US3910792A - Guanazyl and Guanazilium salt compounds as antifog agents for silver halide emulsions - Google Patents

Guanazyl and Guanazilium salt compounds as antifog agents for silver halide emulsions Download PDF

Info

Publication number
US3910792A
US3910792A US465186A US46518674A US3910792A US 3910792 A US3910792 A US 3910792A US 465186 A US465186 A US 465186A US 46518674 A US46518674 A US 46518674A US 3910792 A US3910792 A US 3910792A
Authority
US
United States
Prior art keywords
emulsion
guanazyl
phenyl
guanazylium
compound
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
US465186A
Other languages
English (en)
Inventor
Agostino Baldassarri
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
Application granted granted Critical
Publication of US3910792A publication Critical patent/US3910792A/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

Definitions

  • This invention relates to guanazyl and guanazylium salt compounds as antifog agents for silver halide photographic emulsions.
  • guanazyl and guanazylium salt compounds are very effective agents both used in a photographic element reactively associated with the silver emulsion and in a processing bath adapted for use prior to or during development of emulsion layers. They can also be used in combination with high temperature processing baths containing or not aldehydes as hardening agents. Guanazylium salt compounds have proven to be more efi'ective than guanazyl compounds when directly introduced into a bath to be used prior to or during development of silver halide emulsions.
  • the invention relates in one aspect to a silver halide emulsion having contacted therewith a guanazyl and/or a guanazylium salt compound.
  • the invention relates to a silver photographic element having a silver emulsion layer and a guanazyl and/or a guanazylium salt compound in reactive association therewith (tag. in a layer adjacent the emulsion layer).
  • the invention in a further aspect relates to a method for inhibiting fog in a silver halide photographic emulsion which comprises contacting said emulsion with a guanazyl and/or guanazylium salt compound.
  • the invention further relates to an improved method for processing an exposed silver halide element, which includes treating said element with a series of photographic treatment solutions including a development solution, the improvement comprising contacting said element during said processing with a guanazyl and/or guanazylium salt compound, preferably a guanazylium salt compound, said compound being contained in said development solution and/or in a predevelopment treatment solution.
  • a processing solution The compounds useful according to the present in vention are preferably those represented by the foilowing formulas:
  • R is an aryl group
  • R is an aryl group or a heterocyclic group
  • R is an alkyl group or hydrogen
  • X is an anion such as, for example. halogen (e.g.
  • An aryl group as used in the practice of this invention is a preferably phenyl or naphthyl group with substituents, if any, selected from at least one of halogen, alkyl, alkoxy, perflouroalkyl, haloalkyl, nitro and acyl groups.
  • substituents each have no more than six carbon atoms when attached to the phenyl group and no more than two carbon atoms when attached to the naphthyl group.
  • the total number of carbon atoms in R and R is preferably no more than 12, and for R preferably no more than four carbon atoms.
  • the molecular weight of R and R is preferably no more than 300 and more preferably no more than 200. For R the preferred molecular weight is no more than 60.
  • the heterocyclic group used in the practice of this invention as group R preferably has a total molecular weight of no more than 300 and more preferably at most 200.
  • the most preferred group is pyridine.
  • Substituents in the heterocyclic group are preferably limited to those same substituent groups preferred for the aryl group of R and R, as phenyl.
  • Preferred heterocyclic groups are five and six membered rings, the skeletal structure of such rings consisting of carbon, nitrogen, oxygen, sulfur, and selenium with groups consisting of carbon and nitrogen, with at most one oxygen or sulfur atom most preferred.
  • guanazyls of the present invention were prepared by known processings (Chem. Review 55, 40] (1955), which are based on the reaction of an aryldiazonium salt with a guanylhydrazone, according to the scheme:
  • guanazylium salts thereof were prepared by reacting the guanazyl compounds with a salifying agent (e.g. pycric acid and methylchloride or iodide as known to the skilled in the art).
  • a salifying agent e.g. pycric acid and methylchloride or iodide as known to the skilled in the art.
  • EXAMPLE 2 l-(m-trifluoromethyl-phenyl)-3-phenyl guanazyl 32.2 g (0.2 moles) of m-trifluoromethylaniline in 60 ml of HCl and 260 ml of water are diazotated with 13.8 g of sodium nitrite (0.2 moles) at 02C. A solution of 45 g (0.2 moles) of guanazyl-hydrazone dissolved in l of methanol was prepared apart. The aryldiazonium chloride solution was then dropped into the guanylhydrazone solution at 0C.
  • EXAMPLE 3 1-( pchlorophenyl 3-phenyl-guanazyl 25.5 g (0.2 moles) of p-chloro-aniline in 60 ml of HCl and 60 ml of H 0 were diazotated at 05C with 13.8 g (0.2 moles) of sodium nitrite. A solution consisting of 45 g 0.2 moles) of guanylhydrazone benzaldehyde nitrate in 1 l of methanol was prepared apart. This solution was then cooled at 0C and the aryldiazonium solution, prepared before, dropped therein maintaining the temperature at 0C. 45 g of sodium acetate in 200 ml of water were then added thereto. The pH-value was adjusted from 6 to 8.5 with 30% NaOH. The solid was separated by suction, then washed with water, dried and crystallized from acetic ester.
  • EXAMPLE 4 l-phenyl-3(p-tolyl )-guanazyl 18.6 g (02 moles) of aniline with 60 ml of HCl and 60 ml of H 0 were diazotated with 13.8 g (0.2 moles) of sodium nitrite and the diazo-solution was dropped at 0C into a solution of 47.8 g of p-tolylaldehyde-guanylhydrazone nitrate (0.2 moles) in 2,000 ml of methanol. 45 g of sodium acetate in 200 ml of water were added to the reaction product and the pH-value of the solution, thus obtained, adjusted to 88.5 with 30% sodium hydrate. A powdery product separated. It was then washed, dried and finally purified by crystallization from ethanol.
  • EXAMPLE 5 l -(p-toly1)-3-phenyl-guanazyl 42.8 g (0.4 moles) of p-toluidine were diazotated and the diazo-solution dropped at 0C into a solution of 90 g (0.4 moles) of benzaldehyde guanyl-hydrazone nitrate in 2 l of methanol. A solution of 90 g of sodium acetate and then 30% NaOH, to adjust the pH to 8.5, were then added to the reaction product, thus obtained. A dark-red powdery product separated. It was then washed, dried and purified by crystallization from ethyl acetate.
  • EXAMPLE 6 1-phenyl-3( o-chloro-phenyl )-guanazyl 18.6 g (0.2 moles) of aniline were diazotated and the diazo-solution, at 0C, was added to 51.8 g (0.2 moles) of o-chlorobenzaldehyde guanylhydrazone nitrate in l l of methanol plus 45 g of sodium acetate in 200 ml of water and 30% NaOH to adjust the pH to 1 1. When the diazo-addition approached to the end, an orange-red powdery product started to separate. The raw solid was purified by crystallization from nitromethane.
  • EXAMPLE 7 l-phenyl-3-( pnitro-phenyl )-guanazyl 4.5 g of the p-nitro-benzaldehyde-guanylhydrazone base were dissolved in 400 ml of ethanol. The solution was cooled at -5C and a solution of diazonium chloride, obtained by diazotating 2.02 g (0.022 moles) of aniline, dropped therein. The solution, thus obtained, was poured into 4 l of water and its pH-value adjusted to 12 with 30% NaOH. A solid separated. It was then purified by crystallization from nitromethane.
  • EXAMPLE 8 1-( m'nitro-phenyl -3-phenyl-guanazyl 12 g (0.074 moles) of guanylhydrazone benzaldehyde, as a free base, were dissolved in 200 ml of ethanol and ml of water, cooled at l0C and added with a solution prepared by diazotating 10.5 g (0.076 moles) of m-nitro-aniline in 26.2 ml of HCl. The pH- value was adjusted to 8 with NaOH and an orange colored solid separated rapidly. This solid was then collected, dried and purified by crystallization from ethanol.
  • EXAMPLE 9 1-3diphenyl-guanazylium-chloride 16.2 g (0.1 moles) of guanylhydrazone benzaldehyde were dissolved in 200 ml of ethanol and I00 m1 of water and processed at 10C with a solution obtained by diazotating 9.3 g (0.1 moles) of aniline in 30 ml of HCl. The pH-value of the reaction product was maintained at 5 and the solution concentrated to approximately one half. A brick-red solid separated. It was then purified by crystallization from chloroform.
  • EXAMPLE 12 EXAMPLE l3 l-phenyl-3-(o chlorophenyl)-guanazylium-picrate 3 g (0.0l moles) of l-phenyl-3-(o-chlorophenyl)- guanazyl (example 6) were processed as described in example l2. The product was crystallized from ethanol.
  • EXAMPLE l5 13-diphenyl-guanazylium-picrate 2.66 g (0.01 moles) of l',3-diphenylguanazyl (example l were processed as described in example 12. The product was crystallized from ethanol.
  • EXAMPLE 16 l-( p-chloro-phenyl )-3-phenyl-N-methyl-guanazylium-iodide 3 g (0.0l moles) of l-(p-chloro-phenyl)-3-phenylguanazyl (example 3) in 50 ml of methanol were heated for 7 hours with 10 ml of methyl-iodide. The product was crystallized from ethanol.
  • EXAMPLE l7 l-phenyl-3-(y-pyridine) guanazylium chloride 8.15 g (0.05 moles) of y-pyridinaldehydeguanylhydrazone were dissolved in 20 ml of pyridine and 200 ml of ethanol and further added at 5C with a solution obtained by diazotating 4.65 g (0.05 moles) of aniline in l5 ml of HCl. An orange-red solution having a pH value equal to 6-7 was obtained and an orange-colored crystalline product separated by standing. The product was crystallized from ethanol.
  • EXAMPLE 18 A highly sensitive silver bromo-iodide emulsion, containing 98.2% bromide moles and l.8% iodide moles, was physically ripened, washed, chemically sensitized and further divided into more parts. A part was kept like it was and the others added with compounds Nos. 1-8 of the present invention in the quantities specified in table 3. The said parts were separately coated on a cellulose triacetate base and covered with a gelatin protective layer. Samples of the material, thus obtained, were exposed fresh or incubated to the light of a tungsten lamp and developed for 3' at 20C with a developer having the following composition:
  • the temperature of the developing bath was 35C and the development time 23 seconds. After development, the material was fixed in a bath including glutaraldehyde having the following composition:
  • a highly sensitive emulsion having the same characteristics as that used in example 18, was divided into more parts.
  • EXAMPLE 22 A photographic developer, having the same composition as that described in example 19, was divided into more parts. A part was used without any further addition. the others were added with the quantities specified in table of the new antifoggants of the present invention. Samples of the 3M Medical X-Ray Type R film of the applicant were exposed to the blue light of a tungsten lamp and then developed for 24 seconds at 35C in the prepared developing baths. After development. the material was then fixed in a bath having the same composition as that used in example I) and washed for a total processing time of 90 seconds. The samples. thus obtained, were then read at a'densitometer. The results thereof are shown in table 5.
  • the compounds can be introduced into the bath by using a solvent. as in the case of introduction into the emulsion. or not.
  • the silver halide photographic emulsions of the present 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, polyvinyl alcohol, polyvinyl pyrrolidone, partially hydrolized polyvinyl acetate. polyethylacrylate, polymethylmethacrylate. polyamides, etc.
  • the emulsions of the invention may be chemically sensitized with naturally active gelatine. by addition of chemical sensitizers such as thiourea. allylthiourea. thyocyanates, thiosulphates. 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. antioxidizing agents, developing accelerators. etc.
  • a photographic element comprises one support such as polyester. cellulose acetate, and the like and at least one layer including a silver halide emulsion layer of the above described type coated thereon. Such element can additionally contain other layers, that is, protective layers. interlayers, antihalo layers. filter layers, etc.
  • the guanazyl and guanazylium salt compounds of the invention may be conveniently introduced in the form of solutions into emulsions or any other coating composition during preparation thereof. Although it is generally preferred to incorporate the guanazyl and guanazylium salt compounds of the invention directly into emulsion layers. these compounds may also be incorporated into layers adjacent the emulsion layers so that the silver halide emulsions are again in reactive association therewith.
  • the guanazyl and guanazylium salt compounds are preferably introduced into photographic elements reactively associated with the silver halide emulsions in amounts ranging from about 0.05 to 2 mM/M of silver halide and most preferably from 0.1 to 0.5 mM/M of silver halide.
  • 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 silver halide photographic element with a developing solution.
  • Predevelopment baths are usually (but not I necessarily) acidic and may contain hardeners such as aldehydes and the like.
  • the guanazyl and guanazylium salt 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. hydroquinone phenidone. and various p-phenylene diamine materials. the latter being useful in color development processes.
  • the processing baths of the invention preferably include from about 0.05 to l mM liter of solution.
  • the guanazylium salt compounds are most preferably included in quantities ranging about from 0.l to 1 mM liter of solution.
  • a silver halide photographic emulsion having in reactive contact therewith at least a fog-inhibiting amount of a guanazyl and/or guanazylium salt compound.
  • a silver halide photographic emulsion having in reactive contact therewith at least a fog-inhibiting amount of a guanazyl and/or guanazylium salt compound respectively corresponding to the formulas:
  • R is an aryl group or a heterocyclic group
  • R is an alkyl group or hydrogen
  • X is an anion
  • a silver halide photographic element having a silver halide emulsion layer and a fog-inhibiting amount of a guanazyl and/or guanazylium salt compound in reactive association therewith.
  • a silver halide photographic element having a silver halide emulsion layer and a fog-inhibiting amount of a guanazyl and/or guanazylium salt compound of formulas respectively corresponding to those of claim 2 in reactive association therewith.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
US465186A 1973-05-10 1974-04-29 Guanazyl and Guanazilium salt compounds as antifog agents for silver halide emulsions Expired - Lifetime US3910792A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT49895/73A IT985017B (it) 1973-05-10 1973-05-10 Guanazili e sali di guanazilio come agenti antivelo per emul sioni agli alogenuri d argento

Publications (1)

Publication Number Publication Date
US3910792A true US3910792A (en) 1975-10-07

Family

ID=11271803

Family Applications (1)

Application Number Title Priority Date Filing Date
US465186A Expired - Lifetime US3910792A (en) 1973-05-10 1974-04-29 Guanazyl and Guanazilium salt compounds as antifog agents for silver halide emulsions

Country Status (9)

Country Link
US (1) US3910792A (enExample)
JP (1) JPS5032931A (enExample)
AR (1) AR215832A1 (enExample)
BE (1) BE814853A (enExample)
CA (1) CA1032005A (enExample)
DE (1) DE2422070A1 (enExample)
FR (1) FR2229081B1 (enExample)
GB (1) GB1447738A (enExample)
IT (1) IT985017B (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347310A (en) * 1977-10-14 1982-08-31 Asahi Kasei Kogyo Kabushiki Kaisha Heat developable silver image forming materials

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3071465A (en) * 1961-03-14 1963-01-01 Gen Aniline & Film Corp Fog reduction in silver halide emulsions by 2h-tetrazolium halides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3071465A (en) * 1961-03-14 1963-01-01 Gen Aniline & Film Corp Fog reduction in silver halide emulsions by 2h-tetrazolium halides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347310A (en) * 1977-10-14 1982-08-31 Asahi Kasei Kogyo Kabushiki Kaisha Heat developable silver image forming materials

Also Published As

Publication number Publication date
DE2422070A1 (de) 1974-11-28
BE814853A (fr) 1974-11-12
FR2229081B1 (enExample) 1978-12-08
IT985017B (it) 1974-11-30
AR215832A1 (es) 1979-11-15
GB1447738A (en) 1976-08-25
JPS5032931A (enExample) 1975-03-29
FR2229081A1 (enExample) 1974-12-06
CA1032005A (en) 1978-05-30

Similar Documents

Publication Publication Date Title
JP3323525B2 (ja) 写真ハロゲン化銀乳剤及び金（ｉ）化合物
US4378424A (en) Mesoionic 1,2,4-triazolium-3-thiolates as silver halide stabilizers and fixing agents
JPS59212829A (ja) アリ−ルヒドラジド
US4420554A (en) Silver halide photosensitive materials
US4416977A (en) Silver halide photographic photosensitive material
US3909268A (en) Tetrazolium C-oxy-betaine compounds as antifog agents for silver halide photographic emulsions
US4404390A (en) Mesoionic 1,2,4-triazolium silver halide stabilizer precursors
EP0809137B1 (en) Tellurium complexes as chemical sensitizers for silver halides
US4351896A (en) Mesoionic silver halide stabilizer precursor and use in a heat developable and heat stabilizable photographic silver halide material and process
US3615617A (en) Stabilized photographic material with tetrazole thiocarbonic acid ester
US3982947A (en) Fog-inhibitors for silver halide photography silver halide photographic material containing an iodo benzene compound as antifoggant
JPS5943728B2 (ja) ハロゲン化銀写真材料
US4634660A (en) Development-processing method for silver halide photographic light-sensitive material
US3925086A (en) Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions
US3655391A (en) Azodicarbonamide fog inhibitors
US3910792A (en) Guanazyl and Guanazilium salt compounds as antifog agents for silver halide emulsions
EP0054415B1 (en) Photographic material containing a mesoionic 1,2,4-triazolium-3-thiolate silver halide stabilizing and fixing agent
US4281059A (en) Photographic material
US3951661A (en) Silver halide emulsion containing an arylphosphonium salt as antifoggant
JP2831063B2 (ja) 増強したセンシトメトリー特性を有する写真要素
JPS5943729B2 (ja) ハロゲン化銀写真感光材料
US5667957A (en) Xanthate salts as chemical sensitizers for silver halides
EP0061446B1 (en) Chemically sensitized silver halide photographic emulsions and color photographic elements containing said emulsions
JPS6025774B2 (ja) ハロゲン化銀写真材料の製造方法
JPH02280140A (ja) ハロゲン化銀写真感光材料