Toner composition, process for preparation the same and developer

Pending patent applications

The pending US Patent Application Serial no. (No registration number yet allocated; Applicant's D / 97363), which as the same day This patent application was filed and the disclosure of part this application, describes a toner comprising a resin, a colorant and a coated silica, wherein the coating under Using an alkylsilane was prepared; and the pending U.S. Patent Application Serial no. (Still not allocated registration number; Applicant's D / 97370), the same day as this patent application was filed and the disclosure of part of this application is, discloses a toner with a coated silica with z. B. specific BET properties.

The Ingredients and procedures of pending patent applications, as for example. The coating with an alkylsilane, in certain embodiments of the present invention be used or applied.

background the invention

The This invention relates to toner and developer compositions, and more specifically, positively or negatively charged toner compositions or toner with surface additives on the basis of coated silica. The coated Silicas available from Carbosil and have preferred a primary Particle size range from 25 nm to 55 nm and an aggregate size in the range of 225 nm to drawing 400 nm. The toner according to the present invention through various advantages; they have, for. example excellent stable triboelectric charging characteristics, are substantially insensitive to moisture, especially at humidities 20 to 80 wt .-%, characterized by excellent flow properties from exhibit acceptable triboelectric charging values, z. B. in the range from 15 to 55 microcoulombs per gram, determined z. B. using a Fara daykäfigs, and allow the formation of images with excellent resolution and excellent color intensity. The previously described Toner compositions can coloring Constituents, such as. For example, dyes or pigments, comprising z. B. Carbon black, magnetites or mixtures thereof, or cyan, magenta, yellow, blue, green, red or brown components, or mixtures thereof, so that black and / or colored Images are obtained, and in certain embodiments, the toner for the Two-component development or for component development, wherein no carrier or no carrier will be used used.

The Toner and developer compositions according to the present invention can in the electrophotographic, and particularly in xerographic Imaging and printing production, including color and digital processes under Use of multi-system equipment and machines are used.

State of technology

toner compositions with certain surface additives, including certain silicas, are known. Examples of these Additives include colloidal silicas, such as, for. Example, certain AEROSIL products, such. As R972^®Available from Degussa, metal salts and metal salts of fatty acids, including zinc stearate, Aluminum oxides, cerium oxides, and mixtures thereof, wherein these additives usually in an amount in the range of about 1 wt .-% to about 5 wt .-%, and preferably in an amount in the range of about 1 wt .-% to about 3 are wt .-% used. Some of the aforementioned additives in US Patent Nos. 3590000 and no. 3900588 describes the is disclosure part of this application. There are also Toner known that a mixture of hexamethyldisilazane (HMDZ) and APTES, an aminopropyltriethoxysilane, included.

Toner compositions The charge enhancing contain additives which impart to the toner resin a positive charge, are also known. In US Pat. No. 3893935 is such. As the Use of quaternary Ammonium salts as charge control agents for electrostatic toner compositions described. In the US Pat. No. 4221856 electrophotographic described toners containing a resin of the formula given, the quaternary is ammonium compounds compatible, at least in the formula two of R hydrocarbon groups having 8 to about 22 carbon atoms are and any other group R is hydrogen or a hydrocarbon group having 1 to about 8 Kohlenstoffa<?page 3?>Tomen, and A is an anion, such. B. a sulfate ion, a sulfonate ion, a nitrate ion, a borate ion, a chlorate ion or a halide ion, such as. for example, an iodide ion, a Chloride ion or a bromide ion, see the summary and Disclosure, especially the disclosure in column 3; and a similar Teaching is given in US Pat. No. 4312933, which consists of a divisional application . Of US Patent No. 4291111 is emerged; and a similar Teaching is given in US Pat. No. 4291112, wherein A is an anion is comprising z. B. a sulfate ion, a sulfonate ion, a nitrate ion, a borate ion, a chlorate ion or a halide ion. In US Patent No. 2986521 reversal developer compositions are described, comprising toner resin particles, the fine colloidal silica coated. According to the disclosure in this patent is the development of electrostatic latent images on negatively charged surfaces conducted by a developer composition having a positive triboelectric charge concerning of the colloidal silica is used.

in the US Pat. No. 4338390, the disclosure of which part of this application is, developer compositions are disclosed, the organic Sulfates and sulfonates containing as charge enhancing additives, wherein the additives of the toner composition a positive charge to lend. In US Patent no. 4298672, the disclosure component this application is, positively charged toner compositions described with resin particles and pigment, the alkyl pyridinium as charge enhancing Additives. examples for other publications, the positively charged toner compositions with charge control additives describe, include US Patent Nos. 3944493, no. 4007293, Nr. 4079014, no. 4394430 and no. 4560635, which provide a toner with distearyl is used as a charge additive, describe.

toner compositions with additives that enhance a negative charge, are also known, see, for. example, US Patent Nos. 4411974 and no. 4206064, the disclosure of is part of this application. The '974er patent discloses negatively charged Toner compositions comprising resin particles, pigment and ortho Halogenphenylcarbonsäuren that as charge enhancing Additives. The '064er Patent describes toner compositions with chromium, cobalt and Nickel complexes of salicylic acid, as additives for amplifying the negative charge can be used.

in the US Pat. No. 4404271 describes a toner which z. B. a containing metal complex, represented by the specified in column 2 of formula wherein ME chromium, may be cobalt or iron. Examples of other publications, describe the various metal containing azo dye, wherein the metal can be chromium or cobalt include US patents No. 2891939, no. 2871233, no. 2891938, no. 2933489, Nr. 4053462 and no. 4,314,937th In US Pat. No. 4,433,040, the disclosure component this application is, to toner compositions with chromium and cobalt complexes described azo dyes that of as additives for amplifying negative charge are used. These and other charge enhancing Additives such. As the additives described in US Patents Nos. 5304449, No. 4904762 and no. 5223368 describes the disclosure is part of this application, may, in certain embodiments of the present invention may be used.

The Publications EP-A-592 018, EP-A-716 350 and EP-A-609 770 also describe silica for one Toners with a silane compound and / or a silicone polymer were coated.

Summary the invention

embodiments of the present invention include:

The Invention relates to toner and developer compositions with a Mixture of certain surface additives, wherein the toner characterized by a number of advantages.

The Invention also relates to negatively charged toner compositions, the in the development of electrostatic latent images, including color images, can be used.

The Invention also relates to negatively charged toner compositions, the in the development of electrostatic latent images, including full process color images, can be used.

The Invention also relates to surface additives for toner, which enable rapid mixing of the toner, measured with a Charge spectrograph.

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The Invention also relates to surface additives based of coated silica, the unimodal toner charge distribution enable, determined by a charge spectrograph.

The Invention also relates to certain surface additives, which have a unimodal Charge distribution during the mixing of additional admixed with toner already existing toner enable determined by a charge spectrograph.

The Invention also relates to toner and developer compositions with a mixture of certain surface additives that by itself excellent stable triboelectric charging properties, for. example by triboelectric charge values ​​in the range of 15 to 60 microcoulombs per gram, and preferably in the range of 25 to 40 microcoulombs per Grams, distinguished; Toner and developer compositions with additives based on coated silicon oxides, the moisture insensitive are, in particular, at relative humidities of 20 to 80 wt .-% at temperatures ranging from 15.5 to 26.6 ° C (60 ° to 80 ° F), determined in a test device to determine the sensitivity to humidity; Toner and developer compositions with a mixture of certain surface additives, which negatively charged Toner compositions with desired Mixing properties in the range of 1 second to 60 seconds, preferably enable of less than 30 seconds, determined by a charge spectrograph; toner compositions a surface with a mixture of certain additives which z. B. enable fixing at lower temperature, which allows the production enables high-quality black images or color images; as well as the preparation of toners with a mixture of surface additives based on coated silicon oxides which develop the of images in electrophotographic imaging apparatuses enable, which images have substantially no background fouling have substantially resistant opposite to Grime and consequently have excellent resolution, and wherein the toner compositions in high-speed devices for the electrophotographic reproduction may be used in where more than 60 copies per minute and preferably 60 to 100 copies can be produced per minute.

The Invention also relates to positively charged toner compositions, the in the development of electrostatic latent images, including color images, can be used.

The Invention also relates to positively charged toner compositions, the opposite Moisture, z. B. over relative humidities of 20 to 80 wt .-% at temperatures in the Range from 15.5 to 26.6 ° C (60 to 80 ° F), determined in a test device for determining the sensitivity opposite to Moisture insensitive, which is characterized by desired mixing characteristics in the range of 5 seconds to 60 seconds, preferably of less than 15 seconds and particularly preferably in the range of 1 second to 14 seconds distinguished, determined by a charge spectrograph, and which are characterized by excellent stable triboelectric charging characteristics, z. B. by triboelectric charge values ​​in the range of 20 to 50 microcoulombs per gram, distinguished.

The Invention also relates to the preparation of toners which the development of images in electrophotographic imaging apparatuses enable, which images have substantially no background fouling have substantially resistant opposite to Grime and consequently have excellent resolution, and wherein the toner compositions in high-speed devices for the electrophotographic reproduction may be used in where more than 70 copies per minute can be produced.

The present invention relates to a toner comprising a resin, a colorant Part and coated silica particles, said silica a primary Particle size range from 25 nm to 55 nm and an aggregate size in the range of 225 nm to have 400 nm and wherein the coating using a mixture was prepared from an alkylsilane and an aminoalkylsilane; a Developer comprising this toner; as well as a process for preparing the toner according to claim 9. Embodiments of the invention include a toner, wherein the coating under Use of a mixture comprising 10 wt .-% to 25 wt .-% of a Alkylalkoxysilane and 0.10 wt .-% to 5.0 wt .-% of an aminoalkylalkoxysilane, was produced; a toner wherein the toner further surface additives includes selected of metal oxides, metal salts, metal salts of fatty acids and Mixtures thereof; a toner wherein the toner further surface additives includes selected of titanium oxide, metal salts of fatty acids and mixtures thereof; a Toner wherein the resin is a polyester; a toner wherein the is a polyester resin obtained by the condensation of propoxylated Bisphenol A and a dicarboxylic acid; a toner wherein the resin is a mixture of a polyester obtained during the condensation of propoxylated bisphenol A and fumaric acid, and a gel-containing polyester obtained in the condensate&lt;?page 5?&gt;sation of propoxylated Bisphenol A and fumaric acid, includes; a toner wherein the colorant was carbon black, a cyan Material, a magenta material, a yellow material, red material, an orange material, a green material, a violet material or a mixture thereof; a toner wherein the silica with a mixture of a decylsilane and Aminopropyl silane was coated; a toner wherein the alkyl group 1 to 25 carbon atoms includes; a toner wherein the alkyl group is a Butyl group, a hexyl group, an octyl group, a decyl group, dodecyl or stearyl group; a toner wherein the Silica with a polymer mixture of (1) an alkylsilane and (2) was coated an aminoalkylsilane; a toner wherein coating the titanium oxide or titanium dioxide with an alkylsilane has been; a toner wherein the titanium oxide coated with a decylsilane has been; a toner wherein the silica with a mixture comprising 10 wt .-% to 25 wt .-% of an alkyltrialkoxysilane and 0.10 wt .-% was wt .-% of a to 5.0 aminoalkyltrialkoxysilane, coated; a toner wherein the alkyl group comprises 1 to 25 carbon atoms; a toner wherein the alkyltrialkoxysilane and the aminoalkyltrialkoxysilane were simultaneously or in succession; a toner, wherein the silica with a mixture comprising 5 to 15 wt .-% a Decyltrialkoxysilans and 0.15 wt .-% to 0.50 wt .-% of Aminoalkyltrialkoxysilane, was coated; a toner wherein the silica particles a primary particle size in the range who and where from 25 nm to 55 nm, the coating on a core deposited silicon dioxide; a toner wherein the colorant was a pigment or a dye, and wherein the alkylsilane is a is alkylalkoxysilane; a toner wherein the silica is a primary particle size in the range 30 nm, the silica has to 40nm or where an aggregate size in the range from 300 nm to 375 nm, wherein the silica or a primary particle size in the range from 25 nm to 55 nm or wherein the silica an aggregate size in the range of 200 nm to 275 nm; a toner wherein the coated silica to 10 wt .-% is present in an amount in the range of 1 wt .-%; a Toner, wherein the coated silicon oxide in an amount in the range of 4 wt .-% to 10 wt .-% is present; a toner wherein the titanium oxide in an amount in the range of 1 wt .-% to 5 wt .-% is present, or wherein the titanium oxide in an amount in the range of 1.5 wt .-% to 3.5 wt .-% is present; a toner wherein the metal salt is zinc stearate and is present in an amount in the range of 0.10 wt .-% to 0.60 wt .-% is present; a toner having a triboelectric charge in the range from 15 to 55, or with a triboelectric charge in the range from 25 to 40; a toner wherein the resin is in an amount ranging of 85 wt .-% to 99 wt .-% is present, and wherein the colorant was Wt .-% is present in an amount in the range of 15 wt .-% to 1; a Toner with a unimodal charge distribution as determined with a charge spectrograph; a toner, further comprising a charge additive, a wax or mixtures thereof; a method, wherein the coating from a mixture of an aminoalkylalkoxysilane and a alkyloxysilane will be produced; a toner wherein the coating of the silicon oxide is a polymer and wherein the coating on a core of silica is applied; a toner wherein the coating of the silicon oxide is represented by the following formula <img img-content="cf" img-format="tif" he="43" wi="91" file="00080001.tif" /> wherein a is a repeating Segment of the following formula <img img-content="cf" img-format="tif" he="40" wi="92" file="00090001.tif" />and wherein the coating can be crosslinked; or wherein A is selected from the previously &lt;?page 6?&gt;described repeating segment and a hydroxy; or wherein A is selected from the above-described repeating segment, and an alkoxy; or wherein A selected is from the repeating segment and previously described, a hydroxyl group and an alkoxy group; b is an alkyl group with z. B. 1 to 25 carbon atoms and preferably having 5 to 18 Carbon atoms, and x is the number of segments and is z. B. a number ranging from 1 to 1000 and preferably a number in the Range of 25 to 500, and c is an aminoalkyl group, wherein the Alkyl group, for. Example, contains about 1 to 25 carbon atoms, and c is preferably an aminopropyl group; a toner wherein the coating of a polymer mixture of a decylsilane and aminopropylsilane a was produced; and toner comprising a binder such. B. resin, a colorant Ingredient and surface additives, comprising a mixture of certain silicon oxides, metal oxides, such. as titanium oxides, especially titanium dioxides, and certain Means for adjusting the conductivity, such as. for example, metal salts of fatty acids, ., Such as zinc stearate; and toner compositions comprising a Binder, a colorant Ingredient, optionally additives, such as. For example, additives for controlling of the charge, optionally surface additives, such as, for. example, certain titanium oxides, and means for adjusting the conductivity, such. as zinc stearate, and a surface additive, comprising a silicon oxide coated using a mixture alkylsilanes such. as a decylsilane and an aminopropyl silane, each in appropriate amounts as a mixture for the preparation of Coating of the silicon oxide can be used. The Amount of alkylsilane, such. As a decylsilane, based on the Weight of silica, z. B. is in the range of 5 wt .-% to 25 wt .-%, and preferably, for. Example, in the range of 10 to 20 wt .-%, and the amount of aminoalkylsilane such. as an aminopropylsilane is located, z., in the range of 0.05 wt .-% to 5.0 wt .-% or in the range from 0.05 to about 3 wt .-%. It can eg. B. 100 g silica with 15 g decyltrimethoxysilane and 0.50 g aminopropyltriethoxysilane are mixed, either simultaneously or sequentially. The resulting Silica can then use the decyltrimethoxysilane and aminopropyltriethoxysilane be implemented to the coating on the surface of to form silica. These coated silica can z. B. in an amount in the range of 0.50 wt .-% to 10 wt .-% and preferably in an amount in the range of 2.0 wt .-% to 5.0 wt .-% on the surface be applied toner. The toner may also known surface additives include such. as certain uncoated or coated metal oxides, such as. for example, titanium oxide particles in suitable quantities, for. example, in an amount in the range of 0.50 wt .-% to 10 wt .-%, and preferably in an amount in the range of 1.5 wt .-% to 4 wt .-%, are present, wherein the titanium oxide by using 5 wt .-% to 15 wt .-% coated decyltriethoxysilane or other Decyltrialkoxysilans has been. The toner may also include other surface additives, such as z. B. means for adjusting the conductivity, such as. for example, metal salts of fatty acids, such as. for example, zinc stearate, in an amount of z. B. 0.05 wt .-% to 0.60 wt .-%. The coated silicon oxide and optionally used Additives on the basis of titanium oxide preferably have a primary particle size in the range from 20 nm to 400 nm, more preferably in the range of 25 nm to 55 nm.

The Coating is performed using an alkylalkoxysilane and an Aminoalkylalkoxysilane made, specifically using a reaction mixture of silica, such as, for. example Siliciumdioxidkernen, an alkylalkoxysilane such. B. decyltrimethoxysilane, and a Aminoalkoxysilane such. As a aminopropylalkoxysilane. In the Implementation is a coating or a coating on the Siliciumoxidkernen obtained include optionally remaining alkoxy groups and / or hydroxyl can. The coating is preferably a crosslinked polymeric coating, obtained using a mixture of the alkylsilane and the aminoalkyl represented by the following formula <img img-content="cf" img-format="tif" he="39" wi="91" file="00110001.tif" />wherein a is a repeating Segment is preferably a segment of the formula &lt;?page 7?&gt;<img img-content="cf" img-format="tif" he="38" wi="91" file="00110002.tif" />and wherein the coating can be crosslinked; or wherein A is selected from the above repeating segment and described hydroxy; or wherein A is selected from the above-described repeating segment, and an alkoxy; or wherein A selected is from the repeating segment and previously described, a hydroxyl group and an alkoxy group; b is an alkyl group with z. B. 1 to 25 carbon atoms and preferably having 5 to 18 Carbon atoms, and x is the number of segments and is z. B. a number ranging from 1 to 1000 and preferably a number in the Range of 25 to 500, and c is preferably an aminoalkyl group, wherein the alkyl group z. B. 1 to 25 carbon atoms, and c is preferably an aminopropyl group, and b is preferably a Decyl group. The surface additive on the basis of titanium dioxide can be represented by a similar formula are, with the exception that Si is substituted by Ti.

The Toner compositions according to the present invention may be prepared by Mixing and heating the resin particles, such. as styrene polymers, polyesters and similar thermoplastic resins, colored Waxes, especially waxes having a low molecular weight, and the charge enhancing additives or mixtures of charge additives in a toner extrusion device, such. as in the device ZSK53 available from Werner Pfleiderer, and removing the resulting toner composition from the device are obtained. After cooling, the toner composition is ground, where z. B. the device Sturtevant micronizer can be used, where toner particles having an average volume diameter of less than about 25 micrometers (microns) and preferably having a volume mean diameter in the range 8-12 microns (Microns), as determined by the Coulter Counter device, receive will. Thereafter the toner compositions are classified, and z. B. the device Donaldson Model B classifier can be used to fine toner particles, that is, toner particles having a volume mean diameter of less than about 4 microns remove (microns). Thereafter, the coated silica are and other additives are added by mixing, while maintaining the toner becomes.

Examples of suitable Toner binders include toner resins, especially polyesters, thermoplastic Resins, polyolefins, styrene acrylates, such. As PSB-2700, available from Hercules-Sanyo Inc., preferably in an amount of 57 wt .-%, styrene methacrylate, Styrene butadienes, crosslinked styrene polymers, epoxies, polyurethanes, Vinyl resins, including homopolymers and copolymers of two or more vinyl monomers; and polymeric esterification products of dicarboxylic acids and Diols comprising diphenols. Examples of the vinyl monomers Styrene, p-chlorostyrene, unsaturated Monoolefins, such as. For example, ethylene, propylene, butylene, isobutylene, and etc .; saturated . Monoolefins, such as vinyl acetate, vinyl propionate or vinyl butyrate; Vinyl esters, such as. For example, esters of monocarboxylic acids including methyl acrylate, Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, Phenyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate; acrylonitrile, Methacrylonitrile, acrylamide; Mixtures thereof; and the like., styrene butadiene copolymers with a styrene content ranging from 70 to 95 wt .-%, see the aforementioned U.S. patents, the disclosure of this part Registration is. Furthermore, crosslinked resins, including polymers, copolymers, homopolymers of styrene polymers previously mentioned, can be used.

Examples for the Toner resins include esterification products of dicarboxylic acids and Diols comprising diphenols. These resins are described in US Pat. 3590000 described ben, the disclosure of which part of this application is. Specific examples of Other toner resins include styrene / methacrylate copolymers and styrene / butadiene copolymers; Pliolit materials; Styrenebutadienes, prepared by suspension polymerization, see US Pat. No. 4558108, the disclosure of this part Registration is; Polyester resins obtained in the reaction of bisphenol A and propylene oxide, followed by reaction of the product obtained with fumaric acid, and branched polyester resins obtained in the reaction of dimethyl terephthalate, 1,3-butanediol, 1,2-propanediol, and pentaerythritol, reactive extruded Resins, especially reactive extruded polyesters described crosslinked, in US Pat. No. 5352556, the disclosure of which part of this application is, styrene acrylates, and mixtures thereof. It can also waxes with a weight average molecular weight M_W in the Range from 1000 to 20,000, such as. For example, polyethylene, polypropylene and paraffin&lt;?page 8?&gt;Waxes may be incorporated into the toner compositions, as release agents for the the fixing roller used. The resin is in an amount effective z. B. used in an amount ranging from 50 to 90 wt .-%.

Examples for the coloring Ingredients include pigments, dyes and mixtures thereof, dye mixtures, Pigment mixtures, and the like., In suitable quantities, for. Example, in a Amount in the range of 1 to 20 wt .-%, and preferably in an amount be used in the range of 2 to 10 wt .-%. Specific examples for coloring components include carbon black, such. as REGAL 330^®; Magnetite such. B. the Mobay magnetites MO8029^TM, MO8060^TM; Columbian magnetites; MAPICO BLACKS^TM and superficially treated magnetites; Pfizer magnetites CB4799^TM, CB5300^TM, CB5600^TM, MCX6369^TM; Bayer magnetites BAYFERROX 8600^TM, 8610^TM; Northem Pigments magnetites, NP-604^TM, NP-608^TM; Magnox magnetites TMB-100^TM or TMB-104^TM; , etc .; cyan, magenta, yellow, red, green, brown or blue coloring Ingredients or mixtures thereof such as. For example, the specific phthalocyanines HELIOGEN BLUE L6900^TM, D6840^TM, D7080^TM, D7020^TM, PYLAM OIL BLUE^TM, PYLAM OIL YELLOW^TM. PIGMENT BLUE 1^TMAvailable from Paul Uhlich &amp; Company, Inc., PIGMENT VIOLET 1^TMPIGMENT RED 48^TM, LEMON CHROME YELLOW DCC 1026^TM. ED TOLUIDINE RED^TM and BON RED C^TMavailable Dominion Color Corporation, Ltd., Toronto, Ontario, Novaperm YELLOW FGL^TM, HOSTAPERM PINK E^TM from Hoechst, and CINQUASIA MAGENTA^TMAvailable from EI DuPont de Nemours &amp; Company, and the like.

Ordinary colored Pigments and dyes which can be used include cyan, magenta, and yellow pigments and dyes, and mixtures thereof. examples for the magenta materials include z. B. 2,9-dimethyl-substituted Quinacridone and anthraquinone dyes identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dyes identified in the Color Index as CI 26050, CI Solvent Red 19, and the like. Examples of the cyan materials include copper tetra (octadecyl sulfonamido) phthalocyanine, x-copper phthalocyanine pigments which, listed in the Color Index as CI 74160, CI Pigment Blue, and Anthrathrene Blue, listed in the Color Index as CI 69810, Special Blue X-2137, and the like .; and examples for the yellow materials include diarylide 3,3-dichlorbenzidenacetoacetanilid, a monoazo pigment, listed in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl listed in the Color Index as Foron Yellow SE / GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,5-dimethoxy acetoacetanilide, and Permanent Yellow FGL, and other known dyes, such as. As red, blue, green and the like. dyes.

Examples for Magnetite comprise a mixture of iron oxides (FeO.Fe₂O₃) Comprising the commercially available product MAPICO BLACK^TMAnd the magnetites can be used in the toner composition be included in a suitable amount, eg., in an amount in the The range of 10 wt .-% to 75 wt .-%, and preferably in an amount in the range of 30 wt .-% to 55 wt .-%, based on the weight of of the composition.

The Toner compositions in accordance with the present invention, the contain described charge additives in an effective amount, z. B. in an amount in the range of 1 to 19 wt .-%, and preferably in an amount in the range of 1 to 3 wt .-%, and waxes such as z. B. polypropylenes and polyethylenes commercially available from Allied Chemical and Petrolite Corporation, Epolene N-15, commercially available from Eastman Chemical Products, Inc., Viscol 550-P, a polypropylene with a low weight average molecular weight, available from Sanyo Kasei KK, and the like. The commercially available Polyethylenes having a molecular weight in the range from 1000 to 1500, while the commercially available Polypropylene likely have a molecular weight in the range from 4000 to 7000th Many of Polyethylene and polypropylene compositions used in the invention who can, are described in British Pat. No. 1442835, the disclosure of is part of this application. The wax is in the toner compositions according to the present invention in a suitable amount before, and usually containing toner compositions these waxes in an amount in the range of 1 wt .-% to 15 wt .-%, and preferably in an amount in the range of 2 wt .-% to 10 wt .-%, based on the weight of the Composition. The toner according to the present invention can also contain polymeric alcohols, such as for example. The products under the name UNILIN^®See US Pat. No. 4883736, the disclosure of which is incorporated into this application, with the products under the name UNILIN^® from Petrolite Corporation available are.

The inventive developers include those described toner on the surface of the Silicon oxides are applied, and carrier. The developer compositions can be prepared by mixing the toners with known carrier particles are mixed, comprising coated carrier such. as support from Steel, ferrite and the like. See, US Patent Nos. 4937166 and no. 4935326, the disclosure of which is incorporated into this application, eg. Example in the range of 2 wt .-% toner concentration to 8 wt .-% Tonerkon&lt;?page 9?&gt;concentration. The carrier can be coated, eg. as the coatings described in US Patent No. 4937166 and no. 4935326 describes or with other known coatings. The coating may be a polymer or a polymer blend comprising. The polymer coatings or coatings, ingredients for adjusting the conductivity contain such. as carbon black, z. B. in an amount in the range of 10 to 70 wt .-%, and preferably in an amount in the range of 20 to 50 wt .-%. Specific examples of coatings include fluorocarbon polymers, acrylate polymers, methacrylate polymers, Silicone polymers and the like.

The Invention also relates to image forming methods in which The novel toners be used; in this regard is applied to the already-mentioned patents, as well as to the US patents 4265990 referenced no. 4585884, no. 4584253, no. 4563408 and no., the disclosure of which is incorporated into this application.

The present invention is described in more detail below with reference to examples. However, the invention is not limited to these examples. Comparative Examples are also indicated.

example I

manufacturing of coated silica

200 ml dry n-propanol as the solvent were placed in a 500 ml three-necked round bottom flask is introduced, and then the solvent was flushed with dry nitrogen, to excess oxygen to remove. An amount of 10 ml of solvent was removed and in a small container (volume: added 2 drams). A further quantity of 20 ml was also removed and placed in a scintillation vial. 15 g untreated hydrophilic SiO₂, TL90, available of Cab-O-Sil Corp., having a primary particle size of 30 nm, determined according to the BET method according to Brunauer called, Emmett and Teller, a known technique for determining the surface, calculated from the z under certain assumptions. as the primary particle size can be, and determined an aggregate size of about 300 nm, by measuring the Brownian motion, were introduced into the flask and with a mechanical stirrer stirred in the n-propanol, until the silica wet. While stirring, the mixture was in the inert atmosphere kept. A few drops of diethylamine were added to the 10 ml of solvent, the had been removed, was added and the resulting mixture was ml flask in 500 ml. The mixture was then about 1 hour stirred. Among the 20 ml of solvent were in the scintillation vial 2.25 g and 0.06 g of aminopropyltriethoxysilane decyltrimethoxysilane given. This mixture was added to the 500 ml flask, the SiO₂ contained after previously described 1 hour Pre-treatment had been completed. Then, a heating mantle was attached, and the mixture was stirred and under an inert atmosphere reflux heated. The mixture was heated for about 5 hours and then to room temperature (About 25 ° C) cooled. The mixture was then placed in a tear-shaped flask Flask was attached to a rotary evaporator and the solvent was heating stripped under vacuum. Then, the flask was placed in a vacuum oven incorporated, and the residue was Overnight (about 18 hours) in vacuum at a temperature of 40 ° C completely dry. The obtained silica particles with decylsilane / aminopropylsilane had been coated, have been in a mortar with a pestle pulverized, particles having a primary particle size of 30 nm be, consistent with the BET method, and an aggregate size of 300 nm, were determined by measuring the Brownian motion is obtained.

example II

manufacturing of coated silica

30 g untreated hydrophilic powdery SiO₂cores with a primary Particle size of 40 nm and an aggregate size of about 300 nm were introduced into a 2 l Buechi-pressure reactor and the reactor was sealed. Then, 30 minutes, an inert gas (argon) passed through the reactor to displace atmospheric gases. Then were remaining atmospheric Gases using a vacuum pump from the reactor, and the reactor was at 28 ° C heated. The vacuum valve was then closed, and a vial with triethylamine was attached to the reactor so that the vapor space of the ampoule and the upper region of the reactor were connected to each other, and Triethylamindampf was 15 minutes from the bed Silica introduced. The valve between the ampoule and Reactor was then closed and the valve to the vacuum pump was opened again, and to remove the triethylamine, which is not physically at the surface of the silica had been adsorbed. The reactor was that using a Laude circulating bath containing the reactor shell ver&lt;?page 10?&gt;was connected at 0 ° C cooled. After the reactor from 0 ° C chilled was, were, using an injection pump motor (ISCO Model 260D), 570 g of carbon dioxide (absolutely dry carbon dioxide, available from Praxair) into the cooled Reactor introduced. Was then begun, the contents of the reactor to stir with a speed of 10 revolutions / minute. Then 4.5 g of decyltrimethoxysilane by Shin-Etsu Silicones and 0.12 g aminopropyltrimethoxysilane from PCR Research Chemicals in separate Pressure cells with variable volume in carbon dioxide as a solvent dissolved. The pressure inside the cell was 100 bar, which was sufficient to homogeneous solutions to obtain the two silanes in carbon dioxide. The solution of Decyltrimethoxysilane was first introduced into the 2 l Buechi reactor. The same injection procedure was then with 0.12 g aminopropyltriethoxysilane repeated. After the addition of the second silane, the temperature was of the reactor at 0 ° C maintained and the contents of the reactor was 30 minutes with a rate of 100 revolutions / Mi nute stirred; then stirring was interrupted and the carbon dioxide was of the over the top of Reactor drained. After releasing the pressure, the temperature was the reactor to 28 to 30 ° C elevated. Once set a state of equilibrium at this temperature had coated with decylsilane / aminopropylsilane silica product was removed through held under vacuum overnight (about 18 hours, 3 hours at 150 ° C) and then examined by means of IR spectroscopy.

example III

On Toner resin is prepared by polycondensation of bisphenol A and fumaric acid, wherein a straight-chain polyester which called Resapol HT was is obtained.

On second polyester was prepared by dissolving the resin in Resapol HT added to an extruder having a sufficient amount of benzoyl peroxide was to a crosslinked polyester having a high gel concentration to obtain from about 30 wt .-% gel, see U.S. Patent Nos. 5,376,494, No. 5395723, no. 5401602, no. 5352556 and no. 5227460, in particular the polyester in the '494er described patent, the disclosure of which part of this application is.

example IV

75 Parts by weight of the resin Resapol HT from Example III, 14 parts by weight the polyester of Example III having a gel content of 30 wt .-% and 11.0 parts by weight of Sun Blue Flush, a mixture of 30 wt .-% PB 15: 3 and copper phthalocyanine 70 wt .-% Resapol HT, manufactured Sun Chemicals using a rinsing process to create a high to obtain high-quality pigment dispersion were mixed together and extruded using the extruder ZSK-40th The extruded Mixture was then sprayed and classified to obtain a cyan toner (with 93 wt .-% resin and about 7 wt .-% PB 15: 3) with a toner particle size of about 6.5 micrometres (microns), was determined with a Layson cell obtained.

Comparative example V

30 g of the toner of Example IV were mixed with 150 g of stainless steel beads given vessel in a 9 oz. Then, 0.6 wt .-% TS530 (fumed silica with a primary Particle size of 15 nm, coated with hexamethyldisilazane of Cab-O-Sil Division of Cabot Corp.), 0.9 wt .-% TD3103 (titanium dioxide with a primary particle size of 15 nm, coated with decylsilane made decyltrimethoxysilane from Tayca Corp.) and 0.3 wt .-% zinc stearate L from Synthetic Products Company added. After the ingredients for 30 minutes under Using a roll mill were mixed together, the steel beads were removed from the vessel.

On Developer was prepared by mixing 4 parts of the toner mixture with 100 parts of a carrier (Hoeganaes steel cores, coated with 80 wt .-% of polymethyl methacrylate and 20 wt .-% conductive carbon black) mixed were. The developer was charged in an image forming apparatus tested, which corresponded approximately to the device Xerox 5090, which poor image quality was obtained, most likely due to a decrease of the development properties of the Toner due to the TS530-silica with a small particle size of 15 nm, the TD3103-titanium dioxide with a small particle size of 15 nm and / or the coating on the silica.

Comparative Example VI

On Toner mixture was in the same manner as in Comparative Example V prepared with the exception that 4.2 wt .-% RX515H (fumed Silica having a primary Particle size of 40 nm and &lt;?page 11?&gt;an aggregate size of about 300 nm, coated with a mixture of hexamethyldisilazane and Aminopropyltriethoxysilane, available from Nippon Aerosil Corp.), 2.5 Wt .-% MT5103 (titanium dioxide with a primary particle size of 30 nm, coated with decylsilane manufactured by Tayca Corp.) and 0.3 wt .-% zinc stearate L from Synthetic Products Company together were mixed and applied to the toner surface. After this the ingredients for 30 minutes using a roll mill with one another were mixed, the steel balls were removed from the vessel. A developer was prepared by mixing 4 parts of the toner mixture with 100 parts of a carrier (Hoeganaes steel cores coated with polymethyl methacrylate and 20 wt .-% conductive mixed soot) were. This developer was 90 minutes according to a set mixing program mixed, and the triboelectric charge the toner at the end of 90 minutes was -16.5 microcoulombs / gram. During the 90 minutes Mixing according to a fixed program changed the triboelectric charge and decreased over time. After 90 minutes, additional mixed toner, which after 15 seconds a unimodal charge distribution was observed up to an additional mixing period of 1 for 2 minutes bimodal. This bimodal distribution was already existing toner whose charge had dropped to zero, and additional Toner, the more was charged as the existing toner caused. at a test with the freshly blended toner using a Experimental arrangement similar the device Xerox Corporation 5090, were substandard Images obtained after about 2000 copies were produced. The poor quality the images was mainly by toner with an incorrect polarity and the bimodal charge distribution in the developer machine, simulated with the specified mixing program / the additional Toner addition caused. The use of the toner having a small Charge q / d of nearly zero led a background fouling of the image, while the toner with a high charge q / d (fc / u, femtocoulombs per micron) of about 0.7 or more to the Developers wires adhered, resulting in insufficient development and thus a low image density in areas of the image led.

example VII

On Toner mixture was in the same manner as in Comparative Example VI prepared, except that the component by RX515H 3.2 wt .-% fumed Siliciumoxidkerne (L90-cores) with a primary particle size of 30 nm and an aggregate size of about 300 nm, coated with a mixture of 15 wt .-% decyltrimethoxysilane and 0.4 wt .-% aminopropyltriethoxysilane, wherein the coated Silica from the Cab-O-Sil Division of Cabot Corp. based had been replaced.

On Developer was prepared by mixing 4 parts of the toner mixture with 100 parts of a carrier (Hoeganaes steel cores, coated with 80 wt .-% of polymethyl methacrylate and 20 wt .-% mixed conductive Vulcan carbon black) were. This developer was 90 minutes according to a set mixing program mixed, and the triboelectric charge the toner at the end of 90 minutes was -19.7 microcoulombs / gram. During the 90 minutes Mixing according to a fixed program changed the triboelectric charge does not and did not in the course of time from. After expiry of the 90 minutes of additional toner was added, where after 15 seconds observed a unimodal charge distribution has been. Unlike the developer in Comparative Example VI was the charge distribution of the toner and the existing additional Unimodal toner in this example, whereby no toner having a small Charge (&lt;0.2 fc / u) or in the wrong direction with a charge q / d (femtocoulomb / micron; q is the toner charge and d is the toner diameter) of almost zero or less than zero during the additional 2 minutes of mixing was observed. When using this Toner, high quality copies with an excellent Image density obtained without occurring a substantial background contamination.

example VIII

On Toner mixture was in the same manner as in Comparative Example VI prepared, except that the component by RX515H 3.2 wt .-% fumed Siliciumoxidkerne (L90-cores) with a primary particle size of 30 nm and an aggregate size of about 300 nm, coated with a mixture of 15 wt .-% decyltrimethoxysilane and 0.5 wt .-% aminopropyltriethoxysilane, wherein the coated Silica with the coating from decylsilane / aminopropylsilane of the Cab-O-Sil Division of Cabot Corp. was based, was replaced. A developer was prepared by mixing 4 parts of the toner mixture with 100 parts of a carrier (Hoeganaes steel cores, coated with 80 wt .-% of polymethyl methacrylate and 20 wt .-% conductive carbon black) mixed were. This developer was 90 minutes according to a fixed mixed mixed program, and the triboelectric charge of the toner at the end of 90 minutes was -18.9 Microcoulombs / gram. While the 90 minutes Mixing according to a fixed program changed the triboelectric charge does not and did not in the course of time from. After&lt;?page 12?&gt;90 minutes, mixed with additional toner, where after 15 seconds observed a unimodal charge distribution has been. Unlike the developer in Comparative Example VI was the charge distribution of the toner and the existing additional Unimodal toner in this example, whereby no toner having a small Charge (&lt;0.2 fc / u) or with false positive polarity having a charge q / d of almost zero or less than zero during the additional 2 minutes of mixing was observed. When using this Toner in a Xerox Corporation 5090 test image forming apparatus were high quality copies with an excellent image density obtained without a substantial background contamination occurred.