CA2085809A1

CA2085809A1 - Diallylammonium compounds, processes for their preparation and their use

Info

Publication number: CA2085809A1
Application number: CA002085809A
Authority: CA
Inventors: Ruediger Baur; Hans-Tobias Macholdt
Original assignee: Ruediger Baur; Hans-Tobias Macholdt; Hoechst Aktiengesellschaft
Current assignee: Hoechst AG
Priority date: 1991-12-21
Filing date: 1992-12-18
Publication date: 1993-06-22
Also published as: EP0548826A3; DE59208394D1; JPH06172272A; EP0548826A2; KR930012681A; US5475119A; US5563016A; DE4142541A1; EP0548826B1

Abstract

Abstract of the disclosure:

Diallylammonium compounds, processes for their preparation and their use Ionic monomeric diallylammonium compounds having a targeted combination of diallylammonium cations with selected anions have particularly high and constant charge control properties and very good heat stabilities and dispersibilities.

The compounds according to the invention are outstand-ingly suitable for use as colorless charge control agents in toners and developers for electrophotographic record-ing processes and for use as charge-improving agents in powders and paints for surface coating, in particular in triboelectrically or electrokinetically sprayed powder paints.

Description

3~

HOECHST AKTIENGESELLSCHAFT HOE 91/F 41~ Dr.H~/AL

Description Diallylammonium compounds, proce!~es for their prepara-tion and their use The present invention relates ts~ the technical field of charge control agents in toner3 and developers ~or ~electrophotographic recording processe and in powders and powder-~O~tin~s for ~urface coating.

In electrophotographic recording proce~ses, a "latent charge image" i8 produced on a photoconductor. This i8 effected, for example, by charging a photoconductor by means of a corons di~charge and then ~ub~e~ting the electro~tatically charged sllrface of the photoconductor to imagewise exposure to light, the e~posure causing the charge to drain to the earthed substrate nt the exposed areas.
The "latent charge Lmage" thus produced .is then developed by application of a toner. In the following step, the toner is transferred from the photoconductor onto, for example, paper, textiles, films or plastic, and is fixed, for example, by means of pressure, radiation, heat or the action of a solvent. The used photoconductor i~ then cleaned and is available for a new recording operation.

The optimization of toners is described `in numerous patent specifications, the influence of the ~oner binder (variation of resin/resin components or wax/wax compo-nents), the influ~nce of carriers (in two-component developers) and magnetic pigment~ ~in one component developers), :inter alia, being investigated.

A measure of the toner quality is it~ specific charge q/m (charge per unit mass). In addition to the sign and level of the electrostatic charge, a decisive guality critexium , ~, . - : ::

- ~ , :, ~c~

above all i~ that the desixed charge level iB reached rapidly and that this charge remains constant OVQr a relatively long activation period. In practic~, this i8 of central importance inasmuch as the toner may be exposed to a considerable activation time in the developer mixture, before it i8 ~ransfarred to the photoconductor, since it sometimes remains in the devsl-oper mixture over a period for the product~on of up to sevaral thou~and copies. Mor,eover, the insensitivity of the toner to clLmatic influences, such as temperature and atmospheric humidity, i8 another Lmportant suitability criterion.
~ ,. :
; Both positively and negatively chargeable toners are used in copiers and la~er printers, depending on the type of process and equipment.
~ :.
To obtain electropho~ographic toners or developers having either positive or negative charging, so-called charge control agents are often added. In addition to the sign of the charge control, the extent of the con~rol effect is of importance, ~ince a higher activity allows a smaller amount to be employed. Since toner binders as a rule show a marked dependence of the charging on the activation time, the task of a charge control agent is on the one hand to establish the sign and level of the toner ; 25 charging, and on the other hand to counteract the drift in charging of the toner binder and t~ en~ure that the charging of the toner remains con~tant.
~-i Charge control agents which cannot prevent the toner or - developer from displaying a high charge drift o~er a prolonged period of use (aging) ~ and whi~h can even cause the toner or developer to undergo a rever~al of charge, are therefore unquitable in practice.
Full-color copiers and laser printers opera~e by the principle of trichromism, which necessitates exact color shade matching of the three primary c-olors (yellow, cy~n and magenta). The slightest shifts in color shade even of . .

~ . , , ,~: . ,. ~ j: . .

only one of the three primary colcrs nece~sarily requira~
a shift in the color ~hade of tha other two colors ~o that full-color copies or prints faithful to the origlnal can then al~o be produced.
Because of thi~ precise matc:hing o~ the colori~tic properties of the individual coloring agents to one another, which i8 neces~ary in color toner~, charge control agents which have ab~o]Lutely no intrinRic color are especially important.

In color toners, the three toners of yellow, cyan and magenta must al~o be matched sxactly to one another in respect of their triboelectric propertie~, as well as meeting the precisely defined color requirementq. ~hls triboelectric matching is neces6ary, becau~a in the case of a full-color prin~ or full-color copy, the three color toners (or ~our color toner~, when black i5 al80 included) must be transferred in the same apparatu~ in succession.

It is known that coloring agents can sometimes have a lasting influence on the ~riboelectric charging of toners (H.-T. Macholdt, A. Sieber, Dyeq & Pigments 9 (19883, 119-127; US-PS 4,057,426). Becau~e of the different triboelectric effects of coloring agent~ and the resulting, sometimes very marked influence on ~oner chargeability, it i~ not po~ible simply to ~dd the coloring agents to a toner base recipe compiled once and for all. Rather, it may be nece~sary to compile ~n individual recipe for each coloring agent, for which, ~or example, the nature and amount of the required ~harge control agent are tailor-made pecifically. This procedure i8 correspondingly expensi~e, and ~dditionally accompanie~ the diffi~ulties alrea~y described ln the case of color toners for procecs color (trichromi m).
; Highly active colorless charge con~rol agents which are capable o~ compensating the di~ferent triboelectric properties o:E variou~ coloring agents ~nd of imparting . ,~

, the desired charging to the ~oner are therefore nece~-sary. In this manner, coloring agents with very different triboelectric propertie~ can be employed in the variou~
toners required (yellow, cyan, magenta and, if appro-priate, black) with the aid oi a toner base recipe,compiled once and for all, with one and the same charge control agent.
Moreover, it is important in practice for the charge control agents ~o have a high heat 3tability and be readily dispersible. Typical temperatures for incorpor-ating charge control agents into the toner resin~ are between 100C and 200C when kneaders or extruders, for example, are used. A heat stability o 200C, or even better 250C, is accordingly of great advantage. It i8 also important for the heat stability to be guaranteed over a relatively long period of time (about 30 minutes) and in various binder systems. This is important, since matrix effects which occur again and again lead to premature decomposition of the charge control agent 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. ~ypical toner binders are polymerization, polyaddition and polyconden-sation resins, such as, for example, styrene resins, styrene/acrylate resin , styrene/butadiene resin~, acrylate resins, polyester resins, phenolic resins and epoxy resins, individually or in combination, which can also comprise other contents, ~uch as coloring agents, waxes or flow auxiliaries, or to which thes0 can be subsequently added.
For a good dispersibility, it i8 of great advantage if the charge control agent a~ far as possible has no waxy propertie~, no tackinesc and a meltin~ or softening point of > 150C, preferably > 200C. Tackiness often lead~ to problems during metering into the toner formulat~on, and low melting or soitening points can mean that no homo-geneous distribution i~ achieved during disper~ion, since the material merges, for example, in the form of droplQtS

.
.. . . .
' . ' , ' ' ;, ~ ;"' ~ ~
' ' ` ' . ` : , ' ' :
' ` . ' ` :

~ ?;~ 9 in the carrier material.

Apart from being used in electropho~ographic toner~ nd developer~, charge control agents can al~o be employed for improving electro~tatic charging of powder~ ~nd coatin~s, in particular in triboelectrically or elactro kinetically sprayed powdercoa~ngS~ 6uch ~5 are u~ed ~or surface coating of ob~ects o~, for example, metal, wood, plastic, glas~, ceramic, con~:rete, textile material, paper or rubber. Powder ooat ~ technology i8 used, inter alia, ~or painting small ob~eclts, ~uch as garden furni-ture, camping articles, domestic appliance3, vehicle components, refrigerators and shelves, and for painting workpieces of complicated shape. The powderCoatinSor the powder in general acquires itB electro~tatic charging by one of the following two proces~e~:

a) in the corona process, the powder coatin~or the powder is led pas~ a charged corona and i8 charged during this procedure, b) in the triboelectric or electrokinetic proce6s, use is made of the principle of frictional electricity.
In the spray unit, the powder ~ ting ox the powder acquires an elec~rostatic charging which i8 oppoBite to the charge of the friction partner, in general a hose or spray tube (for example of polytetrafluoroethylene).

A co~bination of the two processe~ i~ al80 pos.~ible.

Epoxy resins, polyester resins containing ~arboxyl and hydroxyl group~, polyurethane resins and acrylic resins, together with the corresponding curing agents, are typically employed a~ powder coating re~in~. Combination~
of resin~ are al80 u~ed. Thu~, for OXampl9, epoxy re~ins are often employed in combinatioA with polyex~er re~ins containing carboxyl and hydroxyl groups.
Typical curing agent components for epoxy resin~ are, for example, acicl anhydrides, Lmidaæoles and dicyandiamide, ; , ,:

. ,: , , . ,, . . ,,~ ,.. ~::

. " , .:
, and derivatives thereof. Typical curin~ &gent components for polye3ter re~ins containing hydroxyl groups are, for example, acid anhydrides, masked isocyanates, bisacyl-urethanes, phenolic re~ins and melamine resin~. Typical S curing agent components for poLyester resin~ containing carboxyl ~roup~ are, for example, triglycidyl i~ocyan-urates or epo~y resins. Typic~l curing agent components which are used in acrylic resins are, for example, oxazolines, isocyana~eR, triglycidyl i~ocyanurate~ or dicarboxylic acids.

The disadvantage of inadequa~e charging iR ob~erv~d above all in powders and powder coatinss, which are ~prayed txiboelectrically or electrokin~tically and have been prepared on the ba~is of polyester resin~, in particular polyesters containing carboxyl group~, or on the ba~is of so-called mixed powders, al~o called hybrid powders.
Mixed powders are understood as mea~ing powderCoatings, the resin ba~e of which comprises a combination o~ epoxy resin and polyester resin containing carboxyl groups. The mixed powders form ~he basis for the powder coatingsmo~t frequently represented in practice. Inadequate charging of the abovementioned powders and powder!coatmss means that the deposition rate and throwing power on the workpiece to be coated are inadequate. (The term throwing power" is a measure of the extent to which a powder or powder coatmgis depo~i~ed on the workpiece to be coated, including on the reverse sides, hollow space~, crevices and, above all, on internal ed~es and corner Colorless charge control agents are claimed in numerous patent specifications. ~owever, the colorles~ charge control agents known to date have a number of disad-vantage~, which everely limit or ~ometLmes rendex impossible use in practice. Thu3, the chromium, iron, cobalt and zi.nc complexes de~cribed in US-PS 4,656,11 also have, in addîtion to the problems of heavy metal~, the disadvantage that they are ~ometimes not really . .

. ,. . :
~ . . .

colorleRs/ and can therefore be u6ed to only a limi~ed extent in color toners or in white or colored powder coatmgs. ~he known c~aternary ammonium compounds, which are suitable per se, are often difficult to disperse, which leads to non-uniform charging of the toner.
Furthexmore, the problem often arise~ that the toner charge produced by the~e compounds i~ not stable over a relatively long ac~iYation perio~ (activation time of up to 24 hours), especially at a high temperature and atmospheric humidity, whi~h then lead~ to enrichment of wTongly or inadequately chargecl toner p~rtiol e~ in the cour~e of a copying or printing proce~s, and therefore bring~ the proce~ to a standstill.

It is furthermore known that ammonium- and immonium-ba~ed charge conkrol agents can be sensitiv~ to light or mechanical effects (US-PS 4,683,188) and can be unstable to heat, and tha~ they form decomposition products which can have an adverse effect on the triboelectric charging of the toner (US-PS 4,684,596) and/or have a deep, often dark brown, intrinsic color. Moreover, they often have waxy pxoperties, are sometimes water-soluble a~d~or have a low activity as char~e control agents.
Charge control agent~ which are suitable per 3e and are based on highly fluorinated ammonium and immonium com-pounds (US-PS 5,069,994~ have the disad~antage of an involved synthesi~, which gives rise to high preparatio~
cost~ for the corresponding sub~tance~, and are not sufficiently heat-~table. Phosphonium ~alt~ are less active as charge control agent~ than ammonium salts (US-PS 4,496,643), and may cause toxicological problems.

Charge control agents based on polymeric ammonium com-pounds sometimes lead to an amin~ ~mell in the toner or developer, and the charqe control properties of ~hese substances may change due to relatively easy oxidation and absorption of moi~ture. Noreover, the oxidation products are colored and therefore cause trouble, above .. .. . . .

:
,:

2¢~5~ 3 all in color toners.

The abovementioned charge control agents for electro-photographic toners and developers are unsuitable for u~e in the predominantly white or clear powder~ and powder S coatmas sprayed triboelectxically or electrokinetically, for example, because of ~heir color. Furthermore, a lack of heat stability severely lLmit~ the u~e of ~uGh charge control agents, 3ince powder c~tings are ~toved, for example, at above 200C for 15 minute~. The charga control agents claimed in US-PS S,069,994 for powders and powder coatLngs are difficult ~o handle bec~u~e of their waxy nature and water-solubility or hygro~copic nature, and can be u~ed to only a limited extent.

The aim of the present invention i8 therefore to discover improved, particularly active, colorlecs cherge control agents, with which, ln addition to ensuring the charge level, it must be ensured that this charge ia reached rapidly and is constant, and the charge control agent should not be sensiti~e to changes in temperature and atmospheric humidity. Moreoverr these compounds ~hould be highly heat stable, above all al~o in the particular carrier material (re~in) over a relatively long period of time, and as far as po~ible water-insoluble, readily dispersible and compatible with the contents of the toner or powder paint. Furthermore, synthe~is o~ the compounds 6hould be not very involved, and their preparation should be inexpensive.

Surprisingly, it ha~ now been found that monomeric diallylammonium compound~ have parkicularly high and constant charge control properties snd very good heat stabilities and dispersibilities by targeted combination of the diallylammonium cations with ~elected anions.

The present invention relate~ to ionic monomeric diallyl-ammonium compound~ of the formula (I) -ir~ ¢ ræ~

~2 a4 R~ ~ ~ Rlo ~ r R~
R~ A~

~ ~2 and mixtures or mi~ed crystals thereof, in which the radical~
R1 to R12 independently of one a~other are each a hydrogen atom, a halogen atoml a hydroxyl radical, a prLmary, secondary or tertia~y amino radical, a carbo~ylic acid or carboxylic a~id ester radical, an acyl radical, a sulf-onic acid or sulfonic acid ester radical, a cyano radical or a ni~ro radical, or are in each case a radical based on an alipha~ic or aromatic hydrocarbon, which can be interrupted by hetero atoms, and ~e i~ in ~ach case the ~toiehiometric equivalent of an inorganic anion, o~ an anion of a heteropolyacid or of a borate of the formula (II) ~13 R,3 - B~

Rl;

in which the radicals R13 to R~ on the borate anion independently o~ one another are aliph~tic or cyclo-aliphatic radicals, or aryl or heteroar~l or aralkyl radical~, it being po~sible for these radicals to be substituted by alkyl(C~-C4), alkoxy(C1-C~) or a~yl radicals or by halogen atoms, or are fluorine atoms t - : ., . ' . .

., ' :. :
~. ,- , or of an organic anion, preferably based on a phenolate, olefinic, aliphatic or ~romatic carbo~late, thiola~e, sulfonate or sulfate, in which the alkyl, al~enyl or aryl radicals can al80 be pexfluorinated, or ba3ed on a disul~o-pyrrolidinium-betaine of the formula (III) 403S-Y X-SO3e ~ (III) R, R~

in which R1~ and R2~ have the meanings given for R1 and R2, and X and Y are in each case a straight-chain or branched aliphatic, saturated or un~aturated alkyl(Cl-Cla) radical or alkoxy(C1-C~9) radical, or A~ i6 a combination of these anions; and mixtures of these compounds and mixed crys~als with mixed anions and/or cations.

Inorganic anions Ae which are employed according to the invention are, for example, F , I , NO3, OH , HSO4, S2, so32~, S2032~, HCO3-, co32~, H2PO~-, HPo~2-, PO~3~, CN-, cyanate, isocyanate, thiocyanate, zinc tetracyanate, zinc te~rathiocyana~e, perchlorate, PF6-, molybdates, such as MoO~2~, thiomolybdates/ ~uch as ~oS~2~, ~r tungstates, such as wo42~. ~owe~er, a combinatlon of these anions i8 al~o possible, in particulsr also in comb~nation with Cl , Br~
or so42~.

Molybdatophosphate~, such as P(Mo3010)~3~, tungsto~
phosphate~, such as P(W30~o)~3-, or ~ilicomolybdate~, for example, are employed according to the inven~ion as an anion of a heteropolyac~d.

.

~¢~

Borates which are employed ~ccording to the inventLon are, preferably, tetrafluobor~te, tetrachloroborate, tetraphenylborate, tetra(fluorophenyl)borate, tetra-(chlorophenyl)borate, te~ratolylborate, tetranaphthyl-borate, tetxa(methoxyphenyl)borate, tetrabiphenylborate,tetrabenzylborate or tetrapyriclylborate~

Organlc anions Ae which are employed according to the invention aro, for example, ethylsulfate, thiolate~
phenolate, nitrophenolate, s,atura~ed or unsaturated aliphatic or cycloaliphatic or aromatic ~rbo~ylate or sulfonate, preferably acctate, lactat~, b~nzoate, the mono- or dianion of dithiodibenzoic acid, ~alicylate, 2-hydroxy-3-naphthoate, 2-hydroxy-6-naphthoate, ethyl-sulfonate, phenylsulfonate or tosylate, and ~urthermore perfluorinated saturated or un~aturat~d aliphatic.or cycloalipha~ic or aromatic carboxylate or ~ulfonate, preferably perfluoroacetate, per~luoro(C1-C30)alkyl benzoate, perfluoroethylsulfonate or perfluoro(C~-C30)-alkylbenzenesulfonate, and saturated or un~aturated aliphatic or cycloaliphatic or aromatic di- or tricar-boxylate, preferably citrate, oxalate or ~uccinate, or di- or trisulfonate, chlorinated and fluorinated ali-phatic, cycloaliphatic or aromatic carboxylates, such as trifluoroacetate, ~nd di~ulfo-pyrrolidinium-betaines of the formula (III) in whi~h Rl~ and R2' are Rl and R2, and X and Y are straight-chain or branched aliphatic, satur-ated or unsaturated alkyl(C1 Cla) or alkoxy~cl-cl8) radi-cal~, preferably alkyl~Cl-C5) or alkoxy(Cl-C5) radical~, polyoxyalkylene radicals, preferably polyoxyethylene and polyoxypropylene radicals, of th~ formula (alkylene(Cl-C5)-O)D-R, in which R is a hydrogen atom or an alkyl(Cl-C~) radical and n i~ a number from 1 to 10.

Compounds of the formula (I) which are preferred in ~he context of the pre&ent invention are those in which Ae is an anion from the group comprising F-, I-, BF~, B(aryl)4~ PF6- or P(Mo3O10)4 ~ or of a ~ .

di6ulfopyrrolidinium-betaine of the formula (III);

R1 and R2, and Rl' and R2' independently of one another are hydrogen atom~, straight-chain or branched, szlturated or unsaturated alkyl~c~-cl8) or slkoxy(C,-C13) radicals, polyoxyalkylene radical~, preferably polyoxyethylene and/or polyoxypropylene radical3, of the formula (alkylene(C~-C5)-O)n-R, in which R i8 a hydrogen atom, an alkyl(Cl-C4) radical or an acyl radical, preferably the acetyl, benzoyl or naphthoyl radical, and n i8 a number from 1 to 10; aryl or heteroaryl radicals, pre~erably phenyl, naphthyl or pyridyl radical~; aralkyl radical~, preferably tolyl radicals; aralkoxy radicalsr preferably methoxyphenyl radicalq; alkaryl radical~, preferably benzyl radicals; or cycloalkyl radicals, preferably cyclopentyl or cyclohexyl radical~, or the abovementioned radicals can contain at least one hetero atom, preferably nitrogen, oxygen, ~ulfur, phos-phorus or a combination thereof, and can be substituted by one or more carboxamide radi-cals, sulfonamide radicals, urethane radicals, ketone radicals, primary, secondary or tertiary amino radicals, nitro radicals, ether radicals, in particular alkylene(C2-C4)-O-alkY~ ~C4) radical 8, alkyl(Cl-C4) radicals, alkoxy(Cl-C4) radical~, aroxy radicals, in particular phenoxy radicals, halogenoalkyl(Cl-C30) radi-cals, halogenoalkoxy(Cl-C3~) radical~ or es~er radicals, in particular -C(O)O-alkyl(Cl-C4), one or more halogen atoms or hydroxyl, carboxyl, sulfonic acid, cyano or mercapto groupe, or a combination thereof, or Rl and R2, ~nd R~' and R2~
together form a saturated or unsaturated, aromatic or non-aromatic 5- to 7-membered ring ystem, pre~erably ~he pyridinium ring system, which can contain further hetero atoms, prefer~bly nitrogen, oxyge~, sulfur or a combina-tion thereof, in the ring, in particular the morpholinium ring system, and which can be substituted and/or modified .. . . . .
~ :, .
.

:

by conden~ation of or bridging to other ring ~y8tem8, in particular the quinolinium ring system; and R3 to Rl2 independently of one ~nother have the meanings givsn S above for Rl and R2, and R1~ and R2~, or are halogen atoms or aroxy radicals, preferably phenoxy radicals;
and mixtures of the6e compounds and mixed crystal~ with mixed anions and/or cations.

Compounds of the formula ~I) which are par~icularly preferred in the context of the pre~ent invention are those in which Ae i9 an anion ~rom the group comprising BF4 and B(aryl) 4-, in which aryl is phenyl, naphthyl, fluoro-phenyl, chlorophenyl, me~hoxyphenyl, biphenyl, pyridyl or tolyl or a combina~ion thereof;

R, and R2 independently of one ano~her are hydrogen atoms, straight-chain or branched, saturated or unsaturated alkyl(Cl-CB) or alkoxy(C~-C8) radicals, aryl or heteroaryl radicalæ, in particular phenyl, naphthyl or pyridyl radicals, aralkyl radical~, in particular tolyl radical , aralkoxy radicals, in particular methoxyphenyl radical~, alkaryl radicals, in particular benzyl radicals, or cycloalkyl radicals, in particular cyclopentyl or cyclo-hexyl radicals,it being possible for the radical~ Rl and R2 to be ~ub~ti-tuted by one or more halogen atoms, hydroxyl, carboxyl, sulfonic acid or carboxamide radicals, in particular -NH-C(O)-alkyl(Cl-C~), sulfonamide radicals, in par~icular -NH-SO2-alkyl(Cl-C~), keto radical~, in particular -C(O)-alkyl~Cl-C~), primary, secondary or terti~ry amino radicals, in particular -NH2, -NH[alkyl(Cl-C~)J- or -N[alkyl(Cl-C~) ]21 nitro radical~, ether radical , in particular alkylene(C2-C~-O-alkyl(C1-C~, alkyl(Cl C4~
3~ radicals, alkoxy(cl-c~ radicals, aroxy radical6, in ", :, ..

. - - . , ~ .............................. : .: ~ :

. .. . . ~ .: :. . . .
.. -, particular phenoxy radicals, halogenalkYl~ Cl-C4 ) radicals, halogenoalkoxy(c1-c4) radicals or e3ter radical 8 ~ in particular -C(O)O-alkyl( Cl-C4 ); and R3 to Rl2 independently of one another have the maanings given above for R1 and R2, or are halogen atoms, and mixtures o~ these compound~ and mixed crystals with mixed anions and/or cations.

Compounds which are e~pecially preferred in the context of the present invention are ~hose of type~ (1) to (7) / ~ (1) to (7 R, R2 in which in compound tl), A9 has the meanings B~4- or B(phenyl)4~, R1 has the meanings H or CH3 and R2 has the meanings CH3, 15 C8Hl7 or H;
in compound (2), Ae i8 an alkyl-3,4-disulfomethyl-pyrrolidinium-betaine of the formula (III), in which X
and Y are in each case alkyl(C1-C5) and Rl~ and R2' are in each case N or CH3, and any desired mixtures or mixed crystals of compounds type~ (1) and (2);
in compound ~3), Ae has the meaning BF~-;
in compound (4), Ae has the meaning B(C6H5 in compound (5), Ae has the meaning PFs-~in compound (6), Ae has the meaning 1,1-dialkyl-3,4-disulfomethyl-pyrrolidinium-betaine, and in compound (7), Ae ha~ the ~eaning P(Mo3O10)43~.

The invention Eurthermore relates to a process for the preparation o:E the compounds of the formula (I~ by anion exchange. The preparation is carried out by adding one or more compound(~) on which the anion ~e is ba~ed, ,..
: . . - . , . , . : ................................... . - : , ., . :, '., : , preferably the sodium ~alt, to a diallylammonlum halide of the formula ~IV) a, ~ Rlo ~

/ \ ~IV~

in which ~al i8 fluorine, chlorine, bromine sr iodine, preferably chlorine or bromine, particularly preferably chlorine, as a solution in water or in a mixture of water and an organic solvent whi~h i8 completely or partly miscible with water, at a temperature between 0C and 100C, preferably 10C and 70C, and a pH of between 3 and 10, preferably 5 and 8, and then, if appropriate, precipitating the compound of the formula (I) according to the invention by ~alting out with halogen containing salts, for example potas3ium chloride. A~ a rule, the compound~ according to the invention are ~o ~paringly lS soluble in water or in the water-solvent mixture men-tioned that they al80 precipi~ate out of the solution without additional ~alting out.
The preparation of:the starting compound~, th~ diallyl-ammonium chlorides, i5 known and i de6cribed ~n deta$1 in the literaturH t~or example Houben-Weyl, "Methoden der Organischen Chemls~ (~ethod~ of Or~anic Chemi~try)"t volu~e E20/2, ~hieme-Verlag, Stuttgart, 1987, 1023-1028;
S. ~arada and ~. Arai, Makromol. Chem. 107, (1~67) 64;
Y. Negi, S. Harada ~nd O. I~hi~uka, J. Polym. Scl. Si (19b7) 64; and US~PS 4,670,594~ he compou~d~ are prepared, for example, by reaction of allyl halides with N,N-dialkyla:Llylamines and quaternization of the diallyl-amine.

. - ! ~ , :

The corresponding Na ~ul~o-betaine (III) can be obtsinod in accordance with US-PS 4,877,885.

In a preferred embodiment, the anion exchange ~ carrled out in a mix~ure of water and i80propan~1,water and isobu ~ ol or water and methyl isobu~l ketone.

In another preferred embodiment, ~he diallylammonium chloride is reacted with sodium tetraphenylborate, sodium tetra-o-fluorophenylborate, sodium tetra-m-fluorophenyl-bor~te, sodium tetra-p-fluorophenylborate, sodium tetra-o-chlorophenylborate, sodium tetra-m-chlorophenylborate, sodium tetra-p-chlorophenylborate, sodium tetra-o-tolyl-borate, sodium tetra-m-tolylborate, sodium Petra-p-tolylborate, sodium tetra-l-naphthylborate, sodium tetra-2-naphthylborate, sodium tetra-o-methoxyphenylborate, sodium tetra-m-methoxyphenylborate, ~odium tetra-p-methoxyphenylborate, ~odium tetra-o-biphenylborate, sodium tetra-m-biphenylborate, ~odium tetra-p-biphe~yl-borate, sodium tetrabenzylborate, sodium tetra-o-pyridyl-borate, sodium tetra-m-pyridylborate, sodium p-pyridyl-borate or sodium tetrafluoroborate~

The compounds according ~o the invention are colorle~sand, by the tarqeted combination of certain monomeric diallylammonium cations with 6elected anion~, have particularly high and constant charge control propert~es and very good heat ~tabilitle~ and dispersibilitie A great industrial advantage of the~e readily disper~ible compounds is that substance~ of th2 same clas~ of ~om-pound can be employed either as posit~ve or as negative charge control agents~ depending on the carrier/resin combination. Either positive or neqat$ve toners can thu~
be prepar~d with the aid of a fixed toner base recipe (comprising toner binder~, coloring a~ents/ ~low auxili-aries and, if appropriate, other compbnents), by choo~ing the desired carrier and/or resin and by a suitable . , .. . .
, . . -2~

cation~anion combination in the compounds according to the invention.

The yn~hesi~, which i~ not ve~r involved, the inexpens-ive preparation, the high ~c~ivity, ~he excellent heat stability an~, in particular, ~ho achievement o~ a significan~ly improved deposition rate and throwing power ~re of quite particular advant:age in ~he C2~e of the compounds according to ths invention, 80 ~ha~ overall a more efficient and more economical utilization of ~prayed powder paint~ results.

The invention furthermore ralates to the use of the compounds according to the invention and of the compound~
of the formula (I) in which the anion Ae c~n al80 be chloride, bromide or ~ulfate, in addition to the meaning~
mentioned, as charge control aqents, individu~lly or in combination, in electrophotographic toners and developer~
which are employed for copying or duplicating masters and for printing electronically, magne~ically or optically stored information or in colorproofing. The compounds according to the invention moreover are ~uitable as charge-improving agents in powders and paints for surface coating of object~ of metal, wood, plastic, gla88~
ceramic, concrete, textile material, paper or rubber, in particular in triboelectrically or electrokinetically sprayed powder ~tings. These compounds furthe~more can also be employed a~ charge-improving agent~ in the form of coatings of carriers or a constituent o~ coatin~ of carriers which are used in developer~ for electrophoto-graphic copying or duplication of ma ters and for print-ing electronically, optically or magnetically ~toradinformation or in colorproofing.

The particulax advantage of the compounds claLmed aceord-ing to the invention i~ that they are colorle~s and have a high charge control effect, and that thi~ i~ constant over a relatively long activation period (up to , . ' '; , .
~; . ., .. , . ., . ;
- ; . ~ , ,,.,. .~ . , , ~5l~

24 hours).

Thus, for example, a test toner comprising l percent by : weight of the compound of type (4) ~hows a charging of -l9 ~C/g after lO minutes, -lB ~C/g after 30 minute~, -15 ~C/g after 2 hour~ and -15 ~C/g after 24 hours (Use Example 1).

A test powder coating compriE;ing 1 percent by weight o~
compound (4) shows a charging of +3 ~C/g after 10 min-utes, +4 ~C/g after 30 minutes, +7 ~C/g after 2 hours and +6 ~C/g after 24 hour~ (U~e Example 5).

The high charge control effec~ become~ clearer if, for comparison, the charging propertie~ of the pure toner binder, for example Dialec S-309, are considered:
(Comparison Example l): -4 ~C/g after 10 minutes, ~ lS -12 ~C/g after 30 minutes, -27 ~C/g after 2 hours, -48 ~C/g after 24 hours; or those of a pure powder coating binder, for example ~Crylcoat 430, are considered (Comparison Example 2): -20 ~C/g after lO minutes, -15 ~C/g after 30 minutes, -8 ~C/g after 2 hours, -4 ~C/g after 24 hours.

It is of great importance in practice that the compounds according to the invention are chemically inert and are readily compatible with binders, for example styrene acrylates, polyesters, epoxide~ and polyurethane~.
: 25 Furthermore, the compound~ are heat-stable and can therefore be incorporated into the customary binder~ by the customary proc2sses (extrusion, kneadi~g) under the usual condition~ (temperatures sf between 100C and :200C) without difficulty. ~he synthesis of the compounds according to the invention i8 not very involved, and the products are obtained in high purity.

The compounds used according to the invention are as a rule homcgeneously incorporated in a concentration of al~out G.01 to - - ~

, . , . :

. ~ :

~5~ 9 about 30 percent by weight, preferably about 0.1 to 5.0 percent by weightt into the bil~der of t:he particulæ toner, ~ elo~er,paint or Powder coating, for examPle b~ extrusion or kneading.

~he char~e control agents for toner8 or charge-$mproving agent~ for powders and paints for surface coating, in particular for triboelectrically or electrokinetically sprayed powder coatings, -an be added here as dried and ground powde~rs, di~per~lonA or ~olu-tions, press-cakes or a masterbaltch, a~ compounds applied t~ suitable carriers, such as, for example, silica gel, TiO2 or Al203, from an aqueouR or non-agueous solution~ or in another form. In principle, the compoun~ employed according to the invention can likewise al~o already be added during preparation of the particular binder, that is to say in the course of polymerization, polyaddition or polyconden~ation thereof.

The level of electrostatic charging of the electrophoto-graphic toners or of the powder co~tmss in which the charg~ control agents according to the invention have been incorporated homogeneously was measured on standard test systems under identical conditions (~uch as the same dispersing times, same par~icle size distribution and same particle form) at about 20C and 50~ relative atmospheric humidity. The electrostatic charging of the toner or powder coatmgWaS effe~ted by swirling with a carrier, i.e. a standardi~ed friction partner (3 part~ by wei~ht of toner per 97 parts by weight of carrier)~ on a roller unit (150 revolution~ per minute). The electrostatic charging wa~ then measured on a customary q/m measurin~ stand (J.H. Dessauer, ~.E. Cl rk, ~Xerography and related Proce ~es", Focal Pres , N.Y., 1965, page 289; and J.F. Hughesr "Electro tat$c Powder Coating", Research Studie~ Press Ltd., ~etchworth, 35 Hertfordshire, England, 1984, Chapter 2). The particle size has a great influence in the de~ermination of the qtm value, which is why strict attention was paid to a ' ' :: . :
. . .
.
.

5~

uniform particle size distribution in the toner and powder ~ tina samples obtained by sifting. An average particle size of 10 ~m is thus aimed at for toners, while an average particle ~ize of 50 ~m is practica~le for powder ~ tlngs.

The tribospraying of the powde;cs and powder coatin~s was carried out with a spray apparatus, for example ~rribo Star from Intec (Dortmund), using a stand~rd spray pipe and star-shaped insert at maximlIm powder throughput with a spraying pres3ure of 3 bar. For thi~, ~he ob~ect to be sprayed was suspended in a ~pray cabin and ~prayed direc~ly from the front, without further mo~ement of the spray apparatus, from a distance of about 20 cm. The particular charging of the sprayed powder was then measured with a "meai3uring instrument for measurement of the triboelectric charge of powders" from Intect (Dortmund). For the measurement, the measurement antenna of the measuring instrument was held directly in the cloud of powder emerging from the fipray appara~us. The current strength resulting from the elec~rostatic charge of the powder coatingor powder wa~ displayed in ~A. The deposition rate was then determined in % by de~ermining the difference in weight between the sprayed and depos-ited powder paint.

The following examples serve to illustrate the invention, without limiting it to these. ~he term "min" means ~minutes" and "h~' means "hours".

Preparation Example 1 Compound (4) 67.36 g (0.25 mol) of a 60% strength by weight aqueous diallylammonium chloride solution were introduced into 1000 ml of deionized water. 92.24 g (0.25 mol) of NaB(C6H5~4 were added to the solution at S0 to 60C in the 5~ 3 course of 3 min, while ~tirring intensively. A voluminous white precipitate occurred. The ~uspension was sub-sequently stirred at 50C for 10 min and cooled to about 20C, and the solid was filtered off with suction and rinsed intensively several timels. Finally, the substance was dried in vacuo under 200 mbar at 90C.

Yield: 111.07 g (99~ of theory) Decomposition: 240C
Elemental analysis:
C 86.0%; H 8.0%; N 3.2~; ~ 2.6% (found) C 86.6%; H 7.9%; N 3.1%; B 3.0% (calculated) Preparation Example 2 Compound (7) A saturated solution of 94.5 g (0.045 mol) of Na3P[Mo3O10]4 lS in 210 ml of water was added to 40.0 g (0.15 mol) of a 60% strength by weight aqueous diallylammonium chloride solution at about 20C. Th~ suspension formed was sub-sequently stirred for 10 min, and the solid was filtered off with suction and washed ~ith cold water until free from chloride. Finally, the substance was dried in vacuo under 200 mbar at 90C.

Yield: 48.6 g (43.5~ of theory) Decomposition > 300C
Elemental analysis:
C 12.1%; H 2.54; N 2.1%; P 1.5% (found) C 11.2%; H 2.7%; N 1.6%; P 1.2% (calculated) Preparation Example 3 Compound (5) A hot solution, at about 50C, of 2i.4 g (0.15 mol) of NaPF6 in 150 ml of deionized water was added to 40.0 g . : - :: . , ~

' ! ~ : i ~
' , :

(O.15 mol~ of a 60% strength by weight aqueou~ diallyl-ammonium chloride solution at 50C, and the mixture wa8 heated to 80C. After 15 minutes, it was allowed to cool, and the volume was doubled by addition of 200 ml of an aqueous 1 normal RCl solution. After cooling to O~C, the solid was filtered off with ~uction and washed with cold water until free form chloride. ~he substance wa~ then dried in vacuo under 200 mbar at 90C.

Yi~ld: 14.1 g (50~ of theory) Decomposition > 260C
Elemental analysiss C 35.1~; H 5.6%; N 5.0%; P 11.3~ (found) C 35.4~; H 5.9%; N 5.1%; P 11.4%; F 42.0% (cal~ulated) Use Example 1 1.0 part of compound (4) were incorpora~ed homogeneously into 99.0 parts of toner binder ("~Dialec S-309" from Diamond Shamrock, styrene/methacrylate copolymer 60:40) by means of a kneader for 45 minutes. ~he mixture was then ground on a univexsal laboratory mill and sub-2~ sequently graded on a ~entrifuqal ~ifter. ~he deciredparticle fraction (4 to 25 ~m) was activated wit~ a carrier of magnetite particles, coated with styrene/meth-acrylate copolymer 90:10, 50 to 200 ~m i~ size of the type ~90 ~m Xerographic Carrier" from Pla-~ma ~aterials Inc. (Manchester, NH, USA).

The measurement was carried out on a customary q/m measuring stand. By using a sieve having a mesh width of 25 ~m, it w~s ensured that no carrier could be carried along when the toner was blown out. The measurements were carried out at about 20C and 50% relative a~mospheric humidity. The following q/m values [~C/g] were measured as a function of the activation time:

, ;~
. .

~g5~
- ~3 -Activation time Charginq q~m [uC~g]
10 min -19 30 min -18 2 h -15 24 h -15 Use Examples 2 and 3 In sach case 1 part of compounds (5) and ~7), correspond-ing to Use Exam~les 2 and 3, were incorporated homogen-eously into in e~ch case 99 part~ of toner ~inder a~
described in Use Example 1. The following q/m values [~C/g] were measured a~ a function o~ the activation time:

Activation tLme Charginq q/m [~C/q]

Use Example 2 3 10 min +3 -5 30 min +5 -10 2 h +2 -16 24 h +2 -20 Use Example 4 1 par~ of compound (4) wa~ incorporated homogeneou~ly into 99 parts of a powder coating binder based on a carboxyl-containing polyester resin, for example ~Crylcoat 430 from UCBiBelgi~m, as de~cribed in ~se Example 1. The following q/m value~ t~C/gl were measured as a function o~ the activation time, a carrier coated with PTFE (polytetrafluoroethylene) being used in~tead of the carrier coated with styrene/acrylate de~cribed in ~se Example 1:

, - ~ .:

;: . . , , , Activation tLme q/m r uC~al 10 min +3 30 min ~4 2 h ~7 5 24 h +6 To determine the deposition rate, 30 g of the te~t powder coatin~ were sprayed under a de:Eined pre~sure through a tribogun as described above. By de~ermining the differ-ence in weight, the amount of powdsr coating deposited could be determined and a deposition rate in ~ could be defined, and, by the charge ~ransfer, a current flow (~A3 could be measured.

Pressure ~barl Current [~l Deposition rate t~]
3 1.4-1.8 52 Comparison Example 1 For measurement of the pure resin binder Dialec 309, the procedure was as in Use Example l, but without kneading in additives.

Activation time qlm ~C/
10 min -4 30 min -12 2 h -27 24 h -48 Comparison Example 2 For determination of the charging properties of ~he pure powder oo~ti~gresin component CryIcoat 430~ tha procedure was as in Comparison Example 1, a carrier coated with P~FE ~polytetrafluoroethylene) being used instead of the magnetite carrier.

Activation time ~/m r~C/~

:' "' :
. ~ : .

10 min -17 30 min -19 2 h -19 24 h -18 For determination of the deposition rate, the procedure was as in Use Example 5.

Pressure [barl Current [~A] eposition rate r %1 3 0.1 5 , Comparison Example 3 For determination o~ the triboelectric charging proper-ties of a comparable polymeric ionic ammonium compound, the procedure was as in Use Example 5:

Activation time ~/m ~uC/ql 10 min -8 30 min -8 2 h -9 24 h -10 For determination of the charactaristic data on tribo-electric powder paint spraying of a comparable polymeric ammonium compound, the procedure was as in Use Exampls 5.

Pressure [barl Current ~A] Deposition rate ~%~
3 0.7-0.9 18 A comparison ~oth with the pure powder coating resin component tComparison Example 2) and with a comparable polymeric ammonium compound (Comparison Example 3; the preparation of the polymeric ammonium compound employed is described in CA-A-2,o51,788, Preparation Example 2) significantly shows a clear impro~ement in the deposition rate by using the ionic diallylammonium monomer according to the invention.

Claims

1. An ionic monomeric diallyliammonium compound of the formula (I) (I) or mixture or mixed crystal thereof, in which the radicals R1 to R12 independently of one another are each a hydrogen atom, a halogen atom, a hydroxyl radical, a primary, secondary or tertiary amino radical, a carboxylic acid or carboxylic acid ester radical, an acyl radical, a sulfonic acid or sulfonic acid ester radical, a cyano radical or a nitro radical, or are in each case a radical based on an aliphatic or aromatic hydrocarbon, which can be interrupted by hetero atoms, and Ae is in each case the stoichiometric equivalent of an inorganic anion, of an anion of a heteropolyacid or of a borate of the formula (II) (II) in which the radicals R13 to R16 on the borate anion independently of one another are aliphatic or cyclo-aliphatic radicals, or aryl or heteroaryl or aralkyl radicals, it being possible for these radicals to be substituted by alkyl(C1-C4), alkoxy(C1-C4) or aryl radicals or by halogen atoms, or are fluorine atoms, or of an organic anion, or Ae is a combination of these anions; or a mixture of such compounds and mixed crystals with mixed anions and/or cations.

2. A compound as claimed in claim 1, wherein the organic anion is one based on a phenolate, olefinic, aliphatic or aromatic carboxylate, sulfonate, thiolate or sulfate, in which the alkyl, alkenyl or aryl radicals can also be perfluorinated, or based on a disulfo-pyrrolidinium-betaine of the formula (III) (III) in which R1' and R2' have the meanings given for R1 and R2, and X and Y are in each case a straight-chain or branched aliphatic, saturated or unsaturated alkyl(C1-C18) radical or alkoxy(C1-C18) radical.

3. A compound as claimed in claim 1 or 2, wherein the anion Ae is an organic anion from the group compris-ing F-, I-, NO3-, OH-, HSO4-, S2-, SO32-, S2O32-, HCO3-, CO32-, H2PO4-, HPO42-, PO43-, CN-, cyanate, isocyanate, thiocyanate, zinc tetracyanate, zinc tetrathiocyanate, perchlorate, PF6-, MoO42-, MoS42- and WO42-, or a combination thereof.

4. A compound as claimed in claim 3, wherein the anion Ae is a combination of the anions mentioned with C1-, Br- and/or SO42-.

5. A compound as claimed in claim 1, wherein the anion Ae is an anion of a heteropolyacid, preferably P(Mo3O10)43-, P(W3O10)43- or a silicomolybdate.

6) A compound as claimed in claim 1, wherein the anion Ae is a borate, preferably tetrafluoroborate, tetra chloroborate, tetraphenylborate, tetra(fluoro-phenyl)borate, tetra(chlorophenyl)borate, tetra tolylborate, tetranaphthylborate, tetra(methoxy-phenyl)borate, tetrabiphenylborate, tetrabenzyl-borate or tetrapyridylborate, or a combination thereof.

7. A compound as claimed in claim 1, wherein the anion Ae is an organic anion from the group comprising ethylsulfate, phenolate, nitrophenolate, thiolate, acetate, lactate, benzoate, the mono- or dianion of dithiodibenzoic acid, salicylate, 2-hydroxy-3-naphthoate, 2-hydroxy-6-naphthoate, ethylsulfonate, phenylsulfonate, tosylate, perfluoroacetate, per-fluoro-C1-C30-alkylbenzoate,perfluoroethylsulfonate, perfluoro-C1-C30-alkylbenzenesulfonate and saturated or unsaturated aliphatic or cycloaliphatic or aromatic di- and tricarboxylate or di- or trisulf-onate, preferably citrate, oxalate or succinate.

8. A compound as claimed in claim 1, wherein the anion Ae is a disulfo-pyrrolidinium-betaine of the formula (III), in which R1' and R2' are R1 and R2, and X and Y are straight-chain or branched aliphatic, satur-ated or unsaturated alkyl(C1-C18) or alkoxy(C1-C18) radicals, preferably alkyl(C1-C5) or alkoxy (C1-C5) radicals, or polyoxyalkylene radicals, preferably polyoxyethylene and polyoxypropylene radicals, of the formula (alkylene(C2-C5)-O)n-R, in which R is a hydrogen atom or an alkyl(C1-C4) radical and n is a number from 1 to 10.

9. A compound as clAimed in claim 1, wherein the anion Ae is an anion from the group comprising F-, I-, BF4-, B(aryl)4-, PF6- or P(Mo3O10)43-, or of a disulfo-pyrrolidinium-betaine of the formula (III);

R1 and R2, and R1' and R2' independently of one another are hydrogen atoms, straight-chain or branched, saturated or unsaturated alkyl(C1-C18) or alkoxy(C1-C18) radicals, polyoxy-alkylene radicals, preferably polyoxyethylene and/or polyoxypropylene radicals, of the formula (alkylene-(C1-C5)-O)n-R, in which R is a hydrogen atom, an alkyl(C1-C4) radical or an acyl radical, preferably the acetyl, benzoyl or naphthoyl radical, and n is a number from 1 to 10; aryl or heteroaryl radicals, preferably phenyl, naphthyl or pyridyl radicals;
aralkyl radicals, preferably tolyl radicals;
aralkoxy radicals, preferably methoxyphenyl radi-cals; alkaryl radicals, preferably benzyl radicals;
or cycloalkyl radicals, preferably cyclopentyl or cyclohexyl radicals, or the abovementioned radicals can contain at least one hetero atom, preferably nitrogen, oxygen, sulfur, phosphorus or a combination thereof, and can be substituted by one or more carboxamide radicals, sulfonamide radicals, urethane radicals, ketone radicals, primary, secondary or tertiary amino radicals, nitro radicals, ether radicals, in particular alkylene(C2-C4)-O-alkyl(C1-C4) radicals, alkyl(C1-C4) radicals, alkoxy(C1-C4) radicals, aroxy radicals, in particular phenoxy radicals, halogeno-alkyl(C1-C30)radicals,halogenoalkoxy(C1-C30)radicals or ester radicals, in particular -C(O)O-alkyl (C1-C4), one or more halogen atoms or hydroxyl, carboxyl, sulfonic acid, cyano or mercapto groups, or a combination thereof, or R1 and R2, and R1' and R2' together form a saturated or unsaturated, aromatic or non-aromatic 5- to 7-membered ring system, preferably the pyridinium ring system, which can contain further hetero atoms, preferably nitrogen, oxygen, sulfur or a combination thereof, in the ring, in particular the morpholinium ring system, and which can be substituted and/or modified by condensation of or bridging to other ring system, in particular the quinolinium ring system; and R3 to R12 independently of one another have the meanings given above for R1 and R2, and R1' and R2', or are halogen atoms or aroxy radicals, preferably phenoxy radicals.

10. A compound as claimed in claim 1 or 9, wherein Ae is an anion from the group comprising BF4 and B(aryl) 4-, in which aryl is phenyl, naphthyl, fluoro-phenyl, chlorophenyl, methoxyphenyl, biphenyl, pyridyl or tolyl or a combination thereof R1 and R2 independently of one another are hydrogen atoms, straight-chain or branched, saturated or unsaturated alkyl(C1-C6) or alkoxy(C1-C6) radicals, aryl or heteroaryl radicals, in particular phenyl, naphthyl or pyridyl radicale, aralkyl radical , in particular tolyl radicals, aralkoxy radicals, in particular methoxyphenyl radicals, alkaryl radicals, in parti-cular benzyl radicals, or cycloalkyl radicals, in particular cyclopentyl or cyclohexyl radicals, it being possible for the radicals R1 and R2 to be substituted by one or more halogen atoms, hydroxyl, carboxyl, sulfonic acid or carboxamide radicals, in particular -NH-C(O)-alkyl(C1-C4), sulfonamide radi-cals, in particular -NH-SO2-alkyl(C1-C4), keto radicals, in particular C(O)-alkyl(C1-C4), primary, secondary or tertiary amino radicals, in particular -NH2, -NH[alkyl(C1-C4)]- or -N[alkyl(C1-C4)]2, nitro radicals, ether radicals, in particular alkylene-(C2-C4)-O-alkyl(C1-C4), alkyl(C1-C4) radicals, alkoxy-(C1-C4) radicals, aroxy radicals, in particular phenoxy radicals, halogenoalkyl(C1-C4) radicals, halogenoalkoxy(cl-c4) radicals or ester radicals, in particular -C(O)O-alkyl(C1-C4); and R3 to R12 independently of one another have the meanings given above for R1 and R2, or are halogen atoms.

11. A compound as claimed in at least one of claims 1, 6 and 8 to 10, wherein Ae has the meaning BF4-, B(phenyl)4- or disulfo-pyrrolidinium-betaine of the formula (III), in which R1' and R2' have the meanings given below for R1 and R2, R1 is hydrogen or methyl, R2 is hydrogen, methyl or octyl, and R3 to R12 are in each case hydrogen.

12. A mixed crystal or mixture of two or more compounds as claimed in at least one of claims 1 to 11.

13. A process for the preparation of a compound as claimed in at least one of claims 1 to 12, which comprises adding one or more compound(s) on which the anion Ae is based, preferably the sodium salt, to a diallylammonium halide of the formula (IV) (IV) in which Hal is fluorine, chlorine, bromine or iodine as a solution in water or in a mixture of water and an organic solvent which is completely or partly miscible with water, at a temperature between 0°C and 100°C, preferably 10°C and 70°C, and a pH ofbetween 3 and 10, preferably 5 and 8, and then, if appropriate, precipitating the compound of the formula (I) according to claim 1 by salting out with halogen-containing salt, for example potassium chloride.

14) The process as claimed in claim 3, wherein the reaction is carried out in a mixture of water and isopropanol, water and isobutanol or water and methyl isobutyl ketone.

15) The process as claimed in claim 13 or 14, wherein the diallylammonium chloride is reacted with sodium tetraphenylborate, sodium tetra-o-fluorophenyl-borate, sodium tetra-m-fluorophenylborate, sodium tetra-p-fluorophenylborate, sodium tetra-o-chloro-phenylborate, sodium tetra-m-chlorophenylborate, sodium tetra-p-chlorophenylborate, sodium tetra-o-tolylborate, sodium tetra-m-tolylborate, sodium tetra-p-tolylborate, sodium tetra-l-naphthylborate, sodium tetra-2-naphthylborate, sodium tetra-o-methoxyphenylborate, sodium tetra-m-methoxyphenyl-borate, sodium tetra-p-methoxyphenylborate, sodium tetra-o-biphenylborate, sodium tetra-m-biphenyl-borate, sodium tetra-p-biphenylborate, sodium tetrabenzylborate, sodium tetra-o-pyridylborate, sodium tetra-m-pyridylborate, sodium tetra-p-pyridyl borate or sodium tetrafluoroborate.

16) The use of a compound as claimed in at least one of claims 1 to 12 as a charge control agent in electro-photographic toners and developers which are employed for copying or duplicating masters and for printing electronically, magnetically or optically stored information or in colorproofing, and as a charge control agent in powders and powder coatings.

17. The use as claimed in claim 16, wherein the ionic monomeric diallylammonium compound is employed, by itself or in a combination, in a concentration of about 0.01 to about 30, preferably 0.1 to 5.0 per-cent by weight.

18. The use of a compound as claimed in at least one of claims 1 to 12, wherein this compound is employed as a charge-improving agent in the form of coatings of carriers or a constituent of coatings of carriers which are used in developers for electrophotographic copying or duplication of masters and for printing electronically, optically or magnetically stored information or in colorproofing.

19. The use of a compound as claimed in at least one of claims 1 to 12, wherein this compound is employed by itself or as a combination as a charge-improving agent 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 electrokinetic-ally sprayed powder coatings.

20. Use according to at least one of claims 16 to 19, characterised in that the anion Ae in the compound of the formula (I) is chloride, bromide or the stoichiometric equivalent of sulfate.