US3393072A - Dioximes as antifoggants in silver halide emulsions - Google Patents

Dioximes as antifoggants in silver halide emulsions Download PDF

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US3393072A
US3393072A US447986A US44798665A US3393072A US 3393072 A US3393072 A US 3393072A US 447986 A US447986 A US 447986A US 44798665 A US44798665 A US 44798665A US 3393072 A US3393072 A US 3393072A
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silver halide
compound
noh
fog
halide photographic
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US447986A
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Ohi Reiichi
Sugiyama Mitsunori
Kawano Hideo
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • 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
    • G03C1/33—Spot-preventing agents

Definitions

  • R and R each represents a'hydrogen atom, a lower alkly group, an aryl' group, a heterocyclicgroup containing an oxygen atom or a nitrogen atom, or a I carboxyl'group and nrepresents 0, l or 2.
  • R and R each represents a'hydrogen atom, a lower alkly group, an aryl' group, a heterocyclicgroup containing an oxygen atom or a nitrogen atom, or a I carboxyl'group and nrepresents 0, l or 2.
  • a salicylaldoxime is used for preventing the formation of airial fog but when the salicylaldoxime is used with 7 at any stage of the production of emulsions but it is preferable to add them after ripening and before coating.
  • the amount of them is suitably 350 g., and more preferably 10-20 g. per 1 kg. of gelatin in a silver halide photographic emulsion layer or a protective coating layer.
  • the amount of compound (II) is suitably 10-100 g. and more preferably 20-50 g. per 1 kg. of gelatin in a silver halide photographic emulsion layer or a protective coating layer.
  • a silver halide photographic emulsion that is used in this invention may be or may not be optically dye sensitized.
  • the silver halide photographic emulsion may be chemically sensitized with a sulfur-containing compound, a noble metal salt, a polyoxyethylene derivative, a polyamine, or a quaternary ammonium salt and also in order to improve the photographic characteristics it may contain a water-soluble polymer such as polyvinyl pyrrolidone.
  • a silver halide photographic emulsion contains a hardening agent, such as, formaline or mucochloric acid, a natural or synthetic surface active agent, and a stabilizer such as a tetraazindene compound
  • a hardening agent such as, formaline or mucochloric acid, a natural or synthetic surface active agent, and a stabilizer such as a tetraazindene compound
  • the addition of the dioxime compound of this invention in the emulsion can suppress effectively the formation of airial fog and black spots without reducing the desirable photographic properties of the photographic material endowed by the addition of these additives.
  • Example 1 A photographic sulfur sensitized, gold sensitized and optically cyanine dye sensitized high-speed panchromatic silver iodobromide emulsion for negative type photographic material, which contain 5 mole percent of silver iodide was dissolved by heating and added with fine particles of iron which had been prepared preliminary for promoting the formation of black spots caused artifically, The solution was divided into four equal volume portions after stirring for 10 minutes. Each of the divided solutions was added with above-stated compound (2) in the amount shown below and coated on a film base followed by drying. After developing for 10 minutes at 20 C., fixing, rinsing with water and drying, the sizes of formed black spots and the numbers of thus formed spots per 0.3 sq. m. were detected, which were shown below.
  • composition of the used developing solution was as follows:
  • Example 2 Amount of compd. Size of spot Relative optical (3) (g./kg.gelatin) (diam.nm1.) density of spot When compound (5) was used instead of compound (3), almost the same results were obtained.
  • Example 3 A photographic sulfur sensitized and optically merocyanine dye sensitized high contrast orthochromatic silver bromochloride emulsion containing 30 mole percent of silver iodide was added with compound (2) in the amount shown below and coated on a film base then dried.
  • the photographic material was developed as follows. That is, the photographic film was immersed in a developing solution for 1 minute at 20 C., exposed in air for 1 minute, and then immersed again in the developing solution for 1.5 minutes. After fixing, rinsing with water, and drying, the optical density of the formed airial fog is as follows:
  • Example 4 A protective coating layer for the high-contrast orthochromatic silver chlorobromide photographic emulsion in Example 3 was added with above-mentioned compound ⁇ 2 1) and treated as in Example 3. The results are shown elow.
  • Example 5 Amount of compd. (2) Amount of compd. (8) Optical density of air fog (gJkg. gelatin) (gJkg. gelatin) When compounds (9), (10) and (11) were used respectively instead of compound (8), almost the same results were obtained.
  • Example 6 Amount of compd. (1) Amo(unt of coinpd. (9) Optical density of g air (gJkg. gelatin) .llrg. gelatin) tog What we claim is:
  • a silver halide photographic material comprising a support and a silver halide photographic emulsion layer, said emulsion layer containing at least one compound shown by the general Formula I NOH NOH xii-wrrm-h-rv (I) wherein R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group, an aryl group, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a nitrogen atom, and a carboxylic group and n represents 0, l and 2.
  • R and R each represents a member selected from the class consisting of a hydrogen atom, OH group, and a lower alkyl group.
  • a silver halide photographic material comprising a support, a silver halide photographic emulsion layer, and a protective layer for the emulsion layer, at least one of said layers containing at least a compound shown by the general Formula I NOH NOH wherein R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group, and aryl group, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a nitrogen atom, and a carbocyclic group and n represents 0, 1 and 2.
  • a silver halide photographic sensitive material comprising a support, a silver halide photographic sensitive emulsion layer, and a protective layer for the emulsion layer, at least one of said layers containing at least a compound shown by the general Formula I NOH NOH wherein R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group, an aryl group, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a nitrogen atom, and a carboxylic group and n represents 0, 1 and 2, and a compound shown by the following general Formula II R (II) wherein R and R each represents a member selected firom the class consisting of a hydrogen atom, OH group, and a lower alkyl group.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

United States Patent This invention relates to photographic materialsand I more particularly to a method forpreventing the formation offog and black spots in'photog'raphic emulsion with dioximecompounds.
' It has'been well known that a photographic emulsion on storage tends to become spontaneously developable without exposure'to light. There is normally a'detectable amount of silver salts reduced during development in the areas where no exposure was given;.this is commonly called fog. The formation of fog is promoted by bad conditions in storage as well as bad conditions in development. When a photographic material wetted by developing solution is exposed to air in development, the formation of fog is particularly promoted and we call it airial fog hereinafter. Moreover fog is also formed by the presbe more remarkably prevented.
ence of fine iron particles or other fine impurity particles contained in supports, gelatin or chemicals. These impurity particles may also enter into photographic materials during the production or treatment of them. And in this case particularly spot-like fog having a high, optical density, which is generally called black spot is usually formed. 7 1. 1
For preventing the formation of such airial fog and black spots the additions of various compounds have been proposed, but their eifects are usually weak and even though some of them are effective they give other bad 'influen'cesysuch as, reduction of sensitivity, deterioration of the quality of gelatin layers, etc.
We. havefound thatthe formation of airial fog and black spots can be remarkably suppressed by-the addition of compounds shown by the following general Formu laI.-" w:
' 1 |IOH won R-'-o (oHz)n-oR" (I) (Wherein R and R each represents a'hydrogen atom, a lower alkly group, an aryl' group, a heterocyclicgroup containing an oxygen atom or a nitrogen atom, or a I carboxyl'group and nrepresents 0, l or 2.) in an emulsion layer and/or a protective layerof halide photographic materials.
Representative compounds of the above mentioned general Formula I, which can be used in this invention, are as follows: i
silver NOH NOH II II Q-C-CHr-C-Ca 3,393,072 Patented July 16, 1968 NOH NOH I The compounds of this invention may be used individually or may be used as a mixture of two or more of 3 these compounds. Further, in another embodiment of this invention the compoundof the above general formula may be used with salicylaldoxime or its derivatives shown by the following general Formula II p CH=NOH (Wherein R" and R each represents a hydrogen atom,
OH group, or a lower alkyl group.)
whereby the formation of airial fog and black spots can Representative compounds of the general Formula II which can be used in this invention are as follows.
@CH=NOH CI-I=NOH @CH=NOH I on,
and
It has been already disclosed in B.P. 623,448 that a salicylaldoxime is used for preventing the formation of airial fog but when the salicylaldoxime is used with 7 at any stage of the production of emulsions but it is preferable to add them after ripening and before coating. There are no limitations for the amount of them but the amount of compound (I) is suitably 350 g., and more preferably 10-20 g. per 1 kg. of gelatin in a silver halide photographic emulsion layer or a protective coating layer. Further, when compound (II) is used together with compound (I), the amount of compound (II) is suitably 10-100 g. and more preferably 20-50 g. per 1 kg. of gelatin in a silver halide photographic emulsion layer or a protective coating layer.
A silver halide photographic emulsion that is used in this invention may be or may not be optically dye sensitized. Moreover, the silver halide photographic emulsion may be chemically sensitized with a sulfur-containing compound, a noble metal salt, a polyoxyethylene derivative, a polyamine, or a quaternary ammonium salt and also in order to improve the photographic characteristics it may contain a water-soluble polymer such as polyvinyl pyrrolidone. Further, in cases where a silver halide photographic emulsion contains a hardening agent, such as, formaline or mucochloric acid, a natural or synthetic surface active agent, and a stabilizer such as a tetraazindene compound, the addition of the dioxime compound of this invention in the emulsion can suppress effectively the formation of airial fog and black spots without reducing the desirable photographic properties of the photographic material endowed by the addition of these additives.
Example 1 A photographic sulfur sensitized, gold sensitized and optically cyanine dye sensitized high-speed panchromatic silver iodobromide emulsion for negative type photographic material, which contain 5 mole percent of silver iodide was dissolved by heating and added with fine particles of iron which had been prepared preliminary for promoting the formation of black spots caused artifically, The solution was divided into four equal volume portions after stirring for 10 minutes. Each of the divided solutions was added with above-stated compound (2) in the amount shown below and coated on a film base followed by drying. After developing for 10 minutes at 20 C., fixing, rinsing with water and drying, the sizes of formed black spots and the numbers of thus formed spots per 0.3 sq. m. were detected, which were shown below.
Amount of N o. of spots No. of spots No. of spots compQund (2) of 21-2 mm. diam. of 0.9-0.1 mm. below 0.09 mm. (gJkg. gelatin) No changes were observed in the photographic properties as well as the physical properties of the emulsion layers.
The composition of the used developing solution was as follows:
Warm water cc 500.0 Metol g 2.0 Sodium sulfite (anhydrous) g 100.0 Hydroquinone g 5.0 Borax g 20.0
Water to 1.0 liter.
Example 2 Amount of compd. Size of spot Relative optical (3) (g./kg.gelatin) (diam.nm1.) density of spot When compound (5) was used instead of compound (3), almost the same results were obtained.
Example 3 A photographic sulfur sensitized and optically merocyanine dye sensitized high contrast orthochromatic silver bromochloride emulsion containing 30 mole percent of silver iodide was added with compound (2) in the amount shown below and coated on a film base then dried. For increasing airial fog artificially, the photographic material was developed as follows. That is, the photographic film was immersed in a developing solution for 1 minute at 20 C., exposed in air for 1 minute, and then immersed again in the developing solution for 1.5 minutes. After fixing, rinsing with water, and drying, the optical density of the formed airial fog is as follows:
Amount of compound (2),
( g./ kg. gelatin) Optical density The composition of the developing solution was as follows:
War-m water ml 500.0 Sodium sulfite (anhydrous) g 30.0 Paraformaldehyde g 7.5 Acid sodium sulfite g 2.2 Boric acid g 7.5 Hydroquinone g 22.5 Potassium bromide g 1.6 Water liters to 1.0
Example 4 A protective coating layer for the high-contrast orthochromatic silver chlorobromide photographic emulsion in Example 3 was added with above-mentioned compound {2 1) and treated as in Example 3. The results are shown elow.
Amount of compd. (1) Optical density (g./kg. gelatin): of air fogs When above-shown compound (6) was used instead of using compound (1), almost the same results were obtained.
Example 5 Amount of compd. (2) Amount of compd. (8) Optical density of air fog (gJkg. gelatin) (gJkg. gelatin) When compounds (9), (10) and (11) were used respectively instead of compound (8), almost the same results were obtained.
Example 6 Amount of compd. (1) Amo(unt of coinpd. (9) Optical density of g air (gJkg. gelatin) .llrg. gelatin) tog What we claim is:
1. A silver halide photographic material comprising a support and a silver halide photographic emulsion layer, said emulsion layer containing at least one compound shown by the general Formula I NOH NOH xii-wrrm-h-rv (I) wherein R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group, an aryl group, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a nitrogen atom, and a carboxylic group and n represents 0, l and 2.
2. A silver halide photographic material comprising a support and a silver halide photographic emulsion layer, said emulsion layer containing at least a compound shown by the general Formula I NOH NOH wherein R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group, an aryl group, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a nitrogen atom, and a carboxylic group and n represents 0, 1 and 2, and at least one compound shown by the following general Formula II (In-I OH=NOH wherein R" and R each represents a member selected from the class consisting of a hydrogen atom, OH group, and a lower alkyl group.
3. A silver halide photographic material comprising a support, a silver halide photographic emulsion layer, and a protective layer for the emulsion layer, at least one of said layers containing at least a compound shown by the general Formula I NOH NOH wherein R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group, and aryl group, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a nitrogen atom, and a carbocyclic group and n represents 0, 1 and 2.
4. A silver halide photographic sensitive material comprising a support, a silver halide photographic sensitive emulsion layer, and a protective layer for the emulsion layer, at least one of said layers containing at least a compound shown by the general Formula I NOH NOH wherein R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group, an aryl group, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a nitrogen atom, and a carboxylic group and n represents 0, 1 and 2, and a compound shown by the following general Formula II R (II) wherein R and R each represents a member selected firom the class consisting of a hydrogen atom, OH group, and a lower alkyl group.
References Cited FOREIGN PATENTS 623,448 5/1949 Great Britain. 533,034 11/1956 Canada.
NORMAN G. TORCI-IIN, Primary Examiner.
R. E. FICI-ITER, Assistant Examiner.

Claims (1)

  1. 2. A SILVER HALIDE PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT AND A SILVER HALIDE PHOTOGRAPHIC EMULSION LAYER, SAID EMULSION LAYER CONTAINING AT LEAST A COMPOUND SHOWN BY THE GENERAL FORMULA I
US447986A 1964-04-23 1965-04-14 Dioximes as antifoggants in silver halide emulsions Expired - Lifetime US3393072A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357419A (en) * 1981-04-02 1982-11-02 Minnesota Mining And Manufacturing Company Covering power in films
US4756997A (en) * 1986-07-23 1988-07-12 Minnesota Mining And Manufacturing Company Photographic silver halide developer compositions and process for forming photographic silver images
WO2008066899A2 (en) 2006-11-28 2008-06-05 Marinus Pharmaceuticals Nanoparticulate formulations and methods for the making and use thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB623448A (en) * 1945-07-30 1949-05-18 Kodak Ltd Improvements in and relating to photographic emulsions
CA533034A (en) * 1956-11-13 W. Vittum Paul Anti-stain agents for photographic color materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA533034A (en) * 1956-11-13 W. Vittum Paul Anti-stain agents for photographic color materials
GB623448A (en) * 1945-07-30 1949-05-18 Kodak Ltd Improvements in and relating to photographic emulsions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357419A (en) * 1981-04-02 1982-11-02 Minnesota Mining And Manufacturing Company Covering power in films
US4756997A (en) * 1986-07-23 1988-07-12 Minnesota Mining And Manufacturing Company Photographic silver halide developer compositions and process for forming photographic silver images
WO2008066899A2 (en) 2006-11-28 2008-06-05 Marinus Pharmaceuticals Nanoparticulate formulations and methods for the making and use thereof

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DE1472893A1 (en) 1969-03-27
BE662962A (en) 1965-08-17
GB1057470A (en) 1967-02-01

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