DE2362666A1 - ELECTROSTATOGRAPHIC MATERIAL - Google Patents

Description

The invention relates to imaging systems and more particularly to improved xerographic development materials, their manufacture and use.

Electrostatography, which is an imaging method, is already known. It relates to education and utilizing latent electrostatic charge patterns to visualize those patterns and reproduce. When a photoconductor is used to form these electrostatic latent images, by first charging and then selectively exposing the photoconductive layer, then this is Imaging process referred to as electrophotography.

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This procedure is commonly known as "xerography". The basic techniques thereof are described in U.S. Patent 2,297,691. Those educated in this way Electrostatic images can be developed or visualized using a finely divided electroscopic Material called toner is deposited. The image obtained in this way can can then be used in a number of ways, e.g. by melting or fixing the image in place and Place or by transferring it to a second surface and fixing it there.

Electrography, which is another broader more general The branch of electrostatography is, in turn, divided into two broad sectors, called xeroprints and electrostatic or TESI recording. No photo-responsive medium is used in electrography. The charging and the selective discharging forms the latent electrostatic image. Xeroprinting, which is the electrostatic analogue of the ordinary Printing is described, for example, in U.S. Patent 2,576,047. The TESI mapping process or the transfer of electrostatic images is known from US Pat. No. 2,285,814. One proceeds in such a way that an electrostatic charge pattern corresponding to a desired reproduction on a uniform one Insulation layer by means of an electrical discharge between two or more electrodes on opposite sides Forms sides of the isolation medium. The lines of force created by the latent electrostatic Image generated are used to control the deposition of the toner material to a Shape image. There are already various powder feed

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Medium and liquid developers and development systems began. Examples of this are the cascade development, as described in US Pat. No. 2,618,552, the magnetic brush development, as described in US Pat. No. 2,874,063, powder cloud development as described in US Pat the US-PS 2,784,109 is described, the touchdown development, as described in US Pat. No. 3,166,432, and fluid development as described in U.S. Patent 2,877. These development systems can, though they are widely used for black and white reproductions, also for other colors and combinations of colors, e.g. for trichromatic color systems of either the additive or the subtractive Color formation type. With full color systems, at least three different colors must be used to to synthesize any desired color so that generally the formation of at least three color separation images and their combination in registration with each other is intended to provide a color reproduction of the Originals to form. Thus, all electrostatographic recording systems must have at least three different ones electrostatic latent images are formed, developed with various color toners, and used for formation of the finished image. For example, 3. an electrostatic latent in color xerography Image resulting from exposure to a first primary color is formed on the photoconductive layer and developed with a toner complementary to the primary color. Be in a similar fashion the subsequent developments of the electrostatic latent images corresponding to the primary colors, done with complementary toners. If one exposes through a color separation negative, then that is Toner to supplement the exposure radiation.

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In a three-color electrophotographic system that If superimposed color images are used, it is necessary that the toners with the exception of the underlying toner are quite transparent so that the differently colored toner images underneath them do not darken and each toner at the same time has sufficient color saturation and lightness which satisfies the colorimetric requirements for the three-color synthesis of natural color images. It becomes obvious, that these requirements are practically opposite, to which the further complication comes, that still it is required that when all the toners are combined they produce a deep black. It was found that it is necessary to achieve deep black tones in a color system, four differently colored To superimpose images including an image recorded in black. Other problems generally arise when using inorganic pigments as coloring materials either in printing inks or in electrophotographic Toners are used because it is difficult to achieve proper color balance and saturation while keeping the colors transparent at the same time. When using inorganic pigments the range of available colors is relatively narrow. It has been shown that these pigments give the materials to which they have already been added in relatively small amounts a certain haze.

In U.S. Patent 3,345,293, colored electrophotographic Described toners, which consist essentially of transparent resin particles, which organic dye pigments contain. These materials should therefore be compared to the materials according to the prior art

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be advantageous because they are more resistant to washout or bleeding of the colors after the toner has melted and because they are specifically suitable for three-color electrophotographic processes because their colors are yellow, cyan, and magenta and because their mixtures are blue, red in pairs and produce green, while the three toners together make a black. Despite the obvious advantages of the toners described in this reference, there are still disadvantages associated with these specific toners, and particularly in the case of the yellow toner when used in an automatic electrophotographic machine. The yellow colorant described in US Pat. No. 3,345,293 consists essentially of about 0.92 to about 1.08 parts by weight of 3,3'-DiChIOr-4 ^l -bis (2 "-acetyl-2" -azo-o- acetotoluidide) biphenyl per 10 parts by weight of an essentially transparent resin. The problems associated with the use of this colorant are that it is not possible to disperse it substantially uniformly in the transparent resin materials and, more significantly, in the undesirable triboelectric properties resulting from its use, thereby producing poor, low contrast and image images a short service life of the device is effected. It has been found that the triboelectric properties of the resulting toner material are not retained under conditions where the toner is exposed to mechanical abrasion, high temperatures and high ambient humidity. However, all of these conditions exist in electrophotographic devices. This leads to a number of problems, such as poor transport from the drum surface to the copy layer, as well as problems with keeping the drum clean. In particular

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it has been found that when used in electrophotographic Devices this toner exerts a striking effect on the carrier, whereby the already present poor triboelectric relationship is further worsened and the performance of the device is detrimental being affected.

In some cases it is very convenient, in contrast to a pigment, to use a dye as a developer in an electrophotographic imaging process. The color fastness in a yellow dye-colorant system is not of the same degree of dispersion as in a pigment-colorant system, addicted. In dye systems the dispersion is almost molecular, i.e. it is a monodispersion so that the dye itself is in a matrix is dissolved, whereby an optimal color value is obtained, which is in contrast to the dispersion as in the case of pigments. There is therefore still a need for yellow dye color systems for use as a developer in electrophotographic imaging processes.

It is therefore an object of this invention to provide a dye-toner material to provide that overcomes the disadvantages described above

It is another object of this invention to provide a dye colorant to provide that in combination with a resin material as a toner for color imaging is used.

It is another object of this invention to provide a new electrostatic Provide dye-toner system.

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It is another object of this invention to provide a new transparent dye-toner system place.

It is a further object of this invention to provide a new transparent dye toner available, which is used in a trichromatic color synthesis of either the additive or subtractive color formation type can be.

It is another object of this invention to provide a new electrophotographic developer place.

It is a further object of this invention to provide a new dye-toner material which is superior has triboelectric properties and that has a superior reproduction and a longer life of the Devices causes.

It is another object of this invention to provide a new one To make dye toner available, in which the Dye colorant is substantially uniformly dispersed in a resin material.

It is another object of this invention to provide a dye To make toner available that its triboelectric properties under conditions of continued Use in an automatic electrophotographic Retains imaging device.

It is another object of this invention to provide a new one To make dye toner available, 'which can be easily and practically completely removed from a drum surface is transferred to a copy sheet.

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It is another object of this invention to provide a relatively pure yellow toner of desired shade and desired Provide sound.

It is another object of this invention to provide an electrophotographic To provide a process using a new yellow dye toner system.

It is another object of this invention to provide an electrophotographic To provide a process in which a new orange dye toner system is used will.

Finally, it is another object of this invention to provide an electrophotographic imaging process pose in which a new brown dye toner system is used.

The invention therefore relates to a new dye-toner system, which is characterized by being a dye coloring agent and a resin material or materials contains, wherein the dye colorant is a compound having the general formula

comprises, wherein the substituents FLj to Rg -Cl, -Br, -F, -

0 0 rj— \

-NHC-CH, or other acylamides, -H, -NH-C - // γ and

other aryl arboxamides, -OCH, and other alkyl or aryl

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ether, -CH, and other alky! groups, - (* yand others

substituted and unsubstituted aryl groups, -CN, -OH, -NHp »-NHCH, and other mono- and disubstituted alkyl- and aryl-substituted amines, -SOpNHp, -SOpNH-CH, and other mono- and disubstituted alkyl and aryl sulfonamides, -COOH, -COOCH, and other alkyl and aryl esters.

Although all combinations of the abovementioned substituents are per se possible, it will be apparent that steric hindrance of bulky substituents in the Rp, Rp, Rβ and Rg positions can make the synthesis difficult. These circumstances are known to the person skilled in the art.

A dye of this type, known as Foron Yellow, and in the Color Index as CI Dispersion Yellow 33 with the structure

SO ₂ NH ₂

as described, "can be prepared by suitable techniques. For example, a one-step condensation of aniline with 4-chloro-3-nitrobenzenesulfonamide, the reaction generally being carried out at elevated temperatures and carried out in an aqueous system which contains an acid binding agent, to absorb the hydrochloric acid formed. The reaction proceeds as follows:

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NH ₂ ⁺ CI

SO, NH.

O ₂ N

SO ₂ NH _;

Further compounds of this general type are Dispersionsgelb 42 CI (Color Index) 10338, which according to known Methods, e.g. according to P. Fischer, Ber. 24, 3794 (1891), Dispersionsgelb 14 CI 10340 (available according to US-PS 1,618,415), Dispersionsgelb 1 CI 10345 (available according to US-PS 1,618,415), SRA Real golden yellow XII CI 10336, produced by condensation of para-chloroaniline with 1-chloro-2-nitrobenzene, Dispersion yellow 26, SRA real yellow X CI 10348, produced by condensation of aniline and 1,4-dichloro-2-nitrobenzene, Dispersion Orange 15 CI 10350 (can be produced according to US Pat. No. 1,618,415), Dispersion Yellow 9 CI 10375 (can be produced according to US-PS 1,618,415), Cellete-Braun R CI 10390, producible by condensation of N- (p-aminophenyl) -N-methyltaurine with 1-chloro-2,4,6-trinitrobenzene, and CI 10385 (can be prepared according to US Pat. No. 1,059,571) and others .

These dyes are different from the known pigment dyes of the same color and are superior to them, since they have the advantages given above, i.e., dyeing fastness that differs from the dispersion is not dependent, and a dispersibility, which is almost molecular. In addition, the strong difference between the dye colorants and superior electrical properties to the other prior art dye colorants and

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especially superior triboelectric properties, making these colorants very suitable for electrophotographic toners and / or developers.

It was found that in a Xerox 720 copier, i.e., a conventional electrophotography automatic imaging device, under controlled conditions stains, such as the benzidine yellow stain, U.S. Patent 3,345,293, a machine life had of 1400 prints. Two commonly used black toners had useful lives of 4200 and 9000 prints while that used in the present invention Foron Yellow had a useful life of over 25,000 prints with no adverse effects showed. It can thus be seen that when the colorants are combined with the inclusion of the US-PS 3,345,293 known yellow colorants, which correspond to the prior art, with suitable resins, to optimize their behavior, and when used in the same machine under identical conditions, the colorant according to the invention a surprising has better behavior and a longer machine life. Namely, after extensive use they tend to the conventional black toners tend to gradually decrease in their triboelectricity until they reach the ultimate failure value reaching after a picture is difficult, if not impossible. These levels are found with the well-known yellow toner life tests For example, not in the case of the yellow toner according to US Pat. No. 3,345, since this toner has a triboelectric behavior steady and extreme drops show, resulting in a shortened machine life and a poor one Behavior of the machine leads. In contrast, they show

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colorants used according to the invention, e.g. foron yellow toner compositions, very stable triboelectric values within a well-defined range acceptable copy quality and operating characteristics over a test search of 25,000 prints. These dyes, especially the Foron Yellow coloring agent, show high triboelectric properties, which are shown in the table I are compiled.

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Table I.

pressure
No. toner
concentrate
tration
(%) Tribo-
elec-
tricer
value
(uc / g) image
density
(1.2) Photorecep- stabi- vacuum-
torsional stress pressure
gene product (in H _o 0)
^v o ^V b (β) ² Tem
pera
door
⁰ C Damp impact
tig- degree
ability mg / g
% developer
running time
min h CO Beginning 1.35 8.26 0.95 11.15 21.1 28 CD
NJ 500 1.47 10.90 0.91. 16.02 21.1 28 CD 1K 1.50 14.30 0.91 21st, 45th 21.1 28 O ~)
CD O
co 1.5Κ 2.12 11.54 0.86 24.46 22.8 27 CD
[Ό 2Κ 1.97 12.93 0.92 25.46 22.8 27 Ah. cn 2.5Κ 1.29 20.05 0.91 25.87 21.1 29 3Κ 1.18 13.73 0.93 16.20 21.1 29 σ 3.5Κ 1, £ 4 7.23 0.91 11.84 21.1 29 .P- 4Κ 0.98 13.32 0.90 13.05 21.1 27 4.5Κ 1.49 12.50 0.91 18.63 21.1 27 5Κ 1.33 10.28 0.88 13.67 21.1 27 5.5Κ 1.23 11.96 0.90 14.71 21.1 27 6Κ 1.69 11.41 0.92 19.28 22.8 27 6.5Κ 1.66 15.30 0.88 25.40 22.8 28 7Κ 2.07 15.62 0.89 32.33 22.8 28 7.5Κ 2.54 14.00 0.89 35.55 21.1 33 8Κ 2.26 14.08 0.92 31.82 22.2 32 8.5Κ 1.94 14.73 0.89 28.58 22.2 32 9Κ 1.47 12.76 0.90 18.75 22.2 32

Table I continued

pressure
No. toner
concentrate
tration
{%) , 25 Tribo-
elec-
tricer '
value
(uc / g) image
density
(1.2) 9 _? 5Κ 1 , 83 12.46 0.91 1OK 1 .70. 9.47 0.88 .ί- 1Ο _Ρ 5Κ 1 , 86 11.01 0.90 Ο
IQ 11Κ 1 , 65 10.08 0.92 11.5K 1 , 40 10.28 0.95 cn 12Κ 1 , 46 10.61 0.89 12 _? 5Κ 1 "49 11.09 0.92 ο
■ οι 13Κ 1 _P. 35 . 8.90 0.89 «" - 13.5Κ 1 , 27 9.28 0.89 14Κ 1 , 62 9.20 0.88 14.5Κ 1 , 39 6.80 0.93 15Κ 1 , 54 8.03 0.89. 16Κ 1 , 11 8.50 0.91 17Κ 1 , 53 9.86 0.88 18Κ 1 , 27 7.98 0.87 19Κ 1 , 41 8.13 0.91 2OK 1 6.18 0.91

Photoreceptor voltages
V_ Vv

Stable vacuum temperature pressure peraproduct (in HpO) door

Humidity

Impact developer · degree runtime min h

15.57
17.34
19.87
18.65
16.96
14.85
16.20
13.26
12.53
11.69
11.02
11.16
13.09
10.95 12.21 10.32 8.72

22.8

22.2

22.2

21.1

21.7

21.7

21.1

22.2

21.1

21.1

21.1

22.2

21.1

21.1

21.1

21.1

21.1

30th

30th

30th

31

31

34

44

52

30th

30th

31

32

38

33

30th

40

36

CO

CD

CO CD

Table I continued

Pressure-
No. toner
concentrate
tration
I ft / 1
I TQ I Tribo-
elec- ■.
tricer
value
(uc / g) image
density
(1.2) Photo prescription
torsional tension
gene
ο b Stabilizer
littoral
product
(G) vacuum
pressure
(in H ₂ O) Tem
pera
door
⁰ C Damp
tig
speed Blow
Degree
mg / g developer
running time
min h 21K 1.41 5.63 0.91 7.94 21.1 31 22K 1.12 7.87 0.86 8.82 21.1 31 23K 1.69 4.81 0.88 8.13 22.8 31 O 24K 1.51 4.73 0.91 7.19 21.1 28 OO 25K 1.49 5.13 0.88 7.65 23.3 27 cn Aug 1.55 10.51 0.90 31 (27-52%) CD

-14ϊ- CD

These values demonstrate the suitability of Foron Yellow for electrophotographic imaging equipment operations up to 25,000 prints.

Any can be used for the toner composition of the present invention suitable resin material can be used. As stated above, essentially transparent resins are ground preferred when the toner is to be used in a three-color electrophotographic system. Although any substantially transparent resin material can be used as the resin component of this toner it is preferred that resins be used in the present invention which have other desirable properties. For example, it is desirable that a resin material is used, which is a non-sticky solid at room temperature, so that handling and the Use in the most common electrophotographic processes is facilitated. Thermoplastic Plastics are desired that have melting points that are significantly above room temperature, but below the temperature at which the usual paper tends to char, so that once the toner images formed thereon or transferred to the paper copy plate, it is acted upon in place can be melted by heat. However, this is not a necessary limitation, as there are also higher melting points Resins can be used and can be fixed to the paper copy sheets by other techniques, for example in such a way that the paper copy sheet bearing the powder image is steamed with a solvent for the resin as generally described in U.S. Patent 2,776,907. The selected resins should expediently have good triboelectric properties

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shafts and sufficient insulation properties have the charge retained so that they can be used in a number of developer systems.

Although any transparent resin having the properties described above can be used in the system of the present invention, particularly good results are obtained using vinyl resins and polymeric esterification products of a dicarboxylic acid and a diol comprising a diphenol. Any suitable vinyl resin can be used in the toners of the present invention, including homopolymers or copolymers of two or more vinyl monomers. Typical vinyl monomers of this type are, for example, styrene, p-chlorostyrene, vinyl naphthalene, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene and the like, vinyl esters such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and the like, esters of ckeckate -methylenaliphatischen monocarboxylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-Chloräthylacrylat, Ehenylacrylat, methyl ei chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like, Acrylnitrilmethacrylnitril, acrylamide, vinyl ethers such as vinyl methyl ether, Vinyl isobutyl ether, vinyl ethyl ether and the like, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and the like, vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride and the like, and N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindyrole and N-vinylindyrole like that, as well as mixtures thereof.

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It is generally found that toner resins containing a relatively high percentage of styrene are preferred because greater image definition and density are obtained when they are used. The styrene resins used can be homopolymers of styrene or styrene homologs or copolymers of styrene with other monomeric groups that have a single methylene group attached to one Carbon atom contained by a double bond. All of the above typical monomer units can copolymerized with styrene by addition polymerization. Styrene resins can also be polymerized formed by mixtures of two or more unsaturated monomer materials with a styrene monomer will. The addition polymerization technique used includes known polymerization techniques such as free radical, anionic and cationic polymerization processes. All of these vinyl resins can be mixed with each other or with other resins, if desired preferably with other vinyl resins that have good triboelectric stability and uniformity Ensure resistance to physical deterioration. However, Ss can also be non-vinyl-like thermoplastic resins are used, including collophone-modified phenol-formaldehyde resins, oil modified epoxy resins, polyurethane resins, cellulose resins, polyether resins and mixtures thereof.

As preferred resin materials for those of the present invention Toner mixtures can also contain polymeric esterification products a dicarboxylic acid and a diol comprising a diphenol can be used. The diphenol starting product has the general formula

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XX ¹

H (OR ¹ ) η-, O - {'^ ^x ) - R - (/ / V- O (OR ") no H

wherein R is substituted and unsubstituted alkylene radicals with 2 to 12 carbon atoms, alkylidene radicals with 1 to 12 carbon atoms and cycloalkylidene radicals with 3 to 12 carbon atoms, R 'and R "for substituted and unsubstituted alkylene radicals with 2 to 12 carbon atoms, alkylenearylene radicals with 8 to carbon atoms and arylene radicals X and X ^{1 are} hydrogen or an alkyl radical having 1 to 4 carbon atoms and n 1 and n ^ are each at least 1 and the average sum of n ^ and ^ is less than 21. Diphenols in which R is an alkylidene radical with Is 2 to 4 carbon atoms and R 'and R "are an alkylene radical having 3 to 4 carbon atoms are preferred because of increased blocking resistance, increased definition of xerographic characteristics, and more complete transition of toner images. Optimal results are obtained with diols in which R 'is an isopropylidene radical and R ¹ and R "are selected from the group consisting of propylene and butylene radicals, since the resins formed from these diols have a higher agglomeration resistance and penetrate the paper receiving sheets extremely quickly under melting conditions Dicarboxylic acids having 3 to 5 carbon atoms are preferred because the resulting toner resin has greater film resistance on reusable imaging surfaces and because it is less susceptible to the formation of fines in machinery.

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can withstand internal operating conditions. Optimal results are with ck-unsaturated dicarboxylic acids including fumaric acid, maleic acid and maleic anhydride obtained because in this case maximum resistance to physical deterioration of the toner as well as rapid melting properties can be obtained. All suitable diphenols can be used that satisfy the above formula. Typical such diphenols are e.g. 2,2-bis (4-ß-hydroxyethoxyphenyl) propane, 2,2-bis (4-hydroxyisopropoxyphenyl) propane, 2,2-bis (4-ß-hydroxyethoxyphenyl) pentane, 2,2-bis (4-ß-hydroxyethoxyphenyl) butane, 2,2-bis (4-hydroxypropoxyphenyl) propane, 2,2-bis (4-hydroxypropoxyphenyl) propane, 1,1-bis (4-hydroxyethoxyphenyl) butane, 1,1-bis (4-hydroxyisopropoxyphenyl) hep tan, 2,2-bis (3-methyl-4-ß-hydroxyethoxyphenyl) propane, 1,1-bis (4-ß-hydroxyethoxyphenyl) cyclohexane, 2,2'-bis (4-ß-hydroxyethoxyphenyl) norbornane, 2,2'-bis (4-ß-hydroxyethoxyphenyl) norbornane, 2,2-bis (4-ß-hydroxystyryloxyphenyl) propane, the polyoxyethylene ether of isopropylidenediphenol, in which both phenolic hydroxyl groups are oxyethylated and the average number of oxyethylene groups per molecule is 2.6, the polyoxypropylene ether of 2-butylidenediphenol, both of which are phenolic Hydroxyl groups are oxyalkylated and the average number of oxypropylene groups per mole is 2.5 and the same. Diphenols in which R is an alkylidene group having 2 to 4 carbon atoms and R 'and R "represent an alkylene group having 3 to 4 carbon atoms are preferred because of greater resistance to blocking, increased definition of xerographic Character properties and a more complete transfer of the toner images can be achieved. Optimal results are obtained with diols in which R isopro-

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is pylidene and R ¹ and R ″ are selected from the group consisting of propylene and butylene, since the resins formed from these diols have a higher resistance to agglomeration and penetrate the paper receiving sheets extremely quickly under melting conditions.

Any suitable di can be used with the diol described above carboxylic acid are reacted in order to produce the toner compositions according to the invention. This can either be substituted ated or unsubstituted, saturated or unsaturated and the general formula

HOOC R " ^f _n5 COOH

where R " ^{1 is} a substituted or unsubstituted alkylene radical with 1 to 12 carbon atoms, arylene radicals or alkylenearylene radicals with 10 to 12 carbon atoms and n, is less than 2. Typical such dicarboxylic acids are, for example, including their anhydrides, the following compounds: oxalic acid, malonic acid , Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, mesaconic acid, homophthalic acid, isophthalic acid, terephthalic acid, o-phenyleneacetic acid-ß-propionic acid, itaconic acid, phitraconic acid, and trauma anhydride, maleic acid, maleic anhydride,. dicarboxylic acids having 3 to 5 carbon atoms are preferred because the resulting toner resins have a greater resistance to film formation on reusable Abbildeoberflächen and because they resist with the engine operating conditions the formation of fines. Optimal results are obtained with <& -ungesätt igen dicarboxylic acids, such as fumaric acid, maleic acid or maleic

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get acid anhydride because in this case a maximum Resistance to physical deterioration of the toner and quick melting properties be achieved. The polymerization esterification products can in turn be copolymerized or with one or several thermoplastic resins, preferably aromatic resins, aliphatic resins or mixtures thereof, be mixed. Typical thermoplastic resins are, for example, collophone-modified phenol-formaldehyde resins, oil-modified ones Epoxy resins, polyurethane resins, cellulosic resins, vinyl resins, and mixtures thereof. When the resin component If the toner contains an added resin, then the added component should be in an amount less than about 50% by weight based on the total weight of the resin present in the toner. A relatively high percentage the polymeric condensation product of the diol and the dicarboxylic acid in the resinous component of the toner is preferred because, with a given amount of material added, there is a greater reduction in the Melting temperature is achieved. Furthermore, sharper images and denser images are obtained when in the toner a high percentage of the polymeric condensation product of the diol and the dicarboxylic acid is present. For familiarization of the added resin into the toner mixture can be any suitable mixing technique, e.g. a hot melt, solvent- and emulsion technique. The resulting resin mixture is substantially homogeneous and highly compatible with pigments and dyes. Where appropriate, the colorant can be applied simultaneously be added with or after the mixing or polymerization stage.

Optimal electrophotographic results are achieved with styrene / butyl methacrylate copolymers, styrene / vinyl toluene

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Copolymers, styrene / acrylate copolymers, polystyrene resins, primarily styrene or polystyrene based resins as generally disclosed in U.S. Reissue patent 25,136 and obtained with polystyrene blends according to US Pat. No. 2,788,288.

Any known toner mixing and comminuting technique can be used can be used to produce the toner composition according to the invention. So For example, the ingredients can be thoroughly mixed by mixing and grinding and then micropulverizing will. In addition, spray drying of a suspension of the constituents, a hot melt, can also be used or a solution of the toner composition can be used.

When carrier materials in connection with the invention Toner mixtures are used in cascade or magnetic brush development, then the Carrier particles can be electrically conductive, insulating, magnetic or non-magnetic, as long as the carrier particles are capable of triboelectrically charging with opposite polarity as the toner particles obtained so that the toner particles adhere to the carrier particles and surround them. When developing a positive To reproduce the electrostatic image, the carrier particles are selected so that the toner particles receive a charge of opposite polarity to that of the electrostatic latent image, so that the toner is deposited in the image areas. Alternatively in the reverse reproduction of an electrostatic latent image, the carriers are selected in such a way that that the toner particles acquire a charge having the same polarity as the electrostatic latent image, so

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that the toner deposition takes place in the non-image areas. Typical carrier materials are e.g. sodium chloride, ammonium chloride, Aluminum Potassium Chloride, Rochelle Salt, Sodium Nitrate, Aluminum Nitrate, Potassium Chlorate, Granular Zircon, granular silicon, methyl methacrylate, glass, Silica, flint, iron, steel, ferrite, nickel, carborundum, and the like. The carriers can be with or can be used without a coating. Many of these supports are shown in U.S. Patents 2,618,551, 2,638,416 and 2,618,552.

A diameter of the finished coated carrier particle between about 50 to about 1000 u is preferred, since the carrier particles then have a sufficient density and a sufficient inertia to adhere to the avoid electrostatic images during the cascade development process. The carrier can with the toner composition can be used in any suitable combination. In general the results are satisfactory when 1 part by weight of toner was used with about 10 to about 200 parts by weight of carrier.

The electrostatic latent image developed by the toner compositions of the present invention can be on any Surface that is able to maintain a charge. For electrophotographic applications a photoconductive member is used to form the electrostatic latent image. The photoconductive Layer can comprise an inorganic or organic photoconductive material. Typical inorganic Materials are e.g. sulfur, selenium, zinc sulfide, zinc oxide, zinc cadmium sulfide, zinc magnesium oxide, cadmium selenide, Zinc silicate, calcium strontium sulfide, cadmium sulfide,

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2 3 r? 6 6

Mercury (II) iodide, mercury (II) oxide, mercury (II) sulfide, indium trisulfide, gallium selenide, arsenic disulfide, arsenic trisulfide, arsenic triselenide, antimony trisulfide, cadmium sulfoselenide and mixtures thereof. Typical organic photoconductors are, for example, triphenylamine, 2,4-bis (4,4 ^! -Diethylaminophenol) -1,3,4-oxadiazole, N-isopropylcarbazole, triphenylpyrrole, 4,5-diphenylimidazolidinone, 4,5-diphenylimidazolidinethione, 4,5 -Bis (4'-aminophenyl) imidazolidinone, 1,5-dicyanonaphthalene, 1,4-dicyanonaphthalene, aminophthalonitrile, nitrophthalodinitrile, 1,2,5,6-tetraazacyclooctatetraen- (2,4,6,8), 2-mercaptobenzothiazole- 2-phenyl-4-diphenylidenoxazolone, 6-hydroxy-2,3-di (p-methoxyphenyl) -benzofuran, 4-dimethylaminobenzylidenebenzhydrazide, 3-benzylideneaminocarbazole, polyvinylcarbazole, (^ -nitrobenzylidene) -p-bromaniline, 2,4-diphenylchinazoline , 1,2,4-triazine, 1,5-diphenyl-3-methylpyrazoline, 2- (4-dimethylaminophenyl) benzoxazole, 3-aminocarbazole, polyvinyl carbazole trinitrofluorenone charge transfer complexes, phthalocyanines, and mixtures thereof.

Any suitable one can be used in the method according to the invention Charging technology can be used. Typical charging methods are e.g. charge deposition, which arises from air breaking in a gap, which is usually referred to as the TESI method, or charging in a vacuum with an electron gun.

Any suitable exposure method can be used for the method of the invention. Typical exposure methods are, for example, reflex, contact, holographic, non-lens slit scanning systems and projection optical systems with lenses that image opaque reflection subjects, and transparent film originals.

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23fi / h66

Any suitable one can be used for the method according to the invention Development processes are used. Typical development systems are e.g. cascade development, the magnetic brush development, the powder cloud development and the liquid development.

Any suitable fixation method can be used for the method according to the invention. Typical fixation methods are e.g. thermal pressure melting, radiation melting, the combined radiation, conductivity and convention melting, cold pressure fixing and the rapid melting.

The invention is illustrated in the examples. All information therein is based on weight.

example 1

A 5% by weight mixture of CI Dispersion Yellow 33 in A styrene butyl methacrylate copolymer resin is prepared in a drum assembly for 1 hour at about 12 rpm. That Material is then poured into a vibratory screw feeder and extruded when the machine is in equilibrium is trained. The extruded strands are taken up at a speed of 18.29 m / min and cooled in a Viasser bath of about 48.9 ° C, whereupon forced air drying takes place. Pellets with a Diameters of 0.16 to 0.8 cm are then comminuted to a mean particle size of 15 microns. This Toner material is then coated with a steel bead carrier coated with a methyl terpolymer according to FIG U.S. Patent 3,627,522 combined and in an electrophotographic imaging machine, namely a copier Xerox model 720, used. The selenium photol

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It is selectively charged, exposed and then developed with the yellow developer. After having 25,000 prints the images still have good contrast, high density, and good looks. The triboelectric Developer's values remain high.

Example 2

The procedure of .Example Ϊ is repeated with the exception that 7% disperse yellow colorant is used.

Example 3

The process of Example 1 is repeated with the exception that the colorant used is Dispersion Yellow 42 CI 10338 at a concentration of 6% .

Example 4

The procedure of Example 1 is repeated except that the colorant is a 4% concentration von Dispersionsgelb 14 CI 10340 is used.

example 5

The process of Example 1 is repeated with the exception that 3% SRA real gold yellow XII CI 10336 is used as the coloring agent.

Example 6

The procedure of Example 1 is repeated with the

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Exception that the coloring agent used is dispersion orange 15 CI IO35O with a concentration of 7% .

Example 7

The procedure of Example 1 is repeated with the exception that the colorant used is Cellete Brown R CI 10390 at a concentration of 6% .

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Claims (14)

29 "23R / 866 claims 1. Electrostatographic material for the development of electrostatic latent images, thereby g e mark that it comprises a resin material and a dye coloring agent, and that the dye coloring agent a compound with the general formula R4 , the substituents R ₁ to Rg wherein -Cl, -Br, -F, - ₂ 0 0 / - \ it 11 // VV -NHC-CEU or other acylamides, -H, -NH-C - // y and other aryl carboxamides, -OCH, and other alkyl or aryl ethers, -CH- * and other alkyl groups, -U y and others substituted and unsubstituted aryl groups, -CN, -OH, -NHp, -NHCH, and other mono- and disubstituted alkyl and aryl-substituted amines, -SO ₂ NH ₂ , -SO ₂ NH-CH, and other mono- and disubstituted alkyl and mean arylsulfonamides, -COOH, -COOCHa and other alkyl and aryl esters. 2. Electrostatographic material according to claim 1, characterized in that the resin from the group of styrene / butyl methacrylate copolymers, styrene / vinyl toluene copolymers, styrene / acrylate copolymers and Polystyrene resins is selected. -30- 09825 / ICm - ³⁰ "■ 23R / 866 3. electrostatographic material according to claim 1, characterized in that the resin is substantially transparent. 4. Electrostatographic material according to claim 1, characterized in that the resin is the polymeric esterification product of a dicarboxylic acid and a diol comprising a diphenol .: 5. Electrostatographic material according to claim 1, characterized in that the resin is a styrene / butyl methacrylate copolymer. 6. Electrostatographic material according to claim 1, characterized in that it further contains a carrier. 7. Electrostatographic material according to claim 6, characterized in that the used Carrier consists of carrier particles which are coated with a methyl terpolymer. 8. Electrostatographic material for developing electrostatic latent images, characterized in that it is a resin material and comprises a dye coloring agent and that the coloring agent is a yellow dye represented by the following formula O ₂ N Ni-] - -31 - Λ0982 5/1074 9. Electrostatographic material according to claim 8, characterized in that it further contains a carrier and that the carrier consists of steel beads coated with a methyl terpolymer are. 10. Electrostatographic material according to claim 9, characterized in that the resin
is a styrene / butyl methacrylate copolymer. 11. An electrostatographic imaging process, characterized in that an electrostatic latent image is formed on a surface and that the surface is brought into contact with an electrostatographic material which comprises a resin material and a dye colorant, the colorant
the general formula corresponds, in which the substituents FLj to Rg -Cl, -Br, -F, 0 0 r. \ -NO ₂ , -NHC-CH ₅ or other acylamides, -H, -NH-C - // y and other aryl carboxamides, -OCH, and other alkyl or aryl ethers, -CB, and other alkyl groups, - / 'γ and others substituted and unsubstituted aryl groups, -CN, -OH, -NH2J -NHCH, and other mono- and disubstituted alkyl -32- 409825/1074 and aryl-substituted amines, -SO ₂ NH ₂ , -SO ₂ NH-CIL ₅ and other mono- and disubstituted alkyl and aryl sulfonamides, -COOH, -COOCH ₃ and other alkyl and aryl esters. 12. The method according to claim 11, characterized in that the developed image is on transferred to a recording surface and fixed the image on the recording surface. 13. The method according to claim 11, characterized in that g ek e η η, that one uses a dye colorant which has the formula O ₉ N, SO ₂ NH ₅ , having. 14.. Method according to claim 13, characterized in that g e k e η η draws that the resin is a styrene / butyl methacrylate copolymer and a carrier used and that the carrier consists of steel carrier beads, which with coated with a methyl terpolymer. 409825/1074