DE1772569B2 - Powdered electrophotographic developer - Google Patents

Description

a) an o- or m-phthalic acid ester,

b) a compound of the formula

R Ο — C

where R is an organic group with 3 to 12 carbon atoms and η is 1, 2 or 3, with a melting point between 45 and 132 C,

c) a compound of the formula

O R '

Il I

S — N — R "

Il

R O

where R is hydrogen, chlorine or bromine, an alkyl group having 1 to 6 carbon atoms or an aryl group and R 'and R "are an alkyl group having 1 to 12 carbon atoms or an aryl group, or

d) a compound of the formula

Cl ₁ ,

Cl ,.

where η is 0, 1, 2 or 3 and m is a number between 0.5 and 2.5 which is the average of all chlorine atoms in the compound.

2. Developer according to claim 1, characterized in that it has an o or as an additive M-phthalic acid ester with a melting point between • 43 and 80 ° C.

3. Developer according to claim 2, characterized in that it contains phthalic acid tohenyl ester as an additive, Contains dihydroabietyl phthalate or dicyclohexyl phthalate.

4. Developer according to claim 1, characterized in that it contains as an additive, based on the weight of the vinyl resin, between 2 and 45 percent by weight of an o- or m-phthalic acid ester .

5. Developer according to claim 1, characterized in that it is used as an additive, based on the Weight of vinyl resin, between 3 and 65 percent by weight, preferably between 5 and 55 percent by weight, a compound of the formula given under b), c) or d) in claim 1 contains.

6. Developer according to claim 1, characterized in that it is used as an additive tetrabenzoic acid pentaerithritol ester contains.

7. Developer according to claim 1, characterized in that it is the least vinyl resin Contains 25 percent by weight of a styrene resin.

8. Developer according to claim 1, characterized in that it is used as a metal sulphate of a fat acid contains zinc stearate.

The invention relates to a powdery electro photoeraphic developer with a toner, de: consists of a pigment or dye, a thermoplastic vinyl resin and an additive, unc with 0.02 to 20 percent by weight of a hydrophobic metal salt of a fatty acid.

The formation and development of images on the surface of photoconductive materials using electrostatic technology Methods is e.g. From US-PS 22 97 691 known.

There are several methods of application

electroscopic particles on the to be developed

known latent electrostatic image. A development method described in US Pat. No. 2,618,552

is known as cascade development.

Another method of developing electrostatic images is the magnetic brush process, the is described, for example, in US Pat. No. 2,874,063.

Another method of developing electrostatic latent images is powder cloud driving, which is described, for example, in US Pat. No. 2,221,776.

Fine further development method is for example in US Pat. No. 3,166,432.

The most frequently used xerographic development method, however, is cascade development.

Powdered electrophotographic developers for the processes described above are already available known. So z. B. in GB-PS 10 42 498 a powdered electrophotographic developer described, which consists of magnetic carrier particles and toner particles, the toner particles in essentially of a mixture of pigmented resin particles and particles of an aliphatic carboxylic acid with 12 to 18 carbon atoms in the molecule.

It is disadvantageous that the toner is subject to mechanical wear, which has an influence on this causes the particles to break into undesirable fine dust particles. The fine toner particles exert an adverse effect on the operation of the machine as it is extremely difficult to re-run usable imaging surfaces are to be removed, in addition, they tend to to get to other parts of the machine and to access critical machine parts such as optical lenses. The formation of fine particles is then prevented when the toner enters Contains tough, high molecular weight resin, which is able to withstand the shear and impact forces to withstand that are applied to the toner in the machine. Unfortunately, many materials can high molecular weight not used in high speed automatic machines because they are not fast enough during a pulse

verbild - heat setting stage can be melted. Attempts to quickly melt a toner having a high melting point using oversized, high-capacity heaters have raised problems in preventing the paper recording media from carbonizing and sufficiently dissipating the heat generated in the melting unit or units. On the other hand, low molecular weight resins, which can be easily melted by heat at relatively low temperatures, are often undesirable because these materials tend to produce thick films on reusable photoconductive surfaces. These films tend to degrade the image and shorten the life of the machine. In addition, low molecular weight resins tend to form tacky images on the recording media, which images often stick to adjacent recording media. Further, toner particles containing low molecular weight resins tend to clump and stick together in both the shipping containers and the electrophotographic machines. Furthermore, the toner material must be capable of assuming a charge of the correct polarity when it comes into rubbing contact with the surface of carrier materials in cascade, magnetic brush or immersion development systems. Some resinous materials, which have many properties which would be desirable for use in electrophotographic toners, poorly display these properties, so that they cannot be used in automatic copying and duplicating machines. Other resins develop these properties well, but form copies which are characterized by low density, poor resolution, or high fog. Furthermore, some resins are unsuitable for processes that employ electrostatic transfer in their practice. Since most thermoplastic materials fail in one or more of the above-identified areas, there is an ongoing need for improved toners and developers.

The object of the invention is to provide an electrophotographic developer in powder form that has better physical and chemical properties than the known developers.

This object is achieved by the invention.

The subject matter of the invention is based on an electrophotographic developer in powder form with a toner composed of a pigment or dye, a thermoplastic vinyl resin and a Addition consists, and with 0.02 to 20 percent by weight of a hydrophobic metal salt of a fatty acid and is characterized by the fact that it is used as an addition

a) an o- or m-phthalic acid ester,

b) a compound of the formula

12 carbon atoms and η is 1, 2 or 3, with a melting point between 45 and 132 ³ C,
c) a compound of the formula

O R '

-S — N — R "

wherein R equals a hydrogen, chlorine or bromine atom, an alkyl group having 1 to 6 carbon atoms or an aryl group and R 'and R "are equal to an alkyl group having 1 to 12 carbon atoms or is an aryl group, or

d) a compound of the formula

Cl,

R-

O-C

where R is an organic group with 3 to where η is 0, 1, 2 or 3 and m is a number between 0.5 and 2.5, which is the average of all chlorine atoms in the compound. contains.

The invention enables the developer to be used in conventional electrophotographic Copying and reproducing devices is resistant to film formation. Furthermore, the developer of the present invention forms copies with reduced fog, is free fluent and resistant to agglomeration. Furthermore, the inventive Developers at higher speeds with a “. melt with little heat input. The inventive Developer produces copies with a high resolution. Another benefit is there in that the developer of the present invention is resistant to abrasion during the development process.

According to one embodiment of the invention, the developer contains as an additive an o- m- ode ^r phthalic acid esters having a melting point between 43 and 8O ⁰ C. This addition a greater storage stability is achieved of the developer.

In the developer, any suitable solid can be substituted or unsubstituted esters of o-phthalic acid or m-phthalic acid can be used. Typical are solid esters of o-phthalic acid and m-phthalic acid Tctrahydrophthalic acid - didodecyl, 4,5 - epoxy ester, Dicyclohexyl phthalate, diphenyl phthalate, dimethyl isophthalate, diethoxyethyl phthalate, Triphenyl phthalate and dihydroabietyl phthalate or the like.

According to a further embodiment of the invention, the developer contains as an additive, based on the Weight of the vinyl resin, between 2 and 45 percent by weight of an o- or m-phthalic acid ester. This configuration ensures maximum resistance of the developer to agglomeration achieved. Optimal results are obtained if the developer is used as an additive, based on the Weight of vinyl resin, between 2 and 15 percent by weight It contains diphenyl phthalate as the toner obtained has excellent durability against creep, high mechanical strength and improved image properties is marked.

According to a further embodiment of the invention, the developer contains as an additive, based on the Weight of vinyl resin, between 3 and 65 percent by weight, preferably between 5 and 55 percent by weight, a connection iler under b), c) or d) given formula. This configuration results in a particularly good behavior of the toner image in terms of mechanical strength, creep resistance and durability.

According to a further embodiment of the invention, the developer contains at least one vinyl resin 25 percent by weight of a styrene resin. This refinement results in a greater degree of image field decomposition and denser copies are obtained.

The styrene resin can be a homopolymer of styrene or styrene homologues or copolymers of styrene with other monomeric groups containing a single methylene group, which is linked to a carbon atom via a double bond.

According to a further embodiment of the invention, the developer finally contains a metal salt Fatty acid zinc stearate. This configuration ensures an exceptionally good melting rate, high cleanability of the electrostatic imaging surface, greater static electricity stability, denser toner images and increased resistance to mechanical Abrasion received.

The developers contain 0.02 to 20 percent by weight of the hydrophobic metal salt of a fatty acid, amounts of 0.05 to 4 percent by weight are preferred, since in this way a maximum Reduction of fog, improved image density and higher image resolution achieved will.

It does not matter whether the entire surface of each toner particle is coated with the metal salt For example, there is enough metal salt present when about 10 to about 16% of the toner particle surfaces are covered with the metal salt. It can be any suitable stable solid hydrophobic metal salt a fatty acid with a melting point above 57 ° C can be used. Optimal results will be obtained when about 0.05 to about 4 weight percent, based on the weight of the toner, of zinc stearate are available on the outer surfaces of the particles in the developing material.

Any suitable vinyl resin having a melting point of at least about 43C can be used. The vinyl resin can be a homopolymer or a copolymer be two or more vinyl monomers.

In general, the suitable vinyl resins used in the toner have average properties Molecular weight between about 3,000 and about 500,000.

The vinyl resins including the styrenic resins can also optionally be mixed with a or more resins are mixed. If the vinyl resin is mixed with another resin, then the added resin is preferably made of a different vinyl resin, since the mixture obtained by a particularly good static electricity stability as well as a uniform resistance to a physical destruction is characterized. The vinyl resins which are suitable for mixing with the styrenic Resin or other vinyl resin can be used by addition polymerization suitable vinyl monomers are prepared. Other thermoplastic resins can also be used mixed with the vinyl resins.

The combination of resin component, dye or pigment and additive should, regardless of whether the resin component, copolymer or a mixture consisting of a homopolymer, a caking temperature of at least 43 ° C and a melt viscosity of less than about 2.5 x 10 ~ ⁴ poises at temperatures up to 232 ^C C. If the toner is characterized by a caking temperature of less than 43 ° C, then the toner particles tend to agglomerate during storage and processing in the machine, with undesirable films also appearing on the surface of reusable photoreceptors, which is disadvantageous affect the image quality. If the melt viscosity of the toner is above approximately 2.5 × 10 -4 * poise at temperatures above 232 ° C., then the developer does not adhere to a recording medium, even under the usual melting conditions such as occur in an electrophotographic apparatus. Rather, it can be removed in a simple manner by rubbing it off.

Typical compounds of the formula b) are, for example: pentaerythritol tetrabenzoate, cane sugar benzoate, Triethylene glycol dibenzoate, glyceryl tribenzoate, neopentyl glycol dibenzoate, trimethylol ethane tribenzoate Od. The like. Exceptionally good results are achieved when pentaerythritol tetrabenzoate as an additive is used. If pentaerythritol tetrabenzoate is used as an additive, then the with regard to resistance to clumping, less tendency to film as well as optimum melting temperatures achieved advantages of sharp copies with high contrast, which only have little or no veil accompanied. The negligible veil in the ultimate The resulting copy is apparently due to a significantly reduced tendency of the toner to stick to the background surfaces of a photoconductor to adhere during development. Therefore, the toners, which contain pentaerythritol tetrabenzoate are preferred.

Typical compounds of the formula c) are, for example: N - cyclohexyl - ρ - toluenesulfonamide, N - ethyl - ρ - toluenesulfonamide, ο - toluenesulfonamide, p-toluenesulfonamide, Ν, Ν-di-p-hydroxyethyl-p-toluenesulfonamide, N, N - dimethylbenzenesulfonamide, N - cyclohexylbenzenesulfonamide, N - cyclohexyl-3,4-dichlorobenzenesulfonamide, N-allyl-p-toluenesulfonamide, N, N-Di-p-hydroxyethyl-p-toluenesulfonamide, N-cyclohexyl-p-toluene sulfonamide or the like.

Typical compounds of the formula d) are, for example: ρ, ρ'-dichlorobiphenyl, 2,4,7,9-tetrachlorobiphenyl, 1,4 - bis - (p - chlorophenyl) - 2 - chlorobenzene, 2,2'-dichloro-4,4 '- (p-chlorophenyl) -biphenyl or the like. Any colorant for the toner particles can be used suitable pigment or dye can be used. Toner colorants are known. Preferably the pigment is based in an amount of from about 3 to about 20 percent by weight based on the total weight of the colored toner. If a dye is used as the toner coloring agent, then you can use considerably smaller amounts

Colorant i l

The developers can ζ. Β. by mixing and grinding the components and then fine pulverization of the mixture obtained.

In general, for a given melt temperature, the quality of the developer decreases as the toner melt viscosity increases. As mentioned above, the melt viscosity of the developer is greater than about 2.5 x 10 ~ ⁴ poises at temperatures above 232 ° C, wherein the developer even under normal melting conditions such as exist in electrophotographic machines, in a suitable manner to a Attach the recording sheet.

If the developers are to be used in a cascade development process, then the Toner an average particle size of less than about 30µ and more to be optimal Have results of preferably between about 4 and about 20 µ. When used in Powder development methods are preferred for particle diameters slightly less than 1μ.

The invention is illustrated in the examples.

B e i s ρ i e 1 1 * 5

A sample of known toner particles is used as a comparative sample. Copies of a standard test nipple are made with the toner in a modified copier. The temperature of the melter is regulated using a proportional temperature device and monitored by a thermocouple placed in the center of the top plate of the melter. The plates of the melter are attached 19 mm apart. The toner images on copy sheets with a size of 203 x 330 mm are transported through the melting device at a speed of 11 sheets per minute, ie at twice as high a speed as is normally usual. In the standard copying machine, since the motor is stalled and overheated when the machine is operated at a speed twice the normal operating speed, a motor which has twice the line output is used. After passing through the melter, the copy sheets are attached to a full-sided abrasive cylinder with a diameter of 120 mm. A conventional cleaning fabric is pressed against the copy sheet by means of a roller pressed on by a spring under a spring pressure of 18.1 kg. By rotating the cylinder carrying the copy sheet, the entire toner image on the copy sheet is rubbed off by rubbing contact with the fabric. A minimum temperature of the melting device is set when all test characters can be read after 5 revolutions of the abrasion cylinder. Conventional carrier beads are used with the toner during the development stage. The minimum temperature of the fuser at which legible copies are obtained with the known toner is 321 C. Many of the copies leaving the fuser have glowing spots, and in some cases flames are observed . Microphotographic examinations of the reusable upper imaging surface show considerable abrasion and destruction of the surface after 5000 cycles.

Example 2

A clay mixture consisting of 7.5 parts by weight of a copolymer of 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, 1.5 parts by weight of pentaerythritol tetrabenzoate and 1 part by weight of carbon black is prepared. The addition; is a hard, dry solid with a melting range of approximately 93 to 95 ° C. The toner mixture has a melt viscosity determined by means of an Instron capillary rheometer of 0.5 · 10 " ⁴ poise to 124 C. After melting and pre-mixing the mass is fed to a rubber mill and thoroughly ground. A uniformly dispersed mass of the additive in the thermoplastic resin body is obtained to about 20 μ finely divided. 1 part by weight of the powdered toner particles is mixed with 0.01 part by weight of zinc stearate components with a size of about 0.5 to about 35 μ and 99 parts by weight of conventional carrier beads and instead of the known developer in the one described in Example 1 Test machine used. The treated clay r gutt produces high resolution copies that are essentially fog free. Under essentially identical test conditions, it is found that the original drive motor can be used if the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is abraded is 266 ° C. This corresponds to a reduction in the temperature of the melting device compared to that for the comparison sample according to the example! 1 required temperature of 55 C. There are no smoldering spots or burning spots on the copies emerging from the melting device. Furthermore, no agglomeration is observed is stored wenr a sample of this toner in a maintained at a temperature of 43 ^r C air circulating oven for a 24 hour period

Example 3

A toner mixture of 8.5 parts by weight of a copolymer of 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, 0.5 part by weight of a mixture of o- and p-toluenesulfonamic and 1 part by weight of carbon black is produced. The additive: is a hard dry solid with a melting point of 105 C. After melting and premixing, the mass is fed to a rubber mill and ground to obtain a uniformly distributed mass of the additive in the thermoplastic resin body. The contained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 7 to about 12 µm. 2 parts by weight of the powdered toner particles are mixed with 0.05 parts by weight of zinc stearate with a size range from about 0.5 to about 35 μ and 98 parts by weight of conventional carrier beads and instead of the known developer ir

509 516/27

the test machine described in Example I was used. The treated toner produces high-quality copies Resolution that are essentially fog-free. Provides under essentially identical test conditions it is found that the original drive motor can be used, the minimum temperature being the Melting device which produces legible copies after 5 revolutions of abrasion of the abrasion cylinder is 288 ° C. This corresponds to a reduction in the temperature of the melting device compared to the temperature of 24 C required for the comparison sample according to Example 1. When the copies exit the melter, there will be no smoldering or burning Bodies observed. Photographic micrographs of the reusable imaging surface show less abrasion and less destruction of the surface after 10,000 cycles than is the case with the imaging surface of Example 1.

Example 4

A toner mixture of 6.5 parts by weight of polystyrene, 2 parts by weight of a polychlorinated polyphenylene and 1.5 parts by weight of carbon black is prepared. The additive consists of a hard dry solid with a melting range of 98 to 105 C., a specific gravity (25 "C / 25" C) of 1.67 and a chlorine content of approximately 58.5 to 60.6 percent by weight. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a uniformly distributed mass of the additive in the thermoplastic resin body. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 10 to about 18 µm. 1.5 parts by weight of the powdered toner particles are mixed with 0.015 parts by weight of iron oleate with a size range from about 5 to about 140 μ and 98.5 parts by weight of conventional carrier beads and used in the test machine described in Example 1 in place of the known developer. The treated toner produces high resolution copies that are essentially foggy. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is abraded is 288.degree. This corresponds to a reduction in the temperature of the melting device compared to the temperature of 33 ° C. required for the comparative sample according to Example 1. When the copies emerge from the melting device, no smoldering or burning spots are observed.

Example 5

A toner mixture of 7.5 parts by weight of a copolymer of 70 parts by weight of styrene and 30 parts by weight of hexyl methacrylate, 1.5 parts by weight of pentaerythritol tetrabenzoate and 1 part by weight Soot is produced. The additive is a hard dry solid with a melting range of 93 to 6 C. After melting and premixing, the mass is fed to a rubber mill and to obtain a mass in which the additive is uniform in the thermoplastic resin body is distributed, thoroughly wed. The resulting mixed mass is cooled and then poured into a jet pulverizer to obtain toner particles having an average Particle size from about 10 to about 20 microns finely divided. 1 part by weight of the powdered toner particles are with 0.025 parts by weight of cobalt palmitate

ίο a size range from about 1 to about 30 μ and 99 parts by weight of the usual carrier beads mixed and used in place of the known developer used in the test machine described in Example 1. The treated toner produces high-quality copies Resolution that are essentially fog-free. Provides under essentially identical test conditions it is found that the original drive motor can be used, the minimum temperature being the Melting device in which readable copies are made after 5 revolutions of the abrasion cylinder is 254 ° C. This corresponds to a decrease in the temperature of the melting device compared to the temperature of 67 C. required for the comparison sample according to Example 1 There will be no smoldering or burning spots when the copies emerge from the melting device observed.

Example 6

A toner mixture of 7 parts by weight of a copolymer of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate and 2 parts by weight of pentaerythritol tetrabenzoate and 1 part by weight Soot is produced. The addition is a

Hard dry solid with a melting range of 94-96 C. The toner composition has a determined using an Instron capillary rheometer melt viscosity of 0.5 x 10 ~ ⁴ poise at 127C. After melting and premixing, it becomes

the mass fed to a rubber mill and to obtain a mass in which the additive in the thermoplastic resin body is evenly distributed, grind thoroughly. The obtained mingled Mass is cooled and then in a

Jet pulverization apparatus finely divided to obtain particles with an average particle size of about 10 to about 20 μm. 1 _{# part by} weight of the powdered toner particles is mixed with 0.01 parts by weight of zinc stearate with a size range from about 0.4 to about 40 μ and 99 parts by weight of glass spheres with an average diameter of about 500 μ and with a silicone terpolymer reaction product of butyl methacrylate, styrene and

Vinyltriäthoxysilan coated and in place of the known developer in that described in Example 1 Test machine used. The treated toner produces very good copies with a high resolution, whereby the veil is negligible. Under essentially

With identical test conditions it is found that that the original drive motor can be used, with the minimum melting temperature, at which readable copies are obtained after abrasion of 5 revolutions of the abrasion cylinder, 271 C

amounts to. This is a decrease in the temperature of the melter compared to that for the Comparative sample according to Example 1 required temperature of 50 "C. When the copies emerge from the

Melting device, no smoldering or burning spots are observed. Microphotographic examinations of the reusable imaging surface after 100,000 cycles show less wear and tear on the surface than is the case with the imaging surface according to Example 1. Furthermore, no agglomeration is observed when a sample of this toner in an air oven, which is maintained at a temperature of 43 ⁰ C, during a time period is stored for 24 hours. Both the quality of the copies produced using this toner and its handling properties are superior to all other toners tested.

• Example 7

A toner mixture of 7 parts by weight of isopropyl methacrylate resin, 2 parts by weight of glyceryl tribenzoate and 1 part by weight of carbon black is prepared. The additive is a hard dry solid with a melting point of 71C. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the additive is evenly distributed in the thermoplastic resin body. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 0.5 to about 1 µm. 1 part by weight of the powdered toner particles is mixed with 0.05 parts by weight of zinc linoleate with a size range of approximately 0.8 to approximately 25 μ and 99 parts by weight of uncoated glass carrier beads with an average particle size of approximately 500 μ and in place of the known developer in the example 1 described test machine used. The treated toner produces good copies with little fog. Under substantially identical test conditions, it is found that the original standard drive motor can be used, wherein the minimum temperature of the fusing device in which legible copies after an abrasion of 5 rotations of the abrasion cylinder are obtained is, 299 ⁰ C. This corresponds to a reduction in the temperature of the melting device compared to the temperatures of 22 ° C. required for the comparative sample according to Example 1. No smoldering or burning spots are observed when the copies exit the melter. Microphotographic examinations of the reusable imaging surface after 10,000 cycles show less wear and tear on the surface than is the case with the imaging surface according to Example 1.

Example 8

60

A toner mixture of 7 parts by weight of a copolymer of 50 parts by weight of propyl methacrylate and 50 parts by weight of methacrylonitrile. I parts by weight of a mixture of o- and p-toluenesulfonamide and 1 part by weight of carbon black are produced. The additive is a hard, dry solid with a melting point of about 105 ° C. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to form a mass in which the additive is evenly distributed in the thermoplastic resin body. The resulting mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 5 to about 16 µm. 1 part by weight of the powdered toner particles is mixed with 0.06 parts by weight of zinc stearate with a size range from about 0.5 to about 20 μ and 99 parts by weight of conventional carrier beads and used in place of the known developer in the test machine described in Example 1. The treated toner produces copies with good resolution that are essentially fog-free. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is worn Temperature of the melting device compared to the temperature of 17 ° C. required for the control sample according to Example 1. No smoldering or burning spots are observed when the copies emerge from the melting device Surface than is the case with the imaging surface according to Example 1.

Example 9

A toner mixture of 7.5 parts by weight of a copolymer of 20 parts by weight of vinyl acetate and 80 parts by weight of vinyl chloride, 1.5 parts by weight of pentaerythritol tetrabenzoate and 1 part by weight of carbon black is produced. After melting and premixing, the mass becomes a rubber mill fed and forming a mass in which the additive in the thermoplastic resin body is evenly distributed, grind thoroughly. The resulting mixed mass is cooled and then to toner particles having an average particle size of about 10 to about 20 μ finely divided. 2 parts by weight of the powdered toner particles are mixed with 0.1 part by weight of zinc stearate ranging in size from about 0.5 to about 20 microns and 98 parts by weight are more common Carrier beads mixed and instead of the known developer in that described in Example 1 Test machine used. The treated toner produces copies that are essentially fog-free Under essentially identical test conditions, it is found that the original drive motor is used can be, being the minimum temperature of the fuser at which readable copies obtained after abrasion of 5 revolutions of the abrasion cylinder, is 293 ° C. This matches with a decrease in the temperature of the melter ^ compared to that for the Like control sample? 3 Example 1 required temperature of 28 ° C. After the copies exit No smoldering or burning spots are observed on the melting device.

13 14

. . a decrease in the temperature of the melting

Example 10 device compared to that for the comparative

A toner mixture of 9 parts by weight of a sample according to Example 1 required temperature

Ethyl methacrylate polymer, 1 part by weight of penta of 28 ^C C. There are no smoldering or burning

erythritol tetrabenzoate and 1 part by weight of carbon black are produced on the spots from the melting device

posed. Observed after melting and a pre-leaking copy,

mix the mass of a rubber mill. . . _

out and while obtaining a mass in which b e ι s ρ ι e

the additive in the thermoplastic resin body A toner blend of 7.5 parts by weight of one is evenly distributed, grind thoroughly. The erio copolymer made from 25 parts of n-butyl methacrylate mixed mass is cooled and resin and 75 parts by weight of acrylonitrile resin, 1.5 closing in a jet pulverizer by weight glyceryl tribenzoate and 1 part by weight for the recovery of toner particles with a through-soot is produced. After melting and pre-cut Particle size from about 5 to unmixed becomes the mass of a rubber mill danger 10 μ finely divided. 1.5 parts by weight of the pulverized 15 and obtained a mass in catfish Toner particles at 0.01 part by weight tend to become the additive and pigment in the thermo-zinc stearate with a size range of approximately plastic resin bodies are evenly distributed, 0.5 to about 40 μ and 98.5 parts by weight do not grind thoroughly. The mixed mass obtained coated glass beads mixed and in place is cooled and then in a Hochgedes known developer in the speed comminution device described in Example 1 below Test machine used. The treated recovery of a toner having a particle size of Toner provides images that are substantially fog-free finely divided about 5 to about 10 microns. 99 weights are. Under essentially identical test conditions for normal carrier beads, 1 counts it is found that the original drive part by weight of the toner and 0.05 part by weight of the zinc motor Can be used, the minimum being 25 stearate with a size range of approximately 0.5 Temperature of the melting device, at which les- to about 40 μ mixed and in place of the bebare Copies after 5 revolutions had been rubbed off by the developer described in Example 1 Abrasion cylinder are obtained, is 282 ° C. benen test device used. The treated This corresponds to a lowering of the temperature. Toner produces good copies which are essentially foggy Melting device compared to that for the 30 are free. Under essentially identical conditions for comparison according to example 1 required temperatures one finds that the original drive temperature of 39 C. After exiting the copies motor can be used, with the minimum from the melting device no smoldering melting temperature, at which legible copies after or burning spots observed. an abrasion of 5 revolutions of the abrasion cylinder

.... 35 ders are obtained, 285 "C. This corresponds to

Example II of _a lowering of the temperature of the melting

A toner blend of 8 parts by weight of a device versus that for the comparative sample

Copolymer of 35 parts by weight of vinyl acetate according to Example 1 required temperature of 36 C.

and 65 parts by weight of acrylonitrile, 1 part by weight of tri-

methylolethane ribenzoate and 1 part by weight of carbon black will not be smoldering or burning

manufactured. The addition is a hard dry hard-spots observed,

substance with a melting point of approximately 74 ^r C. B eis η ie 1 13
After melting and premixing

the mass is fed to a rubber mill and a toner mixture of 5.5 parts by weight of one

thoroughly while obtaining a mass in which 45 copolymer of 90 parts by weight of styrene unc

the addition evenly in the thermoplastic 10 parts by weight of isobutyl methacrylate, 3.5 parts by weight

Resin body is distributed, grind. The obtained divided pentaerythritol tetrabenzoate and 1 part by weight!

mixed mass is cooled and then made into carbon black. The addition is a hard dry egg

a jet pulverizer under Gewin-Solid with a melting range of 94 to 96 "C

tion of toner particles with an average 50 After melting and premixing ir

Particle size from about 7 to about 12 microns fine a Banbury mixer becomes the bulk of a chew

parted. 1 part by weight of the powdered toner particles fed to a chukmill and obtained an egg

is 0.04 parts by weight of zinc stearate with a mass in which the additive in the thermoplastic

Size range from about 0.5 to about 20 μ resin body is evenly distributed, thoroughly ver

and grind 99 parts by weight of glass beads with a 55. The resulting mixed mass is cooled

average diameter of about 500μ. and then in a jet pulverization process

which with a silicone terpolymer reaction direction with recovery of toner particles mi

product made from butyl methacrylate, styrene and vinyl tri- an average particle size of approx

Ethoxysilane coated are mixed and finely divided in place of 10 to 20 μ. 1 part by weight of the pulveri

of the known developer in the toner particles described in Example 1 is 0.01 part by weight

written test machine used. The treated zinc stearate ranged in size from approximately

Toner yeasts good copies that are essentially foggy 0.5 to about 20 µ and 99 parts by weight, not at

are free. Under essentially identical test-drawn glass slide beads with a diameter

conditions one finds that the original drive of 500 μ mixed and in place of the well-known Ent

motor can be used, with the minimum 65 winder in the test voi described in example 1

Melting temperature at which readable copies are used in direction. The treated toner delivers well

an abrasion of 5 revolutions of the abrasion cylinder - high resolution copies that are essentially

ders will be obtained. 293 C. This corresponds to being veil-free. Under essentially identical

Test conditions determine that the original drive motor can be used, with the minimum temperature of the melter, at which readable copies are obtained after abrasion of 5 revolutions of the abrasion cylinder, 266 C amounts to. This corresponds to a lowering of the temperature of the melting device compared to that for the control sample according to Example 1 required temperature of 55 ° C. When the copies emerge no smoldering ι ο or burning spots are observed on the melting device.

Example 14

A toner mixture of 5.5 parts by weight of a copolymer of 80 parts by weight of styrene and 20 parts by weight of ethyl acrylate and 3.5 parts by weight of a mixture of o- and p-toluenesulfonamide and 1.0 part by weight of carbon black is produced. The addition provides a hard dry solid with a melting point of 105 ° C. After grinding and premixing, the mass is fed to a rubber mill and formed a mass in which the additive is uniformly distributed in the thermoplastic resin body. thorough to marry. The resulting mixed mass is cooled and then placed in a jet pulverizer finely divided to give toner particles having an average particle size of about 10 to about 20 microns. 1 part by weight of the powdered toner particles is 0.02 weight steep lead stearate with a size range from about 10 to about 35 μ and 99 parts by weight of the usual carrier in the example 1 described test machine used. The treated toner produces good copies, essentially are veil-free. Under essentially identical test conditions, it is found that the original drive motor can be used, with the minimum temperature of the melter, at which readable copies are obtained after abrasion of 5 revolutions of the abrasion cylinder, 260 ° C amounts to. This corresponds to a lowering of the temperature of the melting device compared to that for the control sample according to the example! required temperature of 61 C. When the copies emerge no smoldering or burning spots are observed from the melting device.

Example 15

A toner mixture of 7.5 parts of a mixed polymer of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate and 1.5 parts of glyceryl tribenzoate and 1.0 part by weight of carbon black is produced. Glyceryl is a dry solid, which has a molecular weight of 404 and a melting point of 71 ⁰ C. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the additive is evenly distributed in the thermoplastic resin body. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 8 to about 22 µm. 1 part by weight of the powdered toner particles is mixed with 0.01 parts by weight of zinc stearate with a size range from about 0.4 to about 40 μ and 99 parts by weight of conventional carriers and used in the test machine described in Example 1 in place of the known developer. The treated toner produces good copies that are essentially fog free. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is abraded is 282 ° C. This corresponds to a reduction in the temperature of the melting device compared to the temperature of 39 ° C. required for the control sample according to Example 1. When the copies emerge from the melting device, no smoldering or burning spots are observed.

Example 16

A toner mixture of 8.0 parts by weight of a copolymer of 70 parts by weight of styrene and 30 parts by weight of vinyl acetate, 1.0 part by weight of trimethylol ethane tribenzoate and 1.0 part by weight of carbon black is produced. De. ' Additive is a hard white crystalline solid with a melting point of 74 C and a molecular weight of 432. After melting and mixing in a Banbury mixer as well as thorough grinding in a rubber mill, a mass is obtained in which the additive is evenly distributed in the thermoplastic resin body. The mixed mass is cooled and then in a Szegvari comminuting device to obtain toner particles pulverized with an average particle size of about 10 to 20 µ. 1 part by weight of powdered toner particles are mixed with 0.03 parts by weight of zinc stearate in a size range of approximately 0.4 to about 40 μ and 99 parts by weight of conventional carrier mixed and in the example 1 described test machine used. The treated toner provides good and essentially fog-free Copies. Under essentially identical test conditions, it is found that the original drive motor can be used, being the minimum temperature of the melting device at which readable Copies obtained after abrasion of 5 revolutions of the abrasion cylinder is 288 ° C. This corresponds to a reduction in the temperature of the melting device compared to that for the Control sample according to Example 1 required temperature of 33C. When the copies come out no smoldering or burning spots are observed on the melter.

Example 17

A toner mixture of 8.0 parts by weight of a copolymer of 85 parts by weight of styrene and 15 parts by weight of vinylidene chloride polymer and 1.0 part by weight of ethylene glycol dibenzoate and 1.0 part by weight of carbon black is prepared. The additive is a hard dry solid with a melting range of 68 to 74 ^° C. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the additive is evenly distributed in the thermoplastic resin body . The mixed mass obtained is cooled and then in a jet pulverization device to obtain toner particles with a thorough-

average particle size of about 8 to 14 α finely divided. 1 part by weight of the powdered toner particles are mixed with 0.01 parts by weight of zinc stearate with a size range from about 0.4 to about 40 μ and 99 parts by weight of a conventional carrier beads and used in place of the known developer in the test machine described in Example 1. The treated toner produces good copies which are essentially fog-free. Under essentially identical test conditions, it is found that the original drive motor can be used with the minimum temperature of the fuser in which legible copies are obtained after 5 revolutions of the abrasion cylinder rub be, is 282 ^° C. This corresponds to a reduction in the temperature of the melting device compared to the temperature of 39 ° C. required for the comparative sample according to Example 1. No smoldering or burning spots are observed when the copies exit the melter.

Example 18

A toner mixture of 6.0 parts by weight of a mixed polymer of 20 parts by weight of styrene and 80 parts by weight of vinyl alcohol and 3.0 parts by weight of n-cyclohexyl-p-toluenesulfonamide and 1.0 part by weight of carbon black is prepared. The additive is a hard, water-insoluble crystalline solid, which is stable up to 149 C in the heat. The melting point is 85X. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the additive is evenly distributed in the thermoplastic resin body. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 10 to 20 µm. 2 parts by weight of the powdered toner particles are mixed with 0.02 parts by weight of zinc palmitate with a size range of about 0.5 to about 35 μ and 98 parts by weight of a carrier consisting of glass spheres coated with ethyl cellulose and having an average diameter of about μ, and mixed on Instead of the known developer in the test machine described in Example 1 used. The treated toner produces good copies that are essentially fog free. Under substantially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is worn is 293 C 55. This corresponds to a reduction in the temperature of the melting device compared to the temperature of 19 ° C required for the comparative sample according to Example 1. No smoldering or burning spots are observed when the copies exit the melter.

white solid with a melting point of 60Ί. After melting and a pre-mixing, the mass of a rubber mill is zt out and ground thoroughly to obtain a mass in which the additive is evenly distributed in the thermoplastic resin body. The mixed mass obtained is cooled and then divided in a jet pulverization device to obtain toner particles m- * jner by average particle size of 10 b, \) _μ f _e j _{n 2} . 1 part by weight of the pulverized Tonerteilchei is 0.04 parts by weight Zinksteara _t with a size range of about 0.4 to about 40 μ and mixed 99 parts by weight of a customary carrier beads and used in place of the known developer as described in Example 1, test machine The treated toner provides good copies that are essentially fog free. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is abraded is 293.degree. This corresponds to a reduction in the temperature of the melting point compared to the temperature of 28 ° C. required for the comparison sample according to Example 1. When the copies emerge from the melting device, no smoldering or burning spots are observed.

Example 20 Example 19

A toner mixture of 6.0 parts by weight of a copolymer of 80 parts by weight of styrene, 65 parts by weight of acrylonitrile and 3.0 parts by weight of n-ethyl-p-toluene-sulfonamide and 1.0 part by weight of carbon black is prepared. The addition provides a hard A toner mixture of 7.5 parts of a copolymer of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate and 1.5 parts by weight of pen'aerythritol tetrabenzoate and 1.0 part by weight of carbon black is produced. The toner has a melt viscosity, measured using the Instron capillary rheometer of 0.5 x 10 ^"4 poises at a temperature of 138 C. The additive is a dry solid with a melting range of 94-96 C. After melting and after premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the additive is uniformly distributed in the thermoplastic resin body. The obtained mixed mass is cooled and then in a Szegvari pulverizer to obtain toner particles having an average particle size from about 10 to 20 microns Part of the toner is 0.03 parts by weight of zinc stearate with a size range of about 0.5 to about 40 microns and 99 parts of a carrier made of glass beads coated with an ethyl cellulose and an average diameter of have about 600 μ, mixed and in place of the known Developer used in the test device described in Example 1. The treated toner produces good copies that are essentially fog free. Under substantially identical test conditions, it is found that the original drive motor can be used, wherein the minimum temperature of the fusing device in which after an abrasion-readable copies of revolutions of the cylinder abrasion is obtained, 288 ⁰ C. This corresponds to a reduction in the temperature of the melting device compared to the temperature of 24 ° C. required for the comparative sample according to Example 1. When Αικιγριαπ

no smoldering or burning spots are observed on the copies from the melter.

Example 21

A sample of the treated toner and carrier described in Example 5 is used in the example 1 used to make copies of a standard test image. Even though the machine is run at 11 copies per minute, the temperature of the melter set to 254 ° C. The quality of adhesion of the toner image is measured in a Taber abrasive device tested. Twenty cycles of the abrasive device are required to achieve a 20% reduction in image density, such as with a densichrome re-recording. inflection unit is determined to achieve.

Example 22

A sample of the comparative toner and carrier described in Example 1 is used to form Used in toner images. The imaging and testing procedure is essentially the same as that the procedure described in Example 21. Less than 2 cycles of the abrasive device are required to obtain an image whose density is reduced by 20%, such as by means of a densichrome reflection unit is measured. The applied toner image can be easily rubbed with a Destroy fingers or thumb.

Example 23

A comparative toner mixture of 9 parts by weight of a mixture of o- and p-toluene sulfonamide and 1 part by weight of nigrosine SSB dye is prepared. The sulfonamide mixture is a hard dry solid with a melting point of 105 ° C. After melting and premixing, the mass is thoroughly ground to obtain a uniform dispersion of dye and sulfonamide. The resulting mixed mass is cooled and finely divided in a Szegvari grinder to achieve an average particle size of about 8 to about 15 microns. The resulting toner is mixed with coated glass carrier beads and cascaded over a surface bearing a negatively charged electrostatic latent image. The deposited toner image is transferred to a sheet of paper and melted ^{at 151 ° C.} If the paper provided with the picture is folded, the picture crumbles along the fold. When an image formed on a sheet by the method described in Example 3 is folded, there is no tearing or peeling of the toner image along the fold.

B e i s ρ i e I 24

A comparative sample of 1 part toner particles which contains the carbon black-colored additive of Example 23 and have an average particle size of about 10 to about 20 μ, as well as 99 parts of common carrier particles are placed in a rotating cylindrical vessel with an inner diameter of 67 cm, the surface speed being 42 m per minute. An investigation of the developer after 50 hours from the start of the test shows that a large amount of undesirable fine powder is present.

Example 25

A toner blend comprising 7.5 parts by weight of a; Copolymer of 80 parts by weight of styrene unc 20 parts by weight of isobutyl methacrylate and 1.5 parts by weight of the additive from Example 23 and 1 part by weight Contains carbon black and has an average particle size of about 10 to about 20 μ, is mixed with 99 parts by weight of conventional carrier particles. The developer obtained is in the rotating cylindrical vessel described in Example 24 swirled. An investigation of the developer 50 hours after the start of the test shows essentially no undesirable Powder is present.

Example 26

It becomes a comparison ion mixture of 7.5 parts by weight a copolymer of 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, 1.5 parts by weight of polyethylene wax and 1 part by weight of carbon black. The wax consists of a dry solid with a melting range of 104 to 110 C. After melting and a Premixing the mass is fed to a rubber mill and for the production of a mass in which the wax is evenly distributed in the thermoplastic resin body, grind thoroughly. The received mixed mass is cooled using liquid nitrogen and then poured into a Szegvari crushing device for the recovery of toner particles with an average Particle size from about 10 to about 20 microns finely divided. Cooling down to a temperature below Room temperature is required in order for the toner material to form a film on the parts of the grinding device to avoid. 1 part of the toner is mixed with 99 parts of a carrier, which consists of glass spheres with an ethyl cellulose coating are coated and have an average diameter of about 600 μ. The received Developer is used to make 8000 copies using a conventional copier machine used. The copies, in particular the copies made towards the end of the test, are characterized by images of very low density and heavy haze. An investigation the roller of the electrophotographic recording apparatus after the test was completed shows that a dense toner film has formed on the surface of the roller.

Example 27

A comparison toner mixture composed of 7 parts by weight of a copolymer composed of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate and 2.0 parts by weight of polyethylene sebacate and 1.0 parts by weight Soot is produced. The additive is a dry solid with a melting point of 76 ° C. After melting and premixing, the mass is fed to a rubber mill and obtaining a mass in which the additive in the thermoplastic resin body is evenly distributed, grind thoroughly. The resulting mixed mass is cooled and then in a jet pulverization device for the extraction of toner particles with a through-

average particle size from about 10 to about 20 μ finely divided. 1 part by weight of the powdered toner particles becomes more common with 99 parts by weight Carrier beads mixed and instead of the known developer in the described in Example I - benen test machine used. The developer obtained is used to produce 10,000 copies in a copier used. The copies made at the end of the test are due to pictures with very low density and characterized by a strong haze. An examination of the roll of the electrophotographic recording device after completion of the test shows that a denser Has formed toner film on the surface of the roller.

Example 28

A toner mixture of ε parts by weight of a copolymer of 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, 1 part by weight of pentaerythritol tetrarenzoate and 1 part by weight of carbon black is produced. The toner composition has a determined using an Instron capillary rheometer melt viscosity of 0.5 ■ 10 ~ ⁴ poise at 130'C. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the additive is evenly distributed in the thermoplastic resin body. The resulting mixed mass is cooled and then finely divided in a Szegvari pulverizer to obtain toner particles having an average particle size of about 10 to about 20 µm. 1 part of the toner is mixed with 0.01 parts by weight of zinc stearate with a size range from about 0.4 to about 40 μ and 99 parts of a carrier consisting of glass spheres which are provided with an ethyl cellulose coating and have an average diameter of approximately 600 μ. The developer obtained is used to make 8,000 copies in a copying machine. Essentially all copies are characterized by sharp, high density images with little background deposition. Examination of the roller of the electrophotographic recording apparatus after the test was completed reveals that a substantially imperceptible toner film has formed on the surface of the roller.

B e i s ρ i e 1 29 5 «

A comparison toner sample, which is essentially identical to the toner described in Example 6, is examined for its caking temperature. The test method is that the toner particles and the temperature every 24 hours is increased by 5 ⁰ C are heated in an air circulating oven at 38 ° C during einrr 24 hour period first. The caking temperature is the temperature at which one has to press lightly with a spatula. in order to return formed gate agglomerates back into the form of finely divided particles. The caking temperature of the comparison sample is 52 "C.

Example 30

A comparison toner mixture of 7 parts by weight of a copolymer of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate, 2 parts by weight of ethyl phthalyl ethyl glycolate and 1 part by weight of carbon black is prepared. The ethyl phthalyl ethyl glycolate is a liquid. After melting and premixing, the mass is fed to a rubber mill and a mass is obtained in which the wax is evenly distributed in the thermoplastic resin body. thoroughly wed. The resulting mixed mass is cooled using liquid nitrogen and then finely divided in a Szegvari crusher to obtain toner particles with an average particle size of about 10 to about 20 μm. The toner particles are then tested according to the method described in Example 29. The toner particles cake together at the initial temperature of 38 ^C C of the test.

Example 31

A comparison toner mixture composed of 7 parts by weight of a copolymer composed of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate, 2 parts by weight of paraffin and 1 part by weight of carbon black manufactured. The paraffin is a dry solid with a melting range of 60 to 62 C. After melting and premixing, the mass is fed to a rubber mill and thoroughly to obtain a mass in which the wax in the thermoplastic resin body is fine is distributed, wed. The resulting mixed mass is cooled using liquid nitrogen and then in a Szegvari comminuting device to obtain toner particles finely divided with an average particle size of about 10 to about 20 microns. The toner particles are then tested according to the method described in Example 29. The toner particles Bake together at the initial temperature of the test of 38 C.

Example 32

A comparative sample containing 1 part colored preformed toner particles of that described in Example 6 Type with an average particle size of about 10 to about 20 microns, is with 99 parts by weight of glass spheres with an average particle diameter of approximately 400 μ, which are coated with ethyl cellulose, mixed and then cascaded over a roller surface, that carries an electrostatic image. The developed image is then electrostatic Paths transferred to a sheet of paper, on which it is melted by heat. The rest Powder is removed from the electrostatic imaging surface using a cleaning cloth of the type described in US Pat. No. 3,186,838. After the copying process 25000 times has been repeated, the copies as well as the electrostatic image bearing surface become visible examined for quality or wear and tear. The copies have sharp contrast lines, wöbe only a minimal haze is observed. An <examination of the imaging surface gives however, numerous scratches, and also eroding effects can be observed.

Example 33

0.1 part of zinc stearate with a particle size distribution of about 0.75μ to about 40μ slowly 1 part of colored preformed toner particles of the type described in Example 6 are admixed. the The developer mixture obtained is then used in a Szegvari shredding device during Grind thoroughly over a period of approximately 10 minutes. Then that is described in Example 32 Development method using a new roller, as well as the milled one described above Mixture that is used in place of the toner described in Example 32, with a relative Humidity of 50% as well as at a temperature of 21 ° C and a relative humidity of 80% and repeated at a temperature of 27 C. Those made using the milled sample Copies have a higher density and a lower solid surface coverage Fog than the copies made using the comparative sample. A visual one Examination of the electrostatic image bearing surface shows less wear than this is the case with the scratched image-bearing surface according to Example 32. In addition, one is considerable less torque required to drive the roller when the stearate additive is used, wherein also, less voltage is required to transfer the toner images to receiving sheets.

Example 34

10 parts of colored preformed toner particles of the type described in Example 6 are slowly admixed with 0.025 part of zinc stearate with a particle size distribution of approximately 0.75 μm to approximately 40 μm. The mixture obtained is then swirled in a closed container for a period of 15 minutes. 1 part of the whirled mixture is mixed with 99 parts of carrier beads which are coated with ethyl cellulose and have an average particle size of approximately 400 μ. The developer mixture obtained is used in the manner described in Example 32 in a cascade development process at a relative humidity of 50% at 21 ° C. and at a relative humidity of 80% at 27 ° C. The fused toner images obtained are denser than the images obtained in Example 33 under both humidity conditions.

Example 35

A toner mixture of 10 parts by weight of carbon black, 85 parts by weight of a copolymer of 65 parts by weight of styrene and 35 parts by weight of n-butyl methacrylate and 5 parts by weight of dicyclohexyl phthalate is produced. This phthalate has a melting point of 6 (TC. After melting and premixing, the mass is ground in a rubber mill to obtain a mass in which the carbon black is evenly distributed in the thermoplastic resin body. The mixed mass obtained is cooled and then μ in a 6s Strahlpulverisierungsvorrichtung for the recovery of toner particles having an average particle size of about 10 to about 15 finely divided. The toner has a melt viscosity voi 0.5 x I0 ~ ⁴ poise at 140 ⁰ C and a caking temperature of 57 ° C. 1 Part by weight of the pulverized toner particles is 0.01 part by weight of zinc stearate particles with a particle size of approximately: to approximately 40 μ and 99 parts by weight of conventional carrier beads mixed and used as a developer in the test machine described in Example 1. Under essentially identical test conditions, it is found that the Use original drive motor The minimum temperature of the melting device at which readable copies are obtained after 5 revolutions of the abrasion cylinder is 299 ° C. This means a reduction in the temperature of the melting device compared to the temperature required for the comparative sample of Example 1 before 22 C. When the copy samples emerged from the toner melting device, no smoldering areas were observed. Microphotographic examinations of the reusable imaging surface show less wear and tear on the imaging surface than is the case with the imaging surface according to Example 1 after 5000 cycles.

Example 36

A toner mixture of 10 parts by weight of carbon black, 80 parts by weight of a copolymer of 65 parts by weight of styrene and 35 parts by weight of n-butyl methacrylate and 10 parts by weight of diphenyl phthalate is produced. This phthalate has a melting point of 67 ^° C. After fusing and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the carbon black is evenly distributed in the thermoplastic resin body. The resulting mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 6 to about 12 µm. This toner has a melt viscosity of 0.5 · 10 ~ ^A poise at 135 ° C. and a caking temperature of 51 ° C. 1.5 parts by weight of the powdered toner particles are mixed with 0.01 parts by weight of zinc stearate particles with a particle size between about 5 and about; 40 μ and 99 parts by weight of conventional carrier beads mixed and used in place of the known developer in the test machine described in Example 1. Under substantially identical test conditions, it is found that the original drive motor can be used, wherein the minimum temperature of the fusing device in which legible copies after an abrasion of 5 rotations of the abrasion cylinder obtained is 285 ⁰ C This corresponds to a reduction in temperature of the melting device compared to the temperature of 36 ° C. required for the comparative sample according to Example 1. When the copy samples emerged from the melting device, no glowing areas were observed. Microphotographic examinations of the reusable imaging surface after 5000 cycles show less wear and tear and less damage to the imaging surface than is the case with the imaging surface according to Example 1.

509516/271

/ Γ

Example 37

A toner mixture of 10 parts by weight of Sudan black, 80 parts by weight of a copolymer of 65 parts by weight of styrene and 35 parts by weight of n-butyl methacrylate and 10 parts by weight of dihydroabietyl phthalate is produced. This phthalate has a melting point of 66 ° C. After melting and premixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the carbon black is evenly distributed in the thermoplastic resin body. The resulting mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 10 to about 15 µm. This toner has a melt viscosity of 0.5-10 ~ ⁴ poise at 135 C, and a caking temperature of 51 C. 1 part by weight of the powdered toner particles is mixed with 0.05 parts by weight of zinc oleate with a particle size range between about 0.5 and about 35 μ and 99 parts by weight of conventional carrier beads and in place of the known. Developer used in the test machine described in Example 1. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is rubbed. This corresponds to a reduction in the temperature of the melting device by 33 ° C. compared to the temperature required for the comparative sample according to Example 1. No smoldering spots are observed when the copy samples exit the melter. Microphotographic examinations of the reusable imaging surface show less wear and tear and less damage to the surface after 5,000 copies than is the case with the imaging surface according to Example 1.

Example 38

A toner blend of 10 parts by weight of carbon black. 75 parts by weight of a copolymer composed of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate and 15 parts by weight of dicyclohexyl phthalate are produced. After melting and premixing, the mass is fed to a rubber mill and a mass is obtained in which the dye is uniformly distributed in the thermoplastic resin body. thoroughly wed. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 6 to about 9 µm. This toner has a melt viscosity of 0.5 x 10 ~ ⁴ poise at 135 ° C and a caking temperature of 54 ^r C. 2 parts by weight of the pulverized toner particles are μ with 0.015 parts by weight of zinc stearate with a size range of about 5 to about 40 and 99 parts by weight of the usual Carrier beads mixed and used in place of the known developer in the test machine described in Example I. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is abraded is 282 ° C. This corresponds to a reduction in the temperature of the melting device by 39 "C compared to the temperature required for the comparison sample according to Example 1. When the copy samples emerged from the melting device, no smoldering areas are observed. Microphotographic examinations of the reusable imaging surface show a lower level after 5000 cycles Wear and less damage to the surface than

This is the case with the imaging surface according to Example 1.

Example 39

A toner mixture of 10 parts by weight of carbon black, 75 parts by weight of a copolymer of 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate and 15 parts by weight of dimethyl isophthalate is produced. After fusing and pre-mixing, the mass is fed to a rubber mill and thoroughly ground to obtain a mass in which the pigment and phthalate are uniformly imparted in the thermoplastic resin body. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 6 to about 9 µm. This toner has a melt viscosity of 0.5 10 ⁴ poise at 138 C and a caking temperature of 54 C. 1 part by weight of the powdered toner particles is 0.01 part by weight of zinc stearate particles with a size range of about 0.5 to about 30 μ and 99 parts by weight of conventional carrier beads mixed and used in place of the known developer in the test machine described in Example 1. Under essentially identical test conditions, it is found that the original drive motor can be used, with the minimum temperature of the melting

device in which readable copies are obtained after abrasion of 5 revolutions of the abrasion cylinder is 293 ^r C. This corresponds to a reduction in the temperature of the melting device compared to that for the comparative sample according to FIG

Example 1 required a temperature of 28 C. When the copy sheet emerges from the melting device, no smoldering areas are observed. Microphotographic examinations of the imaging surface show an after 5000 cycles

less wear and less destruction of the surface than is the case with the imaging surface according to example 1.

Example 40

A toner mixture of 10 parts by weight of carbon black, 65 parts by weight of a copolymer of 90 parts by weight of polystyrene and 10 parts by weight of isobutyl methacrylate and 25 parts by weight of dicyclohexyl phthalate is produced. After melting

and a premixing, the mass is fed to a rubber mill and recovered a mass in which the carbon black as well as the phthalate are uniform in the thermoplastic resin body

are distributed, thoroughly wed. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 10 to about 15 µm. This toner has a melt viscosity of 0.5 x 10 ~ * poise at 121 ⁰ C and a caking temperature of 43 ° C. 1 part by weight of the powdered toner particles is mixed with 0.1 part by weight of zinc oleate with a particle size of about 0.5 to about 25 μ and 99 parts by weight of conventional carrier beads and used in place of the known developer in the test machine described in Example 1. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is abraded is 260.degree. This corresponds to a reduction in the temperature of the melting device compared to the temperature required for the comparative sample according to Example 1 by 61 "C. When the copy sheet emerged from the melting device, no smoldering areas were observed. Microphotographic examinations of the reusable imaging surface show a lower level after 5000 cycles Wear and less destruction of the surface than is the case with the vapor-generating surface according to Example 1.

Example 41

A toner mixture of 10 parts by weight of carbon black, 65 parts by weight of polystyrene and 25 parts by weight of diphenyl phthalate is prepared. After melting and premixing, the mass is ground in a rubber mill to obtain a mass in which the carbon black is uniformly distributed in the thermoplastic resin body. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 10 to about 15 µm. The toner has a melt viscosity of 0.5 × 10 " ⁴ poise at 124 ° C. and a caking temperature of 46 C. 1 part by weight of the powdered toner particles is made up of 0.01 parts by weight of zinc stearate particles with a particle size of about 5 to about 40 μ and 99 parts by weight conventional carrier beads and used in the test machine described in Example 1. Under essentially identical test conditions, it is found that the original drive motor can be used, with the minimum temperature of the melting device at which readable copies after an abrasion of 5 revolutions of the abrasion cylinder are obtained, is 266 ° C. This corresponds to a reduction in the temperature of the melting device compared to the temperature required for the comparison sample according to Example 1 by 55 C. When the copy samples emerge from the toner melting device, no glowing spots are observed Reusable spray-generating surface results after 5000 cycles with less wear and less destruction of the spray-generating surface than is the case with the spray-generating surface according to Example 1.

Example 42

A toner mixture of 10 parts by weight of carbon black, 70 parts by weight of polymethyl methacrylate and 20 parts by weight of dihydroabietyl phthalate is prepared. After melting and premixing, the mass is ground in a rubber mill to obtain a mass in which the carbon black is uniformly distributed in the thermoplastic resin body. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 6 to about 12 µm. The toner has a melt viscosity of 0.5 x 10 ~ ⁴ poise at 130 "C and a caking temperature of 49 ⁰ C. 1 part by weight of the pulverized toner particles with 0.01 parts by weight Bleilinoleatteilchen with a particle size of about 3 to about 35 μ and 99 Parts by weight of conventional carrier beads mixed and used as a developer in the test machine described in Example 1. Under essentially identical test conditions, it is found that the original drive motor can be used, with the minimum temperature of the melting device at which readable copies after an abrasion of 5 Revolutions of the abrasion cylinder are obtained, is 277 ° C. This corresponds to a reduction in the temperature of the melting device by 54 ° C. compared to the temperature required for the comparative sample according to Example 1. No smoldering spots are observed when the copy samples exit the toner fuser. Microphotographic examinations of the reusable imaging surface show less wear and tear and less damage to the imaging surface than is the case with the imaging surface according to Example 1 after 5000 cycles.

Example 43

A toner mixture of 10 parts by weight of carbon black, 75 parts by weight of a copolymer of 90 parts by weight Styrene and 10 parts by weight of vinylidene chloride and 15 parts by weight of diphenyl phthalate is produced. After melting and premixing, the mass is obtained with a Grind the mass in a rubber mill, in which the carbon black in the thermoplastic resin body is uniform is distributed. The resulting mixed mass is cooled and then placed in a jet pulverizer finely divided to obtain toner particles having an average particle size of about 7 to about 12 microns. The toner has a melt viscosity of 0.5x10 "" poise at 135 "C and a caking temperature of 51 "C. 1 part by weight of the powdered toner particles becomes 0.01 part by weight of zinc stearate particles a particle size of about 5 to about 40 microns and 99 parts by weight of uncoated glass spheres mixed and used as a developer in the test machine described in Example 1. Under im essentially identical test conditions, it is found that the original drive motor is used can, with the minimum temperature of the fuser at which readable copies after

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an abrasion of 5 revolutions of the abrasion cylinder is 296 ° C. This corresponds to a Reduction of the temperature of the melting device compared to that for the comparative sample according to the example 1 required temperature around 25 ° C. When the copy samples exit the toner melter no smoldering spots are observed. Microphotographic examinations of the reusable imaging surfaces result in less wear and tear after 5000 cycles and destruction of the imaging surface as in the case of the imaging surface according to Example 1

the case is. . . , ..

Example 44

A toner mixture of 10 parts by weight of carbon black, 80 parts by weight of a copolymer of 70 parts by weight of styrene and 30 parts by weight of vinyl acetate and 10 parts by weight of dicyclohexyl phthalate is produced. After melting and a premixing the composition is ground in a rubber mill to obtain a mass in which the carbon black in the thermoplastic resin body evenly distributed \ s ^f. The obtained mixed mass is cooled and then finely divided in a jet pulverizer to obtain toner particles having an average particle size of about 10 to about 15 µm. The toner has a melt viscosity of 0.5 × 10 "* poise at 138 ¹ C and a caking temperature of 57 ° C. 1 part by weight of the powdered toner particles is mixed with 0.01 parts by weight of zinc stearate particles with a particle size of approximately 5 to approximately 40 μ and 99 Parts by weight of coated carrier beads mixed and used as a developer in the test machine described in Example 1. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the melting device at which readable copies after abrasion of 5 Revolutions of the abrasion cylinder are obtained .293 ° C. This corresponds to a decrease in the temperature of the melting device, as is required for the comparative sample according to Example 1. by 28 ° C. After the copy samples have emerged from the toner melting device, no smoldering areas are observed Investigations d A reusable imaging surface results in less wear and tear and destruction of the imaging surface than is the case with the imaging surface according to Example 1 after 5000 cycles.

Example 45

A toner blend of 10 parts by weight of carbon black. 70 parts by weight of a copolymer composed of 80 parts by weight of styrene and 20 parts by weight of acrylonitrile and 20 parts by weight of dicyclohexyl phthalate is produced. This phthalate having a melting point of 60 ^c C. After melting and a premixing the composition is ground in a rubber mill to obtain a mass in which the carbon black is uniformly dispersed in the thermoplastic resin body. The resulting mixed mass is cooled and then finely divided in a jet pulverization device to obtain toner particles having an average particle size of about 5 to about 14 μm. The toner has a melt viscosity of 0.5 · 10 " ⁴ poise at 127 ^J C and a caking temperature of 49" C. 1 part by weight of the powdered toner particles is mixed with 0.05 parts by weight of cobalt palmitate fragrances with a particle size of about 5 to about 40 μ and 99 parts by weight of uncoated glass carrier beads and used as a developer in the test machine described in Example II. Under essentially identical test conditions, it is found that the original drive motor can be used, the minimum temperature of the fuser at which legible copies are obtained after 5 revolutions of the abrasion cylinder is worn is 27PC. This corresponds to a reduction in the temperature of the melting device by 50 ° compared to the temperature required for the comparison sample according to Example 1. When the copy samples emerge from the toner melting device, no smoldering spots are observed. Microphotographic examinations of the reusable imaging surface show less wear and tear on the imaging surface than is the case with the imaging surface according to Example 1 after 5000 cycles.

Example 46

A comparison toner mixture of 5 parts by weight of carbon black and 90 parts by weight of a polymeric esterification product from a linear alcohol, namely hexamethylene glycol, and a dicarboxylic acid, namely, sebacic acid, is produced. This polymer, namely hexamethylene sebacate, has a Molecular weight of about 20,000 and a melting range of 63 to 69 ° C. After melting and a premix the mass is fed to a rubber mill and recovered a mass in which the carbon black is evenly distributed in the thermoplastic resin body. thorough to marry. The mixed mass obtained is

cooled and then in a jet pulverizer finely divided to give toner particles having an average particle size of about 7 to about 12 microns. 1 part by weight of the powdered toner particles is mixed with 99 parts by weight of conventional carrier beads and used in place of the known developer in the test machine described in Example 1. the After melting, toner images are extremely faint, poorly defined and practically illegible. After un-

Approximately 70 image generation cycles are used to create a dense one Toner film stuck on the surface of the drum of the modified machine.

Example 47

A sample of toner particles of the type described in Example 2 is applied to its imaging Properties tested. 1 part by weight of the powdered toner particles becomes 0.0025 part by weight Zinc stearate particles with a particle size of un-

risk 0.5 to about 40 μ and 99 parts by weight uncoated glass slide beads mixed and used as a developer in that described in Example 46 Test machine used. Under essentially identical test conditions, the obtained toner

⁶ S images very legible and very dense. A slight tarnish was observed on the surface of the roller of the electrophotographic recording apparatus.

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example

A comparative sample containing 1 part colored preformed toner particles of that described in Example 35 Type with an average particle size of about 10 to about 15 microns, is with 99 parts coated glass beads with an average particle size of about 250 microns mixed and then cascaded over a roller surface that carries an electrostatic image. The developed image is then electrostatically transferred to a sheet of paper, on which it is melted. The remaining powder is used by the electrostatic imaging Surface removed by means of a cleaning fabric of the type described in US Pat. No. 3,186,838. After repeating the copying process 25,000 times, the copies as well as the electrostatic Image-bearing surface examined for quality and wear and tear. The copies are sharp Contrasting lines, with the veil being minimal. Examination of the imaging surface shows however, considerable wear and tear.

B e i s ρ i e 1

0.01 part of zinc stearate with a particle size distribution of about 5 to about 40 microns slowly incorporated into 1 part of colored preformed toner particles of the type described in Example 48. The developer mixture obtained is cooled and then placed in a Szegvari shredder Grind thoroughly over a period of approximately 10 minutes. The development process Example 15 is repeated using a new roller, with the above-mentioned milled mixture in place of the toner used in Example 48 at a relative humidity of 50% at 21 ° C and at a relative humidity of 80% at 27 ° C is used. Copies made using the milled Sample produced v / ground results in a solid surface coverage with a higher density than copies made using the comparative sample have been. Microphotographic examinations of the electrostatic image bearing Surface show that the wear is less than on the image-bearing surface according to Example 48. Much less torque is required to drive the roller when the stearate is added is used while a lower voltage is required to place the toner images on receiving trays transferred to.

Example 50

0.01 part of zinc stearate with a particle size distribution from about 5 to about 40 microns slowly in 10 parts by weight of colored preformed Toner particles of the type described in Example 47 are concentrated. The mixture obtained is then vortexed in a sealed container for a period of 15 minutes. Part 1 the swirled mixture is 99 parts of carrier beads with an average Particle size of about 250 microns mixed. The developer mixture obtained is used in a cascade development process according to the manner described in Example 47 at a relative humidity of 80% used at 27 ° C. The fused toner images obtained are denser than those according to the example 49 preserved images.

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Claims (1)

Patent claims: 1. Powdered electrophotographic developer with a toner composed of a pigment or dye, a thermoplastic vinyl resin and an additive, and from 0.02 to 20 percent by weight of a hydrophobic metal salt a fatty acid, characterized in that that he as an addition