US3925086A - Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions - Google Patents

Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions Download PDF

Info

Publication number
US3925086A
US3925086A US235011A US23501172A US3925086A US 3925086 A US3925086 A US 3925086A US 235011 A US235011 A US 235011A US 23501172 A US23501172 A US 23501172A US 3925086 A US3925086 A US 3925086A
Authority
US
United States
Prior art keywords
emulsion
azotetrazole
azotriazole
silver halide
fog
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
US235011A
Other languages
English (en)
Inventor
Agostino Baldassarri
Luigi Cellone
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing 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 Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of USB235011I5 publication Critical patent/USB235011I5/en
Application granted granted Critical
Publication of US3925086A publication Critical patent/US3925086A/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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
    • 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
    • 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
    • G03C1/36—Desensitisers

Definitions

  • ABSTRACT Azotriazoles and azotetrazoles are effective antifogging agents, antistain agents and selective desensitizers for silver halide photographic emulsions, Such agents may be employed in reactive association with the emulsions, or in a processing bath prior to or during development of emulsion layersv 12 Claims, No Drawings AZOTRIAZOLE AND AZOTETRAZOLE ANTIFOG, ANTISTAIN AND SELECTIVE DESENSITIZERS FOR SILVER HALIDE EMULSIONS
  • the present invention relates to the use of azotriazoles and azotetrazoles as anti-fog, anti-stain and/or selective desensitizers for silver halides photographic emulsions.
  • azotriazole and azotetrazole compounds are capable of inhibiting fog when placed in contact with a silver halide emulsion (as by being placed in the emulsion, in a layer adjacent the emulsion, or by being placed in a processing bath which is employed prior to or during development of the emulsion). These compounds have also been found to inhibit stains in silver halide photographic emulsions, and, in larger quantities, to selectively desensitize silver halide emulsions.
  • the present invention relates to a silver halide photographic emulsion having contacted therewith at least a fog-inhibiting amount of an azotriazole or an azotetrazole.
  • the invention relates to a method for in hibiting fog in a silver halide photographic emulsion which comprises contacting the emulsion with an azotetrazole or an azotriazole.
  • the invention relates to an aqueous processing solution for silver halide photographic emulsions adapted for use prior to or during development and containing from about 3 to about 6 milligrams of an azotriazole or an azotetrazole per liter of solution.
  • azotriazoles and azotetrazoles of the present invention preferably correspond to the formula 2 z' I c N N c N l N wherein Z and Z independently represent atoms forming heterocyclic nuclei of the triazole or tetrazole series.
  • sub stituents borne by the heterocyclic nuclei of the azotriazoles and azotetrazoles of the invention include hydrogen, alkyl (e.g., C,C alkyl), alkaline (e.g., C C and aryl (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl having no more than 15 aliphatic carbon atoms, etc.).
  • the azotriazoles and azotetrazoles of the present invention correspond to the formula wherein X is carbon or nitrogen, and each Y group independently represents a hydrogen atom, an alkyl group (e.g., C,C an alkaline group (e.g., C,C or an aryl group (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl containing no more than 20 aliphatic carbon atoms), etc.
  • an alkyl group e.g., C,C an alkaline group (e.g., C,C or an aryl group (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl containing no more than 20 aliphatic carbon atoms), etc.
  • the present invention permits a single class of fog restrainers to be used for many purposes.
  • the triazoles and tetrazoles of the invention are useful both in photographic silver halide emulsions, (e.g., mixed into the emulsion layer or employed in a layer adjacent the emulsion layer) and in photographic processing baths which, for example, are employed either prior to development (as a pre-bath), in the developing bath itself, etc.
  • the azotriazole and azotetrazole compounds of the invention are particularly desirable because they are generally readily soluble in common photographic solvents such as water, alcohol, and aqueous alkaline solutions such as developer solutions.
  • This compound can be usefully introduced into a photographic emulsion or photographic bath in aqueous solutions of sodium carbonate or NaOH.
  • This compound can be usefully introduced into an emulsion or photographic bath in solutions of sodium carbonate or NaOH.
  • This compound can be usefully introduced into a photographic silver halide emulsion or into a photographic bath in ethanol of dimethylformamide solution.
  • This compound can be usefully introduced into emulsions or photographic baths in ethanol solution.
  • This compound can be usefully introduced into emulsions or photographic baths in ethanol solution.
  • This compound can be usefully introduced into emul- Thls compound l be Introduced emul' sions or photographic baths in ethanol solution. 40 Slons or phowgraphlc baths m ethanol soluuon Analysis: Calculated Found Analysis: Calculated Found 5% 22.3% 23.3 c% 38.49 38.42 11% 4.06 4.21 N% 72.10 11.42 N% 56.89 56.28
  • EXAMPLE 7 EXAMPLE 9 1,1'-diallyl-5,5-azotetrazole
  • compound C suitable CH2 CH CH2 N a 5g solvents have been selected, and the solubility of these N L compounds at 20C in these solvents has been determined. The results are reported in the following table 1.
  • EXAMPLE ll EXAMPLE I4 65 Photographic material similar to that of Example 10 A quantity of the developer of Example 10 was divided into two portions. To one portion was added 50 42M of the compound of Example 2. Samples of the photographic material of Example [0, exposed to light was exposed to the light from a tungsten lamp and divided into three samples. One sample was developed in a developer of the following formula:
  • the second sample was identically developed except that the developer containing 200 p.M per liter of the compound of Example 2.
  • EXAMPLE 16 To samples of a medium sensitivity, physically seasoned, washed and chemically sensitized silver bromoiodide emulsion containing 97.5 moles of bromide and 2.5 mole of iodide, were added various amounts of compounds of the present invention, of red mercury iodide (a known selective desensitizer), and of l-phenyl-S-mercaptotetrazole (labeled A).
  • the resulting emulsions were then spread on cellulose triacetate supports, and samples of the corresponding materials were exposed to white light and to X-rays of various energy. The exposed samples were then developed for 3 minutes at 20C in the developer of Example 10.
  • EXAMPLE 17 A cellulose triacetate support was thinly coated with gelatin containing powdered iron. Three samples of the resulting material, drawn at random, were each divided into four parts. On the first part a high sensitivity, silver bromo-iodide containing 98 moles of bromide and 2 mole of iodide were coated. On the other three parts of each sample, the same emulsion to which had been added respectively the compounds of Examples 1 and 2 and the 1-phenyl-S-mercapto-tetrazole (labeled A) were coated. On each element thus obtained a protective gelatin layer was coated. The resulting elements were kept 10 minutes in a cold state and were then developed 10 minutes at 20C in the developer of Example 10. The white and black points on each of the resulting elements were counted.
  • the developed material was fixed in a bath of the following composition: 10
  • the silver halide photographic emulsions of the pres- 30 ent invention are silver chloride, silver bromide and silver iodide emulsions and mixtures thereof such as for example, silver bromoiodide and silver chlorobromide iodide.
  • Such emulsions may include synthetic polymeric gelatin substitutes or additives, such as dextrane,
  • the emulsions of the invention may be chemically sensitized with naturally active gelatin, by addition of chemical sensitizers such as thiourea, allylthiourea, thiocyanates, thiosulfates, etc. Sensitization may be effected by the addition of noble metals, such as gold salts. Spectral sensitizers may be employed in emulsions of the invention, such as cyanine and merocyanine dyes.
  • the emulsions of the invention may include such additives as color couplers, filtering dyes, surfactants, hardeners, stabilizers, additional fog-restrainers, plasticizers, oxidizing agents, developing accelerators, etc.
  • the emulsions of the invention may be coated upon any convenient support such as polyester, cellulose acetate, and the like.
  • the processing baths of the present invention may be photographic pre-baths, such as those known to the art to be useful prior to treatment of a photographic emulsion with a developing solution.
  • Predevelopment baths usually (but not necessarily) are acidic and may contain hardeners such as aldehydes and the like.
  • the azotriazole and azotetrazole compounds of the invention may, of course, also be employed in developing baths.
  • Such baths are normally alkaline and include one or more silver halide photographic developing agents such as hydroquinone, metol, metol-hydroquinone, phenidone, hydroquinonephenidone, and various p-phenylene diamine materials,
  • processing baths of the invention preferably employ from 3 to about 60 milligrams of azotriazole or azotetrazole compound per liter of solution.
  • a silver halide photographic emulsion having contacted therewith at least a fog-inhibiting amount of an azotriazole or an azotetrazole.
  • anti-fogging agent is a 5,5'-azotetrazole-l,l '-disodium salt.
  • a method for inhibiting fog in a silver halide photographic emulsion which comprises contacting said emulsion with an azotetrazole or an azotriazole.
  • a method for inhibiting fog and stain in a silver halide emulsion which comprises contacting said emulsion with an azotriazole or an azotetrazole.
US235011A 1971-03-16 1972-03-15 Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions Expired - Lifetime US3925086A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT4909371 1971-03-16

Publications (2)

Publication Number Publication Date
USB235011I5 USB235011I5 (fr) 1975-01-28
US3925086A true US3925086A (en) 1975-12-09

Family

ID=11269620

Family Applications (1)

Application Number Title Priority Date Filing Date
US235011A Expired - Lifetime US3925086A (en) 1971-03-16 1972-03-15 Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions

Country Status (9)

Country Link
US (1) US3925086A (fr)
JP (1) JPS5547374B1 (fr)
AR (1) AR204386A1 (fr)
BE (1) BE780718A (fr)
CA (1) CA1007092A (fr)
CH (1) CH588092A5 (fr)
DE (1) DE2212550A1 (fr)
FR (1) FR2130240B1 (fr)
GB (1) GB1383211A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046571A (en) * 1975-06-27 1977-09-06 Gaf Corporation Processing solution for use as photographic developer bath and replenisher therefor
WO2014127297A1 (fr) 2013-02-15 2014-08-21 Cambrios Technologies Corporation Procédés pour incorporer des conducteurs transparents à base de nanofils d'argent dans des dispositifs électroniques
US10720257B2 (en) 2013-02-15 2020-07-21 Cambrios Film Solutions Corporation Methods to incorporate silver nanowire-based transparent conductors in electronic devices
US10971277B2 (en) 2013-02-15 2021-04-06 Cambrios Film Solutions Corporation Methods to incorporate silver nanowire-based transparent conductors in electronic devices

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5753327A (en) * 1980-09-17 1982-03-30 Ekuseru Kk Preparing device of hollow molded object having bent part
JPS5770622A (en) * 1980-10-22 1982-05-01 Ekuseru Kk Manufacture of foamed synthetic resin hollow molded article

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453087A (en) * 1946-11-07 1948-11-02 Gen Aniline & Film Corp Photographic developers containing tetrazolyl disulfides as antifogging agents
US2588538A (en) * 1948-08-06 1952-03-11 Ilford Ltd Stabilizers in photographic emulsions and developers
US3563747A (en) * 1966-11-04 1971-02-16 Agfa Gevaert Nv Photographic developing combinations
US3615616A (en) * 1967-10-09 1971-10-26 Agfa Gevaert Nv Photographic light-sensitive silver halide material
US3719604A (en) * 1970-02-03 1973-03-06 Dynamit Nobel Ag Pressurizing-gas-producing charges containing an aminoguanidine tetrazole and an oxygen-liberating or gas-evolving additive

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR810104A (fr) * 1935-08-16 1937-03-15 Ilford Ltd Perfectionnements apportés aux matières tinctoriales

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453087A (en) * 1946-11-07 1948-11-02 Gen Aniline & Film Corp Photographic developers containing tetrazolyl disulfides as antifogging agents
US2588538A (en) * 1948-08-06 1952-03-11 Ilford Ltd Stabilizers in photographic emulsions and developers
US3563747A (en) * 1966-11-04 1971-02-16 Agfa Gevaert Nv Photographic developing combinations
US3615616A (en) * 1967-10-09 1971-10-26 Agfa Gevaert Nv Photographic light-sensitive silver halide material
US3719604A (en) * 1970-02-03 1973-03-06 Dynamit Nobel Ag Pressurizing-gas-producing charges containing an aminoguanidine tetrazole and an oxygen-liberating or gas-evolving additive

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046571A (en) * 1975-06-27 1977-09-06 Gaf Corporation Processing solution for use as photographic developer bath and replenisher therefor
WO2014127297A1 (fr) 2013-02-15 2014-08-21 Cambrios Technologies Corporation Procédés pour incorporer des conducteurs transparents à base de nanofils d'argent dans des dispositifs électroniques
EP3598185A2 (fr) 2013-02-15 2020-01-22 Cambrios Film Solutions Corporation Procédés pour incorporer des conducteurs transparents à base de nanofils d'argent dans des dispositifs électroniques
US10720257B2 (en) 2013-02-15 2020-07-21 Cambrios Film Solutions Corporation Methods to incorporate silver nanowire-based transparent conductors in electronic devices
US10971277B2 (en) 2013-02-15 2021-04-06 Cambrios Film Solutions Corporation Methods to incorporate silver nanowire-based transparent conductors in electronic devices

Also Published As

Publication number Publication date
CH588092A5 (fr) 1977-05-31
USB235011I5 (fr) 1975-01-28
CA1007092A (en) 1977-03-22
FR2130240B1 (fr) 1975-10-24
GB1383211A (en) 1975-02-05
BE780718A (fr) 1972-09-15
DE2212550C2 (fr) 1987-02-12
AR204386A1 (es) 1976-02-06
JPS5547374B1 (fr) 1980-11-29
DE2212550A1 (de) 1972-11-02
FR2130240A1 (fr) 1972-11-03

Similar Documents

Publication Publication Date Title
US4421845A (en) Silver halide photographic light-sensitive material
US3958993A (en) Development inhibitor-releasing type compound for photographic use
US4126461A (en) Black-and-white photographic elements and processes
JPH04267249A (ja) 写真ハロゲン化銀乳剤及び金（ｉ）化合物
GB1586412A (en) Process of producing a silver halide photographic emulsion
JPS59218439A (ja) ハロゲン化銀写真感光材料
US3909268A (en) Tetrazolium C-oxy-betaine compounds as antifog agents for silver halide photographic emulsions
JPH0327038A (ja) 写真感光材料
US3925086A (en) Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions
US4404390A (en) Mesoionic 1,2,4-triazolium silver halide stabilizer precursors
US3023103A (en) Antifoggants and stabilizers for photographic silver halide emulsions
US3791830A (en) Silver halide photographic element containing a reaction product of a heterocyclic mercaptan and a chloroformic acid ester as antifog agent
US3655391A (en) Azodicarbonamide fog inhibitors
US3819380A (en) Azodicarbonamidine salts as silver halide fog inhibitors
JPS588503B2 (ja) カラ−シヤシンカンコウザイリヨウ
JPS5828569B2 (ja) ハロゲン化銀写真感光材料
US4065312A (en) Process for the production of photographic vesicular images in photographic silver halide material
JP2765227B2 (ja) ハロゲン化銀用添加剤としてのモノ−およびジフルオロアセチルフェニルヒドラジン化合物
US3910792A (en) Guanazyl and Guanazilium salt compounds as antifog agents for silver halide emulsions
US4260674A (en) Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency
US4493888A (en) Silver halide photographic light-sensitive material
JPS61259249A (ja) 写真画像の硬調現像法
US5221600A (en) Photographic elements containing development accelerator release compounds
US6361919B1 (en) Silver halide photographic light sensitive material and hydrazine compound employed in it
JPS60217358A (ja) ハロゲン化銀写真感光材料の処理方法