DE3144180A1 - ELECTRICALLY PHOTOSENSITIVE PIGMENT AND USE THEREOF - Google Patents

Description

.3.

Electrically photosensitive pigment and use of the same

The invention relates to an electrically photosensitive pigment and the use of the same in the context of photoelectrophoretic processes Image recording method.

It is well known to record images using photoelectrophoretic To produce image recording processes. Photoflectrophoretic imaging methods are approaching for example in US-PS 2,758,939, 2,940,847, 3,100,426, 3 140 175, 3 143,508, 3 384 565, 3 384 488, 3 615 558, 3,384,566, 3,383,993 and 3,976,485.

In the known photoelectrophoretic image recording method, an image-forming layer is electrically with or from photosensitive pigment particles under the action of an electrical Field exposed and also exposed to an original image of electromagnetic radiation, the opposite of which is electrically photosensitive particles are sensitive. The electrically photosensitive ones Particles are caused to move imagewise, producing a record of the electromagnetic radiation.

Regardless of the photoelectrophoretic applied in the individual case Image recording method is evident that one The electrically photosensitive particles are an essential component of the process. To get an easily recognizable picture, it has been found desirable that the electrically photosensitive particles are colored. 0

/it
It has been shown that there is no direct relationship between the substituents, the hue and other properties of a pigment, for example electrical photosensitivity. For example, a work by Andre Pugin shows "The Influence of Chemical Structures on the Color and Properties of Dioxazines Pigments * ¹ , published in Official

Digest ", pages 782-802, (19θ5) that recognizable because of the many inconsistencies between substituents, hue and other properties of a pigment, researchers in the pigment field are forced to synthesize pigments and to examine each synthesized pigment for its properties.

It has also been found that yellow are electrically photosensitive Pigments especially for carrying out photoelectrophoretic polychrome imaging process based on a subtractive multicolor system are suitable. On the other hand, it has been shown that the known yellow electrically photosensitive Prior art pigments exhibit unsatisfactory properties for one reason or another. So supplies, for example, the widespread "Indofast yellöw" pigment polychrome pictures in which the reproduction of the red and green tones is worse than desired. Furthermore, for example the trans-epindolidione described in US Pat. No. 4,142,890 as a pigment which has an excellent yellow hue has, which is why it is used to carry out photoelectrophoretic Image recording method should be particularly suitable. In practice, however, it has been shown that the trans-epindolidione a has unwanted green absorption.

As a result, there is a need for yellow electrically sensitive sensors Pigments that provide images of a particularly pure yellow hue.

The object of the invention was therefore to improve such find yellow electrically photosensitive pigments.

The invention is based on the knowledge that the problem posed can be achieved with the pigments characterized in the claims. ^v

Accordingly, meta-dimethyl and tetramethyl isomers of trans-Epinddlidions particularly advantageous yellow electrically photosensitive Pigments.

According to a particularly advantageous embodiment of the invention contains the pigment or consists of a mixture of the pigment of '"" (' a) three meta-dimethyl isomers of trans-epindolidione or (b) a mixture of at least three tetramethyl isomers des trans-epindole ion or (c) a mixture of (a) and (b). These Electrically photosensitive pigments are due to purer yellow hues referred to as the well-known trans-epindolidiones.

Contains an electrically photosensitive pigment according to the invention thus at least one epindolidione of the specified structure or a mixture thereof.

The pigments of the invention can be in the form of electrical Use photosensitive materials or products that, apart from at least one of the described trans-epindolidiones, at least have one of the following additives: a liquid or liquefiable electrically insulating carrier, at least one charge control agent, at least one chemical or spectral Sensitizers and, if necessary, additional coloring agents Components (dyes and / or pigments) that may also be electrically photosensitive. Furthermore, such Materials or preparations also contain other or additional additives that are necessary or desirable, to change or increase the properties of the material or product. Such photosensitive materials or Products can be in the form of a suspension, dispersion or in the form of a liquid or liquefiable layer.

They are preferably electrically photosensitive Pigments of the invention to electrically photosensitive pigment mixtures. These mixtures of methyl substituted isomers

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are due to a considerably lower green absorption than that trans-epindolidione and consequently provide photoelectrophoretic Images of excellent properties.

The electrically photosensitive pigments according to the invention can for example in the context of a photoelectrophoretic Use an image recording method that includes the following steps having:

a) an image recording material having a layer of an electrically photosensitive image recording material with a novel electrically photosensitive pigment according to the invention is exposed to the action of an electric field and

b) the recording material becomes an electromagnetic image original Exposing radiation to which the electrically photosensitive pigment is photosensitive with recording an image corresponding to the electromagnetic radiation in the shift.

If the layer is solid, it can at least partially liquefy before, during or after exposure and / or the action of the electric field to cause the migration of the to facilitate electrically photosensitive particles in the layer. Possibilities for achieving at least partial liquefaction will be described later.

The figures serve to explain the invention in more detail. in the individual are shown in:.

Fig. 1 shows a typical apparatus for image recording and for performing a photoelectrophoretic imaging process in the scheme and

Fig. 2 shows the reflection density of mixtures (a) and (b) at different wavelengths compared to the corresponding reflection densities of the trans-epindolidione.

An electrically photosensitive pigment according to the invention can thus, for example, from mixtures (a) or (b) or (a) and (b) consist, containing pigments of the following formula I:

CCH.)

3'n

■ The mixture (a) thus consists of three meta-dimethyl isomers of trans-epindolidione (n - 1). These isomers are 1,7-dimethyl; 1,9-dimethyl- and 3,9-dimethylepindolidione.

The mixture (b) consists of at least three tetramethyl isomers of the trans-epindolidione (n = 2). These isomers are 1,2,7,8-tetramethyl, 1,2,8,9-tetramethyl and 2,3,8,9-tetramethylepindolidione and optionally 2,3,7,8-tetramethylepindolidione.

Mixtures (a) and (b) of this type can be produced, for example, by a process such as that described by CK. Kim and co-workers under the title "A New Synthesis of Dibenzo / E, g7 (T, 5) naphthypyridine-6,12 (5H, 11H) -dione (epindolidione)", in _the journal "Journal of Heterocyclic Chemistry", volume 16 (8), pages 1651-1653, 1979, but starting from compounds with corresponding methyl substituents for the preparation of the pigments

• ♦ * 1

• *

31 «180

-jr-

will. The. The crude epindolidione products obtained can be purified by refluxing with N-methylpyrrolidione, dimethyl sulfoxide or ethylene glycol at temperatures from 190 to 20O ⁰ C, it being possible to use reflux for about 2 hours. After refluxing, the epindolidiones obtained are cooled, filtered, washed with water and dried in vacuo at a temperature of 100.degree.

The electrically photosensitive pigments according to the invention can , as already stated, to in a particularly advantageous manner. Manufacture of electrically photosensitive materials and products process and use in the context of photolectrophoretic imaging processes that combine exposure an electric field and imagewise exposure to electromagnetic radiation. The pigments are suitable is also an excellent way to carry out Bi ^ recording methods, such as those in more detail in the U.S. Patents 3,520,681, 3,770,430, 3,795,195, 4,013,462, 3,707,368,. 3,692,576 and 3,756,812, i.e. H. to carry out processes that are reproduction processes or so-called photoelectrosolographic processes.

In one embodiment, a photoelectrophoretic recording method is an image in a recording material recorded, which is composed of a conductive support or a support with a conductive layer, which is in electrical Contact with a liquefied or partially liquefied imaging agent Layer of an electrically photosensitive material is located. This creates an electrostatic charge pattern in the image-forming layer generated, for example by uniformly charging the layer electrically and exposing it imagewise to activating electromagnetic radiation. The electric

. ft.

photosensitive pigment particles of the image-forming layer that have been irradiated in the imagewise exposure, migrate then through the imaging layer, leaving an undeveloped one Imaging of the charge pattern in the conductive substrate leave behind. This image can then be developed by immersing the element in a solvent containing the exposed or unexposed portions of the image-forming layer are removed or solves.

In another embodiment, a photoelectrophoretic Image recording process is a liquid or partially liquid electrically photosensitive imaging layer between housed two spaced apart electrodes. In this position the layer is then exposed to the action of an electric field and imagewise with activating radiation irradiated. As a result, the cargo-carrying, electrically photosensitive pigment particles from the layer to one or the other electrode surface to produce a Image recording on at least one of the electrodes, the image recording being a positive or negative image of the original image is. The image record can be developed by separating the electrodes. In the case of this method, the layer can of electrically photosensitive material between two carrier sheets to form an imaging material or element be accommodated. A visual record can be made after exposure to the electric field and after exposure develop the original image on at least one of the two sheets by separating the same. The carrier sheets can thereby consist of electrodes. On the other hand, electrodes can also be connected directly to the back of the carrier sheets. Alternatively, one or both of the carrier sheets can also be conductive. In the case of some refinements of the method At least one of the sheets may be transparent to allow exposure of the imaging layer.

* * fc * - but 4 ". ar HK '

In the case of the methods described, the imaging center is the Layer of the electrically photosensitive material at least partially liquid or can at least partially liquefied will. As used herein, the term "partially liquid" means that the sufficient cohesive forces of the material that forms the layer, are weak or can be weakened enough to allow imagewise migration of the electrically photosensitive pigment particles is made possible under the combined influence of activating electromagnetic radiation and electrical radiation Field in the layer of the electrically photosensitive material.

Imaging layers that are not at least partially liquid can be at least partially liquefied by subjecting them to a treatment, for example a heat treatment, treatment with a solvent and / or exposure to solvent vapors, before, during or after a imagewise exposure to electromagnetic radiation and exposure an electric field. Advantageous results can also be obtained if the layer is liquefied after the material has been exposed and has been exposed to the action of a field. In the latter case, the image-generating Layer liquefied in the presence of an electric field and the image is developed using one of the methods described.

The extent to which · the electrically photosensitive particles in The migration of the imaging layers that need to be liquefied can be controlled by changing the thickness and duration the effect of the electric field and / or the intensity and duration of the exposure and / or the time that is applied, while the image-forming layer is a liquefying agent or the medium is exposed, for example to the action of heat and / or exposure to a solvent. For example, if the image-generating layer is only slightly liquefied, they migrate electrosch photosensitive particles only comparatively few

producing an underdeveloped image record. This image layer with the underdeveloped image recording can be keep and develop more fully at a later date. This delayed development can be carried out in a simple manner by the fact that the underdeveloped image layer in a electric field is applied when necessary and that the layer is sufficiently liquefied to keep it exposed to allow electrically photosensitive particles to proceed with the migration. An evolution of visible record The original image is then created using one of the methods described above.

Electrically photosensitive materials or products based on can be produced from the new pigments according to the invention, are thus advantageously made up of electrically photosensitive Pigment mixtures of pigments of the formula I, dispersed in an electrically insulating carrier, e.g. B. one electric insulating liquid or an electrically insulating, liquefiable matrix material, e.g. B. one by the action of heat and / or a solvent liquefiable polymer or a thixotropic polymer.

Such electrically photosensitive elements advantageously contain Materials about 0.05 to about 2.0 parts by weight of the electrical photosensitive pigment on 10 parts by weight of electrically insulating carrier.

For the production of electrically photosensitive materials according to the invention, customary known liquefiable electrically insulating materials can be used Use supports such as those described in U.S. Patents 3,520,681, 3,975,195, 4,013,462, 3,707,368, 3,692,516, and US Pat 3 756 812. A suitable carrier can for example from an electrically insulating liquid such as decane, paraffin or a kerosene fraction, e.g. B. of the Sohio Odorless type Solvent 3440 (made by Standard Oil Company, Ohio).

3 HA180

Furthermore, the carrier can consist, for example, of liquids consisting of isoparaffinic hydrocarbons, for example liquids with a boiling range of 145 to 186 ° C., e.g. B. of the type of commercial product. Isopar G (Manufacturer: Exxon Corporation). Furthermore, the carriers can consist, for example, of a wide variety of halogenated hydrocarbons, e.g. carbon tetrachloride, trichloromonofluoromethane and the like, and of a wide variety of liquid alkylated aromatic hydrocarbons, e.g. B. from alkylated benzenes, e.g. B. xylenes and other alkylated aromatic hydrocarbons such as are known, for example, from US Pat. No. 2,899,335. An example of a commercially available liquid, constructed from alkylated aromatic hydrocarbons carrier material is, for example, one having a boiling range of from 1:57 to about 177 ⁰ C, the _g to 98 volume percent of C to C ^ - Aromater is (commercial product Solvesso 100, manufacturer Exxon Corporation). Regardless of whether the carrier is solid or liquid at room temperature,

ie at about 22 ⁰ C, the electrically insulating carrier should have a

9
Resistance greater than about 10 ohm-cm, preferably greater

12th
than 10 ohm-cm.

Electrically photosensitive materials that can be used to carry out of photoelectrophoretic image recording processes, usually have pigment particles that have an average Particle size from about 0.01 microns to about 20 microns, preferably from about 0.01 to about 5 microns. The particles according to the invention have at least one electrically photosensitive Pigment according to formula I. .

As already stated, the electrically photosensitiveri Materials of the invention also contain non-photo-sensitive substances, for example electrically insulating polymers, charge control agents, organic and inorganic fillers as well as additional dyes and / or pigments to add color tones and / or physical properties of the electrically photOsensitive

-V-

tive pigment particles' change or increase. The particles can also contain other photosensitive compounds, for example sensitizing dyes and / or chemical sensitizers.

Compounds of the formula I can also be combined with polymers combine the repeating organic photoconductive units to produce composite electrically photosensitive particles. Such polymers are described in more detail for example in the reference "Research Disclosure" in Section 19014, Volume 190, February 1980 under the heading "Composite Electrically Photosensitive Particles".

Charge control agents can be used to improve uniformity to improve the charge polarity of the electrically photosensitive particles. Typically, there are charge control agents made of polymers that are mixed with the carrier in the electrically photosensitive materials. Additionally and possibly depending on the increase in uniform charge polarity, the charge control agents often deliver more stable suspensions.

Charge control agents which can be used in an advantageous manner are polymeric charge control agents made from copolymers having at least two different repeating units, viz

(a) one unit at a concentration of at least about

-4
0.5 10 mol / gram of the copolymer, which is derived from monomers consisting of metal salts of sulfoalkyl acrylates and / or methacrylates and metal salts of acrylic and methacrylic acid and

(b) repeating units derived from monomers, which are soluble in the carrier and are present in a concentration sufficient to make the copolymer soluble in the carrier

close.

Examples of such copolymers are: poly (vinyltoluene-co-lauryl methacrylate-co-lithium methacrylate-co-methacrylic acid); Poly (styrene-co-lauryl methacrylate-co-lithium sulfoethyl methacrylate); Poly (vinyl toluene-co-lauryl methacrylate-co-lithium methacrylate); Poly (t-butylstyrene-co-lauryl methacrylate-co-lithium methacrylate-co-methacrylic acid) and poly (t-butylstyrene-co-lithium methacrylate).

Polymeric binders that are used to produce the inventive electrically photosensitive materials can be used, can consist of natural semi-synthetic or synthetic polymers. You can in the electrically insulating support part of the electrically photosensitive material can be dispersed or dissolved. They are used to fix the photoelectrophoretic End image.

Elements suitable for image recording with layers of the Electrically photosensitive material can be produced by customary known methods. Such elements can produced in a simple manner by mixing the components of the photosensitive material in an electrically insulating Liquid or a liquefiable carrier and applying the suspension or dispersion obtained to a carrier under Use of conventional, known coating processes. The carrier used can consist of an insulating or conductive one Carriers exist, depending on the intended use.

The use of an electrically photosensitive material with at least one pigment of the formula I in the context of a photoelectrophoretic Image recording method is described below with reference to Fig. 1, in which an apparatus for performing a photoelectrophoretic image recording method is shown, are illustrated in more detail.

, AS.

The device shown in FIG. 1 has a transparent electrode 1 carried by two rubber drive rollers 10 is that the electrode I over the original image 11 in the direction of Move arrows. The electrode 1 can consist of an optically transparent material, for example glass or an electrically insulating, transparent polymer carrier, e.g. B. made of polyethylene terephthalate coated with a thin, optically transparent, lubricious layer, e.g. B. of tin oxide, indium oxide, nickel and the like. is coated. Optionally, depending on the particular type of photoelectrophoretic image recording process used, the surface may of the electrode 1 have a "dark charge exchange material", for example in the form of a solid solution of an electrically insulating polymer and 2,4,7-trinitro-9-fluorenone, as described in more detail in U.S. Patent 3,976,485.

In pressure contact with the electrode 1 is a second electrode 5 in the form of a guide roller, with the function of a Counter-electrode to electrode 1 for generating the electric field, which in the context of the illustrated photoelectrophoretic Image recording process is to be generated. In typical The electrode 5 has a thin, electrically insulating layer 6 on its surface. The electrode 5 is over a switch 7 connected to a power source. The other side of the power source 15 is connected to the electrode 1, so that / when exposure occurs, switch 7 is closed can be and the electrically photosensitive material 4, which is located between the electrodes 1 and 5, the action can be exposed to an electric field. The electrically photosensitive material 4 usually includes an electrically insulating support as described above.

The electrically photosensitive material 4 is between the electrodes 1 and 5 spread or deformed to form a layer by the material 4 with at least one electrically photosensitive pigment of the Formula I on one or both of the surfaces of the electrodes Γ

«» T «
• «κ ν ν - »■■ ψ ^,. ^

3Η4180

and 5 is applied before performing the image recording process, or in that the dispersion during the implementation of the photoelectrophoretic image recording process is brought between the electrodes 1 and 5.

As can be seen from Fig. 1, the exposure is made of the layer 4 by means of an exposure system with a light source 8, a photographic one to be reproduced Slide 11, a lens system 12 and optionally light filters 13, e.g. B. color filters, the electrically photosensitive Material corresponding to the slide template 11 is exposed. Although in the photoelectrophoretic shown in FIG Image recording system the electrode 1 than opposite the activating radiation of the light source 8 is shown transparent, it is also possible to use the electrically photosensitive material 4 to expose in the gap 21 between the electrodes 1 and 5, in which case none of the electrodes 1 and 5 to be transparent needs. In the case of such a system, the light source 8 and lens system 12 are arranged in such a way that the electrically photosensitive Material 4 can be exposed in the gap 21 between the electrodes 1 and £.

In the case of the device shown in Fig. 1, there is Electrode 5 from a rolling electrode with a conductive core 14, which is connected to the power source 15. The core 14 is again covered with an insulating layer 6, for example with a layer of barite-coated paper. The insulating layer serves to change the charge of the particles of the electrically photosensitive material 4 when the electrode 5 acts prevent or reduce. As a result, the electrode 5, as is the case in photoelectrophoretic image development processes is common to be referred to as a "blocking electrode".

^: 3Η413Ό

Although the electrode S is shown in the case of FIG. 1 as a roller electrode and the electrode 1 as a movable, flat, transparent one Plate electrode, but either one or both of these electrodes can also have other shapes, and for example in the form of ribbon-shaped electrodes or rotating drum electrodes, opaque Plate electrodes and the like are present as are known in the art of photoelectrophoretic imaging. While performing a photoelectrophoretic An image recording method in which the electrically photosensitive material 4 is an electrically insulating liquid Has carrier, the electrodes 1 and 5 are generally in pressure contact with one another or are very close to one another, for example at a distance of less than 50 microns. However, the electrically photosensitive material becomes arranged without a liquid carrier in the gap between the electrodes 1 and 5 or the material contains a carrier such as For example, a material that can be liquefied by the action of heat and / or a solvent and it is in the form of a separate Layer applied to the electrode 1 and / or S, so the Be more than 50 microns apart during the imaging process.

The strength of the electric field applied to the electrodes 1 and during the photoelectrophoretic image recording process can be very different. However, optimal image density and resolution are obtained if the field strength is increased to as high a value as possible without an electrical breakdown of the carrier medium in the Electrode gap is brought about. For example, if an electrically insulating liquid, e.g. B. in the form of isoparaffinic hydrocarbons as a carrier in the image recording device according to Using Fig. 1, the applied voltage across electrodes 1 and 5 is typically about 100 volts to about 4 kilovolts or above.

"31U18O

As already stated, in the case of photoelectrophoretic imaging process the result of the combined exposure to activating radiation and a electric field on the electrically photosensitive material, which in the case of the device shown in Fig. 1 between the electrodes 1 and S. Particularly advantageous results can be achieved when the action of the electrical Field and exposure or irradiation take place at the same time. By suitable selection of the various process parameters, such as field strength, intensity of the activating radiation, incorporation of suitable light-sensitive additives in or with the elec- ■ trisch photosensitive particles made using compounds of formula I have been prepared by adding a persistent or permanent photoconductive material and the like. however, it is possible to change the time of exposure or exposure and the effect of the electric field, such that exposure or exposure and action of the electrical Field can take place one after the other instead of simultaneously.

In the arrangement of the electrically photosensitive material 4 between the image-forming electrodes 1 and 5, the material has an electrostatic charge polarity, either as a result of triboelectric interaction of the particles or as a ^l: olge an interaction of the particles with the carrier material in which they are dispersed which takes place, for example, in conventional liquid electrographic developers which have toner particles which receive a charge when they are dispersed in an electrically insulating carrier liquid.

In the case of photoelectrophoretic imaging processes an image resolution occurs as a result of the combined action of an electric field and activating radiation on the electrically photosensitive material, which is located between electrodes 1 and 5 in the case of the device shown in FIG. This means that in the case of a typical image recording method when generating an electric field between the

-3U4180

./19.

Electrodes 1 and 5, the charge-carrying particles of the electrically photosensitive material in the dark from one of the electrodes Γ or S, depending on which of these electrodes has a polarity that corresponds to the original charge polarity the electrically photosensitive particle is opposite. If the electrically photosensitive material 4 is exposed to a When exposed to activating electromagnetic radiation, it is assumed that there is then a reversal of the charge polarity of the exposed or non-exposed particles. In the case of photoelectrophoretic imaging systems in which the Electrode 1 has a conductive surface, experience the exposed, electrically photosensitive particles 4 when they are in make electrical contact with a conductive surface, a reversal of their original charge polarity as a result of the combined action of the electric field and the activating Radiation. Alternatively, in the case of a photoimmobilized photoelectrophoretic recording (PIER), the surface of the electrode 1 comprises a dark charge exchange material, a Reversing the charge polarity of the unexposed particles, while the charge polarity of the exposed electrically photosensitive Particle is retained when these particles are in electrical

/to the
Contact with dark charge exchange material on the surface of the electrode 1. In any case, when an electric field and activating radiation act on the electrically photosensitive material 4, between the. Electrodes 1 and 5 of a device according to FIG. 1 achieve an effective image resolution, ie an image can be obtained through the electrically photosensitive particles corresponding to the original image. When using a device according to FIG. 1, a visible image can be obtained on the surface of the electrode 1 and a complementary image on the surface of the electrode 5.

After the action of the electric field and after the image The images generated on the surfaces of the electrodes T and / or 5 of the device according to FIG. 1 can be temporarily exposed or be permanently fixed on the electrodes or else on

»3UA180

.30 *

Image receiving materials are transmitted. The final image can be fixed by various methods, for example by applying a resinous cover layer or coating to the surface of the substrate carrying the image. If, for example, the electrically photosensitive material 4 contains a liquid carrier between the electrodes 1 and 5, the image or images that have been produced on the surfaces of the electrodes 1 and / or 5 can be in the form of particles by adding an insoluble polymeric binder Fix carrier liquid. Such binders which can be used for fixing and their use in electrophotographic liquid developers are known. It is also known that binders of this type take up a charge when mixed with a carrier liquid. As a result, they migrate by electrophoretic pathways to the surface of one or the other electrode. According to another embodiment, a coating with a heart-shaped binder (which has been dissolved in the carrier liquid) can be produced on the surface of the electrodes 1 and / or 5 by evaporation of the liquid carrier.

The electrically photosensitive material with at least one pigment according to formula I can be used to produce monochrome images. On the other hand, mixtures of 10 pigments can also be used of formula I and 2.) other electrically photosensitive compounds or pigments of suitable color and photosensitivity for production of neutral or polychrome images. Many of the electrically photosensitive pigments of the formula I have particularly advantageous color tones which are particularly suitable for their use in polychrome image recording processes, in which a mixture of two or more differently colored electrically photosensitive particles is used. Preferably, the particular cyan, magenta, and yellow particles are used to perform in polychrome imaging processes are selected so that their spectral response curves do not noticeably overlap, so that a color separation and a subtractive multicolor image reproduction can be achieved.

* + ir *

The synthesis of electrically photosensitive pigments according to the invention will first be described in more detail below. Synthesis of meta-dimethylepindolidione isomers. Scheme

H ₃ CO-CC-OH

DCC-OB ₊ HO-CC-OCH,

(T)

CH ₃
CH ₃ OH / HC1

Reflux

NH,

(2)

H
H ₃ CO-GCN

(3)

CH.,

N-C-C-OCH

Heat transfer medium 260OC

Polyphosphoric 3 hrs. At 150 ⁰ C

(5)

1.7
1.9
3.9

Isomers

'«- · .. ·.:. .:. \ r · ^: 3Η4180 -yr-

Synthesis of the compound (3)

A 250 ml round-necked flask equipped with a magnetic stirrer was filled with:

22.5 g (0.13 mol) dimethyl dihydroxy fumarate O) 31.0 g (0.29 mol) m-toluidine (2),
100.0ml methanol,

1.3 ml concentrated hydrochloric acid.

The mixture was refluxed for 6 hours and then cooled with stirring overnight. The deposited precipitate was filtered off, washed with methanol, recrystallized from isopropyl alcohol and dried ^{at 65 ° C. in vacuo.} The reaction product, dimethyl bis (m-toluidine, maleate) was obtained in the form of a pale yellow product in a yield of 23.76 g.

Analysis: Ber. : C: 67.8; H: 6.3; N: 7.9; 0: 18.1

Found: C, 65.5; H: 6.0; N: 7.8

The mass spectrum found for the reaction product was correct It corresponds to the assumed structure.

Synthesis of the compound (4)

Into a 1 liter 3-neck round bottom flask were charged: 300ml biphenyl / biphenyl (0 _{2/0 2} O). The mixture was heated to reflux temperature with mechanical stirring. Next, a solution of 2og the compound (3) (0.0565 mol) in 100 mL was added portionwise warm 0 _{2/0 2} O was added over 30 minutes. To

"31.4418 O

When the addition was complete, the reaction mixture was dark red-orange Colour. It was heated to reflux temperature for another 15 minutes before the supply of heat was interrupted and the The reaction mixture was allowed to cool slowly with stirring overnight became. The released methanol was partially separated by means of a Dean-Stark trap. Most of the methanol escaped however, through the opening through which the reaction component was added.

The precipitate was filtered off and washed with 513ml ligroin, from 700ml methanol recrystallized (reduced to Soomi) in vacuo at 6O ⁰ C dried. Compound (4) was obtained in a yield of 4.03 g (0.0125 mol) corresponding to a yield of 221 in the form of a yellow-orange reaction product. The reaction product consisted of / 3- (3-methylanilino) -2-methoxycarbonyl-4- (5 or 7-methyl) quinoline7.

Analysis: Calc .: C: 70.8; H: 5.6; N: 8.7; 0: 14.9 Found: C: 71.3; H: 5.7; N: 8.9

The mass spectrum was consistent with the assumed structure. Synthesis of the compound (5)

A 100 ml round-necked flask equipped with a mechanical stirrer and nitrogen inlet was charged with 4 g (0.0124 mol) of the compound (4) and 50 g of polyphosphoric acid. The mixture was ^{heated to approximately 150 °} C. and left at this temperature for approximately 3 hours. Then the mixture was cooled to 100 ⁰ C before it was slowly poured into 600ml of ice water. The resulting aqueous slurry was stirred over the weekend.

The resulting yellow precipitate was filtered off, washed with water, slurried in about 300 ml of water, filtered again and washed until neutral. The crude reaction product was dried ^{at 100 ° C. overnight in vacuo.} The yield of reaction product was 3.52.8 g.

The crude reaction product was dried twice with 125 ml of boiling N-methylpyrrolidinone, then slurried in hot water, cooled, filtered and dried in vacuo overnight. The yield of the reaction product was 2.982 g in terms of a strong yellow product.

Analysis: Calc .: C: 74.5; H: 4.9; N: 9.6; 0: 11.0

Found: C: 74.3; H: 5.2; N: 9.7

The melting point was above 300 ^° C.

The mass spectrum was consistent with the assumed structure. The mass-to-charge ratio was 290.

Synthesis of the tetramethyl epindolidione isomers

Scheme

H ₃ CO-CC-OH H ₃ CO-CC-OH

NH.

CH ₃ OH

CH.

HCl

(2)

H ₃ CO-CC-

(3)

(Heat transfer medium)

(4)

Polyphosphoric acid

(CH-)

(S)

Possibly also a mixture of 1,2,7,8-; 1,2,8,9-; 2,3,7,8- and 2,3,8,9-tetramethjlepindolidion possible.

, C J- '* ■ ■ * »* J * ■ »-β
t -i »* * * 4 ι · · -

Synthesis of the compound (3)

Into a 300 ml round neck flask were placed: 30 g (0.17 mol) dimethyl dihydroxy fumarate (T), 45 g (0.37 mol) 3,4-dimethylanil in (2), 100ml reagent grade methanol and 2ml concentrated hydrochloric acid. The solution was Heated to reflux temperature for 6 hours and then allowed to cool overnight. The deposited precipitate was filtered off, washed with a small amount of cold methanol and recrystallized from 900ml isopropyl alcohol. The yellow reaction product was dried in vacuo overnight. Thus, 23.063 g (0.052 mol) of the compound dimethyl bis (3,4-dimethylanilino) maleate was obtained (3) received.

The melting point of the compound was 133-135 ⁰ C.

Analysis: Calc .: C: 69.1; H: 6.9; N: 7.3; 0: 16.7

Found: C: 69.2; H: 7.2; N: 7.3

The mass spectrum was consistent with the assumed structure.

Synthesis of the compound (4)

A 1 liter 3-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and an air-cooled reflux condenser was charged with 325 ml of a eutectic biphenyl / biphenyl _{ether mixture (0/0?} O), whereupon the mixture was heated to reflux temperature. To this boiling solvent is a 70 to 80 ⁰ C warm solution of 21,88g of Connection_ was placed in lUbml biphenyl / Biphenylethergemisches f51. The addition took place over a period of 30 minutes using a drying funnel. A stream of nitrogen was blown over the surface of the reaction mixture and exited the system via the reflux condenser. After the addition was complete, the reaction

· ^: · 3Η4180

mixture heated to reflux temperature for 15 minutes and cooled overnight. During the reaction in the Dean-Stark trap approximately 90ml of solvent collected.

The red precipitate which had separated out was filtered off and filled with 50 ml of a fresh biphenyl / biphenyl ether mixture in a funnel washed. The residue was then washed thoroughly with ligroin P95O (petroleum distillate) and air-dried. Thus 16.46 g of crude compound (4) was obtained, which was suspended in 300 ml of refluxing isopropanol. About 150 ml of glacial acetic acid were then added to the suspension heated to reflux temperature, until all of the precipitate had disappeared had solved. The solution was then cooled with stirring and placed in an ice bath cold.

The deposited precipitate was filtered, washed with isopropanol and dried ^{at 65 ° C. in vacuo.} Compound (4) was obtained in a yield of 7.04 g. The melting point of the compound was 236.5-238, O ⁰ C.

The mass spectrogram was consistent with the assumed structure. Synthesis of the compound (5)

In a 100 ml 3-neck round bottom flask equipped with a mechanical stirrer and a drying tube, 5.94 g of compound (4) and 90 g of phosphoric acid were mixed with one another. The mixture was heated in an oil bath heated for 3 hours at 160 ⁰ C. The mixture was then ^{cooled to 100 to 120 °} C. and poured into 750 ml of water in a thin stream. Stirring was continued for 30 minutes and then filtered. The filtrate was washed with water and ^{dried in vacuo at 140 °} C. for several hours.

The dry pigment was ground and dissolved in 180 ml of N-methylpyrrolidinone suspended. The mixture was stirred at reflux temperature for 2 hours and then allowed to cool overnight with stirring calmly. Then hot water was added and the precipitated compound was filtered and dried.

The determined mass spectrum agreed with the assumed structure match.

The following examples illustrate the use of pigments of the formula I in a photoelectrophoretic imaging process. _T

Example · 1 -. ϊ =

An apparatus as shown in FIG. 1 was used. In this device, an advancing film carrier with a conductive coating of optical density was used from 0.1- of the cermet type (C * SiO). as an electrode. 1,. The electrode was in pressure contact with an aluminum roller 14 having a diameter of 10 cm, which was covered with a dielectric paper coated with a poly (vinyl butyral) resin layer. The roller served as electrode 5. Electrode 1 was driven by two rubber drive rollers 10 moved with a diameter of 2.8 cm. The distance between the two rubber drive rollers was 2.5cm, so that an exposure of the electrically pWötöseirsativ particles 4 with activating radiation. Die-Slide-VoTlage 11 that should be reproduced · .should be on the Back of the electrode 1. "-

The slide to be reproduced consisted of "adjacent Stripes of transparent, roteay green and blue Filter. The light source consisted of a tungsten lamp, its light by means of a step wedge with 0.3 neutral density steps was modulated. The residence time in the exposure zone was 10 milliseconds. The voltage between the electrode 5 and the

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V -: ..- - I »- ■■■■■. ■ '■ -' Λ Electrode 1 was 2 KV. Electrode 1 was more negative

Polarity in the case where the electrically photosensitive Material of the layer 4 has a positive electrostatic charge and the electrode 1 was positive in the case where the electrically photosensitive electrostatically charged particles were negatively charged. The speed at which the electrode was moved was about 25 cm per second. An image was recorded on the surface of the electrode 1 and the electrode after simultaneous exposure and action of the electric field on the electrically photosensitive layer 4 from the dispersion of the electrically photosensitive pigment particles in one liquid carrier. The liquid pigment dispersion was introduced into the gap 21 between the electrodes 1 and 5. Know that to be tested pigment of the layer 4 has a suitable electrical photosensitivity, then a negative image of the slide 11 on electrode S and a positive image on electrode generated.

Preparation of the dispersions used for image recording

The dispersions used for imaging became thereby produced that initially a stock solution was prepared from the following components:

Mixture of isoparaffins

aliphatic hydrocarbons + 2.2g

to 98% vol of aromatics (C ₈ -C ₁₂ )

existing solvent ++ _o

with a boiling range of 157-177 C 1.3g

Mixture of styrene vinyl toluene Copolymers +++ -1 »4g Polyoinyltoluene-co-lauryl methacrylate-.

co-lithium methacrylate-co-acrylic acid)

ZS6: 40; 3.6: 0.47 0.1

- «8-Τ -

-30 ·

+ = Isopar G, Exxon Corp.
++ = Solvesso, Exxon Corp.
+++ = Piccotex TOO, Pennsylvania Industrial Chemical Corp.

In each case 5g of the stock solution was placed in a closed container with O, O45g one of the mixtures (a) or (b) and 12g spheres: stainless steel mixed. The dispersion was then 3 hours Grind for a long time in a shaker for the preparation of color mixtures.

The dispersions prepared were then according to the described Procedure tested. It was found that all emulsions tested had advantageous electrical photosensitivity, what as a result, negative imaging on one electrode and positive imaging on the other electrode was obtained.

Example 2

1g of each pigment mixture was refluxed in N-methylpyrrolidinone extracted. Separate pigment dispersions The mixtures (a) and (b) were prepared according to the method described in Example 1. Furthermore, micro ^ crystalline coatings of trans-epindolidione and any of the mixtures prepared were prepared. The Reflection spectra of the coatings produced. From Fig. 2 it can be seen that the trans-epindolidione is a considerably larger one Has absorption in the green part of the spectrum (500 - 59Onm) than the mixtures according to the invention.

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Claims (1)

Reg. No. 126 440 EASTMAN KODAK COMPANY 343 State Street Rochester, New York State United States of America 3Π4180 PATENT LAWYERS Dr.-Ing. Wolff t H. Bartels Dipl.-Chem. Dr. Brandes Dr.-Ing. hero Dipl.-Phys. Wolff APPROVED BEFORE THE GERMAN AND - EUROPEAN PATENT OFFICE 8000 Munich 22, Thiersc hstr. 3 Tel. (089) 293297
Telex 0523325 (patwo d) Telegram address:
wolffpatent, munich postal check account Stuttgart 7211 bank code 6001Q0 70 Deutsche Bank AG, 14/286 30 BLZ 60070070 November 4th 25/28 1981 Electrically photosensitive pigment and use of the same Claims 1i Electrically photosensitive pigment, characterized in that that there is at least one meta-dimethyl or a tetramethyl isomer of the trans-epindolidione of the following formula: in which η ^{a is} 1 or 2, contains or consists of this. Telephone information and orders are only possible after written Confirmation binding 2. Electrically photosensitive pigment according to claim 1, characterized in that it is a mixture of at least three different trans-Epindol.idionisomere, namely (a) 1,7-Dimethyl-trans-epindolidioni 1,9-dimethyl-trans-epindolidione and 3,9-dimethyl-trans-epindolidione and / or (b) 1,2,7,8-tetramethyl-trans-epindolidione, 1,2,8,9-tetramethyl-trans-epindolidione, 2,3,8,9-tetramethyl-trans-epindolidione and optionally 2,3,7,8-tetramethyl-trans-epindolidione contains or consists of such a mixture. 3. Electrically photosensitive material made of an electrically photosensitive pigment, a carrier and optionally also: at least one charge control agent, a chemical and / or spectral sensitizers and other dyes and / or pigments, characterized in that it is a pigment according to an electrically photosensitive pigment of claims 1 or 2 contains. 4. Use of an electrically photosensitive pigment or Material according to one of Claims 1 to 3 in the context of a photoelectrophoretic image recording process.