US 4,145,215 AGrant
Migration Imaging Process and Compositions
Issue Date:1979-03-20
•16 Claims
•1 Drawing Sheets
Abstract
Materials having the following structure ##STR1## have been found useful in migration imaging processes.
Metadata
Assignee
- Eastman Kodak Company
Inventors
- James A. Van Allan
- Frank G. Webster
- George A. Reynolds
Application Information
Application Number:US 8161283
Filing Date:1977-07-15
Priority Date:1977-07-15
Art Unit:166
Classifications
IPC:
G03G 509
Field of Search:
961 R;1.3;1.5;1 PS;1 PE;127
Patent Drawings (1 sheets)
Description
FIELD OF THE INVENTION
This invention relates to electrophoretic migration imaging processes and, in particular, to the use of certain photosensitive pigment materials in such processes.
BACKGROUND OF THE INVENTION
In the past, there has been extensive description in the patent and other technical literature of electrophoretic migration imaging processes. For example, a description of such processes may be found in U.S. Pat. Nos. 2,758,939 by Sugarman issued Aug. 14, 1956; 2,940,847, 3,100,426, 3,140,175 and 3,143,508, all by Kaprelian; 3,384,565, 3,384,488 and 3,615,558, all by Tulagin et al.; 3,384,566 by Clark; and 3,383,933 by Yeh. In addition to the foregoing patent literature directed to conventional photoelectrophoretic migration imaging processes, another type of electophoretic migration imaging process which advantageously provides for image reversal is described in Groner, U.S. Pat. No. 3,976,485 issued Aug. 24, 1976. This latter process has been termed photoimmobilized electrophoretic recording or PIER.
In general, each of the foregoing electrophoretic migration imaging processes typically employs a layer of electrostatic charge-bearing photoconductive particles, i.e., electrically photosensitive particles, positioned between two spaced electrodes, one of which may be transparent. To achieve image formation in these processes, the charge-bearing photosenstitive particles positioned between the two spaced electrodes, as described above, are subjected to the influence of an electric field and exposed to activating radiation. As a result, the charge-bearing electrically photosensitive particles are caused to migrate electrophoretically to the surface of one or the other of the spaced electrodes, and one obtains an image pattern on the surface of these electrodes. Typically, a negative image is formed on one electrode, and a positive image is formed on the opposite electrode. Image discrimination occurs in the various electrophoretic migration imaging processes as a result of a net change in charge polarity of either the exposed electrically photosensitive particles (in the case of conventional electrophoretic migration imaging) or the unexposed electrically photosensitive particles (in the case of the electrophoretic migration imaging process described in the above-noted Groner patent application) so that the image formed on one electrode surface is composed ideally of electrically photosensitive particles of one charge polarity, either negative or positive polarity, and the image formed on the opposite polarity electrode surface is composed ideally of electrically photosensitive particles having the opposite charge polarity, either positive or negative respectively.
In any case, regardless of the particular electrophoretic migration imaging process employed, it is apparent that an essential component of any such process is the electrically photosensitive particles. And, of course, to obtain an easy-to-read, visible image it is important that these electrically photosensitive particles be colored, as well as electrically photosensitive. Accordingly, as is apparent from the technical literature regarding electrophoretic migration imaging processes, work has been carried on in the past and is continuing to find particles which possess both useful levels of electrical photosensitivity and which exhibit good colorant properties. Thus, for example, various types of electrically photosensitive materials are disclosed for use in electrophoretic migration imaging processes, for example, in U.S. Pat. Nos. 2,758,939 by Sugarman, 2,940,847 by Kaprelian, and 3,384,488 and 3,615,558 by Tulagin et al., noted hereinabove.
In large part, the art, to date, has generally selected useful electrically photosensitive or photoconductive pigment materials for electrophoretic migration imaging from known classes of photoconductive materials which may be employed in conventional photoconductive elements, e.g., photoconductive plates, drums, or webs used in electrophotographic office-copier devices. For example, both Sugarman and Kaprelian in the above-referenced patents state that electrically photosensitive materials useful in electrophoretic migration imaging processes may be selected from known classes of photoconductive materials. Also, the phthalocyanine pigments described as a useful electrically photosensitive material for electrophoretic imaging processes in U.S. Pat. No. 3,615,558 by Tulagin et al. have long been known to exhibit useful photoconductive properties.
SUMMARY OF THE INVENTION
In accord with the present invention, a group of materials has been discovered which are useful in electrophoretic migration imaging processes. To the best of our knowledge, none of said materials have been previously identified as photoconductors. Said materials have the following structure: ##STR2## wherein G.sup.1 and G.sup.2, which may be the same or different, represent
(1) an electron withdrawing group such as cyano, acyl, alkoxycarbonyl, nitroaryl, alkylsulfonyl, arylsulfonyl, fluorosulfonyl, and nitro, or
(2) when taken together with carbon atom to which they are attached G.sup.1 and G.sup.2 represent the non-metallic atoms needed to complete a substituted or unsubstituted acidic cyclic nucleus of the type used in merocyanine dyes such as 1,3-inandione; 1,3-cyclohexanedione; 5,5-dimethyl-1,3-cyclohexanedione; and 1,3-dioxan-4,6-dione; etc., or
(3) an acidic heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, such as
(a) a pyrazolinone nucleus such as 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one and 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one,
(b) an isoxazolinone nucleus such as 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one;
(c) an oxindole nucleus such as 1-alkyl-2,3-dihydro-2-oxindoles;
(d) a 2,4,6-triketohexahydropyrimidine nucleus such as barbituric acid or 2-thiobarbituric acid, as well as their derivatives such as those with 1-alkyl(e.g., 1-methyl, 1-ethyl, 1-n-propyl, 1-n-heptyl, etc.) or 1,3-dialkyl (e.g., 1,3-dimethyl, 1,3-diethyl, 1,3-di-n-propyl, 1,3-diisopropyl, 1,3-dicyclohexyl, 1,3-di(.beta.-methoxyethyl), etc.) or 1,3-diaryl (e.g., 1,3-diphenyl, 1,3-di(p-chlorophenyl), 1,3-di(p-ethoxycarbonylphenyl), etc.), or 1-aryl (e.g., 1-phenyl, 1-p-chlorophenyl, 1-p-ethoxycarbonylphenyl), etc.), or 1-alkyl-3-aryl (e.g., 1-ethyl-3-phenyl, 1-n-heptyl-3-phenyl, etc.);
(e) a 2-thio-2,4-thiazolidinedione nucleus such as rhodanine, 3-alkylrhodanines (e.g., 3-ethylrhodanine, 3-allylrhodanine, etc.), or 3-arylrhodanines (e.g., 3-phenylrhodanine etc.);
(f) a 2-thio-2,4-oxazolidinedione (2-thio-2,4(3H,5H)-oxazoledione) nucleus such as 3-ethyl-2-thio-2,4-oxazolidinedione;
(g) a thianaphthenone nucleus such as 3(2H)-thianaphthenone and 3(2H)-thianaphthenone-1,1-dioxide;
(h) a 2-thio-2,5-thiazolidinedione (2-thio-2,5(3H,4H)-thiazoledione) nucleus such as 3-ethyl-2-thio-2,5-thiazolidinedione;
(i) a 2,4-thiazolidinedione nucleus such as 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and 3-.alpha.-naphthyl-2,4-thiazolidinedione;
(j) a thiazolidinone nucleus such as 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 3-phenyl-4-thiazolidinone and 3-.alpha.-naphthyl-4-thiazolidinone;
(k) a 4-thiazolinone nucleus such as 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-ones, 2-diphenylamino-5-thiazolin-4-one;
(l) a 2-imino-2-oxazolin-4-one pseudohydantoin nucleus;
(m) a 2,4-imidazolidinedione(hydantoin)nucleus such as 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 3-phenyl-2,4-imidazolidinedione, 3-.alpha.-naphthyl-2,4-imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedi one, 1-ethyl-3-.alpha.-naphthyl-2,4-imidazolidinedione and 1,3-diphenyl-2,4-imidazolidinedione;
(n) a 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus such as 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidionedione, 3-phenyl-2-thio-2,4-imidazolidinedione, 3-.alpha.-naphthyl-2-thio-2,4-imidazolidinedione, 1,3-diethyl-2-thio-2,4-imidazolidinedione, 1-ethyl-3-phenyl-2-thio-2,4-imidazolidinedione, 1-ethyl-3-.alpha.-naphthyl-2-thio-2,4-imidazolidinedione and 1,3-diphenyl-2-thio-2,4-imidazolidinedione;
(o) a 2-imidazolin-5-one nucleus such as 2-n-propylmercapto-2-imidazolin-5-one;
(p) furan-5-one and
(q) a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom and 1 of said atoms being selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom;
X may be O, S, Se or NR in which R represents a substituted or unsubstituted alkyl, aryl, aralkyl, cycloalkyl, alkenyl or alkynyl and said substituents are selected from the group consisting of hydroxy, alkoxy; aryloxy or halogen;
R.sup.1 and R.sup.2 which may be the same or different, represent alkyl, aryl, --CL.sup.1 (.dbd.CL.sup.2 --CL.sup.3).sub.m .dbd.A.sup.1, --CL.sup.4 .dbd.CL.sup.5 (--CL.sup.6 .dbd.CL.sup.7).sub.n --A.sup.2 or R.sup.1 together with R.sup.4 or R.sup.2 together with R.sup.3 represent sufficient atoms to complete an alkylene bridge;
m and n may be zero, one or two;
L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, and L.sup.7 represent hydrogen, alkyl and aryl; L.sup.1 or L.sup.4 together with either R.sup.3 or R.sup.4 represent the atoms needed to complete a carbocyclic ring;
A.sup.1 represents a basic substituted or unsubstituted heterocyclic nucleus of the type used in cyanine dyes such as,
(a) an imidazole nucleus, 4-phenylimidazole;
(b) 3H-indole nucleus such as 3H-indole, 3,3-dimethyl-3H-indole, 3,3,5-trimethyl-3H-indole;
(c) a thiazole nucleus such as thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole;
(d) a benzothiazole nucleus such as benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 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-dimethyoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole and 6-hydroxybenzothiazole;
(e) a naphthothiazole nucleus such as naphtho1,2-d!thiazole,naphtho2,1-d!thiazole, naphtho2,3-d!thiazole, 5-methoxynaphtho2,1-d!thiazole, 5-ethoxynaphtho2,1-d!thiazole, 8-methoxynaphtho1,2-d!thiazole and 7-methoxynaphtho1,2-d!thiazole;
(f) a thianaphtheno-7',6',4,5-thiazole nucleus such as 4'-methoxythianaphtheno-7',6',4,5-thiazole;
(g) an oxazole nucleus such as 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole and 5-phenyloxazole;
(h) a benzoxazole nucleus such as benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole and 6-hydroxybenzoxazole;
(i) a naphthoxazole nucleus such as naphtho1,2!oxazole and naphtho2,1!oxazole;
(j) a selenazole nucleus such as 4-methylselenazole and 4-phenylselenazole;
(k) a benzoselenazole nucleus such as benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole and tetrahydrobenzoselenazole;
(l) a naphthoselenazole nucleus such as naphtho1,2-d!selenazole, naphtho2,1-d!selenazole;
(m) a thiazoline nucleus such as thiazoline and 4-methylthiazoline;
(n) a 2-quinoline nucleus such as quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline and 8-hydroxyquinoline;
(o) a 4-quinoline nucleus such as quinoline, 6-methoxyquinoline, 7-methylquinoline and 8-methylquinoline;
(p) a 1-isoquinoline nucleus such as isoquinoline and 3,4-dihydroisoquinoline;
(q) a benzimidazole nucleus such as 1,3-diethylbenzimidazole and 1-ethyl-3-phenylbenzimidazole;
(r) a 2-pyridine nucleus such as pyridine and 5-methylpyridine; and
(s) a 4-pyridine nucleus;
A.sup.2 may be the same as A.sup.1 and in addition may represent a substituted or unsubstituted aryl group (e.g., phenyl, naphthyl, anthryl) or a substituted or unsubstituted heterocyclic nucleus such as thiophene, benzob!thiophene, naphtho2,3-b!thiophene, furan, isobenzofuran, chromene, pyran, xanthene, pyrrole, 2H-pyrrole, pyrazole, indolizine, indoline, indole, 3H-indole, indazole, carbazole, pyrimidine, isothiazole, isoxazole, furazan, chroman, isochroman, 1,2,3,4-tetrahydroquinoline, 4H-pyrrolo 3,2,1-ij!quinoline, 1,2-dihydro-4H-pyrrolo3,2,1-ij!quinoline; 1,2,5,6-tetrahydro-4H-pyrrolo-3,2,1-ij!quinoline; 1H,5H-benzoij!quinolizine; 2,3-dihydro-1H,5H-benzoij!quinolizine; 2,3-dihydro-1H,5H-benzoij!quinolizine and 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine, 10,11-dihydro-9H-benzoa!xanthen-8-yl; 6,7-dihydro-5H-benzob!pyran-7-yl;
R.sub.3 represents hydrogen or R.sub.3 together with R.sup.2, L.sup.1 or L.sup.4 and the carbon atoms to which they are attached represent a 5 or 6 membered carbocyclic ring;
R.sub.4 may be the same as R.sub.3 when taken alone or together with R.sup.1, L.sup.1 or L.sup.4 ; except that
(A) R.sup.1 and R.sup.2 cannot both be methyl, phenyl or methyl and phenyl, and
(B) the substituents on A.sup.1 and A.sup.2 cannot result in a quaternary nitrogen.
As indicated hereinabove, G.sup.1 and G.sup.2 when taken together may contain a variety of different substituents such as alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkynyl, dialkylamino, diarylamino or diaralkylamino which may be further substituted by one or more hydroxy, alkoxy, or aryloxy groups or halogens, or various acid substituted alkyl or aryl groups such as carboxymethyl, 5-carboxypentyl, 2-sulfoethyl, 3-sulfatopropyl, 3-thiosulfatopropyl, 2-phosphonoethyl, 3-sulfobutyl, 4-sulfobutyl, 4-carboxyphenyl, 4-sulfophenyl, etc. A.sup.1 and A.sup.2 may contain a variety of different substituents including those listed above as possible substituents on nuclei represented by G.sup.1 and G.sup.2 taken together plus amino, alkylamino, arylamino, aralkylamino, alkoxy, aryloxy, and alkoxycarbonyl.
Unless stated otherwise, alkyl refers to aliphatic hydrocarbon groups of generally 1-20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, heptyl, dodecyl, octadecyl, etc.; aryl refers to aromatic ring groups of generally 6-20 carbon atoms such as phenyl, naphthyl, anthryl or to alkyl or aryl substituted aryl groups such as tolyl, ethylphenyl, biphenylyl, etc.; aralkyl refers to aryl substituted alkyl groups such as benzyl, phenethyl, etc.; cycloalkyl refers to saturated carbocyclic ring groups which may have alkyl, aryl or aralkyl substituents such as cyclopropyl, cyclopentyl, cyclohexyl, 5,5-dimethylcyclohexyl, etc.; alkoxy refers to alkyloxy groups where alkyl is as defined above, such as methoxy, ethoxy, isopropoxy, butoxy, etc.; aryloxy refers to analogous groups where aryl is as defined above, such as phenoxy, naphthoxy, etc.; acyl refers to alkyl, aryl, or aralkylcarbonyl groups such as acetyl, propionyl, butyryl, benzoyl, phenylacetyl, etc.; alkenyl refers to an aliphatic hydrocarbon group of generally 1-20 carbons, which may be further substituted by alkyl or aryl, and which has at least one double bond such as allyl, vinyl, 2-butenyl, etc.; alkynyl refers to an aliphatic hydrocarbon group of generally 1-10 carbons which may be further substituted by alkyl or aryl and which has at least one triple bond such as 2-propynyl, 2-butynyl, 3-butynyl, etc.; alkylene refers to a bivalent aliphatic hydrocarbon group of generally 1-10 carbons such as ethylene, trimethylene, neopentylene, etc.
When used in an electrophoretic migration imaging process, charge-bearing, electrically photosensitive particles formulated from the materials of the present invention are positioned between two spaced electrodes; preferably these particles are contained in an electrically insulating carrier such as an electrically insulating liquid or an electrically insulating, liquefiable matrix material, e.g., a thixotropic or a heat- and/or solvent-softenable material, which is positioned between the spaced electrodes. While so positioned between the spaced electrodes, the photosensitive particles are subjected to an electric field and exposed to a pattern of activating radiation. As a consequence, the charge-bearing, electrically photosensitive particles undergo a radiation-induced variation in their charge polarity and migrate to one or the other of the electrode surfaces to form on at least one of these electrodes an image pattern representing a positive-sense or negative-sense image of the original radiation exposure pattern.
BRIEF DESCRIPTION OF THE DRAWINGS
The FIGURE represents diagrammatically a typical imaging apparatus for carrying out the electrophoretic migration imaging process of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with one embodiment the present invention there is provided a group of materials which are useful in electrophoretic migration imaging processes. Said materials have the structure according to general Formula I wherein:
G.sup.1 and G.sup.2 represent cyano, acyl, alkoxycarbonyl, nitro aryl, alkylsulfonyl, arylsulfonyl, fluorosulfonyl, and nitro, or when taken together with the carbon atom to which they are attached, G.sup.1 and G.sup.2 represent the non-metallic atoms necessary to complete a substituted or unsubstituted nucleus selected from the group consisting of 1,3-indane-dione, 1,3-cyclohexane-dione, 5,5-dimethyl-1,3-cyclohexane-dione; 1,3-dioxane-4,6-dione, 2-isoxazolin-5-one, barbituric acid, thiobarbituric acid and said substituents are selected from the group consisting of alkyl and aryl;
R.sup.1 and R.sup.2 are as previously defined;
A.sup.1 represents a substituted and unsubstituted nucleus selected from the group consisting of thiazole, thiazolidine, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, 2-quinoline, 4-quinoline and 3H-indole;
A.sup.2 represents a substituted or unsubstituted alkyl or aryl group or a nucleus selected from the group consisting of thiazole, benzothiazole, naphthol1,2-d!thiazole, benzoxazole, benzoselenazole, 2-quinoline and 3,3-dimethylindolenine, thiophene, furan, pyran, pyrrole, pyrazole, indoline, indole, carbazole, 1,2,3,4-tetrahydroquinoline, and 2,3,7-tetrahydro-1H,5H-benzoij!quinolizine.
R.sup.3 represents hydrogen or together with R.sup.2, L.sup.1 or L.sup.4, and the carbon atoms to which they are attached, represent substituted or unsubstituted cyclopentene or cyclohexene and R.sup.4 is the same as R.sup.3 when taken alone or together with R.sup.1, L.sup.1 or L.sup.4 and said substituents are selected from the group consisting of alkyl or the halogens;
Said substituents G.sup.1 and G.sup.2 when taken together are selected from the group consisting of alkyl of 1-4 carbons, aryl of 1-14 carbons, aralkyl, cycloalkyl of 3-8 carbons, alkenyl, alkynyl, dialkylamino, diarylamino, or diaralkylamino which may be further substituted by hydroxy, alkoxy, or halogens or various acid substituted alkyl or aryl group such as carboxymethyl, 5-carboxypentyl, 2-sulfoethyl, 3-sulfatopropyl, 3-thiosulfatopropyl, 2-phosphonoethyl, 3-sulfobutyl, 4-sulfobutyl, 4-carboxyphenyl and 4-sulfophenyl; said substituents for A.sup.1 and A.sup.2 may be selected from a variety of different substituents including those listed above as substituents on nuclei represented by G.sup.1 and G.sup.2 taken together plus amino, alkylamino, arylamino, aralkylamino, alkoxy, aryloxy, and alkoxycarbonyl.
R.sup.3 represents hydrogen or together with R.sup.2, L.sup.1 or L.sup.4 and the carbon atoms to which they are attached, represent substituted or unsubstituted cyclopentene or substituted or unsubstituted cyclohexene and R.sup.4 is the same as R.sup.3 when taken alone or together with R.sup.1, L.sup.1 or L.sup.4 and said substituents may be an alkyl group or halogen.
In accordance with another embodiment of the present invention there is provided material within the scope of general Formula I which is useful in electrophoretic migration imaging processes such material having the following structure: ##STR3## wherein:
X represents O, S, and NR in which R is alkyl having 1-8 carbons, aryl having 6-14 carbons or aralkyl.
R.sup.1 and R.sup.2 which may be the same or different, represent alkyl of 1-4 carbon atoms, aryl of 6-14 carbon atoms, --CH(.dbd.CL.sup.2 --CH).sub.m .dbd.A.sup.1 or --CH.dbd.CH--A.sup.2 wherein m is zero or one, L.sup.2 is hydrogen, alkyl of 1-4 carbon atoms, or aryl of 6-14 carbon atoms, A.sup.1 represents benzoxazole, benzothiazole, naphtho1,2-d!thiazole, 2-quinoline or 4-quinoline, and A.sup.2 represents furan, pyran, pyrrole, pyrazole, indoline, carbazole; 1,2,3,4-tetrahydroquinoline; 1,2,5,6-tetrahydro-4H-pyrrole3,2,1-ij!quinoline; 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine; 10,11-dihydro-9H-benzoa!xanthen-8-yl; 6,7-dihydro-5H-benzob!pyran-7-yl; anthryl, alkoxy having 1-4 carbon atoms, aryl having one or more substituents selected from secondary amino groups such as dialkylamino, diarylamino, bis(alkoxycarbonyl)amino, diaralkylamino and pyrrolidino.
In accordance with another embodiment of the present invention, there is provided materials within the scope of general Formula I which are useful in electrophoretic migration imaging processes, said materials having the following structure: ##STR4## wherein
R.sub.2 represents --CH(.dbd.CL.sup.2 --CH).sub.m .dbd.A.sup.1, CH.dbd.CH(--CH.dbd.CH).sub.n --A.sup.2, in which L.sup.2 represents hydrogen or phenyl; m and n represent 0 or 1; A.sup.1 and A.sup.2 represent anthryl, naphthyl, aryl having one or more substituents selected from dialkylamino and alkoxy, pyran, 1,2,5,6-tetrahydro-4H-pyrrolo3,2,1-i!-quinoline and 2,3,6,7-tetrahydro-1H,5H-benzoij!quinoline.
In accordance with yet another embodiment of the present invention there is provided materials within the scope of general Formula I which are useful in electrophoretic migration imaging processes. Such materials have the structure: ##STR5## wherein
R.sup.1 and R.sup.2 which may be the same or different, represent CL.sup.1 .dbd.CH--CH.dbd.A.sup.1, CH.dbd.CL.sup.4 .dbd.CH--A.sup.2 or R.sup.1 taken together with R.sup.4 or R.sup.2 taken together with R.sup.3 may complete an unsubstituted cyclopentene or cyclohexene ring except that both R.sup.1 and R.sup.4 and R.sup.2 and R.sup.3 cannot complete an unsubstituted cyclopentene or cyclohexene ring; L.sup.1 or L.sup.4 when taken together with R.sup.3 or R.sup.4 represent the atoms needed to form a cyclopentene or cyclohexene; A.sup.1 may represent benzoxazole and A.sup.2 may represent a dialkylaminophenyl or a 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine.
In accordance with yet another embodiment of the present invention there is provided materials within the scope of general Formula I which are useful in electrophoretic migration imaging processes. Such materials have the formula: ##STR6## wherein
G.sup.1 and G.sup.2 taken together with the carbon atom to which they are attached represent the non-metallic atoms necessary to complete a substituted or unsubstituted nucleus selected from the group consisting of 1,3-indanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxan-4,6-dione, 2-isoxazolin-5-one, 2-thiobarbituric acid, and barbituric acid and said substituents are selected from the group consisting of cyano, methyl, ethyl and phenyl;
R.sup.1 and R.sup.2 represent methyl, phenyl, --CH.dbd.(CH--CH).sub.m .dbd.A.sup.1 ; or --CH.dbd.CH--A.sup.2 wherein
m is 0 or 1;
A.sup.1 may represent benzoxazole, benzothiazole, naphtho1,2-d!thiazole, 3H-indole and 2-quinoline and A.sup.2 may represent dialkylaminophenyl where alkyl consists of 1-4 carbons, alkoxyphenyl where alkoxy consists of 1-4 carbons, 4-dialkylamino-2-alkoxyphenyl, furan and 2,3,6,7-tetrahydro-1H,5H-benzoij!quinoline.
In general the materials of Formula I which have been found to be electrophotosensitive tend to exhibit a maximum absorption wavelength, .lambda.max, within the range of from about 420 to about 750 nm. A variety of different materials within the class defined by Formula I have been tested and found to exhibit useful levels of electrical photosensitivity in electrophoretic migration imaging processes.
A partial listing of representative such materials is included herein in Tables I through XI.
The materials described by general Formula I may be prepared by the various procedures. The procedures disclosed in U.S. Pat. No. 2,965,486 to Brooker et al., issued Dec. 20, 1960 may be used to prepare any of the compounds falling within the scope of general Formula I.
As indicated hereinabove, the electrically photosensitive material described herein is useful in the preparation of the electrically photosensitive imaging particles used in electrophoretic migration imaging processes. In general, electrically photosensitive particles useful in such processes have an average particle size within the range of from about 0.01 micron to about 20 microns, preferably from about 0.01 to about 5 microns. Typically, these particles are composed of one or more colorant materials such as the colorant materials described in the present invention. However, these electrically photosensitive particles may also contain various nonphotosensitive materials such as electrically insulating polymers, charge control agents, various organic and inorganic fillers, as well as various additional dyes or pigment materials to change or enhance various colorant and physical properties of the electrically photosensitive particle. In addition, such electrically photosensitive particles may contain other photosensitive materials such as various sensitizing dyes and/or chemical sensitizers to alter or enhance their response characteristics to activating radiation.
When used in an electrophoretic migration imaging process in accord with the present invention, the electrically photosensitive material described in Tables I through XI, hereinabove, are typically positioned in particulate form, between two or more spaced electrodes, one or both of which typically being transparent to radiation to which the electrically photosensitive material is light-sensitive, i.e., activating radiation. Although the electrically photosensitive material, in particulate form, may be dispersed simply as a dry powder between two spaced electrodes and then subjected to a typical electrophoretic migration imaging operation such as that described in U.S. Pat. No. 2,758,939 by Sugarman, it is more typical to disperse the electrically photosensitive particulate material in an electrically insulating carrier, such as an electrically insulating liquid, or an electrically insulating, liquefiable matrix material, such as a heat- and/or solvent-softenable polymeric material or a thixotropic polymeric material. Typically, when one employs such a dispersion of electrically photosensitive particulate material and electrically insulating carrier material between the spaced electrodes of an electrophoretic migration imaging system, it is conventional to employ from about 0.05 part to about 2.0 parts of electrically photosensitive particulate material for each 10 parts by weight of electrically insulating carrier material.
As indicated above, when the electrically photosensitive particles used in the present invention are dispersed in an electrically insulating carrier material, such carrier material may assume a variety of physical forms and may be selected from a variety of different materials. For example the carrier material may be a matrix of an electrically insulating, normally solid polymeric material capable of being softened or liquefied upon application of heat, solvent, and/or pressure so that the electrically photosensitive particulate material dispersed therein can migrate through the matrix. In another, more typical embodiment of the invention, the carrier material can comprise an electrically insulating liquid such as decane, paraffin, Sohio Oderless Solvent 3440 (a kerosene fraction marketed by the Standard Oil Company, Ohio), various isoparaffinic hydrocarbon liquids such as those sold under the trademark Isopar G by Exxon Corporation and having a boiling point in the range of 145.degree. C. to 186.degree. C., various halogenated hydrocarbons such as carbon tetrachloride, trichloromonofluoromethane, and the like, various alkylated aromatic hydrocarbon liquids such as the alkylated benzenes, for example, xylenes, and other alkylated aromatic hydrocarbons such as are described in U.S. Pat. No. 2,899,335. An example of one such useful alkylated aromatic hydrocarbon liquid which is commercially available is Solvesso 100 made by Exxon Corporation. Solvesso 100 has a boiling point in the range of about 157.degree. C. to about 177.degree. C. and is composed of 9 percent dialkyl benzenes, 37 percent trialkyl benzenes, and 4 percent aliphatics. Typically, whether solid or liquid at normal room temperatures, i.e., about 22.degree. C., the electrically insulating carrier material used in the present invention is a material having a resistivity greater than about 10.sup.9 ohm-cm, preferably greater than about 10.sup.12 ohm-cm. When the electrically photosensitive particles formed from the materials of the present invention are incorporated in a carrier material, such as one of the above-described electrically insulating liquids, various other addenda may also be incorporated in the resultant imaging suspension. For example, various charge control agents may be incorporated in such a suspension to improve the uniformity of charge polarity of the electrically photosensitive particles dispersed in the liquid suspension. Such charge control agents are well known in the field of liquid electrographic developer compositions where they are employed for purposes substantially similar to that described herein. Thus, extensive discussion of the materials herein is deemed unnecessary. These materials are typically polymeric materials incorporated by admixture thereof into the liquid carrier vehicle of the suspension. In addition to, and possibly related to, the aforementioned enhancement of uniform charge polarity, it has been found that the charge control agents often provide more stable suspensions, i.e., suspensions which exhibit substantially less settling out of the dispersed photosensitive particles.
In addition to the foregoing charge control agent materials, various polymeric binder materials such as various natural, semi-synthetic or synthetic resins, may be dispersed or dissolved in the electrically insulating carrier to serve as a fixing material for the final photosensitive particle image formed on one of the spaced electrodes used in electrophoretic migration imaging systems. Here again, the use of such fixing addenda is conventional and well known in the closely related art of liquid electrographic developer compositions so that extended discussion thereof is unnecessary herein.
The process of the present invention will be described in more detail with reference to the accompanying drawing, FIG. 1, which illustrates a typical apparatus which employs the electrophoretic migration imaging process of the invention.
FIG. 1 shows a transparent electrode 1 supported by two rubber drive rollers 10 capable of imparting a translating motion to electrode 1 in the direction of the arrow. Electrode 1 may be composed of a layer of optically transparent material, such as glass or an electrically insulating, transparent polymeric support such as polyethylene terephthalate, covered with a thin, optically transparent, conductive layer such as tin oxide, indium oxide, nickel, and the like. Optionally, depending upon the particular type of electrophoretic migration imaging process desired, the surface of electrode 1 may bear a "dark charge exchange" material, such as a solid solution of an electrically insulating polymer and 2,4,7,trinitro-9-fluorenone as described by Groner in U.S. Pat. No. 3,976,485 issued Aug. 24, 1976.
Spaced opposite electrode 1 and in pressure contact therewith is a second electrode 5, an idler roller which serves as a counter electrode to electrode 1 for producing the electric field used in the electrophoretic migration imaging process. Typically, electrode 5 has on the surface thereof a thin, electrically insulating layer 6. Electrode 5 is connected to one side of the power source 15 by switch 7. The opposite side of the power source 15 is connected to electrode 1 so that as an exposure takes place, switch 7 is closed and an electric field is applied to the electrically photosensitive particulate material 4 which is positioned between electrodes 1 and 5. Typically electrically photosensitive particulate material 4 is dispersed in an electrically insulating carrier material such as described hereinabove.
The electrically photosensitive particulate material 4 may be positioned between electrodes 1 and 5 by applying material 4 to either or both of the surfaces of electrodes 1 and 5 prior to the imaging process or by injecting electrically photosensitive imaging material 4 between electrodes 1 and 5 during the electrophoretic migration imaging process.
As shown in FIG. 1, exposure of electrically photosensitive particulate material 4 takes place by use of an exposure system consisting of light source 8, an original image 11 to be reproduced, such as a photographic transparency, a lens system 12, and any necessary or desirable radiation filters 13, such as color filters, whereby electrically photosensitive material 4 is irradiated with a pattern of activating radiation corresponding to original image 11. Although the electrophoretic migration imaging system represented in FIG. 1 shows electrode 1 to be transparent to activating radiation from light source 8, it is possible to irradiate electrically photosensitive particulate material 4 in the nip 21 between electrodes 1 and 5 without either of electrodes 1 or 5 being transparent. In such a system, although not shown in FIG. 1, the exposure source 8 and lens system 12 is arranged so that image material 4 is exposed in the nip or gap 21 between electrodes 1 and 5.
As shown in FIG. 1, electrode 5 is a roller electrode having a conductive core 14 connected to power source 15. The core is in turn covered with a layer of insulating material 6, for example, baryta paper. Insulating material 6 serves to prevent or at least substantially reduce the capability of electrically photosensitive particulate material 4 to undergo a radiation induced charge alteration upon interaction with electrode 5. Hence, the term "blocking electrode" may be used, as is conventional in the art of electrophoretic migration imaging, to refer to electrode 5.
Although electrode 5 is shown as a roller electrode and electrode 1 is shown as essentially a translatable, flat plate electrode in FIG. 1, either or both of these electrodes may assume a variety of different shapes such as a web electrode, rotating drum electrode, plate electrode, and the like as is well known in the field of electrophoretic migration imaging. In general, during a typical electrophoretic migration imaging process within electrically photosensitive material 4 is dispersed in an electrically insulating, liquid carrier, electrodes 1 and 5 are spaced such that they are in pressure contact or very close to one another during the electrophoretic migration imaging process, e.g., less than 50 microns apart. However, where electrically photosensitive particulate material 4 is dispersed simply in an air gap between electrodes 1 and 5 or in a carrier such as a layer of heat-softenable or other liquefiable material coated as a separate layer on electrode 1 and/or 5, these electrodes may be spaced more than 50 microns apart during the imaging process.
The strength of the electric field imposed between electrodes 1 and 5 during the electrophoretic migration imaging process of the present invention may vary considerably; however, it has generally been found that optimum image density and resolution are obtained by increasing the field strength to as high a level as possible without causing electrical breakdown of the carrier medium in the electrode gap. For example, when electrically insulating liquids such as isoparaffinic hydrocarbons are used as the carrier in the imaging apparatus of FIG. 1, the applied voltage across electrodes 1 and 5 typically is within the range of from about 100 volts to about 4 kilovolts or higher.
As explained hereinabove, image formation occurs in electrophoretic migration imaging processes as the result of the combined action of activating radiation and electric field on the electrically photosensitive particulate material 4 disposed between electrodes 1 and 5 in the attached drawing. Typically, for best results, field application and exposure to activating radiation occur concurrently. However, as would be expected, by appropriate selection of various process parameters such as field strength, activating radiation intensity, incorporation of suitable light sensitive addenda in or together with the electrically photosensitive particles formed from the material of Formula I, e.g., by incorporation of a persistent photoconductive material, and the like, it is possible to alter the timing of the exposure and field application events so that one may use sequential exposure and field application events rather than convurrent field application and exposure events.
When disposed between imaging electrodes 1 and 5 of FIG. 1, electrically photosensitive particulate material 4 exhibits an electrostatic charge polarity, either as a result of triboelectric interaction of the particles or as a result of the particles interacting with the carrier material in which they are dispersed, for example, an electrically insulating liquid, such as occurs in conventional liquid electrographic developing compositions composed of toner particles which acquire a charge upon being dispersed in an electrically insulating carrier liquid.
Image discrimination occurs in the electrophoretic migration imaging process of the present invention as a result of the combined application of electric field and activating radiation on the electrically photosensitive particulate material dispersed between electrodes 1 and 5 of the apparatus shown in FIG. 1. That is, in a typical imaging operation, upon application of an electric field between electrodes 1 and 5, the particles 4 of charge-bearing, electrically photosensitive material are attracted in the dark to either electrodes 1 or 5, depending upon which of these electrodes has a polarity opposite to that of the original charge polarity acquired by the electrically photosensitive particles. And, upon exposing particles 4 to activating electromagnetic radiation, it is theorized that there occurs neutralization or reversal of the charge polarity associated with either the exposed or unexposed particles. In typical electrophoretic migration imaging systems wherein electrode 1 bears a conductive surface, the exposed, electrically photosensitive particles 4, upon coming into electrical contact with such conductive surface, undergo an alteration (usually a reversal) of their original charge polarity as a result of the combined application of electric field and activating radiation. Alternatively, in the case of photoimmobilized electrophoretic recording (PIER), wherein the surface of electrode 1 bears a dark charge exchange material as described by Groner in aforementioned U.S. Pat. No. 3,976,485, one obtains reversal of the charge polarity of the unexposed particles, while maintaining the original charge polarity of the exposed electrically photosensitive particles, as these particles come into electrical contact with the dark charge exchange surface of electrode 1. In any case, upon the application of electric field and activating radiation to electrically photosensitive particulate material 4 disposed between electrodes 1 and 5 of the apparatus shown in FIG. 1, one can effectively obtain image discrimination so that an image pattern is formed by the electrically photosensitive particles which corresponds to the original pattern of activating radiation. Typically, using the apparatus shown in FIG. 1, one obtains a visible image on the surface of electrode 1 and a complementary image pattern on the surface of electrode 5.
Subsequent to the application of the electric field and exposure to activating radiation, the images which are formed on the surface of electrodes 1 and/or 5 of the apparatus shown in FIG. 1 may be temporarily or permanently fixed to these electrodes or may be transferred to a final image receiving element. Fixing of the final particle image can be effected by various techniques, for example, by applying a resinous coating over the surface of the image bearing substrate. For example, if electrically photosensitive particles 4 are dispersed in a liquid carrier between electrodes 1 and 5, one may fix the image or images formed on the surface of electrodes 1 and/or 5 by incorporating a polymeric binder material in the carrier liquid. Many such binders (which are well known for use in liquid electrophotographic liquid developers) are known to acquire a change polarity upon being admixed in a carrier liquid and therefore will, themselves, electrophoretically migrate to the surface of one or the other of the electrodes. Alternatively, a coating of a resinous binder (which has been admixed in the carrier liquid), may be formed on the surfaces of electrodes 1 and/or 5 upon evaporation of the liquid carrier.
The electrically photosensitive colorant material of Formula I may be used to form monochrome images, or the material may be admixed with other electrically photosensitive material of proper color and photosensitivity and used to form polychrome images. Said electrically photosensitive colorant material of the present invention also may be used as a sensitizer for other electrophotosensitive material in the formation of monochrome images. When admixed with other electrically photosensitive materials, selectively the photosensitive material of the present invention may act as a sensitizer and/or as an electrically photosensitive particle. Many of the electrically photosensitive colorant materials having Formula I have especially useful hues which make them particularly suited for use in polychrome imaging processes which employ a mixture of two or more differently colored electrically photosensitive particles. When such a mixture of multicolored electrically photosensitive particles is formed, for example, in an electrically insulating carrier liquid, this liquid mixture of particulate material exhibits a black coloration. Preferably, the specific cyan, magenta, and yellow particles selected for use in such a polychrome imaging process are chosen so that their spectral response curves do not appreciably overlap whereby color separation and subtractive multicolor image reproduction can be achieved.
The following examples illustrate the utility of the Formula I materials in electrophoretic migration imaging processes.
EXAMPLES 1-82
Imaging Apparatus
An imaging apparatus was used in each of the following examples to carry out the electrophoretic migration imaging process described herein. This apparatus was a device of the type illustrated in FIG. 1. In this apparatus, a translating film based having a conductive coating of 0.1 optical density cermet (Cr.SiO) served as electrode 1 and was in pressure contact with a 10 centimeter diameter aluminum roller 14 covered with dielectric paper coated with poly(vinyl butyral) resin which served as electrode 5. Plate 1 was supported by two 2.8 cm. diameter rubber drive rollers 10 positioned beneath film plate 1 such that a 2.5 cm. opening, symmetric with the axis of the aluminum roller 14, existed to allow exposure of electrically photosensitive particles 4 to activating radiation. The original transparency 11 to be reproduced was taped to the back side of film plate 1.
The original transparency to be reproduced consisted of adjacent strips of clear (W0), red (W29), green (W61) and blue (W47B) filters. The light source consisted of a Kodak Ektagraphic AV434A Carousel Projector with a 1000 watt Xenon Lamp. The light was modulated with a Kodak No. 5 flexible M-carbon eleven step 0.3 neutral density step tablet. The residence time in the action zone was 10 milliseconds. The log of the light intensity (Log I) was as follows:
The voltage between the electrode 5 and film plate 1 was about 2 kv. Film plate 1 was negative polarity in the case where electrically photosensitive particulate material 4 carried a positive electrostatic charge, and film plate 1 was positive in the case where electrically photosensitive electrostatically charged particles were negatively charged. The translational speed of film plate 1 was about 25 cm. per second. In the following examples, image formation occurs on the surfaces of film plate 1 and electrode 5 after simultaneous application of light exposure and electric field to electrically photosensitive material evaluated for use as electrically photosensitive particulate material 4 was admixed with a liquid carrier as described below to form a liquid imaging dispersion which was placed in nip 21 between the electrodes 1 and 5. If the material being evaluated for use as material 4 possessed a useful level of electrical photosensitivity, one obtained a negative-appearing image reproduction of original 11 on electrode 5 and a complementary image on electrode 1.
Imaging Dispersion Preparation
Imaging dispersions were prepared to evaluate each of the materials in Tables I through XI. The dispersions were prepared by first making a stock solution of the following components. The stock solution was prepared simply by combining the components.
A 5 g. aliquot of the stock solution was combined in a closed container with 0.045 g. of the Table I material to be tested and 12 g. of Hamber 440 stainless steel balls. The preparation was then milled for three hours on a paint shaker.
Each of the 82 materials described in Table I through XI were tested according to the just outlined procedures. Each of such materials were found to be electrophotosensitive as evidenced by obtaining a negative appearing image of the original on one electrode and a complementary image on the other electrode. Materials 1, 2, 3, 5, 7, 9, 11, 12, 13, 14, 20, 21, 25, 26, 27, 28, 30, 32, 33, 34, 35, 36, 37, 38, 40, 41, 42, 43, 44, 46, 49, 50, 51, 53, 55, 56, 59, 61, 63, 65, 69, 71, 73, 74, 75, 77, 78 and 80 provide images having good to excellent quality. Image quality was determined visually having regard to minimum and maximum densities, speed and color saturation.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims
We claim:
1. An electrophoretic migration imaging process which comprises subjecting an electrically photosensitive colorant material positioned between at least two electrodes to an applied electric field and exposing said materials to an image pattern of radiation to which the material is photosensitive, thereby obtaining image formation on at least one of said electrodes, the improvement which comprises using as at least a portion of said material, an electrically photosensitive material having the following structure: ##STR128## wherein, X represents O, S, Se or NR in which R represents a substituted or unsubstituted alkyl, aryl, aralkyl, cycloalkyl, alkenyl or alkynyl and said substituents are selected from the group consisting of hydroxy, alkoxy, aryloxy or halogen; G.sup.1 g.sup.2, which may be the same or different represent an electron withdrawing group or when taken together with the carbon atom to which G.sup.1 and G.sup.2 are attached represent the nonmetallic atoms needed to complete a substituted or unsubstituted acidic heterocyclic nucleus selected from the group consisting of 1,3-indandione, pyrazolinone, isoxazolinone, oxindole, 2,4,6-triketohexahydropyrimidine, 2-thio-2,4-thiazolidinedione, 2,-thio-2,4-oxazolidinedione, thianaphthenone, 2-thio-2,5-thiazolidinedione, 2,4-thiazolidinedione, thiazolidinone, 4-thiazolinone, 2-amino-2-oxazolin-4-one; 2,4-imidazolidinedione; 2-thio-2,4-imidazolidinedione; 2-imidazolin-5-one; furan-5-one; and a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom and 1 of said atoms being selected from the group consisting of N, O and S. R.sup.1 and R.sup.2, which may be the same or different, represent alkyl, aryl, --CL.sup.1 (.dbd.CL.sup.2 CL.sup.3).sub.m .dbd.A.sup.1 or --CL.sup.4 .dbd.CL.sup.5 (--CL.sup.6 .dbd.CL.sup.7)--.sub.n A.sup.2 or R.sup.1 together with R.sup.4 or R.sup.2 together with R.sup.3 represent sufficient atoms to complete an alkylene bridge; m and n represents 0, 1 or 2; L.sup.1, l.sup.2, l.sup.3, l.sup.4, l.sup.5, l.sup.6, and L.sup.7 which may be the same or different, represent hydrogen, alkyl and aryl; L.sup.1 or L.sup.4 together with R.sup.3 or R.sup.4 represent the atoms needed to complete a carbocyclic ring; A.sup.1 represents a basic substituted or unsubstituted nucleus selected from the group consisting of imidazole, 3H-indole, thiazole, benzothiazole, naphthothiazole, thianaphtheno-7',6',-4,5-thiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, thiazoline, 2-quinoline, 4-quinoline, 1-isoquinoline, benzimidazole, 2-pyridine and 4-pyridine; A.sup.2 may be the same as A.sup.1 and in addition represent substituted and unsubstituted nucleus selected from the group consisting of aryl, thiophene, benzob!thiophene, naphtho2,3-b!thiophene, furan, isobenzofuran, chromene, pyran, xanthene, pyrrole, 2H-pyrrole, pyrazole, indolizine, indoline, indole, 3H-indole, indazole, carbazole, perimidine, isothiazole, isoxazole, furazan, chroman, isochroman, 1,2,3,4-tetrahydroquinoline, 4H-pyrrolo3,2,1-ij!quinoline, 1,2-dihydro-4H-pyrrolo3,2,1-ij!quinoline, 1,2,5,6-tetrahydro-4H-pyrrolo3,2,1-ij!quinoline, 1H,5H-benzoij!quinolizine, 2,3-dihydro-1H,5H-benzoij!quinolizine, 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine, 10,11-dihydro-9H-benzoa!xanthen-8-yl and 6,7-dihydro-5H-benzoa!pyran-7-yl; R.sup.3 represents hydrogen, or R.sup.3 together with R.sup.2, L.sup.1 or L.sup.4 and the carbon atoms to which they are attached, represent a substituted or unsubstituted 5 or 6-member carbocyclic ring; R.sup.4 may be the same as R.sup.3 when taken alone or together with R.sup.1, L.sup.1 or L.sup.4, and said substituents for G.sup.1 and G.sup.2 when taken together are selected from the group consisting of substituted or unsubstituted alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkynyl, dialkylamino, diarylamino and diaralkylamino and said substituents for A.sup.1 and A.sup.2 are the same as for G.sup.1 and G.sup.2 taken together plus amino, alkylamino, arylamino, aroalkylamino, alkoxy, aryloxy and alkoxy carbonyl; except that (i) R.sup.1 and R.sup.2 cannot both be methyl, phenyl or methyl and phenyl and, (ii) the substituents on A.sup.1 and A.sup.2 cannot result in a quaternary nitrogen.
2. A process according to claim 1 wherein G.sup.1 and G.sup.2 represent cyano, acyl, alkoxycarbonyl, alkylsulfur, arylsulfur arylsulfonyl, fluorosulfonyl, and nitro, or when taken together with the carbon atom to which they are attached represent the non-metallic atoms necessary to complete a substituted or unsubstituted nucleus selected from the group consisting of 1,3-indanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione; 1,3-dioxane-4,6-dione, and 2-isoxazolin-5-one, barbituric acid, thiobarbituric acid and said substituents are selected from the group consisting of alkyl and aryl.
3. A process according to claim 2 wherein A.sup.1 represents a substituted or unsubstituted nucleus selected from the group consisting of thiazole, thiazolidine, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, 2-quinoline 4-quinoline and 3H-indole.
4. A process according to claim 3 wherein A.sup.2 represents a substituted or unsubstituted nucleus selected from the group consisting of thiazole, benzothiazole, naphtho1,2-d!thiazole, benzoxazole, benzoselenazole, 2-quinoline, 4-quinoline and 3,3-dimethyl-indolenine, thiazole, thiophene, furan, pyran, pyrrole, pyrazole, indoline, indole, carbazole, 1,2,3,4-tetrahydroquinoline, and 2,3,7-tetrahydro-1H,5H-benzoij!quinolizine.
5. A process according to claim 4 wherein R.sup.3 represents hydrogen or together with R.sup.2, L.sup.1 or L.sup.4 and the carbon atoms to which they are attached, represent substituted or unsubstituted cyclopentene or substituted and unsubstituted cyclohexene and R.sub.4 is the same as R.sub.3 when taken alone or together with R.sup.1, L.sup.1 or L.sup.4.
6. A process according to claim 1 wherein said material has the structure ##STR129## wherein: X represents O, S, and NR in which R is alkyl having 1 to 8 carbon atoms, aryl having 6 to 14 carbon atoms or aralkyl; R.sup.1 and R.sup.2 which may be the same or different which represents alkyl or 1-4 carbon atoms, aryl of 6-14 carbon atoms, CH(.dbd.CL.sup.2 --CH).sub.m .dbd.A.sup.1 or --CH.dbd.CH--A.sup.2 wherein m is zero or one, L.sup.2 is hydrogen, alkyl of 1-4 carbon atoms, or aryl of 6-14 carbon atoms, A.sup.1 represents benzoxazole, benzothiazole, naphtho1,2-d!thiazole, 2-quinoline or 4-quinoline and A.sup.2 represents furan, pyran, pyrrole, pyrazole, indoline, carbazole; 1,2,3,4-tetrahydroquinoline; 1,2,5,6-tetrahydro-4H-pyrrolo3,2,1-ij!quinoline; 2,3,6,7-tetrahydro-1H,5H-benzoij!quinoline; 10,11-dihydro-9H-benzoa!xanthen-8-yl; 6,7-dihydro-5H-benzob!pyran-7-yl; anthryl, alkoxy having 1-4 carbon atoms, aryl having one or more substituents selected from secondary amino groups dialkylamino, diarylamino, bis(akoxycarbonyl)amino, diaralkylamino and pyrrolidino. R.sup.1 and R.sup.2, which may be the same or different represent methyl, phenyl, --CH.dbd.A.sup.1 or --CH.dbd.CH--A.sup.2, wherein A.sup.1 and A.sup.2 may be the same or different represent dimethylaminophenyl, methoxyphenyl, dipropylaminophenyl, naphthyl, naphto1,2-d!thiazole, diethylamino(methoxy)phenyl, diphenylaminophenyl, diethylaminophenyl.
7. A process according to claim 1 wherein said material has the structure ##STR130## wherein R.sup.2 represents --CH(.dbd.CL.sup.2 --CH).sub.m .dbd.A.sup.1, CH.dbd.CH(--CH.dbd.CH).sub.n --A.sup.2, in which L.sup.2 represents hydrogen or phenyl; m and n represent 0 or 1; A.sup.1 and A.sup.2 represent anthryl, naphthyl, aryl having one or more substituents selected from dialkylamino and alkoxy, pyran, 1,2,5,6-tetrahydro-4H-pyrrolo3,2,1-ij!quinoline and 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine.
8. A process according to claim 1 wherein said material has the structure ##STR131## wherein R.sup.1 and R.sup.2, which may be the same or different, represent CL.sup.1 .dbd.CH--CH.dbd.A.sup.1, --CH.dbd.A.sup.1, --CL.sup.4 .dbd.CH--A.sup.2 or R.sup.1 taken together with R.sup.4 or R.sup.2 taken together with R.sup.3 may complete an unsubstituted cyclopentene or cyclohexene ring except that both R.sup.1 and R.sup.4 and R.sup.2 and R.sup.3 cannot complete an unsubstituted cyclopentene or cyclohexene ring; L.sup.1 or L.sup.4 when taken together with R.sup.3 or R.sup.4 represent the atoms needed for a cyclopentene or cyclohexene ring; A.sup.1 represents benzoxazole and A.sup.2 represent dialkylaminophenyl or 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine.
9. A process according to claim 1 wherein said material has the structure ##STR132## wherein G.sup.1 and G.sup.2 taken together with the carbon atom to which they are attached represent the non-metallic atoms necessary to complete a substituted or unsubstituted nucleus selected from the group consisting of barbituric acid, 1,3-indanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione; 1,3-dioxan-4,6-dione, 2-isoxazolin-5-one; 2-thiabarbituric acid and barbituric acid, and said substituents are selected from the group consisting of cyano, methyl, ethyl and phenyl; R.sup.1 and R.sup.2 represent methyl, phenyl, --CH.dbd.(CH--CH).sub.m .dbd.A.sup.1 ; or --CH.dbd.CH--A.sup.2 wherein m is o or 1; A.sup.1 represents benzoxazole, benzothiazole, naphtho1,2-d!thiazole, 3H-indole and 2-quinoline and A.sup.2 represent dialkylaminophenyl where alkyl consists of 1-4 carbons, alkoxyphenyl where alkoxy consists of 1-4 carbons, 4-dialkylamino-2-alkoxyphenyl, furan and 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine.
10. A process according to claim 1 wherein said material is selected from the group consisting of ##STR133##
11. An electrophoretic migration imaging dispersion comprising an electrically insulating carrier, a charge control agent and an electrically photosensitive colorant material having the structure: ##STR134## wherein, X represents O, S, Se or NR in which R represents a substituted or unsubstituted alkyl, aryl, aralkyl, cycloalkyl, alkenyl or alkynyl and said substituents are selected from the group consisting of hydroxy, alkoxy, aryloxy or halogen; G.sup.1 and G.sup.2, which may be the same or different, represent an electron withdrawing group or when taken together with the carbon atom to which G.sup.1 and G.sup.2 are attached represent the nonmetallic atoms needed to complete a substituted or unsubstituted acidic heterocyclic nucleus selected from the group consisting of 1,3-indandione, pyrazolinone, isoxazolinone, oxindole, 2,4,6-triketohexahydropyrimidine, 2-thio-2,4-thiazolidinedione, 2-thio-2,4-oxazolidinedione, thianaphthenone, 2-thio-2,5-thiazolidinedione, 2,4-thiazolidinedione, thiazolidinone, 4-thiazolinone, 2-amino-2-oxazolin-4-one; 2,4-imidazolidinedione; 2-thio-2,4-imidazolidinedione; 2-imidazolin-5-one; furan-5-one; and a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom and 1 of said atoms being selected from the group consisting of N, O and S. R.sup.1 and R.sup.2, which may be the same or different, represent alkyl, aryl, --CL.sup.1 (.dbd.CL.sup.2 CL.sup.3).dbd..sub.m A.sup.1 or --CL.sup.4 .dbd.CL.sup.5 (--CL.sup.6 .dbd.CL.sup.7)--.sub.n A.sup.2 or R.sup.1 together with R.sup.4 or R.sup.2 together with R.sup.3 represent sufficient atoms to complete an alkylene bridge; m and n represent 0, 1 or 2; L.sup.1, l.sup.2, l.sup.3, l.sup.4, l.sup.5, l.sup.6, and L.sup.7, which may be the same or different represent hydrogen, alkyl and aryl; L.sup.1 or L.sup.4 together with R.sup.3 or R.sup.4 represent the atoms needed to complete a carbocyclic ring; A.sup.1 represents a basic substituted or unsubstituted nucleus selected from the group consisting of imidazole, 3H-indole, thiazole, benzothiazole, naphthothiazole, thianaphtheno-7',6',-4,5-thiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, thiazoline, 2-quinoline, 4-quinoline, 1-isoquinoline, benzimidazole, 2-pyridine and 4-pyridine; A.sup.2 may be the same as A.sup.1 and in addition represents a substituted and unsubstituted nucleus selected from the group consisting of aryl, thiophene, benzob!thiophene, naphtho2,3-b!thiophene, furan, isobenzofuran, chromene, pyran, xanthene, pyrrole, 2H-pyrrole, pyrazole, indolizine, indoline, indole, 3H-indole, indazole, carbazole, perimidine, isothiazole, isoxazole, furazan, chroman, isochroman, 1,2,3,4-tetrahydroquinoline, 4H-pyrrolo3,2,1-ij!quinoline, 1,2-dihydro-4H-pyrrolo3,2,1-ij!quinoline, 1,2,5,6-tetrahydro-4H-pyrrolo3,2,1-ij!quinoline, 1H,5H-benzoij!quinolizine, 2,3-dihydro-1H,5H-benzoij!quinolizine, 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine, 10,11-dihydro-9H-benzoa!xanthen-8-yl and 6,7-dihydro-5H-benzoa!pyran-7-yl; R.sup.3 represents hydrogen, or R.sup.3 together with R.sup.2, L.sup.1 or L.sup.4 and the carbon atoms to which they are attached, represent a substituted or unsubstituted 5 or 6-member carbocyclic ring; R.sup.4 is selected from the same group as R.sup.3, when taken alone or together with R.sup.1, L.sup.1 or L.sup.4, and said substituents for G.sup.1 and G.sup.2 when taken together are selected from the group consisting of substituted or unsubstituted alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkynyl, dialkylamino, diarylamino and diaralkylamino and said substituents for A.sup.1 and A.sup.2 are the same as for G.sup.1 and G.sup.2 taken together plus amino, alkylamino, arylamino, aroalkylamino, alkoxy, aryloxy and alkoxy carbonyl; except that (i) R.sup.1 and R.sup.2 cannot both be methyl, phenyl or methyl and phenyl respectively and, (ii) the substituents on A.sup.1 and A.sup.2 cannot result in a quaternary nitrogen.
12. A dispersion according to claim 11, wherein said material has the structure: ##STR135## wherein: X represents O, S, and NR in which R is alkyl having 1 to 8 carbon atoms, aryl having 6 to 14 carbon atoms or aralkyl; R.sup.1 and R.sup.2, which may be the same or different, represent alkyl of 1-4 carbon atoms, aryl of 6-14 carbon atoms, --CH(.dbd.CL.sup.2 --CH).sub.m .dbd.A.sup.1 or --CH.dbd.CH--A.sup.2 wherein m is zero or one, L.sup.2 is hydrogen, alkyl of 1-4 carbon atoms, or aryl of 6-14 carbon atoms, A.sup.1 represents benzoxazole, benzothiazole, naphtho1,2-d!thiazole, 2-quinoline or 4-quinoline and A.sup.2 represents furan, pyran, pyrrole, pyrazole, indoline, carbazole; 1,2,3,4-tetrahydroquinoline; 1,2,5,6-tetrahydro-4H-pyrrolo3,2,1-ij!quinoline; 2,3,6,7-tetrahydro-1H,5H-benzoij!quinoline; 10,11-dihydro-9H-benzoa!xanthen-8-yl; 6,7-dihydro-5H-benzob!pyran-7-yl; anthryl, alkoxy having 1-4 carbon atoms, aryl having one or more substituents selected from secondary amino groups, dialkylamino, diarylamino, bis(akoxycarbonyl)amino, diaralkylamino and pyrrolidino. R.sup.1 and R.sup.2, which may be the same or different, represent methyl, phenyl, --CH.dbd.A.sup.1 or --CH.dbd.CH--A.sup.2, wherein A.sup.1 and A.sup.2 may be the same or different represent dimethylaminophenyl, methoxyphenyl, dipropylaminophenyl, naphthyl, naptho1,2-d!thiazole, diethylamino(methoxy)phenyl, diphenylaminophenyl, diethylaminophenyl.
13. A dispersion according to claim 11, wherein said material has the structure: ##STR136## wherein R.sup.2 represents --CH(.dbd.CL.sup.2 --CH).sub.m .dbd.A.sup.1, --CH.dbd.CH(--CH.dbd.CH)--.sub.n A.sup.2, in which L.sup.2 represents hydrogen or phenyl; m and n represent 0 or 1; A.sup.1 and A.sup.2 represent anthryl, naphthyl, aryl having one or more substituents selected from dialkylamino and alkoxy, pyran, 1,2,5,6-tetrahydro-4H-pyrrolo3,2,1-ij!quinoline and 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine.
14. A dispersion according to claim 11, wherein said material has the structure: ##STR137## wherein R.sup.1 and R.sup.2, which may be the same or different, represent --CL.sup.1 .dbd.CH--CH.dbd.A.sup.1, --CH.dbd.A.sup.1, --CL.sup.4 .dbd.CH--A.sup.2 or R.sup.1 taken together with R.sup.4 or R.sup.2 taken together with R.sup.3 may complete an unsubstituted cyclopentene or cyclohexene ring, except that both R.sup.1 and R.sup.4 and R.sup.2 and R.sup.3 cannot complete an unsubstituted cyclopentene or cyclohexene ring; L.sup.1 or L.sup.4 when taken together with R.sup.3 or R.sup.4 represent the atoms needed for a cyclopentene or cyclohexene ring; A.sup.1 represents a benzoxazole and A.sup.2 represents a dialkylaminophenyl or a 2,3,6,7-tetrahydro-1H,5H-benzo-ij!quinolizine.
15. A dispersion according to claim 11, wherein said material has the structure: ##STR138## wherein G.sup.1 and G.sup.2 taken together with the carbon atom to which they are attached represent the non-metallic atoms necessary to complete a substituted or unsubstituted nucleus selected from the group consisting of barbituric acid, 1,3-indanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione; 1,3-dioxan-4,6-dione, 2-isoxazolin-5-one; 2-thiabarbituric acid and barbituric acid, and said substituents are selected from the group consisting of cyano, methyl, ethyl and phenyl; R.sup.1 and R.sup.2 represent methyl, phenyl, --CH.dbd.(CH--CH).sub.m .dbd.A.sup.1 ; or --CH.dbd.CH--A.sup.2 wherein m is 0 or 1; A.sup.1 represents benzoxazole, benzothiazole, naphtho1,2-d!thiazole, 3H-indole and 2-quinoline and A.sup.2 represents dialkylaminophenyl where alkyl consists of 1-4 carbons, alkoxyphenyl where alkoxy consists of 1-4 carbons, 4-dialkylamino-2-alkoxyphenyl, furan and 2,3,6,7-tetrahydro-1H,5H-benzoij!quinolizine.
16. A dispersion according to claim 11, wherein said material is selected from the group consisting of: ##STR139##
Patent Citations (1)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3849132 | 1974-11-01 | Wells |