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Publication numberUSRE28240 E
Publication typeGrant
Publication dateNov 12, 1974
Filing dateSep 10, 1973
Priority dateSep 18, 1969
Publication numberUS RE28240 E, US RE28240E, US-E-RE28240, USRE28240 E, USRE28240E
InventorsN.y.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Or x or
US RE28240 E
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Oflice Re. 28,240 Retissued Nov. 12, 1974 28,240 PHOTOSENSITIVE ELEMENTS CONTAINING PI IOTOOXIDANTS CONTAINING HETERO- CYCLIC NITROGEN ATOM SUBSTITUTED BY AN ALKOXY R AN ACYLOXY GROUP Philip W. Jenkins, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y.

No Drawing. Original No. 3,615,568, dated Oct. 26, 1971,

Ser. No. 859,205, Sept. 18, 1969. Application for reissue Sept. 10, 1973, Ser. No. 396,290

Int. Cl. G03c N40, N64 U.S. Cl. 96-90 R Claims Matter enclosed in heavy brackets [1 appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE Novel photosensitive elements and compositions are described. The compositions contain (a) a colorless oxidizable nitrogen-containing organic color generator and (b) a photooxidant containing a heterocyclic nitrogen atom which is substituted by an alkoxy or an acyloxy group. When the photooxidant is exposed to actinic radiation, it causes the oxidation of the color generator to a colored material.

This invention relates to novel photosensitive elements which form an intense color when exposed to actinic radiation and also to novel processes utilizing these elements as well as to novel photosensitive compositions.

The formation of images utilizing dye printout techniques has recently received considerable attention. Processes have been described wherein various leuco compounds have been oxidized to the corresponding leuco dyes utilizing organic polyhalogen compounds or oxidizing agents (Phot. Sci. Eng, 598-103 (1961); US. Pat. No. 3,042,515). In a typical process of this type, a mixture of diphenylmethane and carbon tetrabromide is exposed to a pattern of ultraviolet radiation. The radiation causes the halohydrocarbon to decompose. The decomposition products oxidize the diphenylmethane to the corresponding blue dye.

While the above-described system is very practical, it does have several disadvantages. The use of halohydrocarbons as the photo-oxidant is undesirable since these materials generally do not have panchromatic sensitivity but instead are only sensitive in the ultraviolet and near ultraviolet regions. Furthermore, these materials have poor film shelf life because of their volatility and/or thermal instability. Also, they are not readily removable for purposes of image fixation.

It is, therefore, an object of this invention to provide novel photosensitive compositions.

It is a further object of this invention to provide novel elements containing these compositions.

It is a further object of this invention to provide a novel process utilizing these elements.

These and other objects are accomplished with photosensitive elements containing a composition having (a) an essentially colorless oxidizable nitrogen-containing organic color generator which is stable to oxidation by atmospheric oxygen under normal room and storage conditions, but which is oxidizable to a colored material and (b) a photo-oxidant containing a heterocyclic nitrogen atom which is substituted by either an alkoxy group or an acyloxy group. When this element is struck by actinic radiation (e.g., visible, infrared, ultraviolet, X-ray, etc., including an electron beam), the photo-oxidant decomposes to produce an oxidizing agent. The oxidizing agent causes oxidation of the color generator which results in this materials transposition from an essentially colorless condition to a condition of high coloration. The particular color obtained is dependent upon the nature of the color generator, but practically any color can be obtained using various combinations of color generators.

The properties of the photo-oxidant are such that it is easily stabilized against further decomposition by treating it with an acid or a base at a pH that has no efl'ect on the photo-oxidant.

An advantage of the present invention over prior art systems is that the various photo-oxidants are responsive to various forms of actinic radiation as explained previously, whereas prior art systems are generally limited to response to radiation in the ultraviolet region. Also, the photo-oxidants of this invention are less volatile than the halohydrocarbons which are conventionally used as photooxidants. As such, the film shelf life is improved. A third advantage is that the photooxidants used in the present invention are easily deactivated by treatment with either an acid or base depending on the particular photo-oxidant used.

The novel compositions and elements of this invention have several uses. One of these uses is in printing where a paper is impregnated with the photosensitive composition and then imagewise exposed to the pattern being printed. Other uses include pattern layout for metal working, preparation of blueprints in a diazo process and in microfilming. The materials of the invention are especially useful in microfilming since the resolution obtainable is very good. High resolutions are obtainable since the active particles are of molecular size (i.e., 135 A. for color generator molecules vs. 500 A. for very fine-grain silver halide particles).

Many types of organic compounds function as organic color generators according to the invention. All are characterized as being essentially colorless, containing nitrogen, being stable to oxidation under normal storage conditions in the photosensitive composition and being capable of producing a color in a photo-oxidative process in the presence of a photo-oxidant. The process may be a simple oxidation of the colorless compound to a colored species. The oxidation may initially produce a reactive intermediate which then undergoes a further reaction with a second component of the color generator to produce the final colored species. In some cases, the reactive intermediate combines with the photo-oxidant to produce a color species. Mixtures of color generators may be used. These color generation processes, and the compounds which are adapted for them, are discussed in detail below.

Useful color generators of this invention include the following:

I. Leuco form of dyes-One type of color generator which may form part of the light-sensitive composition is the reduced form of the dye having, in most cases, one or two hydrogen atoms, the removal of which together with one or two electrons produces a dye. Since leuco form of the dye is essentially colorless, or in some instances it may be of a different color or of a less intense shade than the parent dye, it provides a means of producing an image when the leuco form is oxidized to the dye. This oxidation is accomplished by subjecting an intimate admixture of the organic color generator and a photo-oxidant discussed below to a pattern of actinic radiation. The result is the removal of one or two readily removable hydrogen atoms, depending on the structure of the leuco form of the particular dye chosen, with the production of a colored image against a background of unradiated and, therefore, unchanged material. Representative dyes in the leuco form which are operative according to the invention include:

a. Aminotriarylmethanes bis(4-amino-2-butylphenyl) (p-dimethylaminophenyl) methane 3 ,6-bis (diethylamino -9-phenylxanthene 3,6-bis( diethylam ino -9-o-tolylxanthene 3,6-bis(dimethylamino)-9-(o-ch1orophenyl)xanthene 3 ,6-bis dimethylamino -9-ethylxanthene 3 ,6-bis dimethylamino -9- (o-methoxycarbonylphenyl) xanthene 3,6-bis dimethylamino -9-methylxanthene c. Aminothioxanthenes 3,6-bis(diethylamino) -9- (o-ethoxycarbonylphenyl) thioxanthene 3,6-bis(dimethylamino)-9- (o-methoxycarbonylphenyl) thioxanthene 3,6-bis(dimethylamino)thioxanthene 3 ,6-diar1ilino-9-(o-ethoxycarbonylphenyl thioxanthene d. Amino-9,IO-dihydroacridines 3 ,6-bis benzylamino -9, l-dihydro-9-methylacridine 3,6-bis(diethylamino -9-hexyl-9, IO-dihydroacridine 3 ,6-bis diethylarnino -9, l O-dihydro-9-methylacridine 3,6-bis(diethylamino)-9,10-dihydro-9-phenylacridine 3 6-diamino-9-hexyl-9, l O-dihydroacridine 3,6-diamino-9,10-dihydro-9-methylacridine 3,6-diamino-9,lO-dihydro-9-phenylacridine 3,6-bis(dimethylamino)-9-hexyl-9, IO-dihydroacridine 3,6-bis(dimethylamino)-9,10-dihydro-9-methylacridine e. Aminophenoxazines 3,7-bis (diethylamino phenoxazine -dimethylamino-benzo[a]phenoxazine f. Aminophenothiazines 3,7-bis( benzylamino phenothiazine g. Aminodihydrophenazines 3,7-bis benzylethylamino) -5, lfl-dihydro-S-phenylphenazine 3,7-bis (diethylamino --hexy1-5, IO-dihydrophenazine 3 ,7-bis dihexylamino -S l O-dihydrophenazine 3 ,7-bis(dimethylamino)-5-(p-chlorophenyl)-5,10-

dihydrophenazine 3 ,7-diamino-5- (o-chlorophenyl -5, 1 O-dihydrophenazine 3 ,7-diamino-5, 1 fl dihydrophenazine 3,7-diamino-5, 1 O-dihydro-S-methylphenazine 3 ,7-diamino-5-hexyl-5, l O-dihydrophenazine 3 ,7-bis (dimethylamino -5 1 O-dihydrophenazine 3 ,7-bis(dimethylamino)-5,10-dihydro-S-phenylphenazine 3,7-bis(dimethylarnino)-5,10-dihydro-S-methylphenazine h. Aminodiphenylmethanes 1,4-bis bis-pdiethylaminophenyl methyl piperazine bis p-diethylaminophenyl anilinomethane bis p-diethylaminophenyl) l-benzotriazolylmethane bis( p-diethylaminophenyl -2-benzotriazolylmethane bis (p-diethylaminophenyl) p-chloroanilino)methane bis(p-diethylaminophenyl) (2,4-dichloroanilino)methane bis(p-diethylaminophenyl) (methylamino)methane bis(p-diethylaminophenyl) (octadecylamino methane bis( pdimethylaminophenyl) aminomethane bis(p-dimethylaminophenyl anilinomethane 1, l-bis (dimethylaminophenyl)ethane 1,1-bis(dimethylaminophenyl)heptane bis(4methylamino-m-t0lyl)aminoethane i. Leuco indamines 4-amino-4'-dimethylaminodiphenylamine pp-dimethylaminoanilino phenol j. Aminohydrocinnamic acids (cyanoethanes, leuco methines) 4-amino-a,,6-dicyanohydrocinnamic acid, methyl ester 4-anilino-a,fidicyanohydrocinnamic acid, methyl ester 4- (p-chloroanilino) -a,p-dicyanohydrocinnamic acid,

methyl ester a-cyano-4-dimethylaminohydrocinnamamide k. Hydrazines 1-( p-diethylaminophenyl)-2-( 2-pyridyl)hydrazine l-(pdimethylaminophenyl)-2(2-pyridyl)hydrazine 1-(3-methyl-2-benzothiazolyl)-2-(4-hydroxy-l-naphthyl) hydrazine l-(2-naphthyl -2-phenylhydrazine 1-p-nitrophenyl-2-pheny1hydrazine 1-(l,3,3-trimethyl-2-indolinyl)-2-(3-N-phenylcarbamoyl- 4-hydr0Xy-1-naphthyl hydrazine l. Leuco indigoid dyes m. Amino-2,3-dihydroanthraquinones 1,4-dianilino-2,3-dihydroanthraquinone l,4-bis(ethylamino)-2,3-dihydroanthraquinone n. Phenethylanilines N-(2-cyanoethyl -p-phenethylaniline N,N-diethyl-p-phenylethylani]inc N,N-dimethyl-p- 2-( l-naphthyl ethyl] aniline 11. Acyl derivatives of leuco dyes which contain a basic NH groupSuitable compounds which have a basic NH group and which form amides when acylatcd include dihydrophenazines, phenothiazines and phenoxazines. Typical compounds within this class include:

l0-acetyl-3,7-bis(dimethylamino)-phenothiazine 10-(p-chlorobenzoyl)-3,7-bis(diethylamino)- phenothiazine 5,10-dihydro-IO-(p-nitrobenzoyl)-5-phenyl-3,7-

bis-(phenylethylamino)phenazine 10-(p-benzoyl)-3,7-bis(naphthylmethylamino) phenoxazine III. Leucolike compound having no oxidizable hydrogen atom but which are oxidizable to a colored compound-Typical compounds within this class include:

tris( p-dirnethylaminophenyl benzylthiomethane 1tris(p-diethylaminophenyl)methyl-2-phenylhydrazine tris(4-diethylamino-o-tolyl)ethoxycarbonylmethane bis(4-dipropylamino-o-tolyl) (o-fluorophenyl)butoxycarbonylmethane bis [tris (4-diethylamino-o-tolyl methyl] -disulfide IV. Organic amines oxidizable to a colored species such as those described in US. Pat. Nos. 3,042,515 and 3,042,- 517. Typical compounds of this type include:

4,4'-ethylenedianiline diphenylamine N,N-(dimethylaniline 4,4'-methylenedianiline triphenylamine N-vinylcarbazole The photo-oxidizers described herein are inert until struck by actinic radiation such as visible, ultraviolet, infrared, X-ray electron beams, etc. Various photo-oxidizers have different peak sensitivities throughout the spectrum depending on the structure of the compound. As such, the specific photo-oxidizers selected is dependent on the nature of the actinic radiation. When exposed to such radiation, the photo-oxidizer produces an oxidizing agent which oxidizes the color generator to a colored form. Typical photo-oxidizers of this invention have one of the general formulas:

wherein R can be any of the following:

a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, e.g., those set forth in Mees and James, The Theory of the Photographic Process," Macmillan, 3rd ed., pp. 198-232; the methine linkage can be substituted or unsubstituted, CH a 'C (C6H5):!

b. an alkyl radical preferably containing one to eight carbon atoms including a substituted alkyl radical;

c. an aryl radical including a substituted aryl radical such as a phenyl radical, a naphthyl radical, a tolyl radical, etc.;

d. a hydrogen atom;

e. an acyl radical having the formula 3 -C-R9 wherein R is hydrogen or an alkyl group preferably having one to eight carbon atoms;

f. an anilinovinyl radical such as a radical having the formula wherein R is hydrogen, acyl or alkyl; or a styryl radical including substituted styryl radicals,

wherein R is hydrogen, alkyl, aryl, amino, including dialkylamino such as dimethylamino;

R can be either of the following:

a. an alkyl radical preferably having one to eight carbon atoms such as methyl, propyl, ethyl, butyl, etc., including a substituted alkyl radical such as sulfoalkyl, e.g., -(CH SO an aralkyl, e.g., benzyl or pyridinatooxyalkyl salt. e.g (CH -O-Y wherein Y is substituted or unsubstituted pyridinium salt; or etc.,

b. an acyl radical, e.g.,

wherein R is an alkyl radical preferably having one to eight carbon atoms or aryl radical, e.g., methyl, ethyl, propyl, butyl, phenyl, naphthyl, etc.

Q Q and Q each represent the nonmetallic atoms necessary to complete a sensitizing or desensitizing nucleus containing five or six atoms in the heterocyclic ring, which nucleus can contain at least one additional heteroatom such as oxygen, sulfur, selenium or nitrogen, i.e., a nucleus of the type used in the production of cyanine dyes, such as the following representative nuclei: a thiazole nucleus, e.g., thiazole, 4-rnethylthiazole, 3 ethylthiazole, 4-phenylthiazole, S-methylthiazole, 5 phenyl thiazole, 4,5-dimethylthiaz0le, 4,5-diphenylthiazole, 4-(2- thienyUthiazole, benzothiazole, 4-chlorobenzothiazole, 4- or S-nitrobenzothiazole, S-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4 methylbenzothiazole, S-methylbenzothiazole, 6 methylbenzothiazole, fi-nitrobenzothiazole, S-bromobenzothiazole, 6 bromobenzothiazole, 5-chloro-6-nitrobenzothiazole, 4 phenylbenziothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, fi-methoxybenzothiazole, 5 iodobenzothiazole, -iodobenzothiazole, 4 ethoxybenzothiazole, 5 ethoxybenzothiazole, a tetrahydrobenzothiazole nucleus, 5,6-dimethoxybenzothiazole, 5,6-methylenedioxybenzothiazole, 5-hydroxybenzothiazole, G-hydroxybenzothiazole, a-naphthothiazole, B-naphthothiazole, p143 naphthothiazole, 5- metboxy-[3,fl-naphthothiazole, S-ethoxy ,5 naphthothiazole, 8-methoxy-a-naphthothiazole, 7 methoxy-u-naphthothiazole, 4 methoxythianaphtheno-7',6', t,5-thiazole, nitro group substituted naphthothiazoles, etc.; an oxazole nucleus, e.g., 4-methyloxazole, 4-nitro-oxazole, S-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4 ethyloxazolc, 4,5 dimethyloxazole, 5 phenyloxazole, benzfour carbon atoms), e.g., methyl, ethyl, propyl, isopropyl, butyl, decyl, dodecyl, etc., or an aryl group, e.g., phenyl, tolyl, naphthyl, methoxyphenyl, chlorophenyl, nitrophenyl, etc.;

X represents an acid anion, e.g., chloride, bromide, iodide, perchlorate, tetrafluoroborate, sulfamate, thiocyanate, p'toluenesulfonate, methyl sulfate, etc.;

G represents an anilino radical or an aryl radical, e.g., phenyl, naphthyl, dialkylaminophenyl, tolyl, chlorophenyl, nitrophenyl, anilinovinyl, etc.;

R is an alkyleneoxy radical having one to eight carbon atoms in the alkylene chain including an alkylenedioxy radical and an arylenebisalkoxy radical e.g., ethyleneoxy, trimethyleneoxy, tetrarnethyleneoxy, propylideneoxy, ethylenedioxy, phenylenebisethoxy, etc.;

R represents either (1) an alkyl radical including a substituted alkyl (preferably a lower alkyl having one to four carbon atoms) e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl, aralkyl such as benzyl, sulfoalkyl such as B-sulfoethyl, w-sulfobutyl, w-sulfopropyl, or (2) an acyl radical, e.g.,

its.

wherein R is an alkyl including a substituted alkyl or an aryl radical such as methyl, phenyl, naphthyl, propyl, benzyl, etc.

In the above formulas Q preferably completes a pyridine, an indole or a quinoline nucleus.

Typical photo-oxidants included in the scope of this invention are the following:

1. 3-ethyl-l-methoxyoxa-2-pyridocarbocyanine perchlorate 2. 1' ethoxy 3 ethyloxa-2'-pyridocarbocyanine tetrafiuoroborate 3' ethyl 1 methoxy-Z-pyridothiacyanine iodide 1-ethoxy-3'-ethyl-2-pyridothiacyanine tetrafluoroborate 1-benzyloxy-3-ethyl-2-pyridothiacyanine iodide 3'-ethyl-1-methoxy-2pyridothiacarbocyanine iodide 1-etboxy-3'-ethyl-2-pyridothiacarbocyanine tetrafluoroborate anhydro 3 ethyl 1 (3-sulfopropoxy)-2 pyridothiacarbocyanine hydroxide 9. l-benzyloxy 3' ethyl 2 pyridothiacarbocyanine perchlorate 10. 3'-ethyl 1 methoxy-2-pyridothiacarbocyanine perchlorate 11. 1'-methoxy 1,3,3 trimethylindo-2'-pyridocarbocyanine pictrate 12. 3'-ethyl 1 methoxy-4,5-benzo-2-pyridothiacarbocyanine perchlorate 13. l ethoxy 3' ethyl-4',5'-benzo-Z-pyridnthiacarbocyanine tetrafiuoroborate 14. 1' ethoxy 3 ethyloxa-Z'-carbocyanine tetrafiuoroborate 15. 1'-ethoxy-3-ethylthia-2'-cyanine tetrafiuoroborate 16. 1' ethoxy 3 ethylthia-2'-carbocyanine tetrafiuoroborate 17. l ethoxy 3 ethylthia-2'-dicarbocyanine tetrafiuoroborate l8. 1 methoxy 3 methyl-2-pyridothiazolinocarbocyanine perchlorate 19. 3'-ethyl-1-methoxy-4-pyridothiacyanine perchlorate 20. 3 ethyl 1 methoxy-4-pyridothiacarbocyanine perchlorate 21. 1' ethoxy 3 ethyl-4,5-benzothia-2'-carbocyanine tetrafluoroborate 22. 2 B anilinovinyl-l-methoxypyridinium p-toluenesulfonate 23. 1 ethyl 1' methoxy-4,5-benzothia-4'-carbocyanine perchlorate 24. 1 methoxy 2 methylpyridinium p-toluenesulfonate 25. l methoxy 4 methylpyridinium p-toluenesulfonate 26. anhydro 2 methyl-1-(3-sulfopropoxy)pyridinium hydroxide 27. l-ethoxy-Z-methylpyridinium tetrafiuoroborate 28. l-benzyloxy-Z-methylpyridinium bromide 29. 1-ethoxy-2-methylquinolinium tetrafluoroborate 30. 1,1'-ethylencdioxybispyridinium dibromide 31. 1,1-trimethylenedioxybispyridinium dibromide 32. 1,1 tctramethylenedioxybifl2-methylpyridinium)dibromide 33. 1,1 tetramethylcnedioxybis(4-methylpyridinium)dibromide 34. 1,1-tetramethylenedioxybispyridinium dibromide 35. 1,1'-pentamethylenedioxybispyridinium dibromide 36. 1 acetoxy 2 (4 dimethylaminostyryl)pyridinium perchlorate 37. l benzoyloxy 2 (4-dimethylaminostyryl)pyridinium perchlorate 38. 1,3 diethyl-S-ltt-methoxy-2(lH)-pyridylidene)ethylidene]-2-thiobarbituric acid 39. 3 ethyl 5-[(l-methoxy-2(1H)-pyridylidene)ethylidenelrhodanine 40. 1,3 diethyl 5 [(1-methoXy-2(1H)-pyridylidene) ethylidenel-barbituric acid 41. 2- 3,3-dicyanoalky1idene)-1-methoxy-1,2-dihydropyridine 42. 2 [(1 methoxy-2(1H)-pyridylidene)-ethylidene} benzo[b'|-thiophen-3(211)-one-L1-dioxide 43. 3 cyano 5 [t1-methoxy2(1H)-pyridylidene)ethylidene |-4-phenyl2(5H -furanone 44. N-ethoxy-2-picolinium iodide 45. N-ethoxy2-picolinium hexafluorophosphate 46. N-methoxy 2 anilinovinylpyridinium paratoluenesulfonate Photosenstive elements of this invention can be prepared from the color generators and photo-oxidizers of this invention in the usual manner, i.e., by blending a dispersion or solution of the color generator and photooxidizer together with a binder, when necessary or desirable, and coating, impregnating or forming a self-supporting layer from the photosensitive composition.

Binders which may optionally be added to the composition are inert materials that serve to adhere the color generator-photo-oxidizer mixture to a substrate. The binder may also serve to thicken the solution of the composition should this be desirable for specific applications. Representative binders that are suitable for use in the present composition include: styrene-butadiene copolymers; silicone resins; styrene-alkyd resins; silicone-alkyd resins; soya-alkyd resins; poly(vinylchloride); poly(vinylidene chloride); vinylidene chlorideacrylonitrile copolymers; poly(vinyl acetate); vinyl acetatevinyl chloride copolymers; poly(vinyl acetals), such as po1y(vinyl butyral); polyacrylic and methacrylic esters, such as poly- (methylmethacrylate), poly(n butylmethacrylate), poly- (isobutylmethacrylate), etc.; polystyrene, nitrated polystyrene; polymethylstyrene; isobutylene polymers; polyesters, such as poly-(ethylenealkaryloxyalkylene terephthalate); phenolformaldehyde resins; ketone resins; polyamides; polycarbonates; polythiocarbonates; poly(ethyleneglycol co bis hydroxyethoxyphenyl propane terephthalate); copolymers of vinyl haloarylates and vinyl acetate such as poly(vinyl m-bromobenzoate-covinylacetate); ethyl cellulose, poly(vinyl alcohol), cellulose acetate, cellulose nitrate, chorinated rubber, gelatin, etc. Methods of making resins of this type have been described in the prior art, for example, styrene-alkyd resins can be prepared according to the method described in U.S. Pat. Nos. 2,361,019 and 2,258,423. Suitable resins of the type contemplated for use are sold under such tradenames as Vitel PEAOI, Cymac, Piccopale 100, Saran F220, Lexan and Lexan 145. Other types of binders which can be used include such materials as parafiin, mineral waxes, etc.

The substrates are materials which bear the light-sensitive, image-forming compositions as a coating or impregnant. These materials include paper ranging from tissue paper to heavy cardboard; films of plastics and polymeric materials such as regenerated cellulose, cellulose acetate, cellulose nitrate, polyester of glycol and terephthalic acid, vinyl polymers and copolymers, polyethylene, polyvinylacetate, polymethyl methacrylate, polystyrene, polyvinylchloride; textile fabrics; glass; wood and metals. Opaque as well as transparent substrates can be used. Substrates in which the photosensitive components are dissolved or which bear the photosensitive components as a coating on the reverse side of the substrate, i.e., on the side away from the radiation source used for image formation, must be transparent not only in the visible region but to any form of radiation employed. The substrates should be inert to the photosensitive materials.

Solvents which are inert toward the color generator, the binder and the photo-oxidizer are usually employed to dissolve these comronents and thereby mix them together and to provide a fluid medium for a convenient and ready application of the photosensitive composition to substrates. Among the solvents which may be employed in preparing the compositions of this invention are amides such as formamide, N,N-dimethylformamide, N,N dimethylacetamide, hexanimide, styramide; alcohols such as methanol, ethanol, l-propanol, Z-propanol. butanol; glycols such as ethyleneglycol, polyethyleneglycol, etc.; ketones such as acetone, 2-butanone, etc.; esters such as ethylacetate, ethylbenzoate, etc.; ethers such as tetrahydrofuran, dioxane, etc.; chlorinated aliphatic hydrocarbons such as methylene chloride, ethylene chloride, etc.; aromatic hydrocarbons such as benzene, toluene, etc.; and other common solvents such as dimethylsulfoxide, odichlorobenzene, dicyanocyclobutane, l-methyl-Z-oxohexamethylenimine, and various mixtures of the solvents, transparent not only in the visible region but to any form of radiation employed. The substrates should be inert to the photosensitive materials.

Solvents which are inert toward the color generator, the binder and the photo-oxidizer are usually employed to dissolve these components and thereby mix them together and to provide a fluid medium for a convenient and ready application of the photosensitive composition to substrates. Among the solvents which may be employed in preparing the compositions of this invention are amides such as formamide, N,N-dirnethylformamide, N,N-dimethylacetamide, hexanimide, styramide; alcohols such as methanol, ethanol, l-propanol, 2-propanol, butanol; glycols such as ethyleneglycol, polyethyleneglycol, etc.; ketones such as acetone, Z-butanone, etc.; esters such as ethylacetate, ethylbenzoate, etc., ethers such as tetrahydrofuran, dioxane, etc.; chlorinated aliphatic hydrocarbons such as methylene chloride, ethylene chloride, etc.; aromatic hydrocarbons such as benzene, toluene, etc.; and other common solvents such as dimethylsulfoxide, o-dichlorobenzene, dicyanocyclobutane, 1-methyl-2-oxohexamethylenimine, and various mixtures of the solvents.

In preparing the compositions disclosed herein useful results are obtained when the color generator and photooxidizer are mixed in mole ratios within the range from about :1 to about 1:10. The preferred ratio range is 2:1 to 1:2. The binder, when used, is employed in an amount varying from about 0.5 part to 10 parts by weight per part of combined weight of color generator and photooxidizer. The combined weight of color generator and photo-oxidizer in the composition ranges from about 1 weight percent to about 99 weight. A preferred weight range is from about 2 weight percent to about 60 weight percent.

In preparing the compositions disclosed herein useful results are obtained when the color generator and photooxidizer are mixed in mole ratios within the range from about 10:1 to about 1:10. The preferred ratio range is 2:1 to 1:2. The binder, when used, is employed in an amount varying from about 0.5 part to 10 parts by weight per part of combined weight of color generator and photo-oxidizer. The combined weight of color generator and photo-oxidizer in the composition ranges from about 1 Weight percent to about 99 Weight A preferred weight range is from about 2 weight percent to about 60 weight percent.

When the compositions are coated, a wet thickness of about 0.001 inch to about 0.01 inch is utilized, the preferred range being from about 0.002 inch to about 0.006 inch. When the composition is impregnated into a support, suitable amounts of color generator and photo-oxidizer range from about 0.01 mg./in. to about 5.0 mg./ in. of each.

In applying the composition to a supporting substrate, the composition can be sprayed, brushed, applied by a roller or immersion coater, flowed over the surface, picked up by immersion, impregnated or spread by other means. Elements thus formed are dried at room temperature, under vacuum or at elevated temperature.

The elements are then exposed to a pattern of actinic radiation and the image is formed directly on the support. The exposure can be by contact printing techniques, by lens projection, by reflex, by bireflex, from an imagebearing original or any other known technique. Fixing is accompilshed merely by destroying residual photo-oxidant by treating it with alkaline or acid depending on the nature of the photo-oxidant or by the use of a reducing agent to destroy the oxidizing agent present in unexposed areas.

The following examples are included for a further understanding of the invention.

EXAMPLE 1 A composition in the form of a dope consisting of the following materials is coated at a wet thickness of 0.003 inch on a paper support.

G. Color generator 0.1 Photo-oxidant 0.25 Binder[poly(vinyl acetate)] 2.0 Methylene chloride 18.0

The resultant colorless coating is dried at 40 C. for 30 minutes and exposed for 30 seconds behind a halftone positive with a photofiood lamp. The color generator used, photo-oxidant used, and color of the dye image are set forth in the following table I.

Example 1 is repeated except that the light source used is a mercury arc (Filmsort 086). Similar results are obtained.

EXAMPLE 3 A composition in the form of a dope consisting of the following materials is coated at a wet thickness of 0.003 inch on a paper support and dried:

Color generator 0.02 Photo-oxidant(N-ethoxy 2-picolinium hexafluorophosphate 0.04

Binder [poly(vinylbutyral)] 2.0

Methylene chloride 18.0

The element containing a colorless coating is exposed in an imagewise manner to radiation from a mercury arc. The color-generator used and the color of the dye image are set forth in the following table II.

p-(2.2-Dicyanoethyl-N,N-dimethylaniline Yellow. p-( l,2,2 Tricyanoethyl) N,N dimethylaniline Orange. p-Phenylenediamine Gray. Tris(4 diethylamino (4 tolyl)methane trihydro chloride Blue.

EXAMPLE 4 Example 3 is repeated except that the photo-oxidant employed is N-methoxy-Z-anilinovinylpyridinium paratoluenesulfonate. Similar results are obtained. When the photooxidant is omitted, the coating remains colorless.

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.

I claim:

[1. A photosensitive element comprising a support containing a composition comprising a. an essentially colorless, oxidizable, nitrogen containing, organic color generator, which when contained in said composition, is stable to oxidation by atmospheric oxygen under normal room and storage conditions but which is oxidizable to a colored material and b. a photo-oxidant containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, said photo-oxidant being capable of oxidizing said color generator to a colored material when subjected to actinic radiation] 2. A photosensitive element comprising a support containing a composition comprising a. an essentially colorless, oxidizable, nitrogen-containing, organic color generator, which when contained in said composition, is stable to oxidation by atmospheric oxygen under normal room and storage conditions but which is oxidizable to a colored material and b. a photo-oxidant which is capable of oxidizing said color generator to a colored material when subjected to actinic radiation, said photo-oxidant having a formula selected from the group consisting of:

wherein:

R is selected from the group consisting of:

a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes,

[b. an alkyl radical] b. [e] an anilinovinyl radical,

[d. a hydrogen atom,

e. an aryl radical,

f. an aldehyde grouPJ and c. [g.] a styryl radical;

R is selected from the group consisting of:

a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical selected from the group consisting of a cyanoallylidene radical, an alkylcarboxyallylidene radical and an alkylsulfonylallylidene radical;

[R] R is selected from the group consisting of:

a. an alltyl radical and b. an acyl radical;

[X] X- is an acid anion, and, Z represents the atoms necessary to complete a fiveto six-membered heterocyclic nucleus.

[3. The element as defined in claim 2 wherein Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus] 4. The element as defined in claim 2 wherein R is a methine linkage terminated by fiveto six-membered heterocyclic nucleus.

5. The element as defined in claim 2 wherein said composition contains a polymeric binder for said organic color generator and said photo-oxidant.

6. The element as defined in claim 2 wherein said composition is imbibed into the support.

7. The element as defined in claim 2 wherein said composition is coated on the support.

8. The element as defined in claim 2 wherein said component (a) is selected from the group consisting of (1) a leuco dye; (2) an N-acyl derivative of a leuco dye; (3) a substituted triarylmethane wherein the single remaining methane bond is substituted with benzylthio, Z-phenylhydrazino, alkoxycarbonyl or disulfide; and (4) an organic amine.

9. The element as defined in claim 2 wherein said component (b) is selected from the group consisting of:

Q Q and Q [Q each represent the nonmetallic atoms necessary to complete a fiveto six-membered heterocyclic nucleus;

11 is a positive integer of from 1 to 4;

m is a positive integer of from 1 to 3;

[R is an alkyleneoxy radical having one to eight carbon atoms in the alkylene chain;]

g is a positive integer from 1 t0 2;

[X X is an acid anion;

L is a methine linkage;

[R] R is selected from the group consisting of an alkyl radical and an acyl radical;

R [and R are each] is selected from the group consisting of an aryl radical, a hydrogen atom and an alkyl radical;

R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical;

G is selected from the group consisting of an anilinovinyl radical and an aryl radical; and

R and R are each a cyano radical.

[10. A photosensitive element comprising a support having coated thereon a composition comprising a. from about 0.1 to about percent by weight of tris-(pdimethylaminophenyl)methane as a color generator,

b. from about 0.1 to about 10 percent by weight of N-ethoxy-Z-picolinium iodide as a photo-oxidant, and

c. a polymeric binder] [11. A photosensitive element comprising a support having coated thereon a composition comprising a. from about 0.1 to about 10 percent by weight of tris-(p-dimethylaminophenyl)methane as a color generator,

b. from about 0.1 to about 10 percent by weight of N-ethoxy-Z-picolinium hexafiuorophosphate as a photo-oxidant and c. a polymeric binder] 12. A photosensitive element comprising a support having coated thereon a composition comprising a. from about 0.1 to about 10 percent by weight of tris-(p-dimethylaminophenyl)methane as a color generator,

b. from about 0.1 to about 10 percent by weight of N-methoxy 2 anilinovinylpyridinium paratoluenesulfonate as a photo-oxidant and c. a polymeric binder.

[13. A photosensitive composition comprising a. an essentially colorless, oxidizable, nitrogen containing, organic color generator, which when contained in said composition, is stable to oxidation by atmospheric oxygen under normal room and storage conditions but which is oxidizable to a colored material and b. a photo-oxidant containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, said photo-oxidant being capable of oxidizing said color generator to a colored material when subjected to actinic radiation] 14. A photosensitive composition comprising a. an essentially colorless, oxidizable, nitrogen-containing, organic color generator, which when contained in said composition, is stable to oxidation by atmospheric oxygen under normal room and storage conditions but which is oxidizable to a colored material and a photo-oxidant which is capable of oxidizing said color generator to a colored material when subjected to actinic radiation, said photo-oxidant having a formula selected from the group consisting of:

(BR 5R wherein:

b. [c.] an anilinovinyl radical,

[d. a hydrogen atom,

c. an aryl radical,

f. an aldehyde group] and c. [g] a styryl radical;

R; is selected from the group consisting of:

a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical selected from the group consisting of a cyanaallylidene radical, an alkylcarboxyallylidene radical and an alkylsulfonylallylidene radical;

[R] R is selected from the group consisting of a. an alkyl radical and b. an acyl radical;

X [X] is an acid anion; and, Z represents the atoms necessary to complete a fiveto six-membered heterocyclic nucleus.

15. The photosensitive composition as defined in claim 14 wherein Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.

16. The photosensitive composition as defined in claim 14 wherein R is a methine linkage terminated by a fiveto six-membered heterocyclic nucleus.

17. The photosensitive composition as defined in claim 14 wherein said composition contains a polymeric binder for said organic color generator and said photo-oxidant.

18. The photosensitive composition as defined in claim 14 wherein said component (a) is selected from the group consisting of (1) a leuco dye; (2) an N-acyl derivative of a leuco dye; (3) a substituted triarylmethane wherein the single remaining methane bond is substituted with benzylthio, 2-phenyl-hydrazino, alkoxycarbonyl 0r disulfide; and (4) an organic amine.

19. The photosensitive composition as defined in claim 14 wherein said component (b) is selected from the group consisting of wherein:

Q Q and Q, [Q] each represent the nonmetallic atoms necessary to complete a fiveto siX-membered heterocyclic nucleus;

n is a positive integer from 1 to 4;

m is a positive integer from 1 to 3;

[R is an alkyleneoxy radical having one to eight carbon atoms in the alkylene chain;]

g is a positive integer from 1 to 2;

X is an acid anion;

L is a methine linkage;

[R] R is selected from the group consisting of an alkyl radical and an acyl radical;

R; [and R are each] is selected from the group consisting of an aryl radical, a hydrogen atom and an alkyl radical;

R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical;

G is selected from the group consisting of an aminovinyl radical and an aryl radical; and

R and R are each a cyano radical.

20. A process for producing a visible image comprising the steps of A. providing a photosensitive element comprising a support containing a composition comprising a. an essentially colorless, oxidizable, nitrogencontaining, organic color generator, which when contained in said composition, is stable to oxidation by atmospheric oxygen under normal room and storage conditions but which is oxidizable to a colored material and b. a photo-oxidant containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, said photo-oxidant being capable of oxidizing said color generator to a colored material when subjected to actinic radiation, and B. exposing said element to a pattern of actinic radiation.

References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.

UNITED STATES PATENTS RONALD H. SMITH, Primary Examiner W. H. LOUIE, JR., Assistant Examiner US. Cl. X.R.

Page 1 of pages I UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. Re. 28,2 LO

DATED Reissued November 12, 197A INVENTOROSQ Philip W. Jenkins It is certified that error appears in the above-Identified patent and that said Letters Patent are herelg corrected as shown below: Column line 71, that part of formula reading (p-dimethylaminophenyl) should read (p-dimethylaminophenyl)- Column 3, line 6, that part of formula reading (p-methoxyphenyl) should read (P-methoxyphenyl)- line 20, that part of formula reading "(p-aminophenyl)" should read (paminophenyl)- ---5 line 25, "(p-diethylaminophenyl)methane" should be on the preceding line immediately after methane" and also should read p-diethylaminophenyl methane --5 line 26, that part of formula reading "(pdimethylaminophenyl)" should read (p-dimethylaminophenyl)- line 28, that part of formula reading "(p-methoxyphenyl) should read (p-methoxyphenyl)- line 32, that part of formula reading "(p-diethylaminophenyl)" should read (p-diethylaminophenyl3- line 38, that part of formula reading "ethylaminophenyl should read ethylaminophenyl]- --5 line +7, that part of formula reading "(p-diethylaminophenyl)" should read (pethylaminophenyl)- ---5 line 60, that part of formula reading "naphthyl) should read naphthyl)- --5 line 62, that part of formula reading "(p-dimethylaminophenyl)" should read (pdimethylaminophenyl) --line 6 that part of formula reading "naphthyl)" should read naphthyl)- --5 line 69, that part of formula reading "(p-diethylaminophenyl) should read p-diethylaminophenyl --line '72, that part of formula reading (p-diethylaminophenyl should read (p-diethylaminophenyl)- line 7 L, that part of formula reading (p-diphenylaminophenyl) should read (p-diphenylaminophenyl) Column L, line 3, that part of formula reading "naphthyl)" should read naphthyl) --5 line Page 2 of t pages 1 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. :Re. 28,2 LO DATED Beissued November 12, 197

INVENTORQE) :Philip W. Jenkins It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 5, that part of formula reading (p-butylaminophenyl) should read (p-butylaminophenyl --5 line 10, that part of formula reading "(p-diethylaminophenyl should read (p-diethylaminophenyl)- line 1%, that part of formula reading "tolyl)" should read tolyl)- line 16, that part of formula reading 'tolyl)" should read tolyl)- --5 line 18, that part of formula reading "naphthyl) should read naphthyl)- line 36, that part of formula reading (p-dimeth laminophenyl)" should read (p-dimethylamino phenyl line Kl, that part of formula reading o-chlorophenylg" should read (ochlorophenyl)- line 6 that part of formula reading "(o-chlorophenyl)" should read (o-chlorophenyl)- --5 line 73, that part of formula reading "(o-methoxycarbonylphenyl) should read (o-methoxycarbonylphenyl)- Column 5, line 5, that part of formula reading (o-methoxycarbonylphenyl) should read (o-methoxyoarbonylphenyl)- line 9, that part of formula reading (o-ethoxycarbonylphenyl) should read (o-ethoxycarbonylphenyl)- line 11, that part of formula reading "(o-methoxycarbonylphenyl) should read (o-methoxycarbonylphenyl)- line 52, that part of formula reading (p-diethylaminophenyl)l" should read --(p-diethylaminophenyl)l--. Column 6, line 22, that part of formula reading "2(2" should read --2(2--; line 23, that part of formula reading "naphthyl)" should read naphthyl)- line 51, that part of formula reading "bis(naph thylmethylamino) should read bis(naphthylmethylamino) Page 3 of t pages UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION 4 PATENT NO. Re. 28,2 tO DA-TED Reissued November 12, 197A INVENTORtK) Philip W. Jenkins It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: line 68, that part of formula reading "(dimethylaniline" should read -dimethylaniline--. Column 7, line 21, "-CH-" should read -CH= Column 8, line 33, that part of formula reading "R should read --RLt-. Column 9, last line, that part of formu a reading "2,2, t,6" should read --2, t,6--. Column 12, line 22, that part of formula reading "pyridylidene)" should read pyridylidene) 5 line 26, that part of formula reading "ethylidene]" should read ethylidene]- line 35, "Photosenstive should read Photosensitive-. Column 15, line 38, "by a" should read by [a--; line 39, "and an" should read and] an-. Column 16, line 8, "[X]" should read --[X line #6, the enclosing bracket to the left of the formula should be placed to the left of "(C)"; line 50, the enclosing bracket to the left of the formula should be placed to the left of "(D)"; line 56, "(E)" should read -[(E)] 5 line 60, between the two formulas, -and--- should be inserted; line 61, "(F)" should read -[(F)]. Column 17, line #9, "by a" should read by [a--; line 50, "and an" should read and] an-. Column 18, line 3, "c." should read e.--; line 17, "[X1" should read --[X line 53, the enclosing bracket to the left of the formula should be placed to the left of "(C)"; line 58, the enclosing bracket to the left of the formula should be placed to the left of "(D)"; line '71, "(F)]" should read -[(F)] Column 19, line 9, 'X' should read --X---; line 11, "R should be italicized; line 23, "20." should read --[20.-. Column 20, lines 89, "radiation." should read --radiation.]-; after Page t of t pages UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. :Be. 28,2 r0

DATED :Reissued November 12, 197s mvrNroRtX) :Philip w. Jenkins It is certified that error appears in the above l'dentified patent and that said Letters Patent are hereby corrected as shown below:

line 9, the following should be inserted in italics:

--2l. The element as defined in claim 2 wherein Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.--

Signed and Scaled this Thirty-first Day Of August 1976 [SEAL] A rresr:

RUTH C. MASON C. MARSHALL DANN Auesling Officer ('ummissr'rmvr nflarcnrs and Trademarks

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
EP0795790A2 *Feb 27, 1997Sep 17, 1997Eastman Kodak CompanyPeel-developable lithographic printing plate
Classifications
U.S. Classification430/332, 430/343, 204/157.64, 204/157.71
International ClassificationG03C1/73
Cooperative ClassificationG03C1/73
European ClassificationG03C1/73