DE2642826A1 - Liquid hybrid toner for electrostatic copying - contg. two conventional suspension developers one with amphipathic polymer - Google Patents

Abstract

Suspension developer for electrostatic copying contains 0.5-99.5% of a conventional suspension developer (I) of the first type and 99.5-0.5% of a conventional suspension development (II) of the second type, contg. and amphipathic polymer (III). At least one of the developers contains regular(s) and opt. colour(s). At least 15,000 prints can be made with the plates and uniform coloured areas are filled well. Very good resolution can be obtd. in the prodn. of microfiche copies. In an example, (I) was based on a hydrocarbon resin, dispersant and colours, whilst (II) was prepd. from a latex of a vinyl acetate/crotonic acid copolymer and various additives, both in a paraffinic solvent.

Description

Description

Regarding the patent application: Electrophotographic or electrographic Suspension developer "The invention relates to an electrophotographic or electrographic suspension developer (liquid hybrid toner) that built up is made up of two different types of liquid toners. One is a complex one Amphipathic molecule in which at least one fixing part and one dispersion part is polymeric and a control substance is present, where appropriate also a dye may be present in a volatile organic solvent with high electrical power Resistance. The other volatile toner has a fixing agent and a dispersing agent as separate chemical individuals, contains a control substance and a pigment in the above solvent.

The two toners can be mixed in a wide range of amounts, whereby the hybrid toner is particularly suitable for the production of planographic printing forms and microfiche -.

Reproductions by electrostatic processes as well as everywhere there, where otherwise liquid toners or suspension developers are used.

Usual suspension developers contain a volatile organic Solvent system with high electrical resistance various components in Dispersion, in solution or solvated. With these components it can be a thermoplastic fixative, dispersant, and pigment (often Soot) and a control substance that exist as chemical individuals. These Type of known suspension developer is hereinafter referred to as suspension developer first type denotes suspension developers of the second type are characterized by an amphipathic molecule which has at least one polymeric part which at least one other polymer serves as a thermoplastic fixing agent1 Part that serves as a dispersant, so these two parts in the complex Molecule present. The amphiphatic molecule can also be colored as a further part Means) have a chromophore or it can be the dye as a chemical individual be contained in the suspension developer of the second type. In a suspension developer of the second kind there is also a control substance which is not part of the amphipathic Molecule is. How the suspension developer of the first kind is with the second kind a liquid carrier system, which organic volatile solvents with very high electrical resistance. Of the two polymeric parts mentioned above at least one is thermoplastic. This is soluble in the solvent system, part of which is a fixing agent and a dispersing agent. The other polymer Part is insoluble in the solvent system and has a fineness of 25 nm to 25 μm, part of which is a fixative. The suspension developer of the second type has So a continuous phase in the form of the solvent system in which the mentioned polymer unit is dissolved and a disperse phase in the form of the other Polymer unit, so that the amphipathic molecule is to be regarded as a monodisperse particle phase and acts as a fixative and dispersant.

Both types of these suspension developers have special advantages and Disadvantages, the disadvantages of the dispersion developer of the second type being comparative are small, if they exist at all. These disadvantages and especially those of the Suspension developers of the second type are not important for the application of the suspension die Most developers of the second kind for electrostatic purposes, e.g. in the large field of application the office copier.

These minor disadvantages of the second type of suspension developer hinder however, to a certain extent, their use in the manufacture of planographic printing plates and reproductions for microfiches by the electrostatic reproduction method.

It was found that when using suspension developers second type for the production of planographic printing plates, although there are a large number of them of printing pieces, e.g. more than 15,000, during longer operating times the electrostatically built-up image is destroyed.

Planographic printing forms can be made by electrostatic means Deposition of a toner, possibly with a dye, on a flexible surface, which is provided with a layer of a photoconductor in which there is a latent builds up an electrostatic image, which is created by applying the suspension developer is being developed.

Both the photoconductive layer and the toner image are oleophilic; in order to make the image on the carrier usable for a printing form, the Image-free background areas can be made oleophobic by making them hydrophilic. This change can be achieved, for example with an aqueous solution of ferro- or ferricyanide, which are the non-image areas of the photoconductive layer attack. The most commonly used photoconductor is zinc oxide, which is in a Binder layer is located; this can be a commercially available electrostatic reproduction paper be.

In the manufacture of planographic printing forms and also for general purposes there is a serious disadvantage when using the suspension developer of the first type if the original to be reproduced has one or more colored (non-white) Contains areas of appreciable size, e.g. at least 6.35 mm in each dimension. In such cases there was a noticeable toner deposition in these areas, with greater intensity at the periphery than at the center. This disadvantage occurs in the case of suspension developers, the second type does not clear up.

In the case of electrostatic microfiches reproduction, it occurs with application from dispersion developers of the second kind to a slight disadvantage in the form, that the borders of the picture shift somewhat, i.e. deviate somewhat and thus not detectable from the limits of the original what the reproduction deviates probably based on the size of this complex molecule. This disadvantage however, has a particular effect in the production of good enlargements of Microfiche images.

A much more serious drawback in the context of applying to the electrostatic reproduction of microfiche images when using suspension developers The first type was the difficulty of fixing the electrostatically deposited Images on the carrier. The carrier contains a transparent thermoplastic film-forming material Material containing a transparent photoconductor for the construction of the electrostatic latent image which should then be developed. A A widely used photoconductor is poly-N-vinyl carbazole. If the picture is constructed, it must be fixed. This fixation is achieved by heating; however, since the film-forming material is at temperatures such as those required for fixing the image If applied, becomes dimensionally unstable, this can destroy the image come what is unsustainable for the application for microfiche.

The invention now relates to a suspension developer containing both of the above types of suspension developer (hybrid toner) that include those shown above Disadvantages of the individual suspension developer does not have. It can be used for the electrostatic production of planographic printing forms, which at least without destruction Allow 15,000 thrust pads. Achieved with the suspension developer according to the invention get a good "fill in" of uniformly colored areas; apart from the The one according to the invention is suitable for the production of printing plates Suspension developer also for the production of microfiche images by electrostatic Process in which the resolution is particularly good and can be fixed by heat, without affecting the dimensional stability of the thermoplastic in the carrier of the developed image is adversely affected.

The suspension developer according to the invention is also suitable for conventional Office copying process in any apparatus for suspension developers, the the same developer can be used for a wide variety of types and purposes can. In principle, it can be said that the suspension developer according to the invention can be used wherever suspension developers have been used so far for jet printing, for reading out cathode ray screen images and in light printing for cathode ray tubes (pin tubes) and various other transmission methods, such as pressure transmission, vacuum transmission, and electrostatic transmission.

According to the invention, two suspension developers are used in principle work in different ways; they can be used over a wide range of quantities be mixed, such as 0.5% of a suspension developer either the first or the first the second type with the rest of the other type. By setting certain proportions you can still achieve special advantages.

The known suspension developer of the first type has a volatile organic solvent system with an electrical resistance of the order of magnitude of at least about 10951 cm. There is a fixative in this solvent system, dispersed or solvated, a dispersant which generally solvates is a control agent so avatized or dispersed and a pigment such as Carbon black, which is usually present as a dispersion.

The second type of suspension developer is disclosed in US Pat. No. 3,753,760 known. This is generally a solvent system as in the developer of the first kind; it contains a complex amphipathic substance, which at least as polymeric units are a fixing agent and a dispersing agent (dispersant) and possibly also contains a dye or chromophore.

Optionally, the dye is in the second suspension developer Art as a separate chemical individual, i.e. not as part of the complex amphipathic substance. A dye needs neither in the suspension developer first still exist of the second kind, however he mostly desirable. There is no need if the suspension developer according to the invention is exclusive is used for the production of planographic printing plates, but can even be used for a dye still appear desirable in this field of application. At the suspension developer of the second type, the control substance is present outside the amphipathic molecule.

The two suspension developers can be mixed in any device happen like in a freshener, in a ball mill, or a homogenizer by simple manual mixing, which makes you a particularly effective developer Received for the production of planographic printing plates and electrostatic microfich reproductions or for general electrostatic purposes, such as normal office copying processes of any kind or for special devices, such as jet printers, cathode ray tube printers , Photocomposing devices and transmission printers.

Instead of producing the two suspension developers separately, you can one also their constituents at once to the suspension developer according to the invention mix together; this preferably contains a common solvent system, one or more common control substances and dyes. The amphipathic molecule the suspension developer of the second type can be classified as a disperse phase (dispersant) use for the suspension developer of the first kind.

Customary suspension developers of the first type are volatile organic Solvent system with high electrical resistance, namely of at least about 109je. cm. One or more hydrocarbons are preferred as solvents for this, especially as they are commonly used under the name "petroleum fraction".

This includes fractions on the distillation or the catalytic Cracking and polymers of aliphatic monomers that are synthetically or obtained by distillation or cracking. The petroleum fractions are special useful for the suspension developer of the first type because they evaporate quickly; For example, a thin layer evaporates in a few seconds on one Temperature below the char point of the paper, allowing rapid drying is possible; they are not poisonous, they have a slight odor. Will you applied together with soluble film-forming agents, they volatilize completely and leave the film tack-free, so that it does not dry out for a long time is necessary for the image build-up and the image appears dry shortly after the build-up. They are sufficiently mobile to allow the pigment particles to migrate easily, so that the pigment is quickly electrostatically attracted and adhered to the charge image can be; they grip the binding agent of the base and the components thereof do not suggest they do not lead to a dissipation of the electrostatic charge before the pigment is deposited so that any desired contrast can be achieved in addition, they are cheap.

The petroleum fraction, i.e. a paraffinic solvent, should have an evaporation rate at least that of kerosene, however be slower than hexane. Evaporation of the liquid from a thin layer is reached quickly, e.g. in 2 s at a temperature just below the Char point of paper; it is therefore often advisable to check the temperature of the suspension developer for the evaporation to increase after the opaque toner particles on the electrostatic a charge image are deposited. The petroleum fraction should have a low Eauz: -Butano 'number, i.e. less than 35, preferably between 26 and 35 liters. This low KB number reduced the likelihood that the petroleum fraction is the binder attacks the photoconductive layer or the paper size on which the photoconductive Layer is located. The petroleum fraction should be essentially free of liquid aromatics in other words, the liquid aromatics in the solvent system should be make up no more than 2% by weight. The liquid aromatics easily grab the binder of the photoconductive layer, but in concentrations of less than 2% still negligible. The petroleum fraction must have a high electrical resistance have, e.g. in the order of at least Di about 109 #. cm, the constant of electricity must be below 3.5 so that the solvent system does not cause the electrostatic image. The flash point in the closed cup according to Tagliabue should be at least 380C, preferably 49 to 66 ° C. One such solvent can be described as non-flammable.

Paraffinic solvents are non-toxic, they do not have any unpleasant odor and are preferably odorless; they are non-polar. That Solvent system should have a low viscosity, such as between 0.5 and 2.5 cP at room temperature.

The petroleum fraction for the solvent system can be used as different Use commercial products Sol 71, Isopar G, H, E and L, Amsco OMS, Amsco 460 solvents and Amsco odorless inseticide base as well as odorless kerosene These are all paraffinic Solvent with a faint odor. The dielectric constant of sol 71 is at room temperature 2.06. The other solvents have a dielectric constant of the same order of magnitude.

TABEL: Boiling Flame K.B. Aniline spec.

-start -end point number point weight

° C ° C ° C ° C 15 ° C Shell Sol 71 173 203 49.5 26.5 84 0.7563 Isopar H 177 187 50.5 26.9 84 0.7571 Isopar K 176 195 52 26.5 85 0.7587 Isopar L 188 206 63 - 86 0.7674 Amsco OMS 178 147 51.5 27.0 84.8 0.7608 Amsco 460 190 180 65.5 34.5 64 0.8108 Solvent Insecticide Base 190 193 66.5 26.5 80 0.7711 The second ingredient The first type of suspension developer is the fixative, which is found in the solvent system is dispersible or soluble. It serves as a film-forming agent for the developed Image by holding the pigment on the paper backing. The fixative is at Room temperature solid; if it is soluble in the solvent it should be completely be soluble and release the solvent well so that it evaporates completely can and quickly results in a solid, coherent film. This can be done with or without heating. The film must be tack-free, tough and cohesive so that the developed image does not smears or falls off, but one Resists damage. The Fixier i teeWoch should be compatible with the binding agent the photoconductive layer and adhere to it well to lift off the finished image to avoid from the shift. Excellent fixatives that are soluble or insoluble are commercial products such as 1: Resin NC 11 ;; this is a pale thermoplastic acid rosin that has been polymerized and hydrogenated; it has a softening point from 85 to 93 ° C (according to the Hercules drop method), an acid number from 145 to 162 and a density at 200C of 1.065. The acid number is 155 to 165, the degree of hydrogenation about 90% and the average molecular weight 360. About 20% of the resin acids are polymerized. Other suitable fixatives can be found in the following list; the softening point was determined with the exception of the last resin by the Hercules drop method, the last resin, however, by the mercury method.

Resin acid number softening point ° C Lewisol 7 glycerol ester of modified Rosin 8 168 Pentalyn A Pentaerythritol ester of rosin 12 111 Pentalyn C pentaerythritol ester of polymerized rosin 14 135 Pentalyn G modified Pentaerythritol ester of rosin 14 135 Resin acid number softening point (Oc) Pentalyn H pentaerythritol ester of hydrogenated rosin 13 104 Pentalyn K Pentaerythritol esters of dimeric resin acids 14 192 Pentalyn X modified pentaerythritol ester of rosin 14 159 fentalyn 860 pentaerythritol ester 15 172 of dimeric resin acids Polypal glycerol esters of 6 112 esters 10 polymerized rosin Staybelite hydrogenated rosin 165 76 resin Krumbhaar 484 pentaerythritol ester of modified Rosin <1 180-190 "Nevchem 100" is also suitable, i.e. a thermoplastic Petroleum hydrocarbon resin, in which the units of the polymer in the main are aromatic or cyclic.

It is made by polymerizing unsaturated hydrocarbon fractions with boiling points between about 125 and 2500C, density 0.9 to 0.95 at 15.60C. the polymerizable Constituents make up 30 to 90% by weight and the main polymerizable monomers are: Oyclodiene dimers * 5 to 30 % Indene 5 to 20% vinyl toluene 5 to 25% styrene 0 to 10% * such as dicyclopentadiene, Dimethylcyclopentadiene, codimer of cyclopentadiene and methylcyclopentadiene.

The remainder of the dry weight consists of the hydrocarbon fraction essentially of non-polymerizable paraffins, naphthenes and aromatics with at least 8 carbon atoms per molecule and a boiling range of e.g. 125 to 2500C.

The unsaturated hydrocarbon fractions that make up the resin obtained are generally derived from high temperature and low pressure pyrolysis normally liquid or gaseous hydrocarbons with at least 2 carbon atoms.

Cracking can be a byproduct of pyrolysis in which the desired main products are low-boiling olefins and dienes, such as ethylene, propylene, Butene and butadiene are widely used in petrochemicals.

The pyrolysis of liquid and gaseous hydrocarbons for this purpose is known and therefore does not need to be mentioned in more detail. The properties of the commercial product Nevchem 100 "are summarized below: Softening point (Ring and ball) 1000C mean. Molecular weight (determined osmotically) 800 weight ratio O / H (elemental analysis) 10.5 density at 250C 1.09 refractive index at 2500 1.602 iodine number 65 acid number <1 Other useful products are: resin acid number Softening point (° C) Foral 85 fully hydrogenated glycerol ester of rosin 9 82 Cellolyn internally softened 104 pentaerythritol ester of rosin 30 101 Dpolymerx dimeric resin acids 143 152 Pliolite vinyltoluene / acrylate-VTAC-L mixed polymer 6.1 47 Neocryl VinyltoSuene / n-Butyl-B-707 methacrylate / stearyl methacrylate (US-PS 3 378 513) 115 R&K All of the above fixing agents with the exception of the last two are solvatable in one or more of the above solvents. The last both are not solvatable in most solvents, but can be dispersed a suspension developer of the first type can be applied.

The third component of the suspension developer of the first type is a Dispersing agent which is either solvatable or non-solvatable in is the solvent system; however, it is usually solvatable.

The function of the dispersant is one of the pigment particles submicroscopic fineness dispersed in the non-polar solvent system to keep. The dispersant must be compatible with the fixative; it is even useful if the dispersant has the direction of charge the pigment particles supported.

Examples of solid dispersants are "Lube Oil 564" and "FOA 2 ". Lube Oil 564 consists of 50% polymethacrylate and 50% kerosene; so far If the above examples are dispersants, solids are meant, the liquid substances generally only serve as carriers. Another dispersant is "Alkanol DOA", i.e. an oil additive in the form of a terpolymer from a mixture of 50 parts by weight of octadecenyl methacrylate, 10 parts by weight of diethylaminoethyl methacrylate and 40 parts by weight of styrene by polymerization in bulk, solution or dispersion with conventional initiators, such as oxygen-supplying compounds, e.g. benzoyl peroxide and azo compounds such as a, a-azodiisobutyronitrile. The polymerization is preferably carried out in an inert atmosphere (N2 or CO2) at normal temperatures (30 to 150 ° C, depending from the catalyst, preferably 50 to 70 ° C for α, α'-azodiisobutyronitrile as a catalyst).

The polymerization is carried out essentially to the end for all To remove unpolymerized monomers, the residual proportion of monomers should be a maximum Make up 15%.

The above terpolymer is dissolved in kerosene (50:50). The terpolymer is with regard to the various components selected with a view to optimal Balance between.

polar and oil-soluble groups. It has a medium molecular weight of about 50,000.

Further useful dispersants can be found in US Pat. No. 3,048,544, such as alkyl methacrylate maleic anhydride polymer, malinimide polymer, polymers of Reaction products of alkyl methacrylate, polyethylene glycol methacrylate and maleic anhydride and polymers from one Reaction product of alkyl methacrylate, polyethylene glycol methacrylate and the imine of maleic anhydride and tetraethylene pentamine, polyglycol-substituted Polyesters (U.S. Patent 3,083,187) and polyglycol substituted polyamides (U.S. Patent 3,083,188).

The fourth component of the suspension developer of the first type is a Pigment. Any pigment is suitable for this, as is usually the case for suspension developers is applied. These are generally fine powders that are opaque in bulk and able to accept a corresponding electrostatic charge. You are in that Solvent system insoluble. There are different types that can be used for this, such as metal powder (Aluminum), powder of metal oxides (magnetic iron oxides), metal salts (cadmium selenide, Lead iodide, lead chromate), Cyan Blue GT 55-3295 (C.I. 71160 - U.S. Patent 2,486,351), Cibacron Black BG, Cibacron Turkish Blue G, Cibalon Black BGL, Orasol Black BRG, Orasol Black RBL, Acetamine Black CBS, Crocein Purple NEX (C.I. 27290), Fiber Black VF (C.I. 30235), Luxol Fast Black L (Solv. Black 17), Nigrosin Base 424 (see I. 50415 B), Ölschwarz BG (Solv. Black 16), Rotalin Black RM, Sevron Brilliant Red 3 B> Basic Black DSC, Hectolene Black, Azosol Brilliant Blue B (Solv.Blue 9), Azosol Brilliant Green BA (Solv. Green 2), Azosol Fast Brilliant Red B, Azosol Fast Orange RA (Solv. Orange 20), Azosol Fast Qellow GRA (C.I. 13900 A), Basic Black KMPA, Benzofix Black CW-CF (C.I. 35435), Cellitazol BNFV Ex Soluble CF (Disp. Black 9), Celliton Fast Blue AF Ex (Disp.Blue 9), Cyper Black IA (Basic Black 3), Diamin Black CAP Ex (C.I. 30235), Diamond Black EAN Hi (0.1. 15710), Diamond Black PBBA Ex (C.I. 16505), direct deep black EA Ex OF (C.I. 30235), Hansa Yellow G (C.I. 11680), indanthrene black BBK (C.I.59850), Indocarbon CLGS (C.I.53295), Katigen deep black NND Hi (C.I. 53190), Nyliton Black B, Palatine Fast Black WANA (C.I.15711), Rapidogen Black 3 G (Azoic Black 4), Sulfoncyanin Black BA-CF (C.I.26370), Zambezi Black VD Ex (C.I.30015), Azo Oil Black (Solv. Black 12), Iosol Blue 6 G (Solv. Blue 30), Spirit Nigrosine SSB (C.I. 50415), Methyl Violet T (C.I. 42535), Rubanox Red CP-1495 (C.I. 15630), Victoria Blue Molybdate (C.I. 42595), Black M toner, i.e. a mixture of carbon black and black dyes, precipitated on a lacquer toner 8100, i.e.

a mixture of carbon black and black dye, precipitated onto one Lack, Raven 11 RuB d.i. Carbon black with a fineness of about 25 nm, Statex B-12 d.i. Furnace soot with an average size of 33 nm and chrome green.

The fifth component of a suspension developer of the first type is the tax substance. As such, control substances are more electrostatic in liquid development Images known they must be soluble or dispersible in a paraffinic Solvent system and the charging of the fine pigment particles effect or improve.

Examples are Aerosol OT d.i. Di-2-ethylenehexyl sodium sulfosuccinic acid, Aerosol gRd.i. Ditridecyl sodium sulfosuccinic acid, which is aluminum, chromium, zinc and Calcium salts of 3, 5-dialkylsalicylic acid, in which the alkyl group is propyl, isopropyl, Butyl, isobutyl, tert-butyl, amyl, isoamyl and other alkyl groups up to C18 are, or these salts of dialkyl-y-resorcinic acid, isopropylamine salt of dodecylbenzenesulfonic acid, Aluminum, vanadium or tin resinates (the metal resinates are made by adding a solution of metal sulfates to a solution of sodium drinate), Cobalt, iron, lithium, tin and manganese octoate, OLOA 1200, di. a partially imidized Polyamine with oil-soluble polyisobutylene chains and free secondary amines (density at 250C API 22.9 or 0.92 g / cm3, flash point (Cleveland open cup) 1200C, Viscosity at 99 ° C 400 SSU, color according to ASTM D-1500 L55D, nitrogen content 2%, Alkalinity (SM-205-15) 43); Soybean lecithin, aluminum salt of a 50:50 mixture the mono- and di-2-ethylhexyl ester of phosphoric acid, zinc, lead, supfer, cadmium, Aluminum and lisen stearate, zinc and aluminum palmitate, aluminum oleate, copper, Manganese, cobalt and lead linoleate, manganese linol resinate, "Nalcamin G-14II (1- / 2-hydroxyethyl] -2- [mixed Pentadecyl and heptadecyl 7-2-imidazoline, linoleum resinates are metal soaps made from tall oil.

The various components of the suspension developer of the first kind are chemically inert to each other at room temperature and also to the components of the suspension developer of the second kind. All the components of the developer of the first Kinds are selected and mixed solely for their physical nature Properties and not in terms of chemical interactions. Under the conditions of use And the components are heat-stable. A suspension developer of the first kind in one electrostatic development bath does not gel under the working conditions, i.e. at a temperature up to 52 ° C. This heat stability and non-gelation will transferred to the components of the developer of the second type in the invention Developer.

The invention is illustrated by the following examples for a suspension developer first type further explained in the form of a concentrate.

Example 1 40 g "Krumbhaar 484" 15 g "Toner 8100" 15 g "Spirit Nigrosine SSB "5 g" Raven 11 "50 g" Alkanol DOA "150 cm3" Shell Sol 71 "2 g manganese linoleate 2 g aluminum stearate Example 2 25 g "Nevchem 100" 9 g "Toner 8100" 9 g "spirit Nigrosine SSB "120 g" Shell Sol 71 "0.25 g aluminum resinate 17.5 g" Alkanol D04 " Example 3 55 g "Resin NC-11" 17.5 g "Alkanol DOA" 182 g "Shell Sol 71" -0.5 g aluminum stearate 28 g Cyan Blue GT 55-3295 Example 4 25 g "Staybelite" 20 g "Alkanol DOA" 10 g mineral oil 15 g "Toner 8100" 9 g "Statex B-12" 100 g "Isopar K" 1 g stannous octoate That Mineral oil is used to slightly increase the viscosity and thus the sedimentation to reduce the insoluble constituents and finally to prevent drying out of the Concentrate with the formation of crusts or lumps in the pulling part.

Example 5 55 "Resin NC-11" 17.5 g "Lube Oil 564" 1 g aluminum stearate 182 g "Isopar H" 30 g pulveris. Cadmium Selenide Example 6 25 g "Nevchem 100" 20 g "Alkanol DOA" 10 g polymerized castor oil 15 g "Black M Toner'1 9 g" Statex B-12 "100 g" Isopar K "0.5 g cobalt octoate (12% solution in mineral oil) The polymerized Castor oil is used for the same purpose as mineral oil.

Example 7 25 g "Foral 85" 20 g "Alkanol DOA" 10 g polymerized Castor oil 15 g "Toner 8100" 9 g "Statex B-12" 100 g "Isopar G" 0.5 g aluminum stearate Example; 8 25 g "Nevchem 100" 20 g "Alkanol DOA" 10 g polymerized castor oil 15 g "toner 8100 "9 g" Statex B-12 "100 g" Isopar K "0.5 g cobalt octoate (12% solution in mineral oil) Example 9 25 g “Staybelite Resin” 20 g “Alkanol DOA” 10 g polymerized castor oil 15 g "Toner 8100" 9 g "Statex B-12" 100 g "Isopar G" 5 Trop # aluminum resinate (10% Solution in "Isopar G") Example 10 25 g "Staybelite Resin" 20 g "Alkanol DOA "10 g polymerized castor oil 20 g" Statex B-12 "4 g" Cyan Blue GT "1 g aluminum stearate 100 g "Isopar K" All of these concentrates are made by mixing the ingredients in a ball mill and at room temperature or above, e.g. 4300, longer Time, e.g. grinds for 24 hours.

The second type of suspension developer (US Pat. No. 3,753,760) consists of a solvent system, possibly a dye or pigment1 and a complex one Substance containing a multiplicity of polymeric units, at least one of which is solvated in the solvent system and at least one is unsolvated is; the coloring agent can optionally be present as a chromophore in the molecule At least one of the polymer units is resinous and serves as a fixing agent. the unsolvated polymeric unit represents in the solvent system which the continuous phase is a solid with a fineness of 25 nm to 25 μm and that for electrophoretic deposition for image construction on the base, e.g. the electrostatic attraction between the particles and the latent electrostatic image on the print carrier is used.

The solvated polymeric units hold the complex substance in suspension, avoid its settling and thus act as a dispersant. As a result, the complex molecule contains components of several functions of the suspension developer of the first type. The polymeric units that give the molecule its resinous character, should be either the solvated or the unsolvated or both. This complex molecule is said to be "tailor-made", so to speak, i.e. it is an artificial one constructed molecule in which a single compound fulfills several functions, which are necessary in developers of the first type and in a variety of chemical Individuals are present. A control substance is expediently also in the suspension developer of the second kind.

Of particular importance for the suspension developer of the second kind is the solvent system. The solvent system affects the selection of the specifically applicable complex substance. Once there is the solvent system selected, certain parameters for the constituents result from this the suspension developer of the second kind, in particular the complex molecule. Basically any solvent system that is compatible can be used with the developer of the first kind; it must be within the intended device of the developer according to the invention can be applied. Is preferred in developers first and second kind that its solvent system the same, in other words the suspension developer according to the invention has a non-polar solvent system on how it is usually used for the imagewise deposition in the context of electrostatic Applies reproductive processes on a large scale.

However, in the developer of the present invention, not only one can be used use a non-polar but also a polar solvent system, provided that that this is accordingly compatible. Because the developer with non-polar solvent have further practical significance, the invention will hereinafter be applied to a non-polar one continuous phase of the solvent system further explained. As a solvent system organic compounds of the above properties are suitable, as they are in the context of Solvents for the suspension developer of the first type have been mentioned. According to the invention a single solvent system is used for both types of suspension developer at.

The suspension developer of the second type is in principle a "latex developer", because it has the appearance of a natural latex, since it is made of a continuous liquid phase, in which there is an amphipathic polymer as the disperse phase is located. The term "latex" refers to a colloidal suspension of a synthetic Polymers in any liquid as obtained by Emulsion or suspension polymerization. An "amphipathic" substance has an affinity to two different substances, e.g. oil and water or two different phases, so that the one polymeric unit of the amphipathic polymer from the phase to which it has affinity, is solvated, so by the solvent system and the other polymeric unit is not solvated and formed by the same phase thus the disperse phase; as mentioned above, the amphipathic unites Polymer, the fixing agent and the dispersing agent and optionally also the color component in the form of one or more polymeric units or

chromophoric units. This complex molecule, i.e. the amphipathic Polymer1 acts as a molecule and not a mass including pigment particles it, a narrow particle size distribution of the unsolvated particles, which ultimately be deposited on the print carrier by electrostatic development for the Image composition.

It is desirable that the grain size distribution of the unsolvated Particles in the second type of suspension developer within two orders of magnitude, preferably within an order of magnitude. That justifies the name '' monodisperse ".

The second type of suspension developer is prepared as follows: First the solvent system is selected, e.g. a non-polar solvent, like a petroleum fraction; however, other solvents, such as polar solvents, e.g. water1 can be used.

It must be pointed out at this point that the Deposition by electrostatic phenomena, e.g. electrophoresis, not necessarily non-polar solvents for both a suspension developer and first of the second kind required.

There are also suspension developers based on water known (U.S. Patent 3,425,829). Other useful solubilizing systems are besides petroleum fractions and water alcohols, e.g. those with 1 to 6 carbon atoms (ethylene glycol), ethers (ethyl isobutyl ether, Methyl isopropyl ether, C1-G4 alkyl monoethers of ethylene glycol and dioxane), ketones (Acetone, methyl ethyl ketone, methyl isopropyl ketone, ethyl isobutyl ketone), esters (ethyl acetate, Amyl acetate, butyl propionate and the acetates of mono-C1-C4-alkyl ethers of ethylene glycol) as well as halogenated hydrocarbons (chloroform, ethylene dichloride, monochlorobenzene and freon).

After selecting the solvent system, the polymeric framework molecule becomes selected for the second type suspension developer, which is in the solvent system is solvated, i.e. which is soluble up to the limit of solution.

This is followed by a graft or block polymerization or copolymerization carried out in such a way that the unsolvated polymeric chains are chemically are bound to the solvated polymer skeleton.

The mechanism by which these chains are attached to the scaffold polymer does not matter. For example, the chains can be formed first and then be grafted onto the scaffold polymer or else a graft monomer first reacted with the framework polymer, whereupon this monomer then polymerizes is with further graft monomers in the presence of the solvent system.

The unsolvated polymer unit, i.e. the part or chains, derived from a monomer, which is usually wise and preferably from the solvent solvated, reduces the required reaction time and avoids the need for a stabilizer or one multiple solvent system for the developer of the second kind. As the reaction progresses towards the formation of the chains The addition of the monomers to the framework polymer, i.e. the newly formed chains, increasingly unsolvated and eventually become the unsolvated polymers Units that form the disperse phase, despite the fact that the polymeric backbone is still solvated. This conversion initially causes a conversion the clear solution of the solvated backbone polymer and the solvated monomers first in a slightly cloudy state, which then wnd more and more cloudy with increasing Time until a latex is finally formed.

You can also do the opposite by using an unsolvated skeletal polymer is partially solvated by graft or block polymerization.

As mentioned above, suspension developers are currently found in practice to a large extent, especially for use xerocopy,. for these developers will be in general Petroleum fractions as dealt with in the discussion of the developers of the first kind have been applied.

This solvent system will also be used for the complex substance; however, a different solvent system can also be used here.

Assume that the solvent system for the toner is of the second type a petroleum fraction, a framework polymer is selected which is made from such a petroleum fraction is solvated. A frequently used petroleum fraction is odorless white spirit, in which various polymers dissolve, such as naturally occurring high polymers, e.g. raw rubber, refined oxidized linseed oil, degraded rubber and synthetic Polymers such as alkyd resins, polyisobutylene, polybutadiene, Polyisoprene, Polyisobornyl methacrylate, acrylic acid polymers of long chain esters of acrylic or Methacrylic acid such as stearyl, lauryl, isodecyl, octyl, 2-ethylhexyl and hexyl; Butyl ester of acrylic or methacrylic acids, polymeric vinyl esters of long-chain acids, such as Vinyl stearate, vinyl laurate, vinyl palmitate and vinyl myristate, polymeric vinyl alcohol ethers, including polyvinyl ethyl ether (Bakelite EDBM), polyvinyl isopropyl ether, polyvinyl isobutyl ether and polyvinyl n-butyl ether.

From the above examples it can be seen that the polymers have a structure similar to that of the solvent which solvates them, i.e. the polymers and the solvent system have a similar degree of polarity. As long as this similar polarity is maintained, mixed polymers, as well as block and graft copolymers, block and graft polymers, tetrapolymers or multiples homomers / polymers, which generally have a skeleton structure, are used, such as lauryl methacrylate butyl acrylate, t-octyl methacrylate butyl methacrylate, lauryl methacrylate glycidyl methacrylate, 2-ethylhexyl acrylate / acrylic acid, isodecyl methacrylate / diethylaminoethyl methacrylate and vinyl toluene / butadiene; Terpolymers, such as lauryl methacrylate / isodecyl methacrylate / methyl methacrylate, Stearyl methacrylate / cyclohexyl acrylate / methacrylic acid, octyl acrylate / crotonic acid / dodecyl methacrylate, Glycidyl methacrylate / stearyl methacrylate / lauryl methacrylate, lauryl methacrylate / octyl methacrylate / glycidyl methacrylate and isodecyl methacrylate / stearyl methacrylate / acrylic acid and tetrapolymers, e.g., N-vinyl pyrrolidone / butyl acrylate / lauryl methacrylate / stearyl methacrylate and acrylic acid / stearyl acrylate / methyl methacrylate / isodecyl acrylate.

The framework structure can optionally be formed with or without chains will be in a different solvent than it will ultimately be applied i.e. in a different solvent than that of the developer of the second kind other solvent can either be extracted or left as part a multiple solvent system in the second type toner. Some monomers, that would be used to build the backbone polymer are made from white spirit or other solvents are not sufficiently solvated for the developer of the second type, to achieve a desired polymerization therein. In such a case carry out a copolymerization with an insufficiently solvated monomer in a solvent with a higher K.B. number with another monomer, which is solvated by white spirit, as long as the resulting copolymer is sufficient Contains amounts of the second monomer, so that ultimately the backbone polymer from white spirit can be solvated. Such a Mischpolymerisati n can, for example carry out in benzene, the resulting copolymer is precipitated with methanol, freed from solvent, dissolved in white spirit and now serves as a framework polymer during the graft or block polymerization or copolymerization.

Above discussion of the synthetic polymers for the scaffold polymer, which are also often referred to as forerunners are in a white spirit Entlicklersystem not limited to addition polymers, but also condensation polymers can serve as a scaffold or precursor as long as they are supported by an appropriate solvent be solvated, such as self-condensed polymer of 12-hydroxystearic acid.

There is also no restriction on the suspension developer of the second type with regard to the monomers for the preparation of the polymeric components. For a System based on The following are suitable examples of white spirit Framework polymers: (a) Homopolymers of C4 - C22 esters of acrylic or methacrylic acid (Polyhexyl, polyisodecyl, polylauryl, polyte-dradecyl and polystearyl methacrylate or acrylate with molecular weights between about 103 to 106, preferably at least (b) Copolymers of the homopolymers listed under (a) with methyl, ethyl, Isopropyl and propyl esters of acrylic or methacrylic acid with the proviso that the ratios of the unsolvated to the solvated monomers in the corresponding Ratio must be observed in order to solvate the mixed polymer in white spirit to ensure; (c) Copolymers of the above methacrylic and acrylic acid esters with monomers containing other functional groups, such as acrylic, methacrylic, croton, fialein, Atropic, fumaric, itaconic, citraconic acid, acrylic, methacrylic or maleic anhydride, Acryloyl chloride, fiethacryloyl chloride, acrylic or methacrylonitrile, acrylic or Methacrylamides and their derivatives, hydroxyethyl methacrylate or acrylate, hydroxypropyl methacrylate or acrylate, dimethylaminomethyl methacrylate or acrylate, dimethylaminomethyl methacrylate or acrylate, diethylaminomethyl methacrylate or acrylate, diethylaminoethyl methacrylate or acrylate, t-butylaminoethyl methacrylate or acrylate, allyl alcohol and its Derivatives, cinnamic acid and its derivatives, styrene and its derivatives, methallyl alcohol and its derivatives, propargyl alcohol and its derivatives, indene and its derivatives, Norbornene and its derivatives, vinyl ethers, vinyl esters and other vinyl derivatives, Glycidyl methacrylate and acrylate, mono- and dimethyl maleate, mono- and Diethyl maleate, Mono-n-butyl maleate, monobenzyl maleate, mono-2-ethylhexyl or mono-n-octyl maleate and finally mono- or dimethyl fumarate and mono- and diethyl fumarate; (d) homopolymers Olefins (butadiene, isoprene, isobutylene) and copolymers thereof with those listed under (b) Monomers; (e) terpolymers and tetrapolymers thereof; (f) polycarbonates, polyamides, Polyurethanes and polyepoxides.

Polymer chains are now attached to the selected framework polymer (precursor) different polarity attached to that of the solvent, namely by grafting or bulk polymerization which does not solvate from the solvent system and are thus able to form a disperse phase. It does either by block or by graft polymerization, as just stated.

Suitable monomers are those that form polymers that are too polar are to be solvated in white spirit; these are vinyl acetate, methyl, ethyl, Propyl, isopropyl, hydroxyethyl, hydroxypropyl acrylate or

-methacrylate, acrylic or methacrylonitrile, acrylic or methacrylamide, Acrylic or methacrylic acid or anhydride, monomethyl, monoethyl, monobutyl, Monobenzyl, mono-2-hexyl, flono-n-octyl maleate, fionomethyl, monoethyl fumarate, Styrene, vinyl toluene, maleic acid or anhydride and crotonic acid or anhydride. Mixed polymers, terpolymers and polymers of greater complexity with corresponding Polarity can be related to the solvated backbone polymer chosen to form the Latex can be introduced.

Graft polymerization is used to produce the latex and do not represent any ethylenic or other unsaturated bonds for grafting available in the backbone polymer, so can polymers on a saturated backbone polymer Chains are grafted on by activation as they are known. These well-known Activations, however, result in random activation by an initiator on the framework molecule, which then initiate the polymerization of the graft monomer. A preferred method, rather than random activation, is design of the framework molecule for the suspension developer of the second kind, in that the ethylenic Parts containing double bonds or hanging parts are formed, which as starting points for the activation of the initiator for an in situ graft polymerization to serve.

A framework molecule that can be solvated by white spirit can be used for this purpose apply, which is made from a copolymer of stearyl methacrylate-glycidyl methacrylate (27: 1 monomer ratio with a molecular weight of e.g. 10,000-150,000). Methacrylic acid can be reacted with this polymer in the presence of a polymerization inhibitor, to form ethylenically unsaturated bonds for subsequent activation by esterification and finally in situ polymerization or copolymerization.

In this way, precursors for a graft polymerization or produce interpolymerization.

The term "precursor" denotes the above framework polymer, as well as activated framework polymer, which can be used for latex formation.

There are a wide variety of reactions for introducing groups containing pendant ethylenic double bonds into the precursor. If the monomer * is referred to as monomer 1 (this monomer is at least one of two monomers which form the backbone chain and is present in a small proportion * for the backbone chain and which contains multiple bonds before the interpolymerization, which have reacted during the interpolymerization, but are still reactive Groups present) and the additional monomer used to form a precursor is monomer 2 (which latter is selected with regard to the reactivity with monomer 1), then there are z0B0 the following options: Monomer A glycidyl methacrylate or acrylate acrylic or methacrylic acid chloride acrylic acid Methacrylic acid maleic acid crotonic acid alkyl hydrogen maleates alkyl hydrogen fumarates vinyl isocyanate cyanomethylacrylate vinyl-ß-chloroethylsulpho @ methacrylic anhydride acrylic anhydride, maleic anhydride vinyl sulfonic acid vinyl phosphoric acid Monomer B acrylic acid methacrylic acid maleic acid fumaric acid atropic acid allylamine vinylamine-hydroxyethyl- £ aethac and -acrylate flydroxypropyl-methacrylate and -acrylate acrylamide methacrylamide allyl alcohol allylamine vinylamine vinylpyridines glycidyl-methacrylamine vinylamine allylamine-dialkylamine-vinylamino-methacrylates allylamine-alkyl-methacrylamine-vinylamine-allylamine-allyl-methacrylamine-vinyl-amine-allylamine-allyl-methacrylamine-vinyl-amine-allylamine-allyl-methacrylamine-vinyl-amine-allylamine-allyl-methacrylam-vinyl-amine-allylamine-dialkylamine-vinyl-amine-methacrylates Hydroxyalkyl methacrylate Gly ci dyl methacrylate vinylamine allylamine Hydroxyalkyl methacrylate Allyl alcohol N-hydroxymethyl methacrylamides Alkoxymethyl methacrylamides The procedure can also be reversed, ie monomer 2 can be copolymerized into the framework polymer, whereupon monomer 1 is condensed to form the precursor.

Once the precursor is formed, the latex is made, iidem the polymerization of the monomer or comonomers for the additional part, which is preferably * the disperse phase, takes place in connection with the precursor namely in a liquid system in which the precursor or the additional part (polymeric unit) completely solvated and the other part (polymeric purity) is not fully solvated. In the preferred form of suspension developer of the second type, the polymer or polymers are polymerized to form substances which are in the solvent system are not solvated, e.g. in a system based on white spirit and A stearyl methacrylate / glycdiyl methacrylate / methacrylic acid precursor are useful Monomers for the additional part methyl methacrylate or arylate, methyl methacrylate or acrylate, isopropyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinyl toluene, Acrylonitrile and flethacrylonitrile as homopolymers and copolymers or any of the above Substance with maleic anhydride, crotonic acid, acrylic acid, monomethyl, monoethyl, Monobut-v-1, monobenzyl maleate, mono-2-hexylethyl maleate, mono-n-octyl maleate, flonomethyl or Monoethyl fumarate, methacrylic acid, dimethylaminomethyl methacrylate or their terpolymers or tetrapolymers.

During this polymerization, some of the monomers also polymerize to the. solvated backbone polymer to form a block copolymer, the one Form of the complex "tailor-made" molecule of the suspension developer second Type and to stabilize disperse polymer particles that are not grafted, to serve.

The disperse phase, which is essentially the unsolvated polymer Part of the complex amphipathic resin * presence of or in is, optionally also includes ungrafted, unsolvated polymer particles. Although not particularly desirable because of their unsolvated form are, they are permissible and, moreover, they can electrophoretically like that behave so that they can be selectively attracted to electrostatically different charged areas, so that an electrostatic reproduction is established with them leaves.

With a latex of the above type with the complex tailor-made amphipathic Polymers perform the functions of fixation in a single molecule Bonding to the substrate and the dispersion combined to form this polymer behaves accordingly in the electrostatic system. The polymers take the appropriate Charge on and become fixed, but not because of the solvated units settled as internal dispersion takes place.

The complex tailor-made polymer together with the solvent is itself already in connection with a control substance in a dispersion developer second kind useful as there is no visible selective deposition on one another charged substrate, e.g. for the image build-up, which is then suitable as a planographic printing form . In addition, the second type of suspension developer should also have a coloring Component from black to white contain, in other words, the suspended ones Latex particles have the desired color so that a color image is formed when the image is built up results, which is clearly visible and in the desired color.

Pigments or dyes can be added to the latex for coloring and therein in a ball mill or with the help of a mixing process under high Physically * needs to form shear forces disperse.

Any pigment, as is customary, can be used as the pigment used for electrostatic suspension developer; They are very fine, red and opaque in bulk; they are insoluble in the solvent system; as Pigments can be used with substances as discussed in the discussion of the suspension developer of the first kind have been described.

If the disperse phase is colored with a pigment, it should preferably non-reactive with the amphipathic polymer and with the ingredients of the developer of the first type. It is believed that the pigment particles adhere to the unsolvated Latex unit can only be held by second order forces, i.e.

they are thus in the disperse phase of the complex amphipathic Resin held.

Another option is to add pigments or dyes to the latex to bind chemically, in other words to the complex molecule. This chemical Binding can take place to the precursor prior to graft or block polymerization additional chains or attached to the chains, which are then grafted or by block polymerization be introduced into the molecule.

As for the dyes as opposed to the pigments, so can these be used for staining; of the amphipathic polymer and in particular the disperse, unsolvated phase by being driven by second order forces or held by surface adsorption; however, the dyes can also are chemically reacted with the amphipathic polymer either after it Formation or with the precursor or on the chains, which are then grafted on or are polymerized.

The dyes are bound to the second type of suspension developer with second order forces, or surface adsorption, by heating the latex and the dye, e.g., 1 to 12 hours. An example of such dyes are disperse dyes for coloring polyesters and copolymers of acrylonitrile and vinyl chloride, such as Latyl Orange 3R (G.I. Disperse Orange 26), Oalcosperse Yellow GL (C.I. Disperse Yellow 57), Calcosperse Blue B (C.I. Disperse Blue 77), Foron Blue BGL (C.I. Disperse Blue 73); Latyl Brown MS (C.I. Disperse Brown 2) and Latyl Violet BN (C.I. Violet 27). Basic dyes for polyacrylates can also be used, such as Sevron Blue BGL (C.I.

Basic Violet 15), Deorlene Brilliant Red 3B (C.I. Basic Red 26), Oalcozine Acrylic Blue G (C.I. Basic Blue 38), Astrazon yellow-brown GGL (C.I. Basic Orange 30) and Astrazon red 5 BL (C.I. Basic Red 24).

A disperse, unsolvated phase of a copolymer is preferred containing reactive groups which react with the reactive groups of an earomophore are suitable, e.g. basic groups for reaction with acidic dyes. So can for example, a disperse phase of a latex can be used, which is a terpolymer of acrylonitrile, 2-flethyl-5-vinylpyridine and vinyl acetate.

Such a terpolymer can be reaction colored with acidic groups containing dyes, such as Pontacyl Brilliant Blue A (C.I. Acid Blue 7), Calcocid Brilliant Blue FFR (C.I. Acid Blue 104), Femazo Brown N (C.I. Acid Brown 14), Crocein Scarlet N (C.I. Red 73), Oxanal Yellow I (see I. Acid Yellow 63) and Benzyl Black 4BN (G.I. Black 26A).

Such a complex tailor-made molecule has three functions, namely dispersants for fixation and for Staining. This Suspension developer has an essentially monodisperse phase, i.e. very much small variation in grain size.

Another way to make a complex trifunctional The amphipathic resin molecule consists of a disperse copolymer containing Acid groups, react with basic dyes. An example of one Latex is the mixed polymer of vinyl acetate and maleic acid.

This can be dyed with dyes containing basic groups, such as Magenta (0.1. Solvent Red 41, C.I. Wr.42510B), Crystal Violet (C.I. Solvent Violet 9, C.I. No. 42555B), Bismarck Brown (C.I. Solvent Brown 12, C.I. No. 21010B), Victoria Blue BA (C.I. Solvent Blue 4, C.I. No. 44045B), Victoria Blue R (C.I. Solvent Blue 6, C.I. No. 44040R), Victoria Blue 4I2 (C.I. Solvent Blue 2, C.I. No. 43563B), Copying Black SK (C.I. No. 11975), Janus Green B (C.I. No.

11050), Auramine O (C.I. Solvent Xellow 34, C.I. No.

41000B), Victoria Green (C.I. Solvent Green 1, C.I. No.42000B), and Rhodamine (C.I. Solvent Red 49, C.I. lio. 45170B).

Another method of making trifunctional amphipathic Resin molecules is the chemical reaction that binds the paint component to you precursors modified by block or graft polymerization by adding a disperse Phase of a copolymer is formed, which electron accepting groups contains, like then maleic or crotonic acid (Lewis acid), react with dye can precursors. An example of this is a terpolymer of maleic anhydride, Vinyl acetate and styrene on the solvated framework, reacted with a dye precursor, such as bis (p-dimethylaminophenyl) benzotriazyl methane. One with such a substance produced suspension developer of the second type gives a deep blue precipitate.

Is pigment or dye reacted with the added groups of the disperse phase, the amount of pigment can vary from 5 to theoretically 100 90 of the stoichiometrically required amount. However, about 10 to 50 is preferred % of the stoichiometric amount with optimal results at about 25 yo.

There is another way of staining the latices, namely by coloring the precursor itself, i.e. the backbone polymer as solvated Phase and not the disperse, unsolvated phase. For coloring the As a precursor, various methods above can be applied. Particularly preferred however, polymerizing a dye into the precursor itself is before the unsolvated chains are grafted or polymerized onto the framework polymer will.

One can of course also use the disperse phase as well as the solvated phase Stain precursors.

As already explained in detail, you get a stable latex, which contains practically all the necessary components of the second type of suspension developer, namely the solvent system with the complex amphipathic resin, which has solvated and unsolvated polymeric units and which is trifunctional is separate in terms of fixation, dispersion and staining or inclusive n, unreacted colorant. It is also very useful in the suspension developer second kind of introducing one or more control substances, which is very positive affects the color depth and contrast. In electrostatic development a control substance of the appropriate concentration is required in all cases. Of the or the tax substances for Suspension developers of the second type can be the ones used for suspension developers of the first kind.

One uses in the developers according to the invention preferably for both types of suspension develop the same control substance.

The proportions of the various components of the suspension developer the first and second kind can fluctuate in large areas, according to an indication of the quantity or a quantitative ratio of the components for the suspension developer according to the invention appears largely meaningless. These proportions vary with the type of copier, the climate, the machine speed, the type of paper and the experience of the personnel operating the machine, to name just a few factors.

There can also be great fluctuations in the coloring material with the the desired intensity of the dye or pigment or the image. Quite Generally speaking, one can say that the proportions of the individual constituents-> should lie higher or lower <together>, although this is not in a strict one Relationship must be the case.

Taking into account all of these factors and to facilitate the Production of the suspension developer according to the invention should be kept to a minimum and maximum proportions in 1 apply as guide values: For fixing in the developer first Type 0.05 to 5 g; for dispersion in the developer of the first type 0.025 to 5 g; pigment for developers of the first type 0.025 to 5 g; Tax substance for developers of the first kind 0.0005 g to 0.5 g.

Amphipathic polymer for developers of the second type containing one Dye or pigment either chemically bound or by surface adsorption forces held 0.03 to 30 g.

Amphipathic polymer for suspension developers of the second type, if this is not a coloring agent which has reacted or is held by it contains, about 0.03 to 30 g; coloring agent for developers of the second kind, if it 0.03 to 30 g is not reacted or bound to the amphipathic molecule; Tax substance for developers of the second type 1 x 10 6 to 10 g; Remainder solvent system.

Examples for developers of the second kind: Refer to the first nine examples on the precursors, i.e. the formation of the framework polymers, i.e. the framework that amphipathic molecule, its further implementation in the following examples, which relate to the production of the latices from the precursors - follows.

B e i s p i e 1 11 In a clean, dry 226.8 cm3 glass vessel 100 g of 2-ethylhexyl acrylate and 1 g of azobisisobutyronitrile as a polymerization initiator brought in. The glass vessel was placed on a water bath of 75 + 2 ° C and approx Polymerized for 30 min. The temperature rose in about 5 minutes after the start of the reaction to 120 ° C, it was cooled to 90 ° C, the glass vessel was filled with a water bath, loosely covered and in a hot air oven at 90 ° C overnight to complete leave the polymerization.

A water-clear, heavy syrup was obtained.

B e i s i e 1 12 400 g petroleum ether (boiling range 90 to 1200C) were in a 1 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and Brought dropping funnel and kept under moderate reflux at normal pressure. One Solution of 1.2 g of azobisisobutyronitrile in 200 g of 2-ethylhexyl acrylate and 6 g of glycidyl methacrylate were dropped into the refluxing stream at such a rate that the addition was completed in 3 h. The reaction mass could still further at normal pressure Remain at reflux for 2 h, whereupon 4 g of acrylic acid, 0.14 g of 2,6-di-tert-butylphenol and 1 g of lauryl dimethylamine was added.

The whole thing was flushed under nitrogen for a further 12 hours at normal pressure kept at refluxing until about 25% of the glycidyl rings of the copolymer were esterified. The product obtained was a straw yellow viscous liquid.

Example In a 500 cm3 reactor with stirrer, thermometer, reflux condenser and dropping funnel were added 250 g of "Isopar E", heated to 93 + 100 and 250 g of 2-ethylhexyl acrylate containing 1.5 g of azobisisobutyronitrile 1 added dropwise within from 3 h. The mixture was left at 93 + 100 for an additional 3 h to complete the reaction held.

All reactions took place under normal pressure. One got one easily viscous straw-colored liquid.

EXAMPLE 1 14 In a 1 liter reaction flask equipped with a stirrer, thermometer and reflux condenser, 400 g of petroleum ether (boiling range 90 to 1200 ° C.) were introduced and brought to moderate refluxing under normal pressure. A solution from 194 g of lauryl methacrylate, 6 g of glycidyl methacrylate and 3 g Benzoyl peroxide paste (60% by weight in dioctyl phthalate) was added via the 250 cm3 dropping funnel in the reflux condenser. The monomer mixture was added dropwise over a period of 3 hours At refluxing for a further 40 minutes, 0.05 g of lauryldimethylamine were introduced and kept boiling for another hour. Then there were 0.1 g of hydroquinone and 3 g of methacrylic acid introduced and held at refluxing under a nitrogen purge until about 52 so the glycidyl groups were esterified. This took about 16 hours. One received a slightly viscous, straw-colored liquid.

EXAMPLE 1 15 Example 14 is repeated, but the esterification only led up to 25%.

EXAMPLE 16 In a 5 liter glass flask with a heating jacket, stirrer, The thermometer, nitrogen passage and reflux condenser were 2.4 kg of "Isopar G" introduced and heated to 110 + 100 (heating medium triethylene glycol). The heating medium could quickly be exchanged for cooling water.

When the solvent reached the above temperature it was 1.0357 kg of isodecyl methacrylate, 36 g of glycidyl methacrylate and 18 g of a 50% strength by weight benzoyl peroxide paste in dioctyl phthalate was added dropwise over the course of 3 h at the same rate. To When the addition was complete, the reaction mass was kept at the reaction temperature for a further 30 minutes held, then 3 g of lauryldimethylamine added and a further 1 h at the reaction temperature left.

0.6 g of hydroquinone were then introduced and nitrogen was passed through during the esterification, then 18 g of methacrylic acid added and held at the reaction temperature until 25> ó of the glycidyl rings were esterified (about 8 h).

fian received a slightly viscous, straw-colored liquid.

EXAMPLE 1 17 In the system according to Example 16, 1.44 kg of Isopar G "brought to 110 + 100 and then 1.2786 kg of stearyl methacrylate, 32.4 g of glycidyl methacrylate and 16.2 g of 50% by weight benzoyl peroxide paste in dioctyl phthalate together with 720 g of Isopar G were added dropwise over the course of 3 h, the reaction temperature being maintained became. When the monomer addition was complete, the reaction mass was at the reaction temperature held for a further 40 minutes, then 2.8 g of lauryldimethylamine were added and 1 hour at room temperature left, finally X.54 g of hydroquinone were added and nitrogen during passed through the esterification. Then 16.2 g of methacrylic acid were added and the Maintain reaction temperature until 24% of the glycidyl rings have esterified (approx. 7 h). A slightly viscous, straw-colored liquid was obtained.

EXAMPLE 1 18 In a 500 cm3 three-necked round bottom flask with a stirrer, The thermometer, temperature probe and reflux condenser were placed in 197.8 g of Isopar G and heated to 110 + 100 with stirring, then 96 g lauryl methacrylate, 3 g glycidyl methacrylate, 0.74 g benzoyl peroxide (99%), 50 cm3 benzene and 5 g p-phenylazoacrylanilide mixed at room temperature in 30 min, with most, but not all, of p-phenylazoacrylanilide solved. This mixture was in portions of 5 cm3 at intervals of 5 min during Introduced into the boiling solvent for 3 h; the mass was stirred so that åede Portion also had the same composition1 after the last addition the reaction temperature was maintained for a further 45 minutes and then 0.25 g of lauryldimethylamine added. After a further hour at the reaction temperature, 0.05 g of hydroquinone were added introduced and nitrogen passed through. Then 1.49 g of methacrylic acid were added and the temperature of the reaction mass maintained at 110 + 100, until 25% of the glycidyl rings were esterified (about 6 h). The batch was cooled to 5000 and slowly 27 liters Methanol added while stirring continuously.

The precipitated polymer was allowed to settle in 24 hours and was decanted. It was air-dried in one hour at room temperature and then at 50 ° C. for 4 hours. It was then dissolved in 300 cm3 of Isopar G. A deep orange solution was obtained which was used for latex production.

3 e i s T) i e 1 19 In a 500 cm3 reactor with stirrer, thermometer, The reflux condenser and nitrogen inlet as well as the dropping funnel were 197.8 g of Isopar K introduced and heated to 110 + 100. A mixture of 86 g of lauryl methacrylate, 9.9 g of N-1,1,3,3-2etramethylbutyl methacrylamide, 2.97 g of glycidyl methacrylate and 0.74 g of benzoyl peroxide was placed in the dropping funnel and at a constant rate added dropwise in 3 h into the boiling solvent, while this at reaction temperature was held. The polymerization was then allowed to run for 6 hours, a sample yielded one 96,46 above polymerization. Then 0.12 g of lauryldimethylamine were added and 1 h, whereupon 0.05 g of hydroquinone was added and nitrogen was bubbled through. Then 1.49 g of methacrylic acid were introduced and the reaction temperature of 110 + 100 maintained until 25 hó of the glycidyl rings were esterified (about 9 h).

A somewhat viscous, straw-colored liquid was obtained.

The following examples illustrate the preparation of the latices for the second type dispersion developers using the above precursors.

3 e i s p i e 1 20 In a 500 cm3 reactor with stirrer, thermometer and reflux condenser were 360 g of Isopar X, 185 g of vinyl acetate and 30 g of the precursor from Example 14 and 15 g of methyl hydrogen maleate and 4 g of azobisisobutyronitrile were introduced, the reaction temperature adjusted to 85 t 20C and held for 4 h. Then there were more 2 g of azobisisobutyronitrile added to the mass and the polymer sation at the reaction temperature again for 4 hours.

A thin blue-white latex was obtained, the particle size of which was 0.04 to 0.2 / µm.

B e i s p 1 e 1 21 A mixture of 27.5 g of the precursor solution of the example 15, 30 g of methyl methacrylate, 0.5 g of methacrylic acid and 0.4 g of azobisisobutyronitrile was used together with 134 g of petroleum ether (boiling range 60 to 90 ° C) and 29.5 g of Isopar G placed in a 500 cc reactor and under slow reflux for 20 minutes Kept boiling. Then 1.4 g of a 10% strength by weight solution of n-octyl mercaptan were added added in Isopar K, a mixture of 166 g methyl methacrylate, 3.4 g methacrylic acid, 3 g of a 104o solution of n-octyl mercaptan in Isopar K and 0.4 g of azobisisobutyronitrile at a constant speed in the refluxing stream of the cooler within added dropwise from 2.5 h, then another and finally 0.5 h on the refluxing Maintained boiling and cooled to room temperature. fian received a smooth white, somewhat viscous latex, the particle size of which was 0.4 to 1 µm.

B e 1 5 p 1 e 1 22 In a 2 liter three-necked round bottom flask with a stirrer, Thermometer and reflux condenser were made from 848.5 g of Isopar K, 70.7 g of precursor solution Example 18, 471.4 g of vinyl acetate and 9.4 g of azobisisobutyronitrile were used. the The reaction mixture was kept at 860 ° C. for 4 h with constant stirring.

A pale lemon yellow latex with one particle size was obtained of less than 0.2 μm and a solids content of 31.7 e.

B e i 5 p i e 1 23 A mixture of 18 g of the precursor solution from Example 15, 110 g of hydroxypropyl methacrylate, 3 g of azobisisobutyronitrile and 200 g of Isopar K were placed in a 500 cc reactor with constant stirring; the reaction started at 78 to 800C, the temperature rose to a maximum of 1200C and then fell back to 80 ° C. The polymerization was completed in 30 minutes; a small amount of Oversized grain was removed by passing the mass through a nylon sieve, mesh size 74 µm was left. The white latex had a particle size of 0.2 µm.

B e i s p i e 1 24 A solution of 15 g of vinyl ethyl ether polymer with a reduced viscosity of 4+ 0.5 (determined on 0.1 g of polymer in 100 cm³ Benzene at 200C) and a density of 0.968 20 ° C in 285 g of Isopar G was prepared in a 500 cm3 reactor with a reflux condenser by adding the resin was stirred into the solvent at 90 ° C. in small particles over the course of 20 h. the Solution was cooled to room temperature and 185 g of vinyl acetate and 2 g of benzoyl peroxide (99 "ioig) added and heated under reflux to about 950C and at this temperature Held for 4 h. After 45 minutes the solution became cloudy, after 1 hour and 15 minutes it became so viscous that the stirrer could no longer stir and the product appeared as a thick, white cream appeared. After 2 hours the mass became thinner and after 3 hours it had a consistency a heavy cream that it holds on. After the 4 hours a solution of 1.5 g of lauryl peroxide in 30 g of Isopar G were added dropwise over the course of 30 minutes, while the Temperature was kept at 95 + 200. The mass then remained there for 3 hours Temperature. A white latex with a particle size of 0.7 to 1.5 was obtained µm.

B e i s p 1 e 1 25 A mixture of 180 g Isopar K, 100 g vinyl acetate, 15 g of precursor solution from Example 16 and 2 g of azobisisobutyronitrile was in a 500 cm3 flask with thermometer? Stirrer, reflux condenser and internal cooling coil introduced and kept for 4 h with stirring at 86 + 2 ° C; occasionally you have to cool during the initial period of the reaction. A thin white to blue-white color was obtained Latex whose particles are too small for microscopic examination. The latex had a solids content of 33%.

B e 1 5 p 1 e 1 26 In a 5 liter reactor with a heating jacket, thermometer, The stirrer and reflux condenser (Example 16) were 2.16 kg of Isopar K, 180 g of precursor from Example 15, 1.14 kg of vinyl acetate, 60 g of N-vinyl-2-pyrrolidone and 24 g of azobisisobutyronitrile Maintained at 86t 200 for 24 hours. A thin white to blue-white latex was obtained, whose fineness was so great that the particles could no longer be resolved under the microscope could become.

EXAMPLE 1 27 In a 500 cm3 reactor with stirrer, thermometer and reflux condenser, 360 g of Isopar K, 190 g of vinyl acetate, 30 g of precursor were made Example 15, 10 g of crotonic acid and 4 g of azo-bisisobutyronitrile held at 85 + 20 ° C. for 4 hours and 2 g of azo-bisisobutyroatril were added and the polymerization was then repeated for 4 hours continued at the same temperature.

A thin white latex was obtained.

B e i 5 p i e 1 28 In a 500 cm3 reactor with stirrer, thermometer, The temperature controller, reflux condenser, and internal cooling coil were 40 g of lubricating oil additive 564, 284 g Isopar K, 2.2 g benzoyl peroxide (99%) with vigorous stirring to 80 ° C Held for 2 h, then a mixture of 10 g of crotonic acid and 190 g of vinyl acetate at once added, whereupon the reaction mass turned dark brown. Then the temperature brought back to 80 ° C, azobisisobutyronitrile in portions of 0.5 g at intervals added from 10 min to a total of 4.6 g (3 h, 40 min) and then the reaction mass 2 h at 80 + # 2 ° C held. A white latex was also obtained a solids content of 35.7 Vo and a particle size <74 μm.

B e i s p 1 e 1 29 This example shows the coloring of a latex explained in which the dye probably does not react with the latex, although possibly a hydrogen bond can occur. A 100% mixture of Sudan Orange RA (Solvent Yellow 14, C.I. 12055) and Isopar K was rolled in the Eugelmühle for 4 hours; 20 g of this dispersion were added to 100 g of the latex of Example 27 and the whole Maintained at 55 to 5700 for 8 h with stirring. It was then filtered through a nylon sieve with a mesh size of 74 μm and cooled to room temperature. You got one golden orange latex.

The following examples illustrate a second dispersion developer Kind from above latices.

For example, 1,100 grams of the latex of Example 28 was placed in a 500 cc, three neck, round bottom flask introduced with stirrer, reflux condenser and thermometer and Victoria Blue Base BA (C.I. 44045B) was added. The temperature rose to 80 + 50C, at which it was held for 2 h became. The blue latex was cooled and passed through a nylon screen, mesh size 74 / umlzur Filtered removal of residual dye. The colored latex became 2.5 g of a 1% by weight solution of aluminum 3,5-diisopropyl salicylate in Isopar K. added to obtain a concentrate of the developer. 4 g of it were with 2000 cm3 Isopar K diluted on a working suspension developer. This latex is a complex polymer with solvated and unsolvated polymers Units and a coloring unit or chromophore. The tax stuff was one separate connection. Received when used in a conventional copier one blueprints.

EXAMPLE 1 31 The latex of Example 27 was admixed with 13.65 g of Victoria Blue base BA given and kept at 85 + 20C for 3 h.

The dark blue latex was passed through a nylon sieve, mesh size 74 µm, filtered and cooled to room temperature. Then the colored latex became 25 g a 1Woigen solution of aluminum salt of 3.5 di-tert-butyl-y - resorcinic acid in Isopar G added. 4 g of this concentrate were applied to a suspension developer with 2000 cm3 of Isopar G diluted which gave light blue prints.

B e 1 s p 1 e 1 32 The latex of Example 20 was given 6.8 g of auramine 0 and 6.8 g of rhodamine were added and this was kept at 85 t 20C for 3 h.

The light yellow-orange colored latex was passed through a nylon sieve, mesh size 74 µm, filtered and cooled to room temperature. Then 10 g of a 1% Solution of the aluminum salt of 3,5-dibutyl-γ-resorcinic acid in Isopar G was added and this concentrate in which the color component is part of the amphipathic polymer Molecule is 1 (10 g) with 2,000 cm3 of Isopar G for a working developer bath diluted. Extremely bright orange copies were thus obtained.

EXAMPLE 1 33 The latex of Example 20 was given 13.65 grams of Victoria Green added and heated to 85 + 2 0 for 3 h. Which was now dark blue-green latex filtered through a nylon sieve 74 / um and cooled to room temperature. Then 40 g of a solid solution of the aluminum salt of 3,5-di-tert-butyl-y resorcinic acid in Isopar G added and 4 g of this concentrate, in which the carb components Part of the amphipathic polymeric molecule was diluted with 2000 cm3 of Isopar G. Intensive, bright blue-green copies were obtained with this developer bath.

EXAMPLE 1 34 3 g of the latex from Example 25 were added at 0.25 g "Raven 11" rubbed in a mortar, 30 drops of a 1% solution of aluminum salt the 3,5-di-tert. -butyl-y-resorcinic acid added and with a small amount of Isopar K diluted for a concentrate. This concentrate was made to a volume of 2000 cm3 infused with Isopar K; good blacks were obtained with this developer bath Copies.

EXAMPLE 35 The latex of Example 27 was admixed with 13.65 g of crystal Violet (C.I. 42555B) was added and the mixture was heated to 85 + 20C for 3 h.

It was then filtered through a 74 μm nylon mesh and brought to room temperature cooled down. 0.05 g of aluminum drinate was added to the colored latex; 3 g of this Concentrate in which the color component is part of the amphipathic polymer molecule were diluted to 2000 cm³ with Isopar K.

Very good violet copies were obtained with this developer bath.

EXAMPLE 1 36 The latex of Example 27 was given 13.65 grams of magenta (C.I.-42510B) added and heated to 85 + 200 for 3 h, then through a nylon sieve 74 / U1fl filtered and cooled to room temperature. To the colored one The latex was 0.05 g of aluminum resinate and 20 g of a 10% solution of "Aerosol OT "added in Isopar K; 3 g of this concentrate, in which the color component part of the amphipathic polymer molecule were diluted with 200 cc of Isopar G.

Purple copies were obtained from this developer bath.

EXAMPLE 37 4 g of the latex from Example 29 were added with 20 drops a 1% aluminum diisopropyl salicylate solution in Isopar G and this Concentrate diluted with 2,000 cm3 Isopar K. This developer bath was used to obtain yellowish orange copies.

In all of the above examples, the suspension developer contained second Kind of just a single color component. If necessary, however, several coloring agents can also be used Means, preferably two or more, are applied by their interaction to achieve a depth of color such as brown-black, blue-black or parpur-black The suspension developer of the second kind can also be produced in other ways, namely by making the amphipathic polymer in a solvent, in which it. is completely solvated, whereupon another solvent is added in which one type of polymeric unit is not solvated. This second Solvent, however, must be miscible with the first one, 'then you can do the whole thing or remove part of the first solvent. This is an extraordinary one simple way for the production of an amphipathic block polymer as a disperse Phase. An example of this is anionic polymerization one Block polymers of polyisoprene, polystyrene and polyisoprene.

At 5 n 1 e 1 38 9.2 g of styrene were 30 cm 3 of tetrahydrofuran containing 3.3 x 10 flol sodium naphthenate as a catalyst at -800C in a three-necked round bottom flask added to a dry ice bath using a stirrer, thermometer and nitrogen bubbling. The reaction was completed in 15 minutes. fian received a living polystyrene. After finished Polymerization 6.3 g of isoprene were added (still at -800C) so that this polymerize onto the living ends of the polystyrene to form a block copolymer could.

This block copolymer solvated in tetrahydrofuran was an the living ends grafted onto a scaffold polymer by reaction with 3 g of precursor solution from Example 18 at room temperature to give the amphipathic polymer. The precursor or backbone polymer was also solvated in tetrahydrofuran. This polymer then became the solvated phase of a light solvent for the block copolymer. The block blend polymer units came out of solution the end. The nonsolvent was white spirit which solvated at room temperature Amphipathic polymers poly (styrene / isoprene) / poly (lauryl methaclylate-glycidyl methacrylate-methacrylic acid-pphenylazoacrylanilide) was added.

2 g of an above solution of the sodium salt were added to the golden yellow latex of 3,5-di-tert-butyl-γ-resorcinic acid added and to 15 g of this concentrate Given 2,000 cm3 of white spirit; golden yellow copies were obtained with this development bath.

B e i 5 p i e 1 39 100 g of the latex from Example 27 were in a 500cc three-necked round bottom flask with stirrer, reflux condenser and thermometer as well as 1.2 g Victoria Green (C.I.42000B), 2.4 g Bismarck Brown (C.I. 21010B) and 0.3 g Rhodamine Base (C.I. 45170B) and heated to 80 + 5 ° G for 2 h. The black one Latex was filtered through a nylon sieve 74 µm and with 5 cm3 of aluminum resinate solution (10% by weight) added to Isopar H; 6 g of this toner were 2,000 cm3 Isopar H diluted. Dense black copies were obtained from this dispersion developing bath.

B e i 5 p i e 1 40 To 100 g of the latex from Example 25 were 5 cm3 a 1% solution of aluminum 3,5-diisopropyl salicylate in Isopar G, 4 g of this concentrate were diluted with 2,000 cm3 of Isopar G; one got a clear one Image that was visible through light reflection at an acute angle.

For the preparation of the dispersion developer according to the invention one can Use either of the following two approaches: One is to know how stated above, simply mix the previously prepared suspension developer and although in proportions of about 0.5 to 99.5% of a developer or the other developer. The other method is to use the various ingredients to be introduced into the solvent system.

It is repeated again that the suspension developer according to the invention preferably a solvent system used which is suitable for both the developer both the first and second types are suitable, although this is not absolutely necessary. However, if two solvent systems are used, they should be compatible be. Preferably, but not necessarily, be for the two to be mixed Suspension developer applied the same control substances. This increases the probability that the two Developers are not compatible, and decreased the fiaßnatiinen simplified. So Nan can develop the suspension according to the invention directly by freshening and does not have to first separate the two developers make and then mix. Lianche control substances show when used in combination a synergistic effect.

There are control substances that solvate in the solvent system are. The synergism is not necessarily desirable, more so than that Influence of the control substance [shows] in the curve of density versus concentration of the tax substance £ .1 Because of the synergism one can determine the quantities of tax substance to decrease. However, these quantities must be used for each new combination of tax substances can be determined in a simple manner that is usual per se. The amounts of control substance depend also depends on the concentration and type of pigments and color components. In the following Examples are several control substances for a suspension developer according to the invention listed, taking into account the synergistic effect.

There are other considerations that need to be taken into account, namely that the latex of the amphipathic polymer of the suspension developer second Kind at least partially as a dispersant for the suspension developer first Art can work so that you no longer need a dispersant with this or reduce its amount. This complex substance can suffice with certain other components of the suspension developer of the first type available all or part of the required dispersion capacity. The coloring Components from one of the two or both suspension developers can be omitted, even if a visible image is sought, as a coloring component for the visibility is sufficient. Usually, however, it is desirable that both Developer contain a color component that is used in the second kind Can be part of the complex substance. You can use the same coloring for both developers Apply component.

According to the following examples, the suspension developers according to the invention can be prepared in two ways, namely (a) mixing suspension developer the first type with the second type and (b) producing the developer according to the invention by mixing the ingredients without first preparing the developer first and second type, separate from each other.

The active ingredients of the developers according to the invention can vary within so wide limits that the specification of certain proportions or areas does not make sense. In the following, however, approximate flinimal- and maximum values per liter of developing bath according to the invention are given.

Independent fixative (i.e. not bound to the dispersant) 0.0025 to 5 g.

Independent dispersant (i.e. not bound to the fixative) 0.5 to 5 g. The dispersant can be the amphipathic polymer or in addition Dispersant may be Sassent present.

Coloring component-O to 1 g (no coloring component is expedient used for the production of planographic printing plates).

Control substance 1 x 10 6 to 10 g.

Aliphatic polymer 0.05 to 30 g.

Remainder solvent system.

B e i s p i e 1 4.5 g suspension developer concentrate of the first type Example 8 and 0.5 g of suspension developer concentrate of the second type from Example 30 were diluted with 2000cm3 Isopar G. This gives dense black copies without Background coloring.

B e i s p i e 1 42 0.5 g suspension developer concentrate from example 8 and 4.5 g of suspension developer concentrate of the second type from Example 30 were added 2000cm3 Isopar G diluted.

This gave dense blue-black copies.

B e i s p i e 1 43 A suspension developer for the production of Black printing plate is obtained by mixing 8 g of the concentrate of the example 39 with 0.04 g of concentrate from Example 9 and diluting with 2000 cm3 of Isopar G. Man thus gets excellent results in office offset machines.

Example 44 A suspension developer for the production of Microfiche images are obtained by mixing 4 g of concentrate from Example 39 each and 9 and dilute with 2000 cm3 Isopar G.

For example 1 45 0.04 g concentrate from example 10 and 8 g concentrate the end Example 40 with 2000 cm3 Isopar H results in a developer which is excellently suited for flat printing forms.

B e 1 s p i e 1 46 100 g were placed in a ball mill at 370C for 23 h "Domerex", 50 g "Pliolite VTAC-L", 60 g "Toner 8100" and 500 g solvent 460 " mixed. Then a further 100 g of solvent were added and at the same temperature mixed for another hour. To 145 g of the above mixture were 60 g of latex from Example 25 (main component the developer of the second type and dispersant for the components of the developer given and first type) and 0.75 g of aluminum stearate at 37 ° C for 18 h in the ball mill mixed. 5 g of the concentrate according to the invention were then with 2000 cm3 Isopar K diluted.

With this developer, dense black copies with no background coloration were obtained.

It is not necessary to increase the ingredients in the ball mill Mixing temperature, but it is generally sufficient to use a manual or machine Mix at room temperature.

Ex. 1 20 g "Dymeres", 10 g "Pliolite rTA0-L", 8 g "GAF Black fl toner ", 120 g solvent" 460 ", 1 g aluminum stearate and 30 g latex from example 25 were mixed in the ball mill at 37 ° C. for 18 hours. 5 g of this concentrate were dispersed in 2000 cm3 of Isopar K; dense black copies with no background coloration were obtained. In this case the latex acts as a dispersant for the pigment and the control agent.

Example 48 20 g "Domerex", 10 g "Pliolite VTAC-L", 15 g "GAF Black M Toner ", 120;" Solvent 460 ", 2 g lubricating oil" 564- ", 1 g aluminum stearate and 30 g of latex from Example 25 were mixed in a ball mill at 37 ° C. for 18 h and 5 g of the concentrate diluted with 2,000 cm3 of Isopar G.

This developer gave tight black copies with no background discoloration.

Example 1 49 25 g "Staybelite", 80 g latex from example 39, 12 g "Toner 8100", 3 g "Spirit Nigrosine SSB", 6 g "Raven 11", 1 g aluminum stearate, 20 g of "Alkanol DOÄ" and 50 g of "Isopar G" were placed in a ball mill for 40 hours at room temperature mixed and 4 g of this concentrate diluted with 2000 cm3 of Isopar G. One received so densely black. background free copies.

EXAMPLE 50 25 g "Stybelite", 6 g latex from Example 39, 12 g "Toner 8100", 3 g "Spirit Nigrosine SSB", 6 "aven 11", 2 g aluminum stearate, 20 g "Alkanol DOA", 50 g "Isopar G" were 40 hours at room temperature in the ball mill mixed and 6 g of this concentrate with 2000 cm³ Isopar G diluted.

From this developer one obtained dense black background-free Copies.

EXAMPLE 51 25 g of “Staybelite”, 80 g of latex from example 20, colored with Victoria Blue BA Base (4%), 8 g "Toner 8100", 2 g "Spirit Nigrosine SSB ", 4 g" States B-12 ", 10 g" Alkanol DOA ", 10 g polymerized castor oil were mixed in the ball mill at 370C for 39 hours, then 0.75 g of aluminum stearate, 10 g polymerized castor oil and 50 g Isopar K added and another hour mixed, whereupon 3 g of this concentrate with 2000 cm³ of Isopar K were diluted. This developer gave dense, black, background-free copies.

B e i 5 p 1 e 1 52 950 g latex from Example 20, colored with 4% Victoria Blue BA Base, 20 g "Staybelite", 8 to g "Toner 8100", 2 g Spirit Nigrosine SSB ", 4 g "Raven 11", 8 g'Llkanol DOA ", 8 g polymerized castor oil was at 3700 40 h in the ball mill and mixed 25 g of this concentrate with 2000 cm³ of Isopar G and 10 drops of a solution of the aluminum salt of 3,5-diisopropylsalicylic acid in Isopar G. fian received excellent planographic printing plates.

The suspension developer according to the invention can produce three unusual Observe effects in the production of developed images that are used as planographic printing plates (lithographic masters) can be used after etching.

The first effect is the "fill", i.e. the uniformity of the electrostatic Deposition over a densely colored area in such a tied that it is a is a reasonable facsimile of the original in terms of density. As mentioned earlier, is in the case of a suspension developer of the first type, the filling within the periphery of a colored area corresponding to the largest moderate.

Even if such a small proportion of, for example, only 0.5% the Components of the developer of the second type are present in the toner according to the invention the filling is decidedly better. The mark of the improvement of the Filling gradually decreases when larger proportions of the second type of developer Applied If this is the only requirement, it is undesirable to excessive plumbing or even large amounts of developer of the second type or its Constituents in the developers according to the invention are purely for economic reasons apply, all the more so than the cost of the amphipathic substance for fixing agents and dispersants of the developer of the first type.

However, there are other considerations as to how else to run, the proportions of the constituents of the developer of the second type in the invention Appreciate developer. It was found that the use of larger proportions of components of the developer of the second type in the developer according to the invention does not have a reduced influence on the improvement of the filling. There were opportunities have proposed various mechanical solutions to this problem, e.g., developing electrodes immersed in the developer bath and in close proximity to the place where the copy paper goes through, but the results obtained therefrom have been largely unsatisfactory.

The fact that even small amounts of the developer of the second kind are retained to improve the filling in such a simple manner in the developer according to the invention allow was completely surprising. There is currently no explanation for this phenomenon, i.e. the influence of the amphipathic substance on the density the deposition of the pigment particles of the developer of the first type on the electrostatic Charge image.

Another major advantage results from the extension the ability of the developed image to work when using as a planographic printing plate. It was found that despite the short life of Planographic printing plates that can be obtained with the developer of the first type, the service life of planographic printing plates obtained with a developer according to the invention is very important is increased and that this lifespan is at least as great as that one in the case of planographic printing plates which have only been produced with a developer of the second type are, can watch. In other words, improving the filling doesn't work to a deterioration in the service life of the printing plates obtained with the invention Developer; under a lifespan like you would with a developer of the second kind receives; in other words, one achieves simultaneously with the developers according to the invention a better filling and an extension of the life span of the planographic printing plates.

With regard to ensuring usable results in the Life of planographic printing plates is desirable not less than about 1 Part of the components of the developer of the second type to 20 parts of the components of the developer of the first kind to be provided. In connection with the above, the proportions are indicated set, depending on the desired service life and the cost factor. is it is known that for a particular application it does not have the maximum service life The lithographic plate is required so it is unnecessary to have more components of the developer of the second kind than is necessary for this extended service life is.

Another advantage of the developer according to the invention both for the Manufacture of planographic printing plates as in general use in office copiers is that the presence of even small amounts of constituents of developer first type is able to significantly improve the edge contrast of the copies, with in other words, the sharpness of the developed image is improved. Such an improvement in the edge contrast can already be achieved with such small quantities of 0.5% constituents of the developer of the first type in the developer according to the invention to be established.

Economic considerations lead to very large shares do not apply to components of the developer of the second type, but this will improve the contrast not affected by the use of large amounts of components of the developer of the first type in the developer according to the invention.

Another benefit of even small amounts of ingredients The second type of developer in the developer of the present invention is resistance of the separated image against a caustic solvent.

It is a characteristic of the deposited images through application from a developer of the first kind that, if the original is not extremely light, is also etched in lighter areas and this leads to image areas are less oleophilic than others, so that the copies obtained are qualitative are worse than the original. When adding only small amounts of the components however, of the developer of the second type, this disadvantage can be overcome. With Planographic printing plates obtained by developers according to the invention show high uniformity with regard to the resistance to change by the etching solution (wiping water) from oleophilic to hydrophilic. This effect is not worsened by large proportions of substances of the developer of the second type in the developer according to the invention.

The second substantially expanded usefulness of the invention Toner is used in the electrophotographic production of NikroficYfr images. There has not yet been a commercially acceptable toner for the electrostatic Manufacturing of microfilche images. If the developer was used first, the above occurred Difficulties arise because the fixing agent is at higher temperatures during the melting must be heated as it is for the formation of a transparent thermoplastic Support for the transparent photoconductor was necessary, making it dimensionally unstable will. This leads to the fact that adjacent narrow areas of the copies converge may or may appear blurred, making this poor resolution practically unusable Copies leads.

On the other hand, when the second type of developer is used, the edges were the image areas are not a faithful reproduction of the corresponding edges of the original, so that here too there is a deterioration in the resolution due to blurring the edges in the reproduction came up.

For the electrostatic production of microfiche images I've also tried another toner that takes several minutes to solidify needed after development. In the meantime, until the picture hardens, Do not touch the toner. This is in modern working conditions and especially practically impracticable with ScEmell copiers.

All of these disadvantages can be overcome by the inventor so far Avoid developers. Inexplicably, causes the presence of constituents a developer of the first type a complete correspondence of the edge areas of the developed Image with the original; this is true even if there are minimal amounts of developer of the first kind can be used. On the other hand, the presence allows itself to be minimal Amounts of developers of the second type ensure rapid and good fixing of the image Temperatures below those you would use for fixing of developer the first type is needed and under the one where a thermoplastic transparent support would become dimensionally unstable for an organic transparent photoconductor. It is not known whether this reduced hardening temperature is due to the lower one Melting point of the fixing unit of the amphipathic substance or on the ability of the amphipathic substance, a solvent-induced bond with the thermoplastic To enter into porters, or for some other, initially unknown reason. As Whatever the case, the result is there, and for the first time it succeeds, quickly and to produce a microfiche image at low enough temperatures without affecting the resolution is impaired, so that the dissolving ability of the ultimately electrostatic The produced image is only a function of the resolution that you get with the original in the optical reduction, and is otherwise not adversely affected through the reproductive process.

PATENTÄI SFRU CHE:

Claims (1)

PATi; NTANsPRtJo HE suspension developer for electrostatic reproductions, not indicated by 0.5 to 99.5% of a suspension developer known per se first type and 99.5 to 0.5% of a suspension developer known per se, second Kind, containing an amphipathic polymer, wherein in at least one of the suspension developer one or more control substances and optionally one or more color components available. (2) suspension developer according to claim 1, characterized g e k e n n z e i n e t that the solvent system has an evaporation rate of at least The kerosene has, however, slower than hexane, the kauributanol number is below 35 is, it is essentially free of aromatics, the electrical resistance at least 109 # .cm, the dielectric constant less than 3.5 and the flash point (in the open Tagliabue crucible) is at least 37 ° C, it is non-toxic and non-polar is, has no unpleasant odor and the viscosity at room temperature between 0.5 and 2.5 cP. (3) suspension developer according to claim 1 or 2, characterized g e k e It is not noted that in the developer of the first type dissolved in the solvent system contain a synthetic thermoplastic fixing agent and a dispersing agent are. (4) suspension developer according to claim 1 to 3, through this it is not noted that the amphipathic polymer is composed of one Framework polymer and polymeric parts grafted thereon, the amphipathic Polymer consists of two polymeric units, at least one of which is thermoplastic is, the first unit is solvated in the solvent, part of which acts as a Fixing agent and as a dispersing agent, the second unit is in the solvent system insoluble and has a grain size of 25 nm to 25 μm and acts as a fixing agent. (5) suspension developer according to claim 4, characterized g e k e n nz e i c h n e t that the amphipathic polymer is the color component as a further unit contains. (6) Use of the suspension developer according to claim 1 to - in Office copiers for the production of planographic printing plates and for high-quality reproductions by electrostatic copying processes.