DE4029653A1 - Use of polymeric ammonium salts - as charge controlling agents in electrophotographic toners and developers and in powders and powder lacquers - Google Patents

Abstract

Polymeric ammonium salts of mol. wt. 5000-500000 are obtd. by homopolymerisation of monomers of formula (I) or (II) and by copolymerisation of mixts. of two monomers of formula (I)-(III) with a molar monomer ratio of (I):(II) and (I):(III) and (II):(III) of c. 0.5:0.5-0.95:0.05 in the copolymer, opt. with subsequent anion exchange, where R1-R12 and R1'-R12' independently = H, halogen, hydroxyl, prim., sec. or tert. amino, carboxylic acid, carboxylic acid ester, sulphonic acids, sulphonic acid ester, cyano, nitro or a hydrocarbon opt. interrupted by heteroatoms; X- and Y- = stoichiometric equivs. of an organic or inorganic anion or their mixts., and R13-R16 = independently H, Cl, Br, hydroxyl, prim., sec. or tert. amino, carboxylic acid, carboxylic acid ester, sulphonic acids, sulphonic acid ester, cyano, nitro or a hydrocarbon opt. interrupted by heteroatoms.

Description

The present invention relates to the use of polymeric Ammonium compounds based on homopolymers or copolymers Poly (diallylammonium) derivatives and copolymers of Poly (diallylammonium) derivatives with selected Vinyl compounds as charge control agents in toners and Developers of electrophotographic recording methods as well as in powders and powder coatings for surface coating. The compounds of the invention have by targeted Combination of certain polymeric ammonium cations with selected anions particularly high and constant Charge control properties, very good thermal stabilities and Dispersibilities.

In electrophotographic recording method is on produces a "latent charge image" to a photoconductor. This For example, by charging a photoconductor by a corona discharge and subsequent imagewise Exposure of the electrostatically charged surface of the Photoconductor, wherein the exposure to the charge drain to grounded pad is effected at the exposed locations. Subsequently, the thus generated "latent charge image" by Applying a toner developed. In a following Step is the toner from the photoconductor on, for example Transferring paper, textiles, foils or plastic and for example by means of pressure, radiation, heat or Solvent effect fixed. The used photoconductor becomes then cleaned and stands for a new one Recording process available.

In numerous patents, the optimization of toners described, wherein u.a. the influence of the toner binder (Variation of resin / resin components or Wax / wax components), the influence of carriers (at  Two-component developers) and magnetic pigments (in One-component winders).

A measure of toner quality is its specific charge q / m (charge per unit mass). In addition to the sign and height of the Electrostatic charge is above all the fast Reaching the desired charge level and the constancy of this Charge over a longer activation period decisive quality criterion. In practice this is in so far as central to the fact that the toner in Developer mix before transferring to the photoconductor is, can be exposed to a considerable activation time since He partially over a period of time from making up to several thousand copies remain in the developer mix. Moreover, the insensitivity of the toner is against Climate influences, such as temperature and humidity, a another important eligibility criterion.

Find both positive and negatively chargeable toners Use in copiers and laser printers depending on Process and device type.

To electrophotographic toner or developer with either getting positive or negative charge becomes common so-called charge control agents (also charge control agents called) added. It is next to the sign of Charge control the extent of the tax effect of importance because a higher efficiency allows a small amount of use. As toner binder usually has a strong dependence of Charge of the activation time, it is the task of a Ladungssteuermittels, on the one hand sign and height of the Adjusting the toner charge and the other Counteract drift drift of the toner binder and for Constant toner charge.

Charge control means which can not prevent the Toner or developer during prolonged use a high  Charge drift shows (aging) that can even cause that the toner or developer experiences a charge reversal, are therefore unsuitable for the practice.

Full color copiers and laser printers work on the principle the trichromatic, which is an exact shade match of the three Basic colors (yellow, cyan and magenta) are required. Least color shifts even only one of the three Basic colors necessarily requires a hue shift of two other colors, even then faithful to the original To produce full color copies or prints. Because of this in color toners required precise tuning the coloristics of the individual colorants on each other, are Charge control agent absolutely without own color very special important.

For color toners, the three toners must be yellow, cyan, and magenta besides the well-defined color requirements as well exact in terms of their triboelectric properties be coordinated. This triboelectric tuning is required because in full color printing or in the Full color copy successively the three color toner (or four Color toner if black is included) in the same device must be transferred.

Colorants are known to be the triboelectric Charging of toners can have a lasting effect (H.-T. Macholdt, A. Sieber, Dyes & Pigments 9 (1988), 119-27; US-PS 40 57 426). Because of the different triboelectric Effects of colorants and the resulting sometimes very pronounced influence on the Toner chargeability is not possible in one time created toner base formulation as a colorant easy add. Rather, it may be necessary for each Colorants to create their own recipe for which z. B. Type and amount of the required charge control agent specifically be tailored. This procedure is appropriate consuming and comes with color toners for process color  (Trichromy) in addition to those already described Difficulties added.

Therefore, highly effective colorless charge control agents which are able to do the different triboelectric behavior of different colorants too compensate and add the desired charge to the toner to lend. In this way, triboelectric can be very different colorants based on a once created Toner base formulation with one and the same charge control agent in the various required toners (yellow, cyan, Magenta and optionally black). In addition, it is important for the practice that the Charge control agent high thermal stability and good Have dispersibility. Typical incorporation temperatures for charge control agents in the toner resins are included Use of z. As kneaders or extruders between 100 ° C and 200 ° C. Accordingly, a thermal stability of 200 ° C, better still 250 ° C, of great advantage. It is also important that the thermal stability over a longer period of time (about 30 min.) and guaranteed in different binder systems is. This is significant as it reoccurs Matrix effects for premature decomposition of the Charge control agent in the toner resin, whereby a dark yellow or dark brown coloration of the toner resin takes place and the charge control effect is lost in whole or in part. Typical toner binders are polymerization, Polyaddition and polycondensation resins such. Styrene, Styrene acrylate, styrene butadiene, acrylate, polyester, Phenolic and epoxy resins, individually or in combination, still other ingredients, such as colorants, waxes or Flow aids, may contain or in hindsight can get added.

For a good dispersibility it is of great advantage if the charge control agent as possible no waxy Properties, no stickiness and a melt or Softening point of <150 ° C, better <200 ° C, having. A  Tackiness often leads to problems when dosing in the Toner formulation, and low melting or Softening points can lead to dispersion during dispersion no homogeneous distribution is achieved as the material z. B. droplet-shaped in the carrier material.

Except in electrophotographic toners and developers can Charge control also to improve the electrostatic charging of powders and varnishes, especially in triboelectric or electrokinetic sprayed powder coatings, as for surface coating of objects made of, for example, metal, wood, plastic, Glass, ceramics, concrete, textiles, paper or rubber are used. The Powder coating technology comes u.a. when painting Small items, such as garden furniture, camping items, Household appliances, vehicle parts, refrigerators and shelves, as well as when painting complicated shaped workpieces Application. The powder coating or the powder receives its electrostatic charging in general according to one of both of the following procedures:

• a) In the corona process, the powder coating or the powder passed a charged corona and hereby charged,
• b) in the triboelectric or electrokinetic method the principle of friction electricity is used. The powder coating or the powder receives in the sprayer electrostatic charge, which is the charge of the Friction partner, generally a hose or Spray tube (for example made of polytetrafluoroethylene), is opposite.

A combination of both methods is possible.

As powder coating resins are typically epoxy resins,  carboxyl- and hydroxyl-containing polyester resins, Polyurethane and acrylic resins together with the corresponding Hardeners used. Also find combinations of resins Use. For example, epoxy resins are often used in Combination with carboxyl- and hydroxyl-containing Polyester resins used.

Typical hardener components for epoxy resins are, for example Acid anhydrides, imidazoles and dicyandiamide and their Descendants. For hydroxyl-containing polyester resins are typical hardener components, for example, acid anhydrides, blocked isocyanates, bisacylurethanes, phenolic resins, Melamine resins, for carboxyl polyester resins are typical hardener components, for example Triglycidyl isocyanurates or epoxy resins. In acrylic resins come as typical hardener components, for example Oxazolines, isocyanates, triglycidyl isocyanurates or Dicarboxylic acids for use.

The lack of insufficient charging is especially at triboelectrically or electrokinetically sprayed powders and Powder coatings based on polyester resins, in particular carboxyl-containing polyesters, or based on so-called mixed powders, also called hybrid powders, have been prepared to observe. Under mixed powders Powder coatings whose resin base consists of a Combination of epoxy resin and carboxyl group-containing Polyester resin exists. The mixed powders form the basis for the most commonly used in the Prayis powder coatings. Insufficient charging of the above powders and Powder coatings causes the deposition rate and Umgriff on to coating workpiece are insufficient. (The expression "Umgriff" is a measure of the extent to which a powder or Powder coating on the workpiece to be coated, also on backsides, Cavities, gaps and especially on inner edges and corners depositing).

Colorless charge control agents are available in numerous  Patent claims claimed. For example, describe DE-OS 31 44 017, JP-OS 61-236 557 and US-PS 46 56 112 Metal complexes and organometallic compounds, DE-OS 38 37 345, DE-OS 37 38 948, DE-OS 36 04 827, EP-OS 242 420, EP-OS 203 532, US-PS 46 84 596, US-PS 46 83 188 and US-PS 44 93 883 ammonium and Immonium compounds and DE-OS 39 12 396, US-PS 44 96 643 and US-PS 38 93 935 phosphonium compounds and EP-PS 185 509, JP-OS 01-136 166, JP-A 63-060 458, JP-A 62-264 066, US-PS 48 40 863, US-PS 46 39 043, US-PS 43 78 419, US-PS 43 55 167 and US-PS 42 99 898 polymeric ammonium compounds as colorless Charge control agent.

However, the previously known colorless Charge control agents have a number of disadvantages, including the Use in practice greatly restrict or partially to make impossible. Thus, in DE-OS 31 44 017 and US-PS 46 56 112 described chromium, iron, cobalt and zinc complexes and the antimony organyls described in Japanese Laid-Open Publication No. 61-236557 the heavy metal problem also has the disadvantage that they sometimes not really colorless, and thus in color toners or in white or colored powder coatings only limited Application can be found.

The known, in itself suitable, quaternary Ammonium compounds are often difficult to disperse, which leads to uneven charging of the toner. moreover The problem often arises that of these compounds generated toner charge does not last longer Activation period (up to 24 hours activation time) is stable, especially at high temperature and Humidity (EP-OS 242 420), which then in the course of a Copying or printing process for enrichment wrong or not sufficiently charged toner particles and thus the process brings to a halt. It is also known that Ammonia and immonium charge control agents sensitive to light or mechanical effects (EP-OS 203 532, US-PS 46 83 188) and may be thermally labile, and that they form decomposition products that adversely affect  can affect the triboelectric charge of the toner (US-PS 46 84 596) and / or a strong, often dark brown, Have own color (DE-OS 37 38 948, DE-OS 36 04 827, US-PS 44 93 883). In addition, they often show waxy behavior, partly water solubility and / or low potency as Charge control agent.

Proper charge control agent based on high grade fluorinated ammonium, immonium and phosphonium compounds (DE-OS 39 12 396, DE-OS 38 37 345) have the disadvantage of elaborate synthesis, resulting in high production costs for the corresponding substances and are not sufficient thermostable.

Phosphonium salts are less effective as charge control agents as ammonium salts (US-PS 44 96 643, US-PS 38 93 939) and can toxicologically problematic.

Charge control agent based on polymeric ammonium compounds lead partly to Amingeruch the toner or developer, and the charge control properties of these substances may be by relatively slight oxidation and moisture absorption to change. Furthermore, the oxidation products are colored and therefore disturbing especially in color toners (US-PS 48 40 863).

The above-mentioned charge control agents for electrophotographic toners and developers are e.g. B. due their color for use in the predominantly white or clear triboelectrically or electrokinetically sprayed Powders and powder coatings are not suitable. Furthermore, limits lack of thermal stability the use of such Charge control agent strong because powder coatings, for example baked at over 200 ° C for 15 minutes.

The claimed in DE-OS 38 37 345 and DE-OS 36 00 395 Charge control agents for powders and powder coatings are due of waxiness and water solubility or hygroscopicity bad to handle and only partially applicable. The claimed in EP-OS 03 71 528 amines as Charge control agents for powders and powder coatings are due the odor nuisance for practical use problematic.  

The aim of the present invention is therefore to improve to find particularly effective colorless charge control agents in addition to the cargo height, the rapid achievement and the Constancy of this charge must be guaranteed, and the Charge control effect not sensitive to temperature and humidity changes may be. Furthermore these compounds should be highly thermostable, before especially over a longer period of time in the respective Carrier material (resin), as well as possible insoluble in water, good dispersible and compatible with the toner or Powder coating ingredients. Furthermore, the synthesis of the Compounds are less expensive and their production be cost-effective.

Surprisingly, it has now been found that special polymeric ammonium compounds based on homo- or copolymeric poly (dialkyldiallylammonium) derivatives and their Copolymer of poly (diallylammonium) derivatives with selected vinyl compounds particularly effective Charge control agents for electrophotographic toners and Developers are, and moreover, as charge improving agents in powders and varnishes Surface coating, in particular triboelectric or electrokinetically sprayed powder coatings are used can.

Because of their colorlessness, high effectiveness, good Compatibility and dispersibility in common toner and Powder coating resins, their chemical inertness and because of Insensitivity of the charge control effect Temperature and humidity fluctuations are the Compounds in particular for use in color toners or developers for full-color copiers and laser printers after the Principle of trichromatic (subtractive color mixing), but also for colored toner or developer in general and for black toner or developer as well as for powder and  Powder coatings suitable. Furthermore, the are suitable Compounds for the coating of carriers or as Ingredients of Carrier Coatings. A great technical advantage of this well-dispersible Compounds lies in the fact that substances of the same Class of compound according to cation-anion combination either as a positive or negative charge control agent can be used. Thus, problems in the Incorporation in the toner binder and the compatibility with the toner binder after creating a Toner base formula minimized. Thus both positive and negative as well as negative toner based on a solid toner base formulation (consisting of toner binder, colorants, flow aids and optionally other components) by incorporation of the desired control means are produced. In the claimed compounds according to the invention are of very particular advantage of the less expensive synthesis, the cost-effective production, the high effectiveness and the excellent thermal stability.

The present invention thus relates to the use of polymeric ammonium compounds having a molecular weight from about 5,000 to about 500,000 on the basis of Poly (diallylammonium) derivatives or their copolymers, with the molar monomer ratios (I): (II) and (I): (III) and (II): (III) from about 0.5: 0.5 to about 0.95: 0.05 in the copolymer, prepared by homopolymerization of monomers of general formulas (I) or (II) and by copolymerization of mixtures of two monomers of the general formulas (I) to (III) and optionally subsequent anion exchange

wherein the radicals R₁ to R₁₂ and R₁ 'to R₁₂' are each independently a hydrogen atom, halogen atom, a hydroxyl radical, a primary, secondary or tertiary amino radical, a carboxylic acid or carboxylic ester radical, a sulfonic acid or sulfonic acid radical , a cyano or nitro radical or in each case a radical based on a hydrocarbon which may be interrupted by heteroatoms, and the radicals R₁₃ to R₁₆ independently of one another each represent a hydrogen atom, chlorine atom, bromine atom, a hydroxyl radical, a primary, secondary or tertiary amino radical, a carboxylic acid or carboxylic acid ester radical, a sulfonic acid or sulfonic acid ester radical, a cyano or nitro radical or in each case a radical based on a hydrocarbon which may be interrupted by hetero atoms, where R₁ and R₂ or R₁ 'and R₂' independently of one another are hydrogen atoms, straight-chain or branched, sat unsaturated or unsaturated alkyl (C₁-C₁₈) or alkoxy (C₁-C₁₈) radicals, polyoxyalkylene radicals, preferably polyoxyethylene and polyoxpropylene radicals, of the general formula - (alkylene (C₁-C₅) O) _n- R, wherein R is a hydrogen atom, an alkyl (C₁-C₄) radical or an acyl radical, such as the acetyl, benzoyl or naphthoyl radical, and n is a number from 1 to 10, aryl or heteroaryl, such as Phenyl, naphthyl or pyridyl radicals, aralkyl radicals such as tolyl radicals, aralkoxy radicals such as methoxyphenyl radicals, alkaryl radicals such as benzyl radicals, or cycloalkyl radicals such as cyclopentyl or Cyclohexyl, mean and R₁ and R₂ or R₁ 'and R₂' can also combine to form a saturated or unsaturated, aromatic or non-aromatic 5- to 7-membered ring system, such as the pyridinium ring system, the other heteroatoms, preferably nitrogen and / or Oxygen- and / or sulfur atoms, such as the morpholinium ring system, and may be substituted and / or modified by condensation or bridging to other ring systems, such as the quinolinium ring system, wherein R₁ and R₂ and R₁ 'and R₂ 'one or more heteroatoms, such as nitrogen and / or oxygen and / or sulfur and / or phosphorus atoms, and by halogen atoms, hydroxyl, carboxyl, sulfonic acid, cyano or mercapto radicals, carboxamide radicals such as -NH-C (O) -alkyl (C₁-C₄), sulfonamide radicals, such as -NH-SO₂-alkyl (C₁-C₄), urethane radicals, such as -NH-C (O) O- Alkyl (C₁-C₄), keto radicals, such as -C (O) alkyl (C₁-C₄), primary, secondary or tertiary amino radicals, such as -NH [alkyl (C₁-C₄)], -N [Acyl (C₁-C₄)] ₂, nitro radicals, ether radicals, such as -alkylene (C₁-C₄) -O-alkyl (C₁-C₄), alkyl (C₁-C₃₀) -, Alkoxy (C₁-C₃₀) radicals, Aroxy radicals such as phenoxy radicals, haloalkyl (C₁-C₃₀), haloalkoxy (C₁-C₃₀) radicals or ester radicals such as -C (O) O-alkyl (C₁-C₄), may be substituted, and the radicals R₃ to R₁₂ or R₃ 'to R₁₂' are independently hydrogen atoms, halogen atoms, straight-chain or branched, saturated or unsaturated alkyl (C₁-C₁₈) - or alkoxy (C₁-C₁₈) Radicals, polyoxalkylene radicals, preferably polyoxethylene and polyoxpropylene radicals, of the general formula - (alkylene (C₁-C₅) -O) _n -R, wherein R is a hydrogen atom, an alkyl (C₁-C₄) radical or an acyl Radical, such as, for example, the acetyl, benzoyl or naphthoyl radical, and n is a number from 1 to 10, aryl or heteroaryl radicals, such as, for example, phenyl, naphthyl or pyridyl radicals, aralkyl radicals, such as, for example, tolyl Radicals, aralkoxy radicals, for example methoxyphenyl radicals, aroxy radicals, for example phenoxy radicals, alkaryl-res te, such as benzyl radicals, or cycloalkyl radicals, such as cyclopentyl or cyclohexyl, mean and two of the radicals R₃ to R₁₂ or R₃ 'to R₁₂' also to a saturated or unsaturated, aromatic or non-aromatic 5- to 7-membered Ring system can combine, such as the pyridinium ring system, which may contain other heteroatoms, preferably nitrogen and / or oxygen and / or sulfur atoms, such as the morpholinium ring system, and substituted and / or by condensation of or bridging to another Ring systems may be modified, such as the quinolinium ring system, wherein the radicals R₃ to R₁₂ or R₃ 'to R₁₂' one or more heteroatoms, such as nitrogen and / or oxygen and / or sulfur and / or phosphorus atoms and by halogen atoms, hydroxyl, carboxyl, sulfonic acid, cyano or mercapto radicals, carboxamide-Re radicals such as -NH-C (O) -alkyl (C₁-C₄), sulfonamide radicals such as -NH-SO₂-alkyl (C₁-C₄), urethane radicals such as -NH-C (O) O -Alkyl (C₁-C4), keto radicals, such as, for example, -C (O) -alkyl (C₁-C₄), primary, secondary or tertiary amino radicals, such as -NH [alkyl (C₁-C₄)], - N [alkyl (C₁-C₄)] ₂, nitro radicals, ether radicals, for example -alkylene (C₁-C₄) -O-alkyl (C₁-C₄), alkyl (C₁-C₃₀) -, alkoxy (C₁-C₄), C₃₀) radicals, Aroxy radicals such as phenoxy radicals, haloalkyl (C₁-C₃₀) -, haloalkoxy (C₁-C₃₀) radicals or ester radicals such as -C (O) O-alkyl (C₁-C₄ ), and the radicals R₁₃ to R₁₆ independently of one another are hydrogen atoms, chlorine atoms, bromine atoms, straight-chain or branched, saturated or unsaturated alkyl (C₁-C₃₀) radicals, polyoxalkylene radicals, preferably polyoxyethylene and polyoxpropylene radicals, of the general Formula - (alkylene (C₁-C₅) -O) _n -R, wherein R is a hydrogen atom, an alkyl (C₁-C₄) radical or an acyl radical, such as the acetyl, benzoyl or naphthoyl radical, and n is a number from 1 to 10, aryl or heteroaryl radicals, such as Phenyl, naphthyl or pyridyl radicals, aralkyl radicals such as tolyl radicals, aralkoxy radicals such as methoxyphenyl radicals, alkaryl radicals such as benzyl radicals, or cycloalkyl radicals such as cyclopentyl or Cyclohexyl radicals, carboxyl, sulfonic acid or cyano radicals, carboxamide radicals, such as -NH-C (O) -alkyl (C₁-C₄), sulfonamide radicals, such as -NH-SO₂-alkyl (C₁-C₄) C₄), ester radicals such as -C (O) O-alkyl (C₁-C₄), carboxylate radicals such as -OC (O) -alkyl (C₁-C₄), keto radicals such as -C (O) -alkyl (C₁-C₄), lactam radicals, such as

or ether radicals, such as -alkylene (C₁-C₄) -O-alkyl (C₁-C₄), wherein the radicals R₁₃ to R₁₆ one or more heteroatoms, such as nitrogen and / or oxygen and / or sulfur and / or phosphorus atoms, and by chlorine or bromine atoms, hydroxyl, carboxyl, sulfonic acid, cyano or mercapto radicals, carboxamide radicals such as -NH-C (O) -alkyl (C₁-C₄), Sulfonamide radicals, such as -NH-SO₂-alkyl (C₁-C₄), primary, secondary or tertiary amino radicals, such as -NH [alkyl (C₁-C₄)], -N [alkyl (C₁-C₄)] ₂ or nitro radicals may be substituted, and X ^- or Y ^- each denote the stoichiometric equivalent of an organic or inorganic anion or a mixture of organic and / or inorganic anions, and wherein in the case of homopolymerization of monomers of the general formulas (I ) or (II) R₁ and R₂ and / or R₁ 'and R₂' may be identical or different , and wherein in the case of the copolymerization of mixtures of two monomers of the formulas (I) to (III), both the radicals R₁ and R₂ and / or R₁ 'and R₂' and the anions X ^- and Y ^{- may be} identical or different, individually or in combination as charge control agents in electrophotographic toners and developers used for copying or duplicating originals and for printing electronically, magnetically or optically stored information or in color proofing. In addition, the compounds claimed according to the invention are suitable as charge control agents in powders and paints for surface coating of objects made of metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber, especially in triboelectrically or electrokinetically sprayed powder coatings.

In addition, these compounds can also be called charge-improving agent in the form of coatings of Carrier or component of coatings of carriers, the in developers of electrophotographic copiers or Printers are used.

The claimed compounds according to the invention are in one Amount of from about 0.01 to about 30 weight percent, preferably from about 0.1 to about 5 weight percent, homogeneously distributed in the respective toner, developer, lacquer or powder.

Particularly suitable are polymeric ammonium compounds with  a molecular weight of about 20,000 to about 250,000 on the Basis of poly (diallylammonium) derivatives and their Copolymers with molar monomer ratios (I): (II) and (I): (III) and (II): (III) from about 0.5: 0.5 to about 0.95: 0.05 in the copolymer prepared by homopolymerization of monomers of the abovementioned formulas (I) or (II) and by copolymerization of mixtures of two monomers of the above Formulas (I) to (III) and optionally subsequent anion exchange, in which R₁ and R₂ or R₁ 'and R₂' independently Hydrogen atoms, straight-chain or branched, saturated or unsaturated alkyl (C₁-C₈) or alkoxy (C₁-C₈) radicals, Aryl or heteroaryl radicals, such as, for example, phenyl, Naphthyl or pyridyl radicals, aralkyl radicals, such as For example, tolyl radicals, aralkoxy radicals, such as Methoxyphenyl radicals, alkaryl radicals, such as Benzyl radicals, or cycloalkyl radicals, such as Cyclopentyl or cyclohexyl, mean, where the radicals R₁ and R₂ or R₁ 'and R₂' by halogen atoms, hydroxyl, Carboxyl, sulfonic acid residues, carboxamide residues, such as for example, -NH-C (O) -alkyl (C₁-C₄), sulfonamide radicals, such as for example -NH-SO₂-alkyl (C₁-C₄), keto radicals, such as for example -C (O) -alkyl (C₁-C₄), primary, secondary or tertiary amino radicals such as -NH [alkyl (C₁-C₄)], -N [alkyl [C₁-C₄)] ₂, nitro radicals, ether radicals, such as Alkylene (C₁-C₄) -O-alkyl (C₁-C₄), alkyl (C₁-C₄) -, alkoxy (C₁-C₄) -, Aroxy radicals, such as phenoxy radicals, Haloalkyl (C₁-C₄) -, haloalkoxy (C₁-C₄) radicals or Ester radicals, such as, for example, -C (O) O-alkyl (C₁-C₄), may be substituted, and the radicals R₃ to R₁₂ or R₃ 'to R₁₂' independently each other from hydrogen atoms, halogen atoms, straight or branched, saturated or unsaturated alkyl (C₁-C₈) - or Alkoxy (C₁-C₈) radicals, aryl or heteroaryl radicals, such as for example, phenyl, naphthyl or pyridyl radicals, Aralkyl radicals, such as tolyl radicals, aralkoxy radicals,  such as methoxyphenyl radicals, aroxy radicals, such as for example, phenoxy radicals, alkaryl radicals, such as for example, benzyl radicals, or cycloalkyl radicals, such as For example, cyclopentyl or cyclohexyl, mean where the radicals R₁ and R₂ or R₁ 'and R₂' by halogen atoms, Hydroxyl, carboxyl, sulfonic acid residues, carboxamide residues, such as for example, -NH-C (O) -alkyl (C₁-C₄), sulfonamide radicals, such as for example -NH-SO₂-alkyl (C₁-C₄), keto radicals, such as for example -C (O) -alkyl (C₁-C₄), primary, secondary or tertiary amino radicals such as -NH [alkyl (C₁-C₄)], -N [alkyl (C₁-C₄)] ₂, nitro radicals, ether radicals, such as Alkylene (C₁-C₄) -O-alkyl (C₁-C₄), alkyl (C₁-C₄) -, alkoxy (C₁-C₄) -, Aroxy radicals, such as phenoxy radicals, Haloalkyl (C₁-C₄) -, haloalkoxy (C₁-C₄) radicals or Ester radicals, such as, for example, -C (O) O-alkyl (C₁-C₄), may be substituted, and the radicals R₁₃ to R₁₆ independently Hydrogen atoms, straight-chain or branched, saturated or unsaturated alkyl (C₁-C₈) radicals, aryl or Heteroaryl radicals, such as phenyl, naphthyl or Pyridyl radicals, aralkyl radicals, such as, for example, tolyl radicals, Aralkoxy radicals, such as methoxyphenyl radicals, Alkaryl radicals, such as benzyl radicals, Cycloalkyl radicals, such as cyclopentyl or Cyclohexyl radicals, carboxyl, sulfonic acid, cyano radicals, Ester radicals, such as, for example, -C (O) O-alkyl (C₁-C₄), Carboxylate radicals, such as -O-C (O) -alkyl (C₁-C₄), Carboxamide radicals, such as -NH-C (O) -alkyl (C₁-C₄), Sulfonamide radicals, such as -NH-SO₂-alkyl (C₁-C₄), Keto radicals, such as, for example, C (O) -alkyl (C₁-C₄), Lactam radicals, such as

or ether radicals, such as -alkylene (C₁-C₄) -O-alkyl (C₁-C₄), where the radicals R₁₃ to R₁₆ by chlorine or bromine atoms, hydroxyl, carboxyl, sulfonic acid, cyano, Mercapto radicals, carboxamide radicals, such as -NH-CO-alkyl (C₁-C₄), sulfonamide radicals, such as -NH-SO₂-alkyl (C₁-C₄), primary, secondary or tertiary amino radicals, such as For example, -NH [alkyl (C₁-C₄)], -N [alkyl (C₁-C₄)] ₂ or nitro radicals may be substituted, and X ^- and Y ^- each represents the stoichometric equivalent of an anion or a mixture of anions , such as F ^- , Cl ^- , Br ^- , J ^- , NO₃ ^- , OH ^- , HSO₄ ^- , SO₄ ^2- , S ^2- , SO₃ ^₂- , S₂O₃ ^2- , HCO₃ ^- , CO₃ ^2- , H₂PO₄ ^- , HPO₄ ^2- , PO₄ ^3- , CN ^- , cyanate, isocyanate, thiocyanate, zinc tetracyanate, zinc tetrathiocyanate, perchlorate, BF₄ ^- , PF₆ ^- , B (aryl) ₄ ^- , such as. As tetraphenylborate, tetra (fluorophenyl) borate, tetra (chlorophenyl) borate, tetratolyl borate, Tetranaphthylborat, tetra (methoxyphenyl) borate, tetrabiphenylborate, tetrabenzyl borate or Tetrapyridylborat, ethyl and methyl sulfate, phenolate, nitrophenolate, saturated or unsaturated, aliphatic, cycloaliphatic or aromatic Carboxylate or sulfonate, such as. As acetate, lactate, benzoate, salicylate, 2-hydroxy-3-naphthoate, 2-hydroxy-6-naphthoate, ethyl sulfonate, phenyl sulfonate or tosylate, further perfluorinated saturated or unsaturated, aliphatic, cycloaliphatic or aromatic carboxylate or sulfonate, such as. As perfluoroacetate, Perfluoralkylbenzoat, perfluoroethyl or perfluoroalkylbenzenesulfonate, and saturated or unsaturated, aliphatic, cycloaliphatic or aromatic di- and tricarboxylate, such as. As citrate, oxalate or succinate, or di- and trisulfonate, tungstate, molybdate or heteropolyacid anion, such as phosphomolybdate, tungstate, silicomolybdate, tungstate, in particular the anions F ^- , Cl ^- , Br ^- , J ^- , BF₄ ^- , B (aryl) ₄ ^- , PF₆ ^- and P (Mo₃O₁₀) ₄ ^{3- are} suitable.

Very particularly suitable compounds are, for example

• - homopolymers with X ^- = Cl ^- , BF₄ ^- , B (phenyl) ₄ ^- , PF₆ ^- , R₁ = H, CH₃, R₂ = CH₃, C₈H₁₇ and a molecular weight of about 20,000 to about 250,000,
• - Copolymers from with X ^- and Y ^- = Cl ^- , BF₄ ^- , B (phenyl) ₄ ^- , PF₆ ^- , R₁ and R₁ '= H, CH₃, R₂ and R₂' = CH₃, C₈H₁₇, a molecular weight of about 20,000 to about 250 000 and a molar monomer ratio in the copolymer of about 0.5: 0.5 to about 0.95: 0.05,
• - Copolymers from with X ^- and Y ^- = Cl ^- , BF₄ ^- , B (phenyl) ₄ ^- , PF₆ ^- , R₁ = H, CH₃, R₂ = CH₃, C₈H₁₇, R₃ = H, CH₃, R₄ = COOH, C (O) OCH₃ , C (O) OC₂H₅, C (O) NH₂, OC (O) CH₃, CN, a molecular weight of about 20,000 to about 250,000 and a molar monomer ratio in the copolymer of about 0.5: 0.5 to ewa 0, 95: 0.05.

For example, individual compounds may be mentioned

• a homopolymer with a molecular weight of about 100,000,
• a homopolymer with a molecular weight of about 100,000,
• a homopolymer with a molecular weight of about 100,000,
• a homopolymer with a molecular weight of about 100,000,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.95: 0.05,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.95: 0.05,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.95: 0.05,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.95: 0.05,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8 to 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2,
• a copolymer having a molecular weight of about 100,000 and a molar monomer ratio in the copolymer of about 0.8: 0.2.

The preparation of the compounds of the general formulas (I)  bis (III) and their homopolymers or copolymers takes place in well-known manner, which in the literature in detail is described [z. B.B. Butler, R.J. Angelo, J. Am. Chem. Soc. 79 (1957), 3128-31; G.B. Butler in: E.J. Goethals, "Polymeric Amines and Ammonium Salts", Pergamon Press, 1980, 125-42; D.H. Solomon, D.G. Hawthorne, J. Macromol. Sci.-Rev. Macromol. Chem. C15 (1976), 143-64; Houben-Weyl, "Methods of Organic Chemistry ", Vol. XIV / 1, Thieme-Verlag, Stuttgart, 1961, 561-1182; K. Weissermel, H.-J. Arpe, "Industrielle Organic Chemistry ", Verlag Chemie, Weinheim, 1988, 230-51; DD-PS 1 27 729; EP-PS 01 03 698; US-PS 32 88 770].

Thus, the compounds of the general formulas (I) and (II) for example by reaction of allyl halides with N, N-dialkylallylamines or by reduction of alkylnitriles followed by reaction of the amine with allyl halides and quaternization of the diallylamine.

Compounds of general formula (III) are for example, prepared by addition of Hydrogen halides on ethyne, from ethylene chlorohydrin by Reaction with NaCN and alcohols, from esterification of Lactic acid with subsequent thermolysis, by reaction of Ethene with acetic acid, by Friedel-Crafts alkylation of Aromatics with subsequent cracking, by ammoxidation of Propene or catalytic hydrolysis of acrylamide.

Homopolymers of monomers of the general formulas (I) and (II) and copolymers of mixtures of two monomers of general formulas (I) to (III) are prepared by for example, radical homo- or copolymerization under Inert gas in polar solvents, such as water or dimethylformamide, with the help of radical initiators, such as t-butyl hydroperoxide or Ammonium peroxydisulfate, wherein as monomers preferably the Halide salts are used.  

The preparation of the various salts, for example the Compounds (2) to (4), (6) to (8), (10) to (12), (14) to (16), (18) to (20) and (22) to (24) is carried out by Anion exchange, e.g. B. by precipitation from aqueous medium, as described in the preparation examples.

The particular advantage of claimed according to the invention Links is that they are colorless and high Have charge control effect and that this over a longer activation period (up to 24 hours) is.

So z. B. a test toner with 1 weight percent of Compound (3) after 10 min. Charge of -8 μC / g, after 30 minutes from -21 μC / g, after 2 hours from -31 μC / g and after 24 hours of -33 μC / g (Application Example 3). A test toner with 1 weight percent of compound (13) shows the following Behavior: +30 μC / g after 10 min., +25 μC / g after 30 min., +16 μC / g after 2 hours and +12 μC / g after 24 hours (application example 10). A test toner containing 1% by weight of compound (15) shows the following values: -20 μC / g after 10 min., -28 μC / g after 30 min., -33 μC / g after 2 h and -33 μC / g after 24 h. (Application Example 11). A test powder paint containing 1% by weight of the compound (3) shows after 10 minutes a charge of -3 μC / g, -1 μC / g after 30 min., +4 μC / g after 2 hours and +2 μC / g after 24 hours (Application Example 5). A test powder coating with 1 Weight percent of the compound (1) shows after 10 min Charge of -6 μC / g, -7 μC / g after 30 min., -7 μC / g after 2 hr. and -6 μC / g after 24 hours (Application Example 6). The high charge control effect becomes more apparent when Comparison z. B. the charging behavior of the pure Toner binder "Dialec S-309" (Comparative Example 1: -4 μC / g after 10 minutes, -12 μC / g after 30 minutes, -27 μC / g after 2 hours, -48 μC / g after 24 hours) of pure Powder Coating Binder "Alftalat AN 757" (Comparative Example  2: -35 μC / g after 10 min, -32 μC / g after 30 min, -24 μC / g after 2 hours, -13 μC / g after 24 hours) and pure Powder Coating Binder "Alftalat AN 792" (Comparative Example 3: -15 μC / g after 10 min, -17 μC / g after 30 min, -13 μC / g after 2 hours, -2 μC / g after 24 hours). In the Application Examples 7, 8 and 9 is compared with the Comparative Examples 4, 5 and 6, the high charge control effect especially clear, because in addition triboelectric problematic colorants (C.I. Pigment Red 57: 1 and C.I. Solvent Blue 125) were also used.

Of great importance for the practice is that the Compounds claimed according to the invention are chemically inert and well tolerated with binders such. Styrene acrylates, Polyesters, epoxies, polyurethanes, are. In addition, the Compounds thermostable and can thus without Difficulties with the common methods (extruding, Kneading) under the usual conditions (temperatures between 100 ° C and 200 ° C) incorporated into the usual binders become. The synthesis of claimed according to the invention Compounds are inexpensive and the products fall in high purity.

The compounds used in the invention are described in the Usually in a concentration of about 0.01 to about 30 Percent by weight, preferably from about 0.1 to 5.0 Percent by weight, in the respective binder in known Way, z. B. by extrusion or kneading, homogeneous incorporated. In this case, the charge control agents for toner or charge-improving agents for powders and lacquers Surface coating, in particular for triboelectric or electrokinetically sprayed powder coatings, as dried and ground powders, dispersions or solutions, presscakes, Masterbatch, as on suitable carriers, such as. Silica gel, TiO₂, Al₂O₃, reared from aqueous or non-aqueous solution Compounds or added in any other form. As well  can the compounds used in the invention basically already in the production of the respective Binders are added, d. H. in the course of their Polymerization, polyaddition or polycondensation. The amount of electrostatic charge of the electrophotographic toner or powder coatings, in which the charge control agents claimed according to the invention homogeneous were incorporated into standard test systems same conditions (same dispersion times, same Particle size distribution, same particle shape) Room temperature and 50% relative humidity measured. The electrostatic charge of the toner or powder coating took place by turbulence with a carrier, d. H. one standardized friction partner (3 parts by weight of toner on 97 Parts by weight Carrier), on a roller bench (150 revolutions per minute). It was then used on a standard q / m measuring stand the electrostatic charge was measured (compare J. H. Dessauer, H. E. Clark, "Xerography and related Processes", Focal Press, N.Y., 1965, page 289; J.F. Hughes, "Electrostatic Powder Coating ", Research Studies Press Ltd, Letchworth, Hertfordshire, England, 1984, Chapter 2). At the determination of the q / m value, the particle size is of great influence, why in the toner obtained by sighting or Powder coating samples strictly on uniform Particle size distribution was respected.

The following examples serve to illustrate the Invention, without limiting it. The specified Parts mean parts by weight.  

Preparation Examples Preparation Example 1

10 g (0.06 mol) of a homopolymer of diallyldimethylammonium chloride (molecular weight about 100 000 g / mol) are dissolved in 200 ml of water, and 7.5 g (0.07 mol) of sodium tetrafluoroborate, dissolved in 100 ml of water, are slow added dropwise with stirring at room temperature. The white precipitate is filtered off, washed free of chloride with water and dried at 100 ° C in a vacuum oven.
Yield: 12.2 g (92.4% of theory) of compound (2), white powder
Melting point: <300 ° C (decomposition)

Elemental analysis:
45.1% C, 7.5% H, 6.6% N, 35.7 F
gef. 44.5% C, 7.9% H, 6.5% N, 33.4 F

Preparation Example 2

The procedure is as in Preparation Example 1, but instead of sodium tetrafluoroborate, 23.9 g (0.07 mol) of sodium tetraphenylborate are used.
Yield: 27.2 g (98.7% of theory) of compound (3), white powder
Melting point: 225 ° C

Elemental analysis:
86.3% C, 8.1% H, 3.1% N, 2.4% B
gef. 84.2% C, 8.1% H, 3.4% N, 2.0% B

Preparation Example 3

10 g (0.06 mol) of a copolymer of diallyldimethylammonium chloride and diallyloctylammonium chloride (molecular weight about 100,000 g / mol, molar ratio of monomer units in the copolymer about 0.8 to 0.2) are dissolved in 400 ml of water, and 7.5 g (0.07 mol) of sodium tetrafluoroborate dissolved in 100 ml of water are slowly added dropwise with stirring at room temperature. The white precipitate is filtered off, washed free of chloride with water and dried at 100 ° C in a vacuum oven.
Yield: 12.4 g (89.9% of theory) of compound (10), white powder
Melting point: <300 ° C (decomposition)

Elemental analysis:
calc. 48.0% C, 8.0% H, 6.1% N, 33.0% F
gef. 46.9% C, 8.2% H, 6.2% N, 32.7% F

Preparation Example 4

The procedure is as in Preparation Example 3, but instead of sodium tetrafluoroborate 24.0 g (0.07 mol) of sodium tetraphenylborate dissolved in 150 ml of water are used.
Yield: 26.7 g (96.3% of theory) of compound (11), white powder
Melting point: 205-210 ° C

Elemental analysis:
86.2% C, 8.3% H, 3.0% N, 2.4% B
gef. 85.6% C, 8.4% H, 3.3% N, 2.2% B

Preparation Example 5

10 g (0.06 mol) of a copolymer of diallyldimethylammonium chloride and diallylmethyloctylammonium chloride (molecular weight about 100,000 g / mol, molar ratio of monomer units in the copolymer about 0.95 to 0.05) are dissolved in 400 ml of water, and 7.5 g (0.07 mol) of sodium tetrafluoroborate dissolved in 100 ml of water are slowly added dropwise with stirring at room temperature. The pale amber precipitate is filtered off with suction, washed free of chloride with water and dried at 100 ° C in a vacuum oven.
Yield: 9.5 g (72.0% of theory) of compound (14), slightly amber powder
Melting point: 270 ° C (decomposition)

Elemental analysis:
Calcd. 46.0% C, 7.7% H, 6.4% N, 5.0% B
gef. 45.5% C, 8.0% H, 6.7% N, 4.3% B

Preparation Example 6

The procedure is as in Preparation Example 5, but instead of sodium tetrafluoroborate 24.0 g (0.07 mol) of sodium tetraphenylborate dissolved in 150 ml of water are used.
Yield: 25.8 g (95.6% of theory) of compound (15), white powder
Melting point: 240 ° C

Elemental analysis:
86.3% C, 8.2% H, 3.1% N, 2.4% B
gef. 85.7% C, 8.8% H, 3.0% N, 2.2% B

Preparation Example 7

10 g (0.08 mol) of a copolymer of diallyldimethylammonium chloride and acrylamide (molecular weight about 100,000 g / mol, molar ratio of monomer units in the copolymer about 0.8 to 0.2) are dissolved in 400 ml of water, and 9.9 g (0.09 mol) of sodium tetrafluoroborate dissolved in 200 ml of water are slowly added dropwise with stirring at room temperature. The white precipitate is filtered off, washed free of chloride with water and dried at 100 ° C in a vacuum oven.
Yield: 11.6 g (78.2% of theory) of compound (22), white powder
Melting point: <300 ° C (decomposition)

Elemental analysis:
45.4% C, 7.5% H, 7.6% N, 4.8% B
gef. 45.1% C, 7.7% H, 7.4% N, 4.3% B

applications Application Example 1

1.0 part of compound (1) was kneaded by means of a kneader Company Werner (Stuttgart) 45 minutes in 99,0 parts Toner binder ("Dialec S-309" from Diamond Shamrock, Styrene-methacrylate copolymer 60:40) incorporated homogeneously. Subsequently, at the Laboruniversalmühle 100 LU (company Alpine, Augsburg) and then on the centrifugal separator 100 MZR (Alpine company) classified. The desired particle fraction (4-25 microns) was with a Carrier made with styrene-methacrylate copolymer 90:10 50-200 μm coated magnetite particles of the type "90 μm Xerographic Carrier" from Plasma Materials Inc. (Manchester, NH, USA).

The measurement was carried out on a standard q / m measuring stand (company Epping GmbH, Neufahrn). By using a sieve with a mesh size of 25 μm (Gebr. Kufferath, Düren) it was ensured that the toner blows no Carrier could be carried away. The measurements were made Room temperature and 50% relative humidity. Depending on the activation time, the following were q / m values [μC / g] measured:

Activation q / m [μC / g] 10 minutes -4 30 min. -8th 2 hours. -13 24 hours -19

Example 2

0.5 parts of the compound (3) were as in the application example 1 described in 99.5 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes +1 30 min. -5 2 hours. -14 24 hours -26

Application Example 3

1.0 part of compound (3) became as in Application Example 1 described in 99.0 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes -8th 30 min. -21 2 hours. -31 24 hours -33

Application Example 4

2.5 parts of compound (3) were as in application example 1 described in 97.5 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes -1 30 min. -6 2 hours. -15 24 hours -25

Application Example 5

1.0 part of compound (3) became as in Application Example 1 described in 99.0 parts powder coating binder ("Alftalat AN 757 "from Hoechst AG, carboxyl group-containing polyester resin) homogeneously incorporated. Depending on the activation period the following q / m values [μC / g] were measured:

Activation q / m [μC / g] 10 minutes -3 30 min. -1 2 hours. +4 24 hours +2

Example 6

1.0 part of the compound (1) became as in Application Example 1 described in 99.0 parts powder coating binder ("Alftalat AN 792 "of Hoechst AG, hydroxyl-containing polyester resin) homogeneously incorporated. Depending on the activation period the following q / m values [μC / g] were measured:

Activation q / m [μC / g] 10 minutes -6 30 min. -7 2 hours. -7 24 hours -6

Application Example 7

2.5 parts of compound (3) and 2.5 parts of colorant C.I. Solvent Blue 125 were as in Application Example 1 described in 95.0 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes +2 30 min. -2 2 hours. -5 24 hours -9

Application Example 8

2.5 parts of compound (3) and 2.5 parts of colorant C.I. Pigment Red 57: 1 were as in Application Example 1 described in 95.0 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes -21 30 min. -30 2 hours. -35 24 hours -38

Example 9

1.0 part of compound (3) and 5.0 parts of the colorant C.I. Pigment Red 57: 1 were as in Application Example 1 described in 94.0 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes -8th 30 min. -15 2 hours. -25 24 hours -27

Application Example 10

1.0 part of compound (13) became as in Application Example 1 described in 99.0 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes +30 30 min. +25 2 hours. +16 24 hours +12

Example 11

1.0 part of the compound (15) became as in Application Example 1 described in 99.0 parts of toner binder homogeneous incorporated. Depending on the activation duration were the following q / m values [μC / g] are measured:

Activation q / m [μC / g] 10 minutes -20 30 min. -28 2 hours. -33 24 hours -33

Comparative Example 1 (for Application Examples 1 to 4 and 10-11)

100 parts of that described in Application Example 1 Toner binders "Dialec S-309" were added without further Additives as described in Application Example 1 45 Kneaded for minutes in a kneader, then ground, classified and measured at a q / m level. In Depending on the activation time, the following q / m values were used [μC / g] measured:

Activation q / m [μC / g] 10 minutes -4 30 min. -12 2 hours. -27 24 hours -48

Comparative Example 2 (for application example 5)

The procedure was as in Comparative Example 1, but instead the toner binder "Dialec S-309" the powder coating binder "Alftalat AN 757" used. Depending on the Activation time, the following q / m values [μC / g] were measured:

Activation q / m [μC / g] 10 minutes -35 30 min. -32 2 hours. -24 24 hours -13

Comparative Example 3 (for example 6)

The procedure was as in Comparative Example 1, but instead the toner binder "Dialec S-309" the powder coating binder "Alftalat AN 792" used. Depending on the Activation time, the following q / m values [μC / g] were measured:

Activation q / m [μC / g] 10 minutes -15 30 min. -17 2 hours. -13 24 hours -2

Comparative Example 4 (for application example 9)

5.0 parts of colorant C.I. Pigment Red 57: 1 were added as in Application Example 1 described in 95.0 parts Toner binder homogeneously incorporated. In dependence of the activation time, the following q / m values [μC / g] were measured:

Activation q / m [μC / g] 10 minutes -3 30 min. -20 2 hours. -52 24 hours -64

Comparative Example 5 (for application example 8)

2.5 parts of colorant C.I. Pigment Red 57: 1 were added as in Application example 1 described in 97.5 parts Toner binder homogeneously incorporated. In dependence of the activation time, the following q / m values [μC / g] were measured:

Activation q / m [μC / g] 10 minutes +3 30 min. -4 2 hours. -21 24 hours -46

Comparative Example 6 (for application example 7)

2.5 parts of colorant C.I. Solvent Blue 125 were added as in Application example 1 described in 97.5 parts Toner binder homogeneously incorporated. In dependence of the activation time, the following q / m values [μC / g] were measured:

Activation q / m [μC / g] 10 minutes +3 30 min. +5 2 hours. +6 24 hours +5

Claims (12)

1. Use of polymeric ammonium salts having a molecular weight of about 5000 to about 500 000 obtained by homopolymerization of monomers of the general formulas (I) or (II) and by copolymerization of mixtures of two monomers of the general formulas (I) to (III) with a molar monomer ratio of (I): (II) and (I): (III) and (II): (III) from about 0.5: 0.5 to about 0.95: 0.05 in the copolymer with optionally subsequent anion exchange wherein the radicals R₁ to R₁₂ and R₁ 'to R₁₂' are each independently a hydrogen atom, halogen atom, a hydroxyl radical, a primary, secondary or tertiary amino radical, a carboxylic acid or carboxylic ester radical, a sulfonic acid or sulfonic acid radical , a cyano or nitro radical or in each case a radical based on a hydrocarbon which may be interrupted by heteroatoms, and the radicals R₁₃ to R₁₆ independently of one another each represent a hydrogen atom, chlorine atom, bromine atom, a hydroxyl radical, a primary, a secondary or tertiary amino radical, a carboxylic acid or carboxylic acid ester radical, a sulfonic acid or sulfonic acid ester radical, a cyano or nitro radical or in each case a radical based on a hydrocarbon which may be interrupted by hetero atoms, mean, individually or in combination as charge control agents in electrophotographic toners and developers suitable for copying or Duplicating originals and printing electronically, magnetically or optically stored information or used in color proofing and as a charge control agent in powders and powder coatings. 2. Use of polymeric ammonium salts according to claim 1, characterized in that R₁ and R₂ or R₁ 'and R₂' are independently hydrogen atoms, straight-chain or branched, saturated or unsaturated alkyl (C₁-C₁₈) -, alkoxy (C₁-C₁₈) - Radicals, polyoxalkylene radicals of the general formula - (alkylene (C₁-C₅) -O) _n -R, wherein R is a hydrogen atom, an alkyl (C₁-C₄) radical or an acyl radical and n is a number from 1 to 10 is, aryl or heteroaryl radicals, aralkyl, aralkoxy, alkaryl or cycloalkyl radicals, and R₁ and R₂ or R₁ 'and R₂' also to a saturated or unsaturated, aromatic or non-aromatic 5- to 7-membered ring system which may contain other heteroatoms and may be substituted and / or modified by condensation of or bridging to other ring systems, wherein the radicals R₁ and R₂ or R₁ 'and R₂' contain one or more heteroatoms and by Halogen atoms, hydroxyl, carboxyl, sulfonic acid, cyano, mercapto, carboxamide, sulfonamide, urethane, keto radicals, primary, secondary or tertiary amino radicals, nitro, ether, alkyl (C₁-C₃₀) - , Alkoxy (C₁-C₃₀) -, Aroxy-, haloalkyl (C₁-C₃₀) -, haloalkoxy (C₁-C₃₀) - or ester radicals may be substituted. 3. Use of polymeric ammonium salts according to at least one of claims 1 or 2, characterized in that the radicals R₃ to R₁₂ or R₃ 'to R₁₂' are independently hydrogen atoms, halogen atoms, straight-chain or branched, saturated or unsaturated alkyl (C₁-C₁₈) -, Alkoxy (C₁-C₁₈) radicals, polyoxalkylene radicals of the general formula - (alkylene (C₁-C₅) -O) _n -R, wherein R is a hydrogen atom, an alkyl (C₁-C₄) radical or an acyl radical Rest and n is a number from 1 to 10, aryl or heteroaryl radicals, aralkyl, aralkoxy, Aroxy-, alkaryl or cycloalkyl radicals, and two of R₃ to R₁₂ or R₃ 'to R₁₂' also can combine to form a saturated or unsaturated, aromatic or non-aromatic 5- to 7-membered ring system containing further heteroatoms and may be substituted and / or modified by condensation of or bridging to other ring systems, wherein the radicals R₃ to R₁₂ or and R₃ 'to R₁₂' contain one or more heteroatoms and by halogen atoms, hydroxyl, carboxyl, sulfonic acid, cyano, mercapto, carboxamide, sulfonamide, urethane, keto radicals, primary, secondary or tertiary Amino radicals, nitro, ether, alkyl (C₁-C₃₀) -, alkoxy (C₁-C₃₀) -, Aroxy-, haloalkyl (C₁-C₃₀) -, haloalkoxy (C₁-C₃₀) - or ester radicals may be substituted can. 4. Use of polymeric ammonium salts according to at least one of claims 1 to 3, characterized in that the radicals R₁₃ to R₁₆ independently of one another hydrogen atoms, chlorine atoms, bromine atoms, straight-chain or branched, saturated or unsaturated alkyl (C₁-C₃₀) radicals, Polyoxalkylen- Radicals of the general formula - (alkylene (C₁-C₅) -O) _n -R, in which R is a hydrogen atom, an alkyl (C₁-C₄) radical or an acyl radical and n is a number from 1 to 10, aryl- or heteroaryl radicals, aralkyl, aralkoxy, alkaryl or cycloalkyl radicals, carboxyl, sulfonic acid, cyano, carboxamide, sulfonamide, ester, carboxylate, ketolactam or ether radicals, where the radicals R₁₃ to R₁₆ contain one or more heteroatoms and be substituted by chlorine or bromine atoms, hydroxyl, carboxyl, sulfonic acid, cyano, mercapto, carboxamide, sulfonamide radicals, primary, secondary or tertiary amino radicals or nitro radicals can. 5. Use of polymeric ammonium salts after at least one of claims 1 to 4, characterized in that X⁻ and Y⁻ are each the stoichiometric equivalent of a organic or inorganic anion or a mixture of mean organic and / or inorganic anions, and wherein in the case of homopolymerization of monomers of the general Formulas (I) or (II) R₁ and R₂ and / or R₁ 'and R₂' identical or may be different, and in the case of Copolymerization of mixtures of two monomers of the formulas (I) to (III) both the radicals R₁ and R₁ 'and / or R₂ and R₂' as well as the anions X⁻ and Y⁻ be identical or different can. 6. Use of polymeric ammonium salts according to at least one of claims 1 to 5, characterized in that in the formulas (I) and (II) X⁻ and Y⁻ mentioned in claim 1 independently of one another a halide, nitrate, hydroxide, Hydrogen sulphate, sulphate, sulphide, sulphite, thiosulphate, Bicarbonate, carbonate, dihydrogen phosphate, Hydrogen phosphate, phosphate, cyanide, cyanate, isocyanate, Thiocyanate, zinc tetracyanate, zinc tetrathiocyanate,  Perchlorate, BF₄⁻-, PF₆⁻-, B (aryl) ₄⁻-, CH₃OSO₃⁻-, C₂H₅OSO₃⁻-, Phenolate, nitrophenolate anion, a saturated or unsaturated, aliphatic, cycloaliphatic or aromatic carboxylate or sulfonate anion perfluorinated saturated or unsaturated, aliphatic, cycloaliphatic or aromatic carboxylate or Sulfonate anion, a saturated or unsaturated, aliphatic, cycloaliphatic or aromatic di- and Tricarboxylic acid anion or di- and trisulfonic acid anion, a Represent tungstate, molybdate or heteropolyacid anion, these anions may also be in mixed form. 7. Use of polymeric ammonium salts according to at least one of claims 1 to 6, characterized in that in the formulas (I) to (III) mentioned in claim 1 the radicals R₁ and R₂ or R₁ 'and R₂' independently Hydrogen atoms, alkyl (C₁-C₈), cyclopentyl, cyclohexyl, Phenyl, naphthyl, pyridyl, benzyl, tolyl or Methoxyphenyl radicals, wherein said radicals by Halogen atoms, hydroxyl, cyano, mercapto radicals, primary, secondary or tertiary amino radicals or nitro radicals can be substituted and the radicals R₃ to R₁₂ or R₃ 'to R₁₂' independently each other from hydrogen atoms, halogen atoms, alkyl (C₁-C₈) -, Cyclopentyl, cyclohexyl, phenyl, naphthyl, pyridyl, Benzyl, tolyl or methoxyphenyl radicals, wherein the radicals mentioned by halogen atoms, hydroxyl, cyano, Mercapto radicals, primary, secondary or tertiary amino radicals or nitro radicals may be substituted, and the radicals R₁₃ to R₁₆ independently Hydrogen, cyano, alkyl (C₁-C₈), cyclopentyl, Cyclohexyl, phenyl, naphthyl, pyridyl, benzyl, tolyl, Methoxyphenyl, carboxyl, sulfonic acid, carboxamide, Sulfonamide, ester or lactam radicals, wherein the radicals mentioned by chlorine or bromine atoms, hydroxyl, Cyano, mercapto radicals, primary, secondary or tertiary  Amino radicals or nitro radicals may be substituted, and X⁻ and Y⁻ independently of one another are an F⁻-, Cl⁻-, Br⁻-, J⁻-, BF₄⁻-, B (aryl) ₄⁻-, PF₆⁻- or P (Mo₃O₁₀) ₄³⁻-anion, these anions may also be in mixed form. 8. Use of polymeric ammonium salts after at least one of claims 1 to 7, characterized in that in Case of the copolymerization of mixtures of two monomers of in claim 1 said formulas (I) to (III) the molar Monomer ratios of (I): (II) and (I): (III) and (II): (III) in the copolymer of about 0.5: 0.5 to about 0.95: 0.05 be. 9. Use of polymeric ammonium salts after at least one of claims 1 to 8, characterized in that this have a molecular weight of about 20,000 to about 250,000. 10. Use of polymeric ammonium salts after at least one of claims 1 to 9, characterized in that one these individually or in combination in a concentration of about 0.01 to about 30 weight percent. 11. Use of polymeric ammonium salts after at least one of claims 1 to 10, characterized in that these as a coating of carriers or components of Coatings of carriers used in developers for electrophotographic copying or duplication of Templates as well as for printing electronically, optically or magnetically stored information or in color proofing are used. 12. Use of polymeric ammonium salts after at least one of claims 1 to 10, characterized in that these individually or in combination as charge-improving Agent in powders and varnishes for surface coating of Objects of metal, wood, plastic, glass, ceramics,  Concrete, textile material, paper or rubber, in particular in triboelectrically or electronically sprayed Powder coatings are used.