DE2435894A1 - FINALLY DISTRIBUTED TONER PARTICLE COMPOSITION - Google Patents

Description

DR. ING. E. HOFFMANN · DIPL. ING. W. EITLE DR. RER. NAT. K. HOFFMANN

PATENT LAWYERS

D-8000 MÜNCHEN 81 ARABELLASTRASSE 4 TELEPHONE (0811) 911087-89 TELEX 05-29619 (PATHE)

25 601 Kd / dl

Xerox Corporation Rochester, N.Y. (V.St.A.)

dispersed toner particle composition

The invention relates to imaging systems and, more particularly, to improved electrostatographic developing materials, their manufacture and use.

The formation and development of images on the surface of photoconductive materials by electrostatic Means is well known. The basic electrostatographic Methods as described by C. F. Carlson in U.S. Patent 2,297,691 include-; Applying a uniform electrostatic charge to a photoconductive, insulating layer, the Exposing the layer with a chiaroscuro image to the Discharge charge in the areas of the layer that were exposed to light, and the development of the resulting electrostatic latent image by the deposition of a finely divided electroscopic material, which is generally known referred to as "toner" on the image. The toner is usually attracted to those areas of the layer which retain a charge, creating a toner image that

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corresponding to the electrostatic latent image will. This toner image can then be transferred to a support surface, such as paper. The transmitted image can then be applied to the support surface by heat or pressure or by a combination of heat and Pressure can be permanently fixed. Instead of a latent image by uniformly charging the photoconductive layer and subsequent exposure of the layer with a light-dark image one can create the latent image by directly charging the layer in image arrangement. That Powder image can be fixed on the photoconductive layer when the step of transferring the powder image should be avoided. Other suitable fixing agents, such as solvent or coating treatment, can be used instead the aforementioned heat or pressure fixing operations can be set.

Various methods are known for applying the electroscopic toner particles to the electrostatic to be developed to apply latent image. A development method as described by E.N.Wise in U.S. Patent 2,618,552 is known as "cascade development". In this process, a developer material that is proportionate comprises large carrier particles and finely divided toner particles adhering firmly to them electrostatically, applied and over the electrostatic latent image load-bearing surface flowed or dropped. The composition of the carrier particles is like this chosen so that the toner particles are triboelectrically charged to the desired polarity. When the mix If the image-bearing surface falls or flows over it, the toner particles become charged on the Part of the latent image is electrostatically deposited and retained, but they are not deposited on the discharged one or background portions of the image. The biggest

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Part of the toner particles that are accidentally deposited on the background is carried by the flowing carrier removed, apparently due to a greater electrostatic attraction between the toner and the Carrier than between the toner and the discharged background area. The carrier and excess toner will be then returned. This way of working is ideal for the ■ Suitable for developing line copy images.

Another method of developing electrostatic images is the "magnetic brush method ¹¹ , as described, for example, in US Pat. No. 2,874-063. In this method, a developer material containing toner and magnetic carrier particles are carried by a magnet. The magnetic Field of the magnet causes the magnetic carriers to align in a brush-like shape. This "magnetic brush" is brought into contact with the electrostatic image bearing surface and the toner particles are drawn from the brush by electrostatic attraction to the latent image.

Another working method for developing electrostatic latent images is the "powder cloud" process, as it is e.g. from CF. Carlson in U.S. Patent 2,221,776 is described. In this process, a developer material, the electrically charged toner particles in one comprises gaseous medium, passed by the electrostatic latent image bearing surface. the Toner particles are drawn from the gas onto the latent image by electrostatic attraction. This method is particularly suitable for continuous toner development.

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Other development methods, such as "touchdown" development, as described by E.W. Gundlach in U.S. Patent 3,166,432 may be used for such purposes for which they are appropriate.

Although some of the development techniques mentioned above are in commercial use today, most are commercial electrostatographic development technique used what is known as "cascade" development. A general purpose office copier using this development method is disclosed in US Pat U.S. Patent 3,099 94-3. The cascade development technique is generally carried out in a commercially available device by applying a developer mixture the surface has an electrostatic, latent image bearing drum is dropped with a horizontal axis. The developer is from a trough or a basin by means of an endless belt conveyor to the upper part of the drum. After the developer is dropped into the basin along the top quarter of the surface of the drum, it is released by the development system returned to additional electrostatic develop latent images. Small amounts of toner are periodically added to the developer mix replenish the toner used by development. The toner image obtained is generally transferred to a receiving sheet and then by suitable means, such as furnace or radiation melting, melted. The surface of the drum is then reused cleaned. The mapping process is then used for each The copy made by the machine is repeated and is usually repeated many thousands of times during the life of the developer.

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From the description given above, as well as other development techniques, it is apparent that the toner is subject to strong mechanical abrasion, as a result of which the particles often lead to undesirable, dust-like abrasion to be broken. The formation of debris is retarded when the toner is a tough, high molecular weight resin that is able to withstand the shear and impact forces that the toner is exposed to in the machine.

Unfortunately, many high molecular weight materials cannot be used in high speed automatic machines as they are during the powder image heat setting step cannot be melted quickly. Try to get high melting point toners with the help of oversized ones Rapidly melting high capacity heating units raises the problem of preventing the receiving paper sheets from being charred and sufficient removal of the developed from the fusing unit or units Warmth. Therefore, additional devices, such as complex and expensive cooling units, are necessary to the appropriately remove a large amount of heat generated by the melting device. An incomplete removal the heat generated leads to uncomfortable working conditions and damage to heat-sensitive ones Machine parts. Furthermore, the additional space required by the heating and cooling units predominates and the high labor costs of the heating and cooling units often take advantage of the increased machine speed be achieved. On the other hand, vinyl resins are easily heat-melted at relatively low temperatures are, in general, undesirable as these materials tend to smear and produce thick films to form on the reusable, photoconductive surfaces. These films lead to image deterioration and contribute to reducing the service life of the machine

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at. Many low molecular weight vinyl resins will degrade when used in high-speed copier and duplicating machines are exposed to melt conditions. Additionally, some tend to have low melting points Vinyl resins act to form sticky images on the copy sheet that smear easily and often onto others adjacent sheets are transferred. Furthermore, these form Low molecular weight resins in conventional milling equipment often contain substantial amounts of dust, i.e. particulates with sizes below 1 micron, which is undesirable for the operation of the device.

It is also quite important that the toner material composed of resin and dye be capable is to assume a charge of the correct polarity when it is in frictional contact with the surface of substrates in cascade or touchdown development systems is brought. The triboelectric and flow properties of many toners are affected by changes the room humidity adversely affected. For example, the triboelectric values of some toners change with changes relative humidity and are therefore particularly suitable for use in electrostatographic systems in precision automatic machines that produce toners with stable and predictable triboelectric values require, not suitable. Therefore, resins that are suitable for application for toners should be aware of changes insensitive to relative humidity. Another factor affecting the stability of the triboelectric properties Affected by carriers is the tendency of some toner materials to appear on the surface of the toner particles to be "compressed". When developers are used in cascade automatic developing machines and being returned during many cycles, the many collisions result between the carrier and the

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Toner particles occur in the machine, to the fact that those located on the surface of the carrier particles Connect toner particles to the surface of the carrier particles or pressed into them in some other way will. The gradual accumulation of toner materials permanently bound to the surface of the carrier particles leads to a change in the triboelectric value of the carrier particles and directly contributes to the deterioration of the Copy quality due to the gradual destruction of the toner carrying capacity the carrier.

Many known carriers and toners are inherently abrasive. The abrasion between the toner particles, carriers and electrostatographic image surfaces accelerate the mutual destruction of these components. Of the Replacement of the carriers and those carrying the electrostatic image Surface is expensive and time consuming.

Low-melting crystalline polymers would be used as toner materials, which melt at low energy, advantageous. Although crystalline polymers in general show a sharp melting point, however, it has been found that many of these polymers, especially those with low Molecular weight, melt in a narrow range and form low-viscosity liquids that contain the Have a tendency to run and / or run on the transfer sheet. It was also found that crystalline Polymers that have low melting points, in addition, lead to images that are due to their waxy nature of the polymers smear easily.

As most thermoplastic materials are disadvantageous in one or more of the above respects there is a continuing need to improve toners and developers.

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The object of the invention is therefore to provide a developer composition in which the aforementioned Disadvantages are avoided.

Another object of the invention is to provide a toner which can be used in high-speed copying under toner melting conditions. and duplicating devices is stable.

Another object of the invention is to provide a toner that operates at high speeds and with less thermal energy can be melted.

Another object of the invention is to provide a toner which is triboelectric under various humidity conditions is stable.

Another object of the invention is to provide a toner that is resistant to agglomeration during storage and Use is resistant.

Another object of the invention is to provide a toner that can be removed from background areas during image development is easily removable by carrier.

Another object of the invention is to provide a toner which is resistant to smudging and easy to remove electrostatic imaging surfaces can be removed.

Another object of the invention is to provide a toner which reduces the mechanical abrasion of electrostatic imaging surfaces.

Another object of the invention is to provide a toner which operates at low initial electrostatic surface potentials is effective.

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Another object of the invention is to provide a toner which forms dense toner images.

Another object of the invention is to provide a toner which is easily transferable from an electrostatographic imaging surface to a receiving surface.

Another object of the invention is to provide a toner which is resistant to mechanical abrasion during the development process.

Another object of the invention is to provide a toner and a developer which are better physical and have chemical properties than the known toners and developers.

Another object of the invention is to provide an amorphous polyester toner having a low melting range shows acceptable padding temperatures.

The above and other objects are achieved according to the invention, according to which a finely divided toner particle composition is provided which comprises a dye and an amorphous, low-melting, branched, aromatic polyester, the polyester in the polymer chain at least about 30 mol% of at least one divalent radical the end
a) an asymmetric arylene radical of the general formula

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in which / ArJ ^{7 is} a divalent arylene radical with 6 to about carbon atoms, R is hydrogen, an alkyl group with 1 to about 4 carbon atoms, halogen, a sulfo group and their alkali salts, a nitro group, a cyano group, a lower alkoxy group, an amino group, a thio lower alkoxy group or -N (R '), in which each R' can independently be hydrogen or lower alkyl and ρ is 2 or 3, each m is independently a number from 0 to 1 and η is a number from 0 to 3, or

b) an asymmetric alkylene radical of the general formula

in which R "is an alkyl radical having 1 to about 4 carbon atoms, each R ¹ " is independently hydrogen or R ", q is a number from 1 to about 10 and each r is independently a number from 0 to 1, together with at least

c) up to about 10 mole percent of a polyol comprising about 3 to about 15 carbon atoms and about 3 to about 8 hydroxyl groups contains or

d) up to about 10 mol% of a polycarboxylic acid or its Esters having from about 3 to about 60 carbon atoms and about 3 to about 8 carboxyl groups

contains.

As used herein, the term "asymmetrical" is intended to denote a structure that does not have a center of symmetry i.e., it does not contain a point at which a straight line through this point goes through exactly the same neighborhood

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in both directions extending from this point (Organic Chemistry, Cram and Hammond, McGraw-Hill, New York 1959, p. 127). Such asymmetrical structures lead to a disorder in the polymer chain, so that a Order of the polymer molecules in three-dimensional direction cannot occur.

However, it is used in the production of the low-melting, amorphous, branched aromatic polyester, which according to the Invention used, it is believed essential that at least one is used to form the polymers Monomers at least about 3> 0 mole percent of a divalent radical that makes available

a) an asymmetric arylene radical of the general formula

-io Vc-T ^ fAxi Yc ₇ ^ -o -} -

in which / Ar / a divalent arylene radical with 6 to about 18 carbon atoms, R is hydrogen, an alkyl group with 1 to about 4 carbon atoms, halogen, a sulfo group and their alkali salts, a nitro group, a cyano group, a lower alkoxy group, an amino group, a thione lower alkoxy group or -N (R ¹ ), in which each R ^{1 can} independently be hydrogen or lower alkyl and ρ is 2 or 3, each m independently represents a number from 0 to 1 and η a number from 0 to 3, or

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b) an asymmetric alkylene radical of the general formula

/ o \ / ₀

-irO- Vcy-CH (CR ₂ ) ■ -VC - / - Oh

R "

wherein R "is an alkyl radical having 1 to about 4 carbon atoms, each R ¹ " is independently hydrogen or R ", q is a number from 1 to about 10 and each r is independently a number from 0 to 1. As long as one of the monomers is a compound that is "able to provide the required."
Amount of one of the remainder given above is available
place, the choice of the other monomer or monomers is determined only by the requirement that the
The final polymer must be aromatic and that the polymer must have a Vicat softening point of at least about 45 ^° C. and a molecular weight distribution of above 3. For the purposes according to the invention, a polymer is used

considered suitable if there is a specific cons. '

1 5

stand of at least about 10 ^y ohm-cm. In general, such a resistivity can be obtained
when at least about 20 mole percent of an aromatic
Monomers, and preferably at least about 35% of an aromatic monomer can be employed in making the polyester. This aromatic monomer, although not necessary, can be the source of the asymmetric arylene radical defined above.

Illustrative compounds which are capable of the asymmetric arylene radical defined above

0-3-

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in the polymer chain available, can either Arylendicarboxy radicals or arylenedioxy radicals. Illustrative arylenedicarboxy radicals are phthalic acid, isophthalic acid, phthalic anhydride, phenylindanedicarboxylic acid, Diphenyl-m, m'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, Naphthalene-1,6-dicarboxylic acid and the like Illustrative arylenedioxy radicals are resorcinol, catechin, 1,6-naphthalene diol, 1,4-naphthalenediol, 2,7-naphthalenediol, 4-tert. Butylcatechin, m-di (hydroxymethyl) benzene and the like;

Illustrative compounds which are suitable for forming the asymmetric alkylene radical in the polymer chain can be either alkylenedioxy radicals or alkylenedicarboxylic acid radicals, such as 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2-methyl-1 , 3-propylene glycol, polypropylene glycol, 2-methyl-2,4-pentanediol, c < -methyladipic acid, bromo-succinic acid, methyl-succinic acid, C ^ g-uimeric acid (dimer of linoleic acid) and the like.

It has been found that at least about 50 mole percent of at least one of the above-mentioned radicals in the polymer chain are required to give the polymer its amorphous To give nature and the low melting point. If these residues in an amount of below about 30 mol% are present, the polyester obtained is generally crystalline, i.e. it melts in a narrow range, and leading. However, minor amounts, e.g., at least about 20 mole percent, may suitably in cases be used when the other co-monomers used cause sufficient disorder in the polymer chain cause, so that an orientation of the polymer molecules in three-dimensional direction is reduced to a minimum will. The stoichiometry of the polymerization reaction naturally determines the maximum amount of the in the polymer chain present remnants. Lots of the minimum of at least

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about 30 mol% up to the stoichiometric limit can be used in be applied appropriately.

The choice of the remaining co-monomers is only determined by the requirements of the condensation or transesterification reaction and the need to obtain an end product that is aromatic in nature, has a Vicat softening temperature of at least about 45 ° and a molecular weight vertex of greater than 3 . For example, when the required amount of any of the above-defined radicals is introduced by an asymmetric diacid such as phthalic acid, there is no restriction on the other monomer or monomers other than that given above, except that it or they must be able to to react with the diacid to form an aromatic polyester having a Vicat softening temperature of at least about 45 G ^0. Illustrative diols which can be used in a suitable manner are aliphatic diols or aromatic diols, such as ethylene glycol, 1,3-propylene diol, trimethylene glycol, tetramethylene glycol, 1,4-butylene diol, 1,5-pentylene diol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol , Nonamethylene glycol, decamethylene glycol, diaethylene glycol, triaethylene glycol, tetraethylene glycol, p-di (hydroxymethyl) -benzene, cis- and trans-quinitoi, hydroquinone-di- (B-hydroxyaeth, yl) ether, 4,4'-dihydroxybisphenyl, bis- ( 4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenyl methane _? Bis (hydroxyphenyl) ketone, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) sulfone and the like.

In the same way, if a monomer provides the required amount of asymmetric alkylene radical, the remaining monomer or monomers any aromatic diacid or their analogs anhydrides, acid chlorides or their salts. Illustrative monomers are

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Terephthalic acid, trans-hexahydroterephthalic acid, diphenyl-ρ, ρ'-dicarboxylic acid, diphenyl-4,4'-diacetic acid, diphenylmethane-p, p'-dicarboxylic acid, Benzophenone-4,4'-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, 1,2-diphenoxyaethane-p, p'-dicarboxylic acid, 1,3-diphenoxypropane-ρ, ρ'-dicarboxylic acid, 1,4-Diphenoxybutane-p, p'-dicarboxylic acid, ρ (p-carboxybenzoyloxy) benzoic acid and the like. Likewise included are the analogous anhydrides of these acids, if they exist, and the acid chlorides and their salts. If desired, more than one diacid, anhydride, acid chloride, or salt can be used to form one Co-polyesters can be used.

Suitable polyols used as branching agents in polyester resins to achieve a molecular weight distribution of over 3 can be employed are those polyhydroxy compounds containing from about 3 to about 15 carbon atoms and contain from about 3 to about 8 hydroxyl groups. Typical Polyols include sugar alcohols such as glucose, fructose, ribose, maltose and lactose, sugar alcohol anhydrides, Mono- and disaccharides, and their alkylene oxide derivatives. A preferred group of polyols includes sorbitol, 1,2,3,6-hexantetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, Tripentaerythritol, succrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,2,5-trihydroxymethylbenzene and mixtures thereof. Appropriate polycarboxylic acids or their esters used as branching agents in polyester resins are those that can be between about 3 and about Carbon atoms and between about 3 and about 8 carboxylic acid groups contain. Typical polycarboxylic acids and their esters include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid,

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2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1, ^ - dicarbon-2-methylencarbo3q7lpropane, 1,3-dicarboxyl-2-methyl-2-methylenecarboxylpropane, Tetra (methylenearboxyl) methane, 1,2,7 »8-octanetetracarboxylic acid, Empol trimer acids, as available from Emery Industries, Inc., Cincinnati, Ohio, and mixtures thereof.

The aforementioned polyols or polycarboxylic acids and their esters, when used for the production of the polyester resins, give polyester resin compositions having branched structures with a chain length of at least 5 carbon atoms. It has been found that the glass transition temperature of the polyester resins obtained, which generally determines the initial melting temperature of a resinous toner composition, is not significantly influenced by its branched structure. It has been found, however, that the branched polyester toner compositions according to the invention have flatter melt viscosity curves than their linear analogues. They therefore result in a wider temperature range between cold and hot "offset" in contact roller melting systems. In addition, they have higher elasticity and cohesive strength in the melt, which reduces their tendency to settle in the heat. Accordingly, by using these branched polyester compositions, the slope of the melt viscosity curve is significantly reduced and greater temperature differences between cold and hot settling are observed. This expansion of the melting temperature range is in turn only accompanied by slightly higher minimum fixing temperature points, and in this way allows the use of further melting temperature quantities in high-speed electrostatographic machines. As explained in detail in the following examples , the branched ones lead

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Polyester toner compositions according to the invention for an extension of the "melting window" in polyester toners with a low melting temperature. In addition, this expansion of the melting temperature range is achieved without adversely affecting other important electrostatographic properties. The melt viscosity of various branched polyester ^{polymer samples was determined between 120 to 160 0} G on a Ferranti-Shirley viscometer. Although values were obtained at various shear rates, those results at 30 seconds are referred to for simplicity. In general, only low shear sensitivity was observed, that is, at any temperature the viscosity of the sample did not change more than a factor of 4 from 15 to 150 seconds. The melt viscosity temperature behavior of these branched polyester polymer samples was very similar. The polymers had higher viscosity and slightly flatter melt viscosity curves than their linear analogs. The higher molecular weight polymers exhibited higher viscosity. In addition, shear liquefaction and elastic melt behavior at lower shear stresses occurred as the molecular weight and branching of the polyester polymers increased. In other words, the elastic properties of the polymer melt became more pronounced when the Molecular weight of the polymers increases and allows a higher chain entanglement.This leads to a substantial change in the elastic properties of the polymers.A material with a low viscosity will and will deform more easily ne recovery is essentially zero, while a material with high viscosity is less deformed and, due to its longer relaxation time, approximately recovers from this deformation. Although the invention is not limited to this theory, it appears that increasing the

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Molecular weight distribution an increase in the elastic Causes melting behavior of a toner resin composition, which leads to an expanded melting latitude.

A given melt viscosity has been found to correlate well with the meltability of a toner in an oven or radiation fuser. This viscosity is 10 poise at 30 seconds shear rate. The temperature at which the toner reaches this viscosity is called the "isoviscous temperature" and is considered to be the melting temperature of the toner. The higher molecular weight polyesters, that is, those having average molecular weights above about 2,500 and generally between about 3,000 and about 250,000, are particularly useful as toners for use in hot pressure roller melters. In hex-pressure roller melting systems, the "melting window ^{11 of} the polymers is quite important in order to achieve the necessary working ^{width. The" melting window 11} is the temperature range between the initial fixation of the toner on the paper, as measured, for example, with an abrasive machine (Taber Abrader) and the Temperature _t at which the toner is no longer cohesively deposited on the fuser roll due to its low viscosity. The melting window in hexagonal pressure roller melting systems is preferably at least about 25 ° C. in order to ensure the necessary working width.

The branched polyesters can be polymerized by any conventional condensation or transesterification process getting produced. The polymerization can be carried out using polymerization procedures such as the Substanaj solution, Interfacial polymerization and the like. Can be carried out. The molecular weight of the polyester can vary widely, without affecting the amorphous nature of the polymers.

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Preferred are moderate molecular weights, i.e., molecular weights of number averages above about 2,500 for Toners used in both radiant and contact roll melting.

The branched polyester toner compositions according to the invention can be prepared by any well known toner mixing and crushing operation can be established. For example, the ingredients can be intimately mixed by these are mixed and ground and then the resulting mixture is micropulverized. Another Well known procedures for the formation of toner particles are, a suspension, a hot melt or a Spray dry solution of the toner composition or freeze-dry.

Any suitable pigment or dye can be used as the dye for the toner particles. Toner dyes are well known and include e.g. Soot, nigrosine dye, aniline blue, calco oil blue, Chrome yellow, ultramarine blue, quinoline yellow, methylene blue chloride, monastral blue, malachite green, oxalate, lamp soot, Rose Bengal, Monastral Red, Sudan Black BN, and mixtures thereof. The pigments or dyes or Pigments and dyes should be present in the toner in an amount sufficient to make it highly colored so that it gives a clearly visible image on a recording device. For example, where Ordinary electrostatographic copies of typewritten documents are desirable Toner is a black pigment, such as carbon black, or a black dye, such as Sudan Black BN, available from GAF Corporation is available. Preferably, in order to obtain a sufficient color density, the pigment is in an amount from about 1 to about 20 percent by weight

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of the colored toner. Venn the used When toner dye is a dye, much smaller amounts of dye can be used. The dye can be mixed with the resin component before, during or after the polymerization of the resin component. Of course Any dye that inhibits polymerization should be with the resin after it is made be mixed.

When the branched polyester toner compositions According to the invention are used in the cascade development system, the toner should have an average particle diameter of below about 30 microns, and preferably between about 3 and about 15 microns, for optimum Deliver results. When using for powder cloud development methods a particle diameter of slightly less than 1 micron is preferred.

Any suitable, stable, solid, hydrophobic metal salt of a fatty acid having a melting point above about 57 ° C can with the toner compositions according to the invention can be used to facilitate cleaning of the photoreceptor surface. The metal salt should essentially be be insoluble in water. Water-soluble metal salts leave the appropriate electrical properties miss and are affected by changes in humidity that normally occur in the ambient atmosphere, adversely affected. Much of the salts, which are normally considered insoluble, will dissolve however, actually to some extent. In order to effectively achieve the purposes of the invention, should the solubility of the salt can be negligible. Salts with desired specific properties include salts of linear, saturated fatty acids, unsaturated fatty acids, in particular hydrogenated fatty acids and

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_ 21 _

nubstituted fatty acids and mixtures thereof. the Metal salts can be spun or ground with the toner or carrier particles or in the respective. Toner or carrier particles are intimately dispersed. However, the latter embodiment is less more desirable than spinning or grinding mixing, as larger amounts of metal salt are required to produce a to provide a sufficient amount of metal salt on the surface of the developer particles. The metal salts are preferably with the toner material by spinning or processing in a drum of preformed finely divided Metal salt particles mixed with preformed finely divided toner particles. The drum method w.rd continued until the preformed metal salt particles are uniformly distributed throughout the bulk of the toner particles. Excellent toner blends are obtained when the preformed toner particles are mixed with preformed metal salt particles tumbled or mixed in a size between about 0.5 and about 30 microns will. The drum mixed mixtures are preferred because the treated toners obtained are among themselves provide extremely stable image characteristics under greatly changing humidity conditions. When the toner and Developers according to the invention containing metal salt additives, the mixtures obtained have the above discussed desirable properties and are therefore characterized by high melting rates.

When the solid, hydrophobic metal salt of a higher fatty acid is physically mixed or applied as a coating on toner or carrier particles _; rather than being dispersed with the toner matrix, the metal salt is preferably employed in an amount of from about 0.02 to about 10 percent based on the weight of the toner in the final developer mix. Optimal results will be

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obtained with about 0.1 to about 2 % of the metal salt. Although the initial electrostatic image surface potential can be reduced and the abrasion resistance can be improved if the level of the metal salt is increased above about 10%, an undesirable increase in background deposits becomes noticeable. It is not essential that the entire surface of each toner particle is coated with the metal salt, for example, it is sufficient that 10 to 16% of the toner particle surfaces are coated with a metal salt. When the metal salt is dispersed instead of being coated on the toner or carrier particles, relatively more metal salt is necessary to maintain a sufficient amount of free metal salt on the surface of the toner or carrier particles. When less than about 0.02 percent metal salt, based on the weight of the toner, is actually present on the surface of the toner particles, their triboelectric, flow, abrasion, transfer, and image forming properties are essentially the same as toners that are not are treated with a metal salt of a fatty acid.

Excellent results are obtained with zinc stearate. When the toner and developer particles according to the invention with zinc stearate, in particular in an amount of about 0.1 to about 2 percent by weight, based on the total weight of the toner treated, there will be improved photoreceptor cleaning, better flow, better Background, higher density images with lower initial charge voltage and higher machine speeds achieved with less powder. The wear on the drum is also noticeably reduced.

Suitable coated and uncoated substrates for cascade and magnetic brush development are general known. The carrier particles can be electrically conductive,

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be insulating, magnetic or non-magnetic, provided that the carrier particles have a charge with opposite the toner particles assume opposite polarity when brought into close contact with the toner particles so that the toner particles adhere to and surround the carrier particles. If a positive reproduction an electrostatic image is desired, the carrier particle is selected so that the toner particles have a Accept charge having a polarity opposite to that of the electrostatic latent image. Alternatively, if reverse reproduction of the electrostatic image is desired, the supports are selected so that that the toner particles assume a charge of the same polarity as the electrostatic image. Accordingly, the Materials for carrier particles according to their triboelectric properties in relation to the electroscopic Toner selected so that, when mixed or brought into contact with each other, a component of the Developer is positively charged when the other component in the triboelectric series is below the former Component stands, and negative, if the other component in this triboelectric series is above the first Component stands. By appropriate selection of materials in accordance with their triboelectric effects are the polarities of their charges when mixed such that the electroscopic toner particles on the Adhere to the surface of the carrier particles and form a coating thereon and also on that part of the electrostatic, adhere to the image-bearing surface, which has a greater attraction for the toner than that Has carrier particles. Typical carriers are sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, potassium chlarate, granulated zirconium, granulated silicon, Methyl methacrylate, glass, silicon dioxide, iron and its alloys, nickel, steel, ferrites and the like. The carriers

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can be used with or without a coating. Many of the foregoing typical carriers are described by LE Walkup in US Pat. No. 2,618,551, LE Walkup et al in US Pat. No. 2,618,416, and EN Wise in US Pat. No. 2,618,552. A final coated carrier particle diameter of from about 50 microns to about 1,000 microns is preferred because the carrier particles then have sufficient density and inertia to avoid sticking to the electrostatic image during the cascade development process. Adherence of the carrier beads to the electrostatographic surface is undesirable. because deep scratches are formed on the surface during image transfer and drum cleaning, particularly when cleaning is done with a fabric cleaner such as the fabric disclosed by WPGraff, Jr., et al in IJ.S. 186 838 is described. There also occurs a deterioration in printing when the carrier beads adhere to the electrostatic imaging surfaces. Generally speaking, ₍ satisfactory results are obtained when about one part of toner is used with about 10 to about 200 parts by weight of carrier.

The toner compositions according to the invention can be used to develop electrostatic latent images any suitable electrostatic latent image bearing surface can be used, including common photoconductive surfaces and insulating surfaces. Well known photoconductive materials include vitreous selenium, organic or inorganic Photoconductors embedded in a non-photoconductive matrix and the like. Representative patents, which describe photoconductive materials are U.S. Patent 2,803,542, U.S. Patent 2,970,906, U.S. Patent No. 2,803,542. U.S. Patent 3,121,006, U.S. Patent 3,121,00? and U.S. Patent 3,151,982.

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In the examples below, methods for preparing the toner materials according to the invention and their Use for developing electrostatic latent images. These examples, but not the one Comparative examples serve to illustrate various preferred embodiments of the invention. Parts and percentages are by weight unless .. otherwise specified.

example 1

About 582.6 grams of dimethyl terephthalate and about 304.4 grams of 1,2-propanediol were placed in a 1 liter, four-necked resin flask equipped with a thermometer, stainless steel stirrer, glass inlet tube, and reflux condenser. The flask was surrounded by an electric heating mantle. Nitrogen gas was introduced through the glass inlet tube, thereby agitating the reaction mixture and creating an inert atmosphere in the reaction vessel. The stirrer and heating mantle were put into operation and the reaction mixture was heated to about 80 ⁰ G, with about 1.5 S tetrabutyl titanate were charged in the reaction vessel. The reaction mixture was gradually heated to a temperature of about 180 ^° C. over the course of about 6 hours. At a temperature of about 140 ^° C., methanol condensed from the transesterification reaction and this was removed as it formed. The progress of the reaction was followed by the weight of the collected methanol. After about 6 hours of heating, a conversion, based on the collected methanol, of about 75 to 85% was achieved and the heating was discontinued. The reflux cool he was replaced with a pair of 90 ° connecting tubes that led to a 300-500 ml solvent freeze trap that was held in a thermos flask filled with dry ice

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and 'acetone was cooled, was provided. The outlet of the trap was closed by a suitable vacuum system with a laboratory vacuum pump. -When the temperature of the reaction mixture dropped to about 135 ° C, the pressure in the system was gradually reduced to about 10 mm and excess glycol and methanol were distilled off. When the distillation of the glycol apparently stopped, the temperature was gradually increased to 210 ° C. while the pressure was decreased to about 1 mm or less. Approximately 8 hours after the application of the vacuum, no increase in the viscosity of the polymer could be seen. The reaction was ended by reducing the temperature to about 180 ^° C. and allowing the pressure to rise to atmospheric pressure. The polymer was then poured onto an aluminum sheet and allowed to cool.

It has been found that the linear polyester polymer having a softening range from 77 to 102 ⁰ C, a isoviscous temperature of about 113 ⁰ C and a glass transition temperature of about 84 ⁰ C. The polymer had a weight average molecular weight of about 3,000 and a number average molecular weight of about 1,700. The intrinsic viscosity of the polymer in chloroform was about 0.10 dL / g.

Example 2

Following the procedure described in Example 1, about 582.6 grams of dimethyl terephthalate, about 304.4 grams of 1,2-propanediol, and about 4.0 grams of trimethylolpropane were placed in a one-liter, four-necked resin kettle. The reaction mixture was ^{heated to about 80 °} C., about 1.5 g of tetrabutyltitanate being introduced into the reaction vessel. The reaction mixture was gradually heated to a temperature of about 180 ⁰ C within about 6 h, after which a conversion,

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based on the collected methanol, of about 80% was reached and the heating was stopped. A vacuum was applied as described in Example 1, and after about 16 hours at about 210 ^° C. and a pressure of about 0.5, the reaction was now over.

It has been found that the branched polyester polymer having a softening range from 75 to 98 ° C, a isoviscous temperature of about 110 ⁰ C and a glass transition temperature of about 81 ⁰ C. The polymer had a weight average molecular weight of about 12,000 and a number average of about 3,300. The intrinsic viscosity of the polymer in chloroform was about 0.19 dL / g.

Example 3

Following the procedure of Example 1, about 582.6 grams of dimethyl terephthalate, about 304.4 grams of 1,2-propanediol, and about 12.0 grams of trimethylolpropane were placed in a one-liter, four-necked resin kettle. The reaction mixture was ^{heated to about 80 °} C. and then about 1.5 g of tetrabutyl titanate were introduced into the reaction vessel. The reaction mixture was gradually heated to a temperature of about 180 ^° C. over the course of about 6 h, after which a conversion, based on the collected methanol, of about 80% was achieved and the heating was interrupted. A vacuum was applied as described in Example 1, and after about 16 hours at about 210 ^° C. and a pressure of about 0.5 mm, the reaction was complete.

The branched polyester polymer was found to have a softening range of 72 to 95 ° C, isoviscous Temperature of about 115 ° C and a glass transition temperature of about 79 ° C. The polymer had an average

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molecular weight of about 28,000 (weight average) and about 3,300 (number average). The intrinsic viscosity of the Polymer in chloroform was about 0.235 dL / g.

Example 4

Following the procedure of Example 1, about 582.6 grams of dimethyl terephthalate, about 304.4 grams of 1,2-propanediol, and about 20.0 grams of trimethylolpropane were placed in a one-liter, four-necked resin kettle. The reaction mixture was HEATER to about 80 ⁰ C ^, and about 1.5 g of tetrabutyl titanate were added to the reaction vessel. The reaction mixture was gradually heated to a temperature of about 180 ^° C. over the course of about 6 hours, after which a conversion, based on the methanol obtained, of about 80% was achieved and the heating was interrupted. As in both

o game 1 applied, and after about 16 Ii at about 210 C, and the reaction was complete at a pressure of about 0.5 μm "

It has been found that the branched polyester polymer having a softening range from 74 to 103 ⁰ C, a isoviscous temperature of about 119 ⁰ C and a glass transition temperature of about 80 ⁰ C. The polymer had a weight average molecular weight of about 42,000 and about $ 500 (number average). The intrinsic viscosity of the polymer in chloroform was about 0.302 dL / g.

Example 5

According to the procedure of example 1 \ furden about 582.6 grams of dimethyl terephthalate, about 304.4 grams of 1,2-propanediol and about 2.5 grams of pentaerythritol in a 1 liter four neck resin kettle brought in. The reaction mixture

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was heated to about 80 ⁰ G and about 1.5 g of tetrabutyl titanate was placed in the reaction vessel. The reaction mixture was gradually heated to a temperature of about 180 ^° C. over the course of about 6 h, after which a conversion, based on the methanol obtained, of about 80% was achieved and the heating was interrupted. A vacuum was applied as described in Example 1, and after about 16 hours at about 210 ° C. and a pressure of about 0.5 πππ. the reaction was over.

It has been found that the branched polyester polymer having a softening range from 72 to 98 ⁰ C, a isoviscous temperature of about 110 ⁰ C and a glass transition temperature of about 75 C. The polymer had a weight average molecular weight of about 12,000 and a number average of about 2,700. The intrinsic viscosity of the polymer in chloroform was about 0.163 dL / g.

Example 6

Following the procedure of Example 1, about 582.6 grams of dimethyl terephthalate, about 0.44 grams of 1,2-propanediol, and about 6.1 grams of pentaerythritol were placed in a 1 liter, four-necked resin kettle. The reaction mixture was ^{heated to about 80 °} C. and about 1.5 6 tetrabutyl titanate were introduced into the reaction vessel. The reaction mixture was gradually heated to a temperature of about 180 ^° C. over the course of about 6 h, after which a conversion, based on the methanol obtained, of about 80% was achieved and the heating was interrupted. Vacuum was applied as described in Example 1, and after about 16 hours at about 210 ° C. and a pressure of about 0.5 mm, the reaction was complete.

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It has been found that the branched polyester polymer having a 'softening range 72-100 ⁰ C, a isoviscous temperature of about 115 ⁰ C and a glass transition temperature of about 74 ⁰ C. The polymer had a weight average molecular weight of about 25,000 and a number average of about 2,800. The intrinsic viscosity of the polymer in chloroform was about 0.175 cL / g.

Example 7

Following the procedure of Example 1, about 582.6 grams of dimethyl terephthalate, about 304.4 grams of 1,2-propanediol, and about 12.2 grams of pentaerythritol were placed in a one-liter, four-necked resin kettle. The reaction mixture was heated to about 80 ° C. and about 1.5 g of tetrabutyl titanate was added to the reaction mixture. The reaction mixture was gradually heated to a temperature of about 180 ^° C. over the course of about 6 h, after which a conversion, based on the methanol obtained, of about 80% was achieved and the heating was interrupted. A vacuum was applied as described in Example 1, and after about 16 hours at about 210 ^° C. and a pressure of about 0.5 mm, the reaction was complete.

It has been found that the branched polyester polymer having a softening range from 74 to 105 ⁰ C, a isoviscous temperature of about 118 ⁰ C and a glass transition temperature of about 71 ° C. The polymer had a weight average molecular weight of about 110,000 and about 2,850 (number average). The intrinsic viscosity of the polymer in chloroform was about 0.336 dL / g.

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Example 8

Following the procedure of Example 1, about 582.6 grams of dimethyl isophthalate, about 304.4 grams of 1,2-propanediol, and about 12.0 grams of trimethylolpropane were placed in a one-liter, four-necked resin kettle. The reaction mixture was ^{heated to about 80 °} C. and about 1.5 g of tetrabutyl titanate were added to the reaction vessel. The reaction mixture was gradually heated to a temperature of about 180 ^° C. over the course of about 6 h, after which a conversion, based on the methanol obtained, of about 80% was achieved and the heating was interrupted. A vacuum was applied as described in Example 1, and after about 16 hours at about 210 ^° C. and a pressure of about 0.5 ^ a, the reaction was complete.

It has been found that the branched polyester polymer having a softening range of about 65 to 82 ⁰ C, a isoviscous temperature of about 92 ⁰ C and a glass transition temperature of about 69 ° C. The polymer had an average molecular weight of about 25,000 (weight average) and about 3,100 (number average). The intrinsic viscosity of the polymer in chloroform was about 0.216 dL / g.

Example 9

A toner composition was prepared by about 10 wt .-% Black Pearls L carbon black with about 90 wt .-% according to Example 1 resin prepared were mixed. After melting and premixing, the toner composition was fed to a rubber mill and ground intimately to a uniformly dispersed composition of the soot in the resin. The resulting mixture was then cooled and placed in a jet pulverizer finely divided to separate toner particles with a

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average particle size between about 10 and about 15 microns. The toner had an agglomeration temperature of about 62.8 ⁰ O (145 ⁰ F). The "blocking temperature" of a toner is the temperature at which the formation of toner agglomerates is visible to the naked eye. Copies were made using a standard test sample with a developer mix containing about one part by weight of toner and about 99 parts by weight of Xerox ^ 600 carrier beads in a modified Xerox 3 600 copier, which was then passed through a standard Xerox 4000 fuser unit. attached to the exterior of the Xerox 3600 machine. The melt temperature was regulated with a proportional thermocouple and controlled with a thermocouple, with the melt temperature changed in approximately 5.6 ^° C (10 ^° F) increments to determine the fixation temperature for minimum acceptable hold and hot offset. The minimum fixation value is 10-2 "Taber Cycles". The term "Taber Cycles" means the amount of fixation obtained using an experimental method based on the resistance of a fixed toner image to abrasion with a Taber Abrader, Model 174, from Welch Scientific Co. After passing through the melter, the copy sheets are attached to a sample card approximately 10.8 cm (4.25 inches) in diameter and rubbed using a standard CS-10 test wheel. The number of rotations necessary to obtain an approximately 20% reduction in image density is recorded. A minimum melting temperature is when an approximately 20% drop in image density is observed. In general, an abrasion run of 10 + 2 rotations of the abrasion wheel, an acceptable melting. The Minimumschmelζtemperatur is found in that copies melt acceptable with this toner, about 126.7 ° C (260 ⁰ F). The minimum melting temperature at which

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a hot offset occurs to the fuser roll was found to be about 129.3 ° C (265 ⁰ F). The results of this determination clearly indicate a very narrow melting range for this toner composition.

Example 10

A toner composition was prepared by mixing about 10% by weight Black Pearls S carbon black with about 90% by weight resin made according to Example 2. After melting and premixing, the composition was ground in a rubber mill to give a uniformly dispersed composition of the carbon black in the thermoplastic resin. The obtained mixed composition was cooled and then finely divided in a nozzle pulverizer to give toner particles having an average particle size between about 10 and 15 microns. The toner had an agglomeration of about 62.8 ⁰ C (145 ⁰ F). About 1 part by weight of the powdered toner particles was mixed with about 99 parts by weight of Xerox 3600 carrier beads and used in place of the developer in the test apparatus described in Example 9. Under substantially identical test conditions, it was found that the minimum melting temperature, melt at acceptable copies with this toner, about 154- ⁰ C (310 ⁰ F). The minimum melting temperature at which a hot offset occurs to the fuser roll is about 182 ⁰ G (36O ⁰ F). These results clearly show that this toner composition has a slightly higher minimum fusing temperature but a much broader melting range.

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Example 11

A toner composition was prepared by mixing about 10% by weight Black Pearls L carbon black with about 90% by weight resin made according to Example 3. After melting and premixing, the composition was ground in a rubber mill to obtain a uniformly dispersed composition of the bus in the thermoplastic resin. The obtained mixed composition was cooled and finely divided in a nozzle pulverizer to give toner particles having an average particle size between about 10 and 15 microns. The toner had an agglomeration of about 62.8 ⁰ C (145 ⁰ F). About 1 part of the powdered toner particles was mixed with about 99 parts of Xerox 3600 carrier beads and used in place of the developer in the experimental apparatus described in Example 9. Under essentially the same experimental conditions it was found that the minimum melting temperature, melt at acceptable copies with this toner, about 154- ⁰ C (310 ⁰ F). The minimum melting temperature at which a hot offset occurs to the fuser roll is about 188 ° (37o ⁰ P). The results clearly show that this toner composition shows a slightly higher minimum fusing temperature but a much wider melting range.

Example 12

A toner composition was prepared by mixing about 10% by weight of Black Pearls L carbon black with about 90% by weight of the according to Example 4- resin prepared were mixed. After melting and premixing, the composition was ground in a rubber mill to produce a uniformly dispersed composition of the carbon black in the thermoplastic

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To yield resin. The resulting mixed composition was cooled and finely divided in a nozzle pulverizer to give toner particles having an average particle size between about 10 to 15 microns. The toner had an agglomeration of about 60 ⁰ C

P). About 1 part of the powdered toner particles was mixed with about 99 parts by weight of Xerox 3600 carrier alder and used in place of the developer in the experimental device described in Example 9. Under substantially identical test conditions, it was found that the minimum melting temperature, melt at acceptable copies with this toner, C is about 154- ^{0 (0} I 510 ^1). The minimum melting temperature at which a hot offset to the melting roller occurs is approximately 210 ^° C. (410 ^° F.). These results clearly show that this toner composition has a slightly higher minimum fusing temperature, but a much wider melting range.

Example 13

A toner composition was prepared by mixing about 10% by weight Black Pearls L carbon black with about 90% by weight of the resin prepared according to Example 5. After melting and premixing, the composition was ground in a rubber mill to give a uniformly dispersed composition of the carbon black in the thermoplastic resin. The resulting mixed composition was cooled and finely divided in a nozzle pulverizer to give toner particles having an average particle size between about 10 to 15 microns. The toner had an agglomeration ^{temperature of about 60 0} C (140 ⁰ F). About a part of the powdered toner particles became with about

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99 parts by weight of Xerox 5600 carrier beads mixed and used in place of the developer in the experimental device described in Example 9. Under essentially identical Experimental conditions it was found that the minimum

melting temperature at which copies made with this toner will melt acceptably, is about 143 ⁰ C (290 ⁰ F). The minimum melting temperature at which a hot offset to the melting roller occurs is approximately 171 ^° C. (340 ° C.). These results clearly show that this toner composition has a slightly higher minimum fusing temperature but a much wider melting range.

Example 14-

A toner composition was prepared by mixing about 10% by weight Black Pearls L carbon black with about 90% by weight of the resin prepared according to Example 6. After melting and premixing, the composition was ground in a rubber mill to give a uniformly dispersed composition of the bus in the thermoplastic resin. The resulting mixed composition was cooled and then finely divided in a nozzle pulverizer to give toner particles having an average particle size between about 10 and 15 microns. The toner had an agglomeration ^{temperature of about 60 0} C (140 ⁰ P). About 1 part of the powdered toner particles was mixed with about 99 parts by weight of Xerox 3600 carrier beads and used in place of the developer in the experimental apparatus described in Example 9. Under essentially the same experimental conditions it was found that the minimum melting temperature, melt at acceptable copies with this toner, about 149 ° C (300 ⁰ F). The minimum melting temperature at which a hot offset to the

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Melt roll occurs is about 188 ⁰ C (57O ⁰ F). These results clearly show that this toner composition has a slightly higher minimum fusing temperature but a much broader melting range.

example

A toner composition was prepared by mixing about 10% by weight of Black Pearls L carbon black with about 90% by weight of the resin prepared according to Example 7. After melting and yormixing, the composition was ground in a rubber mill to give a uniformly dispersed composition of the carbon black in the thermoplastic resin. The resulting mixed composition was cooled and then finely divided in a nozzle pulverizer to give toner particles having an average particle size between about 10 and 15 microns. The toner had an agglomeration ^{temperature of about 60 0} C (140 ⁰ F). About 1 part of the powdered toner particles was mixed with about 99 parts by weight of Xerox 3,600 carrier beads and used in place of the developer in the experimental apparatus described in Example 9. Under essentially identical experimental conditions, it was found that the minimum melting ^{temperature at which copies made with this toner will melt acceptably is about 149 °} C (300 ^° P). The minimum melting temperature at which a hot offset occurs to the fuser roll is about 221 ⁰ C (4-30 ⁰ F). These results clearly show that this toner composition has a slightly higher minimum fusing temperature but a much wider melting range.

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-58 -

Example 16

A toner composition was prepared by mixing about 10% by weight Black Pearls L carbon black with about 90% by weight of the resin prepared according to Example 8. After melting and premixing, the composition was ground in a rubber mill to give a uniformly dispersed composition of the carbon black in the thermoplastic resin. The obtained mixed composition was cooled and then finely divided in a nozzle pulverizer to give toner particles having a particle size between 10 and 15 microns. The toner had an agglomeration of about 57.2 G ⁰ (155 ⁰ I ^1). About 3/4 part of the powdered toner particles was mixed with about 99 parts by weight of Xerox 3600 carrier beads and used in place of the developer in the experimental device described in Example 9. Under essentially the same experimental conditions, the minimum melting temperature at which copies made with this toner will melt acceptably was found to be about 130 ° C (280 ⁰ J ¹ ). The minimum melting temperature at which a hot offset occurs to the fuser roll is about 177 ⁰ C (35O ⁰ F). These results clearly show that this toner composition has a slightly higher minimum fusing temperature, but a much wider melting range.

The term "developer mix" as used herein is said to be electroscopic toner material or combinations of toner material and carrier material.

Although specific materials and conditions have been given in the preceding examples, they are intended for purposes only serve to illustrate the present invention. Various other suitable additives, dyes and

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ingredients other than those listed above can be used instead of those mentioned in the examples can be used with similar results. Other materials can also be added to the toner become more sensitive to the melt properties or other desirable properties of the system make to achieve a synergistic effect or to improve in other ways too.

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Claims (23)

Claims I 'Λ ./'Peinverteilte toner particle, characterized in that it comprises a dye and an amorphous, low-melting, aromatic polyester, wherein the polyester in the polymer chain at least about 30 mol% of at least one divalent Best from a) an asymmetric arylene radical of the general formula in which / Ar / is a divalent arylene radical having 6 to about 18 carbon atoms, R is hydrogen, an alkyl group having 1 to about 4 carbon atoms, halogen, a sulfo group and its alkali metal salts, a nitro group, a cyano group, a lower alkoxy group, an amino group, a thioniedere Alkoxy group or -N (R. ¹ ). wherein each R 'can independently be hydrogen or lower alkyl and ρ is 2 or 3, each m is independently a number from 0 to 1 and η is a number from 0 to 3, or 509818/1033 ti - b) an asymmetric alkylene radical of the general formula in which R "is an alkyl radical having 1 to about 4 · carbon atoms, each R ¹ " is independently hydrogen or R ", q is a number from 1 to about 10 and each r is independently a number from 0 to 1, together with at least c) up to about 10 mole percent of a polyol comprising about 3 to about 15 carbon atoms and about 3 to about 8 Contains hydroxyl groups, or d) up to about 10 mol% of a polycarboxylic acid or their esters having from about 3 to about 60 carbon atoms and about 3 to about 8 carboxyl groups, contains. 2. Finely divided toner particle composition according to claim 1, characterized in that the amorphous, low-melting, aromatic polyester has a softening temperature of at least about 45 ^° C., a molecular weight distribution of more than 3 and a specific resistance of 15th
at least about 10 ohm / cm. 509818/1033 3. Finely divided toner particle composition according to claim 1 or 2, characterized in that the Polyester contains the remainder of at least about 20 mol% of an aromatic comonomer in its chain, which is polymerizable to form a polyester. 4. Finely divided toner particle composition according to any one of claims 1 to 3 »characterized in that that it is suitable for use in radiation and contact roller melt systems and the polyester has a molecular weight above about 2,500. 5. Finely divided toner particle composition according to one of claims 1 to 3 »characterized in that that it is suitable for hot pressure roll melt systems and that the polyester has an average molecular weight between about 3,000 and about 250,000. 6. Finely divided toner particle composition according to one of claims 1 to 5, characterized in that that the dye is carbon black. 7. Finely divided toner particle composition according to one of claims 1 to 6, characterized in that they are about 1 to about 20% by weight, based on contains the total weight of the toner, a dye. 8. A finely divided toner particle composition according to any one of claims 1 to 7, characterized in that that the toner has an average particle diameter of less than about 30 microns .. 509818/1033 9. A finely divided toner particle composition according to any one of claims 1 to 8, characterized in that the polyester is poly (1,2-propylene terephthalate). 10. A finely divided toner particle composition according to any one of claims 1 to 8, characterized in that the polyester is the condensation product of hydroquinone di-beta-hydroxyethyl ether and isophthalic acid '; is. 11. A finely divided toner particle composition according to any one of claims 1 to 8, characterized in that the polyester is poly (ethylene isophthalate). 12. Finely divided toner particle composition according to one of claims 1 to 8, characterized in that the polyester is poly (ethylene phthalate). 13. Finely divided toner particle composition according to one of Claims 1 to 8, characterized in that the polyester is the condensation product of at least about 20 mole percent 1,2-propylene glycol, hydroquinone di-beta-hydroxyethyl ether and is terephthalic acid. 14. Finely divided toner particle composition according to one of claims 1 to 8, characterized in that the polyester is the condensation product of at least about 30 Mo V / o 1,2-propylene glycol, ethylene glycol and terephthalic acid. 15- Finely divided toner particle composition according to one of claims 1 to 8, characterized in that the polyester is the condensation product of 1,2-propylene glycol, Is terephthalic acid and succinic acid. 509818/1033 16. Peinverteilte toner particle composition according to any one of claims 1 to 15, characterized in that the polyol is a sugar alcohol, sugar alcohol anhydride, Mono- or disaccharide or alkylene oxide derivative thereof. 17. Peinverteilte toner particle composition according to any one of claims 1 to 16, characterized in that the polyearboxylic acid or its ester 1,2,4-benzene ar bon acid, 2,5 »7-naphthalenetricarjonic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid or 1,3-dicarboxyl-2-methylenecarboxy! propane. 18. A powder-distributed toner particle composition according to any one of claims 1 to 17, characterized in that it contains about 0.02 to about 10 percent by weight, based on the weight of the toner composition, of a solid, hydrophobic salt of a fatty acid having a melting point of above about 57 ⁰ O . 19. Use of the finely divided toner particle composition according to any one of claims 1 to 18 in one A developer composition comprising a mixture of the finely divided toner particle composition with carrier particles with relatively opposite triboelectric polarity. 20. Embodiment according to claim 19, characterized in that the carrier particles have a diameter between approximately 50 microns and about 1000 microns. 21. Embodiment according to claim 19 or 20, characterized in that the weight ratio of toner to carrier is between about 1:10 and about 1: 200. 509818/1033 the 22. Use / finely divided toner particle composition according to any one of claims 1 to 18 in admixture with Carrier particles of relatively opposite triboelectric polarity for the development of electrostatic ones latent images, whereby an electrostatic latent image is formed on a surface, contacts the latent image on the surface with the developer composition, thereby causing the toner of the developer composition electrostatically adheres to the latent image and the developed image fixed to the surface. 23. Embodiment according to claim 22, characterized in that that the developed, electrostatic latent image is transferred to the transfer sheet and the transferred, developed image is fixed on it. 509818/1033