Optimum xesults are obtained with diols in which R is isopropylidene and R' and R" are selected from the group consisting of propylene and butylene because the resins formed from these diols possess higher agglomeration resistance and penetrate extremely rapidly into paper receiving sheets under fusing conditions.
Any suitable dicarboxylic acid may be reacted wi~h a diol as described above to form the toner compositions of this invention either substituted or unsubstituted, saturated or unsaturated~ having the general formula:
HOOC R~n COOH
wherein R''`' represents a substituted or unsubstituted alkylene radical having from 1 to 12 carbon atoms, arylene radicals or alkylene arylene radicals having from 10 to 12 carbon atoms and n3 is lass than 2. Typical such dicarboxylic acids including their existing anhydrides are: oxalic acid, malonic acid, succinic acid, glutaric acid~ adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, mesaconic acid, homophthalic acid, isophthalic acid, terephthalic acid, o-phenyleneacetic-beta-propionic acid, itaconic acid, maleic acid, maleic acid anhydride, fumaric acid, phthalic acid anhydride, traumatic acid, citraconic acid, and the like. Dicarboxylic acids having from 3 to 5 carbon atoms are preferred because the resulting toner resins possess greater resistance to film formation ~74~ 6 on reusable imaging surfaces and resist the formation o~
fines under machine operation conditions. Optimum results are obtained wit~ alpha unsaturated dicarboxylic acids including fumaric acid, maleic acid, or maleic acid anhydride because maximum resistance to physical degradation of the toner as well as rapid melting propexties are achieved. The polymerization esterification ]products may themselves be copolymerized or blended with one or more other thermoplastic resins, preferably aromatic resins, aliphatic resins, or mixtures thereof. Typical thermoplastic resins include rosin modified phenol formaldehyde resins, oil modified epoxy resins, polycarbonate, polysulfone, polyphenylene oxide, polyurethane resins, cellulosic resins, vinyl type resins and mixtures thereof. When the resin component of the toner contains an added resin, the added component should be present in an amount less than about 50 percent by weight ba3ed on the total weight of the resin present in the toner. A relatively high percentage of the polymeric diol and dicarboxylic acid condensation product in the resinous component of the toner is preferred because a greater reduction o fusing temperatures is achieved with a given quantity of additive material. Further, sharper images and denser images ar~ obtained when a high percentage of the polymeric diol and dicarboxylic acid condensation product is present in the toner. Any suitable blending technique such as hot melt, solvent, and emulsion techniques may be employed to incorporate the added resin into the toner mixture. The resulting resin blend is substantially homogeneous and highly compatible with pigments and dyes~
Where suitable, the colorant may be added prior to, ~7~66 simultaneously with or subsequent to the blending or polymerization step.
Preferred electrophotographic results with the Solvent Yellow 29 colorant of the instant invention are achieved with styrene-butyl methacrylate copolymers, styrene-vinyl-toluene copolymers, styrene-ac:rylate copolymers, polystyrane resins, predominantly sty.rene or polystyrene based resins as generally described in U. S. Reissue Patent 25,136 to Carlson, and polys~yrene blends as described in U. S. Patent 2,788,288 to Rheinfrank and Jones~ Optimum results are achieved with the Yellow 29 of the instant invention and styrene-n-butylmethacrylate copolymer resins to form a toner of long life and low impaction.
Any well known toner mixing and comminution technique may be employed to provide the toner compositions of the instant invention. For example, the ingredients may be thoroughly mixed by blending, ex rusion and milling and thereaft~r micropulverized. In addition, spray drying a suspension of tha ingreaients, a hot melt or a solution of the toner composition may also be employed.
The toners of the invention may be any size which will result in a satisfactorily developed image, Toners of the invention suitable for use with a carrier in cascade or magnetic aevelopment generally have an average particle size of about 5 microns to about 45 microns. A preferred average particle size range is about 10 microns to about 19 microns to result in a print of maximum density.
Where carrier materials are employed in connection with the toner compositions of the instant invention in cascade and magnatic brush development, the carrier particles employed may be electrically conductive, insulating, magnetic .. . . . .. .
~ ~74~66 or non-magnetic, as long as the carrier particles are capable of triboelectrically obtaining a charge of opposite polarity to that of the toner particles so that the toner particles adhere to and surround the carrier particles. In developing a positive reproduction of an lelectrostatic imaga, the carrier particle is selected so that the toner particles acquire a charge having a polarity opposite to that of the electrostatic latent image so that toner deposition occurs in image areas.
Alternatively, in reversal reproduction of an electrostatic latent image, the carriers are selected so that the toner particles ac~uire a charge having the same polarity as that of the electrostatic latent image resulting in toner deposition in the non-image are~s. Typical carrier materials include:
sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, potassium chlorate, granular zircon, granular silicon, methyl methacrylate, glass, steel, nickel, iron, ferrites, ferro-magnetic materials, silicon dioxide and the like. The carriers may be employed with or without a coating. Many of the foregoing and typical carriers are described by L. E. Walkup in U. S. Patent 2l618,551; L. ~. Walkup et al in U. S. Patent 2 r 638,416; E. N. Wise in U. S. Patent 2,618,552; R. H. Hagenbach et al in U. S. Patent 3,591,503 and 3,533,835 directed to electrically conductive carrier coatings, and B. J. Jacknow et al in U. S. Patent 3,526,533 directed to polymer coated carriers and nodular carriers having pe~bled surface as disclosed in Serial No. 357,988, filed May 7, 1973, now U. SO Patent 3,847,604, a divisional of Serial No. 151,995, filed June 10, 1971, now U. S. Patent -~L~74~6~
3,767,568. An ultimate coated carrier particle diameter between about 50 microns to about 1,000 microns is suitable because the carrier particles 1:hen possess sufficient density and inertia to avoid adherence to the electrostatic images during the cascade development process. A preferred particle size is between about 75 and 4()0 microns. Optimum performance with the toner of the instant invention is about 100 microns for best density images and long life. The carrier may be employed with the toner composition in any suitable combination, generally satisfactory results have been obtained when about 1 part toner is used with about 10 to about 200 parts by weight of carrier.
Preferrad carriers or use with toner compositions of the instant invention are th-ose of nickel berry and terpol~ner coated steal. Nickel berry carriers are a mem~er of a group of nodular carrier beads disclosed in U. S. Patents 3,847,604 and 3,767,568, characterized by a pebbled sur~ace with recurring recesses and protrusions giving the particles a relati~ely large external surface area and composed of nickel.
Such nodular carrier beads have high surface-to-mass ratio as compared with substantially smooth-surfaced carriar beads o~ the same mass. Using the nodular carrier materials, one can obtain the benefits o both large and small carrier beads while avoiding their shortcomings. Nodular carrier particles present a plurality of small spherical surfaces with recesses defining pochets for toner particles.
The nodular carrier beads are three dimensional solids approximately 50 to 1,000 microns in size of roughly berry, cuboid,al, rounded, irregular or spheroidal shape, and with surface irregularities formed by numerous nodules and .
1~7~:~L66 recesses. Though the beads may have randomly spaced voids or a slight d~gree of porosi~y, they should have predominantly solid cores. Preferred carrier beads have generally rounded nodules and are generally sphe:roidal in shape thus giving an appearance reminiscent of a raspberry or cluster of grapes.
Terpolymer carriers '~re disclosed in U. S. Patent 3,526,533. The terpolymer carriers comprise a core coated with a composition which is formed from the addition polymerization reaction between monomers or prepolymers of styrene, methylmethacrylate and unsaturated organo silanes, silanols or siloxanes having from 1 to 3 hydrolyzable groups and an organic group attached directly to the silicon atom containing an unsaturated carbon to carbon linkage capable of addition polymerization. Optimum with the toner of the instant invention is~a steel carrier core coated with the composition of Example XIII of U. S. Patent 3,526,533 to form a methyl terpolymar carrier which provides a developer composition which results in good density coverage and long life~
The electrostatic latent images developed by the toner compositions of the instant invention may reside on any surface capable of retaining charge. In electrophoto-graphic applications a photoconducti~e m mber is employed to form the electrostatic lat~nt Lmage. The photoconductive layer may comprise an inorganic or an organic photoconductive matPrial. Typical inorganic materials include: sulur, selenium, zinc sulfide, zinc oxidet zinc cadmium sulide, zinc magnesium oxide, cadmium selenide, zinc silicate, calcium strontium sulfide, cadmium ~ulfide, mercuric iodide, mercuric oxide, mercuric sulfide, indium trisulfide, gallium selenide, arsenic disulfide, arsenic trisulfide, arsenic ,: . .
~7~166 triselenide, antomony trisulfide, cadmium sulfoselenide and mixtures thereof. Typical organic photoconductors include:
triphenylamine; 2,4-bis(4,4'-diethylamino-phenol)-1,3,4 -oxidiazol; N-isopropylcarbazole; triphenylpyrrol; 4,5 -diphenylimidazolidione; 4,5-diphenylimidazolidinethione;
4,5-bis-(4l-amino-phenyl)-imidazolidinone; 1,5-dicyanonaphthalene;
l,~-dicyanonaphthalene; aminophtha]Lodinitrile; nitrophthalo-dinitrile; 1,2,5,6-tetraazacyclooctatetraene-(2,4,6,8);
2-mercaptobenzothiazole-2-phenyl-4-diphenylidene-oxazolone;
6-hydroxy-2,3-di(p-methoxy-phenyl)-benzofurane; 4-dimethylamino -benzylidene-benzhydrazide; 3,benzylidene-amino-car~azole;
polyvinyl carbazole; (2-nitro-benzylidene)-p-bromo-aniline;
2,4-diphenyl-quinazoline; 1,2,4-triazine; 1,5-diphenyl-3 -methyl-pyra~oline 2-(~'-dimethyI-amino phenyl)-benzoxazole;
3-amino-carbazole; polyvinylcarbazole-trinitro-Eluorenone charge transfer complex; phthalocyanines and mixtures thereof.
The toner of the instant invention is particularly suitàble for use as in the yellow toner in the color electro-photographic imaging processes disclosed in U. S. Patent 3t804,619 and U. 5. Patent 3,909,259, issued September 30, 1975, Joseph Mammino et al. The process disclosed in the ~ -above-referenced patent specifications are multiple develop-ment techniques capable of producing color reproductions employ-ing multiple sequencing of electrophotographic charging, exposing through ~Eilters and developing steps with three different color toners. The toners of magenta, cyan and yellow colors are developed after exposure through green, red and blue filters, respectively.
~7416~
In development and transfer of the three colored toner images, it is necessary that the relationship of the toners with each be such that they cooperate to produce an image of good quality. It is apparent ~hat any one of a number of variables could cause incomplete J improper, or inadequate development so that color balance is thereby shifted resulting in an unaccep1:able color print.
A use of the toners oi. the instant invention is for a sequential three color development proces~ when combined with a methyl terpolymer coated steel carrier and utilized in combination with a copper phthalocyanine pigment identified in the Colour Index as C.I. 74160, C.I. Pigment Blue lS cyan toner and a mathyl terpolymer coated steel carrier and anthraquinone dye identified in the Colour Index as C.I.
607lO, C.I. Disperse Red 15 magenta toner and a nickel berry carrier.
The toners of the instant invention have been found to be optimum for a sequential three color development process when combined with a methyl terpolymer coated s~eel carrier and utilized in combination with a copper tetra-4-(octadecylsulfonamido~ phthalocyanine pigment available from GAF Corporation under the designation of Sudan Blue OS, cyan toner and a methyl terpolymer coated steel carrier; and 2,~-dimethylquinacridone identified in the Colour Index as C.I. Pigment Red 1?2, magenta toner and a nickel berry carrier.
A sequential color electrophotographic process is performed by charging a photoconductive member, exposing said photoconductive~ member to an original to be reproduced through a filter of one! color thereby selectively discharging said photoconductive! member, developing the electrostatic image -2~-- ~ :
7~ 6 formed thereby with a developer of a complementary color, said developer being one member of the group consisting of copper t~tra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpol~mer coated steel carrier;
Colour Index Pigment Red 122, magenta toner and a nickel berry carrier; the toner of the instant invention and a methyl terpolymer coated steel carrier; charging said photoconductor for a second time and selectively expo~ing said photoconductor to the same image through a filter of another primary color, developing the latent electrostatic image formed thereby with a developer of a complementary color, said developer being another member selected from the group consisting of copper tetra-4-(octadecylsulfonamido~
phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; Colour Index Pigment Red 122, magenta toner and a nickel berry carrier; and the toner of the instant invention and a methyl terpolymer coated steel carrier; charging said photoconductive member for a third time, exposing said photoconductor to the same image through a filter of the remaining primary color and developing the latent electrostatic image with a complementary developer~
said developer bsing ~he remaining developer of the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; Colour Index Pigment Red 122, magenta toner and a nickel berry carrier; and the yellow toner of the instant invention and a methyl terpolymer coated steel carrier.
The preferred order of development and method formation of the magenta and cyan toners is as disclosed ~74166 in Example I of aforementioned U. S. Patent No. 3,909,259.
However, any sequence of development of the cyan, magenta and yellow toners may be used to produce satisfactory prints.
To further define the specifics of the present invention, the following examples are intended to illustrate and not limit the particulars of the present system. Parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
A styrene-n-butylmethacrylate copolymeric resin is employed with Colour Index Solvent Yellow 29 colorant so that the colorant comprises three percent of the toner composition by weight. The mixture is blended in a drum tumbler for about an hour at about 10 rpm. The material is then poured into a screw feeder and extruded until machine equilibrium is established. The extruded strands are taken up at the rate of about 50 feet per minute and cooled in a water bath at about 120F followed by forced air drying.
The strands are then cut by a knife device to make pellets having a diameter in the range of from 1/16 to 1/8 of an inch. These pellets are then jetted to about 15 microns average particle size. This toner is then combined with a methyl terpolymer coated steel carrier as before described, to provide an electrostatographic developer. The developer thus produced is employed in an automatic imaging device, a Xerox Model 720 copier, having a magnetic brush develop-ment system. The selenium photoconductor is charged, selectively exposeld, and developed with the yellow developer.
After 25,000 prints are obtained, images continue to be produced which possess good contrast, high image density 3L~7~66 and a desirable appearance. The tribo of ~he developer continues to maintain a high level similar to that as obtained in Table I.
EXAMPLE II
.
The process as outlined in Example I is again employed with the exception that 5 p~rcent dye concentration is employed.
EXAMPLE III
The process as outlined in Example I is again employed with the exception that a 7 percent dye loading is employed.
E~MPhE IV
._ The process as outlined in Example I is again employed with the exception that a styrene resin is employed.
- EXAMPLE V
.
The process as outlined in Example I is again parformed with the exception that the nodular nickel carrier having a pebbled surface commonly referred to as ~ickel berry is ~mployed as described in the above-re~erenced U. S. Patentc 3,847,604 and 3,767,568.
EXA~ær~ VI
The process as described in Example I is a~ain performed with the exceptiQn that the yellow developer obtained is applied to a mylar transparent substrate to produce a yellow imaged transparency.
EXAMPLE VII
.
A yellow developer as produced in Example I is substituted for the yellow developer employed in trichromatic tr~er~ ~r~
-2~-. ' . . ' , : .
- , . ~ .. . . . . ..
; . .
. ~ . . .. ... . . . .. . . . . .
~C~7~16~
electrophotographic imaging process as described in Example I of U. S. Patent 3,804,619.
EXAMPLE VIII
A yellow developer as produced in ~xample V is substituted for the yellow developer employed in trichromatic electrophotographic imaging process as described in Example I
-of aforementioned U. S. Patent No. 3,909,259.
Although the present examples were specific in terms of conditions and materials used, any o~ the above listed typical materials may be substituted when suitable in the above examples with similar results. In addition to -the steps used to carry out the process of the present invention, other steps or modifications may be used if desirable. In addition, other materials may be incorporated in the system of the present invention which will enhance, synergize or otherwise desirably affect the properties of the systems for ~heir present use.
Anyone skilled in the art will have other modifications occur to him based on the teachings of the present invention.
These modifications are intended to be encompassed within the scope of this invention.
.. . . . .. . . ... . . . .
19.5~ 2.2410.42 23.35 .98 .010 20.0K 2.178.71 18.90 1.05 .010 2a.5K 2.2710.42 23.35 .98 .010 21~ OK 1.59lD.93 17.38 .86 .010 21.5K 2.117.89 16.66 1.04 .010 22.OK 2.028.40 16.97 1.04 .010 22.5K 2 .139. 36 19.93 .94` .010 23. OK 1. 828.45 15.36 .82 - .010 24.OK 1.549.58 14.76 .54 .010 25.OK 1.6110.26 16.51 .94 .010 26.OK 1.727.91 13.61 .92 .010 Structurally the Solvent Yellow 29 yellow colorants satisfying the following formula: --C6Hll C6Hll .
differ from the diarylide yellow colorants listed in the Colour ::
Index as C. I. 21090 Pigment Yellow 12 and disclosed in Canadian Patent No. 986~767~ issued April 6~ 1976~ Warren E.
Solodar, satisfying the formula:
~741~6 IH3 l H3 COH Cl Cl HOC
~MEI-OC~C--N=~N=~--C-CO ~
and from the benzidine yellow colorants as disclosed by Bartoszewicz et al listed in the Colour Index as C.I. 21095 Pigment Yellow 14 and satisfying the following formula:
c~3 CH3 CH3 1 0H C1 C1 C_OH H3C
~lHOC- ~ _ I_CO~I~
Any suitable resin material may be used for the toner compositions of the present invention. As previously stated, substantially transparent resins are preferred when the toner is to be used in a three color electrophotographic system. Although any substantially transparent resin material may be utilized as the resin component of this toner, it is preferable that resins having other desirable properties be utilized in this invention. Thus, for example, it is desirable that a resin be used which is a non-tacky solid at room temperature so as to facilitate handling and use in the most common electrophotographic processes. Thermal plastics are Idesirable with melting points significantly above room temperature, but below that of which ordinary paper tends to char so that once the toner images form ~ ~ 7 ~ ~ 6 thereon or transfer to a paper copy sheet it may be employed and fixed to paper copy sheets by other techniques, such as, subjecting the paper copy sheet bearing the powder image to vapors of a solvent for the resin as generally described in U. S. Patent 2,776,907. The resins selected should desirably have good triboelectric properties and have sufficient insulating properties to hold charge so that they may be employed in a number of development systems.
While any suitable transparent resin possessing the properties as above described may be employed in the system of the present invention, particularly good results are obtained with the use o~ vinyl resins and polymeric esterification products of a dicarboxylic acid and a diol comprising a diphenol. Any suitable vinyl resin may be employed in the toners of the present system including homo-polymers or copolymers of two or more vinyl monomers.
Typical such vinyl monomeric units include: styrene;
p-chlorostyrene; vinyl naphthalene; ethylenically unsaturated mono-olefins such as ethylene, propylene, butyIene, isobutylene and the like; vinyl esters such as vinyl chloride, vinyl bromide, ~inyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and the like; esters of alphamethylane aliphatic monocarboxylic acids such as methyl acrylate, ethyl acrylate, n-butylacrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl-alpha~chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like; acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl isobutyl .. ,. . . ~ .
74~6 ether, vinyl ethyl ether, and the like; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and the like; vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride and the like; and N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene and the like; and mixtures thereof.
It is generally found that toner resins containing a relatively high percentage of styrene are preferred since greater image definition and density is obtained with their use. The styrene resin employed may be a homopolymer of styrene or styrene homologs or copolymers of styrene with other monomeric groups containing a single methylene group attached to a carbon atom by a double bond. Any of the above typical monomeric units may be copolymerized with styrene by addition polymerization. Styrene resins may also be formed by the polymerization of mixtures of two or more unsaturated monomeric materials with a styrene monomer.
The addition polymerization technique employed embraces known polymerization techniques such as free radical, anionic and cationic polymerization processes. Any of these vinyl resins may he blended with one or more other resins if desired, preferably other vinyl resins which insure good t:riboelectric stability and uniform resistance against physi.cal degradation. However, non-vinyl type thermoplastic: resins may also be employed including rosin modified phenol formaldehyde resins, oil modified epoxy resins, polyurethane resins, cellulosic resins, polyether resins and mixtures thereof.
~IL074~6 Polymeric esterification products of a dicarboxylic acid and a diol comprising a diphenol may also be used as a preferred resin material for the toner compositions of the instant invention. The diphenol reactant has the general ormula:
X X' H(OR')n10 ~ R ~ O(OR")n2H
wharein R represents substituted and unsubstituted alkylene radicals having from 2 to 12 carbon atoms, alkylidene radicals having from 1 to 12 carbon atoms and cycloalkylidene radicals having from 3 to 12 carbon atoms; R' and R" represent substi-tuted and unsubstituted alkylene radicals having from 2 to 12 carbon atoms, alkylene arylene radicals having from 8 to 12 carbon atoms, and arylene radicals; X and X' represent hydrogen or an alkyl radical having from 1 to 4 carbon atoms;
and nl and n2 are each at least 1 and the average sum of n and n2 is less than 21. Diphenols wherein R represents an alkylidene radical having from 2 to 4 carbon atoms are preferred because greater blocking resistance; increased definition of xerographic characters and more complete transfer of toner images are achieved. Optimum results are obtained with diols in which R' is an isopropylidene radical and R' and R'l are selected from the group consisting of propylene and butylene radicals because tha resins formed from these diols possess higher agglomeration resistance and penetrate extremely rapidly into paper receiving sheets under fusing conditions.
Dicarboxylic acids having from 3 to 5 carbon atoms are ~L~74~66 preferred because the resulting toner resin possesses greater resistance to film formation on reusable imaging surfaces and resist the formation of fines under machine operation conditions~ Optimum results are obtained with alpha unsaturated dicarboxylic acids including fumaric acid, maleic acid or maleic acid anhydride because maximum resistance to physical degradation of the tonar as well as rapid melting properties are achieved. Any suitable-diphenol which satisfies the above formula may be employed.
Typical such dipenols include: 2,2-bis(4-beta hydroxyl ethoxy phenyl)-propane, 2,2-bis(4-hydroxy isopropoxy phenyl) propane, 2,2-bis(4-beta hydroxy ethoxy phenyl) pentane, 2,2-bis(4-beta hydroxy ethoxy phenyl)-butane, 2,2-bis(4-hydroxy-propoxy-phenyl)-propane, 2,2-bis(4-hydroxy -propoxy-phenyl) propane, 1,1-bis(4-hydroxyl-ethoxy-phenyl) -butane, 1,1-bis(4-hydroxyl isopropoxy-phenyl) heptane, 2,2-bis~3-methyl-4-beta-hydroxy ethoxy-phenyl) propane, 1,1-bis(4-beta hydroxy ethoxy phenyl)-cyclohexane, 2,2'-bis ~4-beta hydroxy ethoxy phenyl)-norbornane, 2,2'-bis(4-beta hydroxy ethoxy phenyl) norbornane, 2,2-bis(4-beta hydroxy styryl oxyphenyl) propane, the polyoxyethylene ether of isopropylidene diphenol in which both phenolic hydroxyl groups are oxyethylated and the average number of oxy~thylene groups per mole is 2.6, the polyoxypropylene ether of 2-butylidene cliphenol in which both the phenolic hydroxy groups are oxyalkylated and the average number of oxypropylene groups per mo]e is 2.5, and the like. Diphenols wherein R represents zm alkylidene radical having from 2 to 4 carbon atoms and R' and R" represent an alkylene radical ~ 7~6~
having from 3 to 4 carbon atoms are preferred because greater blocking resistance, increased deinition of xerographic characters and more complete transfer of toner images are achieved. Optimum xesults are obtained with diols in which R is isopropylidene and R' and R" are selected from the group consisting of propylene and butylene because the resins formed from these diols possess higher agglomeration resistance and penetrate extremely rapidly into paper receiving sheets under fusing conditions.
Any suitable dicarboxylic acid may be reacted wi~h a diol as described above to form the toner compositions of this invention either substituted or unsubstituted, saturated or unsaturated~ having the general formula:
HOOC R~n COOH
wherein R''`' represents a substituted or unsubstituted alkylene radical having from 1 to 12 carbon atoms, arylene radicals or alkylene arylene radicals having from 10 to 12 carbon atoms and n3 is lass than 2. Typical such dicarboxylic acids including their existing anhydrides are: oxalic acid, malonic acid, succinic acid, glutaric acid~ adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, mesaconic acid, homophthalic acid, isophthalic acid, terephthalic acid, o-phenyleneacetic-beta-propionic acid, itaconic acid, maleic acid, maleic acid anhydride, fumaric acid, phthalic acid anhydride, traumatic acid, citraconic acid, and the like. Dicarboxylic acids having from 3 to 5 carbon atoms are preferred because the resulting toner resins possess greater resistance to film formation ~74~ 6 on reusable imaging surfaces and resist the formation o~
fines under machine operation conditions. Optimum results are obtained wit~ alpha unsaturated dicarboxylic acids including fumaric acid, maleic acid, or maleic acid anhydride because maximum resistance to physical degradation of the toner as well as rapid melting propexties are achieved. The polymerization esterification ]products may themselves be copolymerized or blended with one or more other thermoplastic resins, preferably aromatic resins, aliphatic resins, or mixtures thereof. Typical thermoplastic resins include rosin modified phenol formaldehyde resins, oil modified epoxy resins, polycarbonate, polysulfone, polyphenylene oxide, polyurethane resins, cellulosic resins, vinyl type resins and mixtures thereof. When the resin component of the toner contains an added resin, the added component should be present in an amount less than about 50 percent by weight ba3ed on the total weight of the resin present in the toner. A relatively high percentage of the polymeric diol and dicarboxylic acid condensation product in the resinous component of the toner is preferred because a greater reduction o fusing temperatures is achieved with a given quantity of additive material. Further, sharper images and denser images ar~ obtained when a high percentage of the polymeric diol and dicarboxylic acid condensation product is present in the toner. Any suitable blending technique such as hot melt, solvent, and emulsion techniques may be employed to incorporate the added resin into the toner mixture. The resulting resin blend is substantially homogeneous and highly compatible with pigments and dyes~
Where suitable, the colorant may be added prior to, ~7~66 simultaneously with or subsequent to the blending or polymerization step.
Preferred electrophotographic results with the Solvent Yellow 29 colorant of the instant invention are achieved with styrene-butyl methacrylate copolymers, styrene-vinyl-toluene copolymers, styrene-ac:rylate copolymers, polystyrane resins, predominantly sty.rene or polystyrene based resins as generally described in U. S. Reissue Patent 25,136 to Carlson, and polys~yrene blends as described in U. S. Patent 2,788,288 to Rheinfrank and Jones~ Optimum results are achieved with the Yellow 29 of the instant invention and styrene-n-butylmethacrylate copolymer resins to form a toner of long life and low impaction.
Any well known toner mixing and comminution technique may be employed to provide the toner compositions of the instant invention. For example, the ingredients may be thoroughly mixed by blending, ex rusion and milling and thereaft~r micropulverized. In addition, spray drying a suspension of tha ingreaients, a hot melt or a solution of the toner composition may also be employed.
The toners of the invention may be any size which will result in a satisfactorily developed image, Toners of the invention suitable for use with a carrier in cascade or magnetic aevelopment generally have an average particle size of about 5 microns to about 45 microns. A preferred average particle size range is about 10 microns to about 19 microns to result in a print of maximum density.
Where carrier materials are employed in connection with the toner compositions of the instant invention in cascade and magnatic brush development, the carrier particles employed may be electrically conductive, insulating, magnetic .. . . . .. .
~ ~74~66 or non-magnetic, as long as the carrier particles are capable of triboelectrically obtaining a charge of opposite polarity to that of the toner particles so that the toner particles adhere to and surround the carrier particles. In developing a positive reproduction of an lelectrostatic imaga, the carrier particle is selected so that the toner particles acquire a charge having a polarity opposite to that of the electrostatic latent image so that toner deposition occurs in image areas.
Alternatively, in reversal reproduction of an electrostatic latent image, the carriers are selected so that the toner particles ac~uire a charge having the same polarity as that of the electrostatic latent image resulting in toner deposition in the non-image are~s. Typical carrier materials include:
sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, potassium chlorate, granular zircon, granular silicon, methyl methacrylate, glass, steel, nickel, iron, ferrites, ferro-magnetic materials, silicon dioxide and the like. The carriers may be employed with or without a coating. Many of the foregoing and typical carriers are described by L. E. Walkup in U. S. Patent 2l618,551; L. ~. Walkup et al in U. S. Patent 2 r 638,416; E. N. Wise in U. S. Patent 2,618,552; R. H. Hagenbach et al in U. S. Patent 3,591,503 and 3,533,835 directed to electrically conductive carrier coatings, and B. J. Jacknow et al in U. S. Patent 3,526,533 directed to polymer coated carriers and nodular carriers having pe~bled surface as disclosed in Serial No. 357,988, filed May 7, 1973, now U. SO Patent 3,847,604, a divisional of Serial No. 151,995, filed June 10, 1971, now U. S. Patent -~L~74~6~
3,767,568. An ultimate coated carrier particle diameter between about 50 microns to about 1,000 microns is suitable because the carrier particles 1:hen possess sufficient density and inertia to avoid adherence to the electrostatic images during the cascade development process. A preferred particle size is between about 75 and 4()0 microns. Optimum performance with the toner of the instant invention is about 100 microns for best density images and long life. The carrier may be employed with the toner composition in any suitable combination, generally satisfactory results have been obtained when about 1 part toner is used with about 10 to about 200 parts by weight of carrier.
Preferrad carriers or use with toner compositions of the instant invention are th-ose of nickel berry and terpol~ner coated steal. Nickel berry carriers are a mem~er of a group of nodular carrier beads disclosed in U. S. Patents 3,847,604 and 3,767,568, characterized by a pebbled sur~ace with recurring recesses and protrusions giving the particles a relati~ely large external surface area and composed of nickel.
Such nodular carrier beads have high surface-to-mass ratio as compared with substantially smooth-surfaced carriar beads o~ the same mass. Using the nodular carrier materials, one can obtain the benefits o both large and small carrier beads while avoiding their shortcomings. Nodular carrier particles present a plurality of small spherical surfaces with recesses defining pochets for toner particles.
The nodular carrier beads are three dimensional solids approximately 50 to 1,000 microns in size of roughly berry, cuboid,al, rounded, irregular or spheroidal shape, and with surface irregularities formed by numerous nodules and .
1~7~:~L66 recesses. Though the beads may have randomly spaced voids or a slight d~gree of porosi~y, they should have predominantly solid cores. Preferred carrier beads have generally rounded nodules and are generally sphe:roidal in shape thus giving an appearance reminiscent of a raspberry or cluster of grapes.
Terpolymer carriers '~re disclosed in U. S. Patent 3,526,533. The terpolymer carriers comprise a core coated with a composition which is formed from the addition polymerization reaction between monomers or prepolymers of styrene, methylmethacrylate and unsaturated organo silanes, silanols or siloxanes having from 1 to 3 hydrolyzable groups and an organic group attached directly to the silicon atom containing an unsaturated carbon to carbon linkage capable of addition polymerization. Optimum with the toner of the instant invention is~a steel carrier core coated with the composition of Example XIII of U. S. Patent 3,526,533 to form a methyl terpolymar carrier which provides a developer composition which results in good density coverage and long life~
The electrostatic latent images developed by the toner compositions of the instant invention may reside on any surface capable of retaining charge. In electrophoto-graphic applications a photoconducti~e m mber is employed to form the electrostatic lat~nt Lmage. The photoconductive layer may comprise an inorganic or an organic photoconductive matPrial. Typical inorganic materials include: sulur, selenium, zinc sulfide, zinc oxidet zinc cadmium sulide, zinc magnesium oxide, cadmium selenide, zinc silicate, calcium strontium sulfide, cadmium ~ulfide, mercuric iodide, mercuric oxide, mercuric sulfide, indium trisulfide, gallium selenide, arsenic disulfide, arsenic trisulfide, arsenic ,: . .
~7~166 triselenide, antomony trisulfide, cadmium sulfoselenide and mixtures thereof. Typical organic photoconductors include:
triphenylamine; 2,4-bis(4,4'-diethylamino-phenol)-1,3,4 -oxidiazol; N-isopropylcarbazole; triphenylpyrrol; 4,5 -diphenylimidazolidione; 4,5-diphenylimidazolidinethione;
4,5-bis-(4l-amino-phenyl)-imidazolidinone; 1,5-dicyanonaphthalene;
l,~-dicyanonaphthalene; aminophtha]Lodinitrile; nitrophthalo-dinitrile; 1,2,5,6-tetraazacyclooctatetraene-(2,4,6,8);
2-mercaptobenzothiazole-2-phenyl-4-diphenylidene-oxazolone;
6-hydroxy-2,3-di(p-methoxy-phenyl)-benzofurane; 4-dimethylamino -benzylidene-benzhydrazide; 3,benzylidene-amino-car~azole;
polyvinyl carbazole; (2-nitro-benzylidene)-p-bromo-aniline;
2,4-diphenyl-quinazoline; 1,2,4-triazine; 1,5-diphenyl-3 -methyl-pyra~oline 2-(~'-dimethyI-amino phenyl)-benzoxazole;
3-amino-carbazole; polyvinylcarbazole-trinitro-Eluorenone charge transfer complex; phthalocyanines and mixtures thereof.
The toner of the instant invention is particularly suitàble for use as in the yellow toner in the color electro-photographic imaging processes disclosed in U. S. Patent 3t804,619 and U. 5. Patent 3,909,259, issued September 30, 1975, Joseph Mammino et al. The process disclosed in the ~ -above-referenced patent specifications are multiple develop-ment techniques capable of producing color reproductions employ-ing multiple sequencing of electrophotographic charging, exposing through ~Eilters and developing steps with three different color toners. The toners of magenta, cyan and yellow colors are developed after exposure through green, red and blue filters, respectively.
~7416~
In development and transfer of the three colored toner images, it is necessary that the relationship of the toners with each be such that they cooperate to produce an image of good quality. It is apparent ~hat any one of a number of variables could cause incomplete J improper, or inadequate development so that color balance is thereby shifted resulting in an unaccep1:able color print.
A use of the toners oi. the instant invention is for a sequential three color development proces~ when combined with a methyl terpolymer coated steel carrier and utilized in combination with a copper phthalocyanine pigment identified in the Colour Index as C.I. 74160, C.I. Pigment Blue lS cyan toner and a mathyl terpolymer coated steel carrier and anthraquinone dye identified in the Colour Index as C.I.
607lO, C.I. Disperse Red 15 magenta toner and a nickel berry carrier.
The toners of the instant invention have been found to be optimum for a sequential three color development process when combined with a methyl terpolymer coated s~eel carrier and utilized in combination with a copper tetra-4-(octadecylsulfonamido~ phthalocyanine pigment available from GAF Corporation under the designation of Sudan Blue OS, cyan toner and a methyl terpolymer coated steel carrier; and 2,~-dimethylquinacridone identified in the Colour Index as C.I. Pigment Red 1?2, magenta toner and a nickel berry carrier.
A sequential color electrophotographic process is performed by charging a photoconductive member, exposing said photoconductive~ member to an original to be reproduced through a filter of one! color thereby selectively discharging said photoconductive! member, developing the electrostatic image -2~-- ~ :
7~ 6 formed thereby with a developer of a complementary color, said developer being one member of the group consisting of copper t~tra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpol~mer coated steel carrier;
Colour Index Pigment Red 122, magenta toner and a nickel berry carrier; the toner of the instant invention and a methyl terpolymer coated steel carrier; charging said photoconductor for a second time and selectively expo~ing said photoconductor to the same image through a filter of another primary color, developing the latent electrostatic image formed thereby with a developer of a complementary color, said developer being another member selected from the group consisting of copper tetra-4-(octadecylsulfonamido~
phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; Colour Index Pigment Red 122, magenta toner and a nickel berry carrier; and the toner of the instant invention and a methyl terpolymer coated steel carrier; charging said photoconductive member for a third time, exposing said photoconductor to the same image through a filter of the remaining primary color and developing the latent electrostatic image with a complementary developer~
said developer bsing ~he remaining developer of the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; Colour Index Pigment Red 122, magenta toner and a nickel berry carrier; and the yellow toner of the instant invention and a methyl terpolymer coated steel carrier.
The preferred order of development and method formation of the magenta and cyan toners is as disclosed ~74166 in Example I of aforementioned U. S. Patent No. 3,909,259.
However, any sequence of development of the cyan, magenta and yellow toners may be used to produce satisfactory prints.
To further define the specifics of the present invention, the following examples are intended to illustrate and not limit the particulars of the present system. Parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
A styrene-n-butylmethacrylate copolymeric resin is employed with Colour Index Solvent Yellow 29 colorant so that the colorant comprises three percent of the toner composition by weight. The mixture is blended in a drum tumbler for about an hour at about 10 rpm. The material is then poured into a screw feeder and extruded until machine equilibrium is established. The extruded strands are taken up at the rate of about 50 feet per minute and cooled in a water bath at about 120F followed by forced air drying.
The strands are then cut by a knife device to make pellets having a diameter in the range of from 1/16 to 1/8 of an inch. These pellets are then jetted to about 15 microns average particle size. This toner is then combined with a methyl terpolymer coated steel carrier as before described, to provide an electrostatographic developer. The developer thus produced is employed in an automatic imaging device, a Xerox Model 720 copier, having a magnetic brush develop-ment system. The selenium photoconductor is charged, selectively exposeld, and developed with the yellow developer.
After 25,000 prints are obtained, images continue to be produced which possess good contrast, high image density 3L~7~66 and a desirable appearance. The tribo of ~he developer continues to maintain a high level similar to that as obtained in Table I.
EXAMPLE II
.
The process as outlined in Example I is again employed with the exception that 5 p~rcent dye concentration is employed.
EXAMPLE III
The process as outlined in Example I is again employed with the exception that a 7 percent dye loading is employed.
E~MPhE IV
._ The process as outlined in Example I is again employed with the exception that a styrene resin is employed.
- EXAMPLE V
.
The process as outlined in Example I is again parformed with the exception that the nodular nickel carrier having a pebbled surface commonly referred to as ~ickel berry is ~mployed as described in the above-re~erenced U. S. Patentc 3,847,604 and 3,767,568.
EXA~ær~ VI
The process as described in Example I is a~ain performed with the exceptiQn that the yellow developer obtained is applied to a mylar transparent substrate to produce a yellow imaged transparency.
EXAMPLE VII
.
A yellow developer as produced in Example I is substituted for the yellow developer employed in trichromatic tr~er~ ~r~
-2~-. ' . . ' , : .
- , . ~ .. . . . . ..
; . .
. ~ . . .. ... . . . .. . . . . .
~C~7~16~
electrophotographic imaging process as described in Example I of U. S. Patent 3,804,619.
EXAMPLE VIII
A yellow developer as produced in ~xample V is substituted for the yellow developer employed in trichromatic electrophotographic imaging process as described in Example I
-of aforementioned U. S. Patent No. 3,909,259.
Although the present examples were specific in terms of conditions and materials used, any o~ the above listed typical materials may be substituted when suitable in the above examples with similar results. In addition to -the steps used to carry out the process of the present invention, other steps or modifications may be used if desirable. In addition, other materials may be incorporated in the system of the present invention which will enhance, synergize or otherwise desirably affect the properties of the systems for ~heir present use.
Anyone skilled in the art will have other modifications occur to him based on the teachings of the present invention.
These modifications are intended to be encompassed within the scope of this invention.
.. . . . .. . . ... . . . .
Claims (16)
1. An electrostatographic material for developing electrostatic latent images comprising a resin material and a colorant, said colorant satisfying the formula:
2. The material of Claim 1 wherein said resin is a member selected from the group consisting of styrene-butylmethacrylate copolymers, styrene-vinyltoluene copolymers, styrene-acrylate copolymers, and polystyrene resins.
3. The material as defined in Claim 1 wherein said resin is substantially transparent.
4. The material as defined in Claim 1 wherein said resin comprises a polymeric esterification product of a dicarboxylic acid and a diol comprising a diphenol.
5. The material as defined in Claim 1 wherein said resin is a styrene-n-butylmethacrylate copolymer.
6. The material as defined in Claim 1 further comprising a carrier.
7. The material as defined in Claim 6 wherein about 1 part of said material is present for about 10 to about 200 parts by weight of said carrier.
8. An electrostatographic imaging process comprising establishing an electrostatic latent image on a surface and contacting said surface with an electrostato-graphic material comprising a resin material and a colorant, said colorant satisfying the formula:
9. The imaging process as defined in Claim 8 further including the steps of transferring said developed image to a receiving surface and fixing said image on said receiving surface.
10. The material as defined in Claim 6 wherein said carrier is a methyl terpolymer coated steel carrier
11. The process as defined in Claim 8 wherein said electrostatographic material further includes a methyl terpolymer coated steel carrier.
12. The material as defined in Claim 6 wherein said carrier is a nickel berry carrier.
13. A color electrophotographic imaging process comprising charging a photoconductive member, exposing said photoconductive member to an original to be reproduced through a filter of one color thereby selectively discharging said photoconductive member, developing the electrostatic image formed thereby with a developer of a complementary color, said developer being one member of the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier;
2,9-dimethylquinacridone identified in the Colour Index as C.I. Pigment Red 122, magneta toner and a nickel berry carrier;
azo dye C.I. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductor for a second time and selectively exposing said photoconductor to the same image through a filter of another primary color, developing the latent electrostatic image formed thereby with a developer of a complementary color, said developer being another member selected from the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier;
2,9-dimethylquinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductive member for a third time, exposing said photoconductive to the same image through a filter of the remaining primary color and developing the latent electrostatic image with a complementary developer, said developer being the remaining developer of the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethylquinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier.
2,9-dimethylquinacridone identified in the Colour Index as C.I. Pigment Red 122, magneta toner and a nickel berry carrier;
azo dye C.I. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductor for a second time and selectively exposing said photoconductor to the same image through a filter of another primary color, developing the latent electrostatic image formed thereby with a developer of a complementary color, said developer being another member selected from the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier;
2,9-dimethylquinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier; charging said photoconductive member for a third time, exposing said photoconductive to the same image through a filter of the remaining primary color and developing the latent electrostatic image with a complementary developer, said developer being the remaining developer of the group consisting of copper tetra-4-(octadecylsulfonamido) phthalocyanine pigment, cyan toner and a methyl terpolymer coated steel carrier; 2,9-dimethylquinacridone identified in the Colour Index as Pigment Red 122, magenta toner and a nickel berry carrier; and azo dye C.I. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel carrier.
14. The method of Claim 13 wherein the magenta toner is anthraquinone dye identified in the Colour Index as C.I. 60710, C.I. Disperse Red 15 .
15. The method of Claim 13 wherein the cyan toner is copper phthalocyanine pigment identified in the Colour Index as C.I. 74160, C.I. Pigment Blue 15.
16. The method of Claim 13 wherein the magenta toner is anthraquinone dye identified in the Colour Index as C.I. 60710, C.I. Disperse Red 15 and the cyan toner is copper phthalocyanine pigment identified in the Colour Index as C.I. 74160, C.I. Pigment Blue 15.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59980875A | 1975-07-28 | 1975-07-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1074166A true CA1074166A (en) | 1980-03-25 |
Family
ID=24401180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,564A Expired CA1074166A (en) | 1975-07-28 | 1976-05-28 | Developer containing a resin and diazo colorant c-1-solvent yellow 29 |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5217024A (en) |
| BR (1) | BR7604781A (en) |
| CA (1) | CA1074166A (en) |
| DE (1) | DE2629471A1 (en) |
| ES (1) | ES450107A1 (en) |
| FR (1) | FR2319928A1 (en) |
| GB (1) | GB1557213A (en) |
| IT (1) | IT1064725B (en) |
| NL (1) | NL7608408A (en) |
| SU (1) | SU691110A3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1118483A (en) * | 1977-05-17 | 1982-02-16 | Toshihiro Kouchi | Developer for electrostatic images and process for preparation thereof |
| JPS57130043A (en) * | 1981-02-06 | 1982-08-12 | Canon Inc | Yellow toner |
| JPH0673026B2 (en) * | 1985-09-30 | 1994-09-14 | 三田工業株式会社 | Color Toner |
-
1976
- 1976-05-28 CA CA253,564A patent/CA1074166A/en not_active Expired
- 1976-06-17 SU SU762373663A patent/SU691110A3/en active
- 1976-06-30 DE DE19762629471 patent/DE2629471A1/en not_active Withdrawn
- 1976-07-21 JP JP51087112A patent/JPS5217024A/en active Pending
- 1976-07-23 GB GB3082376A patent/GB1557213A/en not_active Expired
- 1976-07-23 BR BR7604781A patent/BR7604781A/en unknown
- 1976-07-23 ES ES450107A patent/ES450107A1/en not_active Expired
- 1976-07-27 IT IT2575976A patent/IT1064725B/en active
- 1976-07-28 FR FR7623065A patent/FR2319928A1/en active Granted
- 1976-07-28 NL NL7608408A patent/NL7608408A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2319928B1 (en) | 1979-07-20 |
| FR2319928A1 (en) | 1977-02-25 |
| ES450107A1 (en) | 1977-11-16 |
| SU691110A3 (en) | 1979-10-05 |
| BR7604781A (en) | 1977-08-02 |
| NL7608408A (en) | 1977-02-01 |
| DE2629471A1 (en) | 1977-02-24 |
| JPS5217024A (en) | 1977-02-08 |
| IT1064725B (en) | 1985-02-25 |
| GB1557213A (en) | 1979-12-05 |
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