DE2629471A1 - ELECTROSTATOGRAPHIC MATERIAL FOR THE DEVELOPMENT OF ELECTROSTATIC LATENTER IMAGES - Google Patents

Description

28 048 n / a7a

XEROX CORPORATION, ROCHESTER, N.Y./ USA

Electrostatographic material for development electrostatic latent images

The invention relates to an electrostatographic material for developing electrostatic latent images and in particular improved xerographic. developer materials, their Manufacture and use.

Electrostatography, i.e. the branch of imaging technology, focusing on the formation and use of latent electrostatic

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Charge pattern for recording and reproducing patterns in a more visible way Form is well known. When a photoconductor is used Formation of these electrostatic latent images by first charging and then selective exposure of the photoconductive ones Layer is used, this mapping method is used referred to as electrophotography, or is commonly known as xerography, its basic techniques in the ÜS-PS 2 297 691 have been described. The resulting latent electrostatic images can be made visible by developing a finely divided one electroscopic material called toner. The resulting image can be viewed in a variety of ways be applied or further treated by wise men, for example the image can be melted or fixed in place or transferred and then fixed on a second surface.

The El

Electrography, the other broad general branch of digital statography, is generally divided into two major sections which are known as xeroprinting and electrographic or TESI recording. There won't be any photo-reactive medium is used, the charging and selective discharge of which results in a latent electrostatic image. That Xeroprinting, the electrostatic analog of ordinary printing, is more fully described in U.S. Patent 2,576,047 (Schaffert) described. TESI imaging or electrostatic transfer Images are described in greater detail in U.S. Patent No. 2,285,814, which involves the formation of an electrostatic charge pattern corresponding to a desired reproduction on a uniform insulating layer by means of an electrical discharge between two or more electrodes on opposite one another Includes sides of the insulating medium. The lines of force

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generated by the electrostatic latent image are used to control the deposition of the toner material to form an image. Various developers, both powders and liquids, and development systems are known, including the cascade development described in US Pat. No. 2,618,552 (EN Wise), US Pat. Magnetic brush development generally described in US Pat. No. 2,874,063, the powder cloud development generally described in US Pat. No. 2,784,10? the so-called "touchdown" development _i , which is described in US Pat. No. 3,166,432, and the liquid development which is described in US Pat. No. 2,877,133, inter alia. Although they are widely used for black-and-white reproduction, these developer systems can also be used in other colors and color combinations, e.g. a trichromatic color system of either the additive or subtractive color formation type = in full color systems at least three different colors must be used, to synthesize any other desired color, which generally results in the formation of at least three color deposition images and their combination upon deposition: .... _: . drawing together to form a color reproduction of the original. Therefore, in each of the electrostatographic recording systems sumiadest, three different electrostatic latent images must be formed, developed with different color toners, and combined to form the final image. For example, in color xerography, an electrostatic latent image resulting from the development of a first primary color can be formed on the photoconductive layer and developed with a toner that is complementary to the primary color. Similarly, subsequent developments of electrostatic latent images corresponding to the primary colors can be complementary with

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• Toner materials are reached. If by color separation negatives is exposed, the toner delivers the complement. the negative radiation represent.

Z "find. A three-color Eiektrofctografiesystem in which übereinanderiiegende color images using, it is necessary that the Tonermateriaiien except, are fairly transparent underlying hereunder as not to obscure the differently colored. Toner images" and that each toner sina sufficient color saturation simultaneously as well as luster or color intensity, - "in the colorimetric requirements of the three-color synthesis of natural Fsr ^ -. Ider su: i. It is understandable, that these requirements stand in complete opposition to each other and further This complicates the additional requirement that if all Co: isr i-iciübinated _p these must result in a deep black-3sn ₌ It is stated wordsn _f that for the production of deep black parben in a color system it is necessary four different color images are superimposed including a soh'jcLXz recorded image (black registered) ο additional problems S2: GSL: s in allgeiu ^ inen i- erra inorganic Pigrusnte a.ls coloring either be used in printing inks or electrophotographic toners because it is difficult to achieve an appropriate Farbbalsno3 and saturation below, while the colors are kept transparent? . If inorganic pigments are used ₀ the range of available colors is relatively narrow and it has been found that these pigments materials ^ which they are added, even when using relatively small amounts of an opacity "erleihen.

Bartoszewicz et el has colored in the ÜS-PS 3,345,293

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electrophotographic toner materials comprising substantially transparent resin particles which are organic Contains color pigments. It has been stated that their use over 'known materials thereby It is advantageous that they are more resistant to color bleeding after the toner has melted and they are more specific They are adaptable for use in three-color electrophotographic processes, as their colors are yellow, cyan, magenta and their mixtures give blue, red and green in pairs, while the three toners together produce black, independently However, there are still related disadvantages of the obvious advantages of the toners according to Bartoszewicz et al with these specific toners, especially in the case of yellow toners when they are in an automatic, electrophotographic Find device use. The yellow dye as suggested by Bartoszewicz et al exists essentially from about 0. -92 to about 1.08 parts by weight of 3,3'-dichloro, 4'-bis (2 "- acetyl-2" - azo-o-acetotoluidide) -biphenyl per 10 parts by weight of a substantially transparent resin. The problem with using this colorant is its inability to disperse substantially uniformly in the transparent resin materials. split up and even more evident in the undesirable triboelectric properties that result from its use, the low con-. , trastes and a short service life of the devices to lead. It has been found that the triboelectrics Properties of the resulting toner material under the conditions in which the toner is subject to mechanical abrasion, high Temperatures and high environmental humidity conditions, all common in electrophotographic

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Devices are present, are not maintained. this leads to a variety of problems including poor transfer from the drum surface to the copy sheet as well as maintaining the cleanliness of the drum. In particular, it has been determined that when using In electrophotographic devices, this toner impacts its carrier, thereby making the already present undesirable triboelectric relationship worsens further and thereby adversely affects the operation of the device will.

The invention has for its object to provide a yellow toner material by means of which the above-mentioned Disadvantages are overcome.

Another object of the invention is to provide a yellow coloring agent which can be used in combination with a resin material can be used as a toner for use in color imaging.

The invention is further directed to providing a novel electrostatographic yellow toner.

Another object of the invention is to provide a novel transparent yellow toner.

The invention is also based on the object to provide a new transparent yellow toner that is in a trichromatic Color synthesis of either additive or subtractive color formation type can be used.

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Another object of the invention is to provide a novel electrophotographic developer.

Another object of the invention is to provide a new yellow toner material that is superior to triboelectric Has characteristics and enables superior reproduction and long device operation.

Another object of the invention is to provide of a new yellow toner / in which the yellow colorant is distributed substantially uniformly in a resin material.

The invention is based on the further object of providing a yellow To create toner, its triboelectric properties under the conditions of continuous use in a automatic electrophotographic imaging device be maintained.

Another object of the invention is to provide of a novel yellow toner that is easily and conveniently transferred from a drum surface onto a copy sheet can be completely transferred.

Another object of the invention is to provide a relatively pure yellow toner with desirable shading or coloring and hue.

Another object of the invention is to provide one transparent toner for transparency use.

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Finally, the invention is to provide an electrophotographic Method directed using a new yellow toner.

These and other tasks are, generally speaking, carried out the provision of a new yellow toner comprising a yellow colorant and a resin material or materials comprises, wherein the colorant is a compound which satisfies the following formula:

CH

N = N

-N = N

This dye, which is in the color index under C, I. Solvent Yellow 29, CI. 21230 is classified with a suitable electrophotographic resin such as a styrene-n-butyl methacrylate resin with the formation of a toner and then with a conventional carrier, for example methyl terpolymer coated steel beam creating a very desirable yellow developer for use in the Color electrophotography combined. These are hereinafter referred to as Solvent Yellow 29 developers and Yellow 29 toners and differ significantly from or are superior to those yellow colorants which Bartoszewicz et al and other conventional yellow developers,

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there. has been found to be transparent while other known colorants are opaque. Unlike other yellow developers, these developers are light dispersible and have desirable solubility properties in electrostatographic resins. The most prominent However, property of these developers represents their superior triboelectric property, or "tribo", which it allows these developers to be used with great success in electrophotographic development applications. at Application to an automatic electrophotographic imaging apparatus using developers found that the device has a tendency to impact the toner and the carrier with both known yellows Dyes as well as the Solvent Yellow 29 dye having; however, in the case of the known yellow colorants, the triboelectric property deteriorates experiences and thus device operation is adversely affected, Solvent Yellow 29 developers their triboelectric properties are maintained and in some cases it has been found that they improve with continued impact resulting in superior device operation or life.

It has been found that with continued use of a benzidine yellow toner, such as that by Bartoszewicz et al, in a conventional automatic electrophotographic imaging apparatus, for example a Xerox 720 copier, gives a device life of 1400 prints under controlled conditions while two applied conventional black toners had lifetimes of 4200 and 9000 prints, while one Solvent Yellow

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29 toner composition has a lifespan of more than 25,000 Printing showed no apparent adverse effects. This therefore demonstrates that the known colorants among Inclusion of the yellow coloring agent according to Bartoszewicz et al, when combined with suitable resins for optimization their respective behavior and when used in the same device under identical conditions in no way withstand comparison in terms of life and operation with the toner compositions according to the invention can. In addition, when used extensively in device testing, conventional black toner materials show a tendency to gradually decrease triboelectrically, until they reach an unacceptable final height at which imaging is difficult / if not impossible. These Steps were not clearly revealed in the studies of the life of the known yellow toners, such as with the yellow toners according to Bartoszewicz et al, since these toners show a steady and extreme decrease in the triboelectric Have characteristics that result in a shortened device life and poor device operation. The Yellow 29 toner compositions show often the same as the diarylite yellow compositions, very stable tribo values within a well-defined range with acceptable copy quality and operating characteristics through a test of over 25,000 prints. Furthermore the amount of impact exhibited by this yellow toner and a developer is considerably smaller than that exhibited by conventionally used black developer is generated over an equivalent trial period. From the following Table, Table I - Developer compositions using Solvent Yellow 29 stains ~ is

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can be seen that using developer compositions of Solvent Yellow 29 dye, at least 25,000 print cycles with acceptable copy quality and development characteristics to achieve. It could not be determined that the impact is a problem so this parameter has not been reflected at all. In addition, Solvent Yellow 29 pigment appears to be highly triboelectric even when used in the manner outlined above To show characteristics that are far superior to those determined according to the state of the art what can be seen in the table below.

Table I.

Example 1 toner

Carrier methyl terpolymer coated steel beads, partial

Toner con Tribo small size 100, u background Prints concentration (%) (, uc / gm) Tribo density average 2.43 /
12.42 product , 010 20% RH start 3.09. 12.22 30.18 1.16 , 010 500 3.09 12.65 37.76 , 92 , 010 1, OK 3.07 12.50 39.72 , 87 , 010 1.5K 2.78 13.42 38.38 , 94 , 010 2, OK 2.81 13.11 37.31 , 93 , 010 2.5K 2.71 14.48 36.83 , 97 , 010 3, OK 2.49 14.64 39.25 , 94 , 010 3.5K 2.51 14.06 36.45 , 89 , 010 4, OK 2.04 15.81 35.66 , 81 , 010 4.5K 2.26 15.12 32.26 , 84 , 010 5, OK 2.37 14.57 34.17 , 84 , 010 5.5K 2.59 13.29 34.53 , 89 , 010 6, OK 2.40 13.98 34.42 , 92 , 010 6.5K 2.53 12.50 33.55 , 82 , 010 7, OK 31.63 1.06

12 -

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Toner con - 12 13.16 Tribo density 2629471 14.66 product 14.83 30.53 1.02 background •
Prints 14 _P 9O 34.46 1.04 average Table I (continued) 13.99 42.56 , 88 , 010 7.5K Tribo 11.54 33.67 , 98 , 010 8.5K centering C / uc / gm) 12.42 31.49 , 92 , 010 9.5Κ 2.32 11.00 23.42 , 85 , 010 10.0Κ 2.35 11.14 25.59 , 93 , 010 11.0Κ 2.87 12 _P 94 21.45 , 85 , 010 12.0Κ 2.26 12.33 24.96 1.34 , 010 13.0Κ 2.25 11.89 27.94 1.01 , 010 13.5Κ 2.03 12.50 25.28 , 92 , 010 14.0Κ 2.06 14.75 23 _r 28 , 84 , 010 1 5, OK 1.95 15.14 28.00 1.11 , 010 16.0Κ 2.24 10.42 30.83 · , 66 , 010 16, 5K 2.21 8.71 31.18 , 72 , 010 17.0Κ 2.05 10.42 23 _r 35 , 98 , 010 18.0Κ 1.97 10.93 18.90 1.05 , 010 19.0Κ 2.24 7.89 23.35 , 98 , 01O 19.5Κ 2.09 8.40 17.38 , 86 , 010 20.0Κ 2.06 9.36 16.66 1.04 , 010 20, 5Κ 2.24 8.45 16.97 1, O4 , 010 21.0Κ 2.17 9.58 19.93 .-, 94 , 010 21.5Κ 2.27 10.26 15.36 , 32 , 010 22, OK 1.59 7.91 14.76 > 54 , 010 22, 5Κ 2.11 16.51 , 94 _r 010 23, OK 2.02 13.61 , 92 , 010 24, OK 2.13 , 010 25, OK 1, 82 , 010 26, OK 1.54 1.61 1, 72

Structurally, the Solvent Yellow 29 yellow coloring agents differ, which satisfy the formula below

N = N

-N = N

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of the diarylide yellow dyes used in the Color Indejj as CI. 21090 Pigment Yellow 12 and in U.S. Patent Application Serial No. 197 943 * filed on November 11, 1971, which satisfy the formula

CH ₃

COH

VV NH • OC • C-N = N

Cl

and from the benzidine yellow stains made by Bartoszewicz et al, listed in the Color Index as CI. 21095 Pigment Yellow 14, and those of the following formula suffice:

C-OH

NHOC-C-N = N

CH ₃

C-OH

Il

\> - N = N-C -CO

H ₃ C

Any suitable one can be used for the toner materials according to the invention Find resin material use. As previously stated substantially transparent resins are preferred when the toner is used in a three-color electrophotographic system.

* now U.S. Patent 3,909,259

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should be used. While any substantially transparent resin material can be used as the resin component of this toner, it is preferred that resins having other desirable properties be used in the invention. Thus, for example, desirable that a resin is used _for representing a non-adhesive or tacky solid at room temperature, in order to facilitate its handling and use in most conventional electrophotographic process. Thermoplastics with melting points well above room temperature, but below the temperature at which ordinary paper tends to char, are desirable, so that when the toner image is formed thereon or transferred to a paper copy sheet, it is drawn on and fixed to paper copy sheets by other techniques can be, like _f, for example by suspending the Papierkopierbiattes carrying the powder image, in vapors of a solvent for the resin, as is generally described in U.S. Patent No. 2,776,907. The resins selected should desirably have good triboelectric properties and sufficient insulating properties to hold charge so that they can be used in a variety of development systems.

While any suitable, transparent resins which have the properties listed above can be used in the system according to the invention, particularly good results are obtained when using vinyl resins and polymeric esterification products of a dicarboxylic acid and a diol comprising a diphenol. Any suitable vinyl resin can be used in the toners of the system of the invention, including homopolymers or copolymers of two or more vinyl monomers

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will. Typical vinyl monomer units of this type include: Styrene; p-chlorostyrene; Vinyl naphthalene; ethylenically unsaturated Mono-olefins, such as ethylene, propylene, butylene, Isobutylene and the like; Vinyl esters, such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, Vinyl benzoate, vinyl butyrate and the like; Esters of ^ -Methylene aliphatic Monocarboxylic acids, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, h-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methylol -chloracrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the same; Acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers, such as vinyl methyl ether, vinyl isobutyl ether, Vinyl ethyl ether and the like; Vinyl ketones such as vinyl methyl ketone, vinyl bexyl ketone, methyl isopropenyl ketone and the same; Vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride and the like; and N-vinyl compounds, such as N-vinylpyrrole, N-vinylcarbazole, N-vinyl indole, N-vinyl pyrrolides, and the like; and their Mixtures.

It has generally been found that toner resins containing a relatively high percentage of styrene are preferred because their application results in a greater definition or sharpness and density of the image. The styrene resin used can be a homopolymer of styrene or styrene homologues or copolymers of styrene with other monomer groups represent containing a single methylene group attached to a carbon atom through a double bond is. Any of the typical monomer units listed above can be added to styrene with styrene be copolymerized. Styrene resins can also be polymerized of mixtures of two or more unsaturated

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Monomer materials are formed with a era styrene monomer. The addition polymerization technique used includes known ones Polymerization techniques, such as free radical, anionic and cationic polymerization processes. Any these vinyl resins can be combined with one or more other resins, if desired, preferably other vinyl resins that have good triboelectric stability and uniform resistance exhibit against physical deterioration, are mixed. However, thermoplastic Resins of the light-vinyl type including camphor-modified ones Phenol-formaldehyde resins, oil-modified epoxy resins, Polyurethane resins, cellulosic resins, polyether resins and mixtures thereof are used =

Dia polymeric esterification products of a dicarboxylic acid and a diol comprising a Diphencl _g may also find use as a preferred Harsraaterial for Tonerzusamxensetzung according to the invention. The diphenol reagent has the general formula;

\
C ^(OR!) N O <A ■-F -.^ / ^N> O (OR '')

where R represents substituted and unsubstituted alkylene radicals with 2 to 12 carbon atoms , alkylidene radicals with 1 to 12 carbon atoms, and cycloalkylidene radicals with 3 to 12 carbon atoms, R ¹ and R ″ represents substituted and unsubstituted alkylene radicals with 2 to 12 carbon atoms,

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Represent alkylene-arylene radicals having 8 to 12 carbon atoms and arylene radicals, X and X ^{1 represent} hydrogen or an alkyl radical having 1 to 4 carbon atoms, and n .. and n "are each at least 1 and the average sum of n .. and n _{2 is} less than 21 amounts to. Diphenols in which R is an alkylidene radical having 2 to 4 carbon atoms are preferred because of their greater blocking resistance, increased definition of xerographic properties, and more complete transfer of the toner images. Optimal results are obtained with diols in which R is an isopropylidene radical and R ¹ and R ¹ 'are selected from propylene and butylene radicals, since resins formed from these diols have higher agglomeration resistance and penetrate extremely quickly into paper receiving sheets under melting conditions. Dicarboxylic acids having 1 to 3 carbon atoms are preferred because the resulting toner resin has greater resistance to film formation on reusable image surfaces and resists the formation of fines under the device operating conditions. Optimal results are obtained with dv-unsaturated dicarboxylic acids including fumaric acid, maleic acid or maleic anhydride, since maximum resistance to physical deterioration of the toner and rapid melting are achieved. Any suitable diphenol satisfying the above formula can be used. Typical diphenols of this type include: 2,2-bis (4-beta-hydroxylethoxy-phenyl) -propane, 2,2-bis (4-hydroxy-isopropoxy-phenyl) -propane, 2,2-bis (4-beta-hydroxyethoxy -phenyl) -pentane, 2,2-bis (4-beta-hydroxyethoxyphenyl) -butane, 2,2-bis (4-hydroxy-propoxyphenyl) -propane, 2,2-bis (4-hydroxy- propoxyphenyl) propane, 1,1-bis (4-hydroxyl-ethoxyphenyl) -butane, 1,1-bis (4-hydroxyisopropoxyphenyl) -heptane, 2,2-bis (3-methyl-4 -beta-hydroxy-ethoxy-phenyl) -propane, 1,1-bis (4-beta-hydroxyethoxy-phenyl) -cyclohexane, 2,2'-bis (4-beta-hydroxyethoxy-phenyl) -norbornane, 2, 2'-bis (4-beta-hydroxyethoxyphenyl) -norbornane, 2,2-bis (4-beta-

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hydroxystyroloxyphenyl) propane, the polyoxyethylene ether of isopropylidenediphenol in which both the phenolic hydroxyl groups are oxyethylated and the average number of oxyethylene groups per mole is 2.6, the polyoxypropylene ether of 2-butylidene diphenol in which both the phenolic hydroxyl groups are oxyalkylated and the average number of oxypropylene groups per mole is 2.5 and the like. Diphenols in which R represents an alkylidene group having 2 to 4 carbon atoms and R ¹ and R ¹ 'represent an alkylene group having 3 to 4 carbon atoms are preferred because greater blocking resistance, increased definition of xerographic characteristics and more complete transfer of the toner images are achieved. Optimal results are obtained with diols in which R is isopropylidene and R ¹ and R ¹ 'are selected from propylene and butylene, since resins formed from these diols have higher agglomeration resistance and penetrate paper receiving sheets extremely easily under melting conditions.

Any suitable dicarboxylic acid can be mixed with a diol in the above are reacted in the manner indicated to form the toner materials according to the invention, these either substituted or unsubstituted, saturated or unsaturated, and the general formula

HOOC R " ¹ COOH
ⁿ 3

is sufficient, where R ¹ ″ denotes a substituted or unsubstituted alkylene radical with 1 to 12 carbon atoms, arylene radicals or alkylenearylene radicals with 10 to 12 carbon atoms and n _{3 represents} less than 2. Typical such

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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-phenylene aceto-beta-propionic acid, Itaconic acid, maleic acid, maleic anhydride, fumaric acid, phthalic anhydride, traumatic acid, citraconic acid and the same. Dicarboxylic acids having 3 to 5 carbon atoms are preferred as the resulting toner resins have greater resistance to film formation on reusable imaging surfaces and to formation withstand fines under device operating conditions. Optimal results are obtained with (^ -unsaturated dicarboxylic acids with the inclusion of fumaric acid, maleic acid or maleic anhydride, as a maximum resistance against the physical decomposition of the toner as well as the property of rapid melting achieved will. The polymerization esterification products can copolymerized itself or with one or more others thermoplastic resins are mixed, preferably aromatic resins, aliphatic resins or mixtures thereof, Typical thermoplastic resins include; fighter modified Phenol-formaldehyde resins, oil-modified epoxy resins, polycarbonate, polysulfone, polyphenylene oxide, polyurethane resins, cellulosic resins, vinyl type resins and their mixtures. When the resin component of the toner contains an added resin, the added component should be present in an amount that is less than about 50 percent by weight based on total weight of the resin contained 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 in

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Melting temperatures is reached with a predetermined amount of additive material. In addition, sharper and denser images are obtained when a high percentage of polymeric diol and dicarboxylic acid condensation product is present in the toner. Any suitable mixing technique, such as hot melt, solution and emulsion techniques, can be used to incorporate the added resin into the toner mix. The resulting resin blend is essentially homogeneous and highly compatible with pigments and colors. If this gs ipsc actual k .mi the colorant prior to, or after equilateral αβτ "erraischungs- eggs ζ l ;;,;? Be added nierisierungsstufe.

3a "7cr2 -.; - jte electrophotographic results" are nit dsia Sc 1 "/ SiVi Yello" ·? 2? -Fär ': 3iri.i "' r. ':. il gs ^ iSss isr invention with Sty-"cl-ButTlmethacri'lat-Copoljmerenj styrene-vinyl-toluene-Copolyms :: s:!, Styrcl-Aorylat- Copoiymerenp polystyrene resins, resins on common: ", the styrene or Folys'cyrolgrund base, as they are generally described in the US Reissue patent specification 25 136 (Carlson) _? And with polystyrene mixtures " as they are in the US = -: ?. 2 described 7GÖ £ U3 fRheinfrank and Jones) S are received _r Optimum results are 29 according to the invention and Sc ^^^^ with Yellow - n-butyl methacrylate copolymer resins, forming a :: ^ r.ers with long life and low Received impact or impaction »

Any known toner blending and milling techniques can be used to create the toner materials according to the invention. For example, the components thoroughly mixed by blending, extrusion and grinding and then micrulverization. Furthermore

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can also be spray drying of a suspension of the constituents, hot melting or a solution of the toner composition can be applied.

The toners according to the invention can be of any size which leads to a satisfactorily developed image. Toners according to the invention which are suitable for use with a carrier suitable for cascade or magnetic development generally have an average Particle size from about 5 to about 45 µ. A preferred average particle size range is about 10 to about 19 µ which results in maximum density when printed.

If with the toner materials according to the invention carrier materials The carrier particles used can be used in cascade and magnetic brush development be electrically conductive, insulating, magnetic or non-magnetic as long as the carrier particles are capable triboelectrically to achieve a charge of opposite polarity to that of the toner particles, so that the toner particles adhere to it and surround the carrier particles. In developing a 'positive reproduction of an electrostatic Image, the carrier particle is chosen such that the toner particles acquire a charge equivalent to that of the electrostatic latent image has an opposite polarity, so that the toner deposition in the image areas he follows. Alternatively, in reverse reproduction of an electrostatic latent image the carrier chosen so that the toner particles have a charge of the same polarity as that of the electrostatic acquire latent image, resulting in toner deposition in

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the non-image areas. Typical support materials include: sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, potassium dichlorate, granular zircon, granular silicon, methyl methacrylate, glass, steel, nickel, iron, ferrites, ferromagnetic materials, silicon dioxide and the like. The carriers can be used with or without a coating. Many of the foregoing and typical support materials are disclosed by LE Walkup in U.S. Patents 2,618,551; LE Walkup et al in U.S. Patent 2,638,416; EN Wise in U.S. Patent 2,618,552; RH Hagenbach et al in U.S. Patent No. 3,591,503 and 3,533,835 directed to electrically conductive carrier coatings, and BJ Jacknow et al in U.S. Patent No. 3,526,533 directed to polymer-coated support and spherical or nodular carrier with granular or pitted surface, as disclosed in Serial No. 357,988, filed May 7, 1973, now U.S. Patent 3,847,604, a divisional form Serial No. 151,995, filed June 10, 1971, now U.S. Patent No. 3,847,604. PS 3,767,568 has been described. A final coated carrier particle diameter between about 50 and about 1000µ is suitable because the carrier particles then have sufficient density and inertness to prevent adhesion to the electrostatic images during the cascade development process. A preferred particle size is between about 75 and 400 / rev. Optimal behavior results with the toner according to the invention at about 100 μ, while obtaining images of the best possible density and a long service life. The carrier can be used with the toner material in any suitable combination, with generally satisfactory results having been obtained when using about 1 part of toner

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about 10 to about 200 parts by weight of carrier can be used.

Preferred carriers for use in the toner materials according to of the invention are those made of nickel berry and terpolymer coated steel. Nickelberry Bearer represent links in a group of spherical or nodular carrier beads disclosed in U.S. Patents 3,847,604 and 3,767,568 and are characterized by a grained or grained surface recurring indentations and projections characterized, whereby the particles a relatively large outer Surface area is given and which are composed of nickel. Such spherical or knot-shaped Carrier beads have a high surface-to-mass ratio compared to essentially smooth-surfaced carrier beads of the same mass. Under use The spherical or knot-shaped carrier materials can take advantage of both large and small carrier beads while avoiding their disadvantages. There are a large number of spherical or knot-shaped carrier particles represent small spherical surfaces with indentations that define pockets for the toner particles.

The spherical or knot-shaped carrier beads represent three-dimensional solids with a size of approximately 50 to 1000 microns and have an approximately berry-shaped, cubic, rounded, irregular or spherical shape and have surface irregularities that are formed by numerous nodes and indentations or Indentations. Although the pearls are randomly arranged

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Voids or voids or a small extent Have porosity, they should have predominantly solid cores. Preferred carrier beads generally have rounded nodules and are generally spherical, giving an appearance reminiscent of a raspberry or reminded of a bunch of grapes.

Terpolymer supports are described in U.S. Patent 3,526,533. The terpolymer carriers include a core that is with a Composition is coated, which is due to the addition polymerization reaction between monomers or prepolymers of styrene, methyl methacrylate and unsaturated Organosilanes, silanols or siloxanes that are 1 to 3 hydrolyzable Groups and an organic group attached directly to the silicon atom, which have an unsaturated one Contains carbon-carbon bond, which is capable of addition polymerization, give.Opbimal is with the inventive Toner has a steel support core made with the composition of Example XIII of US Pat. No. 3,526,533 below Forming a methyl terpolymer carrier is coated, whereby a developer material is formed, which to a High density coverage and long lifetimes result.

The electrostatic latent images created with the toner materials have been developed in accordance with the invention can be present on any surface capable of is to withhold charge. In electrophotographic applications, a photoconductive element is used to form the electrostatic latent image applied. The photoconductive layer can be inorganic or organic comprise photoconductive material. Typical inorganic

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2629Λ7Ί

Materials include: sulfur, selenium, zinc sulfide, zinc oxide, zinc cadmium sulfide, zinc magnesium oxide, cadmium selenide, zinc silicate, calcium strontium sulfide, cadmium sulfide, mercury iodide, mercury oxide, mercury sulfide, indium trisulfide, gallium selenide, cadmium sulfide, arsenic sulfide, and their cadmium sulfide, arsenic disulfide. Typical organic photoconductors include: triphenylamine, 2,4-bis (4,4 ^1- diethylaminophenol) -1,3,4-oxidiazole; N-isopropylcarbazole; Triphenylpyrrole; 4,5-diphenylimidazoiidione; 4,5-diphenylimidazolidine ethione; 4,5-bis (4'-aminophenyl) imidazolidinone; 1,5-dicyanonaphthalene; 1,4-dicyanonaphthalene; Aminophthalonitrile; Nitrophthalodinitrile; 1,2,5,6-tetraazacyclooctatetraene (2,4,6,8); 2-mercaptobenzothiazole-2- phenyl-4-diphenylidene-oxazolone; 6-hydroxy-2,3-di (p-methoxyphenyl) benzofurans 4-dimethylaminobenzylidene-benzhydrazide; 3-benzylidene-aminocarbazole; Polyvinyl carbazole; (2-nitro-benzylidene) -p-broitt-aniline; 2,4-diphenyl-quinazoline; 1,2,4-triazine; 1,5-diphenyl-3-methyl-pyrazoline-2- (4-dimethyl-aminophenyl) -benzoxazole; 3-aminocarbazole; Polyvinylcarbazole-trinitro-fluorenone charge transfer complex; Phthalocyanines and their mixtures.

The toner of the present invention is particularly for use in the yellow toner in the color electrophotographic imaging processes disclosed in U.S. Patent 3,804 and U.S. Serial No. 425 48T ^ filed December 17 1973, both of which are hereby incorporated by reference. The in the above mentioned The process described in patents or patent applications represents a multiple development technique that is capable is to produce color reductions, with a multiple sequence

^ 'corresponds to patent application P22 52 113.1, filed October 30, 1972

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_ 2g _

electrophotographic charging, exposure through filters and development stages with three different color toners will. The magenta, cyan, and yellow color toners become green, red, and, respectively, after exposure blue filter developed. When developing and transferring the three color toner images, it is necessary that the relationship of the toners is such that they cooperate with each other to form a good quality image. It is evident that each of a number of variables leads to incomplete, disorderly, or inappropriate development could result in the color balance being shifted, resulting in an unacceptable color print would.

One use of the toners according to the invention lies in one successive three-color development processes when combined with a methyl terpolymer coated steel beam and when used in combination with a copper phthalocyanine pigment, that in the Color Index as CI. 74160, CI. Pigment Blue 15 Cyan Toner is identified and one Methyl terpolymer coated steel beams and an anthraquinone dye, which in the Color Index as CI. 60710, CI. Disperse Red 15 Magenta Toner is identified and a nickel-ball or nickel-berry carrier.

It was found that the toners of the present invention an optimum for a sequential three color development process when combined with a methyl terpolymer-coated steel beam and when used in combination with a copper tetra-4- (octadecylsulfonamido) phthalocyanine pigment represented by GAF Corporation

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available under the name Sudan Blue OS, 'Cyantoner and a methyl terpolymer coated steel beam; and 2,9-dimethylquinacridone identified in the color index as CI. Pigment Red 122, Magenta Toner and a Nickel Ball or Nicke] - represent berry carriers.

A sequential color electrophotographic process is performed by using a photoconductive Element charges, the photoconductive element is an original, that is to be reproduced is exposed to a color through a filter, thereby selectively · the photoconductive Element is discharged, the electrostatic image thereby formed with a developer of a complementary color developed, wherein the developer is an element selected from the group consisting of copper tetra-4- (octadecylsulfonamido) phthalocyanine pigment, Cyan toner and a methyl terpolymer coated steel beam; Color index pigment Red 122, Magenta Toner, and a Nickel Berry Carrier; the toner of the present invention and a methyl terpolymer coated Steel beam is made; charges the photoconductor a second time and selectively the photoconductor the same image through a filter to a different primary color exposes the electrostatic latent image thereby formed with a Developer of a complementary color, the developer being a further element from the group is selected from copper tetra-4- (octadecylsulfonamido) phthalocyanine pigment, Cyan toner and a methyl terpolymer coated steel support; Color Index Pigment Red 122, Magenta toner and a nickel berry carrier; and the toner of the present invention and a methyl terpolymer-coated one Steel beam is made; the photoconductive element a third

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Times charging, exposing the photoconductor to the same image through a filter of the remaining primary color and that latent electrostatic image is developed with a complementary developer, with the 'developer being the remaining Represents developer from the group consisting of copper tetra-4- (octadecylsulfonamido) phthalocyanine pigment, Cyan toner and a methyl terpolymer coated steel support; Color index pigment Red 122, Magenta Toner and a Nickel Berry Carrier; and the yellow toner according to the invention and a methyl terpolymer coated steel beam.

The preferred order of development and methodology of formation of the magenta and cyan toners is " as described in Example I of US Serial No. 425,481, filed December 12, 1973. However, any sequence of development of the cyan, cyan, Magenta and yellow toners can be applied to produce satisfactory prints.

To further explain the peculiarities of the invention, reference is made to the following examples, in which parts and percentages are by weight unless otherwise indicated.

Example I.

A styrene-n-butyl methacrylate copolymer resin is made with Color Index Solvent Yellow 29 stain used in such a way that the colorant comprises 3% of the toner material by weight. The mixture is in a drum tumbling device during

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mixed for about an hour at about 10 rpm. The material is then poured into a screw feeder and extruded until the device is equilibrated. The extruded strands are taken up at a speed of about 15 m (50 feet) per minute, and cooled in a water bath at about 50 ° C (120 ⁰ F) by forced air drying. The strands are then cut by a knife device to produce pellets ranging from 1.6 to 3.2 mm (1/16 to 1/8 inch) in diameter. These pellets are then atomized to an average particle size of about 15 µm. This toner is then combined with a methyl terpolymer coated steel support in the manner described above to give an electrostatographic developer. The developer produced in this way is used in e'.ner's automatic imaging device, a Xerox Model 720 copier, which has a magnetic brush development system. The selenium photoconductor is charged, selectively exposed and developed with the yellow developer. After 25,000 prints, images with good contrast, high image density and a desirable appearance are still obtained. The developer tribo is maintained at a high level in a manner similar to that shown in Table I.

Example II

The procedure given in Example I is repeated, with the exception that one concentration of 5% dye is applied.

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Example III

The procedure given in Example I is repeated, with the exception that a color loading of 7% is applied.

Example IV

The procedure outlined in Example I is repeated with the exception that a styrene resin is used will.

Example V

The procedure given in Example I is carried out again, however, with the exception that a nodular nickel carrier with a pitted surface is used commonly referred to as the nickel berry, is described in U.S. Patent No. 3,847, cited above and 3,767,568.

Example VI

The procedure described in Example I is carried out again, however, with the exception that the resulting yellow developer is produced on a transparent Mylar substrate of a transparency provided with a yellow image is applied.

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Example VII

A yellow developer created in Example I is used in place of the yellow developer used in the trichromatic electrophotographic imaging process was used, which has been described in Example I of ÜS-PS 3,804.

Example VIII

A yellow developer produced according to Example V. was used instead of the yellow deconstructor, that in the trichromatic electrophotographic imaging process of Example I of U.S. Serial No. 425,481; filed December 12, 1973.

While the above examples set out specific conditions and materials, any
the typical materials listed above are used instead, if appropriate, in the preceding examples with similar results, through the steps,
those for carrying out the method according to the invention
In addition to the above, further steps or modifications can be made if desired. In addition, further materials can be introduced into the system according to the invention, which the
Desirably promote properties of the system for its current use.

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Claims (16)

PATENT CLAIMS Electrostatographic material for developing electrostatic lat nter images, labeled ι e t by a resin material and a coloring agent, where the colorant satisfies the formula: OH N = N ^C 6 ^H 11 -N = N ^C 6 ^H 11 2. Material according to claim 1, characterized in that the resin is selected from styrene-butyimethacrylate copolymers, styrene-vinyltoluene copolymers _f styrene-acrylate copolymers and polystyrene resins. 3. Material according to any one of the preceding claims, characterized in that the resin is essentially transparent. - 33 - 709808/1017 4 ·. Material according to any one of the preceding claims, characterized in that the resin a polymeric esterification product of a dicarboxylic acid and a diol comprising a diphenol. 5. Material according to any one of the preceding claims, characterized in that the resin represents a styrene-n-butyl methacrylate copolymer. 6. Material according to one of the preceding claims, characterized in that in addition a carrier is included. 7. Material according to claim 6, characterized in that about 1 part by weight of the toner material is present for about 10 to about 200 parts by weight of the carrier. 8. Material according to one of claims 6 or 7, characterized in that the carrier has a Represents methyl terpolymer coated steel girders. 9. Material according to one of claims 6, 7 or 8, characterized in that the carrier represents a nickel berry carrier. 10. Electrostatographic imaging process, characterized by producing a electrostatic latent image on a surface and contacting the surface with an electrostatographic Material that is a resin material and 709808/101 7 represents a colorant, the colorant of
Formula is sufficient: OH CH 11. Imaging method according to claim 10, characterized in that additionally the stage
the transfer of the developed image to a receiving surface and the fixing of the picture on this receiving surface. 12. The method according to claims 10 or 11, characterized
characterized in that the electrostatographic material further comprises a methyl terpolymer coated steel support. 13. A color electrophotographic imaging process characterized by charging a photoconductive one Element, exposure of the photoconductive element through an original, which can be reproduced is supposed to pass through a filter of one color, making in 70S808 / 1 01 7 selectively the photoconductive element is discharged / developing the electrostatic generated thereby Image with a developer of a complementary color, the developer representing an element that under copper tetra-4- (octadecylsulfonamido) phthalocyanine pigment, Cyan toner and a methyl terpolymer coated steel support; 2,9-dimethylquinacridone in the Color Index as CI. Pigment Red 122, magenta toner, and a nickel berry carrier; Azo dye CI. 21230 Solvent Yellow 29 Yellow Toner and a methyl terpolymer coated steel carrier is charging the photoconductor for the second time and selective exposure of the photoconductor by the same Image through a filter of another primary color, development of the resulting latent, electrostatic Image with a developer of a complementary color, the developer of another element represents that among copper tetra-4- (octadecylsulfonamido) · phtlialocyaninpigment, cyan toner and a methyl terpolymer-coated Steel beams; 2,9-Dimethylquinacridone, identified in the Color Index as Pigment Red 122, Magenta toner and a nickel berry carrier; and Azo dye CI. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel support is selected, charging the photoconductive element for the third time, exposure of the photoconductor through the same image through a filter of the remaining primary color and developing the electrostatic latent image with a complementary developer, the Developer represents the remaining developer who - 36 - 709808/1017 under copper tetra-4- (octadecylsulfonamido) phthalocyanine pigment, Cyan toner and a methyl terpolymer coated steel support; 2,9-dimethylquinacridone, identified in the Color Index as Pigment Red 122, magenta toner and a nickel berry carrier; and Azo dye CI. 21230 Solvent Yellow 29 yellow toner and a methyl terpolymer coated steel beam. 14. The method according to claim 13, characterized in that the magenta toner is an anthraquinone dye represents that in the Color Index as CI. 60710, CI. Disperse Red 15 is identified. 15. The method according to claim 13, characterized in that the cyan toner is copper phthalocyanine pigment represents that in the Color Index as CI. 74160, CI. Pigment Blue 15 is identified. 16. The method according to claim 13, characterized in that the magenta toner is an anthraquinone dye represents that in the Color Index as CI. 60710, CI. Disperse Red 15 is identified and the cyan toner represents copper phthalocyanine pigment listed in the Color Index as CI. 74160, CI. Pigment Blue 15 is identified. 709808/1017