US3295981A - Stabilizing a silver halide emulsion hardened with formaldehyde and mucochloric acid - Google Patents

Stabilizing a silver halide emulsion hardened with formaldehyde and mucochloric acid Download PDF

Info

Publication number
US3295981A
US3295981A US425064A US42506465A US3295981A US 3295981 A US3295981 A US 3295981A US 425064 A US425064 A US 425064A US 42506465 A US42506465 A US 42506465A US 3295981 A US3295981 A US 3295981A
Authority
US
United States
Prior art keywords
formaldehyde
urazole
emulsion
mucochloric acid
silver halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US425064A
Inventor
Kirby M Milton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US425064A priority Critical patent/US3295981A/en
Priority to GB34262/68A priority patent/GB1134874A/en
Priority to FR45304A priority patent/FR1463333A/en
Priority to DE19661547662 priority patent/DE1547662A1/en
Application granted granted Critical
Publication of US3295981A publication Critical patent/US3295981A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C1/30—Hardeners
    • 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

Definitions

  • Mucochloric acid has found wide acceptance in the photographic art as a hardener for photographic emulsions because it is less toxic and less volatile than other hardeners such as formaldehyde and also has less propensity to cause fog in photographic emulsions.
  • the use of urazole with a mucochloric acid hardener tends to eliminate substantially all of the advantages produced by either compound utilized alone in a photographic emulsion.
  • One object of my invention is to provide photographic emulsions containing both a urazole type antifoggant and an aldehyde type hardener in which neither detracts from the effectiveness of the other.
  • Another object of my invention is to provide gelatin-silver halide photographic emulsions containing a stabilizer of the urazole type and as the hardener therein a mixture of mucochloric acid and formaldehyde in proportions in which the advantages of each are utilized.
  • Other objects of my invention will appear herein.
  • compounds which'may be used as antifoggants in accordance with my invention are cyclic hydrazides have the following formula wherein Z represents the atoms required to complete a heterocyclic ring, such as and R and R each are selected from the group consisting of H, alkyl, such as methyl, ethyl, propyl, butyl, amyl, octyl, decyl and dodecyl, substituted alkyl, such as carboxyethyl, sulfopropyl or sulfobutyl, aryl, such as phenyl or naphthyl, and substituted aryl, such as benzyl; and monoacyl and dlacyl derivatives of compounds having the above general formula, such as the monoand di-acetyl, propionyl, butyryl, valeryl, caprylyl, capryl and lauryl derivatives of such compounds.
  • Typical specific useful compounds having the above general formula include urazole, 4-phenyl urazole, l phenyl urazole, 4-et hyl urazole, maleic acid hydrazide and phthalic acid hydrazide.
  • the structural formula of the monoacyl and diacyl derivatives of compounds having the above general formula is not known; specific useful examples of such compounds are diacetyl derivatives of urazole and 4- phenyl urazole. A method for preparing the latter compounds is described in Chemical Abstracts, volume 50, page 12033.
  • the hardening'agent employed is a mixture of mucochloric acid and formaldehyde, the formaldehyde being at least 5% and no morethan 40% of the hardener which is used. Using less than 5% formaldehyde the urazole interferes with the hardening action of mucochloric acid while if the hardener is composed of more than 40% formaldehyde the objectionable features of formaldehyde in considerable proportions become evident to a pronounced degree.
  • the hardener is used in the emulsion in an amount within the range of 0.15%, based on the weight of the gelatin in the emulsion as a rule, although any hardening amount of the mixture of mucochloric acid and formaldehyde will have a hardening effect on the gelatin.
  • Urazole and antifoggants of the urazole type exert an antifogging effect in a photographic emulsion in most any concentration.
  • the urazole compound will be used in my invention in an amount within the range of 0.55% based on the weight of the gelatin in the silver halide emulsion.
  • Example 1 To a negative speed silver bromoiodide emulsion of which approximately 3.6 molar percent of the silver halide was silver iodide was added mucochloric acid at the rate of 1.0 part per 168 parts of gelatin. The emulsion was divided into samples and these samples were further treated as described below and then were coated on polyethylene terephthala-te film support at a coverage of 760 mg. of silver and 835 mg. of gelatin per square foot. The percentage swell of the dry coatings when placed in distilled water was obtained for each with the following results.
  • Example 2 A coarse grain silver bromoiodide photographic emulsion of the X-ray type was coated on film support after the addition of 0.2855 part of mucochloric acid per'l39 parts of gelatin in the emulsion.
  • Various emulsion samples were taken and various addenda were added in accordance with the following table.
  • the various samples of emulsion were coated onto film support at a coverage of 454 mg. of silver and 584 mg. of gelatin per square foot.
  • the samples were processed and the percentage of swell obtained in the developer was observed. The results obtained were as follows.
  • Example 3 An emulsion as referred to in Example 2 was coated onto film support after adding mucochloric acid as referred to in that example. Various emulsion samples were taken, addenda were added in accordance with the following table, and the samples were coated onto cellulose acetate film support at a coverage of 454 mg. of silver and 584 mg. of gelatin per square foot. The thickness of the coatings before and after soaking in water at room temperature was determined in each case and the percent vertical swell in water are given in the following table.
  • Percent vertical Feature swell in water H. Control (contains mucochloric acid) 464 mole+0.2 g. formaldehyde/Ag mole 316
  • Example 4 Samples were prepared and coated onto cellulose acetate film support as described in the preceding example. The samples obtained were processed and the percent .of swell in the developer was observed. The addends and the results obtained in the case of each with and without formaldehyde were as follows:
  • Control (contains mucochloric acid) 254 P. Control+2.19 g. 1-acetyl-4-phenyl 'urazole/Ag mole 252 Q. Control+2.19 g. 1-acetyl-4-phenyl urazole/Ag mole+0.2 g. formaldehyde/Ag mole 206 R. Control (contains mucochloric acid) 276 S. Control+1.54 g. maleic hydrazide monoacetate/ Ag mole 294 T. Control+l.54 g. maleic hydrazide monoacetate/ Ag mole +0.2 g. formaldehyde/Ag mole 259 U.
  • a light sensitive gelatin-silver halide emulson containing as a hardener therein a mixture of mucochloric acid and formaldehyde, the latter constituting 5-40% of the mixture and as an antifoggant therein a compound selected from the group consisting of compounds having the following general formula:
  • Z represents the atoms required to complete a heterocyclic ring and R is selected from the group consisting of H, alkyl and aryl; and the monoacyl and diacyl derivatives of compounds having the above formula.
  • R is selected from the group consisting of H, alkyl and aryl; and the monoacyl and diacyl derivatives of compounds having the above formula.

Description

United States Patent ()fifice 3,295,981 Patented Jan. 3, 1967 3,295,981 STABILIZING A SILVER HALIDE EMULSION HARDENED WITH *FORMALDEHYDE AND MUCOCHLORIC ACID Kirby M. Milton, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Jan. 12, 1965, Ser. No. 425,064 9 Claims. (Cl. 96109) This invention relates to photographic elements, more particularly photographic silver halide emulsions containing fog inhibiting agents and hardeners.
For most photographic applications adequate levels of hardness for the gelatin-silver 'halide photographic emulsions must be maintained. Also it is desirable in such emulsions to have present substances which act as fog inhibitors and stabilizers therein. Ordinarily, photographic emulsions on storage tend to lose sensitivity and become developable without exposure to light. In the processing of photographic emulsions it is important that the emulsion layer maintain satisfactory physical strength so as to resist physical and environmental degradation. Urazole has been considered a very satisfactory additive to photographic emulsions to exert a stabilizing and fog inhibiting effect thereon.
Mucochloric acid has found wide acceptance in the photographic art as a hardener for photographic emulsions because it is less toxic and less volatile than other hardeners such as formaldehyde and also has less propensity to cause fog in photographic emulsions. However, the use of urazole with a mucochloric acid hardener tends to eliminate substantially all of the advantages produced by either compound utilized alone in a photographic emulsion.
One object of my invention is to provide photographic emulsions containing both a urazole type antifoggant and an aldehyde type hardener in which neither detracts from the effectiveness of the other. Another object of my invention is to provide gelatin-silver halide photographic emulsions containing a stabilizer of the urazole type and as the hardener therein a mixture of mucochloric acid and formaldehyde in proportions in which the advantages of each are utilized. Other objects of my invention will appear herein.
I have found that by using the combination of mucochloric acid and formaldehyde as the hardener in a photographic emulsion that in combination with a urazole type antifoggant there appears to be produced almost synergistic effects in regard to emulsion stabilization and hardness, especially during storage. These synergistic effects are noted in photographic silver halide emulsions coated on either cellulose ester supports or on dimensionally stable polyethylene terephthalate film supports.
As the stabilizer or antifoggant, compounds which'may be used as antifoggants in accordance with my invention are cyclic hydrazides have the following formula wherein Z represents the atoms required to complete a heterocyclic ring, such as and R and R each are selected from the group consisting of H, alkyl, such as methyl, ethyl, propyl, butyl, amyl, octyl, decyl and dodecyl, substituted alkyl, such as carboxyethyl, sulfopropyl or sulfobutyl, aryl, such as phenyl or naphthyl, and substituted aryl, such as benzyl; and monoacyl and dlacyl derivatives of compounds having the above general formula, such as the monoand di-acetyl, propionyl, butyryl, valeryl, caprylyl, capryl and lauryl derivatives of such compounds. Typical specific useful compounds having the above general formula include urazole, 4-phenyl urazole, l phenyl urazole, 4-et hyl urazole, maleic acid hydrazide and phthalic acid hydrazide. The structural formula of the monoacyl and diacyl derivatives of compounds having the above general formula is not known; specific useful examples of such compounds are diacetyl derivatives of urazole and 4- phenyl urazole. A method for preparing the latter compounds is described in Chemical Abstracts, volume 50, page 12033.
The hardening'agent employed is a mixture of mucochloric acid and formaldehyde, the formaldehyde being at least 5% and no morethan 40% of the hardener which is used. Using less than 5% formaldehyde the urazole interferes with the hardening action of mucochloric acid while if the hardener is composed of more than 40% formaldehyde the objectionable features of formaldehyde in considerable proportions become evident to a pronounced degree. The hardener is used in the emulsion in an amount within the range of 0.15%, based on the weight of the gelatin in the emulsion as a rule, although any hardening amount of the mixture of mucochloric acid and formaldehyde will have a hardening effect on the gelatin.
Urazole and antifoggants of the urazole type exert an antifogging effect in a photographic emulsion in most any concentration. Ordinarily the urazole compound will be used in my invention in an amount within the range of 0.55% based on the weight of the gelatin in the silver halide emulsion.
The following examples illustrate more specifically the invention:
Example 1 To a negative speed silver bromoiodide emulsion of which approximately 3.6 molar percent of the silver halide was silver iodide was added mucochloric acid at the rate of 1.0 part per 168 parts of gelatin. The emulsion was divided into samples and these samples were further treated as described below and then were coated on polyethylene terephthala-te film support at a coverage of 760 mg. of silver and 835 mg. of gelatin per square foot. The percentage swell of the dry coatings when placed in distilled water was obtained for each with the following results.
Percent swell Feature: in water A. Control (contains mucochloric acid) 320 B. Control+1.0 part urazole per 119 parts of gelatin 490 C. Control+ls0 part of urazole+.5 part formaldehyde :per 119 parts of gelatin 260 Each of the film samples were exposed, developed, fixed and dried and were tested as freshly prepared and after storage for a week at 120 F. It was found that in the case of the film samples without urazole appreciable fogging took place, whereas using urazole in combination with mucochloric acid and formaldehyde hardener in the emulsion not only was swelling in water kept to a minimum but no appreciable fogging effect was obtained.
Example 2 A coarse grain silver bromoiodide photographic emulsion of the X-ray type was coated on film support after the addition of 0.2855 part of mucochloric acid per'l39 parts of gelatin in the emulsion. Various emulsion samples were taken and various addenda were added in accordance with the following table. The various samples of emulsion were coated onto film support at a coverage of 454 mg. of silver and 584 mg. of gelatin per square foot. The samples were processed and the percentage of swell obtained in the developer was observed. The results obtained were as follows.
Film samples were also photographically tested particularly after storage at 120 F. It was found that the samples containing both urazole and mucochloric acidformaldehyde hardener had good stability and as shown by the table above exhibited good resistance to swelling by aqueous solution showing the effectiveness of the.
hardener therein.
Example 3 An emulsion as referred to in Example 2 was coated onto film support after adding mucochloric acid as referred to in that example. Various emulsion samples were taken, addenda were added in accordance with the following table, and the samples were coated onto cellulose acetate film support at a coverage of 454 mg. of silver and 584 mg. of gelatin per square foot. The thickness of the coatings before and after soaking in water at room temperature was determined in each case and the percent vertical swell in water are given in the following table.
Percent vertical Feature: swell in water H. Control (contains mucochloric acid) 464 mole+0.2 g. formaldehyde/Ag mole 316 Example 4 Samples were prepared and coated onto cellulose acetate film support as described in the preceding example. The samples obtained were processed and the percent .of swell in the developer was observed. The addends and the results obtained in the case of each with and without formaldehyde were as follows:
. Percent vertical swell in developer 0. Control (contains mucochloric acid) 254 P. Control+2.19 g. 1-acetyl-4-phenyl 'urazole/Ag mole 252 Q. Control+2.19 g. 1-acetyl-4-phenyl urazole/Ag mole+0.2 g. formaldehyde/Ag mole 206 R. Control (contains mucochloric acid) 276 S. Control+1.54 g. maleic hydrazide monoacetate/ Ag mole 294 T. Control+l.54 g. maleic hydrazide monoacetate/ Ag mole +0.2 g. formaldehyde/Ag mole 259 U. Control+1.l2 g. succinic hydrazide/Ag mole 303 V. Control-1.12 g. succinichydrazide/Ag mole +0.2 .g. formaldehyde/Ag mole 266 W. Control+2.13 g. 4-octyl urazole/Ag-mole 260 X. Control+2.l3 g. 4-octyl urazole/Ag mole+0.2 I
g. formaldehyde/Ag mole 234 The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected with the spirit and scope of the invention as described hereina-bove, and asdefined in the appended claims.
I claim:
1. A light sensitive gelatin-silver halide emulson containing as a hardener therein a mixture of mucochloric acid and formaldehyde, the latter constituting 5-40% of the mixture and as an antifoggant therein a compound selected from the group consisting of compounds having the following general formula:
wherein Z represents the atoms required to complete a heterocyclic ring and R is selected from the group consisting of H, alkyl and aryl; and the monoacyl and diacyl derivatives of compounds having the above formula. 2. The emulsion of claim 1 in which the antifoggant is urazole. I
3. The emulsion of claim 1 in which the antifoggant is amino phthalic hydrazide.
4. The emulsion of claim 1 in which the antifoggant is acetamido phthalic hydrazide.
5. The emulsion of claim 1 in which the antifoggant is dilauramidophthalhydrazide.
6. The emulsion of claim 1 in which the antifoggant is l-acetyl-4-phenyl urazole.
7. The emulsion of claim 1 in which the antifoggant is maleic hydrazide monoacetate.
8. The emulsion of claim 1 in which the antifoggant is succinic hydrazide.
9. The emulsion of claim 1 in which the antifoggant is 4-octyl urazole.
No references cited.
NORMAN G. TORCHIN, Primary Examiner. J. H. RAUBITSCHEK, Assistant Examiner,

Claims (1)

1. A LIGHT SENSITIVE GELATIN-SILVER HALIDE EMULSON CONTAINING AS A HARDENER THEREIN A MIXTURE OF MCOCHLORIC ACID AND FORMALDEHYDE, THE LATTER CONSISTITUTING 5-40% OF THE MIXTURE AND AS AN ANTIFOGGANT THEREIN A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THE FOLLOWING GENERAL FORMULA:
US425064A 1965-01-12 1965-01-12 Stabilizing a silver halide emulsion hardened with formaldehyde and mucochloric acid Expired - Lifetime US3295981A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US425064A US3295981A (en) 1965-01-12 1965-01-12 Stabilizing a silver halide emulsion hardened with formaldehyde and mucochloric acid
GB34262/68A GB1134874A (en) 1965-01-12 1965-12-21 Photographic silver halide emulsions
FR45304A FR1463333A (en) 1965-01-12 1966-01-10 New stabilized and tanned photographic emulsion
DE19661547662 DE1547662A1 (en) 1965-01-12 1966-01-11 Gelatin-silver halide light-sensitive photographic emulsion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US425064A US3295981A (en) 1965-01-12 1965-01-12 Stabilizing a silver halide emulsion hardened with formaldehyde and mucochloric acid

Publications (1)

Publication Number Publication Date
US3295981A true US3295981A (en) 1967-01-03

Family

ID=23684986

Family Applications (1)

Application Number Title Priority Date Filing Date
US425064A Expired - Lifetime US3295981A (en) 1965-01-12 1965-01-12 Stabilizing a silver halide emulsion hardened with formaldehyde and mucochloric acid

Country Status (4)

Country Link
US (1) US3295981A (en)
DE (1) DE1547662A1 (en)
FR (1) FR1463333A (en)
GB (1) GB1134874A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833379A (en) * 1972-01-17 1974-09-03 Konishiroku Photo Ind Developer composition for lithographic printing plates
US4411987A (en) * 1981-11-06 1983-10-25 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833379A (en) * 1972-01-17 1974-09-03 Konishiroku Photo Ind Developer composition for lithographic printing plates
US4411987A (en) * 1981-11-06 1983-10-25 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Also Published As

Publication number Publication date
FR1463333A (en) 1966-06-03
DE1547662A1 (en) 1969-11-20
GB1134874A (en) 1968-11-27

Similar Documents

Publication Publication Date Title
US2716062A (en) 4-hydroxy-6-alkyl-1, 3, 3a, 7-tetrazaindene stabilizers for emulsions sensitized with alkylene oxide polymers
US3287135A (en) Antifoggants for silver halide emulsions on a linear polyester support
US3598598A (en) Fog stabilizers for photographic emulsions
US3232764A (en) Gelatin compositions adapted for the preparation of hardened coatings
US3499761A (en) Silver halide emulsions containing alkyl esters of benzimidazole carbamic acid antifogging agents
US3071465A (en) Fog reduction in silver halide emulsions by 2h-tetrazolium halides
US2772164A (en) Photographic silver halide emulsions containing 1-thia-3, 5, 7-triazaindenes
US3271154A (en) Antifogging and stabilizing agents for photography
US3295981A (en) Stabilizing a silver halide emulsion hardened with formaldehyde and mucochloric acid
US2897081A (en) Antifogging agent and bactericide for photographic emulsions
US2784091A (en) 4-hydroxy-6-alkyl-1, 3, 3alpha, 7-tetrazaindene stabilizers for photographic emulsions sensitized with polyalkylene esters, amides, and ethers
US2708161A (en) Parabanic acid stabilizer for photographic emulsions sensitized with alkylene oxide polymers
US2704716A (en) Melonate and cyamelurate stabilizers for photographic emulsions sensitized with alkylene oxide polymers
US3051570A (en) Antifoggants and stabilizers for photographic silver halide emulsions
US3650759A (en) Silver halide emulsion containing 1.2-glycol as sensitizer and antifoggant
US3901709A (en) Lith-type silver halide photographic material containing a polyalkylene oxide and a heterocyclic mercaptan
US3650760A (en) Alkoxy mercaptophenols as photographic addenda for photographic elements
US3295980A (en) Increased efficiency with mucochloric acid hardening by use of 4-substituted urazoles
US3554758A (en) Photographic light-sensitive material
US3598601A (en) Alkyl esters or organic acids,such as stearyl malate,as antifoggants
US4243748A (en) Light-sensitive silver halide reproduction material
US2319090A (en) Photographic emulsion containing fog inhibitors
US2713541A (en) Stabilized photographic silver halide emulsions
US3600181A (en) Fog reduction of photographic silver halide emulsions by incorporation of a nitrocinnamic acid,or cinnamaldehyde in a contiguous layer
US2735769A (en) Stabilized photographic silver halede