DE1772669A1 - Xerographic developing material - Google Patents

Description

Patent attorneys Dipl.-Ing. F. Weickmann, Dr. Ing.A.Weickmann

D1PL.-ING. H. Weickmann, Dipl.-Phys. Dr. K. Fincke Dipl.-Ing. F. A. Weickmann, Dipl.-Chem. B. Huber

I MONK 27 DEN MÖHLSTRASSE 22, NUMBER 4S3921 / 22 Sch / Ol Oaee No. ? / 638 (D / 1956) RAKK XEROX LIMISKD, London, England Xerographliicaes development material

The present invention relates generally to Bilderaeugungseyeteae and is more particularly directed to improved ones
xerographic devolatilizing materials, their production and
Use.

The xerographic process is used for the first time in U.S. Patent Bore 2 297 691 beeohrleben. During the Durohead the

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This process is first applied to the surface of a photo ~ an equal electrostatic charge is applied to the conductor, whereupon this surface of an image-forming electromagnetic Radiation is exposed through which In more selective Correct the charge at the exposed areas of the photoloiter balanced v / ird, while the charge is retained in the unexposed areas, so in this way forming an electrostatic latent image. This electrostatic latent image is then developed or visibly mowed, through the deposition of a finely divided electroscope! see marking material on the surface of the photoconductor, this marking material generally being referred to as toner. This marking material agrees with the latent electrostatic pattern Picture match. The visible image can flow on can be used in a variety of ways * For example, the image can be viewed in situ on the photoconductive insulator. It can also be fixed on the photoconductive insulator or on a second surface, for example on a Paper sheet, transferred and fixed on this, depending on whether the photoconductive insulation material again should be used, as is the case when photoconductive insulators made of amorphous selenium are used reach. Re-use is not intended if such zerographic plates are used on which the image using pre-

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lying zinc oxide as well as using a binder film is fixed.

Vegetables of US Pat. No. 2,297,691 were dusted with various fuders, for example from bear moss, copal gum, oumarone-indene hair, as well as with various powdered dyes or the like, for the purpose of developing the latent electrostatic image of this. Various other development materials and methods have also been suggested. Some of these development methods consist of a brush development as described in US Pat. No. 3,015,305, a powder staining de-luxing method such as described in US Pat 2,551,582 1st, a Eintauchentwioklung (see U.S. Patent 3,010,842), a Schleifenentwloklung (loop development), as el · in U.S. Patent 2,761,416 is described and, in a donor development l (donor development) which for example, the subject of U.S. Patent No. 2,895,847. Today, however, cascade development, which is described in US Pat. No. 2,618,552, is widely used in xerography. This decoiling method is carried out by rolling or cascading a coil over the surface carrying the latent electrostatic image, whereby

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the developer coating consists of relatively large carrier particles put together, vote! each carrier particle has a multitude of fine particles that adhere to its surface olectrostatically Maxkation parts known as toner particles, wearing. When this mixture is rolled or cascaded over the surface bearing the image, the toner particles become electrostatically deposited on the charged areas of the image, while on the non-charged background areas There is no deposition of the image, and there are toner particles that happen to be on these non-charged sites .fall, physically by electrostatic attraction of the carrier particles, which are in close proximity to these unbound toner particles, removed The result of this development process is an excellent background-free copy of the electrostatic image, which is visibly mauht through the Tonertellohen, which adhere electrostatically to the surface of the picture. Used in conjunction with one of these development processes a reusable zerographic plate, for example a xerographic plate made of amorphous selenium, applied, then the image from the toner cartridges is transferred to a second sheet, for example a sheet of paper, which is in contact with the toner image by a sticky transition or by an electrostatic transition Transition (see US Patent No. 2,576,047)

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Transferred and fixed on this second layer. After the image has been removed from the surface of the xerographic plate containing amorphous selenium, the plate surface can be cleaned, whereupon it is available for reuse in a subsequent xerographic cycle. The toner resins are typically thermoplastic materials which are selected such that they have melting points significantly above the ambient temperatures occurring are (generally above 82 ⁰ O (180 °?)). In most cases, these toner hares are fixed to the paper by means of a gap caused by radiant heating.

Use most other electrostatographic methods the development described above or a similar one, using the same marking material (toner). These methods only differ in that Nature of the formation of the latent electrostatic charge pattern that is developed (see, for example, U.S. Patents 2,576,047 and 3,064,259) cream cheese of a different method, such as that disclosed in U.S. Patent No. 3,081 is described, a conductive grid with a plurality of openings, which the image area to be reproduced define, attached opposite a conductive pad electrode, whereupon a voltage between this pad electrode and the grid is applied so that, if finely divided electrostatographic toner particles smaller than

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the openings in the grid, on the surface of the grid be applied opposite the pad electrode, the electrostatic field generated by the voltage source Particles through the openings in the grid to form a toner image on the backing electrode in the configuration of the openings on the grille. Spankedene Surfaces can be "introduced as above the grid and the support or support electrode" so that the Particle image is captured and formed on such interposed surfaces. UnahhHnglg from the surface, on which the toner image is sprayed, it can be fixed on this surface or transferred to another surface and fixed thereon.

What all these electrostatographic systems have in common Characteristic is that they are lines of force of an electric Field for controlling the deposition of finely divided marking materials or toner materials on a surface are used, thereby forming an image with the toner particles.

In addition, see the development powder or toner materials, as described in US Pat. No. 2,297,691, a variety of other toner materials have been developed, wherein sioh these materials especially for a · use in the more recent development methods, for example in the

Kaslcadenentwicklungeme-chode described, are suitable. These nouon toner materials generally consist of various improved resins mixed with various pigments such as HuS. In this context be on the US Pat. No. 2,659,670, which is an ionic resin made from a rosin-modified phenol / Describes formaldehyde, US-Relssue-Patent 25 136, which has a special xerographic material sum that using Stvrolhomopolvmerisaten, - Copolvmerisaten or polymer mixtures is produced, as well as on US Pat. No. 3,079,342 is referred to, which is made with a plasticizing Stvrol / methacrylate copolymer resin, deals.

So far, these toners have generally been made by that the softened resin and pigment have been thoroughly mixed to form a uniform dispersion, for example by mixing these ingredients in a rubber mill or the like, whereupon this material is used Generation of small ropes is pulverized, in most common this division of the. Harz / Pigaent-Diepereion through a jet powder veil of the material. If auoh after this Toner manufacturing method some excellent toners could be produced, so stick to this method deenooh no oh some drawbacks to · For example, in general

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Get toner particles that are fairly wide within a fairly wide range Vary in size. Even if the average Particle size of the toner particles produced according to this method is generally between about 5 and about 10 microns, then particles are often obtained that have a Submicron in size or greater than 20 u exhibit. In addition, the method described is tin batch process that works slowly, is expensive and an odor and dust nuisance with sioh bring.:. In addition, this method lays down for toner production with regard to the materials used, there are certain restrictions, since the resin / pigment dispersion is sufficient Dimensions must be brittle so that they can be pulverized at an economically justifiable production speed can be. The problem that arises with regard to this requirement is that if the Resin / pigment dispersion all in one for one with high speed pulverization carried out is sufficiently brittle to cause it to form during pulverization Particle tends to be in an even broader particle size range fall, the percentage of fines being relatively high. In addition, such highly brittle materials suffer often further pulverization when used for development in xerographic copiers. In addition, zero-graphic developers or toners are required still meet other requirements, of which the following

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the following should be mentioned:

They need to be stable during storage, not allowed to move agglomerate, must have the triboelectric properties required for development, must have good images must not form a film or fog on the xerographic selenium plate and must have a low melting point for heat melting own. Most thermoplastic materials include one or more of the above do not meet the requirements mentioned above, there is a continuous Need for Improved Toners and Developers.

The aim of the present invention is therefore to obtain one Toners, which no longer has the disadvantages indicated above. The toner particles of the present invention have a improved uniformity due to their particle size In addition, they are resistant to agglomeration. The toner particles according to the invention can easily be removed from reusable xerographic images Remove suction surfaces. They also provide images with high resolution. You can also search for one faster and more economical processes can be produced. You are opposed to pilming on xerography resistant to image absorbing surfaces. In addition, own the inventions xerographleohen loner and developer * material physical and chemical properties, which

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Superior to those of the previously known toners and developers are.

The present invention provides a xerographic toner composed of spherical particles containing a colorant and a hair, since it has been produced as a latex in the presence of at least one chain transfer agent. The resin is prepared by an aqueous emulsion polymerization, has a glass transition temperature (Tg) of about 30 to about 65 ⁰ C and has an average molecular weight between about 10,000 and about 500,000. An average molecular weight within this range is obtained by the The relative amount of the organic chain transfer material present during the polymerization of the resin is regulated. Regulating the molecular weight of the hardness is twofold in order to keep the level of the toner resins within the temperature limits given by the xerographic copying and duplicating processes . TfMn resin molecular weight of at least about 10,000 prevents the formation of toner fines in automatic machines and improves the resistance of the toner to compressive coating on the surfaces of the carrier beads. Xrfindungegemäse is a new and improved method for

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Position of electrostatographic sonar created, whereby toner parts can be obtained without a noticeably improved uniformity in terms of molecular weight and particle size. The new toner produced according to the invention also has a unique spherical shape which is particularly suitable for cascade development. In addition, it has been found that this new toner production process is able to produce an ioner with an extremely small partial size. Both the regularity similar in particle size and the fineness of the particles are responsible for ensuring that a toner is obtained which has a high resolving power and can be used for virtually any electrostatographic development process, a-Bchliesslioh the methods described above. The maximum resolution of an electrostatographic system, for example a xerographic system, is limited by the largest toner particles that are present in the toner batch which is used before the development of the latent electrostatic image, regardless of the particular development method used. Even if an optical system and a xerographic plate are capable of generating latent electrostatic images with a high resolution, the resolution of the overall system is nevertheless reduced if the latent image is developed with a toner that is not suitable for xerography. which contains particles of one size

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those greater than the dimensions of any part of the latent Image is »The method according to the invention according to dom manufactured toner is compared to known toners for the production of high resolution images in two ways think. First of all, it is through what is invented according to the invention Method possible, a loner with an extremely small To produce particle sweetness. In addition, the particle size range of the toner produced is noticeably narrowed »so that the formation of particles is prevented» their OrOsse goes beyond the size of the euro son. In addition, it can In contrast to the hitherto known, oharge-wise carried out cycling, driving can be carried out continuously, explosive or flammable solvents are only used to a limited extent and, under certain circumstances, the use of such solvents can be dispensed with. Also When carrying out the method according to the invention, there are no dust or environmental nuisances, as well as MhnHohe Inconvenience.

The inventive method consists in the principle of a Vaeserlatex of the usual Hareee in the presence at least a set transfer agent, followed by the Yasser latex Teraisoht with a dyeing sheet and then attached this combined system to the usual partial size is spray dried. Albeit any of the known harmless development materials that are electroscopic and

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when heated in the sprinkler head, leads to formation a water latex can be used, so it has nonetheless generally pointed out that electrically insulating, water-insoluble thermoplastic polymeric addition reaction products, such as in the U.S. Reissue Patent 25,136 and U.S. Patent 3,079,342 for forming toners of many desirable Properties for a xerographic copying especially are suitable. Different types of addition polymerisation resins can of course be used for other purposes can be used. The use of any of these addition polymerization resins generally enables one Combination of swti those for the soner manufacturing process required levels. Thus, by the simple measure of using an emulsion polymerisation dee karate the Vaeserlatex at the same time as the end product of the polymerisation process « are formed. The use of emulsion polymerization also leads to the formation of a very stable one Latex, which is characterized by the fact that the polymer particles, that are dispersed in it, are uniform, so that the last particles obtained in the spray drying have a smooth overall size. The production is smaller Polymerizatteilohen in the emulsion can during the Snulsionspolymerieation by introducing an "organic chain transfer agent" as well as an emulsifying agent or surface-active agent into the emulsion before the polymerization

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become light. By using a relatively large amount a surfactant in the water at the initial Stirring the monomer into d & 3 water produces a relatively large number of small, swollen monomer micelles formed in the emulsion, the micelles having essentially the same number of small polymer particles in the subsequent to the addition of the polymerization initiator Form polymerization.

Ee can be any suitable vinyl monomer in the present invention Process are used. Vinyl monomers can be defined as solo monomers that have the characteristic Have an ethylenically unsaturated structure> 0 «OC and are able to undergo addition polymerization. Typical vinyl monomers are, for example, the following Compounds: Seter of saturated alcohols nit mono- and polybasic unsaturated acids such as alkyl aylates and -aeAaorylate, Halogenacrylate, Ditäthylaaleate or mixtures of such compounds, vinyl and ylnylidene halides, such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene or mixtures of these compounds, vinyl esters, e.g. vinyl acetate, unsaturated aromatic compounds, e.g. styrene and various alkyletyrenes, p-chlorostyrene, p-bromostyrene, 2,4-dichlorostyrene, vinyl naphthalene, p-methoxyetyrene or mixtures of these compounds, unsaturated

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Aside, ie for example acrylamide, methaorylane or Mixtures of these compounds, unsaturated nitriles, such as for example acrylonitrile, methacrylonitrile, haloorylnitrile, Phenylacrylonitrile, vinylidenecyanide or mixtures of these compounds, H-substituted unsaturated amides, such as for example Η, Η-Diaiethylaorylamid, ff ~ Hethylaorylaiaid or mixtures of these compounds, conjugated butadienes, such as, for example, butadiene, isoprene, or mixtures of these Compounds, unsaturated ethers, such as divinyl ethers, Diallyl ether, vinyl alkyl ether or mixtures of these compounds, unsaturated ketones, such as, for example Tinyl acetone, vinyl alkyl ketone or mixtures of these compounds, unsaturated aldehydes and aoetals such as acrolein and its aoetals, methacrolein and its Aoetals or mixtures of these compounds, unsaturated heteroyclic compounds such as vinylpyridine, Vinylfuran, Vinylounaron, 9-Vinylearbasol and mixtures of these compounds, unsaturated aliiyklieoha compounds, such as vinyloyclopentane, vinylcyclohexane or Mieohungen these compounds, unsaturated Thiorerblndüngen, such as vinyl thioethers, unsaturated hydrocarbons such as ethylene, propylene, Oumarone, Indene, Xerpene, polymerizable carbon dioxide fractions, Isobutylene or mixtures of these compounds, allyl compounds such as allyl alcohol, allyl ester Diallyl phthalate, triallyl cyanurate or the like.

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Any suitable homopolymer, copolymer or terpolymer the materials specified above can be used in the process according to the invention. Polymers the types specified to create are, for example, polyvinyl butyral, Copolymers of methacrylic acid with methyl acetate aorylate, with acrylonitrile or with styrene, copolymers of clay, vinyl acetate with maleic anhydride, copolymers of Nitrostyrene with diethyl maleate, copolymers of styrene with acrylic acid and methacrylic acid and their esters or the like

In addition, any suitable surface-active agent, namely any cationic, anionic or nonionic surface-active agents in the method according to the invention © ingeaetst become · Xypisohe examples of surface active Agents are naphthalenic soaps or sulphonates, sulphonation products of oleoerides or their fatty acids, sulfonated derivatives of prayers of monovalent and polyvalent Alcohols, esterification products from fatty acids and sulfonated monohydric alcohols, sulfonated derivatives of fatty acid esters ^ such as the diamyl or Diootyl ester of Hatrixmsulf © succinic acid, sulfonation products of fatty amides, ketones, aldehydes and nitrides, sulfonation products of natural and synthetic alcohols, for example alkyl sulfates and sulfonates, phosphoric and pyrophosphoric esters of fatty alcohols, such as

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for example the sodium sal of 2 ~ ethylhexyl phosphate, aminocarboxylic acids, sulfonated aromatic hydrocarbons, such as the sodium alkylaryle sulfates and sulfonates, alkylated alkyl sulfonates, sulfonated o and chlorosulfonated Paraffin hydrocarbons, sulfated3 and sulfonated derivatives non-ionic compounds such as, for example Sodium alkylaryl polyether sulfates and sulfonates, aliphatic " Amines and their derivatives, aromatic amines with jetted acid chains, Pettamine and aliphatic DlAmine, quaternttre Ammo- | Niura compounds (bases and halides) »such as btiepielsweiee

ohlorid, Dodeoyltrimethylammoniumohlorid »Tetradeoyltrimethylammoniumohlorldy Hexadecyltrimethnylammoniumohlorid, Ootadeoyli ^ rtrn ^^^ yT » "ψότι lwn o hlorlfl» Amines _t the ei ohane- and ba- mono-derivatives of Aamino- and ba- mono-derivatives, derived from Aaminoethanolamines, and their derivatives of polyethanol from A, as well as their polyethanol-derivatives, and their polyethane-olamines or other salts of ethylene oxide, Xondeneatlona products from letteubetanien e as well as hire derivatives with ethylene oxide, for example the polyoxyalkylene ethers of partial lauric, palmitic, stearic or 01 * acidic acids, as well as condensation products with phenolic oxides, especially compounds containing ethylene oxide, and other side chains of dodeoylphenol with ethylene oxide. In some cases, one, two or more surface-active agents can also be used as an

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mation of the properties of the taulsl on, for example the Stability, the MiBeile control and the particle size, to use »The relative amount of surfactant used is preferably less than about 3% by weight, based on the weight of the whole non-aqueous reaction mixture, since the toner material obtained under changing ambient humidity conditions has a greater triboelectric stability. Optimal stability of the emulsion and of the toner polymer obtained is then achieved when about 0.25 to about 1.5% by weight, based on the total weight of the non-aqueous reaction mixture, the surfactant can be used

Any suitable catalysis or Inletlierungssyetem can be used in the implementation of the emulsion polymerization process, for example, one can use the catalysis proceeding via free BadUcals using "in ·· Peroxy de _{s of} a persulfate or a benzo compound or use UY-Idoht Catalyst, such as a peroxide or a persulfate, such as aanoniuapulfate »used, then the redox pon of the catalysis proceeding via free radicals, with a water-soluble reducing agent such as hatriuasulphite, hatriurab sulphate or iron (II) sulphate is used , additionally one

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be set »ao that one faster polymerization at relative low temperatures if necessary, suitable secondary initiators, such as tart.-butyl hydroperoxide, before or during the polymerization stage for Requirement for complete conversion of the monomer can be added.

Even if it is tap water, it has a low content of more- * | has valuable metal ions that can be used for the production of the emulsions, then it is plasticized or deionized Water to be preferred, as in this way a more precise control of the emulsion, especially with regard to the polymorphism and prevention a flocculation of the monomer and polymer components, is achieved.

Any suitable release agent can be used with the invention Use aaulsionepoljjeeriwvtionsverfahren. Typical chain transfer agents are, for example, the following Compounds: hexyl mercaptan, lauryl meroaptan, n-butyl meroiptan, tert-butyl meroaptan, n-] iodeoylai «r: captan, n-aayl- ■ ercapptane, Ethyl meroaptoacetate, fhio-B-naphthol, xthyl thioglycolate, Xthanethiol, butanethiol, triophenol, 5-ithoxypropanethiol, Dodecanethiol, Biieopropyljquithogen, PentaphenylMthane, or carbon tetrabronide. You Sobwefe7. containing Xett «n-

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Transfer agents are preferred because the relative amount of chain transfer agent required to modify the molecular weight of the emulsion polymer is usually less than the amount that must be used when other chain transfer agents are used. Satisfactory results are obtained when about 0.5 to about 3 % by weight, based on the total weight of the non-aqueous components in the reaction mixture, of the chain transfer agent are used. As mentioned above, control of the molecular weight of the polymer is easy to achieve Sohnelstereloh dee Tonerharses below the upper Sohmelsgrensen keep from rerographic copy and duplication machines. The bar has a consistently high molecular weight of at least about 10,000 but prevents the formation of undesirable fine particles in automatic machines and improves the resistance of the toner to the cartridges due to impact. It is known that toner particles are normally swollen on the surface of paper and should therefore flow into the surface of a lufnahoeoberflädie "as paper" at a temperature below the discoloration or charring point of the paper. Usual toner sump temperatures, such as those given in some of the patents cited above, for example, fluctuate between approximately 85.degree. C. and approximately the carbonization point of the

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Papers. The charring of the paper is, as in the TJS patent 2,753,308 is specified, at about 175 ⁰ C. Tonersehmelztemperaturen down to about 65 ⁰ C are satisfactory. If the toner melting range is reduced to below approximately 65 ^° C., the tendency of the toner particles to form undesired agglomerates during processing and storage increases considerably. Yinyl monomers polymerized in the absence of a chain transfer agent often tend to form polymers with undesirably high molecular weights.Toner resins with an average molecular weight greater than about 500,000 resist flow into the surface of paper receiving sheets and form poorly adhered or unfixed images. By adjusting the relative amount of a chain transfer agent in a reaction mixture, one can see the average view! control of the monomer units in the polymer molecules ultimately obtained. Increasing the amount of chain transfer agent present decreases the molecular weight of the polymer formed. The relative amount of a chain transfer agent to be used depends on the particular chain transfer agent used and on the monomer (s) used, the polymerization conditions (e.g. the extent to which the emulsion is stirred and the temperature) and the desired average molecular weight. Methods for determining the approximate consensus

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tion of a chain transfer agent to be used to achieve of the desired polymer molecular weight bind known and are, for example, by F. R. Mayo, in "Journal American Chemical Society "» Volume 65, page 2324 (1943) and by P.J. Flory, in "Principles of Polymer Chemistry", Cornell University Pressι page 138 (1953) described «Die Schmelzoder Merge temperatures are measured using a Fisher-Johns melting point apparatus determined.

As is known, there is an emulsion polymerisation process to be carried out in that water, a surfactant, an initiator as well as the monomeric precursor of the to Forming polymers are mixed · When mixed, the molecules of the surfactant in the Water phaae-regulated groups called micelles. Part of the monomer is dissolved in these micelles. In addition, relatively large groups of monomers are duroh the surface-active reinforcement and often also through the rest " the mixture stabilized during the polymerization process * It is assumed that these monomer droplets serve as monomer reservoirs which are later distributed as required in the polymerization reaction. Xcontacts a duroh the water diffusing initiator a monomer res, then he can initiate the polymerization, provided that sioh the system is at a suitable temperature. With continued

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During the course of polymerisation in the cell, the monomer contained in it is used up. The used monomer is replenished by diffusion from the large monomer droplets, whereby the micelles are gradually converted into polymer saddle cells swollen by the monomer. Both during and after the polymerization, the surface-active agent is concentrated at the water / polymer interface, so that running or coagulation of the cells is prevented. To prepare the toner resins of the present invention, the chain transfer agent described above can be used in conjunction with any suitable conventional soul polymerization process. If necessary, common buffers, such as, for example, a phosphate, amino acids or polyamines, can be added during or after the polymerization. The emulsion can contain between about 10 and about 50 weight percent, based on the total weight of the emulsion, of a monomeric material. A monomer content between about 30 and about ( 40% by weight is preferred because greater emulsion stability is obtained when the emulsion contains less than about 40% by weight of the monomer. Greater polymer yields are achieved when the monomer content is at least about 30% by weight amounts to.

Any suitable dyeing process can be used to

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give the desired color to toner resins according to the invention, the dyeing being carried out before drying. The colorant used can either be water soluble, whereby ee In this case only added and in the reaction smell must be dissolved, or consist of a water-insoluble dye, in this case this first in brought an aqueous suspension and then the reaction mixture must be added. The colorant can be added to the reaction mixture at any stage of the polymerization process can be added prior to removal of the aqueous liquid. However, one must ensure that none Colorants which inhibit polymerization can be used if the colorant is added prior to polymerization will. It can therefore in suitable catfish pigment ·, colored pigments, water-soluble dyes, water-insoluble Dyes or other suitable colorants, such as powdered metals, are used Typical pigments and dyes are, for example, the following substances: Monastral-örün, Celliton-Blue, Viotoria-Green S, Spirit-Blue, IRN-100 (iron powder), carbon black, neutral red, Congo red, Titanox A-Io (an anatase titanium dioxide fragment), cadmium yellow or anthraquinone red. Any suitable dye or dye can be used. Dye class can be used to color the suspension. Typical acidic dyes are, for example, anthraquinone C.I. acid blue 127 "Triphenylmethane O.I. Acid Blue 103" AzIn O.I. Acid Blue 98, Xanthene C.I. Acid Violet 9t Nitroso O.I. Acid · -

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green 1, Monoaso-CI-acid yellow 29 »Diaso-GI-acid green 20, xanthene-σ.I.-acid red 92, ohinolin-CI-acid yellow 5 and disazo-GI« acid orange 79 · typical basic dyes are, for example, thiazole-CI- basic yellow 1, etonimine-GI-basic yellow 2 or aoridine-0.I.-basic yellow 4. Typical dispersed dyes are, for example, nitroaoetamine yellow 2 RZ-CI-Dispers yellow 1, Azo-Dispers-Red 1, anthraquinone GI-Dispers- Violet-Celanthrene-Red, Anthraquinone-GI-Dispers-Blue 9, Aminoketone-CI-Dispers-urttn 1, Azo-OI-Dispers-Black 9, CI RuBe 18, 19, 16, 1, 7, 12, 24 and 27 and Diazo-CI-Food Black 1. The pigment or dye should be present in an amount sufficient to strongly color the toner so that it forms a clearly visible image on a recording element. In order to achieve sufficient density, the pigment is preferably used in an amount τοη approximately 1 to approximately 20% by weight, based on the total weight of the colored toner. If a dye is used as the toner colorant, then much smaller amounts of the dye can be used.

As mentioned above, satisfactory results are obtained with toner resins oin average molecular weight between about 10,000 and about 500,000 and a IInfriertemperatur (Tg) have between about 30 and about 85 ⁰ O. The freezing temperature can be

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th methods can be determined, for example by measuring the dynamic modulus of a resin against its temperature and recording the two parameters, the measuring of the dynamic modulus, for example, by the rotary pendulum method can be done. Among other things, the polymeric molecules are usually heated, they are first in a glass-like state, with the dynamic modulus remaining fairly constant with increasing temperature until the freezing or glass transition temperature (Tg) is reached, at which a sharp increase in the dynamic modulus is observed, in addition, the occurrence of a peak is noted, above this temperature the polymer is in a chewy-like state with a lower modulus than that of the peak, and it remains in this state even if the temperature is increased over a considerable range. Eventually the melting point or the first transition temperature (Tm) is reached, at which temperature a second and generally much larger peak appears in the dynamic modulus. Outside of this peak, the resin is in a viscous flowing state. Another method for measuring the glass transition temperature is described by QKDyvik et al in "SPE Transactions ⁿ , Volume 4» Vr. 2 (1964). The freezing temperature of many copolymers can be measured using the Glass Temperature Analyzer SP-222 from Rohm * Haas Company,

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Philadelphia, Pennsylvania. Preferably, the emulsion polymerization resins should have a glass transition temperature between about 40 and about 60 ⁰ O and an average molecular weight between about 20,000 and 300,000. Toner hold of at least about 20,000 which resins having a Tg of at least about 40 ⁰ C and an average molecular weight, show a greater resistance to iilmbildung on the surfaces re-usable xerographisoher plates "a reduced Heigung" to caking and agglomeration as well as improved resistance against the formation of a coating on the surface of carrier beads. Toner resins with a Zg of less than about 80 ⁰ O and an average molecular weight of less than about 300,000 are preferred, because less energy let required to the toner, this Hare · welohe contain au fix to paper. Optimal xerographic properties are achieved when the resins one-Tg "wipe about 50 to about 75 ⁰ O and an average molecular weight between about 30,000 and 50,000 be sit" en. Toners with a Tg of between about 50 and about 75 ⁰ and an average molecular weight between about 30,000 and 150,000 have a long life in automatic copier and duplicating machines and are particularly suitable for use in high-speed decade development. Exceptionally good results

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These are achieved with styrene / alkyl methacrylate copolymers, which have the molecular weight given above and the Xg defined above, in particular when the alkyl radical of the methacrylate is 3-6 carbon atoms contains. Toners that contain these copolymers are characterized by an extremely long service life in the machine oil and form excellent colored toner images, which are essentially free of background. Copolymers of styrene and alkyl methaorylates in which the alkyl group

Contains 3-6 carbon atoms are therefore the ones to be avoided harae according to the invention.

The spray drying stage consists in spraying the solution of dye and waeserlatex into small droplets, mixing them with a gas and keeping the door in suspension in the oil until the liquid has been expelled from the droplets by evaporation. As a result of the heat and the surface tension, the resin parts converge in each drip tray and unsole the dyeing compound enclosed in the tray. Most often during the spray drying air as the gas for the Trook-, voltage level used · Bas Ga * is aufgabelst such ₉ that the temperature of Harstellohen on one! Point is increased at which they run, so that many small Te High to consider when Atomization has been formed in the form of a droplet, with the formation of a small hard spherical shape

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Toner particles, which enclose a colorant which has been present in the droplets, come together.

The colorant must be added to the reaction mixture before the spray drying stage. If the colorant is insoluble in water, it must of course be suspended in the reaction mixture. This can be done in the simplest way by simply using a commercially available | aqueous suspension of the desired pigment is added, followed by thorough mixing. Commercially available aqueous suspensions of carbon black pigments, such as "Aquablak ^n, from Columbian Carbon Company, Inc. commercialized, have erwieean be very acceptable in this Besiehung Pa. Some of these suspensions against" shock "are pretty empidndlioh is, It is preferable to add these pigment suspension ions to the aqueous reaction solution with gentle stirring in order to avoid precipitation of the pigment from the suspension than the size of the finished toner particles, so that a consistency of the product is promoted and the colorant is incorporated in the toner particles

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a pigment with a smaller particle size the formation a more stable and more uniform suspension, as well as more uniformly colored toner particles but has the consequence aqueous suspensions of the desired pigment Not commercially available, then these suspensions can thereby That dae pigment can be made with water and a suitable surfactant is mixed. Water suspensions from other water-resistant liquid dyes » Agents can also be used for addition to the aqueous reaction mixture by the same method. If water-soluble dyes are used as colorants, then you can either directly in the aqueous Reaktlonsmisohung be dissolved or dissolved in water, whereupon the addition of this solution iu the subsequent aqueous reaction mixture. As mentioned above, the colorant of the aqueous reaction solution before the spray drying stage sugeeetst are · BIe addition can also be carried out before or after the polymerization of the monomer material take place. The colorant is preferably added to the aqueous reaction solution after the polymerization des Honomerenmaterials and In no oh more preferred catfish just before the spray drying stage sugesetst as this way a greater scope for the selection of the coloring agent given 1st. If you keep a uniform dispersion of colorant and hare in water and controls the solid consistency in the final mixture of dye and water

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serlatex, then the final toilet size of the generated fan can be controlled in a simple way by regulating the size of the droplets that are generated by the spray droplet in the spray drying system. This result is obtained because if the percentage of water in each droplet is the same and the droplets are the same size, the amount of water removed from each droplet in the drying process is the same, so that an equal amount of resin and pulp is used Production of the finished part remains. To set optimal spray drying concentrations, the latex solids content is adjusted, for example by dilution, to about 10 to about 20 weight percent. If the ester concentration is adjusted to below about 10% by weight, then the process becomes less economical. Solids concentrations that are noticeably higher than about 50% by weight favor the formation of undesirably large toner particles. The number of polymer parts ( from the latex in a drip and consequently the number of polymer parts that are present in the finished toner particles) is preferably relatively large, so that these latex parts form a well-shaped, hard β toner particle and that contained in the spray-dried liquid drip Colorants are used, regardless of whether the colorant is a water-insoluble material in suspension or in water

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soluble material is in solution. This catfish is. the size of the polymer particles used in the emulsion depends directly on the size of the desired finished toner particles, with smaller polymer particles being preferred for the production of satisfactory toner particles of smaller sizes. For most purposes it has proven to be advantageous if the electrostatographic toners have a size of approximately 0.5 to approximately 80 μm, the size depending on the particular intended use of the toner. If toner particles are to be produced with a final durometer below about 20 microns, then it is important to keep the polymer particles in the water latex below about 6000 2 units (diameter). Toner particles are old one Durohmeeeer in the lower region dee from O _"9 are made 5 to 80 u extending Durohmeseerbereichee then ee is preferred, this Polymerisatteilohen in the latex, if possible below 6000 Å-Binheiten and vorsugsweiee at about 1000 ^ units or less to keep. It is beneficial to make the Folymerl saddle rows so small "that a relatively large" number of these particles can be contained in each finished toner particle. It has been found quite generally that the size of the polymer particles in the latex can never be too small, but rather that the oil can exceed the maximum limits given above. The colorants are firmly bound in the toner cells, which assume a uniform spherical shape »

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so that no free colorant can be found in the final product is. In addition, the use of smaller polymer particles in the water latex contributes significantly to the stability of the Latex at · The spherical shape is obviously created when a large number of small polymer beads is used to form a toner particle, since these particles assume a roughly spherical shape before they converge completely. Are the inventive Toner mixtures used in cascade development processes, ™ then the toner should have an average part diameter less than about 30 u and preferably between about 5 and 17 u for best results

Suitable surfaced and non-coated materials for cascade and magnetic brush development are known. They can Trägertellohen electrically conductive, insulating, magnetic or nioht be magnetic, provided (that it has a charge accept that has a polarity which is that of the toner particles is opposite when the Trägerteilohen be brought into tight contact with the toner particles, so that the Toner particles adhere to and surround the carrier parts

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electrostatic latent image is opposite. On the other hand, there will be a negative reproduction of the electrostatic Image is desired, then the carrier particles are selected in such a way that the! Toner particles take on a charge which has the same polarity as the electrostatic image. In addition, the materials used for the carrier particles depend on their triboelectrical properties Reference to the electroscopic toner selected »so that» if these particles are mixed with the toner materials or brought into mutual contact »a component of the Developer is positively charged »if the other component is below the first component in the triboelectric case» he stands, and is negatively charged when the other component is above the first component in the triboelectrisohen Row is found. By appropriate selection of materials depending on their triboelectrisohen effects the polarities of their charge during mixing are selected in such a way that the electroscopic toner particles adhere to and coat the carrier particles, and they also adhere to those Parts of the surface bearing an electrostatic image adhere which is more attractive the toner particles in comparison bu the attraction fttr possess the carrier particles. Typical carriers are, for example, sodium chloride, ammonium chloride, ammonium potassium chloride, Roohelle sals, sodium nitrate, aluminum citrate, potassium alcohol, granular zirconium, granular silicon, methyl methaorylate, glass,

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Silica or the like. The carriers can be used with or without a coating. Many of the typical supports mentioned above are described in U.S. Patents 2,618,551, 2,638,416 and 2,618,552. Here, a diameter of the coated carrier particles between about 50 and about 1000 μ is preferred, since these particles then possess sufficient density and inertia to adhere to nioht dtn electrostatic images during the Kaekadenentwioklungsverfahrens. Adhering of carrier beads to surfaces of xerographic orphans is undesirable, since deep scratches are formed on the surface during image transfer and during cleaning of the rollers, especially when cleaning is carried out using a fabric cleaner, for example in U.S. Patent 3,186,838. In addition, there is no printing when carrier spheres adhere to xerographic imaging surfaces. Iu general, satisfactory results are obtained "when about 1 part of toner is used with about 10 to about 200 (weight parts of the carrier.

The toner compositions of the present invention can be used to develop electrostatic latent images on any corresponding surface bearing a latent electrostatic image, including photoconductive surfaces, be used. Known photovoltaic materials are

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for example vitreous selenium, organic or inorganic photoconductors embedded in a non-photoconductive matrix are, organic or inorganic photoconductors embedded in a photoconductive matrix, or the like. Representative patents in which photoconductive materials are mentioned; are, for example, U.S. Patent Numbers 2,805,542, 2,970,906, 3,121,006, 3,121 and 3,151,982.

The following examples serve to explain the toner materials according to the invention and their use in more detail for developing latent images. Unless otherwise stated, the parts and percentages relate to the Consecrated. Spray drying is used in the following examples a Bowen Laboratory Spray Roota Anti-Corruption that uses Manufactured by Bowen Engineering Zno., Forthbranoh, New Jersey will. This device, which is designed for laboratory scales consists of a conical drying device with a concurrent air flow and has a replaceable spray head, which is mounted near the top of the drying chamber, with the spray head is located inside the dry air distribution ring. Any of the known atomization methods can be used, such as they are normally used in spray dryers, for example centrifugal or vortex pressure nozzles. Except-

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you can use any known atomization process, for example a pneumatic atomization or a two-fluid atomization, a jet of the liquid leaving the nozzle by means of a sioh at high speed moving gas stream is divided. You can also get a Atomization by ultrasound resonance or by impact the flow of liquid against a solid surface produce. The atomizing device used in the following examples has a spinning loaf-like device, in which the liquid is broken up by discharging it at a high speed from the outside of a rotating base plate. This type of atomizer is preferred if any solids, such as a pigment, are suspended in the liquid, as others Atomizing nozzles often occur during atomization due to friction due to these moving at high speed Solids are destroyed · When using one of these atomizing devices is the size of the finished products | toner particles a function of the consistency of the solids in the trupfohen as well as the size of the duroh the atomization device generated (droplets · Venn also the droplet size generated by the atomizing device of different Factors relating to the particular type of atomizing device used depends, so this drip size riohtet but primarily according to the radius and the rotation speed, with what sioh the above described

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Spinning disc atomizing device rotates. If atomization is a complicated and not yet fully understood phenomenon, the best results are likely to be achieved if the empirical guidelines given in the following examples are observed. Unless otherwise stated, the spinning disc atomization device used is a disc which has a radius of 25 mm (1 inch) and rotates at 50,000 rpm, with different particle sizes being generated, mainly depending on the concentrations of pesticides in the liquid, as in the examples emerges. Other systems may, of course, require a change in the radius of the spinning disc, the speed and the pesticide concentration in order to achieve appropriate particle sizes. After the liquid has been atomized to the appropriate droplet size, it moves through the heated dry air until the water has been driven off by evaporation. This evaporation is accelerated by the high surface: mass ratio of the droplets and the warmth of the air. The time during which these drips are kept in suspension in the dry air is referred to as "dwell ^11. When the dried toner cells leave the drying air chamber, they must not be so sticky that they stick to the walls of the apparatus or agglomerate in the collecting device . It turned out-

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provided that the desired result is achieved when using the preferred thermoplastic polymers can be that such a temperature of the listed Drying air (input drying air) is maintained that the particles leaving the spray dryer are just below their melting or jointing temperature are while a higher drying air supply temperature (drying air input temperature), as the water evaporates after the droplets have been heated for the first time a cooling of the run-off particles has as a result. Optionally, the dried toner particles can be included Exit from the air chamber by means of a cool air stream quenched to ensure that they do not agglomerate in the collector · However, this stage is not common and is not used with the materials normally used. The outlet end of the Spray drying device is made with a syklon-like pro— connected collecting device, from which the finished dried particles at the end of the process · eatnoaneu can.

example 1 Sin Tonerhare is made from the following materials}

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Parts by weight 5 65 5 35 0, 2 0, 2 240

Material
Styrene

n-butyl methacrylate
Ammonium persulfate
Katriuinmetabieulfite

Sodium alkyl aryl ether sulfate
(27 #Lge aqueous solution),
Triton W-30

Lauryl mercaptan
Deionized water

About 120 parts by weight of the deionized water and about 2 parts by weight of the surfactant are placed in a vessel equipped with a water-cooled condenser, an electric stirrer, an inert gas bubbler, and a thermocouple. The apparatus is purged with argon, followed by a temperature of about 25 ⁰ O is stirred. The monomers and the mercaptan are re-set with continuous stirring, which is followed by the introduction of the Hatrlum metabisulphite, dissolved in about 60 parts by weight of water. The ammonium persulphate and about 60 parts by weight of water are then added. The temperature of the Reaktionsmisohung is to a maximum of about 80 ⁰ O allowed to rise and maintained at this value for a period of about 2 hours with constant stirring. The emulsion becomes aneol-flowing

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cooled with stirring and then sifted through a cheese bag. A sample of the copolymers produced by this method has a glass transition temperature (Tg) of about 67 ⁰ C and an average molecular weight of about 180000 · The emulsion is prepared by adding deionized water to a solids content of about 15 wt ^ set. A spray-drying liquid is prepared from this emulsion by adding 1 part by weight of Aquablak 41 per 4 parts of J of the emulsion. Aquablak 41 is a suspension of 25 weights of carbon black with a diameter of 9 mn in water and is brewed on the market by the Columbian Carbon Company. This spray drying liquid is then applied using a spider-ear atomizer under a pressure of about 5-3 kg / cm (75 psi) at a boiling rate of about 80 ml per hour and a suctioned drying air at a temperature of about 93 ⁰ O (200 ⁰ I) and an Aueetoestemperature of about 77 ⁰ C (170 ° 7) spray-dried. A qualitatively good, medium-fine powder is thus obtained, the main quantity of the rope lengths being approximately 7 and approximately 11 µm. This powder provides good xerographic images which can be easily reflexed if an appropriate test is carried out in a conventional xerographic copier using a cacade-developing method. Furthermore, there is no agglomeration

09822/15 64 ORIGINAL BATHROOM

tion of the toner particles after storage of said particles in a maintained at a temperature of about 43 C (11O ⁰ P) Luftsirkulationsofen (time: about 24 hours) "beobaohtet.

Example 2 A toner resin is made from the following materials:

material Place of worship Styrene 65 n-butyl methacrylate 35 Ammonium persulfate 1 Sodium alkylaryl ether sulfate 1 (27 aqueous solution) lauryl mercaptan 1.5 Deionized water 240

About 120 parts by weight of a deionized water and about 2 parts by weight of the surfactant are incorporated into the reactor described in Example 1. The device is flushed with carbon and stirred at room temperature. The monomers and the mercaptan are added aneohliessend with stirring. They obtained mixture is heated to about 75 ⁰ O, after which the ammonium persulfate, as well as the rest of the water are added. The reaction becomes isothermal at approximately 75 ^° C during

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carried out over a period of 2 1/2 hours. The emulsion is then cooled with riots and sieved through a sieve. A sample of the copolymer produced by this process has a Tg of approximately 67 ⁰ O and an average molecular weight of approximately 90,000. The setting of the solids content of the emulsion, the addition of carbon black and the spray drying are repeated in the manner described in Example 1. The spherical toner particles obtained give excellent xerographic images of high density, which can be fixed in a simple manner in a conventional xerographic copying machine. This Xoner are also compared with the formation of films on the surfaces re-usable image forming surfaces resistant I also no tendency is dee Loners to form agglomerates observed when the toner particles in a (11O ⁰ F) oven maintained at a temperature of about 45 ⁰ C be stored for a period of approximately 24 hours.

Example 5 Sin toner resin is made from the following materials: Material divided into parts

Styrene 65

n-butyl methacrylate 35

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Aluminum persulfate 1 Sodium alcaryl ether sulfate 1

(27 ^ aqueous solution)

Lauryl mercaptan 3 Deionized water 240

The polymerization method described in Example 2 is repeated using the components described above. A sample of the copolymer produced has a Tg of approximately 67 ⁰ O and an average molecular weight of approximately 50,000. Spherical toner particles are obtained which have properties which correspond to the properties of the toner particles obtained in Example 2.

Example 4

Example 2 is repeated, with the exception that the amount of JLquablak added to the emulsion is reduced with the BUfIw. HIe ^ other conditions ⁰ IbA * ■ essentially the same. Saber it turns out. that a toner with a good quality is always achieved, which has approximately the same tellohen size. Only the blackness of the particles is somewhat reduced.

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Example 5

Example 4 is repeated with the exception that a double disc atomizer is used which operates at a loading speed of 0.45 legs per minute and a speed of 21,000 rpm. Under these conditions it is found that the particle size varies between approximately 6 and approximately 8 μ (diameter), with good pigmentation being achieved. Very good quality, sharply defined images are obtained if this Xoner is in | a common xerographic copier is used *.

Example 6

Dae Example 5 is repeated, that except "the SprühtrocknungsflUssigkeit about 20 <f> contains solids. The temperature of the ejected air is about 71 ⁰ C (160 °?), While the Besohlokungsgeeohwindlgkeit is adjusted to about 0.6 kg (1.3 pounds) per Hinute. Under these conditions, a black, free-flowing Xoner is produced, the majority of the toner particles having a size between approximately 5 and approximately 7 η (Durohmeseer).

Example 7

Example 6 is repeated with the exception that the "! Led drying ^{air has a temperature of approximately 116 0} O (24O ⁰ F). The temperature of the discharged air is

BATH ORIGINAL

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about 77 ⁰ O (170 ⁰ P), before the feed rate is set at about 1.1 kg (2.5 pounds) per minute. The size of the generated 2 particles scliv / ankt mainly between about 7 and about 11 μ.

Examples 5, 6 and 7 above are carried out in a Bowen spray dryer with a size of 2.10 m (7 feet) carried out.

Example 8

In carrying out this example, an emulsion is prepared and pigmented in the manner described above in connection with Example 2, with the exception that the formulated spray-drying liquid is diluted down to a solids content of approximately 10%. The spray drying takes place in a pneumatic atomization device with a filling speed of about 80 al per minute and an air pressure of about 5t 3 kg / om (75 pel). The dryer is operated at a temperature of sugefühxten loft of about 82 ⁰ O (180 ⁰ P) and at a Auestosstemperatur of about 66 ⁰ O (150 ⁰ P). Spherical particles are obtained, the majority of which have a diameter of about 1 micron.

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Example 9

A sample of the emulsion described in Example 3 is used to prepare a spray drying liquid with a solids content of approximately 12.5% by weight. About 102 g of the spray-drying liquid obtained are made up of about 11 g of Aquablak 15 and a soot suspension with a particle size of about 20 0921 which contains about 30 pg by weight of the soot. Piping Sprühtrooknungsmisohung is spray dried using a Spinnsoheibensprühvorrichtung provided with a Beschiokungsgescbwindigkelt of about 80 ml per Hinute, a IMieendruck of about 7 »0 kg / cm (100 psi), a" ugefUhrten drying air having a temperature of about 88 ⁰ C (190 ⁰ P) and a temperature of the expelled air of approximately 43 ⁰ C (110 ⁰ F). Spherical particles are obtained, the majority of which have a size of approximately 5-7 microns. In this case, too, it is found that good xerographic images are obtained when the Xoner is tested in a conventional xerographic copier.

Example 10 A toner resin is made from the following materials; Material flewiohteteila

Styrene 70

Vinyl acetate 30

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Jijsmonium persulfate 1 Pioethyl ester of sodium "- Eulfobernsteinnäuro (Aerosol Oi) 2.5 Lauryl mercaptan 1

! • distilled water 190

About 100 parts by weight of the distilled water and about 2.5 parts by weight of the surfactant are added to the reaction kettle as described in Example 1. The device is flushed with nitrogen, whereupon it is stirred at room temperature. The monomers and the mercaptan are prepared while stirring. You mixture is erhitet to about 75 ⁰ C, after which the Anmoniumpersulfat and the remaining water are eugeaetat. The reaction is carried out isothermally at about 75 ⁰ O for a period of about 3 hours, so that an essentially complete conversion of the monomers is ensured. The emulsion is then cooled and sieved while stirring. A sample of the copolymers has a eraeugten! Pg of approximately 76 ⁰ O and a molecular weight of about 175 thousandth the setting of the solids content of the emulsion "the Zugabo of carbon black, and spray-drying are carried out according to the procedure described in Example 1. The spherical toner particles obtained give good xerographic images and easily melt below the usual ones

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Toner melting conditions. There is no inclination of the loner observed to form agglomerates when the toner particles (P ⁰ 110) are stored during a time period of about 24 hours in an air circulating oven at a temperature of about 43 ⁰ C.

Example 11 Bin toner resin is made from the following materials! Material parts by weight Vinyl acetate 20 Vinyl chloride 80 Annaonitsaper sulfate 0 »5 Sodium thiosulfate 0.3 Sodium lauryl sulfate 3 Thiophenol 1 Deionized water 160

About 100 parts by weight of the deionized water and about 3 parts by weight of the surfactant are placed in a reaction kettle of the type described in Example 1. The apparatus is purged with argon "is followed by stirring at 25 ⁰ C. The monomers and the thiophenol are added with stirring. The mixture obtained is initially mixed with the remaining ingredients. The reaction will

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"imter pressure at about 70 ⁰ C over a period of about 3 hours durohgoftihrt whereby Oine substantially complete conversion of the monomers is ensured. The emulsion is anschliesaend cooled and sieved. A sample of the copolymer produced has a! Eg of approximately 72 ⁰ C and an average molecular weight of about 130,000. The adjustment of the esters content of the emulsion, the addition of carbon black and the spray drying are carried out according to the manner described in Example 2. The spherical toner particles obtained give good xerographic images and melt easily under the usual toner melting conditions is no inclination of the Xoner but formation of agglomerates observed when the toner particles (110 F ⁰⁾ can be stored for a period of about 24 hours in an air circulating oven at a temperature of about 43 ⁰ O.

Example 12 A toner resin is made from the following materials: Material Qewioht parts Vinyl chloride 40 Methyl acrylate 60

Hydrogen peroxide (3% by weight 30 # aqueous solution)

Peracetic acid (10 Qewiohts-jCige 10 aqueous solution)

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Sodium salt of alkylaryl

polyether sulfonate (72 # mixture), 2

Tamol SN

Thio-B-naphthol 0.6 Deionized Water 150

About 90 parts by weight of the deionized water and about 2 parts by weight of the surfactant are placed in a reaction kettle of the type described in Example 1. The apparatus is purged with carbon dioxide and stirred at room temperature. The monomers and the mercaptan are added with stirring. The resulting mixture is heated to about 60 ⁰ C, is added after which the rest borrowed ingredients. The reaction is carried out isothermally at a temperature of approximately 60 ⁰ O for a period of 2 hours. Baduroh ensures that essentially a complete conversion of the monomers takes place. The emulsion is ansohliessend cooled with stirring and "sieved A sample of the copolymer produced has a Xg of about 34 ⁰ O, and an average molecular weight of about 250000. The setting of? Eetstoffgehaltse of the emulsion, the addition of carbon black as well as the spray drying after in Example 2 described method carried out. The spherical toner particles obtained give good xerographic images and easily melt under the usual toner syrup conditions. There will be no

1 0 9 8 2 2/1 5 5 A ^ ₀ original

narrowing the observed! toner to form agglomerates when the toner particles (P 11O ⁰⁾ are stored for a period of about 24 hours in an air circulating oven at a temperature of about 43 ⁰ C.

Example 13

A toner resin is made from the following materials:

Material Qeviohtstelle Styrene 65

n-butyl methacrylate 35

Ammonium persulfate 0.5 Sodium metabisulphate 0.5 Diootyl ester of sodium sulfo-

succinic acid 1

Hexyl mercaptan 2 Distilled water 240

About 110 parts by weight of the distilled water and 1 part by weight of the surfactant are placed in a reaction kettle of the type described in Example 1. The device is flushed with nitrogen, where * at 25 ⁰ O is stirred. The monomers and the mercaptan are then sugesetst while stirring. The remaining ingredients are then added with continuous stirring. The reaction is allowed to continue as long as

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until a maximum temperature τοη 80 ⁰ G is reached. These temperature of ⁰ G 8Q is maintained for about 4 hours, su ensure a substantially complete conversion of the monomers. The emulsion is then cooled and sieved while stirring. A sample of the copolymer produced has a Tg of about 67 ⁰ C and an average molecular weight of about 90000. The solids content of the Eaulsion-56 is set GewichtB solids using distilled water to approximately 10x. About 10 | Weight s-jC, based on the weight of the latex Feetatoffe, of a Sosin blue dye are added to the emulsion, whereupon the resulting solution is stirred by means of a Bronaon-Sonifier-Ultrasohallmisohere. You mieohung is usually spray-dried in the catfish described in Example 1. The spherical toner particles obtained give excellent xerographic images and easily melt under the usual toner maintenance conditions. Said no tendency of the foners to agglomeration is observed if they are stored for a period of about 24 hours in an air circulation ^{oven kept at a temperature τοη uagefKhr 43 0} O (110 ^{0 I).}

Example 14

lin fonerharz is produced using the following materials »

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material Parts by weight Vinylidene chloride 20th Vinyl chloride 80 Amraoniurapulphate 0.5 Hatrium metabisulflt 0.5 Sodium lauryl ethoxylate sulfate (28 #Lge Misοhung), Supex SS 6th n-butyl mercaptan 1.5 Deionized water 150

About 75 parts by weight of the deionized water and about 6 parts by weight of the surfactant are placed in a pressure vessel of the type described in Example 1. The device is purged with argon while stirring at room temperature. The monomers and the mercaptan are initially dissolved while stirring. The mixture obtained is ^{heated to approximately 25 0} O, whereupon the remaining constituents are added. The reaction is carried out under Brück, a maximum temperature of approximately 70 ⁰ O being allowed. They temperature is maintained at 70 ⁰ O tent during a span of about 4 hours to substantially complete conversion of the monomers to gewährloioten. The emulsion is then cooled and sieved while stirring. A sample of the copolymer produced has a Tg of about 51 ⁰ C to dee setting? Estatoffgehaltos of the emulsion, the addition of Rufl and the SprUh-

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■ AD ORJG « _NAt

drying are carried out according to the manner described in Example 5. The spherical sonor particles obtained provide excellent xerographic images and easily melt under the usual toner melting conditions. Ee is observed no tendency of the toner to form agglomerates "when the toner particles are stored in a maintained at a temperature of about 43 ° C (110 ⁰ P) oven over a period of about 24 hours.

Example 1 5

A toner resin is made up of the following Styrene Materials made material ethyl methaorylate Parts by weight Αητι *> τϊ1ΐ ™ ηρ «τί" ΐ1 f «rt 50 Aerosol MA. (80 weights 50 Mixture) 2 Lauxyl mercaptan Distilled water 1.5 2 240

About 140 parts by weight of the distilled water and about 2 parts by weight of the surfactant are included a reaction vessel of the type described in Example 1 filled. The device is flushed with argon, with stirring at the temperature of the cylinder. The monomers and the mercaptan are added with stirring. The mixture obtained is

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heat to about 80 ⁰ C, was sugeeetzt whereupon the ammonium persulfate, as well as the remaining water. The reaction is carried out isothermally at approximately 80 ^° C. for a period of approximately 3 hours, which ensures that an essentially complete conversion of the monomers takes place. Pie emulsion is then cooled and sieved while stirring. A sample of the copolymers produced besitst a · Ig of about 62 ⁰ O, and an average molecular weight of about 40000. The setting dee Peststoff fetched the emulsion, the addition of carbon black, and spray-drying are carried out according to the procedure described in Example 1 catfish. The spherical toner particles obtained give good xerography with no images and so melts under then bad toner melt conditions. No increase in the toners but the formation of agglomerates is observed when the tonartallohan is stored in an air circulation oven maintained at a temperature of approximately 43 ⁰ O (110 °?) For a period of approximately 24 hours.

Example 16

Bin Tonerhara is made from the following materials:

Material Qawiohtatrle styrene 80

Xthyl aorylate 40 Potassium persulfate 1

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BAD ORiGJNAL Octylphenylpolyäthorsyäthanol

(70 weight mixture), Triton X-405 3

Lauryl mercaptan 2 Deionized water 240

About 100 parts by weight of the deionized water and about 3 parts by weight of the surfactant are placed in a reaction kettle of the type described in Example 1. The device is septtlt bit of carbon dioxide, | stirring at room temperature. They monomer and the mercaptan are ansohliessend sugesetst stirring · mix is heated to about 75 ⁰ O, whereupon as "Kaliumpereulfat and restliohe water · be added to the reaction is conducted isothermally at about 75 ⁰ O over a period of about 4 hours This ensures that an essentially complete conversion of the monomers has taken place. The emulsion is cooled down and sieved with stirring. Sine sample of the copolymer produced has a Xg of about 41 ⁰ O, and an average molecular weight of about 85000. It setting Feet solid content of the emulsion, the addition of carbon black, and spray-drying are carried out according to the procedure described in Example 2 catfish. The spherical toner particles obtained give excellent xerographic images and easily melt under the usual toner melting conditions. Ee there is no tendency for the toner to form agglomerates ·!?, *

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observed when the toner particles held Luftsirkulationsofen be stored for a period of about 24 hours at a at a temperature of about 43 ⁰ C (110 ⁰ F).

Example 17 A toner resin is made from the following materials:

Material Qewiohtsteile Styrene 65

n-butyl methacrylate 35

Ammonium persulfate 0.5 Sodium bisulfite 7.5

"Hatriumsala from AlkylarylpolT & thtr * · sulfonatt X ^ iton X-200 ■ 4

Dodecylne ^ kaptan 0.5 Soot (15% by weight aqueous Mixture) s Aquablack U 33 Delonated water 160

About 100 parts by weight of the deionized water and about 4 parts by weight of the surfactant are placed in a reaction kettle of the type described in Example 1. The device is flushed with nitrogen, with stirring at 25 ^° C. The monomers and the mercaptan are added with stirring. You will use Aquablaok Ü mixture

1 09822/1564 "

with continuous stirring, followed by the addition of the remaining ingredients. The reaction temperature is allowed to ^{rise to 75 °} C. whereupon it is held at this value for about 2 hours in order to ensure that an essentially complete conversion of the monomers is achieved. The emulsion is cooled and sieved aneohlieeeend with stirring. A sample of the copolymer produced after the removal of the carbon black shows a Xg of about 67 ⁰ C The emulsion is diluted with deionized water ™ at a solids content of about 20 Gewiohts-jG and NaOH following the procedure described in Example 6 spruhgetrooknet. The spherical toner particles obtained provide excellent xerographic images and smoothness under the usual toner fusion conditions. There is not observed the Veigung! Toner to form agglomerates ^ when the toner particles are in a stored during a period of about 24 hours at a temperature of ungefKhr 43 ⁰ C (110 °?) Luftzirkulationeofen held. {

It should be pointed out that the specified monomers were not included the main part of the resins used in the invention dismantle existing units. This does not mean that J β do oh the presence of other monomeric units or reactants the end. For example, some may be commercially available Materials such as styrene contain minor amounts of homologues. There can be any smaller amount of it

109822/1554

Substitute compounds are present in the materials according to the invention.

The materials and conditions given in the examples have only exemplary character. It can be different other toner resins, additives, colorants and other components other than those specified above instead of In the examples are used, with similar results are obtained. Other materials, such as common Stop materials (for example sodium poly sulfide, vatriundimethyldlthlooarbamate. Hydroquinone or phenylhydraein) to improve the handling of the systems sugeeetst.

109822/155 *

Claims (24)

Claims Γ? ** ι * 7Γ '' 'ι ί -' ΤίΓΓΓΤΤ ιΙ J ι '"TmT 1. Spherical xerographic toner particles, characterized in that that they consist of a surfactant, at least one chain transfer agent, a colorant and a vinyl polymer, the Vinyl polymer has a Tg of about 30 to about 85 ⁰ C and an average molecular weight between | about 10,000 and about 500,000. 2. The toner particles of claim 1, characterized in that the polymer has a melting temperature between about 65 and about 175 ⁰ O. 3.! Donor particles according to claim 1, characterized in that the polymer is a copolymer of a styrene monomer with an alkyl methacrylate monomer. j 4. Xerographic developer composition, characterized in that it consists of spherical toner particles which consist of a surface-active agent, at least one chain transfer agent, a colorant and a vinyl polymer, the polymer having an Ig value of approximately 30 to approximately 85 ^° C. and an average Molecular growth between approximately 10,000 and approximately 500,000, as well as considerably larger X-carriers BAD ORlG ¹ NAL 109822/1554 "consists. 5. Enbwicklersucsutimonsetzung according to claim 4 »characterized in that They contain about 1 part by weight of the spherical toner particles and about 10 to about 200 parts by weight which contains carrier pots. That the toner particles have about 50 to about 1000 μ 6. Eatwicklerzueammensetaung according to claim 5, characterized daduroh an average marriage part size of less than about 20 μ and an average dl · Txägerkügeichen Tellohengröese Bwieohen. 7 * A process for the production of lerographic toner cartridges according to claims 1-3 »characterized in that an aqueous emulsion is produced from water, a size-active agent, a vinyl monomer material and at least one chain transfer agent, the nucleus. by polymerizing the Vinyliionoaerenmaterial in the presence of an initiator to form a polymer with a Tg-Vert of about 30 to about 85 ⁰ O and an average molecular weight BWisohen about 10,000 and about 500,000 in a latex, a colorant is added to the latex to form a spray drying mixture is, the Sprührooimnngintl leads to the formation of small droplets, dl in a gas suspen- 1 09822/1554 ^ _{0 0 RIG} , _NAL are dated, is atomized, the! droplets are kept in suspension in the gas while heat is applied is left until the water runs into the droplets, with the colorant trapped in the dropper and the resulting dry toner particles are collected. 8. The method according to claim 7 »characterized in that the emulsion used between about 0.5 and about 3 parts by weight, based on the total weight of the nonaqueous Materials in the emulsion, de · chain transfer agent contains. 9 · The method according to claim 6, characterized in that the chain transfer agent used is a sulfur containing compound. 10. The method of claim 7, daduroh in that the μ ▼ erwendete emulsion is less than about 3 wt ^, based on the total weight of the nioht-aqueous materials in the emulsion, the surfactant contains. 11. The method according to claim 7, characterized in that the polymer used has an average molecular weight between about 20,000 and about 300,000. 109822/155 4 bad original 12. The method according to claim 11, characterized in that thea the polymer used has an average molecular weight between about 30,000 and about 150,000. 13. The method of claim 7, daduroh in that the polymer used an Ig zwisohen about 40 and has about 80 ⁰ C. 14. The method according to claim 7 characterized daduroh "indicates that the polymer used twisohen an Ig having about 50 to about 75 ⁰ C. 15. Method according to Claim 7 »characterized in that the polymer used has a melting temperature between about 65 and about 175 ° C. 16. The method according to claim 7 »daduroh characterized in that the spray drying chemistry used is less than approximately 20% by weight, based on the total weight of the non-aqueous materials in the smile ion, of the dye contains. 17. Method according to Claim 7 »daduroh characterized that dae polymer used an Oopolymerisat from a 109822/1554 - 65 is styrene monomer with an alkyl methacrylate monomer. 18. Procedure according to. Claim 17t characterized in that the alkyl group of the alkyl methacrylate has 3-6 carbon atoms contains. 19. The method according to claim 7, characterized in that the Sprühtrocknungsfltiesigkeit is sprayed to such IeIlchengrösse that the Ff contained in each droplet itstoffe finished · Seilohen solid having a diameter of less than about 20 μ form. 20. The method according to claim 1, characterized in that an aqueous emulsion is prepared, the waeeer, a surface-active agent, a vinyl monomer material, at least one chain transfer agent and up to about 20% by weight, based on the total weight of the non-aqueous material in the emulsion, of a dyeing I by containing the emulsion by polymerization of the Vinylmonomerenmaterials in the presence of an initiator to form a polymer bit a Tg of about 30 to about 85 ⁰ O, an average molecular weight BVisehen about 10,000 and about 500,000 and a Melting temperature between about 65 and about 175 ⁰ C is converted into a latex, a spray drying solution with a PET content Bwischen ungt- 109822/1554 ^ ₀ original for 10 and about 20% by weight, based on the total weight spray drying is not formed, i.e., the spraying of the liquid with the formation of small droplets, which are suspended in a gas, is atomized, the droplets produced being of such a size that the particles contained in each droplet a finished, solid rope with a diameter of less than about 20µ results in "dl" droplets in The suspension can be kept in the gas while heat is applied until the water enters the gas Droplet has run and the colorant is included in the droplets, and the resulting dry Toner particles are collected. 21. The method according to claim 20? characterized in that the spray drying liquid is thereby atomized » that a stream from the spray drying liquid against a rotating disk is straightened. 22. The method according to claim 20, characterized in that the polymer used is an Oopolymerieat from one Styrene monomer with an alkyl ethaorylate monomer 1st. 23. Images Diffraction process for forming a toner image, characterized in that an electrostatic latent Image is generated on a surface and the electrical ORIGINAL 109822/1554 static latent image with the spherical xerographic Toner particles according to claims 1-3 is contacted, wherein at least one rope of the spherical xerographisohen Toner particles are attracted and retained therefrom in accordance with the electrostatic latent image. 24. Imaging method for forming a toner image a surface, characterized in that an electrostatic latent image is generated on a surface, | whereupon the electrostatic latent image with the xerographic The developer according to claim 4 is contacted, wherein at least a part of the spherical toner particles in accordance with the electrostatic latent image is attracted and held by it. 109822/1554