DE2025503A1 - Xerographic developer materials - Google Patents

Description

Patent attorneys Dipl.-Ing. F. Weickmann,

Dipl.-Ing. H. Veickmann, Dipl.-Phys. Dr. Dipl.-Ing. F. A. Weickmann, Dipl.-Chem. B. Huber

S MUNICH 86, DEN

PO Box 860 820

MÖHLSTRASSE 22, CALL NUMBER 48 3921/22

H / Kn Z. 375

(XD / 2635)

Xerox Corporation, Rochester, N.Y., USA

Xerographic Developer Materials II

The invention relates to imaging systems, particularly improved ones xerographic developer materials, their manufacture and use.

The electrostatic formation and development of images on the surface of photoconductive materials is well known. In the underlying xerographic process as described by CP. Carlson in U.S. Patent 2,297,691, j an even electrostatic charge is applied to a photo j conductive insulating layer is applied, the layer is exposed with a light-dark image in order to reduce the charge in the exposed -Ge-

offer the layer to dissolve and the latent, elec- <■ A trostatic image is developed by placing a fine-grained image on the image;

dispersed electroscopic material, referred to in the art as j "toner", precipitates. The toner will normally held by the areas of the layer, which a charge retained, creating a toner image that corresponds to the electrostatic latent image. This powder picture can then be transferred to a support surface such as paper. The transferred image can then be printed on the carrier

000849 / V / 0 0

ORIGINAL INSPECTED

Surface can be permanently fixed, for example by heat. Instead of creating a latent image through uniform Loading of the photo-conductive layer and the subsequent exposure of the layer with a light-dark image can be done create the latent image directly by placing the layer in Image configuration is charging. The powder image can be fixed on the photoconductive layer when removing the Transfer step of the powder image is desired. It can- ~ other suitable fixing measures, such as solvent or coating treatment, take the place of the aforementioned heat setting.

Various methods are known for applying the electroscopic particles to the latent, electrostatic image to be developed. One development method as described in U.S. Patent 2,618,552 is known as "cascade" development. In this method, a developer material comprising relatively large carrier particles which are electrostatically coated with finely divided toner particles is conveyed to the surface bearing the electrostatic latent image and rolled or cascaded over this surface. The composition of the carrier particles is chosen so that the toner particles are triboelectrically charged to the desired polarity. Once the mixture cascades or rolls over the image-bearing ' T " surface, the toner particles are electrostatically deposited and trapped on the charged portion of the latent image; they are not deposited on the uncharged or background portions of the image. Most of the toner particles that happen to be deposited on the background are likely to be removed by the rolling carrier due to the greater electrostatic attraction between the toner and the carrier than between the toner and the discharged background. The carrier and excess toner are then recycled. This technique is extremely well suited for developing line copy images.

0098 49/1700

Another method of developing electrostatic images is a method in which a "magnetic brush" is used (magnetic brush process), as for example in the U.S. Patent 2,874,063. This process uses a developing material, toner and magnetic carrier particles contains, carried by a magnet. The magnetic one Field of the magnet causes an alignment of the magnetic carrier ■ in a brush-like arrangement. This "magnetic Burate "is related to the image bearing the electrostatic image The surface and the toner particles are attracted to the latent image by electrostatic attraction from the brush.

Another technique for developing electrostatic, latent ones Images is the "PulverwoJ-ke" process (powder cloud process) t as described, for example, in US Pat. No. 2,221 is described. In this method, a developer material, containing electrically charged toner particles in a gaseous fluid, guided along the surface containing the latent electrostatic Image carries. The toner particles are attracted to the latent image from the gas by electrostatic attraction. This method is particularly useful in continuous tone development.

Other development methods, such as "touchdown" development, those in de. ' U.S. Patent 3,166,432 can be used as appropriate.

Although some of the above development techniques nowadays technically applied, the most commonly used technical, xerographic development method is the as "Cascade" development known .technique. An office copier for general purposes using this development process is described in U.S. Patent 3,099,943. the Cascading is generally used in a device for sale carried out by passing a developer mixture over the top of an electrostatic latent image bearing Drum, which has a horizontal axis, cascaded. Of the

009849/1700

Developer comes from a tub or from a collection container ' conveyed to the upper part of the drum by means of a conveyor belt. The developer is cascaded downwards over part of the surface of the drum into the sump and then via the development system for the further development of electro-static, traced back latent images. Periodically, small amounts of toner are added to the development mix to compensate for the toner depleted by development. This procedure is then used for each generated by the machine Copy is repeated and is usually repeated many thousands of times over the useful life of the developer.

Although all of the above development techniques and others are currently almost exclusively for black and white reproduction are used, they are also capable of producing images in other colors and color combinations. As in others Color systems form the electrophotographic color systems generally to trichromatic color synthesis, either after additive or subtractive coloring. If therefore If electrophotographic systems work entirely in color, toner or developer particles must be of at least three different types Colors can be used to synthesize another desired color. Generally, at least three images are separated with each other Color (color separation images) produced and combined in accordance with each other to form a colored reproduction to form a full-color original. In color xerography, as described, for example, in US Pat. No. 2,962,374, at least three latent electrostatic images are produced by using a xerographic plate with different optical color separation images exposed. Each of these latent, electrostatic images is colored differently Toner developed, then the three toner images are combined to form the final image. This combination of the three golf toner images is generally made on a copy sheet, such as paper, on which the toner images are permanent be fixed. The most common technique for fixing this-

009849/1700

ser toner images on the paper sheet is accomplished by application of a resin ^v toner containing a colorant and by heat fusing the toner images on the copy sheet. The images can also be fixed using other techniques, such as treating them with solvent vapor.

In tricolor electrophotographic systems, the toners must be essentially transparent so that none of the three toner color pairs are present the differently colored toner images under it are darkened and yet each toner must have enough color saturation and brightness possess, so that the colorimetric requirements of the color synthesis of natural color images are met. Besides that it is very desirable that the color saturation of the three toners is so high and that they have the correct color tones, so that the three colors together create a deep black. It was found that this goal was achieved with electrophotographic Color reproduction systems as well as in many 'usual Color reproduction systems including full color printing, was practically impossible to achieve. To overcome this Problem, these systems generally use the overlay of four differently colored images. The additionally used The color is black and requires the creation of a fourth image for the black with additional equipment. and coverage problems. In general, problems also arise when inorganic pigments are used as coloring material, either in printing inks or in electrophotographic Toning because it is difficult to achieve the right color balance and saturation while at the same time the colors should remain transparent. Further problems arise with the use of inorganic pigments because the range of available colors is relatively narrow and because they also are usually opaque themselves, they generally make the materials to which they are added cloudy, even if they are added in relatively small amounts.

009849/1700 original 'inspected

U.S. Patent 3,385,293 describes a colored elec * - trophotographic toner made from essentially transparent resin particles, which contain organic color pigments. These toners proved to be proved to be more resistant to bleeding when the toner was melted than the previously known toners. In addition, these materials could are used in electrophotographic tricolor processes because they use the colors yellow, cyanine blue and magenta (purple red) and their paired mixtures produce the colors blue, red and green, while the three toners together produce black. Even though those described in the aforementioned U.S. Patent special toners have many advantages over the known toners that contain inorganic pigments or organic dyes nonetheless, there are certain disadvantages with certain of these specific toners, including the both of the aforementioned magenta toners, especially when used in an automatic electrophotographic machine. The two cited in U.S. Patent 3,385,293 referenced above Megenta dyes consist of a Monastral Red B, -RT79OD, a 2, g-dimethylquinacridone color pigment, which is believed to have been made according to Example 5 "of US Pat. No. 3,085,023 and Rhodamine Y, RT612D, a color pigment of a phosphotungstate-molybdic acid-xanthene varnish, Color Index No. 45 160, Color Index Pigment Red No. "81.

A disadvantage of using the magenta dyes of US Pat. No. 3,385,293 is that these dyes do not dissolve practically uniformly in transparent resin materials. Another disadvantage of using these magenta dyes is that the density of the resulting magenta, red and black images is low. Yet another disadvantage of using these dyes is that the triboelectric properties of the resulting toner material under conditions in which the toner mechanical abrasion, high temperatures and high humidity, all of these conditions are common in electrophotographic machines _{9 can} not be maintained «This in turn leads to a

9849/1700

• - 7 -

poor transfer from the drum surface to the copy sheet, as well as problems with keeping the drum clean Another disadvantage of using these magenta inks is that they produce images whose tint is undesirable for many purposes is. In particular, it does not appear to be a pure magenta color. This leads to even more coloring difficulties, for example, when a yellow image is superimposed on the impure magenta image to obtain a red image. The fact, The fact that the magenta colors are impure also adversely affects the purity and density of black images when the magenta, yellow and cyanine images are superimposed on each other will.

The aim of the present invention is therefore to eliminate the disadvantages mentioned above. The invention therefore provides a magenta color which is used in combination with a resin material as a toner is used. It is therefore also a new magenta toner and has created a new transparent magenta toner that is used to create or uses magenta images will match the generated magenta images with yellow images to overlay, or vice versa, to get red images, or used together with yellow and cyanine images is used to create black images by superimposing them.

The invention also relates to a new electrophotographic Developer and a new magenta toner, the magenta color being substantially uniform in a resin material dissolves and the new stomach toner when used in an electrophotographic Method essentially delivers dense (strong) images.

The present invention also provides a new magenta tone tone created that its triboelectric properties under mechanical abrasion, high temperature and high humidity conditions and which is easily and virtually completely transferred from a drum surface to a copy sheet leaves. .

0-09849 / 1700

The invention provides a relatively pure magenta toner having a desirable shade and hue. She creates a new one transparent magenta toner that is used to make magenta colored To produce images with desirable shade and tint, or that of overlaying the magenta images with yellow Images, or vice versa, to produce red images with a desirable shade and tint, or the one together with yellow and cyanine-colored pictures is used to create black images with a desirable shade and tint by overlaying them.

The present invention also describes electrophotographic processes using a novel magenta toner use a new electrophotographic developer containing a new magenta toner.

The above objects and objects of the present invention and others, generally speaking, are reached by a new magenta toner is created comprising a resin material and a magenta color, the color being 1-amino-4-hydroxyanthraquinone contains.

It was found that i-amino-4-hydroxyanthraehinone, in contrast to Every other known magenta color, possesses certain unique properties that, surprisingly, make it a very good one highly preferred dye for use in an electrophotographic Toner and more specifically for use in a transparent electrophotographic toner. For example, i-amino-4-hydroxyanthraquinone dissolves, in contrast to the well-known magenta colors, quickly and essentially evenly in suitable resin materials. They also supply toners made with 1-amino-4-hydroxyanthraquinone when used in an electrophotographic process, images have been substantially denser with a more desirable one Shading and tinting as toners that contain familiar magenta colors. Also, keep the magenta toners that came with this

009849/1700

highly preferred dye produced have been their tribeelectric Properties under mechanical abrasion, high temperature and high humidity conditions found in electrophotographic Machines are common. The same cannot be said of known magenta toners, which in many cases become conductive under high humidity conditions and poor toner transfer from the platen to the copy sheet as well as toner build-up and associated drum cleaning problems. This is not the case with Toners containing 1-amino-4-hydroxyanthraquinone. In the end deliver clear magenta toners containing 1-amino-4-hydroxyanthraquinone unlike any other known transparent magenta toner, dense magenta images that can be overlaid with yellow images, or vice versa, to to produce denser and purer red images than previously known, or together with yellow and cyanine-colored images can be used to produce denser and purer black images ^ than previously known ^ by overlaying. Besides that The red and black images produced in this way have a more desirable shade and tint than those previously known red and black images,

Any suitable resin material can be used for the toner of the present invention Invention can be used. Substantially transparent resin materials are preferred when the toner is in an electrophotographic Three-color system should be used. Although essentially any transparent resin material as a resin component of the toner, it is preferred to use resins having other desirable properties in the present Invention to use *. For example, it is desirable to use a resin that is a non-sticky solid at room temperature to facilitate handling and use facilitated in the most common electrophotographic processes will. It is also desirable that the resin be a thermoplastic resin having a melting point that is clear is above room temperature but below the temperature,

009840/1700 ■. '

the ordinary paper tends to char, so if Once the toner image has been formed or transferred onto the paper sheet, it is in place and body can be fused by applying heat to it. It should be noted, however, that this is not absolute is necessary because resins with a higher melting point can be used and on paper copies using others Techniques can be melted, for example "by using the paper copy that carries the powder image with fumes Solvent for the resin treated, for example, as described in US Pat. No. 2,776,907. Of course you can Toners are fused onto other surfaces because of their heat transfer and wetting properties Regulate the required amount of heat to melt the toner. In addition, it is desirable that the toner resins have good triboelectric properties Have properties and insulate enough to retain the charge, so that they can be used for development in various electrostatographic work techniques can be used, including the cascade development of latent, electrostatographic images as described in U.S. Patents 2,618,552 and 2,638,416 and others in the art known development techniques as well as for electrostatic powder image transfer described in US patents 2,576,047 and 2,626,865.

Although any suitable transparent resin for the toner of the present invention Invention, particularly good results are obtained when using vinyl resins and polymeric esterification products a dicarboxylic acid and a diol comprising a diphenol.

Any suitable vinyl resin can be used in the toners of the present invention be used. The vinyl resin can be a homopolymer or a copolymer of two or more vinyl monomers. To typical monomeric units, the sur production of Vinyl polymers can be used include? Styrene,

009843/1700

p-chlorostyrene, vinyl naphthalene, ethylenically unsaturated mono-. Olefins such as ethylene, propylene, butylene, isobutylene and the like; Vinyl esters, such as vinyl chloride, vinyl bromide, vinyl fluoride, Vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, and the like; Esters of aliphatic Oc-methylene-monocarboxylic acids, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, Dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, Methyl-CX-chloroacrylate, methyl methacrylate, ethyl methacrylate, Butyl methacrylate and the like; Acrylonitrile, methacrylonitrile, Acrylamide, vinyl ethers, such as vinyl methyl ether, vinyl isobutyl ether, Vinyl ethyl ether and the like; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and like; Vinylidene halides, such as vinylidene chloride, vinylidene chlorofluoride and the same; and N-Viny! compounds, such as-N-Vinylpyrrole, IT-vinyl carbazole, ΐΓ-vinyl indole, F-vinyl pyrrolidine and the same; and mixtures thereof. In general, suitable vinyl resins used in the toner have an intermediate one Molecular weight between about 3000 to about 500,000,

Toner resins containing a relatively high percentage of styrene resin are preferred. The presence of a styrene resin is preferred, since a given amount of additive material will achieve greater image sharpness. In addition, you get powerful ■ more images if at least about 25% by weight based on the = Total weight of the resin in the toner, a styrene resin in the toner available. The styrene resin can be a homopolymer of styrene or styrene homologues or a copolymer j

of styrene with other monomeric groups, in which a single \ methyl group is bonded by a double bond to a carbon atom ■ j. Typical monomeric materials produced by! Addition polymerizations that can be copolymerized with styrene include: p-chlorostyrene, vinyl naphthalene; Ethylenically unsaturated mono-olefins such as ethylene, propylene, butylene, isobutylene and the like; Vinyl esters such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, and the like; Esters of aliphatic CX methylene

98 ^ 9/1700

monocarboxylic acids, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, Isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloro- ' Ethyl acrylate, phenyl acrylate, methyl- (X-chloroacrylate, Methy1-methacrylate, Ethyl methacrylate, butyl methacrylate and the like; Acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers, such as vinyl methyl ether, Vinyl isobutyl ether, vinyl ethyl ether and the like; Vinyl ketones, such as vinyl methyl ketone, vinyl hexyl ketone, Methyl isopropenyl ketone and the like; Vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride and the like; and N-vinyl compounds, such as N-vinyl-pyrrole, N-vinyl-carbazole, N-vinyl indole, N-vinyl pyrrolidine and the like and mixtures of that. The styrene resins can also be obtained by polymerizing mixtures of two or more of these unsaturated monomers Materials are made with a styrene monomer. The term "additive polymerization" is intended to include known polymerization techniques such as free radical, anionic and cationic polymerization processes. ;

The vinyl resins including styrene type resins can also, if desired, with one or more other urines be mixed. When the vinyl resin is mixed with another resin, the resin added is preferably another one Vinyl resin, as the resulting mixture has particularly good triboelectric stability and uniform resistance to physical damage is marked. The vinyl resins to be mixed with the styrene type resin or the other vinyl resin can be used by addition polymerization of any suitable vinyl monomer such as those described above Vinyl monomers. Other thermoplastic Resins can also be blended with the vinyl resins of the present invention. Too typical thermoplastic Non-vinyl type resins include; Rosin modified Phenol-formaldehyde resins, oil-modified epoxy resins, polyurethane resins, cellulosic resins, polyether resins and mixtures of that. If the resin component of the toner contains styrene, which is mixed with another unsaturated monomer

0Θ9849 / 1700

• _ 13 -

is merized or a mixture of polystyrene and another Resin, so is a styrene component of at least about 25 wt .- $, based on the total weight of the resin present in the toner, preferred because stronger images are obtained.

Any suitable polymeric esterification product can also be used Dicarboxylic acid and a diol comprising a diphenol as preferred resin material for the toner of the present invention can be 'used'. The diphenol can have the general formula own: '

· ■ '■ ··' ■ χ χ »

H- (OR ¹ L 0- / 7. V \ -Ry / \ 0. :( 0RL ^ \ / \ / ⁿ 2

wherein R 'substituted and unsubstituted alkylene radicals with 2 to 12 carbon atoms, alkylidene radicals with 1 to 12 carbon atoms and cycloalkylidene radicals having 3 to 12 carbon atoms represents;

R 'and R "- independently substituted and unsubstituted Alkylene radicals with 2 to 12 carbon atoms, alkylene-arylene radicals with 8 to 12 carbon atoms and arylene radicals;

X and 7, ^f, independently of one another, represent hydrogen or an alkyl radical having 1 to 4 carbon atoms; and

n.j and np each mean at least 1 and the mean sum of n-j and ^ is less than 21.

Diphenols, in which R denotes an alkylidene radical with 2 to 4 carbon atoms and R ¹ and R "denote an alkylene radical with 3 to 4 carbon atoms, are preferred because they have greater blocking resistance and greater xerographic sharpness

Ö09849 / 1700

-H-

Characters and a more complete transfer of the toner images is achieved. Optimal results are obtained with moles in which R ^{f is} an isopropylidene radical and R 'and R "represent, independently of one another, propylene or butylene radicals, since the resins formed from these diols have greater agglomerate stability and extremely quickly drop Dicarboxylic acids with 5 to 5 carbon atoms are preferred, since the resulting toner resins are more resistant to film formation on reusable imaging surfaces and withstand the formation of fine grain fractions under machine operating conditions. Optimal results are obtained with OC -unsaturated dicarboxylic acids "Also fumaric acid, maleic acid or maleic anhydride, since maximum resistance to physical damage to the toner and rapid meltability are achieved. It is assumed that the presence of the unsaturated bonds in the OC-unsaturated dicarboxylic acids is responsible for the resin moles." cooling gives greater strength without adversely affecting the melting and crushing behavior. Any suitable diphenol represented by the above formula can be used. Typical diphenols having the above general structure include: 2,2-bis (4-β-hydroxy-ethoxyphenyl) propane; 2,2-bis (4-Hydroxy-isopropoxyphenyl) -propane5 2 ₉ 2-bis (4 ~ ß-Hydroxy-ethoxyphenyli-p ^ ntanj 2,2-bis (4-ß-Hydroxy-ethoxyphenyl) butane; 2.2 bis (4-hydroxypropoxy-phenyl) -propan5 2,2-bis (4-hydroxypropoxy-pheriyl) - ^ propane ι 1 ₉ 1-bis (4-hydroxy-ethoxy-phenyl) -butane | 1,1-bis' (4-Hydroxy-isopropoxy ~ ° phenyl) »heptane5 2,2-bis (3 ~ methyl-4-ß-hydroxy-ethoxy-phenyl) -propane5 1,1-bis (4 = ß ~ hydroxy-ethoxy ~ phenyl) -cyclohexan5 2 ₉ 2'-bis (4-ß-hydroxy-ethoxy = phenyl) -norbornane; 2,2 ~ bis (4-ß-hydroxy-styryloxyphenyl) -propane _s the polyoxyethylene ether of isopropylidenediphenol, in which both pheno metallic = hydroxyl groups are oxyäthyliert and the average number of oxyethylene groups = Liehe per mole of _2? 6 ^ is the Polyoxypropylenäther-2-butylidenediphenol ₈ in which both hydroxyl groups phenolisehe, oxyalkylier-b and the "durohsohnittliohe

149/1700 '

Number of oxypropylene groups per mole is 2.5, and the like. Diphenols in which R is an alkylidene radical are preferred 2 to 4 carbon atoms and R 'and R "independently of one another denote an alkylene radical having 3 to 4 carbon atoms, since greater blocking resistance, greater sharpness of xerographic Characters and a more complete conversion of the Toner images is achieved. Optimal results are obtained with moles in which R is isopropylidene and R 'and R "are, independently of one another, prop2 / len or butylene, since those from these diols Resins formed have higher agglomeration resistance and under melting conditions extremely quickly in the paper Penetrate recording sheets.

Any suitable dicarboxylic acid can be mixed with those described above Diols are reacted to form the toner resins of the present invention. These acids can be substituted, unsubstituted, be saturated or unsaturated. These acids possess the general formula: ■

HOOC R '·· COOH
n ₅

where R ^'11 denotes a substituted or unsubstituted alkylene radical having 1 to 12 carbon atoms, arylene radicals or alkylene- · arylene radicals having 10 to 12 carbon atoms and n ^ is less than 2. In the present description and in the claims, the term dicarboxylic acid is also intended to include anhydrides of such acids, if such anhydrides exist. Typical dicarboxylic acids include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, mesaconic acid, homophthalic acid, isophthalic acid, terephthalic acid, o-phenyl anhydric acid, maleic anhydric acid, ß-propionic acid, it Fumaric acid, phthalic anhydride, traumatic acid, citraconic acid and the like. Dicarboxylic acids with 3 to 5 carbon atoms are preferred, since the resulting toner resins have greater resistance to film formation on reusable images.

0 0 9 8 A 9/1 7 0 0

~ 16 -

have application surfaces and the formation of fine-grain fractions " withstand the machine's operating conditions. ' Optimal results are obtained with CX -unsaturated dicarboxylic acids, including fumaric acid, maleic acid or maleic anhydride, as maximum resistance to physical Damage to the toner and rapid melting is achieved. Although it is not entirely clear, it is believed that the presence of the unsaturation in the Oi unsaturation Dicarboxylic acids give the resin molecules greater strength without affecting the melting and crushing behavior is adversely affected.

The polymeric esterification product used in the toners of the present invention can be copolymerized if desired or blended with one or more other thermoplastic resins. When it comes to another thermoplastic Resin is mixed, the added resin is preferably an aromatic resin, aliphatic resin or a mixture thereof. because the resulting mixture has a particularly uniform consistency and high predictability of the physical properties from batch to batch is characterized. Lots of thermoplastic Resins can be blended with the above-mentioned ester resins. Typical thermoplastic resins include: Turpentine-modified phenol-formaldehyde resins, oil-modified Epoxy resins, polyurethane resins, cellulosic resins, vinyl type resins, and mixtures thereof. When the resin component of the toner a contains added resin, the added component should be in an amount of less than about 50 wt .- ^, based on the total weight of the resin present in the toner. Preferred is a relatively high percentage of the condensation product of polymeric diol and dicarboxylic acid in the resin component of the toner, since a greater reduction in melting temperatures is achieved with a given amount of additive material will. In addition, sharper and stronger images are obtained if a high percentage of the condensation product consists of polymeric Diol and dicarboxylic acid are present in the toner. Any suitable mixing technique such as hot melt, solvent and emulsion

Q Θ 9 8 4 9/1 7 0 0

Sion techniques can be used to incorporate the added resin into the toner mixture. The resulting resin mixture or copolymer is practically homogeneous and highly compatible with pigments and dyes. Where appropriate, the dye can be added before, simultaneously with, or after the mixing or polymerization stage.

Although any suitable vinyl resin or polyester-alkyd resin is preferred for use in the toner of the present invention, optimal electrophotographic results with styrene-butyl methacrylate copolymers, styrene-vinyltqluol copolymers, styrene-acrylate copolymers, polystyrene resins, predominantly resins based on styrene or polystyrene, as in the ent uSr Pat No. 25 136, for polystyrene, and mixtures, such as are described in U.S. Patent '2,788,288, achieved.

Although any suitable additive to the resin portion of the magenta toner material can be added to the present invention, it is very desirable to use a polyvinyl butyral resin such as e.g. Vinylite XYHL from the Bakelite Company, because of its solidifying properties Effect on the toner matrix and because of its improving influence on the electroscopic properties of the toner, to add. Particularly good results are obtained when this .Polyvinyl butyral resin additive in an amount of about 1 part by weight of polyvinyl butyral resin in about 10 parts by weight of the resin part of the toner is contained.

6098-49 / 1700

The toner compositions of the present invention can · can be made by any of the well known toner blending and comminuting techniques. For example, ■■ the ingredients are carefully mixed by mixing and grinding the components. and then the resulting mixture be micropulverized. Another well known technique for making toner particles is spray drying a Suspension, a hot melt or a solution of the toner composition. . -

If the toner blends of the present invention are to be used in a cascade development process, the toner should have an average particle diameter of. less than about 30µ and preferably between about 5 and about 17 / x for optimal results. For use in powder cloud development, particle diameters of slightly less than 1 µm are preferred. .

9849/1700

Suitable coated and uncoated carrier materials for cascade and magnetic brush development are well known in the art. The carrier particles can be electrically conductive, insulating, magnetic or non-magnetic, provided that the carrier particles acquire a charge of opposite polarity to that of the toner particles when they are brought into close contact with the toner particles, so that the toner particles adhere to the carrier particles and surround them. If a positive reproduction of an electrostatic image is desired, the carrier particles are chosen so that the toner particles assume a charge of opposite polarity to that M of the electrostatic latent image. On the other hand, when reverse reproduction of the electrostatic image is desired, the carriers are chosen so that the toner particles acquire a charge with the same polarity as that of the electrostatic image. The materials for the carrier particles are therefore selected according to their triboelectric properties with regard to the electroscopic toner so that when they are mixed or if they are brought into accidental contact, one component of the developer is positively charged when the other component is below of the first component in the tri-iboelectric series and is negatively charged when the other component is above the first component m in the triboelectric series. By correct selection of the materials according to their triboelectric effects, the polarities of their charge during mixing are such that the electroscopic toner particles adhere to and coat the surface of the carrier particles and also adhere to the portion of the electrostatic image bearing surface which has a greater attraction for the toner than the carrier particles. Typical carriers include sodium chloride, ammonium chloride, aluminum-potassium chloride, Rochelle salt, Sodium nitrate, aluminum nitrate, potassium chlorate, granular zirconium, granular silicon, methyl methacrylate, glass, silicon dioxide and the like. The carriers can be used with or without a coating. Many of the above, and typical carriers are described in U.S. Patents

8 49/1700

- 2ο -

Writings 2 618 551; "2 638 416 and 2 618 552 described. A; maximum diameter of the coated carrier particles between about 50 / u to about 1000 μ is preferred because the carrier particles then have sufficient density and inertia so that an adhesion to the electrostatic Images during the cascade development process is avoided. Adhesion of carrier grains to the surface of the xerographic drum is undesirable because of the formation of deep scratches on the surface during the image transfer and drum cleaning steps, especially where cleaning is carried out with a cloth cleaner such as the fabric described in U.S. Patent 3,186,838. When carrier grains adhere to the xerographic imaging surfaces, printing erasure also occurs. Generally speaking, satisfactory results are obtained using about 1 part of toner with about 10 to about 200 parts by weight of carrier will.

The toner compositions of the present invention can be used to create latent electrostatic images on a suitable electrostatic latent image bearing surface, including conventional photoconductive surfaces. Well known photoconductive materials include vitreous selenium, organic or inorganic photoconductors embedded in a non-photoconductive matrix ■ organic or inorganic photoconductors embedded in a photoconductive matrix and the like. Representative Patents disclosing photoconductive materials include U.S. Patents 2,803,542; 2 970 906} 3,121,006; 3 121 007 and 3 151 982.

The following examples describe and compare methods of making toner materials of the present invention "and their use to develop electrostatic latent images. Unless otherwise specified, the parts and percentages represent parts and percentages by weight.

009849 / 170.0

example 1

A magenta toner mixture is prepared which contains about 7.5 parts by weight of a copolymer of about 65 parts by weight of styrene and about 35 parts by weight of butyl methacrylate, an additive that comprises about 0.7 parts by weight of polyvinyl butyral, and about 1 part by weight of a dye containing 1-amino- Includes 4-hydroxyanthraquinone. After melting and premixing, the composition is placed in a rubber mill and carefully ground until a uniformly dispersed composition of the dye is retained in the thermoplastic resin body. The resulting mixed composition is cooled and then finely divided in a nozzle pulverizer to obtain magenta toner particles having an average particle size of about 5 to about 20 / rev. To test the utility and effectiveness of this powdered magenta toner composition, it is deposited on an electrostatic latent image on an image bearing surface by mixing the toner into a two-component, cascade-type developer, as described in US Pat. No. 2,618,551 , and the mixture cascades across the electrostatic latent image bearing surface. The image is developed by deposition of the powdered toner and the powder image is electrostatically transferred to a paper transfer fabric and then fused in place in a heated oven. The results show that this toner material has excellent electrical properties. Excellent magenta images of high resolution, practically free of background and of pure color, with excellent shading and tint, are obtained. It is also found that once the toner images have been formed on the surface of the photoconductive insulating layer by the electrophotographic technique, that the toner particle image can easily be transferred from this surface by electrostatic transfer to a hard copy, as in UiJ Pfifcentsohrift 2 576 047 described, oov / Le after others. Überbelungfrteolmiken can be transferred, di.e Lm Faohgeibie t

BADORlG ₁ NA ₁ .

are well known. The magenta toner produced is in

Combination tested with pictures made with yellow and cyanine stains Toners described in U.S. Patent 3,345,293, i.e., images having magenta planes Toners made come with yellow images, the cyanine image, and yellow and cyanine images Images superimposed together, and vice versa. In no case bleeding of the colors is noticeable. In addition, they are Red and black images produced with the gold combinations are denser and purer and have a more desirable one Shading and tint than the previously known red and black images.

Examples 2 to 8

Example 1 is repeated again and again, instead of the in Example 1 used 7.5 parts by weight of styrene-butylmeth-. acrylate copolymer, 0.7 parts by weight polyvinyl butyral additive and 1 part by weight of 1-amino-4-hydroxyanthraquinone the following toner formulations are used:

About 6.5 parts by weight of polystyrene, about 0.6 parts by weight of polyvinyl butyral and about 1.5 parts by weight of i-amino-4-hydroxyanthraquinone in Example 2; ■ ■

about 7-5 'parts by weight of a copolymer made from about 70 Parts by weight of styrene and about 30 parts by weight of hexyl methacrylate, K.rLn polyvinyl butyral additive and about 1 part by weight 1-amino-4 "hydroxyanthraquinone in Example 3;

e tv / a B parts by weight of a copolymer of about 35 parts by weight of Leri vinyl acetate and about 65 parts by weight of acrylonitrile, no polyvinyl butyral additive and about 1 part by weight of 1-amino-4-hydroxyanobhraquinone in Example 4;

about 515 weights of a copolymer of about 80 weights share styrene and about 20 Gev / iohbs bark Äthylacrylab,

0Ö98A9 / I700

BATH ORIGINAL

with about 0.5 parts by weight of polyvinyl butyral additive and about " 1 part by weight of 1-amino-4-hydroxyanthraquinone in Example 5;

about 95 parts by weight of a polymeric condensation product of 2.2 ^! bis (4-hydroxyisopropoxyphenyl) propane and fumaric acid with about 0.85 parts by weight of polyvinyl butyral additive and about 5 parts by weight of 1-amino-4-hydroxyanthraquinone in Example 6;

about 95 parts by weight of a polymeric condensation product of 2,2-bis (3-Methy1-4-ß-hydroxyethoxyphenyl) propane and maleic anhydride, no polyvinyl butyral additive, and about 5 parts by weight of 1-amino-4-hydroxyanthraquinone in Example 7; and

about 97 parts by weight of a polymeric condensation product from 1,1-bis (4-ß-hydroxy-ethoxyphenyl) -cyclohexane and succinic acid, no polyvinyl butyral additive and about 3 parts by weight of 1-amino-4-hydroxyanthraquinone in Example 8;

The toners of Examples 2 to 8 are tested as in Example 1. The results from each of the above examples show that the toner material has excellent electrical properties owns. In any case, excellent magenta-colored images of high resolution, practically free of background, are obtained and in pure color with excellent shade and tint. In addition, it is established in each case that, when the toner images have formed on the surface of the photoconductor layer, the toner particle image can easily be transferred from this layer onto a sheet of paper. if the produced toners of Examples 2 to 8 in combination with cyanine and / or yellow images, as in Example 1 are described, tested, the red and black images produced are found to be denser, cleaner, and more desirable Shades and tints than the previously known red and black images, after all, is in no bleeding of the colors was found in any of the cases.

009849/1700

-24.- Examples 9 to 11

Examples 1, 2 and 3 are repeated, with the exception that in any case the magnetic brush development as described in US Pat. No. 2,874,063 instead of the Cascade development is applied. In particular, the • toner materials of Examples 1, 2 and 3 are each with magnetic Carrier particles mixed and held by a magnet. The magnetic field of the magnet causes the alignment of the magnetic carrier to a brush-like configuration. The "magnetic brush" is related to that of the electrostatic one In each case, the image-bearing surface and the toner particles are grounded by electrostatic attraction to the latent Image attracted. As in Examples 1, 2 and 3, the resulting images are of excellent quality and color.

While specific pigment-resin combinations are given above as toner formulations, it should be understood that any resin, including any substantially transparent resin having the proper electroscopic properties for use in electroscopic processes, can be used in the toner formulations. Although it is preferable that these resins be thermoplastic or uncured thermosetting resins so that they can be fused on the copy by the application of heat , "this property is not absolutely necessary for the resins since they are made using others Techniques, including the solvent vapor technique described above, can be fused The pigment to resin ratio for each of the toners described above is not absolutely critical and can vary.

The terms developer and development material as they are hior should include electroscopic toner materials or combinations of toner material and carrier material.

0098A9 / 1700

While specific materials and conditions are given in the preceding examples, they are intended only to illustrate the present invention. Various other suitable toner resins, additives, dyes, and other components such as those enumerated above can be substituted for those in the examples with similar results. Other materials, such as plasticizers, can also be added to the toner in order to sensitize it, to obtain a synergistic effect or otherwise to improve the melting properties
improve or achieve other desirable properties of the system, such as a modification of the triboelectric properties.

Other modifications of the present invention are envisaged.
Those skilled in the art are suggested by the present description, but they are within the scope of the present invention.

0 0 9 8 4 9/1700 originally inspected

Claims (32)

Claims (iy Electrophotographic developer material, the toner particles contains, characterized by a resin and a dye ,, v / obei the dye i-amino-4-hydroxyanthraquinone includes. 2. Developer according to claim 1, characterized in that the resin is substantially transparent. 3. Developer according to claim 1 or 2, characterized in that that the resin includes polyvinyl butyral. " 4. Developer according to one of claims 1 to 3, characterized in that that contain about 1 part by weight of polyvinyl butyral in each about 10 parts by weight of the resin part of the toner is. 5. Developer according to one of claims 1 to 4, characterized in that that the resin comprises a vinyl resin. 6. Developer according to one of the claims. 1 to 4, characterized in that that the resin is a polymeric esterification product of a dicarboxylic acid and a mole that comprises a diphenol, includes. 7. Developer according to one of claims 1 to 6, characterized in that the resin is a non-sticky pest substance is at room temperature. 8. The developer according to any one of claims 1 to 7 _t ~ characterized in that the resin is a thermoplastic material. 0098A9 / 1700 ■ - 2.7 - 9. Developer according to one of claims 1 "to 8, characterized in that that the resin has a melting point which is substantially above room temperature. O. Developer according to claim 2, characterized in that it . contains a relatively high percentage of styrene resin. 11. A developer according to claim 2, characterized in that less than about 25% by weight of the total weight of the resin Represent styrene resin. 12. Developer according to one of claims 1 to 11, characterized in that that the resin comprises a mixture of at least two resins in addition to polyvinyl butyral. • - 13. Developer according to claim 2, characterized in that the resin includes a mixture of at least two vinyl resins ^. . · 14. The developer according to claim 5, characterized in that the vinyl resin is a styrene-butyl methacrylate copolymer, styrene-vinyltoluene copolymer, styrene-acrylate Misehpolymerisat, polystyrene resin is mainly based on polystyrene, polystyrene blend or a mixture thereof, 15. Developer according to claim 5, characterized in that the Vinyl resin contains a styrene-butyl methacrylate Misohpolymerisa.t '. 16. Developer according to claim 6, characterized in that the Dicarboxylic acid is chosen among the general acids Formula ':. H . OOCR "· COOH ⁿ 3 ■. ■■ "■ and their anhydrides, in which R ¹ '· the alkylene radical with 1 to • 12 carbon atoms, alkenylene radical .mit 1 to 12 carbon atoms 0 0 9849/170 0 atoms, arylene radical and alkylene-arylene radical with 10 to 12 * Is carbon atoms and n ·, is less than 2. 17. Developer according to claim 6, characterized in that the diphenol has the following general formula: ^{H (0H1)} »i ° - <\ /> - ^E - <\ ι / λ ^{0 (E} " ° wherein R is the alkylene radical having 2 to 12 carbon atoms, Denotes alkylidene radical with 1 to 12 carbon atoms and cycloalkylidene radical with 3 to 12 carbon atoms; R ¹ and R ″, independently of one another, denote alkylene radicals with 2 to 12 carbon atoms and alkylene-arylene radical with 8 to 12 carbon atoms; X and X ^f, independently of one another, denote hydrogen and alkyl radicals having 1 to 4 carbon atoms; and n. | and rip each mean at least 1, and the average sum of n. | and np is less than 21. 18. Developer according to claim 6, characterized in that the dicarboxylic acid has 3 to 5 carbon atoms. 19 «Developer according to claim 6, characterized. That the dicarboxylic acid is an iX-unsaturated dicarboxylic acid. 20. Developer according to claim 6, characterized in that the polymeric esterification product is a condensation product from 2,2-bis (4-hydroxy-isopropoxyphenyl) -propane and fumaric acid is, 009849/1700 - 23. - 21. Developer according to claim 6, characterized in that · ■ the polymeric esterification product is a condensation product of 2,2-bis- (4-hydroxy-isopropoxyphenyl) propane and Is 2,2-dimethylfumaric acid. 22. Developer according to claim 6, characterized in that the polymeric esterification product is a condensation product of 2,2-bis- (4-hydroxy-butoxyphenyl) propane and fumaric acid is. 23. Developer according to claim 6, characterized in that the polymeric esterification product is a condensation product from 2,2-bis- (4-hydroxy-butoxyphenyl) -propane and Is 2,2-dimethylfumaric acid. 24. Developer according to claim 6, characterized in that the polymeric esterification product is a condensation product of 2,2-bis (4-hydroxy-ethoxyphenyl) propane and fumaric acid is. . * 25. Developer according to one of claims 1 to 24 »characterized in that that it contains carrier beads for the toner particles and the carrier beads are much larger than that Are toner particles. 26. Developer according to claim 25, characterized in that the carrier beads are essentially magnetic, 27. Developer according to claim 25 or 26, characterized in that that the carrier beads have an average particle size from about 50 to about 1000 / u. 28. The developer according to any one of claims 25 to 27, characterized in that _t he etv / a a weight! " part contains toner particles and about 10 to about 200 parts by weight carrier pearls. 00 9 8 4 9/1700 29. Developer according to one of claims 25 "to 28, characterized in that the toner particles have an average size of up to about 30 μ . 30. Developer according to claim 29, characterized in that the toner particles have an average size between approximately 5 and 17 μ . 3i \ electrophotographic imaging process, characterized in that a toner image is produced by an electrostatic latent image is formed on a surface and the surface is contacted with an electrophotographic developer material as claimed in any one of claims 1 to 30, whereby at least a part of the de-curler is attracted to and retained on the surface in accordance with the electrostatic, latent image. 32. The imaging method according to claim 31, characterized in that the toner image is also transferred to a receiving surface and the toner image is transferred with it Receiving surface is merged. 0-9 849/1700