Biscationic acid amide and acid imide derivatives as charge controllers

Use of biscationic acid imide and acid imide derivatives whose anion is the stoichiometric equivalent of one or more organic or inorganic, mixed or non-mixed anions, the compounds also being able to exist as mixed crystals with different cations, individually or in combination, as charge controllers for toners and developers employed for electrophotographic copying or multicopying of originals and for printing electronically, optically or magnetically stored data or in color proofing, and as charge controllers for powders and powder paints.

The present invention relates to the use of biscationic acid amide 
derivatives and acid imide derivatives as colorless charge controllers in 
toners and developers for electrophotographic recording processes. Due to 
the controlled chemical linkage of specific acid amide groupings or acid 
imide groupings with two components in each case containing ammonium or 
phosphonium, combination of these units taking place via the particular 
amide nitrogens or imide nitrogens, the compounds according to the 
invention have particularly high and constant charge control properties, 
excellent heat stabilities and a very good dispersibility. 
In electrophotographic recording processes, a "latent charge image" is 
generated on a photoconductor. This is effected, for example, by charging 
of a photoconductor by a corona discharge and subsequent imagewise 
exposure to light of the electrostatically charged surface of the 
photoconductor, the exposure to light causing the charge to drain to the 
earthed substrate at the exposed points. The "latent charge image" thus 
produced is then developed by application of a toner. In a subsequent 
step, the toner is transferred from the photoconductor to, for example, 
paper, textiles, films or plastic, and is fixed there, for example by 
pressure, radiation, heat or the action of solvents. The used 
photoconductor is then cleaned and is available for a new recording 
operation. 
The optimization of toners is described in numerous patent specifications, 
the influence of the toner binder (variation of resin/resin components or 
wax/wax components), the influence of controllers or other additives or 
the influence of carriers (in two-component developers) and magnetic 
pigments (in one-component developers), inter alia, being investigated. 
A measure of the toner quality is its specific charge q/m (charge per unit 
measure). In addition to the symbol and level of the electrostatic charge, 
a critical quality criterion is that the desired charge level is achieved 
rapidly and that this charge remains constant over a relatively long 
activation period. In practice, this is of central importance inasmuch as 
the toner may be exposed to a considerable activation time in the 
developer mixture before it is transferred to the photoconductor, since it 
sometimes remains in the developer mixture for a period for production of 
up to several thousand copies. The insensitivity of the toner to climatic 
influences, such as temperature and atmospheric humidity, is moreover 
another important suitability criterion. 
Both positively and negatively chargeable toners are used in copiers and 
laser printers, depending on the type of process and apparatus. 
So-called charge controllers (also called charge control agents) are often 
added in order to obtain electrophotographic toners or developers with 
either positive or negative triboelectric charging. In addition to the 
symbol of the charge control, the extent of the controlling effect is of 
importance, since a higher activity allows a small amount to be used. 
Since toner binders by themselves as a rule show a marked dependence of the 
charging on the activation time, the object of a charge controller is on 
the one hand to establish the sign and level of the toner charge and on 
the other hand to counteract the charge drift of the toner binder and 
ensure a constant toner charge. 
Charge controllers which cannot prevent the toner or developer from 
displaying a high charge drift over a prolonged use period (ageing), and 
which can even cause the toner or developer to undergo a charge reversal, 
are therefore unsuitable in practice. 
Full color copiers and laser printers operate by the trichromism principle, 
which necessitates exact matching of the color shades of the three primary 
colors (yellow, cyan and magenta). The slightest shifts in color shade 
even of only one of the three primary colors necessarily require a shift 
in color shade of the other two colors so that full color copies and 
prints which are true to the original can also then be produced. 
Because of this precise matching of the coloristic properties of the 
individual coloring agents to one another which is required in these color 
toners, charge controllers with absolutely no intrinsic color are 
especially important. 
In the case of color toners, the three toners of yellow, cyan and magenta 
must also be matched to one another exactly in respect of their 
triboelectric properties, as well as meeting precisely defined 
color-related requirements. This triboelectric matching is necessary, 
because the three color toners (or four color toners, if black is also 
included) must be transferred in succession in the same apparatus for a 
full color print or full color copy. 
It is known that in some cases color agents can very adversely influence 
the triboelectric charging of toners (H.-T. Macholdt, A. Sieber, Dyes & 
Pigments 9 (1988), 119-27, U.S. Pat. No. 4,057,426). Because of the 
different triboelectric effects of coloring agents and the resulting, in 
some cases very pronounced, influence on toner chargeability, it is not 
possible to add them as the exclusive coloring agent in a toner base 
recipe compiled once and for all. Rather, it may be necessary to establish 
an individual recipe for each coloring agent, for which, for example, the 
nature and amount of charge controller required are tailor-made 
specifically. This procedure is correspondingly involved and additionally 
adds to the difficulties already described in color toners for process 
color (trichromism). 
Highly active colorless charge controllers which are capable of 
compensating the different triboelectric properties of various coloring 
agents and of imparting the desired charge to the toner are therefore 
required. In this manner, coloring agents which have very different 
triboelectric properties can be employed in the various toners required 
(yellow, cyan, magenta and if appropriate black) with the aid of a toner 
base recipe compiled once and for all using one and the same charge 
controller. It is moreover important in practice for the charge controller 
to have a high heat stability and good dispersibility. Typical 
temperatures for incorporating charge controllers into the toner resins 
are between 100.degree. C. and 200.degree. C. if, for example, kneaders or 
extruders are used. A heat stability of 200.degree. C., and preferably 
even 250.degree. C., is accordingly a great advantage. It is also 
important for the heat stability to be ensured over a prolonged period of 
time (about 30 minutes) and in various binder systems. Typical toner 
binders are polymerization, polyaddition and polycondensation resins, such 
as, for example, styrene resins, styrene acrylate styrene butadiene 
resins, acrylate resins, polyester resins, amide resins, amine resins, 
ammonium resins, ethylene resins, phenolic resins and epoxy resins, 
individually or in coordination, which can also contain other 
constituents, or to which other constituents can be added subsequently, 
such as coloring agents, waxes or flow auxiliaries. 
This is important, since constantly occurring matrix effects lead to 
premature decomposition of the charge controller in the toner resin, which 
means that the toner resin becomes dark yellow or dark brown in color and 
the charge control effect is completely or partly lost. 
For a good dispersibility it is of great advantage if the charge controller 
as far as possible has no wax-like properties, no tackiness and a melting 
or softening point of &gt;150.degree. C., and preferably &gt;200.degree. C. 
Tackiness often leads to problems during metering into the toner 
formulation, and low melting or softening points can mean that no 
homogeneous distribution is achieved when the substance is dispersed in, 
since the material combines, for example in droplet form, in the carrier 
material. 
Colorless charge controllers are claimed in numerous patent specifications. 
Thus, for example, DE-OS 3144017, U.S. Pat. No. 4,656,112 and JP-OS 
61-236557 describe metal complexes and metal organyls, DE-OS 3837345, 
DE-OS 3738948, DE-OS 3604827, EP-OS 242420, EP-OS 203532, U.S. Pat. Nos. 
4,684,596, 4,683,188 and 4,493,883 describe ammonium and immonium 
compounds and DE-OS 3912396, U.S. Pat. Nos. 3,893,939 and 4,496,643 
describe phosphonium compounds as colorless charge controllers for 
electrophotographic toners. 
Nevertheless, the colorless charge controllers known to date have a number 
of disadvantages which severely limit or sometimes render impossible their 
use in practice. The chromium, iron, cobalt and zinc complexes described 
in DE-OS 3144017 and U.S. Pat. No. 4,656,112 and the antimony organyls 
described in JP-OS 61-236557 thus also have, in addition to the problems 
of heavy metals, the disadvantage that in some cases they are not actually 
colorless, and therefore are of only limited use in color toners. 
The known quaternary ammonium compounds, which are suitable per se, are 
often difficult to disperse, which leads to non-uniform charging of the 
toner. In addition, the problem often arises that the toner charge 
generated by these compounds is not stable over a prolonged activation 
period (up to 24 hours activation time), especially at a high temperature 
and atmospheric humidity (EP-OS 242420), which then leads to a build-up of 
incorrectly or inadequately charged toner particles in the course of a 
copying or printing process and hence brings the process to a standstill. 
It is furthermore known that ammonium- and immonium-based charge 
controllers are sensitive to light or mechanical effects (EP-OS 203532 and 
U.S. Pat. No. 4,683,188) and can be unstable to heat, and that they form 
decomposition products which may have an adverse effect on triboelectric 
charging of the toner (U.S. Pat. No. 4,684,596) and/or have a deep, often 
dark brown, intrinsic color (DE-OS 3738948, DE-OS 3604827 and U.S. Pat. 
No. 4,493,883). Moreover, they often display wax-like properties, in some 
cases water-solubility and/or a low activity as charge controllers. 
Charge controllers which are suitable per se and are based on highly 
fluorinated ammonium, immonium and phosphonium compounds (DE-OS 3912396 
and DE-OS 3837345) have the disadvantage of an involved synthesis, which 
results in high preparation costs for the corresponding substances, and 
they are not sufficiently stable to heat. Phosphonium salts are less 
active as charge controllers than ammonium salts (U.S. Pat. Nos. 3,893,939 
and 4,496,643) and may cause toxicological problems. 
As well as being used in electrophotographic toners and developers, charge 
controllers can also be employed to improve triboelectric charging of 
powders and paints, in particular in triboelectrically or 
electrokinetically sprayed powder paints, such as are used for surface 
coating of objects of, for example, metal, wood, plastic, glass, ceramic, 
concrete, textile material, paper or rubber. 
Powder paint technology is used, inter alia, for painting small objects, 
such as garden furniture, camping articles, domestic appliances, small 
components for vehicles, refrigerators and shelving, and for painting 
workpieces of complicated shape. The powder paint or powder in general 
contains its electrostatic charge by one of the following two processes: 
a) In the corona process, the powder paint or powder is passed over a 
charged corona and becomes charged during this operation. 
b) In the triboelectric or electrokinetic process, the principle of 
frictional electricity is used. The powder paint or powder is given, in 
the spray apparatus, an electrostatic charge which is opposite to the 
charge of the friction partner, in general a flexible hose or spray pipe 
(for example of polytetrafluoroethylene). 
A combination of the two processes is also possible. The powder paint 
resins employed are, typically, epoxy resins, polyester resins containing 
carboxyl and hydroxyl groups and acrylic resins, together with the 
corresponding curing agents. Combinations of resins are also used. Thus, 
for example, epoxy resins are often employed in combination with polyester 
resins containing carboxyl and hydroxyl groups. 
Typical curing agent components for epoxy resins are, for example, acid 
anhydrides, imidazoles and dicyandiamide and derivatives thereof. Typical 
curing agent components for polyester resins containing hydroxyl groups 
are, for example, acid anhydrides, masked isocyanates, bisacylurethanes, 
phenolic resins and melamine resins, and typical curing agent components 
for polyester resins containing carboxyl groups are, for example, 
triglycidyl isocyanurates or epoxy resins. Typical curing agent components 
which are used in acrylic resins are, for example, oxazolines, 
isocyanates, triglycidyl isocyanurates or dicarboxylic acid as the curing 
agent component. 
The lack of an inadequate charge is to be observed, above all, in 
triboelectrically or electrokinetically sprayed powders and powder paints 
which have been prepared on the basis of polyester resins, in particular 
polyesters containing carboxyl groups, or on the basis of so-called mixed 
powders, also called hybrid powders. Mixed powders are understood as 
meaning powder paints, the resin base of which consists of a combination 
of epoxy resin and polyester resin containing carboxyl groups. Mixed 
powders form the basis of the powder paints represented most often in 
practice. 
The aim of the present invention was therefore to discover improved, 
particular active colorless charge controllers with which, in addition to 
the charge level, rapid achievement and constancy of this charge had to be 
ensured, and with which the charge effect should not be sensitive to 
changes in temperature and atmospheric humidity. These compounds moreover 
had to be highly heat-stable, above all also over a prolonged period of 
time in the particular carrier material (resin), and water-insoluble, 
readily dispersible and compatible with the toner contents. Moreover, the 
synthesis of the compounds should not be very complex and their 
preparation should be inexpensive. 
Surprisingly, it has now been found that specific biscationic acid amide 
derivatives and acid imide derivatives are particularly active charge 
controllers for electrophotographic toners and developers, and moreover 
can also be employed as charge-improving agents in powders and paints for 
surface coating, in particular electrokinetically sprayed powder paints. 
Because of their colorlessness, high activity, good compatibility and 
dispersibility in customary toner resins and chemical inertness, and 
because of the insensitivity of the charge controlling effect to variation 
in temperature and atmospheric humidity, the compounds are particularly 
suitable for use in color toners or developers for full color copiers and 
full color laser printers operating by the trichromism principle 
(substractive color mixing), and also for colored toners or developers in 
general and for black toners or developers. The compounds are furthermore 
also suitable for coating carriers. 
A great technical advantage of these readily dispersible compounds lies in 
the fact that substances of the same class of compounds can be employed 
either as positive or as negative controllers, depending on the 
cation/anion combination. Problems during incorporation into the toner 
binder and of compatibility with the toner binder after a toner base 
recipe has been compiled are thus minimized. 
Either positive or negative toners can thus be prepared from a solid toner 
base recipe (consisting of toner binders, coloring agent, flow auxiliary 
and if appropriate other components) by incorporating in the desired 
controller. 
It is particularly advantageous that the synthesis of the compounds claimed 
according to the invention is not particularly involved and their 
preparation is very inexpensive. 
The present invention thus relates to the use of biscationic acid amide 
derivatives and acid imide derivatives of the general formula (I) and/or 
(II) and/or (III) 
##STR1## 
in which R.sub.1 to R.sub.8 independently of one another are a hydrogen 
atom, a hydrocarbon radical, which can be interrupted by hetero atoms, 
such as, for example, straight-chain or branched, saturated or unsaturated 
alkyl groups having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, 
polyoxyalkylene groups, preferably polyoxyethylene or polyoxypropylene 
groups, of the general formula -(alkylene-O)n-R, in which R is an H atom 
or an alkyl(C.sub.1 -C.sub.4) group or acyl group, such as, for example, 
the acetyl, benzoyl, or naphthoyl group, and n is a number from 1 to 10, 
preferably from 1 to 4, mono- or polynuclear cycloaliphatic radicals 
having 5 to 12 carbon atoms, such as, for example, cyclohexyl or 
cyclopentyl groups, mono- or polynuclear aromatic radicals, such as, for 
example, phenyl, naphthyl, tolyl, or biphenyl radicals, or araliphatic 
radicals, such as, for example, the benzyl radical, in which the 
aliphatic, cycloaliphatic, araliphatic and aromatic radicals can be 
substituted by acid groups, preferably carboxylic acid and/or sulfonic 
acid groups, or salts, amides or esters thereof, alkyl(C.sub. 1 -C.sub.4), 
hydroxyl or alkoxy(C.sub.1 -C.sub.4) groups or primary, secondary or 
tertiary amino groups, such as, for example, N-monoalkyl(C.sub.1 
-C.sub.4)amino or N-dialkyl (C.sub.1 -C.sub.4)-amino groups, and by 
fluorine, chlorine or bromine atoms, the aliphatic radicals preferably by 
1 to 45 fluorine atoms, and in which the aliphatic, cycloaliphatic, 
araliphatic or aromatic ring systems can contain one or more hetero atoms, 
such as, for example, nitrogen and/or oxygen and/or sulfur and/or 
phosphorus atoms, and in which, independently of one another, R.sub.1 and 
R.sub.2 together with K, or R.sub.4 and R.sub.5 together with K' can be 
closed to form a saturated or unsaturated, preferably aromatic ring system 
having 5 to 7 atoms, which can contain further hetero atoms, preferably 
nitrogen and/or oxygen and/or sulfur atoms, and in which the particular 
ring system can in turn be substituted and/or modified by condensation on 
or bridging to further ring systems, and in which, in the case where 
R.sub.1 or R.sub.2, or R.sub.4 or R.sub.5 form a double bond to K or K', 
R.sub.3 or R.sub. 6 has no meaning, are, and/or one of the radicals 
R.sub.1, R.sub.2 or R.sub.3 can close together with R.sub.7, or one of the 
radicals R.sub.4, R.sub.5 or R.sub.6 can close together with R.sub.8 to 
form an aliphatic bridge of 2 to 5 carbon atoms, and in which A and A' are 
organic bridge members, and preferably independently of one another are 
straight-chain or branched, saturated or unsaturated alkylene men, pets 
having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, mono- or 
polynuclear cycloaliphatic members, such as, for example, cyclohexylene or 
cyclopentylene, mono- or polynuclear aromatic members, such as, for 
example, phenylene, naphthylene, tolylene or biphenylene, or araliphatic 
members, such as, for example, benzylene, xylylene, mesitylene, benzoylene 
or benzoyleneamide, in which the aliphatic, cycloaliphatic, araliphatic 
and aromatic members can be substituted by acid groups, preferably 
carboxylic acids and/or sulfonic acid groups, or salts or amides thereof, 
alkyl(C.sub.1 C.sub.4), hydroxyl or alkoxy(C.sub.1 -C.sub.4) groups or 
primary, secondary or tertiary amino groups, such as, for example, 
N-monoalkyl(C.sub.1 -C.sub.4)amino or N-dialkyl(C.sub.1 -C.sub.4)amino 
groups, and by fluorine, chlorine or bromine atoms, and the aliphatic 
members preferably by 1 to 45 fluorine atoms, and in which the aliphatic, 
aromatic and araliphatic ring systems can contain one or more hetero 
atoms, such as, for example, nitrogen and/or oxygen and/or sulfur and/or 
phosphorus atoms, and in which W.sup.1, W.sup.2 and W.sup.3 independently 
of one another represents an organic bridge member, such as, for example, 
a straight-chain or branched, saturated or unsaturated aliphatic bridge 
member having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, a 
polyoxyalkylene member, preferably a polyoxyethylene or polyoxypropylene 
member, of the general formula --CH.sub.2 --O--(alkylene[C.sub.1 -C.sub.5 
]--O)--m--CH.sub.2 --, in which m is a number from 0 to 10, preferably 
from 1 to 4, a mono- or polynuclear cycloaliphatic bridge member having 5 
to 12 carbon atoms, such as, for example, cyclopentylene or cyclohexylene, 
a mono- or polynuclear aromatic bridge member, such as, for example, 
phenylene, naphthylene, tolylene or biphenylene, or an araliphatic bridge 
member, such as, for example, benzylene, in which the aliphatic, 
cycloaliphatic, araliphatic and aromatic members can be substituted by 
acid groups, preferably carboxylic acids and/or sulfonic acid groups or 
salts, amides or esters thereof, hydroxyl, alkyl(C.sub.1 -C.sub.4) or 
alkoxy(C.sub.1 -C.sub.4) groups or primary, secondary or tertiary amino 
groups, such as, for example, N-monoalkyl(C.sub.1 -C.sub.4)amino or 
N-dialkylamino(C.sub.1 -C.sub.4) groups, and by fluorine, chlorine or 
bromine atoms, and the aliphatic members preferably by 1 to 45 fluorine 
atoms, and in which the aliphatic intermediate members and the 
cycloaliphatic, the araliphatic and the aromatic ring systems can contain 
one or more hetero atoms, such as, for example, nitrogen and/or oxygen 
and/or sulfur and/or phosphorus atoms, and in which W.sup.1 is a divalent, 
W.sup.2 a tetravalent and W.sup.3 a trivalent intermediate member, and in 
which W.sup.1, in the case of the general formula (I), can also be a 
direct bond, and K and K' independently of one another is a nitrogen, 
phosphorus, arsenic or antimony, preferably a nitrogen atom, and the anion 
X.sup..crclbar. is the stoichiometric equivalent of one or more mixed or 
non-mixed anions, it being possible for the compound also to be present as 
a mixed crystal with various cations of the general formula (I) to (III), 
individually or in combination as charge controllers in 
electrophotographic toners and developers which are employed for 
electrophotographic copying or multicopying of originals and for printing 
electronically, optically or magnetically stored data or in color 
proofing. 
The compounds claimed according to the invention are moreover suitable as 
charge controllers in powders and paints for surface coating of objects of 
metal, wood, plastic, glass, ceramic, concrete, textile material, paper or 
rubber, in particular in triboelectrically or electrokinetically sprayed 
powder paints. The compounds claimed according to the invention are 
present in an amount of about 0.01 to about 30 percent by weight, 
preferably 0.1 to about 5 percent by weight, as a homogeneous distribution 
in the particular toner, developer, paint or powder. These compounds can 
moreover also be incorporated as charge-improving agents into the coating 
of carriers which are employed in developers of electrophotographic 
copiers or printers. 
Compounds which are particularly suitable are those in which K and K' are 
nitrogen, R.sub.1 to R.sub.6 independently of one another are H atoms or 
straight-chain or branched alkyl groups (C.sub.1 -C.sub.6), such as, for 
example, methyl, ethyl, n-propyl, iso-propyl, tertiary butyl, pentyl 
and/or hexyl, and those in which, independently of one another, R.sub.1 
and R.sub.2, or R.sub.4 and R.sub.5, incorporating K or K', can be closed 
together to form a saturated or unsaturated, heterocyclic ring system 
having one or more nitrogen atoms as the hereto atom, such as, for 
example, pyrrole, pyrroline, pyrrolidine, pyrazole, pyrazolone, 
pyrazoline, hexamethyleneimine, imidazole, oxazole, thiazole, triazole, 
pyridine, piperidine, pyrazine, piperazine, pyrimidine or morpholine, in 
which these ring systems can in turn be substituted, preferably by 
straight-chain alkyl(C.sub.1 -C.sub.4) groups, or can be enlarged by 
condensation or bridging to ring systems such as quinoline, indole, 
indoline, purine, quinoxaline, benzothiazole, acridine, benzoquinoline, 
carbazole, benzophenazine, phenanthroline, bipiperidine, bipyridine, 
phenazine, benzacridine or nicotine, and in which R.sub.3 and/or R.sub.6 
are a hydrogen atom or an alkyl(C.sub.1 -C.sub.4) group, and in which 
R.sub.3 and/or R.sub.6 can also be omitted completely if there is a double 
bond between K or K' and an adjacent atom in the ring system formed by 
incorporation of K or K', R.sub.7 and R.sub.8 are a hydrogen atom, and A 
and A' independently of one another is a --CH.dbd.C(COOH)--CH.sub.2 --, 
--CH.sub.2 --(CH.sub.2 --CH.dbd.CH--)n or --(CH.sub.2 --)n bridge member 
where n is 1 to 12, preferably 1 to 4, or a phenylene, naphthylene or 
##STR2## 
bridge member, W.sup.1 [lacuna] a phenylene, naphthylene, cyclohexylene, 
(CH.sub.2)q, where q is 1 to 12, or a (CH.sub.2 --O(CH.sub.2 --CH.sub.2 
-O).sub.r --CH.sub.2 --bridge member, where r is 1 to 4, W.sup.2 is a 
phenylene or naphthylene bridge member, in which the carboxyl groups 
required for imide formation are in each case in the ortho-position 
relative to one another in the case of phenylene and in the ortho- and/or 
periposition relative to one another in the case of naphthylene, or an 
ethylenediaminetetramethylene bridge member and W.sup.3 is a phenylene or 
naphthylene bridge member, in which at least two carboxyl groups 
participating in the imide bond are in the ortho- or peri-position 
relative to one another, and the third carboxyl group can be in any 
desired position relative to these, and in which, in the case where A, A' 
and W.sup.1, the phenylene bridge members are bridged to the particular K 
or K' on the one side and to the imide or amide nitrogen on the other 
side or substituted by the particular carbonyl functions in the 1,2; 1,3; 
or 1,4-position, preferably in the 1,3 and 1,4-position, the naphthylene 
bridge members in the 1,2 to 1,8 and in the 2,3 to 2,8 position and the 
cyclohexylene bridge members in the 1,2; 1,3; or 1,4-position, preferably 
in the 1,3 or 1,4-position, and the anion X.sup..crclbar. is the 
equivalent or equivalents of a corresponding organic or inorganic anion, 
in the case of monovalent inorganic anions, for example BF.sub.4 
.sup..crclbar., B(aryl).sub.4 .sup..crclbar., such as, for example, 
tetraphenylborate, chlorotetraphenylborate, methyltetraphenylborate, 
tetranaphthylborate, tetrafluorophenylborate, tetramethoxyphenylborate, 
tetrabiphenylborate, tetrabenzylborate or tetrapyridylborate, 
PF.sub.6.sup..crclbar., SCN.sup..crclbar., HSO.sub.4.sup..crclbar., 
F.sup..crclbar., Cl.sup..crclbar., Br.sup..crclbar., I.sup..crclbar., 
CN.sup..crclbar., ClO.sub.4.sup..crclbar., sulfate, hydrogen sulfate, zinc 
tetracyanate, zinc tetrathiocyanate, tungstate, molybdate, 
phosphomolybdate and -tungstate and silicomolybdate- and tungstate, and of 
organic anions, for example ethyl- and methyl-sulfate, saturated or 
unsaturated aliphatic or aromatic carboxylate or sulfonate, such as, for 
example, acetate, lactate, oxalate benzoate, salicylate, 
2-hydroxy-3-naphthoate, 2-hydroxy-6-naphthoate, ethylsulfonate, 
phenylsulfonate, 4-toluenesulfonate or 4-aminotoluene-3-sulfonate, and 
furthermore perfluorinated, saturated or unsaturated, aliphatic or 
aromatic carboxylate or sulfonate, such as, for example, perfluoroacetate, 
perfluoroalkylbenzoate, perfluoroethylsulfonate or 
perfluoroalkyl-benzenesulfonate, and saturated and unsaturated aliphatic 
or aromatic di- or tricarboxylic acid or di- and trisulfonic acid anions, 
are the anions BF.sub.4.sup..crclbar., B(aryl).sub.4.sup..crclbar., 
PF.sub.6.sup..crclbar., SCN.sup..crclbar., CH.sub.3 
SO.sub.4.sup..crclbar., C.sub.2 H.sub.5 SO.sub.4.sup..crclbar., 
HSO.sub.4.sup..crclbar. and P[Mo.sub.3 O.sub.10 ].sub.4.sup.3.crclbar. 
being particularly suitable. 
Examples of individual compounds which may be mentioned are: 
3 
Compound Cation Anion 
1.1a 
##STR3## 
2 .times. BF.sub.4.sup..crclbar. 1.1b " 2 .times. 
PF.sub.6.sup..crclbar. 
1.1c " 
##STR4## 
1.1d " 2 .times. SCN.sup..crclbar. 1.1e " 2 .times. CH.sub.3 
SO.sub.4.sup..crclbar. 
1.2a 
##STR5## 
2 .times. BF.sub.4.sup..crclbar. 1.2b " 2 .times. 
PF.sub.6.sup..crclbar. 
1.2c " 
##STR6## 
1.2d " 2 .times. SCN.sup..crclbar. 1.2e " 2 .times. CH.sub.3 
SO.sub.4.sup..crclbar. 
1.3a 
##STR7## 
2 .times. BF.sub.4.sup..crclbar. 
1.3b " 
##STR8## 
1.4a 
##STR9## 
2 .times. BF.sub.4.sup..crclbar. 
1.4b " 
##STR10## 
1.5a 
##STR11## 
2 .times. BF.sub.4.sup..crclbar. 
1.5b " 
##STR12## 
1.6a 
##STR13## 
2 .times. BF.sub.4.sup..crclbar. 
1.6b " 
##STR14## 
1.7a 
##STR15## 
2 .times. BF.sub.4.sup..crclbar. 
1.7b " 
##STR16## 
1.8a 
##STR17## 
2 .times. BF.sub.4.sup..crclbar. 
1.8b " 
##STR18## 
1.9a 
##STR19## 
2 .times. BF.sub.4.sup..crclbar. 
1.9b " 
##STR20## 
1.10a 
##STR21## 
2 .times. BF.sub.4.sup..crclbar. 
1.10b " 
##STR22## 
1.11a 
##STR23## 
2 .times. BF.sub.4.sup..crclbar. 1.11b " 2 .times. 
PF.sub.6.sup..crclbar. 
1.11c " 
##STR24## 
1.11d " 2 .times. SCN.sup..crclbar. 1.11e " 2 .times. CH.sub.3 
SO.sub.4.sup..crclbar. 
2.1a 
##STR25## 
2 .times. BF.sub.4.sup..crclbar. 
2.1b " 
##STR26## 
3.1a 
##STR27## 
2 .times. BF.sub.4.sup..crclbar. 3.1b " 2 .times. 
PF.sub.6.sup..crclbar. 
3.1c " 
##STR28## 
3.1d " 2 .times. SCN.sup..crclbar. 3.1e " 2 .times. CH.sub.3 
SO.sub.4.sup..crclbar. 
3.2a 
##STR29## 
2 .times. BF.sub.4.sup..crclbar. 3.2b " 2 .times. 
PF.sub.6.sup..crclbar. 
3.2c " 
##STR30## 
3.2d " 2 .times. SCN.sup..crclbar. 3.2e " 2 .times. CH.sub.3 
SO.sub.4.sup..crclbar. 
3.3a 
##STR31## 
2 .times. BF.sub.4.sup..crclbar. 
3.3b " 
##STR32## 
3.4a 
##STR33## 
2 .times. BF.sub.4.sup..crclbar. 
3.4b " 
##STR34## 
3.5a 
##STR35## 
2 .times. BF.sub.4.sup..crclbar. 
3.5b " 
##STR36## 
4.1a 
##STR37## 
2 .times. BF.sub.4.sup..crclbar. 
4.1b " 
##STR38## 
5.1a 
##STR39## 
2 .times. BF.sub.4.sup..crclbar. 
5.1b " 
##STR40## 
6.1a 
##STR41## 
2 .times. BF.sub.4.sup..crclbar. 6.1b " 2 .times. 
PF.sub.6.sup..crclbar. 
6.1c " 
##STR42## 
6.1d " 2 .times. SCN.sup..crclbar. 6.1e " 2 .times. CH.sub.3 
SO.sub.4.sup. .crclbar. 
6.2a 
##STR43## 
2 .times. BF.sub.4.sup..crclbar. 6.2b " 2 .times. 
PF.sub.6.sup..crclbar. 
6.2c " 
##STR44## 
6.2d " 2 .times. SCN.sup..crclbar. 6.2e " 2 .times. CH.sub.3 
SO.sub.4.sup..crclbar. 
6.3a 
##STR45## 
2 .times. BF.sub.4.sup..crclbar. 
6.3b " 
##STR46## 
6.4a 
##STR47## 
2 .times. BF.sub.4.sup..crclbar. 6.4b " 2 .times. 
PF.sub.6.sup..crclbar. 6.4c " 2 .times. SCN.sup..crclbar. 6.4d " 
##STR48## 
6.4e " 2 .times. CH.sub.3 SO.sub.4.sup..crclbar. 
6.5a 
##STR49## 
2 .times. BF.sub.4.sup..crclbar. 
6.5b " 
##STR50## 
7.1a 
##STR51## 
2 .times. BF.sub.4.sup..crclbar. 
7.1b " 
##STR52## 
8.1a 
##STR53## 
2 .times. BF.sub.4.sup..crclbar. 
8.1b " 
##STR54## 
9.1a 
##STR55## 
2 .times. BF.sub.4.sup..crclbar. 
9.1b " 
##STR56## 
10.1a 
##STR57## 
2 .times. BF.sub.4.sup..crclbar. 
10.1b " 
##STR58## 
11.1a 
##STR59## 
2 .times. BF.sub.4.sup..crclbar. 11.1b " 2 .times. 
PF.sub.6.sup..crclbar. 
11.1c " 
##STR60## 
11.1d " 2 .times. SCN.sup..crclbar. 11.1e " 2 .times. CH.sub.3 
SO.sub.4.sup..crclbar. 11.1f " 2/3 .times. P[Mo.sub.3 O.sub.10 
].sub.4.sup.3.crclbar. 
12.1a 
##STR61## 
2 .times. BF.sub.4.sup..crclbar. 
12.1b " 
##STR62## 
13.1a 
##STR63## 
2 .times. BF.sub.4.sup..crclbar. 13.1b " 2 .times. 
PF.sub.6.sup..crclbar. 
13.1c " 
##STR64## 
13.1d " 2 .times. SCN.sup..crclbar. 
13.1e 
##STR65## 
2 .times. CH.sub.3 SO.sub.4.sup..crclbar. 13.1f " 2/3 .times. 
P[Mo.sub.3 O.sub.10 ].sub.4.sup.3.crclbar. 
13.2a 
##STR66## 
2 .times. BF.sub.4.sup..crclbar. 
13.2b " 
##STR67## 
13.2c " 2 .times. CH.sub.3 SO.sub.4.sup..crclbar. 
13.3a 
##STR68## 
2 .times. BF.sub.4.sup..crclbar. 
13.3b " 
##STR69## 
13.3.c " 2 .times. CH.sub.3 SO.sub.4.sup..crclbar. 
14.1a 
##STR70## 
2 .times. BF.sub.4.sup..crclbar. 
14.1b " 
##STR71## 
15.1a 
##STR72## 
2 .times. BF.sub.4.sup..crclbar. 
15.1b " 
##STR73## 
16.1a 
##STR74## 
2 .times. BF.sub.4.sup.- 
16.1b " 
##STR75## 
The preparation of the compounds of the general formula (I) to (III) is 
carried out in a manner which is known per se and is described in detail 
in the literature (for example Houben-Weyl, "Methoden der Organischen 
Chemie (Methods of Organic Chemistry)", Georg Thieme Verlag, 1985, Volume 
E 5, part 2, pages 924-1134 and loc. cit. 1958, Volume 11/2, pages 
591-630). 
The compounds (I) are thus prepared, for example, by reaction of the 
aliphatic, cycloaliphatic, araliphatic or iso- or heterocyclic aromatic 
dicarboxylic acids or suitable dicarboxylic acid derivatives, such as, for 
example, esters, amides, acid chlorides or acid anhydrides thereof, with 
amines or amino compounds which contain at least one tertiary and at least 
one primary or secondary amino group, in an inert reaction medium or in 
excess amine as the reaction medium, and subsequent bis-protonation with 
an inorganic or organic acid or bis-quaternization with a suitable 
quaternizing reagent. The use of dicarboxylic acid dihalides or of 
dicarboxylic acid diesters as starting substances is preferred for the 
preparation of the compounds (I). The aminolysis of dicarboxylic acid 
diesters, in particular the dimethyl or diethyl ester, with amines at 
elevated temperature, the alcohol formed being distilled off, is 
particularly preferred as the preparation process. 
The compounds (II) are prepared, for example, by reaction of the aliphatic, 
cycloaliphatic, araliphatic or iso- or heterocyclic aromatic 
tetracarboxylic acids or suitable derivatives, such as, for example, 
esters, amides, acid chlorides or acid anhydrides thereof, in particular 
monoor dianhydrides thereof, with amines or amino compounds which contain 
at least one tertiary and at least one primary amino group, and subsequent 
bis-protonation with an inorganic or organic acid or bis-quaternization 
with a suitable quaternizing reagent. The reaction can be carried out 
either under acid catalysis in an aqueous medium or in aliphatic or 
aromatic carboxylic acids or in mixtures of water and such carboxylic 
acids. A particularly suitable carboxylic acid is acetic acid. However, 
the compounds (II) can also be prepared, if appropriate under acid 
catalysis, in optionally substituted, aliphatic or aromatic hydrocarbons 
at elevated temperature, the water formed being removed from the 
circulation. Particularly suitable hydrocarbons which may be mentioned are 
toluene, xylene, chlorobenzene and o-dichlorobenzene. All diimide-forming 
tetracarboxylic acids can in principle be used as the tetracarboxylic 
acids. Aromatic tetracarboxylic acids in which in each case two carboxylic 
acid groups are in the ortho- or peri-position relative to one another are 
preferred. The compounds (III) are prepared by a suitable combination of 
the processes described for the compounds (I) and (II). 
All the suitable inorganic and organic acids and all the suitable 
alkylating agents are in principle possible for the bis-protonation or 
bis-quaternization. Particularly suitable acids are hydrochloric acid, 
sulfuric acid and acetic acid. Preferred alkylating agents are alkyl 
halides and dialkyl sulfates, in particular methyl iodide, methyl chloride 
and dimethyl and diethyl sulfate. Possible reaction media for carrying out 
the alkylation are, preferably, inert reaction media, such as, for 
example, dimethylformamide or aromatic hydrocarbons. However, anhydrous or 
aqueous alcohols, such as, for example, isobutanol or the isobutanol/water 
azeotrope having a water content of about 16%, are also suitable. In 
individual cases, the quaternization can also be carried out in an aqueous 
medium. 
The various salts are prepared by anion exchange, for example by 
precipitation form an aqueous or aqueous-alcoholic medium, as described in 
the preparation examples. The particular advantage of the compounds 
claimed according to the invention is that they are colorless and have a 
high charge controlling effect, and that this charge controlling effect is 
constant over a long activation period (up to 24 hours). Thus, for 
example, a test toner containing only 1 % by weight of the compound (1.1a) 
shows a charge of +9 .mu.C/g after 10 minutes, +9 .mu.C/g after 30 
minutes, +6 .mu.C/g after 2 hours and +3 .mu.C/g after 24 hours (Example 
3). The high charge controlling effect becomes all the more clearer if, 
for example, the charging properties of the pure carrier material Dialec 
S309 is considered by comparison (comparison example; 10 minutes: -4 
.mu.C/g; 30 minutes: -12 .mu.C/g; 2 hours: -27 .mu.C/g; 24 hours: -48 
.mu.C/g). As well as establishing the desired charge polarity and level, 
the compounds claimed according to the invention must also keep the high 
charge drift of more than 40 .mu. C/g constant. 
Another advantage of the compounds claimed according to the invention is 
that the charge controlling effect of a compound can be changed in small 
steps merely by varying the anion. For example, if, instead of the 
BF.sub.4.sup..crclbar. salt mentioned in Example 1, the 
PF.sub.6.sup..crclbar. salt of the same cation is employed (compound 
1.1b), a corresponding test toner shows a charge of +7 .mu.C/g after 10 
minutes; +7 .mu.C/g after 30 minutes; +4 .mu.C/g after 2 hours and +3 
.mu.C/g after 24 hours (Example 2). It is moreover also possible to 
reverse the polarity of the symbol of the charge controlling effect by 
choosing a suitable anion. For example, if the 
##STR76## 
salt of the cation discussed is employed (compound 1.1c), instead of the 
positive charge controlling effect, a negative charge controlling effect 
is found (Example 1; 10 minutes: -27 .mu.C/g; 30 minutes: -27 .mu.C/g; 2 
hours: -25 .mu.C/g; 24 hours: -23 .mu.C/g). The charge controlling effect 
of the compounds claimed according to the invention is moreover highly 
insensitive to variations in atmospheric humidity (Example 3). 
It is of great importance in practice that the compounds claimed according 
to the invention are chemically inert and readily compatible with carrier 
materials, such as, for example, styrene acrylates, polyesters, epoxides, 
polyurethanes and the like. In addition, the compounds are stable to heat 
and can therefore be incorporated into the customary carrier materials 
without difficulty using the customary processes (extrusion, kneading) 
under the customary conditions (temperatures of between 100.degree. C. and 
200.degree. C.). the synthesis of the compounds claimed according to the 
invention is not particularly involved and the products are obtained in a 
high purity. 
The compounds used according to the invention are as a rule incorporated 
homogeneously in a concentration of about 0.01 to about 30 percent by 
weight, preferably about 0.1 to about 5.0 percent by weight, into the 
particular carrier material in a known manner, for example by kneading in 
or extrusion. The charge controller for toners or charge-improving agent 
for powders and paints for surface coating, in particular for 
triboelectrically or electrokinetically sprayed powder paints, can be 
added here as dried and ground powders, dispersions or solutions, 
press-cakes, a masterbatch, as compounds absorbed onto suitable carriers, 
such as, for example, silica gel, TiO.sub.2 or Al.sub.2 O.sub.3, form 
aqueous or nonaqueous solution, or in another form. The compounds employed 
according to the invention can likewise in principle also already been 
added during the preparation of the particular binders, that is to say in 
the course of the polymerization, polyaddition or polycondensation 
thereof. The level of the electrostatic charge of the electrophotographic 
toners in which the charge controllers claimed according to the invention 
were incorporated homogeneously was measured by standard test systems 
under identical conditions (such as the same dispersion times, same 
particle size distribution, same particle shape) at room temperature and 
50% relative atmospheric humidity. The particular toner was conditioned in 
a climatic chamber for the measurement at room temperature and 90% 
relative atmospheric humidity. The toner was activated in a two-component 
developer by swirling with a carrier (3 parts by weight of toner per 97 
parts by weight of carrier) on a roller bench (150 revolutions per 
minute). The electrostatic charge was then measured on a customary q/m 
measuring stand (cf. J.H. Dessauer, H.E. Clark, "Xerography and related 
Processes", Focal Press, N.Y., 1965, page 289). The particle size has a 
great influence on the determination of the q/m value, which is why strict 
attention was paid to a uniform particle size distribution of the toner 
samples obtained by sizing. 
The following examples serve to illustrate the invention without limiting 
it thereto. The parts stated are parts by weight.

PREATION EXAMPLES 
EXAMPLE A 
Amide Formation 
149.2 g (0.73 mol) of terephthaloyl dichloride are stirred into 3.5 1 of 
anhydrous toluene, and 180.0 g (1.76 mol) of 3-dimethylamino-1-propylamine 
are then added dropwise at 20.degree. to 30.degree. C. in the course of 30 
minutes. The mixture is stirred at this temperature for 5 hours, 
subsequently heated at 50.degree. to 60.degree. C. and 70.degree. to 
80.degree. C. for in each case 1 to 2 hours and then heated under reflux 
for 4 hours. The resulting product is filtered off with suction at 
20.degree. to 30.degree. C., washed with toluene and dried at 100.degree. 
C. in a vacuum drying cabinet. 292.4 g (0.72 mol) of the bisamide are 
obtained in the form of the bishydrochloride. The product is dissolved in 
450 ml of water, and 180 g of 33 % strength sodium hydroxide solution are 
added at 0.degree. to 5.degree. C. in the course of 30 minutes. During 
this operation, the bisamide precipitates out in coarsely crystalline 
form. After the mixture has been stirred at 0.degree. to 5.degree. C. for 
one hour, the product is filtered off with suction, washed with 90 ml of 
ice-water and dried at 100.degree. C. in a vacuum cabinet. 
Characterization: 
White powder, melting point 172.degree.-174.degree. C. 
.sup.1 H-NMR (in DMSO-d.sub.6): 1.65 (quintet, 4 methylene-H), 2.13 
(singlet, 12 methyl-H), 2.28 (triplet, 4 methylene-H), 3.30 (quartet, 4 
methylene-H), 7.90 (singlet, 4 phenylene-H), 8.63 (triplet, 2 amide-H) 
ppm. 
Quaternization 
66.8 g (0.2 mol) of the amide are stirred into 1.6 1 of toluene, and 100.8 
g (0.8 mol) of dimethyl sulfate are added at 20.degree. to 30.degree. C. 
in the course of 10 minutes. The mixture is stirred at 20.degree. to 
30.degree. C. for 1 hour and then heated under reflux for 5 hours. After 
cooling to 20.degree. to 30.degree. C., the product is filtered off with 
suction, washed with toluene and dried at 100.degree. C. in a vacuum 
cabinet. 
Characterization: 
White powder, melting point 180.degree. C. 
.sup.1 H-NMR (in D.sub.2 O): 2.18 (multiplet, 4 methylene-H), 3.20 
(singlet, 18 methyl-H), 3.50 (multiplet, 8 methylene-H), 3.75 (singlet, 6 
methyl-H), 7.88 (singlet, 4 phenylene-H) ppm. 
Anion Exchange 
A solution of 13.7 g (40 mmol) of sodium tetraphenylborate in 50 ml of 
water is added dropwise to 100 ml of a solution of 10.0 g (17 mmol) of the 
quaternized compound at room temperature, while stirring. During this 
operation, compound 1.1c precipitates out as a white precipitate. The 
precipitate is filtered off with suction, washed with water and dried in a 
circulating air cabinet at 60.degree. C. 
Characterization: 
White powder, melting point 255.degree. C. 
.sup.1 H-NMR (in DMSO-d.sub.6): 1.98 (multiplet, 4 methylene-H), 3.03 
(singlet, 18 methyl-H), 3.38 (multiplet, 8 methylene-H), 6.96 (multiplet, 
40 phenyl-H), 7.95 (singlet, 4 phenylene-H), 8.64 (triplet, 2 amide-H) 
ppm. 
EXAMPLE B 
Amide Formation 
The amide was formed as described in Example A. 
Salt Formation 
5.0 g (15 mmol ) of the amide are suspended in 50 ml of water, and 2N 
acetic acid is added until a pH of 7 is reached, during which the amine 
dissolves. A solution of 13.7 g (40 mmol) of sodium tetraphenylborate in 
50 ml of water is then added dropwise, whereupon the product precipitates 
out as a thick white precipitate. The reaction mixture is stirred at room 
temperature for 30 minutes, the precipitate is filtered off with suction 
and washed with water and finally the reaction product, compound 1.2c is 
dried at 60.degree. C. in a circulating air cabinet. 
Characterization: 
White powder, melting point 197.degree. C. 
.sup.1 H-NMR (in DMSO-d.sub.6): 1.85 (multiplet, 4 methylene-H), 2.71 
(singlet, 12 methyl-H), 3.00 (multiplet, 4 methylene-H), 3.35 (multiplet, 
4 methylene-H), 6.96 (multiplet, 40 phenyl-H), 7.93 (singlet, 4 
phenylene-H), 8.63 (triplet, 2 amide-H ) ppm. 
EXAMPLE C 
Amide Formation 
109.5 g (0.75 mol) of dimethyl succinate are dissolved in 459 g (4.5 mol) 
of 3-dimethylamino-1-propylamine. The mixture is then heated under reflux 
for 10 hours. Since the boiling point drops considerably due to the rapid 
onset of splitting off of methanol, it is ensured, by occasional 
distillation of a methanol-amine mixture, that the temperature in the gas 
phase remains above 125.degree. C. Toward the end of the reaction time, 
the temperature in the gas phase is above 130.degree. C. About 200 g of 
methanol/amine mixture are distilled off in the course of the reaction. 
The mixture is then cooled to 20.degree. to 30.degree. C. and the reaction 
product which has crystallized out is filtered off with suction. Further 
product can be precipitated out of the filtrate by three-fold dilution 
with benzine. The product is washed free from amine with benzine and dried 
at 100.degree. C. in a vacuum cabinet. 
Characterization: 
White powder, melting point 126.degree.-128.degree. C. .sup.1 H-NMR (in 
DMSO-d.sub.6): 1.48 (quintet, 4 methylene-H), 2.08 (singlet, 12 methyl-H), 
2.20 (triplet, 4 methylene-H), 2.25 (singlet, 4 methylene-H), 3.05 
(quartet, 4 methylene-H), 7.78 (triplet, 2 amide-H) ppm. 
Quaternization 
85.8 g (0.3 mol) of the amide are introduced into 610 ml of anhydrous 
dimethylformamide. A clear solution rapidly forms at room temperature. 189 
g (1.5 mol) of dimethyl sulfate are then added dropwise at 30.degree. to 
40.degree. C. in the course of about 15 minutes. After a short time, a 
thick crystal slurry is formed, which changes into a readily stirtable 
suspension on heating to 60.degree. C. The suspension is subsequently 
stirred at 60.degree. to 70.degree. C. for 5 hours and, after cooling to 
0.degree. to 5.degree. C., the product is filtered off with suction. It is 
washed thoroughly with toluene and dried in a vacuum cabinet at 
100.degree. C. 
Characterization: 
White powder, melting point 152.degree. C. .sup.1 H-NMR (in DMSO-d.sub.6): 
1.85 (multiplet, 4 methylene-H), 2.33 (singlet, 4 methyl-H), 3.05 
(singlet, 18 methyl-H), 3.20 (multiplet, 8 methylene-H), 3.40 (singlet, 6 
methyl-H), 7.95 (triplet, 2 amide-H) ppm. 
Anion Exchange 
10.0 g (18.5 mmol) of the quaternized product were precipitated with 13.7 g 
(40 mmol) of sodium tetraphenylborate analogously to the salt formation 
described in Example A, to give the compound 6.1c. 
Characterization: 
White powder, melting point 245.degree. C. 
.sup.1 H-NMR (in DMSO-d.sub.6): 1.81 (multiplet, 4 methylene-H), 2.37 
(singlet, 4 methylene-H), 3.02 (singlet, 18 methyl-H), 3.12 (quartet, 4 
methylene-H), 3.24 (multiplet, 4 methylene-H), 6.97 (multiplet, 40 
phenyl-H), 7.90 (triplet, 2 amide-H) ppm. 
EXAMPLE D 
Amide Formation 
The amide was formed as described in Example C. 
Salt Formation 
The salt formation with 13.7 g (40 mmol) of sodium tetraphenylborate was 
carried out analogously to the salt formation described in Example B, 5.0 
g (17.5 mmol) of the amide described in Example C being employed. Compound 
6.2c is obtained as the product. 
Characterization: 
White powder, melting point 183.degree. C. 1H--NMR (in DMSO-d.sub.6): 1.72 
(multiplet, 4 methylene-H), 2.38 (singlet, 4 methylene-H), 2.68 (singlet, 
12 methyl-H), 2.95 (multiplet, 4 methylene-H), 3.12 (quartet, 4 
methylene-H), 7.01 (multiplet, 40 phenyl-H), 7.92 (triplet, 2amide-H) ppm. 
EXAMPLE E 
Imide Formation 
218.0 g (1.0 mol) of pyromellitic dianhydride are stirred in 1.2 1 of 
glacial acetic acid, and 306 g (3.0 mol) of 3-dimethylamino-1-propylamine 
are added dropwise at 40.degree. to 50.degree. C., while cooling. The 
mixture is then heated under reflux for 3 hours, 920 ml of 
o-dichlorobenzene are added and the majority of the glacial acetic acid is 
distilled off. The mixture is then heated, while passing over a stream of 
nitrogen and distilling of the residual glacial acetic acid, until the 
boiling point of o-dichlorobenzene is reached, and heating is continued 
under reflux for 6 hours. After the mixture has been cooled to 20.degree. 
to 30.degree. C., the product which has precipitated out is filtered off 
with suction, washed with benzine and dried at 100.degree. C. in a vacuum 
cabinet. 
Characterization: 
White powder, melting point 186.degree.-188.degree. C. 
.sup.1 HN13 MR (in DMSO-d.sub.6): 1.75 (quintet, 4 methylene-H), 2.08 
(singlet, 12 methyl-H), 2.25 (triplet, 4 methylene-H), 3.68 (triplet, 4 
methylene-H), 8.15 (singlet, 2 phenylene-H) ppm. 
Quaternization 
77.2 g (0.2 mol) of the imide are stirred in 600 ml of dimethylformamide, 
and 126.0 g (1.0 mol) of dimethyl sulfate are added dropwise at 30.degree. 
to 40.degree. C. in the course of 20 minutes, while cooling. The mixture 
is heated at 130.degree. to 135.degree. C. for 5 hours and, after cooling 
to 20.degree. to 30.degree. C., the product is filtered off with suction. 
The product is washed with toluene and dried at 100.degree. C. in a vacuum 
cabinet. 
Characterization: 
White powder, melting point 197.degree. C. 
.sup.1 H--NMR (in D.sub.2 O): 2.23 (multiplet, 4 methylene-H), 3.15 
(singlet, 18 methyl-H), 3.48 (multiplet, 4 methylene-H), 3.73 (singlet, 6 
methyl-H), 3.88 (triplet, 4 methylene-H), 8.33 (singlet, 2 phenylene-H) 
ppm. 
Anion Exchange 
The anion exchange with 13.7 g (40 mmol) of sodium tetraphenylborate is 
carried out analogously to the anion exchange described in Example A, 10.0 
g (16 mmol) of the quaternized compound mentioned above being employed, to 
give the compound 11.1c as the product. 
Characterization: 
White powder, melting point 295.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 2.08 (multiplet, 4 methylene-H), 2.97 
(singlet, 18 methyl-H), 3.36 (multiplet, 4 methylene-H), 3.70 (triplet, 4 
methylene-H), 6.98 (multiplet, 40 phenyl-H), 8.28 (singlet, 2 phenylene-H) 
ppm. 
EXAMPLE F 
Imide Formation 
71.5 g (0.25 mol) of naphthalene-1,4,5,8-tetracarboxylic acid 
1,8-monoanhydride are stirred into 500 ml of glacial acetic acid, and 93.8 
g (0.75 mol) of N-(3-aminopropyl)-imidazole are added dropwise at 
40.degree. to 50.degree. C., while cooling gently. The mixture is then 
heated under reflux for 6 hours. The resulting solution of the reaction 
product is poured into 2.5 l of water, and 1.01 kg of 33% strength sodium 
hydroxide solution are then added dropwise at 20.degree. to 30.degree. C., 
while cooling, so that the product precipitates out. The product is 
filtered off with suction, washed thoroughly with water and dried at 
100.degree. C. in a vacuum cabinet. 
Characterization: 
White powder, melting point 260.degree.-263.degree. C. 
Quaternization 
96.4 g (0.2 mol) of the imide are stirred into 600 ml of dimethylformamide, 
and 189.0 g (1.5 mol) of dimethyl sulfate are added dropwise at 30.degree. 
to 40.degree. C. in the course of 10 minutes, while cooling gently. The 
mixture is then stirred at 130.degree. to 135.degree. C. for 5 hours. 
After the mixture has been cooled to 20.degree. to 30.degree. C., the 
product, compound 13.2c is filtered off with suction, washed with 100 ml 
of dimethylformamide and then with toluene and dried at 100.degree. C. in 
a vacuum cabinet. 
Characterization: 
White powder, melting point 261.degree. C. 
.sup.1 H--NMR (in D.sub.2 O): 2.35 (quintet, 4 methylene-H), 3.68 (singlet, 
6 methyl-H), 3.95 (singlet, 6 methyl-H), 4.10 (triplet, 4 methylene-H), 
4.39 (triplet, 4 methylene-H), 7.60 (multiplet, 4 imidazoyl-H), 8.40 
(singlet, 4 naphthylene-H), 8.86 (singlet, 2 imidazoyl-H)ppm. 
USE EXAMPLES 
EXAMPLE 1 
One part of the terephthalic acid derivative 1.1c (for the synthesis of the 
compound, see Preparation Example A) was dispersed homogeneously in 99 
parts of toner binder (.sup.R Dialec S 309 from Diamond Shamrock 
(styrene/methacrylic copolymer)) by means of a kneader from Werner & 
Pfleiderer (Stuttgart) for 30 minutes. The dispersion was then ground on a 
100 LU universal laboratory mill (Alpine, Augsburg) and subsequently 
classified on a 100 MZR centrifugal sizer (Alpine). 
The desired particle fraction was activated with a carrier of magnetite 
particles of size 50 to 200 .mu.m coated with styrene/methacrylic 
copolymer 90:10, of the type "90 .mu.m Xerographic Carrier" from Plasma 
Materials Inc. 
The measurement is carried out on a customary q/m measuring stand (in this 
context cf. J. H. Dessauer, H. E. Clark "Xerography and related 
Processes", Focal Press, N.Y. 1965 page 289); using a sieve of mesh width 
25 .mu.m (508 mesh per inch), Gebruder Kufferath, Duren, it was ensured 
that no carrier can be entrained when the toner is blown out. The 
measurements were made at room temperature and 50% relative atmospheric 
humidity, deviating experimental conditions being noted in the examples in 
question. 
The following q/m values [.mu.C/g] were measured as a function of the 
activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -27 
30 minutes -27 
2 hours -25 
24 hours -23 
______________________________________ 
EXAMPLE 2 
1 part of the terephthalic acid derivative 1.1b (for the synthesis, see 
below) was incorporated homogeneously into 99 parts of toner binder as 
described in Example 1. The following q/m values [.mu.C/g] were measured 
as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +7 
30 minutes +7 
2 hours +4 
24 hours +3 
______________________________________ 
Synthesis 
The preparation of the amide and the quaternization were carried out 
analogously to Preparation Example A. Instead of NaB-(phenyl).sub.4, the 
KPF.sub.6 salt was employed for the anion exchange. 
Characterization: 
White powder, melting point 265.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 1.98 (multiplet, 4 methylene-H), 3.04 
(singlet, 18 methyl-H), 3.37 (multiplet, 8 methylene-H), 7.92 (singlet, 4 
phenylene-H), 8.63 (triplet, 2 amide-H) ppm. 
EXAMPLE 3 
1 part of the terephthalic acid derivative 1.1a (for the synthesis, see 
below) were incorporated homogeneously into 99 parts of toner binder as 
described in Example 1. The following q/m values [.mu.C/g] were measured 
as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +9 
30 minutes +9 
2 hours +6 
24 hours +3 
______________________________________ 
The following q/m values [.mu./C/g] were determined at 90% relative 
atmospheric humidity: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +6 
30 minutes +7 
2 hours +7 
24 hours +3 
______________________________________ 
Synthesis 
The preparation of the amide and the subsequent quaternization were carried 
out analogously to Preparation Example A, the solution being concentrated 
to 30 ml and cooled to 2.degree. C. to obtain the precipitate. 
Instead of NaB-(phenyl).sub.4, an NaBF.sub.4 salt was employed for the 
anion exchange. 
Characterization: 
White powder, melting point 228.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 1.99 (multiplet, 4 methylene-H), 3.05 
(singlet, 18 methyl-H), 3.38 (multiplet, 8 methylene-H), 7.93 (singlet, 4 
phenylene-H), 8.62 (triplet, 2 amide-H) ppm. 
EXAMPLE 4 
1 part of the terephthalic acid derivative 1.2c (for the synthesis, see 
Preparation Example B) was incorporated homogeneously into 99 parts of 
toner binder as described in Example 1. The following q/m values [.mu.C/g] 
were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -27 
30 minutes -32 
2 hours -32 
24 hours -31 
______________________________________ 
EXAMPLE 5 
One part of the succinic acid derivative 6.1c (for the synthesis, see 
Preparation Example C) was incorporated homogeneously into 99 parts of 
toner binder as described in Example 1. The following q/m values [.mu.C/g] 
were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -31 
30 minutes -34 
2 hours -33 
24 hours -22 
______________________________________ 
EXAMPLE 6 
One part of the succinic acid derivative 6.1b (for the synthesis, see 
below) were incorporated homogeneously into 99 parts of toner binder as 
described in Example 1. The following q/m values ].mu.C/g] were measured 
as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -5 
30 minutes -7 
2 hours -8 
24 hours -7 
______________________________________ 
Synthesis 
The preparation of the amide and the quaternization were carried out 
analogously to Preparation Example C. 
Instead of NaB-(phenyl).sub.4, a KPF.sub.6 salt was employed for the anion 
exchange. 
Characterization: 
White powder, melting point 208.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 1.83 (multiplet, 4 methylene-H), 2.35 
(singlet, 4 methylene-H), 3.02 (singlet, 18 methyl-H), 3,12 (quartet, 4 
methylene-H), 8.25 (multiplet, 4 methylene-H), 7.86 (triplet, 2 amide-H) 
ppm. 
EXAMPLE 7 
One part of the succinic acid derivative 6.2c (for the amide formation, see 
Preparation Example C, salt formation analogous to Preparation Example B) 
was incorporated homogeneously into 99 parts of toner binder as described 
in Example 1. The following q/m values [.mu.C/g] were measured as a 
function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -35 
30 minutes -38 
2 hours -40 
24 hours -32 
______________________________________ 
EXAMPLE 8 
One part of the 1,4-cyclohexanedicarboxylic derivative 3.2b (for the 
synthesis, see below) was incorporated homogeneously into 99 parts of 
toner binder as described in Example 1. The following q/m values [.mu.C/g] 
were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -6 
30 minutes -8 
2 hours -11 
24 hours -12 
______________________________________ 
Synthesis 
The preparation of the amide and the quaternization were carried out 
analogously to Preparation Example C, dimethyl 
1,4-cyclohexanedicarboxylate being employed instead of dimethyl succinate. 
The KPF.sub.6 salt was employed for the anion exchange. 
Characterization: 
White powder, melting point 298.degree. C. 
.sup.1 H-NMR (in DMSO-d.sub.6): 1.35 (multiplet, 4 methylene-H), 1.8 
(multiplet, 8 cyclohexylene-H), 2.05 (multiplet, 2 cyclohexylene-H), 3.05 
(singlet, 18 methyl-H), 3.25 (multiplet, 4 methylene-H), 3.25 (multiplet, 
4 methylene-H), 7.78 (triplet, 2 amide-H) ppm. 
EXAMPLE 9 
One part of the 1,4-cyclohexanedicarboxylic acid derivative 3.2c (for the 
synthesis, see below) was incorporated homogeneously into 99 parts of 
toner binder as described in Example 1. The following q/m values [.mu.C/g] 
were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -35 
30 minutes -37 
2 hours -37 
24 hours -40 
______________________________________ 
Synthesis 
The preparation of the amide and the quaternization were carried out 
analogously to Preparation Example C, dimethyl 
1,4-cyclohexanedicarboxylate being employed instead of dimethyl succinate. 
Instead of KPF.sub.6, the NaB-(phenyl).sub.4 salt was employed for the 
anion exchange. 
Characterization: 
White powder, melting point 255.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 1.35 (multiplet, 4 methylene-H), 1.8 
(multiplet, 8 cyclohexylene-H), 2.05 (multiplet, 2 cyclohexylene-H), 3.03 
(singlet, 18 methyl-H), 3.1 (multiplet, 4 methylene-H), 3.25 (multiplet, 4 
methylene-H), 6.95 (multiplet, 40 phenyl-H), 7.8 (triplet, 2 amide-H) ppm. 
EXAMPLE 10 
1 part of the pyromellitic acid derivative 11.1c (for the synthesis, see 
Preparation Example E) was incorporated homogeneously into 99 parts of 
toner binder as described in Example 1. 
The following q/m values [.mu.C/g] were measured as a function of the 
activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -13 
30 minutes -20 
2 hours -22 
24 hours -18 
______________________________________ 
EXAMPLE 11 
1 part of the pyromellitic acid derivative 11.1a (for the synthesis, see 
below) was incorporated homogeneously into 99 parts of toner binder as 
described in Example 1. The following q/m values [.mu.C/g] were measured 
as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -3 
30 minutes -5 
2 hours -8 
24 hours -9 
______________________________________ 
Synthesis 
The preparation of the imide and the quaternization were carried out 
analogously to Preparation Example E. Instead of NaB-(phenyl)4, an 
NaBF.sub.4 salt was employed for the anion exchange. 
Characterization: 
White powder, melting point &gt;300.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 2.12 (multiplet, 4 methylene-H), 3.05 
(singlet, 18 methyl-H), 3.35 (multiplet, 4 methylene-H), 3.71 (triplet, 4 
methylene-H), 8.26 (singlet, 2 phenylene-H) ppm. 
EXAMPLE 12 
1 part of the pyromellitic acid derivative 11.1d (for the synthesis, see 
below) was incorporated homogeneously into 99 parts of toner binder as 
described in Example 1. The following q/m values [.mu.C/g] were measured 
as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +9 
30 minutes +8 
2 hours +4 
24 hours +0.3 
______________________________________ 
Synthesis 
The preparation of the imide and the quaternization were carried out 
analogously to Preparation Example E. Instead of NaB-(phenyl)4, a KSCN 
salt was employed for the anion exchange. 
Characterization: 
White powder, melting point 285.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 2.10 (multiplet, 4 methylene-H), 3.06 
(singlet, 18 methyl-H), 3.41 (multiplet, 4 methylene-H), 3.70 (triplet, 4 
methylene-H), 8.24 (singlet, 2 phenylene-H) ppm. 
EXAMPLE 13 
1 part of the pyromellitic acid derivative 11.1b (for the synthesis, see 
below) was incorporated homogeneously into 99 parts of toner binder as 
described in Example 1. The following q/m values [.mu.C/g] were measured 
as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -3 
30 minutes -8 
2 hours -11 
24 hours -11 
______________________________________ 
Synthesis 
The preparation of the imide and the quaternization were carried out 
analogously to Preparation Example E. Instead of NaB-(phenyl)4, the 
KPF.sub.6 salt was employed for the anion exchange. 
Characterization: 
White powder, melting point &gt;300.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 2.08 (multiplet, 4 methylene-H), 3.03 
(singlet, 18 methyl-H), 3.38 (multiplet, 4 methylene-H), 3.72 (triplet, 4 
methylene-H), 8.27 (singlet, 2 phenylene-H) ppm. 
EXAMPLE 14 
1 part of the pyromellitic acid derivative 11.1a (for the synthesis, see 
below) was incorporated homogeneously into 99 parts of toner binder as 
described in Example 1. The following q/m values [.mu.C/g] were measured 
as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -7 
30 minutes -16 
2 hours -25 
24 hours -32 
______________________________________ 
Synthesis 
The preparation of the imide and the quaternization were carried out 
analogously to Preparation Example E. Instead of NaB-(phenyl).sub.4, an 
Na.sub.3 [P(Mo.sub.3 O.sub.10).sub.4 ] salt was employed for the anion 
exchange. 
Characterization: 
Yellowish powder, melting point &gt;300.degree. C. 
.sup.1 H--NMR (in DMSO-d.sub.6): 2.13 (multiplet, 4 methylene-H), 3.10 
(singlet, 18 methyl-H), 3.42 (multiplet, 4 methylene-H), 3.73 (triplet, 4 
methylene-H), 8.22 (singlet, 2 phenylene-H) ppm. 
EXAMPLE 15 
1 part of the pyromellitic acid derivative 11.1e (the synthesis of the 
methyl sulfate salt is described in Preparation Example E) was 
incorporated into 99 parts of toner binder as described in Example 1. The 
following q/m values [.mu.C/g] were measured as a function of the 
activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +7 
30 minutes +7 
2 hours +6 
24 hours +3 
______________________________________ 
EXAMPLE 16 
1 part of the naphthalenetetracarboxylic acid derivative 13.2c (for the 
synthesis, see Preparation Example F) was incorporated homogeneously into 
99 parts of toner binder as described in Example 1. The following q/m 
values [.mu.C/g] were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +12 
30 minutes +10 
2 hours +7 
24 hours +4 
______________________________________ 
EXAMPLE 17 
1 part of the naphthalenetetracarboxylic acid derivative 13.3c (for the 
synthesis, see below) was incorporated homogeneously into 99 parts of 
toner binder as described in Example 1. The following q/m values [.mu.C/g] 
were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -1 
30 minutes -1 
2 hours -7 
24 hours -10 
______________________________________ 
Synthesis 
The preparation of the imide and the quaternization were carried out 
analogously to Preparation Example F, 2 parts of 
##STR77## 
prepared by reaction of 4-nitrobenzoyl chloride with 
3-dimethylamino-1-propylamine and subsequent reduction of the nitro group, 
being employed as the amine component. 
Characterization: 
White powder, melting point &gt;300.degree. C. (decomposition) 
.sup.1 H--NMR (in DMSO-d.sub.6): 2.6 (multiplet, 4 methylene-H), 3.5 
(singlet, 18 methyl-H), 3.8 (multiplet, 8 methylene-H), 4.1 (singlet, 6 
methyl-H), 7.6 (multiplet, 4 phenyl-H), 8.2 (multiplet, 4 phenyl-H), 8.9 
(singlet, 4 naphthyl-H) ppm. 
EXAMPLE 18 
1 part of the naphthalenetetracarboxylic acid derivative 13.1a (for the 
synthesis, see below) was incorporated homogeneously in 99 parts of toner 
binder as described in Example 1. The following q/m values [.mu.C/g] were 
measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +7 
30 minutes +4 
2 hours +1 
24 hours -2 
______________________________________ 
Synthesis 
The preparation of the imide and the quaternization were carried out as 
described in Preparation Example F, 2 parts of 
3-dimethylamino-1-propylamine being employed as the amine component. The 
anion exchange was carried out with NaBF.sub.4 analogously to that 
described in Example A. 
Characterization: 
White powder, melting point &gt;300.degree. C. .sup.1 H--NMR (in 
DMSO-d.sub.6): 2.20 (multiplet, 4 methylene-H), 3.05 (singlet, 18 
methyl-H), 3.46 (multiplet, 4 methylene-H), 4.19 (triplet, 4 methylene-H), 
8.68 (singlet, 2 naphthylene-H) ppm. 
EXAMPLE 19 
1 part of the naphthalenetetracarboxylic acid derivative 13.1c (for the 
synthesis, see below) was incorporated homogeneously into 99 parts of 
toner binder as described in Example 1. The following q/m values [.mu.C/g] 
were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -3 
30 minutes -7 
2 hours -11 
24 hours -14 
______________________________________ 
Synthesis 
The preparation of the imide and the quaternization were carried out as 
described in Preparation Example F, 2 parts of 
3-dimethylamino-1-propylamine being employed as the amine component. 
The anion exchange was carried out with NaB-(phenyl) as described in 
Example A. 
Characterization: 
White powder, melting point &gt;287.degree. C. (decomposition) .sup.1 H--NMR 
(in DMSO-d.sub.6): 2.13 (multiplet, 4 methylene-H), 3.00 (singlet, 18 
methyl-H), 3.45 (multiplet, 4 methylene-H), 4.16 (triplet, 4 methylene-H), 
6.90 (multiplet, 40 phenyl-H), 8.71 (singlet, 2 naphthylene-H) ppm. 
COMISON EXAMPLE TO EXAMPLES 1 TO 19 
100 parts of the toner binder Dialec S 309 described in Example 1 were 
kneaded in a kneader without further additives for 30 minutes as described 
in Example 1, and were then ground, classified and measured on a q/m 
measuring stand. 
The following q/m values [.mu.C/g] were determined as a function of the 
activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -4 
30 minutes -12 
2 hours -27 
24 hours -48 
______________________________________ 
EXAMPLE 20 
1 part of the terephthalic acid derivative 1.1a employed in Example 3 was 
incorporated homogeneously into 99 parts of a powder paint binder 
(.RTM.Alftalat AN 757 from Hoechst AG, polyester resin) by a procedure 
analogous to that described in Example 1. The following q/m values 
.mu.C/g] were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -7 
30 minutes -8 
2 hours -8 
24 hours -6 
______________________________________ 
COMISON EXAMPLE TO EXAMPLE 20 
100 parts of the powder paint binder Alftalat AN 757 described in Example 
20 were kneaded in a kneader without further additives for 30 minutes as 
described in Example 1, and then ground, classified and measured on a q/m 
measuring stand. The following q/m values [.mu.C/g] were measured as a 
function of the activation time 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -35 
30 minutes -32 
2 hours -24 
24 hours -13 
______________________________________ 
EXAMPLE 21 
1 part of the compound 16.1a (for the synthesis, see below) was 
incorporated homogeneously into 99 parts of Dialec S 309 as described in 
Example 1. The following q/m values [.mu.C/g] were measured as a function 
of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes +21 
30 minutes +19 
2 hours +16 
24 hours +9 
______________________________________ 
Synthesis 
101.5 g (0.5 mol) of terephthaloyl dichloride are dissolved in 2.3 1 of 
toluene, and 120 g (1.2 mol) of N-methylpiperazine are added dropwise at 
20.degree. to 30.degree. C., while cooling. The mixture is stirred at 
20.degree. to 30.degree. C. for 1 hour, subsequently heated up to the 
reflux temperature over hours and boiled under reflux for 4 hours. After 
the mixture has been cooled to room temperature, the product is filtered 
off with suction, washed with toluene and dried. The dry product is 
dissolved in 400 ml of water, the solution is clarified with active 
charcoal and kieselguhr and the bisamide is precipitated by addition of 
33% strength NaOH at 0.degree. to 5.degree. C. The bisamide is filtered 
off with suction, washed with water and dried at 100.degree. C. in vacuo. 
66 g (0.2 mol) of the dry bisamide are dissolved in 640 ml of 
dimethylformamide, and 76 ml (0.8 mol) of dimethyl sulfate are added 
dropwise at room temperature over a period of 15 minutes, while cooling 
gently. 
The mixture is then heated at 60.degree. to 70.degree. C. for 5 hours and 
the product is subsequently filtered off with suction at 0.degree. to 
5.degree. C., washed with toluene and dried at 100.degree. C. in vacuo. 
Yield 109 g (quantitative yield) of white powder 
Molecular weight 582 
Melting point &gt;300.degree. C. 
.sup.1 H--NMR (in D.sub.2 O): 3.28 (singlet, 12 methyl-H), 3.53 (multiplet, 
8 H piperazino-H), 3.73 (singlet, methyl-H of the methyl sulfate anion, 
mostly hydrolyzed to hydrogen sulfate), 3.88 (multiplet, 4 piperazino-H), 
4.13 (multiplet, 4 piperazino-H), 7.60 (singlet, 4 phenylene-H) ppm. 5.0 g 
(9 mmol) of the above compound are dissolved in 20 ml of water at room 
temperature. 2.2 g (20 mmol) of sodium tetrafluoroborate in 25 ml of water 
are then slowly added, during which the reaction mixture becomes very 
thick due to the crystals which precipitate out. The mixture is diluted to 
250 ml with water and the colorless crystals are then filtered off with 
suction. After washing with water, the product is dried at 100.degree. C. 
in a vacuum drying cabinet. 
Yield: 3.8 g (79.1 % of theory) of the compound 16.1a, colorless crystals 
Molecular weight: 534 
Melting point: &gt;300.degree. C. .sup.1 H--NMR (in DMSO-d.sub.6) 3.20 
(singlet, 12 methyl-M), 3.48 (singlet, 8 piperazino-H), 3.83 (singlet, 8 
piperazino-H), 7.56 (singlet, 4 phenylene-H) ppm. 
EXAMPLE 22 
1 part of the compound 16.1a described in Example 21 was incorporated 
homogeneously into 99 parts of Alftalat AN 757 powder paint binder by a 
procedure analogous to that described in Example 1. The following q/m 
values [.mu.C/g] were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -26 
30 minutes -22 
2 hours -16 
24 hours -9 
______________________________________ 
EXAMPLE 23 
1 part of the compound 16.1a described in Example 21 was incorporated 
homogeneously into 99 parts of Crylcoat 430 powder paint binder (polyester 
resin containing carboxyl groups from UCB, Belgium) by a procedure 
analogous to that described in Example 1. The following q/m values 
[.mu.C/g] were measured as a function of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -7 
30 minutes -8 
2 hours -9 
24 hours -7 
______________________________________ 
COMISON EXAMPLE TO EXAMPLE 23 
100 parts of the Crylcoat 430 powder paint binder described in Example 23 
were kneaded in a kneader without further additives for 30 minutes, as 
described in Example 1, and were then ground, classified and measured on a 
q/m stand. The following q/m values [.mu.C/g] were measured as a function 
of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -20 
30 minutes -15 
2 hours -9 
24 hours -7 
______________________________________ 
EXAMPLE 24 
One part of the compound 16.1b (for the synthesis, see below) was 
incorporated homogeneously into 99 parts of Dialec S 309 as described in 
Example 1. The following q/m values [.mu.C/g] were measured as a function 
of the activation time: 
______________________________________ 
Activation time [.mu.C/g] 
______________________________________ 
10 minutes -19 
30 minutes -22 
2 hours -25 
24 hours -21 
______________________________________ 
Synthesis 
The procedure is as in Preparation Example 21, with the difference that 
instead of sodium tetrafluoroborate, 7.0 g (20 mmol) of sodium 
tetraphenylborate, dissolved in ml of water, are used. 
Yield: 7.6 g (84.6% of theory) of the compound 16.1b, white powder 
Molecular weight: 998 
Melting point: 292.degree. C. (decomposition) 
.sup.1 H--NMR (in DMSO-d.sub.6): 3.19 (singlet, 12 methyl-H), 3.46 
(singlet, 8 piperazino-H), 3.82 (singlet, 8 piperazino-H), 7.03 
(multiplet, 40 phenyl-H), 7.55 (singlet, 4 phenylene-H) ppm.