US3397986A - Photographic emulsion stabilized with bis (p-acylamidophenyl) disulfides - Google Patents

Photographic emulsion stabilized with bis (p-acylamidophenyl) disulfides Download PDF

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US3397986A
US3397986A US421994A US42199464A US3397986A US 3397986 A US3397986 A US 3397986A US 421994 A US421994 A US 421994A US 42199464 A US42199464 A US 42199464A US 3397986 A US3397986 A US 3397986A
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bis
silver halide
disulfide
photographic
disulfides
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Allan G Millikan
Arthur H Herz
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • This invention relates to stabilized photographic compositions. More particularly, this invention relates to the stabilization of photographic silver halide emulsions. In a specific aspect, this invention relates to inhibiting development of spontaneous fog without adversely affecting the sensitivity of a photographic silver halide emulsion.
  • organic disulfides have been described as being effective in preventing an increase in fog and to stabilize or control the keeping quality of photographic emulsions.
  • many of these organic disulfides are not elTective antifoggants unless they are used in combination with other materials and still others cause objectionable desensitization of the emulsion.
  • US. Patent 2,440,110 discloses that organic disulfides such as diphenyl disulfide or ditolyl disulfide must be used in combination with sulfinic or seleninic acids or their salts to obtain acceptable stabilization. It is evident, therefore, that the state of the art will be enhanced by providing photographic silver halide emulsions which are stabilized by organic disulfides which are not subject to the aforementioned deficiencies.
  • Another object of this invention is to provide a method for stabilizing photographic silver halide emulsions.
  • Another object of this invention is to provide a method of stabilizing photographic silver halide emulsions without adversely affecting, to any substantial extent, the sensitivity of the emulsion.
  • Still another object of this invention is to provide photographic silver halide emulsions which are stabilized with organic disulfides.
  • each R is a trifluoromethyl, alkyl or aryl radical. It is obvious that the 0 all group is an acyl radical derived from an aliphatic or aromatic carboxylic acid.
  • the R groups except in the case of trifluoromethyl, are hydrocarbon and generally contain up to about 20, preferably up to 10, carbon atoms.
  • the preferred alkyl groups contain 1-10 carbon atoms.
  • Suitable R groups include, for example, trifluoromethyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, octyl, decyl, dodecyl, eicosyl, phenyl, tolyl, naphthyl, anthryl, and the like.
  • examples of the disulfide employed in the practice of this invention include bis(p-acetamidophenyl)disulfide,
  • a convenient method for preparing the bis(p-acylamidophenyl)disulfide stabilizers employed in practicing this invention comprises reacting 4,4'-diamidodiphenyl disulfide with the appropriate carboxylic acid anhydride as represented by the following equation:
  • each R is as defined hereinbefore.
  • the reaction generally takes place at relatively mild temperatures, for example, temperatures up to about C. Normal atmospheric pressures are preferably employed although pressures substantially below or above normal atmospheric pressures can be used. If desired, the reaction can be carried out in an inert organic vehicle, and will go to completion in a relatively short period, generally not more than about 4 hours.
  • the resulting bis(p-acylamidophenyl)disulfides can then be isolated by conventional procedures, for example, filtering, Washing and drying. The synthesis of bis(p-acetamidophenyl)disulfide by this procedure is shown in Berichte 38, p.
  • the stabilizing concentration of the bis(p-acylamidophenyl)disulfide employed in a given emulsion is subject to wide variation, depending upon the effects desired, degree of ripening, silver content of the emulsion, etc. In general, a concentration in the range of about .001 to about 10, preferably about .1 to about 1 gram per mole of silver halide is adequate.
  • the stabilizer can be incorporated directly into the silver halide emulsion layer or it can be present in an adjacent layer. It is generally desirable to use higher concentrations of stabilizer when it is used in an adjacent layer rather than in the silver halide emulsion layer. Exposure of the treated emulsion in conventional photographic testing apparatus such as an intensity scale sensitometer, will reveal the most advantageous concentration for the present stabilizers in a particular emulsion. Such techniques are well known to those skilled in the art.
  • the stabilizers of this invention can be added to the photographic composition using any techniques suitable for this purpose. For example, they can be dissolved in a suitable solvent and added directly to the silver halide emulsion or they can be added to the emulsion in the form of a dispersion similar to the technique used to incorporate certain types of color forming compounds (couplers) in a photographic emulsion.
  • the solvent should be selected so that it has no harmful effects upon the emulsion, in accordance with usual practice, and organic solvents or diluents are preferred. Examples of suitable solvents or diluents include ethanol, acetone or the like.
  • the stabilizing addenda employed in the practice of this invention can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic, panchromatic and infrared emulsions, they are also useful in X-ray and other non-optically sensitized emulsions. They can be added to the emulsions before or after any optically sensitizing dyes which may be used. They are particularly effective in sulfur and gold sensitized silver halide emulsions. Various silver salts can be used as sensitive salts, including, for example, silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide or silver chloroiodide.
  • the subject addenda can be used in emulsions intended for color photography, for example, emulsions containing color forming couplers or emulsions to be developed by salts containing couplers or other color generating materials.
  • gelatin In the preparation of the silver halide dispersions employed for preparing silver halide emulsions there can be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative or a synthetic resin, for example, a polyvinyl compound, although gelatin is preferred.
  • the photographic emulsions stabilized according to this invention can be coated on a wide variety of supports.
  • Typical supports include those generally employed for photographic elements, as exemplified by cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials as well as glass, paper, metal, wood and the like.
  • Supports such as paper that are coated with a-olefin polymers, particularly polymers of a-olefins containing 2-10 carbon atoms, as for example, polyethylene, polypropylene, ethylene butene copolymers and the like, can also be employed.
  • the photographic emulsions and elements can also contain additional additives, particularly those known to be beneficial in photographic emulsion-s, as exemplified by optical sensitizers, speed increasing materials, gelatin hardeners, plasticizers and the like.
  • Example 1 The disulfides disclosed herein stabilize photographic emulsions against increases in fog and decreases in speed even upon storage at increased temperatures and humidity.
  • bis(p-acetamidophenyl)disulfide is incorporated into a negative, high speed gelatino silver bromoiodide emulsion containing a yellow dye forming coupler. The emulsion is coated on a cellulose acetate film base.
  • three samples of the identical emulsion, one sample containing no antifoggant compound, one containing ditolyl disulfide and one containing diphenyl disulfide are coated on cellulose acetate film base in the same manner. Samples of the prepared photographic elements are then incubated for 7 days at F. and 50% relative humidity, exposed for second in the form of film strips in an intensity scale sensitometer (Kodak Type Ib) and developed for 12 minutes at 75 F.
  • the developer employed has the following formula:
  • a negative silver image and a yellow dye image is formed.
  • the silver image and the residual silver halide are removed by treatment with a conventional ferricyanide bleach followed by a hypo fixing bath leaving a yellow negative dye image.
  • the bis(pacylamidophenyl)disulfides of this invention impart substantial stabilizing and antifogging properties to photographic silver halide emulsions. It is also significant to note that the practice of this invention does not result in substantial loss in speed with the improved stability.
  • Table 1 illustrates that aryl disulfides having unsubstituted aromatic rings or aromatic rings containing such substituents as alkyl groups are ineffective to impart stabilizing or antifoggant properties to photographic silver halide emulsions.
  • such aryl disulfides require the presence of various sulfinic or seleninic acids or salts to exhibit any stabilizing effects. Such additional additives are, of course, not necessary with the specific organic disulfides employed in the practice of this invention.
  • Example 2 deleterious afiFect on the stability and/or speed of the photographic silver halide emulsion.
  • Example 3 deleterious afiFect on the stability and/or speed of the photographic silver halide emulsion.
  • the procedure of Example 3 is repeated with bis(p-acetamidophenyl)disulfide and bis[o-(N-ethyl)acetamidophenyl] disulfide which has the formula:
  • Example 3 related structurally to bis(p-acetamidophenyl)disulfide shows a substantial deleterious effect upon the speed and/ or fog of a photographic emulsion when it is used in place of the latter. This same deleterious effect is exhibited by other ortho substituted aryl disulfides such as di-o-formylethylaminodiphenyldisulfide when they are employed in the above procedure.
  • this invention provides silver halide emulsions that are stabilized with antifoggant addenda which do not cause substantial desensitization or loss in speed.
  • R-ji-EO s s Q-E-E-R where each R is selected from the group consisting of alkyl, trifluoromethyl and aryl.
  • Rii M EAR where each R is selected from the group consisting of alkyl, trifluoromethyl and aryl.
  • each R is selected from the group consisting of alkyl, trifluoromethyl and aryl.
  • each R is an alkyl radical containing up to 20 carbon atoms.
  • each R is an alkyl radical containing 1-10 carbon atoms.
  • each R is an alkyl group containing 1-10 carbon atoms.
  • each R is an aryl radical containing up to 20 carbon atoms.
  • each R is an alkyl radical containing up to 20 carbon atoms.
  • a sulfur and gold sensitized negative, high speed gelatino silver bromoiodide emulsion which is stabilized with about .09 gram per mole of silver halide of bis(pacetamidophenyl) disulfide.

Description

United States assignors to Eastman Kodak Company, Rochester, N.Y., 5
a corporation of New Jersey No Drawing. Filed Dec. 29, 1964, Ser. No. 421,994 14 Claims. (Cl. 96109) ABSTRACT OF THE DISCLOSURE The stabilization against fog of photographic silver halide emulsions using bis(p-acylamidophenyl)disulfides is disclosed.
This invention relates to stabilized photographic compositions. More particularly, this invention relates to the stabilization of photographic silver halide emulsions. In a specific aspect, this invention relates to inhibiting development of spontaneous fog without adversely affecting the sensitivity of a photographic silver halide emulsion.
It is known that photographic silver halide emulsions on storage tend to lose sensitivity and to become spontaneously developable without exposure to light. There is normally a detectable amount of the silver salt reduced during development in the area where no exposure was given; this is commonly called fog and sometimes called chemical fog where it is necessary to distinguish between it and the effects of accidental exposure to radia tion.
Certain organic disulfides have been described as being effective in preventing an increase in fog and to stabilize or control the keeping quality of photographic emulsions. However, many of these organic disulfides are not elTective antifoggants unless they are used in combination with other materials and still others cause objectionable desensitization of the emulsion. For example, US. Patent 2,440,110 discloses that organic disulfides such as diphenyl disulfide or ditolyl disulfide must be used in combination with sulfinic or seleninic acids or their salts to obtain acceptable stabilization. It is evident, therefore, that the state of the art will be enhanced by providing photographic silver halide emulsions which are stabilized by organic disulfides which are not subject to the aforementioned deficiencies.
Accordingly, it is an object of this invention to provide stabilized photographic silver halide emulsions.
Another object of this invention is to provide a method for stabilizing photographic silver halide emulsions.
Another object of this invention is to provide a method of stabilizing photographic silver halide emulsions without adversely affecting, to any substantial extent, the sensitivity of the emulsion.
Still another object of this invention is to provide photographic silver halide emulsions which are stabilized with organic disulfides.
Other objects will become apparent from an examination and consideration of the specification and claims that follow.
In accordance with this invention, it has been found that photographic silver halide emulsions can be stabilized and the development of spontaneous fog substantially inhibited by the use of at least one bis(p-acylamidophenyl) disulfide having the formula:
where each R is a trifluoromethyl, alkyl or aryl radical. In view of the teachings of US. Patent 2,440,110, it
could not have been predicted that the substituted phenyl disulfides employed in the practice of this invention would be effective stabilizers for photographic silver halide emulsions and prevent the development of spontaneous fog. Thus, US. Patent 2,440,110 indicates that structurally closely related organic disulfides, i.e., aryl disulfides having unsubstituted aromatic rings and aromatic rings containing such substituents as carboxylic acid, primary amino or alkyl groups, do not exhibit antifoggant activity. Furthermore, as shown by Example 4, set out hereinafter, other seemingly slight changes in the chemical structure of the disulfide have significant deleterious effects upon the speed, stability and/or development of spontaneous fog of photographic silver halide emulsions containing such disulfide.
As already indicated, the stabilizers employed in the practice of this invention have the formula:
I t l where each R is a trifluoromethyl, alkyl or aryl radical. It is obvious that the 0 all group is an acyl radical derived from an aliphatic or aromatic carboxylic acid. The R groups, except in the case of trifluoromethyl, are hydrocarbon and generally contain up to about 20, preferably up to 10, carbon atoms. The preferred alkyl groups contain 1-10 carbon atoms. Suitable R groups include, for example, trifluoromethyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, octyl, decyl, dodecyl, eicosyl, phenyl, tolyl, naphthyl, anthryl, and the like. Hence, examples of the disulfide employed in the practice of this invention include bis(p-acetamidophenyl)disulfide,
bis (ptrifluoroacetarnidophenyl disulfide, bis (p-butyramidophenyl) disulfide,
bis (p-propionamidophenyl) disulfide,
bis (p-octanamidophenyl) -disulfide, bis(p-decanamidophenyl)disulfide,
bis (p-pentadecanamidophenyl) disulfide, bis (p-benzamidophenyl) disulfide,
bis p-naphthamidophenyl) disulfide and the like.
A convenient method for preparing the bis(p-acylamidophenyl)disulfide stabilizers employed in practicing this invention comprises reacting 4,4'-diamidodiphenyl disulfide with the appropriate carboxylic acid anhydride as represented by the following equation:
R-ii-iI-O-s-swhere each R is as defined hereinbefore. The reaction generally takes place at relatively mild temperatures, for example, temperatures up to about C. Normal atmospheric pressures are preferably employed although pressures substantially below or above normal atmospheric pressures can be used. If desired, the reaction can be carried out in an inert organic vehicle, and will go to completion in a relatively short period, generally not more than about 4 hours. The resulting bis(p-acylamidophenyl)disulfides can then be isolated by conventional procedures, for example, filtering, Washing and drying. The synthesis of bis(p-acetamidophenyl)disulfide by this procedure is shown in Berichte 38, p. 1134 (1905) and lEI O Nil-R 1120 2RCOOH 3 Beilstein Organ. Chem, vol. XIII, p. 544 (1930). As is obvious to those skilled in the art, other bis(p-acylamidophenyl) disulfides used in practicing this invention can be prepared in the same manner by employing the appropriate carboxylic acid derivative in the reaction.
The stabilizing concentration of the bis(p-acylamidophenyl)disulfide employed in a given emulsion is subject to wide variation, depending upon the effects desired, degree of ripening, silver content of the emulsion, etc. In general, a concentration in the range of about .001 to about 10, preferably about .1 to about 1 gram per mole of silver halide is adequate. The stabilizer can be incorporated directly into the silver halide emulsion layer or it can be present in an adjacent layer. It is generally desirable to use higher concentrations of stabilizer when it is used in an adjacent layer rather than in the silver halide emulsion layer. Exposure of the treated emulsion in conventional photographic testing apparatus such as an intensity scale sensitometer, will reveal the most advantageous concentration for the present stabilizers in a particular emulsion. Such techniques are well known to those skilled in the art.
The stabilizers of this invention can be added to the photographic composition using any techniques suitable for this purpose. For example, they can be dissolved in a suitable solvent and added directly to the silver halide emulsion or they can be added to the emulsion in the form of a dispersion similar to the technique used to incorporate certain types of color forming compounds (couplers) in a photographic emulsion. The solvent should be selected so that it has no harmful effects upon the emulsion, in accordance with usual practice, and organic solvents or diluents are preferred. Examples of suitable solvents or diluents include ethanol, acetone or the like.
The stabilizing addenda employed in the practice of this invention can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic, panchromatic and infrared emulsions, they are also useful in X-ray and other non-optically sensitized emulsions. They can be added to the emulsions before or after any optically sensitizing dyes which may be used. They are particularly effective in sulfur and gold sensitized silver halide emulsions. Various silver salts can be used as sensitive salts, including, for example, silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide or silver chloroiodide. The subject addenda can be used in emulsions intended for color photography, for example, emulsions containing color forming couplers or emulsions to be developed by salts containing couplers or other color generating materials.
In the preparation of the silver halide dispersions employed for preparing silver halide emulsions there can be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative or a synthetic resin, for example, a polyvinyl compound, although gelatin is preferred.
The photographic emulsions stabilized according to this invention can be coated on a wide variety of supports. Typical supports include those generally employed for photographic elements, as exemplified by cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials as well as glass, paper, metal, wood and the like. Supports such as paper that are coated with a-olefin polymers, particularly polymers of a-olefins containing 2-10 carbon atoms, as for example, polyethylene, polypropylene, ethylene butene copolymers and the like, can also be employed.
In addition to the antifogging addenda, the photographic emulsions and elements can also contain additional additives, particularly those known to be beneficial in photographic emulsion-s, as exemplified by optical sensitizers, speed increasing materials, gelatin hardeners, plasticizers and the like.
This invention can be further illustrated by the following examples of preferred embodiments thereof although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
Example 1 The disulfides disclosed herein stabilize photographic emulsions against increases in fog and decreases in speed even upon storage at increased temperatures and humidity. To illustrate, bis(p-acetamidophenyl)disulfide is incorporated into a negative, high speed gelatino silver bromoiodide emulsion containing a yellow dye forming coupler. The emulsion is coated on a cellulose acetate film base. For comparison, three samples of the identical emulsion, one sample containing no antifoggant compound, one containing ditolyl disulfide and one containing diphenyl disulfide are coated on cellulose acetate film base in the same manner. Samples of the prepared photographic elements are then incubated for 7 days at F. and 50% relative humidity, exposed for second in the form of film strips in an intensity scale sensitometer (Kodak Type Ib) and developed for 12 minutes at 75 F. The developer employed has the following formula:
Water to 1.0 liter.
A negative silver image and a yellow dye image is formed. The silver image and the residual silver halide are removed by treatment with a conventional ferricyanide bleach followed by a hypo fixing bath leaving a yellow negative dye image.
The results of sensitometric tests on the samples are summarized by the data set out in Table 1 below. In Table 1, as well as in the tables appearing in the following examples, speeds indicated are a function of the exposure necessary to give a density of 0.2 above background fog, the initial control speed being taken as 10.0 in each case; and the concentrations of addenda, if any,
are indicated as grams of addenda per mole of silver halide.
As can be observed from the above table, the bis(pacylamidophenyl)disulfides of this invention impart substantial stabilizing and antifogging properties to photographic silver halide emulsions. It is also significant to note that the practice of this invention does not result in substantial loss in speed with the improved stability. In contrast, Table 1 illustrates that aryl disulfides having unsubstituted aromatic rings or aromatic rings containing such substituents as alkyl groups are ineffective to impart stabilizing or antifoggant properties to photographic silver halide emulsions. As shown in US. Patent 2,440,110, such aryl disulfides require the presence of various sulfinic or seleninic acids or salts to exhibit any stabilizing effects. Such additional additives are, of course, not necessary with the specific organic disulfides employed in the practice of this invention.
Example 2 deleterious afiFect on the stability and/or speed of the photographic silver halide emulsion. To illustrate, the procedure of Example 3 is repeated with bis(p-acetamidophenyl)disulfide and bis[o-(N-ethyl)acetamidophenyl] disulfide which has the formula:
The results of sensitometric tests are as follows:
TABLE 4 Concentration After 7 days at 120 F., After 14 days at 120 F., Addenda of Addenda Initial Test 50% relative humidity 50% relative humidity (grams/mole of AgX) Speed Fog Speed Fog Speed Fog Control 0 100 14 102 21 33 78 Bis(p-acetamidophenyl)disulfide 09 110 09 120 10 78 18 o 95 10 112 10 73 18 Bis[o-(N-ethyl)-acetamidophenyl]-disulfide 06 132 12 107 18 60 30 D0 40 110 .11 105 .12 62 .18
directly after coating. The results of sensitometric tests are as follows:
As will be observed from the above table, the bis-[o-(N- ethyl)acetamidophenyl]disulfide, although quite closely Similar results are obtained when bis(p-trifiuoroacetamidophenyl disulfide, bis (p-propionamidophenyl disulfide or bis(p-butyramidophenyl)disulfide is substituted for bis(p-acetamidophenyl)disulfide in the above procedure.
Example 3 related structurally to bis(p-acetamidophenyl)disulfide shows a substantial deleterious effect upon the speed and/ or fog of a photographic emulsion when it is used in place of the latter. This same deleterious effect is exhibited by other ortho substituted aryl disulfides such as di-o-formylethylaminodiphenyldisulfide when they are employed in the above procedure.
Thus, this invention provides silver halide emulsions that are stabilized with antifoggant addenda which do not cause substantial desensitization or loss in speed.
Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected without departing from the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
TABLE 3 Concentra- After 7 days at tion of Addenda Initial Test 120 F., rela- Addenda (grams/mole tive humidity of AgX) Speed Fog Speed Fog Control 0 100 14 102 20 Bis(p-acetomadophenyl)disulfide. 09 110 09 120 10 D0 3 95 10 112 10 As pointed out hereinabove, seemingly slight changes in the chemical structure of the emulsion addenda employed in the practice of this invention have a marked We claim: 1. A photographic silver halide emulsion stabilized with a compound having the formula:
R-ji-EO s s Q-E-E-R where each R is selected from the group consisting of alkyl, trifluoromethyl and aryl.
2. A photographic silver halide emulsion stabilized with about .001 to about 10 grams per mole of silver halide of a compound having the formula:
Rii M EAR where each R is selected from the group consisting of alkyl, trifluoromethyl and aryl.
3. A photographic silver halide emulsion stabilized with about .1 to about 1 gram per mole of silver halide of a compound having the formula:
where each R is selected from the group consisting of alkyl, trifluoromethyl and aryl.
4. A photographic silver halide emulsion stabilized with a compound having the formula:
where each R is an alkyl radical containing up to 20 carbon atoms.
5. A photographic silver halide emulsion stabilized with a compound having the formula:
Where each R is an alkyl radical containing 1-10 carbon atoms.
6. A photographic silver halide emulsion stabilized with about .1 to about 1 gram per mole of silver halide of a compound having the formula:
where each R is an alkyl group containing 1-10 carbon atoms.
7. A photographic silver halide emulsion stabilized with a compound having the formula:
Rif JaQiiA.
where each R is an aryl radical containing up to 20 carbon atoms.
8. A photographic silver halide emulsion stabilized with about .001 to about 10 grams per mole of silver halide of bis(p-trifiuoroacetamidophenyl)disulfide.
9. A photographic silver halide emulsion stabilized with about .001 to about 10 grams per mole of silver halide of his p-acetamidophenyl disulfide.
10. A sulfur and gold sensitized negative, high speed gelatino silver halide emulsion stabilized with about .001 to about 10 grams per mole of silver halide of a compound having the formula:
Where each R is an alkyl radical containing up to 20 carbon atoms.
11. A sulfur and gold sensitized negative, high speed gelatino silver halide emulsion stabilized with about .001 to about 10 grams per mole of silver halide of bis(pacetamidophenyl) disulfide.
12. A high speed gelatin-0 silver bromoiodide emulsion stabilized with about .25 gram per mole of silver halide of bis(p-acet-amidophenyl)disulfide.
13. A high speed orthochrornatically sensitized gelatino silver bromoiodide emulsion stabilized with about .25 gram per mole of silver halide of bis(p-acetamidophenyl) disulfide.
14. A sulfur and gold sensitized negative, high speed gelatino silver bromoiodide emulsion which is stabilized with about .09 gram per mole of silver halide of bis(pacetamidophenyl) disulfide.
References Cited UNITED STATES PATENTS 6/1934 Brooker et al. 96109 7/1956 Ballard 96109
US421994A 1964-12-29 1964-12-29 Photographic emulsion stabilized with bis (p-acylamidophenyl) disulfides Expired - Lifetime US3397986A (en)

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DE19651472883D DE1472883A1 (en) 1964-12-29 1965-12-22 Silver halide photographic emulsion
FR44111A FR1467298A (en) 1964-12-29 1965-12-29 photographic emulsion stabilized by organic sulfur compounds
GB55099/65A GB1110371A (en) 1964-12-29 1965-12-29 Photographic materials

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Cited By (18)

* Cited by examiner, † Cited by third party
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US3728126A (en) * 1969-03-07 1973-04-17 Agfa Gevaert Nv Silver halide emulsion containing an organic selenium compound antifogging agent
US3779757A (en) * 1971-01-12 1973-12-18 Agfa Gevaert Nv Silver complex diffusion transfer process utilizing an aromatic disulfide
US3926632A (en) * 1971-09-13 1975-12-16 Agfa Gevaert Nv Photographic silver halide lith material
US4607001A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Divalent chalcogenide fog inhibiting agents for silver halide photography
US4607000A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Amido substituted divalent chalcogenide fog inhibiting agents for silver halide photography
US4740438A (en) * 1986-12-10 1988-04-26 Eastman Kodak Company Organic disulfides as image dye stabilizers
US5217859A (en) * 1992-04-16 1993-06-08 Eastman Kodak Company Aqueous, solid particle dispersions of dichalcogenides for photographic emulsions and coatings
US5219721A (en) * 1992-04-16 1993-06-15 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
EP0599199A1 (en) * 1992-11-19 1994-06-01 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic disulfides and sulfinates
US5356770A (en) * 1992-05-29 1994-10-18 Eastman Kodak Compamn Color photographic materials and methods with stabilized silver chloride emulsions
US5364754A (en) * 1992-04-16 1994-11-15 Eastman Kodak Company Silver halide photographic emulsions precipitated in the presence of organic dichalcogenides
US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
US5418127A (en) * 1993-05-28 1995-05-23 Eastman Kodak Company Water-soluble disulfides in silver halide emulsions
US5443947A (en) * 1993-11-30 1995-08-22 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing thiosulfonate/sulfinate compounds
US5601970A (en) * 1995-01-03 1997-02-11 Eastman Kodak Company Photographic elements exhibiting improved stability
US5652090A (en) * 1996-03-15 1997-07-29 Eastman Kodak Company Silver halide photographic elements containing dithiolone compounds
US5962210A (en) * 1998-01-12 1999-10-05 Eastman Kodak Company Color paper with improved wet abrasion sensitivity
US6492101B1 (en) 2001-04-03 2002-12-10 Eastman Kodak Company Silver halide emulsions precipitated in the presence of ortho-substituted water-soluble disulfides

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US1962133A (en) * 1933-05-18 1934-06-12 Eastman Kodak Co Photographic emulsion containing certain disulphides as antifoggants
US2756145A (en) * 1953-12-31 1956-07-24 Eastman Kodak Co Silver halide emulsions containing a diamino diphenyl amine stabilizer

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* Cited by examiner, † Cited by third party
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US1962133A (en) * 1933-05-18 1934-06-12 Eastman Kodak Co Photographic emulsion containing certain disulphides as antifoggants
US2756145A (en) * 1953-12-31 1956-07-24 Eastman Kodak Co Silver halide emulsions containing a diamino diphenyl amine stabilizer

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3728126A (en) * 1969-03-07 1973-04-17 Agfa Gevaert Nv Silver halide emulsion containing an organic selenium compound antifogging agent
US3779757A (en) * 1971-01-12 1973-12-18 Agfa Gevaert Nv Silver complex diffusion transfer process utilizing an aromatic disulfide
US3926632A (en) * 1971-09-13 1975-12-16 Agfa Gevaert Nv Photographic silver halide lith material
US4607001A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Divalent chalcogenide fog inhibiting agents for silver halide photography
US4607000A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Amido substituted divalent chalcogenide fog inhibiting agents for silver halide photography
EP0201201A2 (en) * 1985-04-04 1986-11-12 EASTMAN KODAK COMPANY (a New Jersey corporation) Amido substituted divalent chalcogenide fog inhibiting agents for silver halide photography
EP0201201A3 (en) * 1985-04-04 1988-09-21 Eastman Kodak Company Amido substituted divalent chalcogenide fog inhibiting agents for silver halide photography
US4740438A (en) * 1986-12-10 1988-04-26 Eastman Kodak Company Organic disulfides as image dye stabilizers
EP0271322A2 (en) * 1986-12-10 1988-06-15 EASTMAN KODAK COMPANY (a New Jersey corporation) Organic disulfides as image dye stabilizers
EP0271322A3 (en) * 1986-12-10 1989-02-01 Eastman Kodak Company Organic disulfides as image dye stabilizers
EP0566080A2 (en) * 1992-04-16 1993-10-20 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
US5364754A (en) * 1992-04-16 1994-11-15 Eastman Kodak Company Silver halide photographic emulsions precipitated in the presence of organic dichalcogenides
US5217859A (en) * 1992-04-16 1993-06-08 Eastman Kodak Company Aqueous, solid particle dispersions of dichalcogenides for photographic emulsions and coatings
EP0566080A3 (en) * 1992-04-16 1995-01-04 Eastman Kodak Co Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides.
US5219721A (en) * 1992-04-16 1993-06-15 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
US5356770A (en) * 1992-05-29 1994-10-18 Eastman Kodak Compamn Color photographic materials and methods with stabilized silver chloride emulsions
US5328820A (en) * 1992-11-19 1994-07-12 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic disulfides and sulfinates
EP0599199A1 (en) * 1992-11-19 1994-06-01 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic disulfides and sulfinates
US5418127A (en) * 1993-05-28 1995-05-23 Eastman Kodak Company Water-soluble disulfides in silver halide emulsions
US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
US5443947A (en) * 1993-11-30 1995-08-22 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing thiosulfonate/sulfinate compounds
US5601970A (en) * 1995-01-03 1997-02-11 Eastman Kodak Company Photographic elements exhibiting improved stability
US5652090A (en) * 1996-03-15 1997-07-29 Eastman Kodak Company Silver halide photographic elements containing dithiolone compounds
US5962210A (en) * 1998-01-12 1999-10-05 Eastman Kodak Company Color paper with improved wet abrasion sensitivity
US6492101B1 (en) 2001-04-03 2002-12-10 Eastman Kodak Company Silver halide emulsions precipitated in the presence of ortho-substituted water-soluble disulfides

Also Published As

Publication number Publication date
FR1467298A (en) 1967-01-27
GB1110371A (en) 1968-04-18
DE1472883A1 (en) 1969-01-09

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