DE2832462A1 - ELECTRIC PHOTOSENSITIVE PARTICLES FOR THE PERFORMANCE OF ELECTROPHORETIC IMAGE PRODUCTION PROCESSES - Google Patents

Description

The invention relates to electrically photosensitive pigment particles for performing electrophoretic imaging processes.

Electrophoretic imaging processes are disclosed, for example, in U.S. Patents 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 and 3 383 993 are known. In addition to the usual electrophoretic imaging processes described in these patents is another type of image reversal electrophoretic imaging process disclosed in U.S. Patent 3 976 485 became known. This method described in this patent specification is also referred to as a so-called photoimmobilized electrophoretic recording process or PIER process for short.

In the known electrophoretic imaging processes, a layer of an electrostatic one is typically used Photoconductive particles having charge, i.e., electrically photosensitive particles, are spaced two apart arranged electrodes, one of which may be transparent, housed. In order to generate an image in the known method To achieve, the electrically photosensitive particles arranged between the electrodes are exposed to the action of an electrical And exposed to radiation to which the particles are sensitive. As a result, the migrate electrically photosensitive particles electrophoretic to the surface of one or the other of the two at a distance mutually arranged electrodes, with the generation of images on the electrode surfaces. Typically it will be a negative Image is generated on one electrode and a positive image is generated on the opposite electrode. An image resolution takes place in the various known electrophoretic imaging processes as a result of a change in the charge polarity of either the exposed electrically photosensitive particles (in the case of the commonly known electrophoretic imaging processes) or the exposed electrically photosensitive Particles (in the case of electrophoretic imaging.

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Positioning method of the type known from US Pat. No. 3,976,485), so that the image generated on an electrode surface ideally consists of electrically photosensitive particles of a charge polarity, namely either negative or positive polarity is built up and the image on the surface of the electrode is opposite Charge polarity is built up in the ideal case from electrically photosensitive particles, which are opposite Have charge polarity, i.e. a positive or negative charge polarity.

In any case, regardless of the type of electrophoretic applied Process, electrically photosensitive particles are required to carry out the process. To an easily visible To obtain an image, it is essential that these electrically photosensitive particles be colored as well as electrically photosensitive are.

There has therefore been no lack of attempts to find particles which have both an advantageous electrical photosensitivity have as well as good coloring properties.

It is known the most varied types of electrically photosensitive To use particles in performing electrophoretic imaging processes. Such particles are for example, in U.S. Patents 2,758,939, 2,940,847, 3,384,488 and 3,615,558.

To a large extent, electrically photosensitive and / or photoconductive particles for performing electrophoretic imaging processes from known classes of photoconductive materials selected for the production of conventional photoconductive recording materials, i.e. photoconductive Plates, drums or belts are used, which in turn can be used to carry out electrophotographic office copying processes are. From US-PS 2,758,939 and 2,940,847 it is known, for example, that electrically photosensitive particles for the implementation of electrophoretic imaging processes

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can be selected from known classes of photoconductive materials. It is also known, for example, that the Phthalocyanine pigments disclosed in U.S. Patent 3,615,558 as being useful in performing electrophoretic imaging processes specified have photoconductive properties.

The invention was based on the knowledge that the following compounds listed are excellent for performing electrophoretic imaging processes. These compounds are not compounds that have already been described as photoconductors.

The invention thus relates to electrically photosensitive particles for carrying out electrophoretic image production processes, which are characterized in that they consist of a compound of one of those specified in the claims Formulas exist or contain such a compound.

In the given formulas:

Il

11 0 \ ' \

I. a! - CL == £ CL-CIT = ^ = C 0 or

m ν /

^X C = N

It

11. A ² = CL ⁴ - CL ⁵ = * = CL ~ CL ⁷ = * = ^ \)

C = N R

represent in detail:

m and η each * * 0, 1 or 2;

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ι η

L to L each have a carbon atom or an alkyl,

Aralkyl or aryl radical or two of L, L and L and two each of L, L, L and L collectively the atoms necessary to complete a carbocyclic ring;

R represents a hydrogen atom or a

Alkyl or aryl radical;

A represents an optionally substituted one

Aryl radical, for example of the phenyl, naphthyl or anthryl series or optionally one substituted heterocyclic nucleus, e.g., a thiophene; Benzo / b_7thiophene-; Naphtho- / 2,3_ / thiophene-; ΡμΓαη-; Isobenzofuran; Chromene; Pyran; Xanthene; Pyrrole; 2H-pyrrole-; Pyrazole-; Indolizine; Indoline-; Indole; 311-indole-; Indazole-; Carbazole-; Pyrimidine-; Isothiazole; Isoxazole-; Furazan; Chroman; Isochroman; 1,2,3 ^ tetrahydroquinoline-; 4H-pyrrolo / ~ 3,2,1-ij _ / quinoline-; 1,2-dihydro-4H-pyrrolo / 3,2,1-ij_ / quinoline-; 1,2,5,6-tetrahydro-4H-pyrrolo / 3,2,1-ij -7quinoline-; 1H, 5H-benzo / ~ ij_7quinolizine-; 2,3-dihydro-1H, 5H-benzo / ij_7quinolizine-; 2,3-Dihydro-III, 511-benzo / ij_7quinolizine-; 2,3,6,7-tetrahydro-1H, 5H-benzo / ~ ij_7quinolizine-; 10,11-dihydro-QH-benzo / a_7xanthen-8-yl or 6,7-dihydro-5H-benzo- / ~ b_7pyran-7-yl nucleus it being possible for the nuclei to be substituted, for example, by a heterocyclic secondary amino radical and / or an alkoxy, amino, arylamino, dialkylamino, diarylamino, alkyl and / or aryl radical and / or halogen atoms;

A stands for a basic, optionally

substituted heterocyclic nucleus, consisting of:

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a) an imidazole nucleus, e.g., an imidazole or 4-plienylimidazole nucleus;

b) a 3fi-indole nucleus, e.g., a 3H-indole; 3,3-dimethyl-3H-indole ~ or a 3,3,5-trimethyl-3H-indole nucleus;

c) a thiazole nucleus, e.g., a thiazole; 4-methylthiazole-; 4-phenylthiazole-; 5-methylthiazole-; 5-phenylthiazole-; 4,5-dimethylthiazole-; 4,5-diphenylthiazole or a 4- (2-thienyl) thiazole nucleus;

d) a benzothiazole nucleus, e.g., a benzothiazole; 4-chlorobenzothiazole-; 5-chlorobenzothiazole-; 6-chlorobenzothiazole-; 7-chlorobenzothiazole-; 4-i-methylbenzothiazole-; 5-iIethylbenzothiazol-; 6-methylbenzothiazole-; 5-bromobenzothiazole-; 6-bromobenzothiazole-; 4-phenylbenzothiazole-; 5-phenylbenzothiazole-; 4-methoxybenzothiazole-; 5-methoxybenzothiazole-; 6-methoxybenzothiazole-; 5-iodobenzothiazole-; 6-iodobenzothiazole-; 4-ethoxybenzothiazole-; 5-ethoxybenzothiazole-; Tetrahydrobenzothiazole-; 5,6-dimethoxybenzothiazole-; 5,6-dioxymethylene benzothiazole; 5-hydroxybenzothiazole-; or 6-hydroxybenzothiazole nucleus;

e) a naphthothiazole nucleus, e.g., a naphthol 1,2-d_7-thiazole-; Naphtho / ~ 2,1-d_7thiazole-; Naphtho / "2,3-d_7-thiazole-; 5-methoxynaphtho / 2,1-d_ / thiazole-; 5-ethoxynaphtho / ~ 2,1-d_ / thiazole-; 8-methoxynaphtho ^ ~ 1,2-d _ / - thiazole or a 7-methoxynaphtho / 1,2-d_ / thiazole nucleus;

f) a thianaphtheno-7 ', 6', 4,5-thiazole nucleus, e.g. 4'-methoxythianaphtheno-7 ', 6', 4,5-thiazole nucleus;

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g) an oxazole nucleus, e.g., a 4-methyloxazole; 5-methyloxazole-; 4-phenyloxazole-; 4,5-diphenyloxazole-; 4-ethyloxazole-; 4,5-dimethyloxazole or a 5-phenyloxazole nucleus;

h) a naphthoxazole nucleus, e.g. a naphtho / 1,2 _ / - oxazole- or a naphtho / 2,1_ / oxazole nucleus;

i) a selenazole nucleus, e.g. a 4-methylselenazole or a 4-phenylselenazole nucleus;

j) a benzoselenazole nucleus, e.g., a benzoselenazole; 5-chlorobenzoselenazole-; 5-methoxybenzoselenazole-; 5-hydroxybenzoselenazole or a tetrahydrobenzoselenazole nucleus;

k) a naphthoselenazole nucleus, for example a naphtho- ^ ~ 1,2-d_7 ~ or a naphthol 2,1-d_ / selenazole nucleus;

1) a thiazoline nucleus, e.g., a thiazoline or a 4-methylthiazoline nucleus;

2-

m) a y-quinoline nucleus, e.g., a quinoline; 3-methylquinoline-; S-methylquinoline-; 7-methylquinoline-; 8-methylquinoline-; 6-chloroquinoline-; 8-chloroquinoline-; 6-methoxyquinoline-; 6-ethoxyquinoline-; 6-hydroxyquinoline-; or an 8-hydroxyquinoline nucleus;

n) a 4-quinoline nucleus, e.g., a quinoline; 6-methoxyquinoline-; 7-methylquinoline or a 8-methylquinoline nucleus;

o) a 1-isoquinoline nucleus, e.g. an isoquinoline or a 3,4-dihydroisoquinoline nucleus;

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ρ) a benzimidazole nucleus, e.g. a 1,3-diethylbenzimidazole or a 1-ethyl-3-phenylbenzimidazole nucleus;

q) a 2-pyridine nucleus, e.g., a pyridine or 5-methylpyridine nucleus;

r) a 4-pyridine nucleus;

s) a thiazoline nucleus;

t) an acenaphthothiazole nucleus or

u) a benzoxazole nucleus.

Alkyl radicals are to be understood here preferably as those with 1 to 20 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, Butyl, heptyl, dodecyl or octadecyl radicals. The aryl radicals mentioned here preferably have 6 to 20 carbon atoms and preferably consist of residues of the phenyl, naphthyl or anthryl series. These aryl radicals can optionally through Be substituted by alkyl and / or aryl radicals. This means that the aryl radicals, for example, from such radicals as tolyl, Ä'thylphenyl- or Biphenylresten can exist. Among aralkyl radicals alkyl radicals substituted by aryl radicals are to be understood, for example benzyl or phenethyl radicals.

Under carbocyclic radicals are to be understood here saturated carbocyclic rings, which are optionally replaced by alkyl, aryl or Aralkyl substituents of the structure indicated can be substituted. This means that the carbocyclic radicals, for example from cyclopropyl, cyclophenxl, cyclohexyl or 5,5-Dimethylcyclohexylresten may exist. The ones mentioned here Alkoxy radicals are preferably alkyloxy radicals in which the alkyl radical has the meaning given. Typical alkoxy radicals are thus for example methoxy, ethoxy, isopropoxy and Butoxy residues.

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When used in the context of electrophoretic imaging processes, the electrically photosensitive particles according to the invention are spaced apart between at least two
arranged electrodes housed.

The particles are preferably electrical in one
contain insulating carrier, for example an electrically insulating liquid or an electrically insulating, liquefiable matrix, for example a fo-xotropic or by the action of
Heat and / or solvent softenable material that is placed between the electrodes. The one between the electrodes
Housed electrically photosensitive particles are then exposed to the action of an electric field and imagewise exposed, namely with a radiation, the opposite
they are sensitive. As a result, the electrically photosensitive particles experience a radiation-induced change in their charge polarity and migrate to one or the other
the electrode surface to form an image on at least one of the electrode surfaces, which is
is a positive or negative image of the original.

In the drawing, a device for implementation is schematically an electrophoretic imaging process shown in which the inventive electrically photosensitive Particles can be used.

According to a particularly advantageous embodiment of the invention, the particles correspond to one of the formulas I or II, in which
mean:

A is a 2,3,6,7-tetrahydro-1H, 5H-benzo / ~ ij_ / quinolizine nucleus
or an optionally substituted phenyl radical, which is optionally substituted by one or more alkoxy, dialkylamino,
Morpholino, di-p-tolylamino and / or pyrrolidino radicals can be substituted;

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A is an optionally substituted heterocyclic nucleus, namely a thiazole; Thiazoline-; Benzothiazole; Naphthothiazoles Benzoxazole-; Benzoselenazole-; 2-quinoline-; 4-quinoline or a 3H indole nucleus;

17th
L to L, m and η have the meanings already given.

In general, particles with a compound have one of the Formulas I and II a maximum absorption wavelength max from about 420 to 750 nm.

The following table shows typical ones which can be used according to the invention Connections listed.

The compounds of the formulas I and II can be prepared, for example, by processes as described in the journal "· ** ¹¹¹¹ ·

American Chemical Society ", ^ 5, page 959 (1913) and in Journal of American Chemical Society, 7J5> Pp. 5326 to 5363 (1951) and U.S. Patents 2,165,339 and 2,956,881 to be discribed.

Table I.

S t ruc ture fο rme1

hue

CH-CH = CH-CF]

N /

C ₂ H ₅

CH-CH

Purple yellow

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Continuation from Table I.

[j \ = CH-CH = CH-CH

purple

CH-CH

■ N '
CH, ι
γη
^L 2 5

purple

CH-CH = CH-CH = CH-CH = fY blue green

C ₂ H ₅

1-CH = CH-CH

^έ 2 ^Η 5

purple

■ N '

CH-CH = CH-CB

Cl

purple

CH ₃ CH ₃

C ₂ H ₅

blue

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Continuation from Table I.

CH, CH

1-CH = CH

C ₉ H ₁

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green

/ = CH-CH = CH-CH

O.

CH,

CO- ™ -? -

'"CH

C ₂ H ₅

Purple orange

CH

^C 2 ^H 5

orange

CC) -

CH-CH = CH-CH

^έ 2 ^Η 5

purple

Continuation from Table I.

y = ^cH -

CH-

^C 2 ^H 5

CO-

CH-CI

^C 2 ^H 5

orange

orange

'= C- CH = CH- CH ■ Ν' « ι Ο

^C 2 ⁿ 5

purple

^C 2 ^H 5

^: C-CH = CH-CH t

purple

> - 'CH-

CoH _c

CH = CH-CIt

orange

purple

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Continuation from Table I.

^C 2 ^H 5

blue

N /

CH,

\ Jl

orange

22 I A ) = CH-CI

C η 2 ^U 5

^C 2 ^H 5 "

0.

CH-C

24 C ₇ H, -N; CH-CH = CH-CH

CH-Ch = CH-CH = CH-CH:

C ₂ H ₅

pink

purple

blue

green

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Continuation from Table I.

CH-QI = CII-CIi

purple

27 ^αΐ ~ ^N * / CH-CII = CH-CII = Ch-CH = ^ ^ purple

CH-CH

orange

OCII

3 CH

^CI * 3

CII '

S N =

CH = CH-CH

orange

purple

- 20a -

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28324S2

i4

Continuation from Table I.

pink

pink

orange

CH, CH

Reddish brown

orange

CC ₂ H ₅ ) ₂ N 9 ^

purple

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Continuation from Table I.

CH ₃ CH ₃ QI ₃ CII ₃

CiI-CH = CH

blue

CH, CH,

CH-CH

orange

CH ₃ CH ₃

CH-CH

orange

Those for performing electrophoretic imaging processes certain electrically photosensitive particles advantageously have an average Particle size from about 0.01 microns to about 20 microns, especially from about 0.01 to about 5 microns. In a typical way the particles used to carry out electrophoretic imaging processes represent dyes or Pigments.

The electrically photosensitive particles of the present invention may optionally contain various non-photosensitive components e.g. electrically insulating polymers, charge control agents, a wide variety of organic and inorganic fillers as well as the various other additional color

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substances or pigments, to change or improve the coloring and physical properties of the electrical photosensitive particles. Furthermore, the electrically photosensitive particles of the invention can be other photosensitive ones Contain substances, e.g. a wide variety of sensitizing dyes and / or chemical sensitizers, in order to reduce their Modify or increase response characteristics to the radiation to which they are sensitive.

As stated earlier, when performing electrophoretic Image production process the electrically photosensitive Particles typically placed between two or more spaced electrodes one or both of which can be transparent to the radiation which is electrically photosensitive to the radiation Particles are sensitive to light, i.e. which are transparent to the activating radiation.

The electrically photosensitive particles can be placed between the electrodes in a simple manner in the form of a dry powder and then subjected to a typical electrophoretic imaging process, for example a process as known from US Pat. No. 2,758,939.

In a particularly typical manner, the electrically photosensitive Particles dispersed in an electrically insulating carrier, e.g., an electrically insulating liquid or a electrically insulating, liquefiable matrix, e.g. one that can be softened by the action of heat and / or solvents Polymer or a thixotropic polymer. Are dispersions of electrically photosensitive particles in an electrically insulating If the carrier is used, it has proven to be expedient, about 0.05 parts by weight to about 2.0 parts by weight electrically photosensitive To use particles to 10 parts by weight of electrically insulating carrier.

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The customary known carriers can be used to prepare the carrier dispersions, ie electrically insulating liquids, for example decane, paraffin and kerosene fractions (for example Sohio Oderless Solvent 3440, manufacturer Standard Oil Company, Ohio, USA). It is also possible to use, for example, a wide variety of isoparaffinic liquid hydrocarbons, for example hydrocarbon fractions with a boiling range of 145 to 186 ⁰ C (e.g. Isopar G, manufacturer Exxon Corporation) and a wide variety of halogenated hydrocarbons, e.g. carbon tetrachloride and trichloromonofluoromethane, and a wide variety of alkylieite aromatic liquid hydrocarbons, e.g. alkylated benzenes, for example xylenes and other alkylated aromatic hydrocarbons, such as are known, for example, from US Pat. No. 2,899,335. Such liquid alkylated aromatic hydrocarbons are, inter alia, also commercially available, for example under the trade name Solvesso 100, manufacturer Exxon Corporation. A suitable consisting of alkylated aromatic hydrocarbons fraction (Solvesso 100) beispielsv ^r else a boiling range of about 157 ⁰ C to about 177 ⁰ C and consists of 91 of xylene to $ 16 from other Ilonoalkylbenzolen to 34% of dialkylbenzenes to 37 % from trialkylbenzenes and 4 * from aliphatic components. Typically, irrespective of whether the carrier is ^{solid or liquid at normal room temperature, ie about 22 °} C., the electrically insulating carrier has a resistance of over

9 12

10 ohms / cm, preferably above about 10 ohm / cm. Will the electrically photosensitive particles according to the invention are applied in a carrier, for example in one of the above The electrically insulating liquids mentioned above can be incorporated with the most varied of customary known additives. For example, a wide variety of charge control agents can be added to the suspension used for imaging in order to ensure the uniformity of the charge polarity of the electrically photosensitive present in the liquid suspension Particles to improve. The customary known charge control agents, such as those used, for example, for production, can be used here liquid electrographic developer can be used. Typically, such charge control agents are poly-

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mere compounds contained in the liquid carrier of the suspension can be mixed in. It has been shown that the addition of charge control agents, in addition to improving the uniformity of charge polarity, often for manufacture of more stable suspensions, i.e. suspensions. in which the dispersed electrically photosensitive particles settle considerably less rapidly than in the case of suspensions without the addition of charge control agents.

In addition to the charge control agents mentioned, a wide variety of polymeric binders can be added. These Binders can be of natural, hemisynthetic or synthetic origin and in the electrically insulating carrier dispersed or dissolved. With their help, the produced particle images can be fixed on the electrodes. the The use of such fixing agents is common, which is why it does not need to be discussed in more detail.

The drawing serves to explain the invention in more detail. In the drawing is one for performing an electrophoretic A device suitable for the imaging process is shown in the diagram.

The device has a transparent electrode 1 which can be moved by two drive rollers 10 in the direction indicated by the arrows. The electrode 1 can consist of a Layer made of an optically transparent material, e.g. glass or an electrically insulating, transparent polymer layer carrier, E.g. made of polyethylene terephthalate, the substrate with a thin, optically transparent, conductive Layer, e.g. made of tin oxide, indium oxide or nickel can be coated. If necessary, depending on the applied in the individual case Process type, the surface of the electrode 1 can be a "thin charge." exchange material ", e.g. in the form of a solid solution of 2,4,7-trinitro-9-fluorenone in an electrically insulating Polymer. Reference is made in this connection to US Pat. No. 3,976,485.

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At a distance from the electrode 1 and in pressure contact with the same is the second electrode 5, which in the present case is designed as a roller electrode or guide electrode and represents the counter electrode to the electrode 1. The electrode 5 typically has a thin electrically insulating layer 6. The electrode 5 is connected to one side of the power source 15 via the switch 7. The opposite side of the power source 15 is connected to the electrode 1 so that when an exposure is _s, the switch 7 is closed and the particles 4 of electrically action are exposed to a field. The electrically photosensitive particles 4 are typically dispersed in an electrically insulating carrier.

The electrically photosensitive particles 4 can thereby be arranged between the electrodes 1 and 5 that the particles either can be applied to one or both of the surfaces of the electrodes 1 and 5 before the method or in that they are between the electrodes 1 and 5 x ^ during the Performing the electrophoretic imaging process.

As can be seen from the drawing, the exposure of the electrically photosensitive particles 4 is carried out by an exposure system from a light source 8, the original 11 to be reproduced, e.g. a photographic slide, a lens system and if necessary radiation filters 13, for example color filters, itfor by the electrically photosensitive particles 4 accordingly the template 11 are irradiated image-correct.

Although the device shown in the drawing represents an electrode 1 which is used for the radiation from the light source 8 is permeable, it is also possible to place the electrically photosensitive particles 4 in the gap 21 between the electrodes 1 and 5 to irradiate without one of the electrodes 1 or 5 needing to be permeable or transparent. In such a Device, the light source 8 and the lens system 14 can be arranged so that the particles 4 in the gap 21 between the

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Electrodes 1 and 5 are exposed.

In the device shown in the drawing, the electrode 5 is formed into a roller electrode which has a having conductive core 14 which is connected to the power source 15. This core is in turn made with a layer an insulating material 6, for example a baryta-coated paper. The insulating material 6 has the task to prevent the electrically photosensitive particles 4 from a radiation-induced change in charge upon contact with the electrode 5 are subject. At least the layer 6 should reduce this tendency of the particles. As a result, can the electrode 5 can also be referred to as the so-called "blocking electrode", as is the case in the field of electrophoretic imaging processes is common.

Although the electrode 5 is shown in the present case in the form of a roller electrode and the electrode 1 in the form of a flat plate electrode, both of these electrodes can also have other shapes and, for example, the form of band-shaped electrodes, rotating roller electrodes, plate electrodes and the like, v. ^{r which} they are common in the case of performing electrophoretic imaging processes.

In general, when performing a typical electrophoretic Image production process in which the electrically photosensitive particles 4 in an electrically insulating liquid carriers are dispersed, the electrodes 1 and 5 are in pressure contact in front of or are very close to each other, i. e. their distance from one another is usually Xieniger than 50 microns. On the other hand, become the electrically photosensitive particles 4 simply dispersed in an air gap between electrodes 1 and 5 or in a carrier such as a layer of a material which can be softened or otherwise liquefied by the action of heat in the form of a Layer placed on the electrode 1 and / or 5, so these electrodes can be spaced more than 50 microns apart

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have during the image making process.

The strength of the electric field that is applied to the electrodes 1 and 5 during the implementation of the method, can be very different. It has been found, however, that in general an optimal image density and an optimal resolution then can be obtained when the field strength is as great as possible, i.e. has as high a value as possible, without an electrical Breakthrough of the carrier takes place in the gap between the electrodes. If, for example, an electrically insulating carrier is used Liquid used, for example an isoparaffin hydrocarbon-based carrier, so when using a device as shown in the drawing, which is attached to the electrodes 1 and 5 typically applied voltages are from about 100 volts to about 4 kilovolts or more.

When the method is carried out, images as a result of the combined action of an activating radiation and a Electric field generated on the electrically photosensitive particles 4 between the electrodes 1 and 5. Typically done, the field action and the exposure simultaneously to achieve particularly advantageous results. Through suitable Selection of the various process parameters, for example the field strength, the intensity of the activating radiation Addition of suitable photosensitive additives to the electrically photosensitive particles or by using such additives with the particles, by adding a persistent photoconductive material and the like, however, it is also possible to change the time sequence to change exposure and field action in such a way that exposure and field action can occur one after the other, instead of at the same time.

The electrically photosensitive particles 4 accommodated between the electrodes 1 and 5 have an electrostatic charge polarity either as a result of a triboelectric effect of the particles on or as a result of an action by the carrier in which the particles are dispersed on the latter, e.g. electrically insulating liquid, as in the case of conventional liquid

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ger electrographic developer made from toner particles that take up a charge when placed in an electrically insulating Carrier liquid are dispersed.

An image resolution takes place when performing the electrophoreti · = see imaging as a result of exposure to a process electric field and activating radiation on the electric photosensitive particles between electrodes 1 and 5 the device shown in the drawing are dispersed. This means that when performing a typical imaging process when an electric field is applied to the electrodes 1 and 5, the electrically photosensitive particles 4 in the dark either attracted to electrode 1 or 5, depending on that which of these electrodes has a polarity that corresponds to the original charge polarity of the electrically photosensitive Particle is opposite. The particles 4 become more activating When exposed to radiation, neutralization or reversal of charge polarity is believed to occur, either in the case of the exposed or in the case of the unexposed particles.

In the case of a typical electrophoretic imaging process in which the electrode 1 has a conductive surface has, the exposed, electrically photosensitive particles 4 when they are in electrical contact with the conductive surface, a change (usually a reversal) of their original charge polarity as a result of the combined action of an electric field and activating radiation.

In the case of the photoimmobilized electrophoretic recording method (PIER) in which the surface of the electrode 1 has a layer of a dark charge exchange material (See US Pat. No. 3,976,485) alternatively, a reversal of the charge polarity of the unexposed particles is obtained, while the exposed electrically photosensitive particles their original Maintain charge polarity when these particles are in

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electrical contact with the dark charge exchange material of the Electrode 1 come. In jsiem case, when one acts Electric field and activating radiation on the electrically photosensitive particles 4 between the electrodes 1 and 5 of the In the drawing device shown achieve an effective image resolution, so that an image pattern by the electrically Photosensitive particles is generated, which corresponds to the template activating radiation. Typically at Using a device of the type shown in the drawing, a visible image on the surface of the electrode 1 and a complementary image on the surface of the electrode 5.

Following the action of the electric field and following exposure to activating radiation, the images generated on the surface of electrodes 1 and 5 can be temporarily or permanently fixed on these electrodes or else transferred to image receiving materials. The fixation of the particle images can be achieved by various conventional methods, for example by applying a resinous cover layer to the surface of the substrate carrying the image. If the electrically photosensitive particles 4 are dispersed, for example, in a liquid carrier between the electrodes 1 and 5, the image or images generated on the surfaces of the electrodes 1 and / or 5 can be fixed by adding the carrier liquid adding a polymeric binder. Many such binders (known to be used in liquid electrophotographic developers) are known to undergo a change in charge polarity when mixed with a carrier liquid, and hence the binder particles themselves electrophoretically to the surface of one or the other of the electrodes hike. Alternatively, it is possible to produce a layer of a resinous binder (as can be used, for example, in the carrier liquid) on the surface of the electrodes 1 and / or 5 after the liquid carrier has been evaporated.

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The electrically photosensitive particles which can be used according to the invention, with or from compounds of the formulas I and II suitable for the production of monochrome images or after mixing with other electrically photosensitive particles Use color tones and suitable photosensitivity to produce polychrome images.

The electrically photosensitive particles of the present invention can also be used as sensitizers for others electrically photosensitive particles in the manufacture of use monochrome images. The particles which can be used according to the invention are combined with other electrically photosensitive substances mixed, the electrically photosensitive particles according to the invention can be used selectively as sensitizing agents. and / or as electrically photosensitive particles act.

Many of the electrically photosensitive particles of the invention have particularly advantageous shades / why they where a mixture of zx \ ^r ei or more differently colored electrically photosensitive particles is used can be used as part polychrome electrophoretic imaging processes in a particularly advantageous manner. If such a mixture of electrically photosensitive particles of different colors is produced, for example in an electrically insulating carrier liquid, this liquid mixture of particles can have a black hue. Preferably, cyan, magenta and yellow particles are selected for performing polychrome electrophoretic imaging processes so that their spectral response curves do not appreciably overlap, thereby enabling color separation and the production of multicolor subtractive images.

The following examples are intended to illustrate the invention in more detail. They describe the use of compounds of the formulas I and II in the context of an electrophoretic imaging process .

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Examples 1 to 39: Device used

An apparatus as shown in the drawing was used to carry out the process. Served as electrode 1 a film carrier with a conductive layer of monop "Cermet-It Material" (Cr'SiO) with an optical density of 0.1. The electrode 1 was in pressure contact with an aluminum roller 14 with a diameter of 10 cn with a dielectric Paper, i.e. one coated with a poly (vinyl butyral) resin coated Ραχ.-ier. The aluminum roller 14 served as electrode 5. Electrode 1 was on two Cummi drive rollers 10 with a diameter of 2.8 cm. The two drive rollers 10 were at such a distance from one another, that a one inch opening symmetrical about the axis of the aluminum roll 14 was created, thereby reducing exposure of the electrically photosensitive particles 4 was made possible with activating radiation. The slide template 11, the should be reproduced was adhered to the Pvbackseite of the electrode 1.

The slide to be reproduced consisted of strips of Wratten filters lying next to one another, namely a clear one Filter (WO), a red filter (VJ29), a green filter (W61) and a blue filter (W47B). The light source used existed from a projector with a 1000 watt xenon lamp. The light was through a step wedge with 11 density levels one Neutral density modulated by 0.3. The residence time in the exposure zone was 10 milliseconds. The logarithm of the light intensity (Log I) was as follows:

Log I.

filter WHERE Transparent W29 Red W61 green ΙΪ47Β blue

Erg / cm / Sec. 8th 5.34 7th 4.1 S. 4.1 4.1

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The voltage applied to electrodes 1 and 5 was about 2 kV. The electrode 1 had a negative polarity in the case in which the electrically photosensitive particles 4 had a positive electrostatic charge. The electrode 1 was the Positive polarity electrode in cases where the electrically photosensitive particles 4 were negatively charged. The advancing speed of the electrode 1 was about 25 cm per second. In the case of these examples, there was a picture on the surfaces of the electrodes 1 and 5 with simultaneous exposure to light and the action of an electric field the electrically photosensitive particles 4 which were in a liquid carrier generated. The pond dispersion was housed in the gap 21 between the electrodes 1 and 5. In the case where the particles 4 have sufficient electrical Showed photosensitivity, a negative image of the original 11 on the electrode 5 and a complementary image on the electrode 1 is generated.

Preparation of the imaging dispersions

Starting from the compounds listed in Table I, various dispersions were prepared.

A starting solution composed of the components indicated below was used to prepare the dispersions. This initial solution was made by simply combining the individual components.

Isoparaffin hydrocarbons with a boiling point range of 145 to 186 ° C

(Isopar G) 2.2 g

Alkylated aromatic hydrocarbons with a boiling point range of 157 to

177 ⁰ C (Solvesso 100) '1.3 g

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Polyvinyltoluene-styrene copolymer

(Piccotex 100) 1.4 g

Mixed polymer of vinyl toluene,

Lauryl methacrylate, lithium methacrylate

and methacrylic acid in proportion

56: 40: 3.6: 0.4 (PVT) 0.1 g

In a closed container 5 g of each of the described Starting solution with 0.045 g of a compound of Table I. and 12 g stainless steel balls (Hamber 440) together united. The mixture was then shaken in a paint-making shaker for 3 hours.

Each of the 39 compounds listed in Table I was tested.

It was found that each of the compounds tested had advantageous electrophotosensitive properties, which is evident from this showed that each had a negative image of the original artwork on one of the electrodes and a complementary image on the other Electrode was generated. The image quality was determined visually. In all cases, beneficial images were made with advantageous minimum and maximum densities, good sensitivity and get color saturation.

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Claims (1)

Reg.No. 125 676 PATENT AGENCIES EASTIjAN KODAK COMOPANY, 343 State Street, Rochester, New York State, United United States of America Electrically photosensitive particles for use in electrophoretic imaging processes PATE N TANSPR 0 C K E H.Bartels Dipl.-Chem. Dr. Brandes Dr.-Ing. Hero Dipl.-Phys. Wolff 8 Munich 22, Thierschstrasse Tel. (089) 293297 Telex 0523325 (patwod) Telegram address: wolffpatent, munich postal check account Stuttgart 7211 (BLZ 60010070) Deutsche Bank AG, 14/28630 (BLZ 60070070) Office hours: 8 a.m. to 12 p.m., 1 p.m. to 4.30 p.m. except Saturdays July 14, 1978 25/2 \ ij Electrically photosensitive particles for carrying out electrophoretic imaging process, characterized in that it consists of a compound of one of the following Formulas: I. CL II. CL- 2 p _T 3
- CL = C. O
Il
^c \
O
C = N
t
R. ^ CL ⁶ - O
It
CO ^ C = N R. -CL ⁷ - or where mean: m and η = 0, 1 or 2; L ¹ to L ⁷ individually in each case a hydrogen atom or a Alkyl, aralkyl or aryl radical or two of L, L and L on the one hand and / or two of L, L, L and L on the other hand, the 80980S / 103Ö ORIGINAL INSPECTED completion of a carbocyclic Uin ^ it is necessary Atoms; P. a hydrogen atom or an alkyl or Aryl radical; Λ an optionally substituted. "Ryl radical or an optionally substituted one heterocyclic plagues, the substituents of which are composed of heterocyclic secondary amino radicals and / or alkoxy ", amino, arylamine, dialkylamino, Diarylamino, alkyl or aryl radicals and / or halogen atoms exist; A is an optionally substituted basic one heterocyclic nucleus consisting of an imidazole; 311-indole-; Thiazole; Benzothiazole; Naphthothiazole-; Thianaphthieno-7 ', 6', 4, 5-thiazole-; üxazol-; Naphthoxazole-; Selenazole-: benzoselenazole-; Naphthoselenazole-; Thiazoline-; 2-quinoline-; 4-quinoline-; 1-isoquinoline-; Benzimidazole; 2-pyridine-; 4-pyridine-; Thiazoline-; Acenaphthothiazole or a benzoxazole nucleus exist or contain one. 2. Electrically photosensitive particles according to claim 1, characterized characterized in that they consist of a compound of the formula I or contain one in which Λ represents one 2,3,6,7-tetrahydro-1H, 5II-benzo / ij_ / quinolizine nucleus or an optionally substituted phenyl radical whose substituents are selected from alkoxy, dialkylamino, morpholine) -, Di-p-tolylamine or pyrrolidino radicals exist. 3. Electrically photosensitive particles according to claim 1, characterized characterized in that they consist of a compound of the following formula or contain such a compound: 809885/1030 Cn-CH = CII-CIi = CIl-CII: C ₇ IL ; ii-CK = CH-cii- C _? II _r ■ J CII CII-CII = CII N ¹
CJI 80988S / 1Ö30 Γ \\ N = CII-C = CII ^C 2 ^H 2 ^H 5 > = CII-C = Cl • ^C 2 ^H 5 CH ₇ ^{L b} H-CH = CH-CII: ^C 2 ^H 5 CO - ^ f ^έ 2 ^Η 5 CH-CH- ", C-CH = CH-CI N / ι ΓΗ C ₂ H ₅ I09Ö8B / 1Ü30 ^ = C-CH = CH-CH CiI, 3 16) I. _N ) = CH-CH ^ r J // v CH -N V = CH-CH-CH-CB = C I ^έ 2 ^Η 5 ¹ CH-CH = CH-CH 809885/1030 19) 20) 21) CH-CH CII = ³ \ 23) N. H ₃ C CH CH, CH CH-CH = CH CH, CH. CH-CH or 80988S / 103D.