DE1772248A1 - Toner for making electrostatic images visible - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS,

PATENT LAWYERS 1 * 7 * 7 O O / MONKS 23. S I E G E S S T R A 38 E 28 · TEL EFO N 34 60 67 · TE L EG R A M M-A D R ES 8 E: IN VEN T / M O N C H EN D 283 (j / e) Hünchen, 1 Ä.V. 1968 CANON CAMERA CO., INC., Tokyo / Japan

"Toner for visualizing electrostatic images ⁿ

■ Priority: April 22, 1967 ./ Japan Registration no .: 42-25512

Di "This invention relates to new toner for visualizing electrostatic Picture, would take procedure which electrostatic example, by means of electrostatic photography ₉ up *, electrostatic printing methods and the like have been obtained..

To make electrostatic images visible, dry development processes have been used so far, for example the magnetic brush process, the cascade development method or the powder cloud development method , using fine powdery toners made of natural or synthetic resins. which one has incorporated coloring substances, such as soot, while fine powders have been used for wet development processes, which from with a control or stabilizing substance coated pigment particles exist, for which alkyd resins or

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or linseed oil are suitable.

Other types of developers have also met with interest, in particular so-called liquid-liquid developer systems, where a liquid colored with dye or pigments is used as a toner substance. Such toners for liquid-liquid developer systems consist of a solvent, an oil, a fatty acid or a resin, with the actual color substance being dissolved in these carrier materials.

From the foregoing it follows that the best known species of toners generally in the form of a suspension or solution are present, which are generally made from natural or synthetic urine or in the special case of liquid-liquid developer systems liquid carrier materials and a dye suspended or dissolved therein In the case of these toners, it is ultimately about a two-component system, wherein one component has fixing properties and the other component is a dye.

Such two-component developer systems, however, have certain Disadvantages on. First, it is technically extremely difficult to get the dye completely homogeneous in the carrier material Disperse EU. There is also a risk that the developed Images become discolored as a result of rubbing or other mechanical action.

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For the preparation of a dry toner from a styrene resin and you will call, for example, the solid styrene resin Heat melted and then sets nan RuA eu of the aisle eu and carefully disperses it in the mixture through a kneading treatment. The co obtained in the form of black lumps Dispersion is then treated in a reduction device, whereby one obtains a finely divided product «which is the real one Represents toner. But even if you get the hot melt des Harees by means of a high-efficiency dispersing device kneaded with the soot, for example using a Valeen chair, and even if such a device is carried out by a well-trained skilled worker for a long period of time is always to be found in the dispersion product numerous larger grains of carbon, some of which have come together r η are formed by carbon particles, and it is therefore It is technically practically impossible to produce a completely homogeneous dispersion on these catfish rn the soot parts eu aggregates even during the downsizing » process β takes place and these aggregates are then separated from the carrier or binder and therefore soot particles are always present in the finished toner as those which do the fixing interfere with the toner substance. In the manufacture of liquid de-localizing stars on the other hand, calls together in a ηa system with an alkyd resin in a highly effective dispersing device, for example on a whale chair or in one Colloid mill, kneaded and the paste-like Misohung thus obtained is then in a carrier medium, for example a petroleum fraction, diapered to form a fluid suspension.

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In this case too, however, it is practically impossible to completely homogeneously disperse the carbon black in the alkyd resin and in the In the practical application of the clay, newly formed aggregates of the soot are always deposited and therefore the color carrier is only incomplete dispersed.

If, therefore, the not fully dispersed by means of the usual Toner produced visible images on the surface if it is severely rubbed or scratched, so carbon is removed from the binder released and numerous lines or stripes are formed on the pictures, which give them an unsightly appearance.

When using liquid developer systems where the dye is dissolved in a liquid phase, there is no risk of the image being damaged by rubbing, however, such developer systems have other pocket parts. Venn ntmlioh a solvent, such as alcohol, which the dye dissolves, drops accidentally onto the visualized image, the dye is partially dissolved and becomes in this way get a blurred image with spots.

Recently, Serial Mo. Io, 897/66 is recommended in the US application been able to remedy this disadvantage · by being a reactive Binder chemically converts with a reactive dye and then this newly formed chemical compound as a toner substance used. Since such toner substances can be produced by means of a wide variety of chemical syntheses and since the simple ones

substances built up by a chemical combination of the binding agent

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and the coloring matter are each preserved in their molecular state, if such toners are completely dispersed and even if the powder is too fine, there is the certainty that that the dye cannot separate from the binder. Such toners therefore have excellent stability, high definition and high definition in practical use Developing power. But even in such a case of a chemical one Combination system is not always a practical one Use actually produce suitable toner, because this is the special type of binder and the special type of reactive dye in terms of their chemical reactivity must be considered. Depending on the choice the binder and the reactive dye can therefore trotsdem Toners are obtained, which have various disadvantages, For example, it may happen that the chemical conversion «Wiping the raw materials is extremely slow. In addition, the reaction product formed can decompose or door tend to discolour, or it is not suitable for to bend the desired shade. Furthermore you can electric charges of the same polarity as the electrostatic ones Develop charges of the image so that it is impossible a positive · image and instead «an undesirable negative image emerges. A weakening of the electrical charge can also lead to a barely visible image arises during development. Another disadvantage can be that dl · manufacture of the clays KU is expensive to tine economically enable practical application,

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A new type of toner has now been invented for the Visualization of electrostatic images found, which are very suitable for practical use and on chemiechea Paths can be synthesized. These new toners are suitable for both dry and new development processes. Farther No expensive dispersing devices are required for their generation, and there is still no need for specialist personnel sun operation and maintenance of solo devices required. Also exists with the new chemically produced toners there is no danger of decomposition, discoloration, discoloration or the Entetehene & n sharp images, but they are stable and leave sioh very well in the desired quality and in a reproducible manner. Another benefit of the new toner is there in the fact that they can be manufactured very well for a price. AuAerdea let you see the new toners in one fora fully fiohwarsen phase, as well as in the most diverse colored Make modifications and they also have protective properties. The toners according to the invention for the visualization of electrostatic images are characterized by the fact that they consist of the reaction product «between aliphatic» aromatic and / or heterocyclic acid halides or aliphatic, aromatic and / or heterocyclic Halides are each more than 5 carbon atoms in the molecule and a dye old is a primary or secondary Amino group la molecule consist · The aliphatic »aromatic and / or heterocyclic best of the acid halides bsw. Halides can be saturated or unsaturated, substituted or uneubstituted.

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Typlicht erfindungsgeitfUto ohesisohe toners are accordingly get the following equations:

(1) R.COX ♦ D.NH ₂ »R.CONH.D + HX,

(2) R.COX ♦ D.NH - i R.COK.D ♦ HX,

»Ι

V ^R l

(5) RX ♦ D.NH ₂ * R.NH.D ♦ HX and

(*) RX ♦ D.HH— ^ R.N.D ♦ HX,

where R and R ₁ each mean an aliphfttisohe, sroMitisehe or · heterooyolisohe group, while D is the remainder of the substance bolelcul · and X is a halogen atom.

The reaction product present in the invention alipnati or aroaati or heterooyolite groups give the toner the necessary fixing properties.

As starting coHpenents for the production of the new toners see, for example, the following halides or acid halides: propionyl chloride, butyryl chloride, valeryl chloride, Capronylohlorid, Caprylchlorid, Suoeinylohlorid, Adipoylohlorid, Cinnaeoylohlorid, Phtbaloy! Chlorid, Propylohlorid, Propylbroeld, Butyl chloride, Xsobutylbroadd, t-Aaylchlorid ,, Hexyibroaid, Ootylohlorid, ! «Urylohlorid, stearic acid chloride, stearylbroKLd, Oil insture chloride, adipyl chloride, broaanleol, bromine-di ·· thy1-aniline, Diehlorbensol, Triehlorbentol, Phthalylchlorid, 2-Methylohinolin-4-oarbonsAureehlorid, Antipyrine chloride, dipyrroline chloride and

Purane acid chloride. αδπ γ> ριπμδι

009849/0758 original

Mixtures of such halides can also be used for the reaction or acid halides can be used.

The invention used as a further starting material Dyes must have a primary or secondary amino group in the Exhibit molecule. For example, acidic azo dyes are suitable for this, for example anthracene red G.G., quinone real red 4 BL and Supramin Red BBL, direct azo dyes, such as Direct Violet 0, Bensopurprin 8B and Diamin Schwäre RO, basic azo dyes, for example chrysoidin, Bismarck * Braun G and Bismarck Braun R, dyes of the antraquinone series, such as Alisarin Real Blue R, Anthraohinone Blue SRX, Alisarin Sky Blue B and Alisarin Direct Blue, dyes of the Indigotype, such as Indanthrene gray 6B, sulphide-type dyes such as Sulfur Schwärs T and dyes of the triphenylmethane series, for example aniline blue and Parafuohsin, also quinonimine dyes of the type des Safranine type β T, aniline black, Zndulin 5 and nigrosine bases, finally dyes of the phthalocyanine series, see B. TetraCÜ-amino-kupf erphthalocyanine blue.

Depending on the number of carbon atoms in the aliphatic Groups, for example the alkyl group, and the molecular structure of the dye used for the reaction as well as each According to the reaction conditions which are used, Ban receives the toners according to the invention in solid, semi-solid or liquid form State. The new toners can therefore be used for a wide variety of development methods, for example for «ine Dry development in the solid-solid systera, for the powder cloud development in a solid-gas system, for liquid development using a solid-liquid system,

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for an Eniulslonnentwicklung with a Plussig-PlÜBslg system and for lever development with a flas fluid system.

Eb was further found »da £ in particular for the manufacture black coloring toners, which are most widely used in practice find ,, with advantage reaction product® of fatty acid halides and in particular petts acid cavities with glycosine bases

themselves
can be detected because such® reaction products turn black in the course of the reaction *, so that a satisfactory depth of color can be obtained even without the use of HuS.

By varying the relative proportions of the fatty acid chloride to the Nigrosinbas®, products can be manufactured in any transition state from solid to liquid Ί: 1 a semi-solid product and when a weight ratio of 6: 1 is used in a paste-like product, while a weight ratio of 8 i 1 leads to a liquid toner product. Accordingly, the solubility of the reaction products obtained in the solvent also varies depending on the weight ratio ₉ in which Auagangematerlalisn are implemented together. This influence on the solubility is of great importance, especially in the production of liquid emulsion-type developers.

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If the solvent is a petroleum product, which is the main thing from xsoparaffins with about 12 carbon atoms exists, the best effect will be from reaction products obtained in which oleic acid chloride and nigrosine base in the same proportion of about 6: 1 can be implemented with one another. AlIa this Reaction products are sohön sohwars colored and do not show dtη Violet tioh, which is the property of the higrosine base that has not been surrounded is.

The toners according to the invention can be used both by means of dry development processes as well as by means of ^^ development processes for making the electrostatic images visible. For The TrookenentwieklungDverfahren the toner substance with for example Iron filings or Qlaskügalohen vermiaoht »so that the the finished developer contains about 1 - io by weight of the toner substance. The well-known method of cascade development can then be used for development or the magnetic brush development can be used or the toner is finely dispersed in the air and it becomes the powder » Cloud development method applied. For a new development the toner substance, on the other hand, is dispersed in a liquid carrier medium, For example, a petroleum fraction, the one high electrical Has resistance and dl · electrostatic charge the images are not affected, and this · dispersion is then means a common method, for example by dipping, bouncing, Spray or the like, applied to the surface, which carries the electrostatic charge of the picture.

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The conversion products used as toner according to the invention obtained either by static electricity or as a result of an electrical interfacial potential, which is caused by the touch of the

Toner substances with the carrier material, such as iron filings, glass beads

originate from
Chen, air or petroleum / a positive or negative charge.

The toneroubstan «is therefore depending on the same or opposite Charging the electroutat picture attracted or repelled and this makes the electrostatic image visible. If one case is a positive copy and 1 «another g Pail received a negative copy.

In the case of a response procedure, it is also possible to use a use conductive liquid such as water *

Know the toner substances chemically produced according to the invention still to be treated »in order to give them a predetermined electrostatic charge KU and thus the selectivity with regard to the electrostatic Image IU regulate.

Such a chemical treatment consists in that in the chemical structure of the molecule an electron accepting or an electron donating group is retained and this chemically Treatment can be for the binder as well as for either the dye or both reaction components the unsetsung, during the implementation or can be carried out with the reaction product itself after the implementation.

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Such a chemical treatment consists in “at least one • some of the electron accepting or electron donating groups in the binder or the dye removed or new • introduces or by completely chemically changing these groups.

Electron accepting and electron donating groups are well known from the literature, for example the following: Electron accepting groups are the nitro group, the carboxyl group, the cyano group, the hydroxyl group and halogen atoms. Electron donating groups are the amino groups the ammonium group, the sulphonium group, the oxonium group, the phoephonium group and the pyridine group.

The examples illustrate the invention. example 1

5 parts of sufficiently dried nigrosine base are dissolved in 150 ml of dioxane and then set with stirring and cooling to ο - lo ° C 5 parts Triäthjrlatdn hintu. One gives by riveting add 5 parts of oleic acid chloride slowly and dropwise to the solution hinsu. After allowing the reaction mixture to stand for 30 minutes it is heated to 90 ° C and then for 4 hours stirred at this temperature whereupon the reaction mixture cool itAt.

The liquid is filtered off and the trietbylamine hydrochloride and dioxane are removed from the piltrate under reduced pressure.

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A black, sticky residue remains. Precipitation of this Httokstandes from a hot benzene-methanol mixture gives a black, paste-like product. The IR spectrum of this reaction product shows an absorption maximum at 1670 en " ¹ , which indicates the formation of a new acid amide bond. This confirms that it is calibrated in the 0.5 part of the paste-like product thus obtained is dispersed in 100 parts of an isoparaffinic solvent, whereby a toner liquid for the development of electrostatic images is obtained Toner substance is treated, it forms a very sharp and clear black positive image * which also has excellent reproducibility in the color tones and is completely fixed on the photographic paper.

According to the same procedure, a reaction product of myrietic acid chloride and nigrosine is prepared which, according to the analysis, has the following composition: C * 78.5 %% H 7 * 9 % $ H 7.8 %, Asohe content »0 %, on the other hand results an analysis of the suevst mentioned Umsetzungeproduktes from Oleinsgurechlorid and nigrosine the following composition: 0 '77 # 8% _t H "4.2%, N' 11.4%, ash content of 21 ^ ug. FIG. 1 shows the CR spectrum of the reaction product with hydrochloric acid chloride and FIG. 2 shows the CR spectrum of the reaction product with acid chloride.

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Example 2

C ₁₈ H ₃₇ Br ♦

Cl

In one. The full neck of 500 ml of fitting capacity, which is equipped with a stirrer and a tin reflux condenser, is made from 200 parts of absolute alcohol and 8 g of metallic sodium an alcoholate. After the addition of 53 parts of ethyl salieylate and 117 parts of stearylbroaid, the mixture is refluxed for 24 hours. After cooling, the reaction mixture is poured into a solution of 600 μl of water and 12 μl of concentrated hydrochloric acid. Extracting a with Xther gives aan IHo parts of a yellow oil. To theseA Ol 3o parts by weight Kaliuahydroxyd, Jo parts of water and alcohol 7o parts hinsugesetst and three permanent · Brhits' s under Rfiokfluft is the Beaktionsaisehung hydrolyzed · One obtains as 152 parts of the old Stearylbroaid veritherten Salisylslureaethylesters.

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119 parts of thionyl chloride are added to 58 parts of this unsetung product added and the mixture is refluxed for a further 3 hours, whereupon the excess of the thionyl chloride removed and on this catfish 61 parts of the chlorinated reaction products » receives.

In a four-necked flask with a capacity of 2oo ml, 5g

Well-dried Nlgroslnbase dissolved in 150 al of dioxane and then added to 5 parts of triethylanine. After the mixture ^{has cooled to ί 0-10 0} C, nan slowly adds 6 parts of the above

The described chloride reaction product is heated under reflux for 4 hours to a temperature of 90 ° -100 ° C. and then allowed to cool. The reaction mixture is then filtered and the filtrate is freed from dioxane and triethylaain. This gives a black, sticky mass which, after the accidents, turns a hot Benaol methanol solution into a viscous paste-like product. In a chroaatografisohen analysis using Xthylasetat and cellusolve ia ratio 1 1 1 as Kntwieklerflüssigkeit receives aan einsigen a black spot, while SiOH up the 'used as Ausgangsaaterlal Kigrosln in 7 Xoaponenten · * splits which, rose-pink with a yellow, orange, red, violet-λ th, blue and black color fleoks. This confirms that a uniform black substance has formed due to the Ebeal reaction.

0.5 part of the black paste is dispersed in 100 parts by volume an isoparaffinic solvent and thus receives a developing liquid.

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A sheet of photographic paper is made with this developer liquid banded, which is a negatively charged electrostatic has a latent image. A positive copy is obtained through this development treatment, which deeply sohwarse tJbrsese having.

Example 3

10 parts of aniline hydrochloride are dissolved in water, then 5 parts of concentrated hydrochloric acid are added and the solution falls to an oesant volume of 300 bits of water. AnsohlieAend setst nan Io parts of an aqueous 3o £ weight water · * stoffperoxydlOsung hineu, stirred for 1 hour, then more Io parts adds the aqueous WaseerstoffperoxydlOsung hineu and stirred for a further H hours at 35 ⁰ C until SiOH the Reaktionsaasse by forming Anilinsehwars sohwars colored. This product is filtered off, washed with water and dried. 2 parts of the anilinechware dye produced in this way are dissolved in 150 parts of dry pyridine and then set on with cooling

_β olein

at O to Io C slow 7 parts / acid chloride himu. After 50 minutes the mixture is brought to XHo -ISo ⁰ C and stirred for 11 hours at this temperature. After the reaction has ended, the mixture is cooled and then acidified by adding concentrated hydrochloric acid, whereby the reaction product is separated off and precipitated. The precipitate is carefully washed with water, dried and further washed with an isoparaffinic solvent to give a dark brown colored paste.

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One disperses 0.5 parts of this paste in 100 parts by volume of the isoparaffinic solvent and treated with this liquid developer a sheet of photographic paper that has a negatively charged electrostatic latent image «On this A negative copy becomes visible.

Example *

A four-necked flask of 1 liter capacity, which is equipped with a reflux condenser, thermometer and stirrer, is charged with 30 parts of dried nigrosine base which is dissolved in 800 parts of dry dioxane. This is done by adding 3o parts of dry triethylamine. The mixture is kept at a temperature of 0-10 ° C. Then 60 parts of isostearic acid chloride are added dropwise. The mixture is stirred for 30 minutes, then heated to 95 ° -100 ° C. and mixed for 4 hours. stirred for a long time at this temperature, after which it was allowed to cool. After filtering the reaction mixture, the filtrate is concentrated under reduced pressure and then aqueous methanol with a water content of 10% is added. In this way a black, viscous mass is deposited, which is ^{washed 2 - 3 times:} with 95% methanol and then dried, whereby a black powder is obtained. 5 parts of this powder are sugesetst -I su loo parts of cyclohexane and dispersed for 10 days using a ball mill. A liquid developer is made from this by dispersing 10 parts of the paste thus obtained in 100 parts of cyclohexane. If a sheet of photographic paper with a negatively charged electrostatic latent image is treated with this liquid developer, a deeply sohwars-colored positive copy is obtained, which has a high fixing stability. ₀ O 9 8 4 9 / O 7 5 8

Example 5

A four-necked flask of 1 liter capacity, which with equipped with a reflux condenser, thermometer and stirrer is, with a solution of 41 parts of dry nigrosine charged in 800 parts of dry dioxane and then 3o parts of dry triethylamine are added. After cooling the liquid 25 parts of acrylic acid chloride are added dropwise to the mixture at a temperature of 0 ° -lo ° C. and then the mixture is stirred for 30 hours. The mixture is then heated to 95 ° -100 ° C. and stirred for 4 hours, after which it is cooled leaves. The reaction mixture is then filtered to give the filtrate water is added and a black precipitate separates out as a result. This precipitate is washed with methanol and then dried to a black fuI precursor. 7 * 8 parts this powder is dissolved in 200 parts of dimethylformamide and then 16 parts of laurylamine are added. In addition, an alcoholate consisting of 0.05 parts is added to the mixture metallic sodium and io parts of tertiary butanol 1st, heated to 120-130 ° C. and stirred for 3 hours this temperature. After cooling, the reaction mixture is poured into Hasser and a black precipitate is obtained. which is filtered off. The precipitate is carefully washed with methanol and then dried, giving a black Powder received. 5 parts of this ·· powder will add up to 10 parts grind an isoparaffinic solvent, for example Io for days in a ball mill.

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Io parts of the paste-like product thus obtained are then an isoparaffinic solvent dispersed in 1,000 parts. This gives a liquid Sntvlokier. If a sheet Photo paper is a negatively charged electrostatic latent Bild «it this liquid developer is treated« ao you get a sohwarse fosltiv copy, which is fixed on the photo paper is fixed.

example 6th

A four-hall flask with a capacity of 2oo al, which is equipped with a reflux condenser, thermosetcr and stirrer, is charged with a solution of 7 parts of dry insulin in 15e parts of dry dioxane and then 13 parts of dry triethyl gas are added. This mixture is maintained at a Tesperatur O - held 1O ⁰ G and then "ground dropwise hinsugegeben 13 parts MyrlstitisäurochlOrid. Raob 3o-sinütigea stirring, the temperature is heated to 95 ° loo ° C and with stirring H 8td. kept at this temperature for a long time, after cooling, the reaction solution is filtered. The filtrate is concentrated under reduced pressure and then aqueous methanol is present with a water content of 20 % , as a result of which a dark green colored viscous mass separates. 5 Toilets of this powder were treated with 100 parts of an isoparaffinic solution in a ball chair for 10 days, whereby a paste-like product was obtained.

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Io parts of this paste are seen in looo parts of an isoparaffin Solvent dispersed. Forget a sheet of photo paper ■ it has a negatively charged electrostatic latent image treated with this developing fluid »you get a sohwarsa Positive copy which is firmly fixed on the paper.

Example 7

5 parts of well-dried nigrosine base are dissolved in 150 ml of dioxane and then 5 parts of triethylamine are added. This mixture is cooled to ο - lo ° C and then 5 parts of oleinsture chloride are added dropwise at slow speed while stirring. After the mixture has been left to stand for 30 minutes, it is heated to 90 ° -100 ° C., stirred for 1 hour at this temperature and then cooled. The liquid is filtered and the filtrate is freed from triithylamine and dioxane under reduced pressure, whereby a so-white viscous mass is obtained. By falling over this very warm mass from a hot benzol-methanol mixture, a warm paste is obtained. 0.5 part of this paste is dispersed together with O ₉ I parts of a hydrated bear in 100 parts of an isoparaffinic solvent and treated in a ball mill for 10 days. 20 parts of the dispersion thus formed are then mixed with 1000 parts of the isoparaffinic solvent. if the developer fluid is used as in Example 1, a black positive copy is obtained which, owing to the control effect of the hydrogenated hardness on the charge of the parts of the toner residue, is very satisfactory.

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Example 8

A four-necked flask with a capacity of 1 liter is filled with a solution of 40 parts of dry nigrosine in fioo parts of dry dioxane and then 24 parts of dry triethylamine are added.This mixture is kept at a temperature of 0 - lo ° C, whereupon 45 Share Eruoaslura drop by drop over the course of 30 minutes while stirring. This mixture is stirred for another high H hours at 95 -. Loo ° C and lä £ t them to cool. The Roaktionsmisehung is filtered and the filtrate is mixed with aqueous methanol (water content 2o JO, whereby a so-white viscous mass separates out. The precipitate is washed 2 to 3 times with 95% methanol and dried, whereby a heavy powdery product is obtained * This Sohwarse powder is ground in a ball mill to an average particle size of 10yU and then mixed with a reduced iron powder with an average particle size of 2oo ^ u. For a sheet of photographic paper with a negatively charged electrostatic latent image with this powder appearance using magnetic resilience is developed, a very satisfactory black positive copy is obtained

The novel & s toner are sure not only sum visualization of latent images in electrophotography, but also sum Siohtbarmaohen of various electrostatic images as static means of seogenannten charge-free process _r ■ the PZP-complicated plant, the electrostatic printing process, electronic "j playback method etc. can be obtained.

In every pail you get a real developer effect. BADORiGiNAiI 'j

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Claims (9)

Claims 1. Toner for making electrostatic images visible, consisting of the reaction products between aliphatic, aromatic and / or heterocyclic acid halides or aliphatic, aromatic and / or heterocyclic halides »Each has more than 5 carbon atoms in the molecule and a dye with a primary or secondary amino group in the molecule. 2. The toner of claim 1 having the formula R.CONH.D bsw. R. CON. D. t "1 or bsw. R. H.D R.NH.D R ₁ where ^x R and R ₁ denote an aliphatic, aromatic or heterocyclic group and D is the remainder of the dye molecule. 3. Toner according to Claim 1 and 2, characterized in that because the synthesis product is derived from the nigrosine base 0098 4 9/0758 BAD ORIGINAL 4. Toner according to Claim 1 and 2, characterized in that that the conversion product is derived from aniline wares. 5. Toner according to Claim 1 and 2, characterized in that that the Uasetsungsprodukt derives from insulin. 6. Toner according to claim 3 -5, characterized in that that see the conversion product of ulsftureehlorid or | Myristic chloride derived. 7. Toner according to requirements 3-5, because it is known, daA is the onset product of isostearic chloride derives « 8. Toner according to claims 3 - 5 »daduroh recognized, see the usage product from the Bit Stearylbroaid derived saliojlelureeethy! ester. 9. Toner according to claims 3-5 »daduroh gekenniehnet, see the set product derived from erueasiure.