DE2020839B2 - Electrophotographic suspension developer - Google Patents

Description

—CON

15th

- ^ p

a dektrophotograptai-

20th

-CH ₂

CH ₂ = C

(I)

where X equals the group

-COOC _n H _{2n + 1} -OCOC _n H _{2n + 1}

-OC _n H _{2n + 1} -C _n H _{2n + 1}
or

-CH ₂ OC _n H ₂

_{n + 1}

fromltoU,

orC _n H _{2n +} , and «= an integer

the group

-COOC _n H _2n -N (C _n H _{2n + 1} ) ₂

-COO-N (C _n -H _{2 n + 1} ) ₃

H
-CON (C _n H ₂ ,, _{+ 1} ) ₂

_3S

whole

from 6 to 7 and Y equals one

-COO-N (C _n H _{2n + 1} OH) ₃

Y ₁ equals a hydrogen ^ -

CH ₂ = C

45

CH ₂ = C

(HD

where X ₁ equals the group ^ _n ^ _g , _{eich the} group

-COCl -CONH ₂ COOCH ₂ CH ₂ Cl 5o ^ _οο ^ _οη -OCH ₂ CH ₂ OH -COOH

55

-CH CH ₂

_COOCH ₂ CH "CH ₂

_{withn =} an integer of Ibis 8, the group> _χ

N ^

O __ _C _O-CH ₂ -CH = CH ₂ II ο

-CH-CH ₂ -O-CH ₂ CH ₂ -CH CH,

-COOCH ₂ CH CH ₂

-CH ₂ -CH ₂ -CH CH _:

- / ~~ V-NO ₂ or

-OH

and Y ₂ is a hydrogen atom or a methyl group, the molar ratio of compound of formula II to compound of formula I between 0.1: 9.9 and 3: 7 and the molar ratio of compound of formula III to compound of formula I between 1: 4 and 2: 3.

The hitherto customary electrophotographic suspension developers for developing latent electrostatic Images are produced in such a way that pigment or dye particles are superficial coated with resins, oils and the like that simultaneously control polarity and stabilize dispersion and the obtained toner in a carrier liquid of high insulation resistance and lower Dielectric constant dispersed. Vegetable resins are suitable as resin or oil components, hydrogenated rosin. Linseed oil, alkyd resins, styrene resins, phenol modified resin, acrylic resins, synthetic Rubber, ethyl cellulose and the like. Such resins or oils serve to give the toner particles a distinctive character to grant positive or negative polarity and their uniform dispersion in the carrier liquid to ensure. The toner particles contained in the known suspension developers are with the The disadvantage is that they have a relatively pronounced polarity in the first time after production has taken place show and form a perfect dispersion, but that on the pigment or dye particles adsorbed resin gradually passes into the carrier liquid over time, resulting in blurring polarity and precipitate formation of dull coagulation and consequently deteriorated Fusing performance and developing blurred image copies. In addition, they have known toner particles contained in electrophotographic suspension developers have a relatively large particle size and poor transparency, making them particularly unsuitable for multicolor electrophotography makes, because thereby the selective light wave absorption and reflection door the partial colors purple. Blue-green and yellow impaired and thus an inadequate color balance, a deteriorated resolution, ultimately no lack of fidelity to the original of the color image copy and the like can be achieved.

It is an object of the invention to provide an electrophotographic suspension developer create, whose arbitrarily colored toner particles have a pronounced positive or negative polarity and are dispersion-stable over a long period of time, and the production of multicolor copies of images allowed.

The invention relates to an electrophotographic suspension developer of the type mentioned at the beginning Kind, which is characterized in that 3 the toner is made from a reaction product of a dye or pigment with compounds of the formulas I and II or I and III

Colored plastics are known per se and are used as pigments for inks, printing inks and paints and used as dyes for coloring high molecular materials, fibers and the like they are manufactured in such a way that one either chemically attaches a dye to a reactive compound binds or an amino group-containing polymer is first diazotized and then with a Coupler couples colored plastics produced in this way, however, are not suitable as toners in electrophotegraphic Suspension developers because, firstly, they are not in the carrier liquids required for this, such as η-hexane, n-heptane or the like. Are dispersible and, secondly, do not have the polarity that to run a rapid electrophoresis according to the charge distribution (or the lines of force) in the electrostatic latent image to be developed is sufficient.

In contrast to this, the colored toners used in electrophotographic suspension developers according to the invention do not suffer from the above-mentioned disadvantages. Since they contain a proportion of monomers of the formula I in the form of a vinyl compound with a strong affinity for the carrier liquid and a proportion of monomers either of the formula II or of the formula III in the form of a vinyl compound with a functional residue that is able to charge the toner particles negatively or positively, the properties of the individual components can be used by binding these two types of compound together to reactive dye particles. Monomers of the formula I have as radical X a long-chain alkyl radical with a strong affinity for the carrier liquid, while at the same time the radical Y ₁ in the monomers of the formula 11 or the radical Y ₂ in the monomers of the formula III ensures that the colored plastic is in the Carrier liquid has a pronounced negative polarity - when using monomers of the formula II or positive - when using monomers of the formula III.

Some examples of compounds of formula 1 are given below:

Acrylic acid hexyl ester,

Lauryl methacrylate,

Stearyl acrylate,

Methacrylic acid octyl ester,

Acrylic acid tridecyl ester,

Pentadecyl methacrylate,

Methacrylic acid hexadecyl ester,

2-ethylhexyl methacrylate,

Vinyl caproate,

Vinyl stearate,

Vinyl caprylate,

Vinyl myristic ester,

Vinyl palmitate,

Vinyl heptanoate,

Hexyl vinyl ether,

2-ethylhexyl vinyl ether,

15th

20th

Stearyl vinyl ether, tridecyl vinyl ether, hexadecyl vinyl ether, Allyl caproate, allyl laurate, allyl stearate, allyl palmitate, Allyl myristic acid, acrylic caprylate, hexene,

Pents,

Nuns,

Dodecene, hexadecylene, tridecylene, octene or mixtures thereof.

The following are some examples of connections called the formula II:

Dimethylaminoethyl methacrylate, dibutylaminoethyl methacrylate, Acrylic acid dioctylaminohexyl ester, acrylamide, dimethylacrylamide, dibutyl acrylamide, Dioctylacrylamide, methylacrylamide, ethylacrylamide, butylacrylamide, Cydohcx}! Acrylamide, Phenyl acrylamide, benzyl acrylamide, Methacrylic acid ^ -chloroethyl ester, p-chlorostyrene, p-aminostyrene, o-aminostyrene, p-dimethylaminostyrene, 2-vinylpyridine, 4-vinylpyridine, p-acetamidostyrene, p-Acetdimethylaminostyrene, p-Acetoctylaminostyrene, Trimethylaminoacrylate, triethanolaminoacrylate,

Trioctylamino acrylate or mixtures thereof.

Examples of compounds of the formula III are given below:

2,3-epoxypropyl acrylate, hydroxyethyl methacrylate, Methacrylic acid ^ -epoxypropyl ester, methacrylic acid allyl ester, Allyl alcohol, butadiene oxide, acrylic acid, acrylic glycidyl ether, p-vinylbenzoic acid glycidyl ester, 2-methyl-5,6-epoxy-1-hexene, p-nitrostyrene, Vinylbenzoic acid, o-nitrostyrene, p-hydroxystyrene, or mixtures thereof.

All monomers formerly used with these monomers are suitable for reaction with the monomers mentioned Compounds incoming dyes, e.g. B. Tetra - 4 - amino copper phthalocyanine, 2,4,6 - tri- (4 - amino - 1 - anthraquinonylamino) -1,3,5 - triazine, 2,4-dichloro-p-phenylenediamine and the like, whereby the respective amino group diazotized before the reaction.

The following are dyes suitable for producing the colored toner of electrophotographic recording materials according to the invention specified.

35

40

50

55

60

CH ₃
N = C

N-CH

C ₆ H ₅

NH ₂

CH,

Red dye

CH ₃

OH

CH

OH SO ₃ Na

SO ₃ Na

409 522/335

OH

SO ₃ Na

OH

SO ₂ NH-C ₅ H ₅

Η, Ν— <

CH,

SOaNa / X-NH,

SO ₃ Na OH

_N H ₂ -yv \ _Y _{Vn = n}

^ CH ₂

SO ₃ Na S 0, Na

Blue dye

(XcJ0 " ^{n <QHs) 2CI}

NH- / V-NH ₁

SO ₃ Na

HO

SO ₃ Na

NHCOCH ₃

Black dye

SO ₃ Na

SO ₃ Na

In the preparation of those contained in electrophotographic suspension developers according to the invention, colored toners are nonionic surfactants such as B. polyethylene glycol monolaurate, Polyethylene glycol monostearate, polyoxyethylene oleyl ether, polyoxyethylene acetyl ether, polyoxyethylene alkyl allyl ether, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polycxyethylene sorbitan monolaurate, Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate or sorbitan trioleate, in amounts of about 0.1 to 2%. based on the total weight of all substances.

Colored toners with negative polarity are obtained by combining a compound of formula 1 with a compound of the formula 11 and those having positive polarity by combining a compound of formula 1 with a compound of formula III in the specified M oil ratio range, addition a dye previously diazotized in the usual way, preferably heating the entire mass for 1 to 10 hours in the presence of a catalyst to a temperature of 30 to 100 ° C.

The reaction of the monomer mixtures with the dye takes place via the diazo radical following likely reaction scheme:

CH ₃

CH ₅ =

COOCH ₃

CH ₃

/ \ COOCH ₃ COOCH ₃

CH ₃

COOCH ₂ CH ₂ N (CH ₃ ) J

/ CH ₃

\ COOCa ₃ } _m

/ CH ₃

-CH ₂

—C-

\, COOCH ₂ CH ₂ N (CHa) ₂ ,

The reactive dye is usually used based on the weight of the Monomers, about 10 to 30%. The catalyst, on the other hand, is added in an amount that each, based on the weight of the total mixture, in the case of monomers of the formulas 1 and 11 about 20 to 50% and in the case of monomers of the formein I and 111 is about 20 to about 40%. Reaction accelerating catalysts include Compounds of the general formula

CH ₂ = C

COOR

in which Z denotes a hydrogen atom or the methyl radical and R _{denotes the C “H 2) 1 + 1} radical with η = 1, 2, 3 or 4, e.g. B. methacrylic acid methyl ester, ethyl ester or butyl ester, acrylonitrile or other acrylic or methacrylic acid esters.

In preparing an electrophotographic suspension developer according to the invention, the colored toner and some dispersant, e.g. B. toluene, a toner concentrate prepared, which is then suspended in a suitable amount of a conventional carrier liquid with a specific resistance of more than 10 ⁹ ohm · cm. Suitable carrier liquids are e.g. B. ligroin or commercially available paraffinic or isoparaffinic petroleum hydrocarbons.

The toner particles suspended in electrophotographic suspension developers according to the invention have a very small particle size (0.01 to 0.1 μ), so that they even through the densest Run filter paper (with a pore size of 0.25 μ) through it. That associated with the dye or pigment Polymer is chemically bonded to the dye or pigment particles so that no precipitation or Coagulation occurs, as it is unavoidable with the usual unwinders due to the resin or ©! Separation This leaves electrophotographic suspension developers in accordance with the invention Even over long periods of time (more than 1 year) it is uniformly dispersible and clear Preserve polarity. The very small particle size of the toner particles also offers the advantage that the ultimately obtained image copy has a high resolution and regardless of the type of

Charge pattern shows no edge effect. Further is because of this in connection with the high particle transparency, especially in electro-color photography a selective absorption and reflection of white light ensures that also the laws of color of the three component colors is true, so that the final multicolor copy is color balanced and Fidelity to the original is of high quality.

The following examples are intended to explain the invention in more detail.

example 1
Making a Blue Toner

A suspension of 3.5 g of finely divided tetra-4-aminocopper phthalocyanine in 40 ml of water is mixed with a mixture of 43.4 g of concentrated hydrochloric acid and 40 ml of water. The resulting hydrochloric acid solution is stirred for 30 minutes at a temperature of 0 to 5 ° C., a mixture of 8 g of ice and an aqueous solution of 1.6 g of sodium nitrite is added all at once at the same temperature, and stirring is continued for 15 minutes. The Diazosalzlösung obtained is mixed with an emulsion of 5 g of methyl methacrylate, 10 g of lauryl methacrylate, 1 g and 1.0 g Methacrylsäuredimethylaminomethylester Polyoxyäthylensorbitanmonostearat in 30 ml of water and polymerized by heating to a temperature of 60 to 70 ⁰ C for 2 hours. When the polymerization has ended, the solution is extracted with 500 ml of toluene and the extract is concentrated to 50 ml. The residue is poured into 200 ml of methanol. A methanol-insoluble, highly viscous, bluish-purple plastic precipitates out, which is purified by redissolving it in 50 ml of toluene and reprecipitating it with methanol.

Overall, 7.5 g of a blue toner becomes more excellent Transparency and dispersibility obtained with a pronounced negative polarity.

Example 2
Making a Blue Toner

With the addition of 1 g of polyethylene glycol monostearate, an emulsion of 5 g of methyl methacrylate, 15 g of lauryl methacrylate and 3 g of hydroxylethyl methacrylate in 30 ml of water. This emulsion is mixed with a diazo salt solution obtained according to Example 1, under Warming to a temperature of 60 to 70 ° C for about 2 hours, then cooled and stirred with 500 ml of toluene extracted. 450 ml of toluene are removed from the extract, whereupon the remaining extract in 200 ml of methanol is poured. A blue-colored resin substance separates out and through Redissolving three times in 50 ml of toluene each time and reprecipitation with 200 ml of methanol each time and final drying is cleaned.

In total, 11.5 g of a blue toner becomes more excellent Transparency and dispersibility obtained with a pronounced positive polarity.

Example 3
Making a Yellow Toner

5 g of 2,4,6-tris- (4-amino-1-anthraquinonylamino) -1,3,5-S-triazine are suspended in 150 g of concentrated hydrochloric acid, at a temperature of 0 ⁰ C all at once with a solution of 1.7 g of sodium nitrite in 8.5 ml of water are added and the mixture is diazotized for 30 minutes at a temperature of about 0 to 2 ° C. The resulting diazo salt solution is treated with sulfamic acid to remove excess sodium nitrite and filtered. The filtrate obtained is mixed with an emulsion which has been prepared by adding 1 g of polyoxyethylene oleyl ether (nonionic surface-active agent) to a solution of 10 g of lauryl methacrylate, 5 g of diniethylaminomethyl methacrylate and 1 g of p-aminostyrene in 30 ml of water. The mixture obtained is allowed to react for 2 hours with a gradual increase in temperature to 80 to about 90 ° C., after which the reaction solution obtained is extracted with 500 ml of toluene. 450 ml of toluene are evaporated from the extract; the remaining extract is mixed with 200 ml of methanol.

A yellow plastic separates out, which by redissolving it three times in 50 ml of toluene each time and reprecipitation is purified with 200 ml of methanol each time.

In total, 13.5 g of a yellow toner becomes more excellent Transparency and dispersibility obtained with a pronounced negative polarity.

Example 4
Making a Yellow Toner

The diazosaizi solution obtained according to Example 3 is a mixture of 10 g of lauryl methacrylate, 5 g of ethyl acrylate, 3 g of glycidyl methacrylate and 30 ml of water were added and washed through

Addition of 1 g of the surface-active mentioned in Example 3 " Emulsified by means of. The emulsion obtained becomes with a gradual increase in temperature allowed to react to 80 to about 90 ° C for 2 hours, whereupon in the manner described in Example 3 a yellow plastic is deposited and cleaned.

A total of 12 g of a yellow toner becomes excellent in transparency and dispersibility with a pronounced positive polarity. The color transparency of one containing this toner Image copy produced by the suspension developer is very good.

Example 5

Making a Red Toner

4.7 g of a dye which vun by diazotization 2,6-dichloro-p-phenylenediamine and coupling of the diazo compound with 3-oxynaphthoic acid-m-aminoanilide is obtained are suspended in 35 g of concentrated 35% hydrochloric acid and in diazotized this form by adding 1.6 g of sodium nitrite. Be in the obtained diazonium salt solution 15 g lauryl methacrylate, 5 g methacrylic

butyl acid ester, 2 g vinyl benzoate and 30 ml Thoroughly stir in water, then slowly increase the temperature to 80 to about 90 ° C for 2 hours is polymerized. The polymerization product, a yellow plastic, is described as in Example 3

separated and cleaned.

In total, 12.5 g of a red toner becomes more excellent The transparency and dispersibility with a pronounced negative polarity are obtained

Color transparency of an image copy produced with a suspension developer containing these toners is very good.

Example 6
Making a Red Toner

A mixture of 15 g lauryl methacrylate, 5 g methyl methacrylate, 2.5 g allyl methacrylate and 30 ml of water with the addition of 1 g of sorbitan monolaurate (nonionic surface-active Medium) emulsified. The emulsion obtained is produced with that according to Example 5 Diazonium salt solution mixed, with gradual temperature rise to 80 to about 90 ° C for 2 hours stirred for a long time and, after cooling, worked up in the manner described to give a purified red toner.

A total of 9.5 g of a red toner becomes excellent in transparency and dispersibility a pronounced negative polarity. The color transparency of one containing this toner The image copy produced by the suspension developer is very good,

The toners produced in the manner described are used for the production of electrophotographic Suspension developers are used by first kneading them with a dispersing agent to form a Processed toner concentrate and then in this form in the final carrier liquid be suspended.

The individual suspension developers have the following composition.

Table I.

Colored
toner
according to
example

2 3

lot

5g

5g
5g

7.5 g

5g

Dispersants

commercial petroleum hydrocarbon 50 g
n-hexane 40 g
n-heptane 40 g

Ligroin 50 g

n-heptane 45 g

commercial petroleum hydrocarbon + commercial isoparaffinic hydrocarbon 50 g
(in a ratio of 7: 3)

Carrier liquid

commercial isoparaffinic

Hydrocarbon 1000 ml

commercial petroleum hydrocarbon ¹ 000 ml commercial isoparaffinic

Hydrocarbon 1000 ml

commercial petroleum hydrocarbon +

commercially available isoparaffin scissors

Hydrocarbon 1000 ml

(in a ratio of 4: 6)

other commercial petroleum hydrocarbons + commercial »isoparaffinic

Hydrocarbon 1000 ml

(in a ratio of 3: 6)

commercial hydrocarbon -

isoparaffinic 1000 ml

These six suspension developers have the properties given in the following table Π:

Tabel

Suspensions polarity Particle size DispeiMonsMabiliiäl Polarity stable developer according to
example negative <0.25 u No precipitation at No change in 1 15,000 U miii Run of more than 1 year positive <0.25 μ desgi the same 2 Negative- <0.25 μ the same the same 3 positive <0.25 μ the same the same 4th positive <0.25 ; ι the same desel. 5 positive < 0.25 μ the same the same 6th

An electrophotographic recording material with zinc oxide and a styrene / methacrylic acid butyl ester / Glycidyl methacrylate / acrylic acid copolymer (molar ratio 60: 32: 5: 3) in the light-sensitive photoconductive layer is first charged with a -6KV corona discharge, then by exposure to a latent electrostatic image vcvse'r.v.n: imi finally with a suspension developer of the type described. In each case there is a sharp, positive one or negative color copy received. If the recording material is sequentially - under again-

Δ09 «5/335

high charge and development - exposed against the partial color separations of a multicolored original and then developed with the suspension developers of Examples 4, 2 and 5, one is obtained sharp multicolored image copy.

Example 7

In the same way as in the previous examples is made using the dyes and monomers listed in Table III below produced a number of colored toners. Each 1 part by weight of the respective toner is with 2 to about Parts by weight of a commercially available petroleum hydrocarbon are kneaded to form a toner concentrate that then in 1000 ml each of a commercially available isoparaffinic hydrocarbon as a carrier liquid is dispersed. All suspension developers obtained have correspondingly favorable properties like the suspension developers of the previous examples and the polarity given in Table III

Table III

dye

15th

dye

Tetra

4-amino-

copper-

phthalo-

cyanine

Vinyl connection tower to be moved

Methacrylic acid

hexadecyl ester 15 g

4-vinylpyridine .... 2 g of methyl methacrylate 5 g

Acrylic vinyl

hexyl ester 25 g

p-nitrostyrene 35 g

Ailyl myristic

ester 20 g

o-aminostyrene .... 25 g butyl myristic acid 8 g

1-octene 10 g

Styrene 5 g

Benzylacrylamide ... 3 g methacrylic acid

butyl ester 5 g

Tridecyl vinyl ether. 15g

Acrylic glycidyl ether. 8 g methacrylic acid

hexyl ester 25 g

Acrylonitrile 10 g

Acrylic acid oayl ester 20 g

Acrylic acid

2,3-epoxypropyl-

ester 8 g

Methacrylic acid ester 10 g

Acrylic acid hexyl

ester 50 g

Methacrylic acid dibutylamino-

ethyl ester Ig

Methacrylic acid alcohol 5 g

Polarity ι

negative

positive

negative

negative

positive

positive

negative

40

45

50

55

60

2,4,6-tri-

(4-amino-

1-anthra-

quinonyl

amino) -

1,3,5,6-tri-

azin

10g

2,6-dichloro

p-phenylene-

diamine

/ i-oxy-

naphthoeic

acid-

m-amino-

chloride

lied Vinyl compound to be converted

Caproic acid vinyl

ester 60 g

Dimethylacrylamide 3 g methacrylic acid ester 20 g

Palmitic acid allyl

ester 45 g

Triethanolamine acrylate .. 5 g butyl acrylate 15 g

Allyl laurate-2-methyl-

5,6-epoxy ether 10 g

Palmitic acid vinyl

ester 10 g

Methacrylic acid ester 21 g

i-Hexen 20 g

p-nitrostyrene 5 g

Methacrylic acid

heptadecyl ester 30 g

Methacrylic acid

ethyl ester 20 g

Palmitic acid vinyl

ester 35 g

p-vinylbenzoic acid 2.5 g glycidylhexyl methacrylate .. 2.5 g of butyl methacrylate 15g

Palmitic acid allyl

ester 60 g

Benzyl acrylamide ... 6 g

Methacrylic acid ester 18 g

Hexadecylene 40 g

p-dimethylamino

styrene 5 g

2-ethylhexyl methacrylate .. 15g butyl methacrylate 20 g

Stearic acid vinyl

ester 50 g

Acrylic acid 15 g

Methacrylic acid

2,3-epoxy ester 5 g

Methacrylic acid ester 18 g

Palmitic acid vinyl

ester 30 g

2-chloroethyl methacrylate ... 3.5 g methacrylic acid dioctylaminohexyl

ester 3 g

Acrylic acid butyl

cster 15g

polarity

negative

negative

positive

positive

positive

negative

negative

negative

negative

Claims (1)

Patent claims: 1. Electrophotographic suspension developer with a toner which is a reaction product of a compound of the formula CH ₂ = C -t (D 10 where X equals the group —COOC _n H, " ₊₁ , -OCOC _n H _{2n + 1} , -OC _n H _{2n + 1} , -C _n H _{2n + 1} or —CH ₂ OC _n H _{2n + 1} with" = is an integer from 6 to 7 and Y is a hydrogen atom or a methyl group, and either a compound of the formula Y ₁ CH ₂ = C (H) X. wherein X _{1 is the} same as the group COCl -CONH ₂ COOCH ₂ CH ₂ Cl -o- / ~ Vnh ₂ N (C _n H _{2n + 1} ), with η = an integer from 1 to 8, of the group 3 ° 35 the group halogen —CON with R = a group 40 45 50 55 60 orC _n H, _{n +} y and n = an integer from 1 to 12, of the group —COOC _n H _2n -N (C "H _2n - ₊₁ ) ₂ , -COO-N (C _n -H _2n . ₊₁ ) ₃
H —CON (C _n H ₂ ^ ₊₁ J ₂ with η = an integer from "> to 5 and ti - an integer from 1 to 8 or the group —COO-N ^ (C _n H _{2n + 1} OH) ₃ with n = 1 or 2, and Y ₁ is a hydrogen or chlorine atom or a methyl group, or a compound of the formula CH, = C (III) wherein X _{2 is the} same as the group
-COOC ₂ H ₄ OH
-OCH ₂ CH ₂ OH -COOH -CH CH ₂ -COOCH ₂ CH CH ₂ O
-CO-CH ₂ -CH = CH ₂ Il ο -CH ₂ -O-CH ₂ -CH CH ₂ O
-CH-CH ₂ -O-CH ₂ CH ₂ -CH CH ₂ - / ~ \ -COOCH ₂ CH CH ₂ -CH ₂ -CH ₂ -CH CH ₂ NO, or OH and Y _{2 is} equal to a hydrogen atom or a methyl group, the molar ratio of compound of formula II to compound of formula I between 0.1: 9.9 and 3: 7 and the molar ratio of compound of formula HI to compound of formula I between 1: 4 and 2: 3, characterized in that the toner 2 020 Reaction product of a dye or _ with compounds of the formulas I and II _The fund UI exists. τ suspension developer according to claim 1, _the group Hurcb DA in that the toner from a Sion product of an amino group läSuffs with compounds of the formulas 1 and II or I and III f suspension developer according to claim 1, DA, in ± Z that the toner from a .o SSionsprodukt from 10 to 30 weight percent ^ _{R = a} group £ κ mff or pigment and 90 to 7CGewichts-L ^a OCE VeSungen of formulas I and II "which consists of I and III halogen