Photographic emulsions and elements capable of forming direct-positive images

FIELD OF THE INVENTION
The present invention is directed to silver halide emulsions and photographic elements useful in forming direct-positive images. More specifically, this invention is directed to internal latent image-forming silver halide emulsions containing a nucleating agent and to photographic elements containing these emulsions. This invention is also directed to processes of forming direct-positive images.
BACKGROUND OF THE INVENTION
Photographic elements which produce images having an optical density directly related to the radiation received on exposure are said to be negative-working. A positive photographic image can be formed by producing a negative photographic image and then forming a second photographic image which is a negative of the first negative, that is, a positive image. A direct-positive image is understood in photography to be a positive image that is formed without first forming a negative image. Positive dye images which are not direct-positive images are commonly produced in color photography by reversal processing in which a negative silver image is formed and a complementary positive dye image is then formed in the same photographic element. The term "direct reversal" has been applied to direct-positive photographic elements and processing which produces a positive dye image without forming a negative silver image. Direct-positive photography in general and direct reversal photography in particular are advantageous in providing a more straight-forward approach to obtaining positive photographic images.
One conventional approach for obtaining direct-positive photographic images is to employ silver halide emulsions which are initially surface fogged. Surface fog is imagewise removed in exposed areas. When a photon is absorbed by a silver halide grain, a hole (a positive charge) and an electron are released in the silver halide crystal. Migration of the hole to the grain surface results in oxidation of a metallic silver atom (fog) to its ionic form, thereby reducing the developability of the grain. The present invention is totally inapplicable to surface-fogged direct-positive emulsions.
A second conventional approach to forming direct-positive images, to which the present invention relates, is to use photographic elements employing internal latent image-forming silver halide grains. After imagewise exposure, the silver halide grains are developed with a surface developer, that is, one which will leave the latent image sites within the silver halide grains substantially unrevealed. Simultaneously, either by uniform light exposure or by the use of a nucleating agent, the silver halide grains are subjected to development conditions that would cause fogging of a negative-working photographic element. The internal latent image-forming silver halide grains which received actinic radiation during imagewise exposure develop under these conditions at a comparatively slow rate, as compared to the internal latent image-forming silver halide grains not imagewise exposed. The result is a direct-positive silver image. In color photography, the oxidized developer that is produced during silver development is used to produce a corresponding positive, direct reversal dye image. Multicolor direct reversal photographic images have been extensively investigated in connection with image-transfer photography.
It has been found advantageous to employ nucleating agents in preference to uniform light exposure in the process described above. The term "nucleating agent" is employed herein to mean a fogging agent capable of permitting the selective development of internal latent image-forming silver halide grains which have not been imagewise exposed in preference to the development of silver halide grains having an internal latent image formed by imagewise exposure.
While nucleating agents have been long known to the photographic art, recent interest has focused on identifying nucleating agents that are effective in relatively low concentration levels and that can be incorporated directly into silver halide emulsions. Exemplary of known incorporated nucleating agents are those disclosed by Whitmore U.S. Pat. No. 3,227,552, Lincoln et al U.S. Pat. No. 3,615,615, Spence et al U.S. Pat. No. 3,718,470, Kurtz et al U.S. Pat. Nos. 3,719,494 and 3,734,738, Lincoln et al U.S. Pat. No. 3,759,901, Leone et al U.S. Pat. Nos. 4,030,925 and 4,080,207, Adachi et al U.S. Pat. No. 4,115,122, von Konig et al U.S. Pat. No. 4,139,387, and U.K. Pat. Nos. 2,011,391 and 2,012,443.
Spence et al U.S. Pat. No. 3,718,470 discloses some of the compounds employed in this invention as nucleating agents to be useful as intermediates in synthesizing spectral sensitizing dyes. Jones et al U.S. Pat. No. 3,563,754, Vanassche et al U.S. Pat. No. 4,059,450, and Minara et al Defensive Publication No. T967,002 disclose as sensitizers or desensitizers (but not nucleating agents) compounds containing a p-aminostyryl group attached to a heterocyclic nucleus of the type found in cyanine dyes.
SUMMARY OF THE INVENTION
In one aspect this invention is directed to a silver halide emulsion comprised of silver halide grains capable of forming an internal latent image and, absorbed to the surface of the silver halide grains, a nucleating agent. The nucleating agent is a compound of the formula ##STR1## wherein
Z.sup.1 represents the atoms completing an aromatic carbocyclic nucleus of from 6 to 10 carbon atoms;
Y.sup.1 and Y.sup.2 are independently selected from among a divalent oxygen atom, a divalent sulfur atom, and ##STR2##
Z.sup.2 represents the atoms completing a heterocylclic nucleus of the type found in cyanine dyes;
A is an adsorption promoting moiety;
m and n are 1 or 2; and
R.sup.1, R.sup.2, and R.sup.3 are independently chosen from the group consisting of hydrogen, alkyl, aryl, alkaryl, and aralkyl and R.sup.1 and R.sup.3 are additionally independently chosen from the group consisting of acyl, alkenyl, and alkynyl, the aliphatic moieties containing up to 5 carbon atoms and the aromatic moieties containing 6 to 10 carbon atoms.
In another aspect this invention is directed to a photographic element comprised of a support and at least one layer of a silver halide emulsion as described above.
In still another aspect this invention is directed to a process of surface developing an imagewise exposed photographic element as described above to produce a visible direct-positive image. The improvement comprises developing in the presence of the nucleating agent of formula I, identified above.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to formula I, above, the nucleating agents employed in the practice of this invention are characterized by containing an aromatic carbocyclic nucleus of from 6 to 10 carbon atoms, such as a phenyl or naphthyl nucleus. In a preferred form Z.sup.1 represents the atoms completing a phenyl nucleus. The aromatic carbocyclic nucleus is linked through a divalent chalcogen, such as divalent oxygen or sulfur atom, or a trivalent nitrogen atom to a vinylene group which is in turn bonded to a carbon atom of a heterocyclic nucleus of the type found in cyanine dyes. To facilitate description these nucleating agents are hereinafter referred to as vinylene nucleating agents.
The aromatic carbocyclic nucleus can be unsubstituted (e.g., phenyl or naphthyl), in which case R.sup.1 is hydrogen and m is 1. The divalent vinylene group can also be unsubstituted, in which case R.sup.2 is hydrogen. When Y.sup.2 is ##STR3## R.sup.3, which satisfies the third valence of the nitrogen atom, can be hydrogen.
It is also contemplated that the aromatic carbocyclic nucleus, the trivalent nitrogen atom, and the vinylene group can be substituted, each independently of the other. In preferred substituted forms, R.sup.1, R.sup.2, and R.sup.3 can be selected from among alkyl, aryl, alkaryl, and aralkyl substituents. For example, R.sup.1, R.sup.2, and R.sup.3 can be independently selected from among alkyl groups, such as, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, and neo-pentyl; aryl groups, such as, phenyl and naphthyl; alkaryl groups, such as, p-tolyl, o-tolyl, xylyl, and 2,3,5-trimethylphenyl; and aralkyl groups, such as, benzyl and phenethyl. In further preferred forms R.sup.1 and R.sup.3 can additionally be selected independently from among acyl, alkenyl, and alkynyl substituents. Preferred acyl substituents are carboxyl substituents, such as, formyl, acetyl, propanoyl, butanoyl, and pentanoyl. Exemplary preferred alkenyl substituents are vinyl and allyl. Exemplary preferred alkynyl substituents are propargyl and 3-butynyl. In the foregoing preferred forms of R.sup.1, R.sup.2, and R.sup.3, the aliphatic moieties contain up to 5 carbon atoms and the aryl moieties contain 6 to 10 carbon atoms. In a specifically preferred form, R.sup.1, when present as a substituent, is linked to the aromatic carbocyclic nucleus through Y.sup.1, which can be divalent chalcogen, such as a divalent oxygen or sulfur atom, or ##STR4##
Linked to the vinylene group in formula I is a heterocyclic nucleus of the type found in cyanine dyes. That is, Z.sup.2 completes a 5- or 6-membered heterocyclic ring containing at least one, typically one or two, nonmetallic hetero atoms chosen from the group consisting of chalcogen, such as, oxygen, sulfur, and selenium, and nitrogen, the remaining ring atoms being carbon. In a preferred form a benzo group is fused to the heterocyclic ring.
In a specifically preferred form the heterocyclic nucleus in the compound of formula I can be ##STR5## wherein
A is an adsorption promoting moiety;
n and p are 1 or 2;
R.sup.4 represents a ring nitrogen substituent of the type found in cyanine dyes;
Z.sup.3 completes a heterocycle forming at least one 5- or 6-membered ring containing 1 or 2 hetero atoms in the ring chosen from the group consisting of oxygen, sulfur, selenium, and nitrogen, the remaining ring atoms being carbon; and
X is an acid anion, if required to satisfy charge neutrality.
In preferred forms Z.sup.3 represents the nonmetallic atoms required to complete a heterocyclic nucleus having from 5- to 6-atoms in a heterocyclic ring, which can contain a second hetero atom, e.g., a hetero oxygen, sulfur, or selenium atom, or a second nitrogen atom, such as, a thiazole nucleus (e.g., thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 4,5-dimethylthiazole, and 4,5-diphenylthiazole), a benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 4-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 5-methoxybenzothiazole, 6-iodobenzothiazole, and 5,6-dimethoxybenzothiazole), a naphthothiazole nucleus (e.g., .alpha.-naphthothiazole, .beta.-naphthothiazole, 5-methoxy-.beta.-naphthothiazole, 8-ethoxy-.alpha.-naphthothiazole, and .beta.,.beta.-naphthothiazole), a thianaphtheno-7',6',4,5-thiazole nucleus (e.g., 4'-methoxythianaphtheno-7',6',4,5-thiazole), an oxazole nucleus (e.g., 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, and 4,5-diethyloxazole), a benzoxazole nucleus (e.g., benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6dimethylbenzoxazole, 5-ethoxybenzoxazole, 5,6-dichlorobenzoxazole, and 5-hydroxybenzoxazole), a naphthoxazole nucleus (e.g., .alpha.-naphthoxazole, .beta.-naphthoxazole, and .beta.,.beta.-naphthoxazole), a selenazole nucleus (e.g., 4-methylselenazole and 4-phenylselenazole), a benzoselenazole nucleus (e.g., benzoselenazole, 5-chlorobenzoselenazole, 6-methoxybenzoselenazole, 5-hydroxybenzoselenazole, and a tetrahydrobenzoselenazole), a naphthoselenazole nucleus (e.g., .alpha.-naphthoselenazole, .beta.-naphthoselenazole, and .beta.,.beta.-naphthoselenazole), a thiazoline nucleus (e.g., thiazoline and 4-methylthiazoline), a 2-pyridine nucleus (e.g., 2-pyridine and 5-methyl-2-pyridine), a 4-pyridine nucleus (e.g., 4-pyridine and 3-methyl-4-pyridine), a 2-quinoline nucleus (e.g., 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-chloro-2-quinoline, 8-chloro-2-quinoline, 4-methoxy-2-quinoline and 8-hydroxy-2-quinoline, a 4-quinoline nucleus (e.g., 4-quinoline, 5-methyl-4-quinoline, 7-methyl-4-quinoline, and 8-chloro-4-quinoline), a 1-isoquinoline nucleus (e.g., 1-isoquinoline and 3,4-dihydro-1-isoquinoline), a 3-isoquinoline nucleus (e.g., 3-isoquinoline), a 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, and 3,3,7-trimethylindolenine), an imidazole nucleus (e.g., imidazole, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, and 1-alkyl-4,5-dimethylimidazole), a beinzimidazole nucleus (e.g., benzimidazole, 1-alkylbenzimidazole, 1-arylbenzimidazole, and 5,6-dichlorobenzimidazole), or a naphthimidazole nucleus (e.g., 1-alkyl-.alpha.-naphthimadazole, 1-aryl-.beta.-naphthimidazole, and 1-alkyl-5-methoxy-.beta.-naphthimidazole).
R.sup.4 can be any ring nitrogen substituent found in cyanine dyes. Such substituent is commonly an alkyl group having 1 to 18 carbon atoms, such as, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. R.sup.4 can alternatively be an aryl group (e.g., phenyl or naphthyl), an alkaryl group (e.g., tolyl, ethylphenyl, and xylyl), an aryllkyl group (e.g., benzyl and phenethyl), or an alkenyl group (e.g., allyl, propenyl, 1-butenyl, and 2-butenyl). The above hydrocarbon groups when present in cyanine dyes are frequently in turn substituted with halogen atoms or groups such as hydroxy, alkoxy, carboxy, sulfo, sulfato, alkanoyloxy, and alkoxycarbonyl groups. It is generally preferred that the aliphatic moities of the R.sup.4 substituent contain 5 or fewer carbon atoms while the aromatic moieties contain 6 to 10 carbon atoms. The aromatic moieties are most preferably phenyl groups.
It is well understood in the art that heterocyclic nuclei of cyanine dyes promote their adsorption to silver halide grain surfaces. Hence, the nucleating agents of this invention, which contain a cyanine dye heterocyclic nucleus, require no other adsorption promoting moiety to achieve effective association with silver halide grain surfaces. However, since higher degrees of adsorption to silver halide grain surfaces can reduce the concentration of nucleating agent required to produce efficient nucleation, it is recognized that an additional adsorption promoting moiety can be usefully incorporated into the nucleating agent.
The adsorption promoting moiety can be chosen from among those known to promote adsorption of photographic addenda to silver halide grain surfaces. For example, a wide variety of such moieties are known and used in the photographic art to adsorb stabilizers, antifoggants, and sensitizing dyes to silver halide grain surfaces. Typically such moieties contain a sulfur or nitrogen atom capable of complexing with silver or otherwise exhibiting an affinity for the silver halide grain surface. The adsorption promoting sulfur atom can be present in the form of a thiacarbonyl or mercapto group. Particularly useful mercapto groups are attached to a carbon atom of a carbocyclic or heterocyclic aromatic ring and may tautomerize to a thiacarbonyl form. Particularly useful thiacarbonyl groups can be present in acyclic moieties, such as thiourea moieties, or in heterocyclic nuclei (typically 5- or 6-membered heterocyclic rings) of the type found in stabilizers, antifoggants and merocycanine spectral sensitizing dyes. Thio moieties, such as found in thiazole nuclei exhibit sufficient affinity for silver halide grain surfaces to enhance adsorption. Nitrogen atom containing adsorption promoting moieties are typified by those containing a trivalent nitrogen atom with a displaceable hydrogen atom appended. The trivalent atom is usually a member of a 5- or 6-membered heterocyclic ring of the type found in stabilizers, antifoggants, and cyanine spectral sensitizing dyes.
The adsorption promoting moiety A can be any moiety which enhances the nucleating agent's capability of being adsorbed to the silver halide grain surface. In structural terms, such moieties can include adsorption promoting groups selected from the following classes:
nitrogen-containing heterocyclic groups bearing an ionizable hydrogen atom, for example, triazole and benzotriazole radicals, and in particular 1,2,3-benzotriazole-5-yl; tetrazole radicals, and in particular 5-tetrazolyl; benzimidazole radicals, particularly 1,3-benzimidazol-5-yl; imidazole, indazole, triazole, imidazotetrazole, and pyrazolotriazole radicals as well as hydroxytetraazindene and -pentaazaindene radicals, such as 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene radicals;
heterocyclic groups having at least one ring nitrogen and at least one further ring atom which is oxygen, sulfur, or selenium, for example, thiazole, benzothiazole, naphthothiazole, thiazoline, thiazoline thione, thiazolidine, thiadiazole, and rhodanine radicals as well as oxygen and selenium analogues thereof; for example, benzoxazole and benzoselenazole radicals;
groups bearing mercapto groups or groups which can tautomerize to the thiol form; for example, radicals of alkyl thiols or derivatives such as cysteine; or heterocyclic rings bearing a mercapto group, such as, benzothiazole-2-thiols, benzoxazole-2-thiols, 1-phenyl-5-mercaptotetrazoles, and 1,2,3-benzotriazine-4-thiones; and
groups containing the function ##STR6## for example, radicals of alkyl or aryl substituted thioamides (including thioureas), thiohydanoins, thiobarbituric acids, and their derivatives; for example, thioacetamides or thioanilides, thiosemicarbazides, and dithiocarbamates.
In addition to a group of the type identified above capable of complexing with silver or otherwise producing an affinity for the silver halide grain surfaces, the adsorption promoting moiety can (but need not) include a divalent linking group of any synthetically convenient form providing an attachment to the heterocyclic nucleus. Among specifically contemplated linkages are amido, sulfonamido, carbamoyl, sulfamoyl, and ester divalent linking groups, preferably in combination with divalent hydrocarbon or hydrocarbonoxy linking groups, such as, alkylene, alkyleneoxy, and phenylene groups, wherein the alkylene groups contain from 1 to 5 carbon atoms. Such divalent linking groups, when present, are artifacts of compound synthesis and exhibit only a secondary influence on the activity of the compounds prepared. It is therefore apparent that such divalent linking groups can be chosen from among a wide variety of known linking groups.
A preferred class of adsorption promoting groups are thioamides of the formula ##STR7## wherein
A.sup.2 is .dbd.N--R.sup.5, --S--, or --O--;
Q represents the atoms necessary to complete a 5-membered heterocyclic nucleus; and
R.sup.5 is chosen from among hydrogen, phenyl, alkyl, alkylphenyl, and phenylalkyl, the alkyl groups in each instance containing from 1 to 5 carbon atoms.
The adsorption promoting groups have a 5-membered heterocyclic thioamide nucleus such as a 5-thiazoline-2-thione, thiazolidine-2-thione, 4-oxazoline-2-thione, oxazolidine-2-thione, 2-pyrazoline-5-thione, pyrazolidine-5-thione, indoline-2-thione, or 4-imidazoline-2-thione. A specifically preferred subclass of heterocyclic thioamide nuclei is formed when Q is as indicated in formula (IV) ##STR8## wherein X is S or O. Specifically preferred illustrations of such values of Q are 2-thiohydantoin, rhodanine, isorhodanine, and 2-thio-2,4-oxazolidinedione nuclei. It is believed that some 6-membered nuclei, such as thiobarbituric acid, may be equivalent to 5-membered nuclei embraced within formula (IV). These and more complex variant absorption promoting groups are disclosed in Leone et al U.S. Pat. 4,080,207, the disclosure of which is here incorporated by reference.
The thioamide adsorption promoting groups useful in the practice of this invention need not form a heterocyclic ring in order to be effective. For example, the thioamide group can take the form of a thiourea group. Preferred thiourea groups are those of the formula ##STR9## wherein R.sup.6, R.sup.7, and R.sup.8 can be independently selected from the group described above in connection with R.sup.2, provided at least one of R.sup.6, R.sup.7, and R.sup.8 is hydrogen and at least one of R.sup.6 and R.sup.7 is other than hydrogen, and R.sup.6 and R.sup.7 can together form a heterocyclic nucleus having a 5- or 6-membered ring, wherein the ring atoms are chosen from the class consisting of nitrogen, carbon, oxygen, sulfur, and selenium atoms. It is preferred that up to two of the ring atoms be hetero atoms and the remaining ring atoms be carbon atoms. The ring necessarily contains at least one nitrogen atom. Exemplary rings include morpholino, piperidino, pyrrolidinyl, pyrrolinyl, thiomorpholino, thiazolidinyl, 4-thiazolinyl, selenazolidinyl, 4-selenazolinyl, imidazolidinyl, imidazolinyl, oxazolidinyl, and 4-oxazolinyl rings. Specifically preferred rings are saturated or otherwise constructed to avoid electron withdrawal from the remaining nitrogen atom of the thiourea moiety.
The adsorption promoting group in another preferred form can be of the formula ##STR10## wherein n is an integer of 1 to 4.
The preferred adsorption promoting groups can be of the type described in Leone et al U.S. Pat. Nos. 4,030,925, 4,031,127, and 4,080,207, Leone Ser. No. 105,317, filed Dec. 19, 1979, and Sidhu et al Research Disclosure, Vol. 176, December 1978, Item 17626, the disclosures of which are here incorporated by reference.
Illustrative specific vinylene nucleating agents useful in the practice of this invention are those set forth below in Table I.
TABLE I
NA-1 2-(.beta.-anilinovinyl)-3-methylbenzothiazolium p-toluene sulfonate
NA-2 2-[.beta.(N-methylanilino)vinyl]-3-methylbenzothiazolium p-toluene sulfonate
NA-3 2-[.beta.-(o-methylthio-N-methylanilino)vinyl]-1-methylquinolinium p-toluene sulfonate
NA-4 2-[.beta.-(N-propargylanilino)vinyl]-3-ethylbenzoxazolium bromide
NA-5 2-[.beta.-(p-N-methylaminophenoxy)vinyl]-3-methylbenzothiazolium chloride
NA-6 2-[.beta.-(o-methoxy-N-methylanilino)vinyl]-3-methyl-benzothiazolium p-toluene sulfonate
NA-7 2-[.beta.-(N-propargylanilino)vinyl]-3-ethylbenzoselenazolium bromide
NA-8 2-[.beta.-(N-propargylanilino)vinyl]-1,3-diethyl-5,6-dichlorobenzimidazolium bromide
NA-9 2-[.beta.-(o-propargylthio-N-propargylanilino)vinyl]-3-methylbenzothiazolium bromide
NA-10 2-[.beta.-(o-methylthio-N-propargylanilino)vinyl]-3-methylbenzothiazolium p-toluene sulfonate
NA-11 2-[.beta.-methyl-.beta.-(o-propargylthio-N-methylanilino)vinyl]-3-methylbenzothiazolium bromide
NA-12 2-[.beta.-(N-propargylanilino)vinyl]-3-methylbenzothiazolium bromide
NA-13 2-[.beta.-N-methylanilinovinyl]-3-methyl-6-acetamidobenzothiazolium p-toluene sulfonate
NA-14 2-[.beta.-(N-methylanilino)vinyl]-3-methyl-6-(N'-ethylthioureido)benzothiazolium bromide
The vinylene nucleating agents can be employed with any conventional photographic element capable of forming a direct-positive image containing, coated on a photographic support, at least one silver halide emulsion layer containing a vehicle and silver halide grains capable of forming an internal latent image upon exposure to actinic radiation. As employed herein, the terms "internal latent image silver halide grains" and "silver halide grains capable of forming an internal latent image" are employed in the art-recognized sense of designating silver halide grains which produce substantially higher optical densities when coated, imagewise exposed and developed in an internal developer than when comparably coated, exposed and developed in a surface developer. Preferred internal latent image silver halide grains are those which, when examined according to normal photographic testing techniques, by coating a test portion on a photographic support (e.g., at a coverage of from 3 to 4 grams per square meter), exposing to a light intensity scale (e.g., with a 500-watt tungsten lamp at a distance of 61 cm) for a fixed time (e.g., between 1.times.10.sup.-2 and 1 second) and developing for 5 minutes at 25.degree. C. in Kodak Developer DK-50 (a surface developer), provide a density of at least 0.5 less than when this testing procedure is repeated, substituting for the surface developer Kodak Developer DK-50 containing 0.5 gram per liter of potassium iodide (an internal developer). The internal latent image silver halide grains most preferred for use in the practice of this invention are those which, when tested using an internal developer and a surface developer as indicated above, produce an optical density with the internal developer at least 5 times that produced by the surface developer. It is additionally preferred that the internal latent image silver halide grains produce an optical density of less than 0.4 and, most preferably, less than 0.25 when coated, exposed and developed in surface developer as indicated above, that is, the silver halide grains are preferably initially substantially unfogged and free of latent image on their surface.
The surface developer referred to herein as Kodak Developer DK-50 is described in the Handbook of Chemistry and Physics, 30th edition, 1947, Chemical Rubber Publishing Company, Cleveland, Ohio, page 2558, and has the following composition:
______________________________________Water, about 125.degree. F. (52.degree. C.) 500.0 ccN-methyl-p-aminophenol sulfate 2.5 gSodium sulfite, desiccated 30.0 gHydroquinone 2.5 gSodium metaborate 10.0 gPotassium bromide 0.5 gWater to make 1.0 liter.______________________________________
Internal latent image silver halide grains which can be employed in the practice of this invention are well known in the art. Patents teaching the use of internal latent image silver halide grains in photographic emulsions and elements include Davey et al U.S. Pat. No. 2,592,250, Porter et al U.S. Pat. No. 3,206,313, Milton U.S. Pat. No. 3,761,266, Ridgway U.S. Pat. No. 3,586,505, Gilman et al U.S. Pat. No. 3,772,030, Gilman et al U.S. Pat. No. 3,761,267, and Evans U.S. Pat. No. 3,761,276, the disclosures of which are hereby incorporated by reference.
The internal latent image silver halide grains preferably contain bromide as the predominant halide. The silver bromide grains can consist essentially of silver bromide or can contain silver bromoiodide, silver chlorobromide, silver chlorobromoiodide crystals and mixtures thereof. Internal latent image-forming sites can be incorporated into the grains by either physical or chemical internal sensitization. Davey et al, cited above, for example, teaches the physical formation of internal latent image-forming sites by the halide conversion technique. Chemical formation of internal latent image-forming sites can be produced through the use of sulfur, gold, selenium, tellurium and/or reduction sensitizers of the type described, for example, in Sheppard et al U.S. Pat. No. 1,623,499, Waller et al U.S. Pat. No. 2,339,083, McVeigh U.S. Pat. No. 3,297,447, and Dunn U.S. Pat. No. 3,297,446, as taught in the patents cited in the preceding paragraph. Internal latent image sites can also be formed through the incorporation of metal dopants, particularly Group VIII noble metals, such as, ruthenium, rhodium, palladium, iridium, osmium and platinum, as taught by Berriman U.S. Pat. No. 3,367,778. The preferred foreign metal ions are polyvalent metal ions which include the above-noted Group VIII dopants, as well as polyvalent metal ions such as lead, antimony, bismuth, and arsenic. In other preferred embodiments, the silver halide grains may be formed in the presence of bismuth, lead or iridium ions. In a preferred approach, the internal latent image sites can be formed within the silver halide grains during precipitation of silver halide. In an alternate approach, a core grain can be formed which is treated to form the internal image sites and then a shell deposited over the core grains, as taught by Porter et al, cited above.
The silver halide grains employed in the practice of this invention are preferably monodispersed, and in some embodiments are preferably large-grain emulsions made according to Wilgus German OLS No. 2,107,118, which is incorporated herein by reference. The monodispersed emulsions are those which comprise silver halide grains having a substantially uniform diameter. Generally, in such emulsions, no more than about 5 percent by number of the silver halide grains smaller than the mean grain size and/or no more than about 5 percent by number of the silver halide grains larger than the mean grain size vary in diameter from the mean grain diameter by more than about 40 percent. Preferred photographic emulsions of this invention comprise silver halide grains, at least 95 percent by weight of said grains having a diameter which is within 40 percent and preferably within about 30 percent of the mean grain diameter. Mean grain diameter, i.e., average grain size, can be determined using conventional methods, e.g., such as projective area, as shown in an article by Trivelli and Smith entitled "Empirical Relations Between Sensitometric and Size-Frequency Characteristics in Photographic Emulsion Series" in The Photographic Journal, Volume LXXIX, 1939, pages 330 through 338. The aforementioned uniform size distribution of silver halide grains is a characteristic of the grains in monodispersed photographic silver halide emulsions. Silver halide grains having a narrow size distribution can be obtained by controlling the conditions at which the silver halide grains are prepared using a double run procedure. In such a procedure, the silver halide grains are prepared by simultaneously running an aqueous solution of a silver salt, such as silver nitrate, and an aqueous solution of a water-soluble halide, for example, an alkali metal halide such as potassium bromide, into a rapidly agitated aqueous solution of a silver halide peptizer, preferably gelatin, a gelatin derivative or some other protein peptizer. Suitable methods for preparing photographic silver halide emulsions having the requred uniform particle size are disclosed in an article entitled "Ia: Properties of Photographic Emulsion Grains", by Klein and Moisar, The Journal of Photographic Science, Volume 12, 1964, pages 242 through 251; an article entitled "The Spectral Sensitization of Silver Bromide Emulsions on Different Crystallographic Faces", by Markocki, The Journal of Photograhic Science, Volume 13, 1965, pages 85 through 89; an article entitled "Studies on Silver Bromide Sols, Part I. The Formation and Aging of Monodispersed Silver Bromide Sols", by Ottewill and Woodbridge, The Journal of Photographic Science, Volume 13, 1965, pages 98 through 103; and an article entitled "Studies on Silver Bromide Sols, Part II. The Effect of Additives on the Sol Particles", by Ottewill and Woodbridge, The Journal of Photographic Science, Volume 13, 1965, pages 104 through 107.
Where internal latent image sites have been formed through internal chemical sensitization or the use of metal dopants, the surface of the silver halide grains can be sensitized to a level below that which will produce substantial density in a surface developer, that is, less than 0.4 (preferably less than 0.25) when coated, exposed and surface developed as described above. The silver halide grains are preferably predominantly silver bromide grains chemically surface sensitized to a level which would provide a maximum density of at least 0.5 using undoped silver halide grains of the same size and halide composition when coated, exposed and developed as described above.
Surface chemical sensitization can be undertaken using techniques such as those disclosed by Sheppard, Waller et al, McVeigh or Dunn, cited above. The silver halide grains can also be surface sensitized with salts of the noble metals, such as, ruthenium, palladium and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith et al U.S. Pat. No. 2,448,060, and as antifoggants in higher amounts, as described in Trivelli et al U.S. Pat. Nos. 2,566,245 and 2,566,263. The silver halide grains can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Pat. No. 2,487,850, polyamines, such as diethylene triamine (Lowe et al U.S. Pat. No. 2,518,698), polyamines, such as spermine (Lowe et al U.S. Pat. No. 2,521,925), or bis(.beta.-aminoethyl)sulfide and its water-soluble salts (Lowe et al U.S. Pat. No. 2,521,926).
The photographic silver halide emulsion layers and other layers of the photographic elements can contain various colloids alone or in combination as vehicles. Suitable hydrophilic materials include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives, e.g., cellulose esters, gelatin, e.g., alkali-treated gelatin (cattle bone or hide gelatin) or acid-treated gelatin (pigskin gelatin), gelatin derivatives, e.g., acetylated gelatin, phthalated gelatin, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, collodion, agar-agar, arrowroot, albumin, as described in Yutzy U.S. Pat. Nos. 2,614,928 and '929, Lowe et al U.S. Pat. Nos. 2,691,582, 2,614,930 and '931, 2,327,808, and 2,448,534, Gates et al U.S. Pat. Nos. 2,787,545 and 2,956,880, Himmelmann et al U.S. Pat. No. 3,061,436, Farrell et al U.S. Pat. No. 2,816,027, Ryan U.S. Pat. Nos. 3,132,945, 3,138,461, and 3,186,846, Dersch et al U.K. Pat. No. 1,167,159 and U.S. Pat. Nos. 2,960,405 and 3,436,220, Geary U.S. Pat. No. 3,486,896, Gazzard U.K. Pat. No. 793,549, Gates et al U.S. Pat. Nos. 2,992,213, 3,157,506, 3,184,312 , and 3,539,353, Miller et al U.S. Pat. No. 3,227,571, Boyer et al U.S. Pat. No. 3,532,502, Malan U.S. Pat. No. 3,551,151, Lohmer et al U.S. Pat. No. 4,018,609, Luciani et al U.K. Pat. No. 1,186,790, Hori et al U.K. Pat. No. 1,489,080 and Belgian Pat. No. 856,631, U.K. Pat. No. 1,490,644, U.K. Pat. No. 1,483,551, Arase et al U.K. Pat. No. 1,459,906, Salo U.S. Pat. Nos. 2,110,491 and 2,311,086, Fallesen U.S. Pat. No. 2,343,650, Yutzy U.S. Pat. No. 2,322,085, Lowe U.S. Pat. No. 2,563,791, Talbot et al U.S. Pat. No. 2,725,293, Hilborn U.S. Pat. No. 2,748,022, DePauw et al U.S. Pat. No. 2,956,883, Ritchie U.K. Pat. No. 2,095, DeStubner U.S. Pat. No. 1,752,069, Sheppard et al U.S. Pat. No. 2,127,573, Lierg U.S. Pat. No. 2,256,720, Gaspar U.S. Pat. No. 2,361,936, Farmer U.K. Pat. No. 15,727, Stevens U.K. Pat. No. 1,062,116, and Yamamoto et al U.S. Pat. No. 3,923,517.
Photograhic emulsion layers, and other layers of photographic elements, such as, overcoat layers, interlayers, and subbing layers, as well as receiving layers in image-transfer elements, can also contain alone or in combination with hydrophilic water-permeable colloids as vehicles or vehicle extenders (e.g., in the form of latices), synthetic polymeric peptizers, carriers and/or binders such as poly(vinyl lactams), acrylamide polymers, polyvinyl alcohol, and its derivatives, polyvinyl acetals, polymers of alkyl, and sulfoalkyl acrylates, and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, acrylic acid polymers, maleic anhydride copolymers, polyalkylene oxides, methacrylamide copolymers, polyvinyl oxazolidinones, maleic acid copolymers, vinylamine copolymers, methacrylic acid copolymers, acryloyloxyalkylsulfonic acid copolymers, sulfoalkylacrylamide copolymers, polyalkyleneimine copolymers, polyamines, N,N-dialkylaminoalkyl acrylates, vinyl imidazole copolymers, vinyl sulfide copolymers, halogenated styrene polymers, amineacrylamide polymers, and polypeptides, as described in Hollister et al U.S. Pat. Nos. 3,679,425, 3,706,564, and 3,813,251, Lowe U.S. Pat. Nos. 2,253,078, 2,276,322 and '323, 2,281,703, 2,311,058, and 2,414,207, Lowe et al U.S. Pat. Nos. 2,484,456, 2,541,474, and 2,632,704, Perry et al U.S. Pat. No. 3,425,836, Smith et al U.S. Pat. Nos. 3,415,653 and 3,615,624, Smith U.S. Pat. No. 3,488,708, Whiteley et al U.S. Pat. Nos. 3,392,025 and 3,511,818, Fitzgerald U.S. Pat. Nos. 3,681,079, 3,721,565, 3,852,073, 3,861,918, and 3,925,083, Fitzgerald et al U.S. Pat. No. 3,879,205, Nottorf U.S. Pat. No. 3,142,568, Houck et al U.S. Pat. Nos. 3,062,674 and 3,220,844, Dann et al U.S. Pat. No. 2,882,161, Schupp U.S. Pat. No. 2,579,016, Weaver U.S. Pat. No. 2,829,053, Alles et al U.S. Pat. No. 2,698,240, Priest et al U.S. Pat. No. 3,003,879, Merrill et al U.S. Pat. No. 3,419,397, Stonham U.S. Pat. No. 3,284,207, Lohmer et al U.S. Pat. No. 3,167,430, Williams U.S. Pat. No. 2,957,767, Dawson et al U.S. Pat. No. 2,893,867, Smith et al U.S. Pat. Nos. 2,860,986 and 2,904,539, Ponticello et al U.S. Pat. Nos. 3,929,482 and 3,860,428. Ponticello U.S. Pat. No. 3,939,130, Dykstra U.S. Pat. No. 3,411,911, Dykstra et al Canadian Pat. No. 774,054, Ream et al U.S. Pat. No. 3,287,289, Smith U.K. Pat. No. 1,466,600, Stevens U.K. Pat. No. 1,062,116, Fordyce U.S. Pat. No. 2,211,323, Martinez U.S. Pat. No. 2,284,877, Watkins U.S. Pat. No. 2,420,455 , Jones U.S. Pat. No. 2,533,166, Bolton U.S. Pat. No. 2,495,918, Graves U.S. Pat. No. 2,289,775, Yackel U.S. Pat. No. 2,565,418, Unruh et al U.S. Pat. Nos. 2,865,893 and 2,875,059, Rees et al U.S. Pat. No. 3,536,491, Broadhead et al U.K. Pat. No. 1,348,815, Taylow et al U.S. Pat. No. 3,479,186, Merrill et al U.S. Pat. No. 3,520,857, Bacon et al U.S. Pat. No. 3,690,888, Bowman U.S. Pat. No. 3,748,143, Dickinson et al U.K. Pat. Nos. 808,227 and '228, Wood U.K. Pat. No. 822,192, and Iguchi et al U.K. Pat. No. 1,398,055.
The layers of the photographic elements can be coated on a variety of supports. Typical photographic supports include polymeric film, wood fiber, e.g., paper, metallic sheet and foil, glass and ceramic supporting elements provided with one or more subbing layers to enhance the adhesive, antistatic, dimensional, abrasive, hardness, frictional, antihalation, and/or other properties of the support surface.
Typical of useful polymeric film supports are films of cellulose nitrate and cellulose esters, such as, cellulose triacetate and diacetate, polystyrene, polyamides, homo-polymers and co-polymers of vinyl chloride, poly(vinyl acetal), polycarbonate, homo-polymers and co-polymers of olefins, such as, polyethylene and polypropylene, and polyesters of dibasic aromatic carboxylic acids with divalent alcohols, such as poly(ethylene terephthalate).
Typical of useful paper supports are those which are partially acetylated or coated with baryta and/or a polyolefin, particularly a polymer of an .beta.-olefin containing 2 to 10 carbon atoms, such as, polyethylene, polypropylene, copolymers of ethylene and propylene.
Polyolefins, such as, polyethylene, polypropylene and polyallomers, e.g., copolymers of ethylene with propylene, as illustrated by Hagemeyer et al U.S. Pat. No. 3,478,128, are preferably employed as resin coatings over paper, as illustrated by Crawford et al U.S. Pat. No. 3,411,908 and Joseph et al U.S. Pat. No. 3,630,740, over polystyrene and polyester film supports, as illustrated by Crawford et al U.S. Pat. No. 3,630,742, or can be employed as unitary flexible reflection supports, as illustrated by Venor et al U.S. Pat. No. 3,973,963.
Preferred cellulose ester supports are cellulose triacetate supports, as illustrated by Fordyce et al U.S. Pat. Nos. 2,492,977, '978, and 2,739,069, as well as mixed cellulose ester supports, such as, cellulose acetate propionate and cellulose acetate butyrate, as illustrated by Fordyce et al U.S. Pat. No. 3,739,070.
Preferred polyester film supports are comprised of linear polyester, such as illustrated by Alles et al U.S. Pat. No. 2,627,088, Wellman U.S. Pat. No. 2,720,503, Alles U.S. Pat. No. 2,779,684, and Kibler et al U.S. Pat. No. 2,901,466. Polyester films can be formed by varied techniques, as illustrated by Alles, cited above, Czerkas et al U.S. Pat. No. 3,663,683, and Williams et al U.S. Pat. No. 3,504,075, and modified for use as photographic film supports, as illustrated by Van Stappen U.S. Pat. No. 3,227,576, Nadeau et al U.S. Pat. No. 3,501,301, Reedy et al U.S. Pat. No. 3,589,905, Babbitt et al U.S. Pat. No. 3,850,640, Bailey et al U.S. Pat. No. 3,888,678, Hunter U.S. Pat. No. 3,904,420, and Mallinson et al U.S. Pat. No. 3,928,697.
The photographic elements can employ supports which are resistant to dimensional change at elevated temperatures. Such supports can be comprised of linear condensation polymers which have glass transition temperatures above about 190.degree. C., preferably 220.degree. C., such as, polycarbonates, polycarboxylic esters, polyamides, polysulfonamides, polyethers, polyimides, polysulfonates and copolymer variants, as illustrated by Hamb U.S. Pat. Nos. 3,634,089 and 3,772,405, Hamb et al U.S. Pat. Nos. 3,725,070 and 3,793,249, Wilson Research Disclosure, Volume 118, February 1974, Item 11833, and Volume 120, April 1974, Item 12046, Conklin et al Research Disclosure, Volume 120, April 1974, Item 12012, Product Licensing Index, Volume 92, December 1971, Items 9205 and 9207, Research Disclosure, Volume 101, September 1972, Items 10119 and 10148, Research Disclosure, Volume 106, February 1973, Item 10613, Research Disclosure, Volume 117, January 1974, Item 11709, and Research Disclosure, Volume 134, June 1975, Item 13455. Both Research Disclosure and Product Licensing Index are published by Industrial Opportunities, Ltd., Homewell, Havant, Hampshire PO9 1EF, United Kingdom.
The vinylene nucleating agents of this invention can be employed in any desired concentration that will permit a degree of selectivity in developing imagewise silver halide grains capable of forming an internal latent image, which grains have not been imagewise exposed, as compared to silver halide grains containing an internal latent image formed by imagewise exposure.
It is preferred to incorporate the vinylene nucleating agents into the silver halide emulsions in concentrations of from 10.sup.-5 to about 10.sup.-2 mole per mole of silver halide. Where an efficient adsorption promoting moiety is incorporated in the vinylene nucleating agent, such as a thioamide (particularly a thiourea) or a triazole, as described above, it is generally unnecessary to provide nucleating concentrations in excess of about 10 .sup.-3 mole per mole of silver halide. On the other hand, where such adsorption promoting nuicleating agents are absent and the heterocyclic nucleus is being relied upon to promote adsorption to the silver halide grains, it is generally preferred that the nucleating agents be incorporated in a concentration of at least 10.sup.-4 mole per mole of silver halide. Where the vinylene nucleating agent is to be adsorbed to the surface of the silver halide grains, it can be adsorbed using the procedures well known to those skilled in the art for adsorbing sensitizing dyes, such as, cyanine and merocyanine dyes, to the surface of silver halide grains.
A simple exposure and development process can be used to form a direct-positive image. In one embodiment, a photographic element comprising at least one layer of a silver halide emulsion as described above can be imagewise exposed to light and then developed in a silver halide surface developer.
It is understood that the term "surface developer" encompasses those developers which will reveal the surface latent image on a silver halide grain, but will not reveal substantial internal latent image in an internal image-forming emulsion, and under the conditions generally used develop a surface-sensitive silver halide emulsion. The surface developers can generally utilize any of the silver halide developing agents or reducing agents, but the developing bath or composition is generally substantially free of a silver halide solvent (such as water-soluble thiocyanates, water-soluble thioethers, thiosulfates, and ammonia) which will disrupt or dissolve the grain to reveal substantial internal image. Low amounts of excess halide are sometimes desirable in the developer or incorporated in the emulsion as halide-releasing compounds, but high amounts of iodide or iodide-releasing compounds are generally avoided to prevent substantial disruption of the grain. Typical silver halide developing agents which can be used in the developing compositions of this invention include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and color developing agents, that is, primary aromatic amine developing agents, such as, aminophenols and para-phenylenediamines. The color developing agents are preferably employed in combination with black-and-white developing agents capable of acting as electron transfer agents. Illustrative of useful surface developers are those disclosed in Ives U.S. Pat. No. 2,563,785, Evans U.S. Pat. No. 3,761,276, Knott et al U.S. Pat. No. 2,456,953, and Juoy U.S. Pat. No. 3,511,662.
Where the developing agents are initially entirely incorporated in the photographic elements, the remaining components (e.g., water, activators to adjust pH, preservatives, etc.) normally present in surface developers constitute what is commonly referred to as an activator solution. Except for the omission of the developing agent, activator solutions are identical to developer solutions in composition and are employed identically with incorporated developing agent photographic elements. Subsequent references to developing compositions are inclusive of both developer and activator solutions.
The surface developers are alkaline. Conventional activators, preferably in combination with buffers, such as, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate or sodium metaphosphate, can be employed to adjust pH to a desired alkaline level. The amounts of these materials present are selected so as to adjust the developer to a pH in the range of from 10 to 13, preferably from about 10.2 to 12.0.
The developing compositions used in the process of this invention can contain certain antifoggants and development restrainers, or, optionally, they can be incorporated in layers of the photographic element. For example, in some applications, improved results can be obtained when the direct-positive emulsions are processed in the presence of certain antifoggants, as disclosed in Stauffer U.S. Pat. No. 2,497,917, which is incorporated herein by reference.
Typical useful antifoggants include benzotriazoles, such as, benzotriazole, 5-methylbenzotriazole, and 5-ethylbenzotriazole, benzimidazoles, such as, 5-nitrobenzimidazole, benzothiazoles, such as, 5-nitrobenzothiazole and 5-methylbenzothiazole, heterocyclic thiones, such as, 1-methyl-2-tetrazoline-5-thione, triazines, such as, 2,4-dimethylamino-6-chloro-5-triazine, benzoxazoles, such as, ethylbenzoxazole, and pyrroles, such as, 2,5-dimethylpyrrole and the like.
Improved results are obtained when the element is processed in the presence of the antifoggants mentioned above. The antifoggants can be present in the processing solution during development or incorporated in the photographic element. It is preferred to incorporate the antifoggant in the processing solution. Concentrations of from about 1 mg to 1 gram per liter are contemplated, with concentrations of from about 5 to 500 mg per liter being preferred. Optimum antifoggant concentrations are a function of the specific antifoggant, element, and processing solution employed.
The essential features of the vinylene nucleating agents of this invention and the silver halide emulsions and photographic elements in which they are incorporated, as well as procedures for their use and processing, are described above. It is appreciated that, in preferred photographic applications, the emulsions and elements can contain additional features which are in themselves well known to those familiar with the photographic arts. Further, these applications can entail conventional modifications in the procedures described above. A variety of such features are disclosed in Research Disclosure, Volume 176, December 1978, Item 17643, the disclosure of which is herein incorporated by reference, particularly Paragraph II, Emulsion washing; Paragraph IV, Spectral sensitization and Desensitization; Paragraph V, Brighteners; Paragraph VI, Antifoggants and stabilizers; Paragraph VIII, Absorbing and scattering materials; Paragraph X, Hardeners; Paragraph XI, Coating aids; Paragraph XII, Plasticizers and lubricants, Paragraph XIII, Antistatic layers; Paragraph XIV, Methods of addition; Paragraph XV, Coating and drying Procedures; Paragraph XVI, Matting agents; Paragraph XVIII, Exposure; Paragraph XIX, Processing (as applied to post-development processing and paragraphs G, H, I, and J, relating to amplification); Paragraph XX, Developing agents; and Paragraph XXI, Development modifiers.
It is specifically contemplated that the vinylene nucleating agents of the present invention can be employed in combination with conventional nucleating agents of the quaternary ammonium salt, hydrazine, hydrazide, and hydrazone type, such as those cited above to illustrate known nucleating agents. The conventional nucleating agents can be incorporated in the photographic element in previously taught concentrations, typically up to 2 grams per mole of silver. The conventional nucleating agents can also be present in the developer in previously taught concentrations, typically up to about 5 grams per liter. Since the use of conventional nucleating agents is not essential to the practice of this invention, no minimum concentration is required; however, when employed, conventional nucleating agents are preferably present in a concentration range of from about 10 to 500 mg per mole of silver when present in the emulsion and from about 0.1 to 1 gram per liter when present in the developer.
The silver halide emulsions can be spectrally sensitized with cyanine, merocyanine, and other polymethine dyes and supersensitizing combinations thereof well known in the art. Spectral sensitizers in conventional surface-sensitive emulsions are comparably effective in the emulsions of this invention. In general, they enhance nucleation. Nonionic, zwitterionic and anoinic spectral sensitizers are preferred. Particularly effective are carboxy-substituted merocyanine dyes of the thiohydantoin type described by Stauffer et al U.S. Pat. No. 2,490,758.
Effective red sensitizers are the carbocyanines of formula (VII) ##STR11## wherein
each of Z.sup.1 and Z.sup.2 represents the atoms necessary to form a benzothiazole, benzoselenazole, naphthothiazole, or naphthoselenazole, the benzothiazole and benzoselenazole being preferably 5- and/or 6-substituted with groups such as lower alkyl, lower alkoxy, chloro, bromo, fluoro, hydroxy, acylamino, cyano, and trifluoromethyl,
G represents hydrogen and lower alkyl, preferably ethyl or methyl,
each of R.sup.1 and R.sup.2 represents lower alkyl or hydroxy-(lower)alkyl, at least one of R.sup.1 and R.sup.2 being preferably acid-substituted(lower)alkyl, such as, carboxyethyl, sulfopropyl, and sulfatoethyl,
X represents an acid anion, and
n is 1 or 2.
Particularly effective are certain supersensitizing combinations of the above dyes with each other and with dyes or other adsorbed organic compounds having polarographic oxidation potentials (E.sub.ox) of about 0.3 to 0.9 volt. Many such combinations are described in Mees U.S. Pat. No. 2,075,048, Carroll et al U.S. Pat. Nos. 2,313,922, 2,533,426, 2,688,545, and 2,704,714, Jones U.S. Pat. No. 2,704,717, and Schwan U.S. Pat. No. 3,672,898, and include, as well, the acid-substituted analogues thereof well known in the art.
Effective green sensitizers are carbocyanines and cyanines of formulas (VIII) and (IX) ##STR12## wherein
each of Z.sup.1 and Z.sup.2 represents the atoms necessary to form benzoxazole and benzimidazole nuclei, benzimidazole being substituted in the 3-position by lower alkyl or aryl, and preferably in the 5- and/or 6-positions with groups selected from fluoro, chloro, bromo, lower alkyl, cyano, acylamino and trifluoromethyl, and the benzoxazole ring preferably substituted im the 5- or 6-positions with lower alkyl, lower alkoxy, phenyl, fluoro, chloro, and bromo,
Z.sup.3 represents the atoms necessary to form benzothiazole, benzoselenazole, naphthothiazole, naphthoselenazole, or 2-quinoline,
Z.sup.4 represents the atoms necessary to form 2quinoline,
G represents lower alkyl and, if at least one of Z.sup.1 and Z.sup.2 forms benzimidazole, hydrogen,
each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represents lower alkyl or hydroxy(lower)alkyl, at least one of R.sup.1 and R.sup.2 and of R.sup.3 and R.sup.4 being preferably acidsubstituted(lower)alkyl such as carboxyethyl, sulfopropyl, and sulfatoethyl,
X represents an acid anion, and
n is 1 or 2.
Particularly effective are certain supersensitizing combinations of the above dyes, such as those described in Carroll et al U.S. Pat. Nos. 2,688,545 and 2,701,198 and Nys et al U.S. Pat. No. 2,973,264, and their acid-substituted analogues well known in the art.
Effective blue sensitizers are simple cyanines and merocyanines of formulas (X) and (XII) ##STR13## wherein
each of Z.sup.1 and Z.sup.2 represents the atoms necessary to form benzothiazole, benzoselenazole, naphthothiazole and naphthoselenazole nuclei which may be substituted with groups such as chloro, methyl or methoxy, chloro, bromo, lower alkyl, or lower alkoxy,
Z.sup.3 represents benzothiazole, benzoselenazole which may be substituted as in Z.sup.1 and Z.sup.2, and a pyridine nucleus,
Q.sup.1 and Q.sup.2 together represent the atoms necessary to complete a rhodanine, 2-thio-2,4-oxazolidinedione or 2-thiohydantoin ring, the latter having a second nitrogen atom with a substituent R.sup.5,
m represents 0 or 1,
each of R.sup.1, R.sup.2 and R.sup.3 represents lower alkyl or hydroxy(lower)alkyl, at least one of R.sup.1 and R.sup.2 being preferably acid-substituted(lower)alkyl such as carboxyethyl, sulfopropyl, and sulfatoethyl,
R.sup.4 and R.sup.5 represent lower alkyl and hydroxy(lower)alkyl, and R.sup.4 additionally can represent carboxyalkyl and sulfoalkyl,
X is an acid anion, and
n is 1 or 2. (Lower alkyl in each occurrence of Formulas VII to XI includes from 1 to 5 carbon atoms.)
The photographic elements are preferably color photographic elements which form dye images through the selective destruction, formation or physical removal of dyes.
The photographic elements can produce dye images through the selective destruction of dyes or dye precursors, such as silver-dye-bleach processes, as illustrated by A. Meyer, The Journal of Photographic Science, Volume 13, 1965, pages 90 through 97. Bleachable azo, azoxy, xanthene, azine, phenylmethane, nitroso complex, indigo, quinone, nitro-substituted, phthalocyanine and formazan dyes, as illustrated by Stauner et al U.S. Pat. No. 3,754,923, Piller et al U.S. Pat. No. 3,749,576, Yoshida et al U.S. Pat. No. 3,738,839, Froelich et al U.S. Pat. No. 3,716,368, Piller U.S. Pat. No. 3,655,388, Williams et al U.S. Pat. No. 3,642,482, Gilman U.S. Pat. No. 3,567,448, Loeffel U.S. Pat. No. 3,443,953, Anderau U.S. Pat. Nos. 3,443,952 and 3,211,556, Mory et al U.S. Pat. Nos. 3,202,511 and 3,178,291, and Anderau et al U.S. Pat. Nos. 3,178,285 and 3,178,290 as well as their hydrazo, diazonium, and tetrazolium precursors and leuco and shifted derivatives, as illustrated by U.K. Pat. Nos. 923,265, 999,996, and 1,042,300, Pelz et al U.S. Pat. No. 3,684,513, Watanabe et al U.S. Pat. No. 3,615,493, Wilson et al U.S. Pat. No. 3,503,741, Boes et al U.S. Pat. No. 3,340,059, Gompf et al U.S. Pat. No. 3,493,372, and Puschel et al U.S. Pat. No. 3,561,970 can be employed.
The photographic elements can produce dye images through the selective formation of dyes, such as by reacting (coupling) a color-developing agent (e.g., a primary aromatic amine) in its oxidized form with a dye-forming coupler. The dye-forming couplers can be incorporated in the photographic elements, as illustrated by Schneider et al, Die Chemie, Volume 57, 1944, page 113, Mannes et al U.S. Pat. No. 2,304,940, Martinez U.S. Pat. No. 2,269,158, Jelley et al U.S. Pat. No. 2,322,027, Frolich et al U.S. Pat. No. 2,376,679, Fierke et al U.S. Pat. No. 2,801,171, Smith U.S. Pat. No. 3,748,141, Tong U.S. Pat. No. 2,772,163, Thirtle et al U.S. Pat. No. 2,835,579, Sawdey et al U.S. Pat. No. 2,533,514, Peterson U.S. Pat. No. 2,353,754, Seidel U.S. Pat. No. 3,409,435, and Chen Research Disclosure, Volume 159, July 1977, Item 15930.
In one form, the dye-forming couplers are chosen to form subtractive primary (i.e., yellow, magenta, and cyan) image dyes and are nondiffusible, colorless couplers, such as, two- and four-equivalent couplers of the open chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol, and naphthol type hydrophobically ballasted for incorporation in high-boiling organic (coupler) solvents. Such couplers are illustrated by Salminen et al U.S. Pat. Nos. 2,423,730, 2,772,162, 2,895,826, 2,710,803, 2,407,207, 3,737,316, and 2,367,531, Loria et al U.S. Pat. Nos. 2,772,161, 2,600,788, 3,006,759, 3,214,437, and 3,253,924, McCrossen et al U.S. Pat. No. 2,875,057, Bush et al U.S. Pat. No. 2,908,573, Gledhill et al U.S. Pat. No. 3,034,892, Weissberger et al U.S. Pat. Nos. 2,474,293, 2,407,210, 3,062,653, 3,265,506, and 3,384,657, Porter et al U.S. Pat. No. 2,343,703, Greenhalgh et al U.S. Pat. No. 3,127,269, Feniak et al U.S. Pat. Nos. 2,865,748, 2,933,391, and 2,865,751, Bailey et al U.S. Pat. No. 3,725,067, Beavers et al U.S. Pat. No. 3,758,308, Lau U.S. Pat. No. 3,779,763, Fernandez U.S. Pat. No. 3,785,829, U.K. Pat. No. 969,921, U.K. Pat. No. 1,241,069, U.K. Pat. No. 1,011,940, Vanden Eynde et al U.S. Pat. No. 3,762,921, Beavers U.S. Pat. No. 2,983,608, Loria U.S. Pat. Nos. 3,311,476, 3,408,194, 3,458,315, 3,447,928, and 3,476,563, Cressman et al U.S. Pat. No. 3,419,390, Young U.S. Pat. No. 3,419,391, Lestina U.S. Pat. No. 3,519,429, U.K. Pat. No. 975,928, U.K. Pat. No. 1,111,554, Jaeken U.S. Pat. No. 3,222,176 and Canadian Pat. No. 726,651, Schulte et al U.K. Pat. No. 1,248,924, and Whitmore et al U.S. Pat. No. 3,227,550.
The photographic elements can incorporate alkali-soluble ballasted couplers, as illustrated by Froelich et al and Tong, cited above. The photographic elements can be adapted to form nondiffusible image dyes using dye-forming couplers in developers, as illustrated by U.K. Pat. No. 478,984, Yager et al U.S. Pat. No. 3,113,864, Vittum et al U.S. Pat. Nos. 3,002,836, 2,271,238, and 2,362,598, Schwan et al U.S. Pat. No. 2,950,970, Carroll et al U.S. Pat. No. 2,592,243, Porter et al U.S. Pat. Nos. 2,343,703, 2,376,380, and 2,369,489, Spath U.K. Pat. No. 886,723 and U.S. Pat. No. 2,899,306, Tuite U.S. Pat. No. 3,152,896, and Mannes et al U.S. Pat. Nos. 2,115,394, 2,252,718, and 2,108,602.
The dye-forming couplers upon coupling can release photographically useful fragments, such as, development inhibitors or accelerators, bleach accelerators, developing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers, and desensitizers. Development inhibitor-releasing (DIR) couplers are illustrated by Whitmore et al U.S. Pat. No. 3,148,062, Barr et al U.S. Pat. No. 3,227,554, Barr U.S. Pat. No. 3,733,201, Sawdey U.S. Pat. No. 3,617,291, Groet et al U.S. Pat. No. 3,703,375, Abbott et al U.S. Pat. No. 3,615,506, Weissberger et al U.S. Pat. No. 3,265,506, Seymour U.S. Pat. No. 3,620,745, Marx et al U.S. Pat. No. 3,632,345, Mader et al U.S. Pat. No. 3,869,291, U.K. Pat. No. 1,201,110, Oishi et al U.S. Pat. No. 3,642,485, Verbrugghe U.K. Pat. No. 1,236,767, Fujiwhara et al U.S. Pat. No. 3,770,436, and Matsuo et al U.S. Pat. No. 3,808,945. DIR compounds which do not form dye upon reaction with oxidized color-developing agents can be employed, as illustrated by Fujiwhara et al German OLS No. 2,529,350 and U.S. Pat. Nos. 3,928,041, 3,958,993, and 3,961,959, Odenwalder et al German OLS No. 2,448,063, Tanaka et al German OLS No. 2,610,546, Kikuchi et al U.S. Pat. No. 4,049,455, and Credner et al U.S. Pat. No. 4,052,213. DIR compounds which oxidatively cleave can be employed, as illustrated by Porter et al U.S. Pat. No. 3,379,529, Green et al U.S. Pat. No. 3,043,690, Barr U.S. Pat. No. 3,364,022, Duennebier et al U.S. Pat. No. 3,297,445, and Rees et al U.S. Pat. No. 3,287,129.
The photographic elements can incorporate colored dye-forming couplers, such as those employed to form integral masks for negative color images, as illustrated by Hanson U.S. Pat. No. 2,449,966, Glass et al U.S. Pat. No. 2,521,908, Gledhill et al U.S. Pat. No. 3,034,892, Loria U.S. Pat. No. 3,476,563, Lestina U.S. Pat. No. 3,519,429, Friedman U.S. Pat. No. 2,543,691, Puschel et al U.S. Pat. No. 3,028,238, Menzel et al U.S. Pat. No. 3,061,432, and Greenhalgh U.K. Pat. No. 1,035,959, and/or competing couplers, as illustrated by Murin et al U.S. Pat. No. 3,876,428, Sakamoto et al U.S. Pat. No. 3,580,722, Puschel U.S. Pat. No. 2,998,314, Whitmore U.S. Pat. No. 2,808,329, Salminen U.S. Pat. No. 2,742,832, and Weller et al U.S. Pat. No. 2,689,793.
The photographic elements can produce dye images through the selective removal of dyes. Negative or positive dye images can be produced by the immobilization of incorporated color-providing substances as a function of exposure and development, as illustrated by U.K. Pat. Nos. 1,456,413, 1,479,739, 1,475,265, and 1,471,752, Friedman U.S. Pat. No. 2,543,691, Whitmore U.S. Pat. No. 3,227,552, Bloom et al U.S. Pat. No. 3,443,940, Morse U.S. Pat. No. 3,549,364, Cook U.S. Pat. No. 3,620,730, Danhauser U.S. Pat. No. 3,730,718, Staples U.S. Pat. No. 3,923,510, Oishi et al U.S. Pat. No. 4,052,214, and Fleckenstein et al U.S. Pat. No. 4,076,529.
The photographic elements can contain antistain agents (i.e., oxidized developing agent scavengers) to prevent developing agents oxidized in one dye image layer unit from migrating to an adjacent dye image layer unit. Such antistain agents include ballasted or otherwise nondiffusing antioxidants, as illustrated by Weissberger et al U.S. Pat. No. 2,336,327, Loria et al U.S. Pat. No. 2,728,659, Vittum et al U.S. Pat. No. 2,360,290, Jelley et al U.S. Pat. No. 2,403,721, and Thirtle et al U.S. Pat. No. 2,701,197. To avoid autooxidation the antistain agents can be employed in combination with other antioxidants, as illustrated by Knechel et al U.S. Pat. No. 3,700,453.
The photographic elements can include image dye stabilizers. Such image dye stabilizers are illustrated by U.K. Pat. No. 1,326,889, Lestina et al U.S. Pat. Nos. 3,432,300 and 3,698,909, Stern et al U.S. Pat. No. 3,574,627, Brannock et al U.S. Pat. No. 3,573,050, Arai et al U.S. Pat. No. 3,764,337, and Smith et al U.S. Pat. No. 4,042,394.
This invention is particularly useful with photographic elements used in image transfer processes or in image transfer film units.
Image transfer systems include colloid transfer systems, as illustrated by Yutzy et al U.S. Pat. Nos. 2,596,756 and 2,716,059, silver salt diffusion transfer systems, as illustrated by Rott U.S. Pat. No. 2,352,014, Land U.S. Pat. No. 2,543,181, Yackel et al U.S. Pat. No. 3,020,155, and Land U.S. Pat. No. 2,861,885, imbibition transfer systems, as illustrated by Minsk U.S. Pat. No. 2,882,156, and color image transfer systems, as illustrated by Research Disclosure, Volume 151, November 1976, Item 15162, and Volume 123, July 1974, Item 12331.
Color image transfer systems (including emulsion layers, receiving layers, timing layers, acid layers, processing compositions, supports, and cover sheets) and the images they produce can be varied by choosing among a variety of features, combinations of which can be used together as desired.
Film units can be chosen which are either integrally laminated or separated during exposure, processing and/or viewing, as illustrated by Rogers U.S. Pat. No. 2,983,606, Beavers et al U.S. Pat. No. 3,445,228, Whitmore, Canadian Pat. No. 674,082, Friedman et al U.S. Pat. No. 3,309,201, Land U.S. Pat. Nos. 2,543,181, 3,053,659, 3,415,644, 3,415,645, and 3,415,646, and Barr et al U.K. Pat. No. 1,330,524.
A variety of approaches are known in the art for obtaining transferred dye images. The approaches can be generally categorized in terms of the initial mobility of dye or dye precursor. (Initial mobility refers to the mobility of the dye or dye precursor when it is contacted by the processing solution. Initially mobile dyes and dye precursors as coated do not migrate prior to contact with processing solution.)
Dye image-providing compounds are classified as either positive-working or negative-working. Positive-working dye image-providing compounds are those which produce a positive transferred dye image when employed in combination with a conventional, negative-working silver halide emulsion. Negative-working dye image-providing compounds are those which produce a negative transferred dye image when employed in combination with conventional, negative-working silver halide emulsions. (The foregoing techniques, such as those referred to in Research Disclosure, Vol. 176, December 1978, Item 17643, paragraph XXIII-E.) When, as in the present invention, the silver halide emulsions are direct-positive emulsions, positive-working dye image-providing compounds produce negative transferred dye images and negative-working dye image-providing compounds produce positive transferred dye images.
Image transfer systems, which include both the dye image-providing compounds and the silver halide emulsions, are positive-working when the transferred dye image is positive and negative-working when the transferred dye image is negative. When a retained dye image is formed, it is opposite in sense to the transferred dye image.
A variety of dye image transfer systems have been developed and can be employed in the practice of this invention. One approach is to employ ballasted dye-forming (chromogenic) or nondye-forming (nonchromogenic) couplers having a mobile dye attached at a coupling-off site. Upon coupling with an oxidized color developing agent, such as a para-phenylenediamine, the mobile dye is displaced so that it can transfer to a receiver. This negative-working image transfer approach is illustrated by Whitmore et al U.S. Pat. No. 3,227,550, Whitmore U.S. Pat. No. 3,227,552, and Fujihara et al U.K. Pat. No. 1,445,797, the disclosures of which are here incorporated by reference.
In a preferred image transfer system according to this invention employing negative-working dye image-providing compounds, a cross-oxidizing developing agent (electron transfer agent) develops silver halide and then cross-oxidizes with a compound containing a dye linked through an oxidizable sulfonamido group, such as a sulfonamidophenol, sulfonamidoaniline, sulfonamidoanilide, sulfonamidopyrazolobenzimidazole, sulfonamidoindole or sulfonamidopyrazole. Following cross-oxidation, hydrolytic deamidation cleaves the mobile dye with the sulfonamido group attached. Such systems are illustrated by Fleckenstein U.S. Pat. Nos. 3,928,312 and 4,053,312, Fleckenstein et al U.S. Pat. No. 4,076,529, Melzer et al U.K. Pat. No. 1,489,694, Deguchi, German OLS No. 2,729,820, Koyama et al, German OLS No. 2,613,005, Vetter et al German OLS No. 2,505,248, and Kestner et al Research Disclosure, Volume 151, November 1976, Item 15157. Also specifically contemplated are otherwise similar systems which employ an immobile, dye-releasing (a) hydroquinone, as illustrated by Gompf et al U.S. Pat. No. 3,698,897 and Anderson et al U.S. Pat. No. 3,725,062, (b) para-phenylenediamine, as illustrated by Whitmore et al Canadian Pat. No. 602,607, or (c) quaternary ammonium compound, as illustrated by Becker et al U.S. Pat. No. 3,728,113.
Another specifically contemplated dye image transfer system which is negative-working reacts an oxidized electron transfer agent or, specifically, in certain forms, an oxidized para-phenylenediamine with a ballasted phenolic coupler having a dye attached through a sulfonamido linkage. Ring closure to form a phenazine releases mobile dye. Such an imaging approach is illustrated by Bloom et al U.S. Pat. Nos. 3,443,939 and 3,443,940.
In still another negative-working system, ballasted sulfonylamidrazones, sulfonylhydrazones or sulfonylcarbonylhydrazides can be reacted with oxidized para-phenylenediamine to release a mobile dye to be transferred, as illustrated by Puschel et al U.S. Pat. Nos. 3,628,952 and 3,844,785. In an additional negative-working system, a hydrazide can be reacted with silver halide having a developable latent image site and thereafter decompose to release a mobile, transferable dye, as illustrated by Rogers U.S. Pat. No. 3,245,789, Kohara et al, Bulletin Chemical Society of Japan, Volume 43, pages 2433 through 2437, and Lestina et al Research Disclosure, Volume 28, December 1974, Item 12832.
Image transfer systems employing negative-working image dye-providing compounds are also known in which dyes are not initially present, but are formed by reactions occurring in the photographic element or receiver following exposure. For example, a ballasted coupler can react with color developing agent to form a mobile dye, as illustrated by Whitmore et al U.S. Pat. No. 3,227,550, Whitmore U.S. Pat. No. 3,227,552, Bush et al U.S. Pat. No. 3,791,827, and Viro et al U.S. Pat. No. 4,036,643. An immobile compound containing a coupler can react with oxidized para-phenylenediamine to release a mobile coupler which can react with additional oxidized para-phenylenediamine before, during or after release to form a mobile dye, as illustrated by Figueras et al U.S. Pat. No. 3,734,726 and Janssens et al German OLS No. 2,317,134. In another form, a ballasted amidrazone reacts with an electron transfer agent as a function of silver halide development to release a mobile amidrazone which reacts with a coupler to form a dye at the receiver, as illustrated by Ohyama et al U.S. Pat. No. 3,933,493.
An image to be viewed can be transferred from the image-forming layers. A retained image can be formed for viewing as a concurrently formed complement of the transferred image. Positive transferred images and useful negative retained images can be formed with the direct positive silver halide emulsions of this invention when imaging chemistry is negative-working. Images retained in and transferred from the image-forming layers are illustrated by U.K. Pat. No. 1,456,413, Friedman U.S. Pat. No. 2,543,691, Bloom et al U.S. Pat. No. 3,443,940, Staples U.S. Pat. No. 3,923,510, and Fleckenstein et al U.S. Pat. No. 4,076,529.
Where mobile dyes are transferred to the receiver a mordant is commonly present in a image dye-providing layer. Mordants and mordant containing layers are described in the following references which are incorporated by reference: Sprague et al U.S. Pat. No. 2,548,564, Weyerts U.S. Pat. No. 2,548,575, Carroll et al U.S. Pat. No. 2,675,316, Yutzy et al U.S. Pat. No. 2,713,305, Saunders et al U.S. Pat. No. 2,756,149, Reynolds et al U.S. Pat. No. 2,768,078, Gray et al U.S. Pat. No. 2,839,401, Minsk U.S. Pat. Nos. 2,882,156 and 2,945,006, Whitmore et al U.S. Pat. No. 2,940,849, Condax U.S. Pat. No. 2,952,566, Mader et al U.S. Pat. No. 3,016,306, Minsk et al U.S. Pat. Nos. 3,048,487 and 3,184,309, Bush U.S. Pat. No. 3,271,147, Whitmore U.S. Pat. No. 3,271,148, Jones et al U.S. Pat. No. 3,282,699, Wolf et al U.S. Pat. No. 3,408,193, Cohen et al U.S. Pat. Nos. 3,488,706, 3,557,066, 3,625,694, 3,709,690, 3,758,445, 3,788,855, 3,898,088, and 3,944,424, Cohen U.S. Pat. No. 3,639,357, Taylor U.S. Pat. No. 3,770,439, Campbell et al U.S. Pat. Nos. 3,958,995 and 4,193,795; and Ponticello et al Research Disclosure, Vol. 120, April 1974, Item 12045.
One-step processing can be employed, as illustrated by U.K. Pat. No. 1,471,752, Land U.S. Pat. No. 2,543,181, Rogers U.S. Pat. No. 2,983,606 (pod processing), Land U.S. Pat. No. 3,485,628 (soak image-former and laminate to receiver) and Land U.S. Pat. No. 3,907,563 (soak receiver and laminate to image-forming element) or multi-step processing can be employed, as illustrated by Yutzy U.S. Pat. No. 2,756,142, Whitmore et al U.S. Pat. No. 3,227,550, and Faul et al U.S. Pat. No. 3,998,637.
Preformed reflective layers can be employed, as illustrated by Whitmore Canadian Pat. No. 674,082, Beavers U.S. Pat. No. 3,445,228, Land U.S. Pat. Nos. 2,543,181, 3,415,644, '645 and '646, and Barr et al U.K. Pat. No. 1,330,524 or processing-formed reflective layers can be employed, as illustrated by Land U.S. Pat. Nos. 2,607,685 and 3,647,437, Rogers U.S. Pat. No. 2,983,606, and Buckler U.S. Pat. No. 3,661,585.
Generally, the image transfer film units in accordance with this invention comprise:
(1) a photographic element comprising a support having thereon at least one silver halide emulsion layer containing radiation-sensitive internal latent image silver halide grains and a vinylene nucleating agent, the emulsion layer preferably having in contact therewith an image dye-providing material,
(2) an image-receiving layer, which can be located on a separate support and superposed or adapated to be superposed on the photographic element or, preferably, can be coated as a layer in the photographic element,
(3) an alkaline processing composition,
(4) means containing and adapted to release the alkaline processing composition into contact with the emulsion layer, and
(5) a silver halide developing agent located in at least one of the photographic element and alkaline processing composition so that the processing composition and developing agent, when brought together, form a silver halide surface developer.
In highly preferred embodiments, the film units of this invention contain a support having thereon a layer containing a blue-sensitive emulsion and in contact therewith a yellow image dye-providing material, a red-sensitive silver halide emulsion and in contact therewith a cyan image dye-providing material, and a green-sensitive emulsion and in contact therewith a magenta image dye-providing material, and preferably all of said image dye-providing materials are initially immobile image dye-providing materials.
The terms "diffusible" (or "mobile") and "immobile" (or "nondiffusible"), as used herein, refer to compounds which are incorporated in the photographic element and, upon contact with an alkaline processing solution, are substantially diffusible or substantially immobile, respectively, in the hydrophilic colloid layers of a photographic element.
The term "image dye-providing material", as used herein, is understood to refer to those compounds which are employed to form dye images in photographic elements. These compounds include dye developers, shifted dyes, color couplers, oxichromic compounds, dye redox releasers, etc, as described above in connection with positive-working and negative-working image transfer systems.
In one preferred embodiment, the receiver layer is coated on the same support with the photosensitive silver halide emulsion layers, the support is preferably a transparent support, an opaque layer is preferably positioned between the image-receiving layer and the photosensitive silver halide layer, and the alkaline processing composition preferably contains an opacifying substance, such as carbon or a pH-indicator dye which is discharged into the film unit between a dimensionally stable support or cover sheet and the photosensitive element.
In certain embodiments, the cover sheet can be superposed or is adapted to be superposed on the photosensitive element. The image-receiving layer can be located on the cover sheet so that it becomes an image-receiving element. In certain preferred embodiments where the image-receiving layer is located in the photosensitive element, a neutralizing layer is located on the cover sheet.
Increases in maximum density can be obtained in color image transfer film units containing internally sulfur and gold-sensitized emulsions of the type described by Evans U.S. Pat. No. 3,761,276, and sulfonamidonaphthol redox dye-releasing compounds of the type described by Fleckenstein British Pat. No. 1,405,662, by incorporation into the emulsion layers of a variety of chemical addenda generally recognized in the art as antifoggants or development inhibitors, as well as hydrolyzable precursors thereof. Many of these compounds also provide improved stabilization of sensitometric properties of liquid emulsion and of the storage life of the coated emulsion. The effects, shown in film units of the type described in Examples 40 through 42 of British Pat. No. 1,405,662, are in addition to the effect of 5-methylbenzotriazole in the processing composition even when the latter is present in quantities as high as 4 grams per liter. Effective compounds in general are selected from the group consisting of (a) 1,2,3-triazoles, tetrazoles and benzotriazoles having an N-R.sup.1 group in the heterocyclic ring, wherein R.sup.1 represents hydrogen or an alkali-hydrolyzable group, or (b) heterocyclic mercaptans or thiones and precursors thereof, mostly having one of the formulas (XII) or (XIII): ##STR14## wherein
Z comprises the atoms necessary to complete an azole ring, and
R.sup.2 represents, in addition to the groups specified above for R.sup.1, a metal ion.
The compounds are generally employed at concentrations less than about 300 mg per mole of silver, each compound having an optimum concentration above which development and/or nucleation are inhibited and D.sub.max decreases with increasing concentration. Specifically preferred antifoggants and stabilizers, as well as other preferred color image transfer film unit and system features, are more specifically disclosed in Research Disclosure, Volume 151, November 1976, Item 15162, the disclosure of which is hereby incorporated by reference.
A more detailed description of useful image transfer film units and systems is contained in the patents relating to image transfer cited above, the disclosures of which are here incorporated by reference. A specific preferred image-transfer film unit and image transfer system is that disclosed by Leone et al U.S. Pat. No. 4,030,925, cited above, and here incorporated by reference.
In a specific preferred form the photographic elements of this invention are intended to produce multicolor images which can be viewed in the elements or in a receiver when the elements form a part of a multicolor image transfer system. For multicolor imaging at least three superimposed color-forming layer units are coated on a support. Each of the layer units is comprised of at least one silver halide emulsion layer. At least one of the silver halide emulsion layers, preferably at least one of the silver halide emulsion layers in each color-forming layer unit and most preferably each of the silver halide emulsion layers, contain an emulsion according to this invention substantially as described above. The emulsion layers of one of the layer units are primarily responsive to the blue region of the spectrum, the emulsion layers of a second of the layer units are primarily responsive to the green region of the spectrum, and the emulsion layers of a third of the layer units are primarily responsive to the red region of the spectrum. The layer units can be coated in any conventional order. In a preferred layer arrangement the red responsive layer unit is coated nearest the support and is overcoated by the green responsive layer unit, a yellow filter layer and a blue responsive layer unit. The layer units each contain in the emulsion layers or in adjacent hydrophilic colloid layers at least one image dye-providing compound. Such compounds can be selected from among those described above. Incorporated dye-forming couplers and redox dye-releasers constitute exemplary preferred image dye providing compounds. The blue, green and cyan responsive layer units preferably contain yellow, magenta and red image dye providing compounds, respectively.
The preparation of compounds useful as nucleating agents in the practice of this invention is generally known. An exhaustive description of the methods used for the synthesis of such compounds is given for example in F. M. Hamer's book, The Cyanine Dyes and Related Compounds, Interscience Publishers, John Wiler & Sons, New York, 1964 (pp 447 et seq.). These methods can be used to prepare the nucleating agents of the invention.
A few examples of preparation of compounds useful as nucleating agents are given hereafter.
COMPOUND NA-1
2-[.beta.-anilinovinyl]-3-methylbenzothiazolium p-toluene sulfonate
112 g of 2,3-dimethyl-benzothiazolium p-toluene sulfonate were introduced into 200 ml of xylene. The mixture was heated to 70.degree.-80.degree. C. and a previously prepared mixture of 75 g of ethyl o-formiate, 93 g of aniline and 50 ml of xylene and 1 ml of sulfuric acid as a reaction catalyst was added with good stirring. An orange colored product was obtained (Yield: 80%, m.p. 244.degree. C.).
______________________________________Analysis: C.sub.23 H.sub.22 N.sub.2 O.sub.3 S.sub.2Percent: C H N S______________________________________Calculated: 63.01 5.02 6.39 14.61Found: 62.18 4.83 6.23 16.01______________________________________
COMPOUND NA-2
2-[.beta.-(N-methylanilino)vinyl]-3-methylbenzothiazolium p-toluene sulfonate
To 100 ml of acetone were added 13.3 g of 3-methyl-2-.beta.-anilinoethylidene benzothiazoline. The mixture was stirred, then 10 g of methyl p-toluenesulfonate were added. The reagents were left in contact for 72 hours. A solid was formed, collected and drained, then recrystallized from a mixture of ethanol and ether (m.p. 138.degree. C.).
______________________________________Analysis: C.sub.24 H.sub.24 N.sub.2 O.sub.3 S.sub.2 (mol. weight: 452)Percent: C H N______________________________________Calculated: 63.71 5.38 6.19Found: 60.66 5.45 5.92______________________________________
COMPOUND NA-3
2-[.beta.-(o-methylthio-N-methylanilino)vinyl]-1-methylquinolinium p-toluene sulfonate
15.2 g of 1-methyl-2-(3-methyl-2-benzothiazolinylidene)quinolinium p-toluene sulfonate were dissolved in 120 ml of toluene. 10 g of methyl p-toluene sulfonate were added. The precipitate formed was drained and recrystallized from methanol.
______________________________________Analysis: C.sub.27 H.sub.28 N.sub.2 O.sub.3 S.sub.2 (mol. weight: 492)Percent: C H N S______________________________________Calculated: 65.85 5.69 5.69 13.00Found: 62.73 5.70 5.37 13.07______________________________________
COMPOUND NA-4
2-[.beta.-(N-propargylanilino)vinyl]-3-ethylbenzoxazolium bromide
13.2 g of .beta.-anilinoethylidene ethyl-3-benzoxazoline were dissolved in 250 ml of acetone; 6 ml of propargyl bromide were added at room temperature. Crystals were formed after 2 hours of contact. Stirring was continued for 24 hours. The product was filtered off and recrystallized from a methanol/ether mixture (m.p. 198.degree. C.).
______________________________________Analysis: C.sub.20 H.sub.19 BrN.sub.2 O (mol. weight: 383)Percent: C H N______________________________________Calculated: 62.66 4.96 7.30Found: 61.76 4.75 7.20______________________________________
COMPOUND NA-5
2-[.beta.-(p-N-methylaminophenoxy)vinyl]-3-methylbenzothiazolium chloride
To 200 ml of ethanol were added 34.4 g of p-hydroxymethylaminobenzene sulfate and 11.2 g of potassium hydroxide. This mixture was stirred for 30 minutes, its temperature being maintained between 5.degree.-10.degree. C. 40.6 g of 2-(N-benzoylanilinovinyl)-3-methylbenzothiazolium chloride were added. A solubilization occurred first, then a precipitation while a strong red color was formed. The product was drained, washed with acetone and recrystallized from a methanol/ether mixture (m.p. of the purified product 262.degree. C.).
______________________________________Analysis: C.sub.17 H.sub.17 ClN.sub.2 OS (mol. weight: 332.5)Percent: C H N Cl S______________________________________Calculated: 61.35 5.11 8.42 10.67 9.67Found: 59.15 5.12 8.36 10.77 9.52______________________________________
COMPOUND NA-6
2-[.beta.-(o-methoxy-N-methylanilino)vinyl]-3-methylbenzothiazolium p-toluene sulfonate
To 250 ml of ethanol were added 46.8 g of 2-[.beta.-(o-methoxyanilino)vinyl]-3-methylbenzothiazolium p-toluene sulfonate; 10 g of pelleted potassium hydroxide were added and the mixture was stirred for 30 minuted at room temperature. A gummy material was obtained.
500 ml of water were added; the half-gummy, half-crystalline material formed was filtered and dissolved in 500 ml of toluene; it was dried on potassium hydroxide, filtered and 18.6 g of methyl p-toluene sulfonate (0.09 mole) were added to the toluene solution. The mixture was allowed to rest for 24 hours; a precipitate was formed and filtered, then recrystallized from a methanol/ether mixture (m.p. of the purified product: 188.degree. C.).
______________________________________Analysis: C.sub.25 H.sub.26 N.sub.2 O.sub.4 S.sub.2 (mol. weight: 488)Percent: C H N S______________________________________Calculated: 62.24 5.39 5.80 13.2Found: 61.85 5.20 5.79 14.4______________________________________
COMPOUND NA-7
2-[.beta.-(N-propargylanilino)vinyl]-3-ethylbenzoselenazolium bromide
In 200 ml of ethanol were dissolved 5.03 g of 3-ethyl-2-anilinovinylbenzoselenazolium p-toluene sulfonate. 1 g of pelleted potassium hydroxide was added at room temperature and stirring was continued for 4 hours. The precipitate was drained and extracted with benzene. To the benzene solution were added 2 g of propargyl bromide which were left in contact for 72 hours. The precipitate formed was drained and recrystallized from a methanol/ether mixture (m.p. of the product thus purified: 200.degree. C.).
______________________________________Analysis: C.sub.20 H.sub.19 BrN.sub.2 Se (mol. weight: 446)Percent: C H N______________________________________Calculated: 53.81 4.26 6.27Found: 53.59 4.32 6.28______________________________________
COMPOUND NA-8
2-[.beta.-(N-propargylanilino)vinyl]-1,3-diethyl-5,6-dichlorobenzimidazolium bromide
11.4 g of 1,3-diethyl-5,6-dichloro-2-anilinovinyl-benzimidazolium p-toluenesulfonate were added to 25 ml of ethanol. 2 g of pelleted potassium hydroxide were added and the mixture (sparingly soluble at the beginning of the reaction) was stirred and slowly solubilized. Then the base froze. It was drained after two hours of contact and extracted with toluene. 10 g of propargyl bromide were added to the toluene solution, then it was stirred for 72 hours at room temperature; the product was drained and recrystallized from a methanol/ether mixture (m.p. of the purified product: 144.degree. C.).
______________________________________Analysis: C.sub.22 H.sub.22 BrCl.sub.2 N.sub.3 --CH.sub.3 OH (mol.weight: 511)Percent: C H N______________________________________Calculated: 54.11 5.09 8.21Found: 53.02 5.14 8.29______________________________________
COMPOUND NA-9 2-[.beta.-(o-propargylthio-N-propargylanilino)vinyl]-3-methylbenzothiazolium bromide
In 20 ml of acetone, were dissolved 2 g of 3-propargyl-2-[(methyl-3'-benzothiazolinylidene)methyl]benzothiazoline. 2 ml of propargyl bromide were added. A precipitate was rapidly formed. The mixture was stirred and cooled, then the precipitate was filtered out and washed with acetone. The material was recrystallized from a methanol/ether mixture.
______________________________________ Analysis: C.sub.22 H.sub.19 BrN.sub.2 S.sub.2 (mol. weight: 455)Percent: C H N______________________________________Calculated: 58.02 4.19 6.15Found: 57.52 4.18 6.12______________________________________
COMPOUND NA-10
2-[.beta.-(o-methylthio-N-propargylanilino)vinyl]-3-methylbenzothiazolium p-toluene sulfonate;
The procedure described for the synthesis of Compound NA-9 was used, but methyl p-toluene sulfonate was substituted in place of propargyl bromide.
______________________________________Analysis: C.sub.27 H.sub.26 N.sub.2 O.sub.3 S.sub.3 (mol. weight: 522)Percent: C H N______________________________________Calculated: 62.06 4.98 5.36Found: 61.90 4.94 5.15______________________________________
COMPOUND NA-11
2-[.beta.-methyl-.beta.-(o-propargylthio-N-methylanilino)vinyl]-3-methyl-benzothiazolium bromide
To 20 ml of benzene, were added 3.12 g of 2,3-dimethyl-[3'-methylbenzothiazolinylidene)methyl]-2-benzothiazoline (1/100 mol.). The suspension was stirred at room temperature. 4 ml of propargyl bromide were added. A gum was formed. After 2 hours rest, benzene was decanted and the residue was washed with acetone.
The residue was dissolved in ethanol and filtered. The filtrate was poured into hexane and the product crystallized out; it was drained and washed with hexane (m.p. 170.degree. C.).
______________________________________Analysis: C.sub.21 H.sub.21 BrN.sub.2 S.sub.2 (mol. weight: 445)Percent: C H N______________________________________Calculated: 56.63 4.71 6.29Found: 54.19 4.63 6.01______________________________________
COMPOUND NA-12
2-[.beta.-(N-propargylanilino)vinyl]-3-methylbenzothiazolium bromide
26.6 g of N-anilinoethylidene methyl-3-benzothiazoline were suspended in 250 ml of acetone. 13 g of propargyl bromide were added in one portion. The mixture was stirred for 72 hours at room temperature. The precipitate formed was filtered out and recrystallized from a methanol/acetone/ether mixture. The product was drained and washed with acetone.
______________________________________Analysis: C.sub.19 H.sub.17 BrN.sub.2 S (mol. weight: 385)Percent: C H N______________________________________Calculated: 59.22 4.41 7.27Found: 58.61 4.31 7.25______________________________________
COMPOUND NA-13
2-[.beta.-N-methylanilinovinyl]-3-methyl-6-acetamidobenzothiazolium p-toluene sulfonate
COMPOUND NA-14
2-[.beta.-(N-methylanilino)vinyl]-3-methyl-6-(N'-ethylthioureido)benzothiazolium bromide
(a) Preparation of 2-(.beta.-anilinovinyl)-3-methyl-6-acetamidobenzothiazolium p-toluene sulfonate
A solution of 6.05 g of ethyl o-formate and 3.8 g of aniline in 50 ml of xylene containing a trace of concentrated sulfuric acid was added to a suspension of 14 g of 2,5-dimethyl-6-acetamidobenzothiazolium p-toluene sulfonate. The mixture was heated for 4 hours at 80.degree. C; it was completely dissolved, then reprecipitated. The solid formed (13 g, yield: 73.5%) was filtered out, washed with acetone and recrystallized from methanol.
(b) Preparation of 2-(.beta.-N-methylanilinovinyl)-3-methyl-6-acetamido-benzothiazolium p-toluene sulfonate
To a solution of 6.5 g of the preceding material in 65 ml of methanol were added 4 g of 30% sodium methylate. The solution left for 5 hours at room temperature became green, the precipitate formed was filtered out, washed with water and acetone and placed in a cartridge of a Kumagawa extractor. After extraction with 200 ml of benzene (the insoluble residue in the cartridge was elminiated) and concentration of the benzene, 65 ml of acetone and 3 g of methyl p-toluene sulfonate were added. The solution was refluxed for 2 hours. The yellow product (4 g, yield: 60%) which precipitated was filtered out and washed with ether.
(c) Preparation of 2-[.beta.-(N-methylanilino)vinyl]-3-methyl-6-amino-benzothiazolium bromide
A suspension of 2.475 g of the preceding material in 6 ml of 25% hydrochloric acid was refluxed for 1 hour. After solubilization, then reprecipitation, 0.6 g of potassium bromide were added and stirring was continued for 1 hour at room temperature. After neutralization with an aqueous solution of sodium hydroxide, the precipitate (1.6 g, yield: 87.5%) was filtered out and dried.
(d) Preparation of 2-[.beta.-(N-methylanilino)vinyl]-3-methyl-6-(N'-methylthioureido)benzothiazolium bromide
0.55 g of ethyl isothiocyanate were added to a solution of 1.47 g of the preceding material in 150 ml of ethanol. The solution was refluxed for 1 hour 30 minutes under a nitrogen atmosphere. The precipitate formed was filtered out and washed with ether (1.1 g, yield 60%).

The following examples illustrate the use of the vinylene compounds as nucleating agents for internal latent image-forming direct-positive emulsions.
EXAMPLES 1 THROUGH 3
A gelatino-silver bromide emulsion capable of forming an internal latent image of the type disclosed in Evans U.S. Pat. No. 3,761,276 was employed. The emulsion was internally sulfur and gold sensitized and surface sulfur and gold sensitized to a lesser extent to provide a high ratio of internal to surface chemical sensitization. The emulsion contained cubic silver bromide grains having an average diameter of 0.6 micron. (The average grain diameter is the diameter of a circle equal in area to the mean projected area of the silver halide grains.)
To various samples of the emulsion were added a nucleating agent, the nucleating agent and the amount being identified in Table II. Each emulsion sample was separately coated on a poly(ethylene terephthalate) photographic film support at a coverage of 125 mg/dm.sup.2 of gelatin and 50 mg/dm.sup.2 of silver.
The resulting photographic elements were then given a sensitometric exposure with a light source having a temperature of 2850.degree. K. A sample of each element was developed in Developer A below and another sample was developed in Developer B below. Both developers were surface developers; that is, they did not develop the internal latent image. Both developers produced direct-reversal images.
______________________________________Developer AElon 1 gAscorbic acid 10 gSodium metaborate 40 gWater to make 1 literpH 10.2Developer BElon 1 gAscorbic acid 10 gSodium metaborate 40 gBenzotriazole 0.1 gWater to make 1 literpH adjusted to 12.3 with KOH______________________________________
TABLE II__________________________________________________________________________Nucleating Agent Developer A Developer B Amount Development DevelopmentCompound (mg/Ag Time TimeNo. mole) (minutes) D.sub.min D.sub.max (minutes) D.sub.min D.sub.max__________________________________________________________________________NA-9 200 16 0.08 2.60 8 0.23 2.00NA-12 150 14 0.08 2.45 8 0.15 2.30NA-11 200 20 0.06 1.95 9 0.12 2.30__________________________________________________________________________
EXAMPLES 4 AND 5
An internal image silver bromide emulsion was prepared by the procedure of Example 1. To a first sample of this emulsion were added 400 mg per silver mole of Compound NA-2, and to a second sample were added 40 mg per silver mole of Compound NA-14. These two emulsion samples were coated on a polyolefin-coated photographic paper support at a coverage of 5 mg/dm.sup.2 of silver and 27.5 mg/dm.sup.2 of gelatin. This emulsion contained 6 mg/dm.sup.2 of a yellow dye-forming coupler having the following formula: ##STR15##
A gelatin layer was then coated over each emulsion layer.
Each sample was exposed as in Example 1, then processed for 4 minutes at 38.degree. C. in the surface developer having the following composition:
______________________________________Developer C______________________________________Benzyl alcohol 16 mlN-ethyl-N-methyl-sulfon-amidoethyl-2-methyl-p-phenylenediamine sesqui-sulfate 6 gPiperidino hexose reductone 0.5 gSodium sulfite 1.5 gPotassium carbonate 30 gBenzotriazole 10 mgWater to make 1 literpH: 10.5______________________________________
Processing was finished as follows:
______________________________________Stop bath 20 secondsBleach-fixing 1 minuteWashing 2 minutes.______________________________________
In both cases a yellow positive image was obtained whose characteristics are given in Table III.
TABLE III______________________________________Nucleating Agent Amount mg/mole Ag D.sub.min D.sub.max______________________________________NA-2 400 0.14 1.90NA-14 40 0.12 2.05______________________________________
When the procedure described above was repeated with a third sample lacking vinylene compound incorporated as a nucleating agent, substantially no positive image was discernible at the end of 4 minutes, but after 12 minutes a positive image was visible. Thus, the nucleating agents of the present invention are capable of significantly accelerating the formation of a positive image.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Number	Name	Date
T967002	Mihara et al.	Feb 1978
3227552	Whitmore	Jan 1966
3563754	Jones et al.	Feb 1971
3615615	Lincoln et al.	Oct 1971
3718470	Spence et al.	Feb 1973
3719494	Kurtz et al.	Mar 1973
3734738	Kurtz et al.	May 1973
3759901	Lincoln et al.	Sep 1973
4030925	Leone et al.	Jun 1977
4059450	Vanassche et al.	Nov 1977
4080207	Leone et al.	Mar 1978
4115122	Adachi et al.	Sep 1978
4139387	von Konig et al.	Feb 1979

Number	Date	Country
2011391	Jul 1979	GBX
2012443	Jul 1979	GBX

Photographic emulsions and elements capable of forming direct-positive images

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