EP0326433A2 - Photographische Hochkontrastmaterialien, die Mikrokristalldispersionen von Hydrazinen enthalten - Google Patents

Photographische Hochkontrastmaterialien, die Mikrokristalldispersionen von Hydrazinen enthalten Download PDF

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Publication number
EP0326433A2
EP0326433A2 EP89300866A EP89300866A EP0326433A2 EP 0326433 A2 EP0326433 A2 EP 0326433A2 EP 89300866 A EP89300866 A EP 89300866A EP 89300866 A EP89300866 A EP 89300866A EP 0326433 A2 EP0326433 A2 EP 0326433A2
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EP
European Patent Office
Prior art keywords
silver halide
hydrazine
particle size
microcrystals
photographic silver
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.)
Granted
Application number
EP89300866A
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English (en)
French (fr)
Other versions
EP0326433B1 (de
EP0326433A3 (de
Inventor
Kevin P. Minnesota 3M Research Ltd Hall
George W. Beebe
Edmund C. Newman
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
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Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0326433A2 publication Critical patent/EP0326433A2/de
Publication of EP0326433A3 publication Critical patent/EP0326433A3/de
Application granted granted Critical
Publication of EP0326433B1 publication Critical patent/EP0326433B1/de
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Expired - Lifetime legal-status Critical Current

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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
    • G03C1/061—Hydrazine compounds
    • 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

Definitions

  • This invention relates to negative acting silver halide photographic materials and in particular to high contrast photographic materials containing water-insoluble hydrazines.
  • Hydrazines find a variety of uses in silver halide photography. They have been used in negative working surface latent image forming silver halide emulsions to increase speed and/or contrast. They have been used in direct positive internal latent image forming emulsions as nucleating agents such as those described in US Patent Specification No. 3227552 and reviewed in Research Disclosure No. 235 (1983) item 23510.
  • the most effective hydrazines employed in silver halide photographic systems possess a combination of substituents to balance activity and stability.
  • the stability of hydrazines is increased by attaching directly to one of the nitrogen atoms a tertiary carbon atom, such as the carbon atom of an aromatic ring.
  • the art has long recognised that the activity of these stabilised hydrazines can be advantageously modified by the direct attachment of an acyl group to the remaining nitrogen atom.
  • the most commonly employed hydrazines are 1-­acyl-2-arylhydrazines.
  • Silver halide emulsions and/or developers containing hydrazines are disclosed, for example, in United States patent Specifications Nos. 2419975, 2563785, 3227552, 3386831, 3730727, 4030925, 4031127, 4080207, 4168977, 4224401, 4243739, 4243739, 4245037, 4255511, 4266013, 4272614, 4276364, 4323643, 4478928 and British Patent Specifications Nos. 1560005, 1579956, 2034908A and 2066492B.
  • US Patent Specification No. 2419975 discloses that high contrast negative images are obtained in silver halide photographic emulsions by the addition of hydrazine compounds.
  • a highly alkaline developer is required having a pH of approximately 12.8, this is very susceptible to air oxidation and is too unstable to be stored or used for long periods.
  • Subsequent research has developed alternative hydrazines which allow a lowering of pH to reduce adverse effects incurred by aerial oxidation of the developer.
  • US Patent Specification No. 4168977 discloses the use of a hydrazine with the formula: R1NHNHCHO in which: R1 represents an aryl group, in combination with silver chlorobromide or silver chlorobromoiodide emulsions. This combination is capable of functioning at a lower pH than the hydrazines of US Patent No. 2419975 and a pH of 11.5 is exemplified.
  • US Patent Specification No. 4224401 discloses the use of a hydrazine of the formula: R1NHNHCOR2 in which: R1 is an aryl group; and R2 is a hydrogen atom, C1 to C3 alkyl or phenyl optionally substituted with substituents which are preferably electron withdrawing, in combination with silver bromide or silver iodobromide emulsions.
  • R1 is an aryl group
  • R2 is a hydrogen atom, C1 to C3 alkyl or phenyl optionally substituted with substituents which are preferably electron withdrawing, in combination with silver bromide or silver iodobromide emulsions.
  • This combination is also functional at a pH lower than that disclosed in US Patent No. 2419975 and a pH of 11.5 is exemplified when R2 is hydrogen.
  • US Patent Specification No. 4323643 discloses silver halide photographic emulsions containing a hydrazine of the general formula: in which: R1 and R2 each represents hydrogen, an aliphatic group, an aromatic, or a heterocyclic group; R3 represents hydrogen or an aliphatic group, and X represents a divalent aromatic group.
  • R1 and R2 each represents hydrogen, an aliphatic group, an aromatic, or a heterocyclic group
  • R3 represents hydrogen or an aliphatic group
  • X represents a divalent aromatic group.
  • US Patent Specification No. 4560638 discloses the use of a related class of arylhydrazines in which the aryl group is substituted by a group of the formula: R - X - - X1 - in which: one of X and X1 represents N-H, the other represents a divalent chalcogen and R represents an aliphatic or aromatic residue. The use of these compounds is said to give improved dot quality and low levels of pepper fog.
  • European Patent Publication No. 217310 discloses contrast promoting agents of the formula: in which: X represent NR5R6, or OR7; R1 and R2 independently represent hydrogen, substituted or unsubstituted alkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, alkylaminoalkyl or arylalkyl having up to 18 carbons; cycloalkyl; phenyl or naphthyl; alkylphenyl, cyanophenyl, halophenyl or alkoxyphenyl substituents; R3 represents hydrogen, benzyl, alkoxybenzyl, halobenzyl or alkylbenzyl, provided that if neither R1 nor R2 is hydrogen, then R3 is hydrogen; R4 represents a divalent aromatic group which may be substituted or unsubstituted; R5, R6 and R7 independently represent hydrogen, alkyl, hydroxylalkyl, haloalkyl, alkoxyalkyl
  • R1 and R3 or R1 and R2 can be linked to form a heterocyclic ring system containing 3 to 10 atoms.
  • R5 and R6 can be linked to form a heterocyclic ring system containing 3 to 10 atoms.
  • hydrazides are of the general formula: R3 - NR4 - NR5 - G - X in which; R3 represents an aryl group, one of R4 and R5 is a hydrogen and the other is selected from hydrogen, aryl sulphonyl and trifluoroacetyl, G represents carbonyl, sulphonyl, sulphoxy, phosphoryl or an N-substituted or unsubstituted imino group and X is a moiety such that at a pH in the range of 9.5 to 12.5 in the presence of an oxidised hydroquinone a cyclisation reaction takes place cleaving the moiety -G-X from the remainder of the molecule and forming a cyclic structure comprising atoms of the moiety -G-X.
  • the hydrazines referred to above have limited solubility in water.
  • the hydrazines have been treated by techniques used for the addition of other additives to photographic emulsion.
  • the hydrazine is typically dissolved in a solvent selected from organic solvents compatible with water, eg. alcohols, glycols, ketones, esters, amides and the like which exert no adverse influences on the photographic characteristics, and the solution is added to the photographic elements.
  • the hydrazines have also been added to photographic emulsion in oil dispersions by methods used when water-­insoluble (so-called oil soluble) couplers are added to emulsions.
  • oil soluble water-­insoluble
  • 2419974 discloses a method of dissolving the water insoluble hydrazines in water immiscible organic solvents and dispersing this solution into water which may contain dispersing or wetting agents and gelatin, this dispersion then being added to a suitable gelatin silver halide emulsion.
  • US Patent Specification No. 4474872 discloses a process of adding a dispersion of a substantially water-­insoluble photographic additive to a photographic emulsion.
  • the dispersion is prepared by mechanically grinding and dispersing the photographic additive in a form of fine grain having a size of 1 micron or less in an aqueous system adjusted to a pH value of 6 to 8 and controlled to a temperature of 60 to 80°C.
  • the additive is included in the photographic emulsion without the need of an organic solvent.
  • the photographic additives disclosed include spectral sensitising dyes, antifoggants, colour couplers, dyes, sensitizers, hardeners, ultraviolet absorbing agents, antistatic agents, brightening agents, desensitizers, developers, discolourisation inhibitors and mordants. There is no disclosure of the use of this method for the addition of hydrazines.
  • water-insoluble hydrazine compounds may be advantageously incorporated into photographic silver halide emulsions in the form of an aqueous dispersion of microcrystals.
  • a negative acting photographic silver halide material capable of producing a high contrast image comprising a photographic silver halide emulsion in association with a water-insoluble hydrazine in which the water-insoluble hydrazine is present as microcrystals having a mean particle size of not more than 10 microns distributed through the photographic silver halide emulsion, or in a layer adjacent thereto.
  • the hydrazines employed in the invention are water-­insoluble i.e. they possess a solubility of less than 0.1% in water at 20°C.
  • the hydrazines may be selected from any of the water insoluble hydrazines known in the art and many examples will be found in the literature cited hereinbefore.
  • hydrazines will be of the general formula: in which: R10 represents an aliphatic, aromatic or heterocyclic group and R11, R12 and R13 independently represent hydrogen or an aliphatic, aromatic or heterocyclic group.
  • Preferred hydrazines are of the general formula: R14 - NR15 - NR16 - G - X in which; R14 represents an aryl group, one of R15 and R16 is a hydrogen and the other is selected from hydrogen, aryl sulphonyl and trifluoroacetyl, G represents carbonyl, sulphonyl, sulphoxy, phosphoryl or an N-substituted or unsubstituted imino group and
  • X is hydrogen, alkyl, aryl or a moiety such that at a pH in the range of 9.5 to 12.5 in the presence of an oxidised hydroquinone a cyclisation reaction takes place cleaving the moiety -G-X from the remainder of the molecule and forming a cyclic structure comprising atoms of the moiety -G-X.
  • Particularly preferred hydrazines are those in which -G-X represents:
  • the dispersions of hydrazines may be prepared by mechanical attrition of solid hydrazine in an aqueous medium by means of a colloid mill or similar device or preferably by mixing a solution of the hydrazine in a water miscible solvent with an aqueous medium under conditions of rapid agitation such that rapid precipitation of the hydrazine as a finely divided solid dispersion occurs.
  • Suitable water miscible solvents are, for example, acetone, tetrahydrofuran (THF), dimethylformamide, dimethylsulphoxide or N-methyl-2-­pyrrolidone.
  • the aqueous medium in which the hydrazine is dispersed preferably contains a water soluble polymer such as gelatin and/or a surfactant in order to assist and stabilise uniform dispersion of the solid hydrazine.
  • the dispersion technique allows a relatively narrow distribution of hydrazine crystallite sizes to be reproducibly made generally within the range of mean particle size of 0.01 to 10 microns, typically 0.05 to 1.0 microns, for subsequent addition to the gelatin silver halide emulsion.
  • mean particle size 0.01 to 10 microns, typically 0.05 to 1.0 microns, for subsequent addition to the gelatin silver halide emulsion.
  • at least 95% of the particles have a particle size of less than 10 microns, preferably less than 5 microns, most preferably less than 1 micron. Any large particles formed (greater than 10 microns) may be removed by filtration.
  • a sedimentation field flow fractionation technique may be used.
  • the results from this equipment assume that the particles are spherical, although in reality some may be needle-shaped. From the graph of number of particles against particle diameter the mean particle size and dispersity of distribution can be assessed. Because of approximations which may have to be made relative to the refractive index of the particles (and density if a weight distribution is plotted) the results may vary by ⁇ 50% relative to the true value.
  • microscopy may be used to assess the particle distribution.
  • the details of the 0.25 micron silver bromochloride emulsion coating formulation used are: (per mole of silver halide) Dye 40ml of 1% green sensitising dye anhydro-5,5′-dichloro-9,ethyl-3,3′-­bis(3-sulphopropyl)oxacarbocyanine.
  • the above mixture was then coated together with a hydrazine formulation onto a polyester base having suitable antihalation backing.
  • a triazine hardened gelatin top coat was also employed.
  • the resulting coatings were then processsed in the standard fashion as follows. The elements were exposed using an exposing device having a tungsten filament source with the light attenuated by a neutral density graduated filter in order to assess speed and contrast. Similar exposures were made through a Kodak "Ultratec" half-tone screen to assess dot quality.
  • the coatings were evaluated for quality of coating, speed, contrast and half tone dot quality.
  • the dispersions A2 and B2 were obtained by running the Sylverson Homogeniser at full speed and allowing the hydrazine solution to slowly run into the gelatin/­surfactant solution, typically at 20ml/minute.
  • the hydrazine solution entered the aqueous solution by means of tube arranged such that its orifice lay near the homogeniser head.
  • the homogeniser was allowed to run for a further minute. After this the dispersion was allowed to stand to reduce the amount of foam present. Filtration then gave a ready to use dispersion.
  • Table 1 also includes a subjective comparison of the half tone dots produced by exposing the film through an Eastman Kodak grey "Ultratec" screen and a continuous tone wedge, the film then being processed in the standard manner.
  • the dispersion into a gelatin solution containing surfactant can be achieved from a variety of organic solvents such as dimethylformamide and dimethylsulphoxide as well as tetrahydrofuran and methanol in the case of hydrazine B; however, dimethylformamide is preferred from a practical point of view. In this way an essentially monodisperse crystallite dispersion of mean particle size around 0.1-0.2 microns was produced in the case of hydrazine B. In order to remove any particularly large particles of hydrazine the dispersion can be filtered.
  • the crystallites of hydrazine A resulted from A2 were found to have a mean particle size of approximately 5 microns (determined by measuring particle diameters by microscopy).

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19890300866 1988-01-29 1989-01-30 Photographische Hochkontrastmaterialien, die Mikrokristalldispersionen von Hydrazinen enthalten Expired - Lifetime EP0326433B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8802024 1988-01-29
GB888802024A GB8802024D0 (en) 1988-01-29 1988-01-29 High contrast photographic materials containing microcrystal dispersions of hydrazines

Publications (3)

Publication Number Publication Date
EP0326433A2 true EP0326433A2 (de) 1989-08-02
EP0326433A3 EP0326433A3 (de) 1991-01-16
EP0326433B1 EP0326433B1 (de) 1996-04-03

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EP19890300866 Expired - Lifetime EP0326433B1 (de) 1988-01-29 1989-01-30 Photographische Hochkontrastmaterialien, die Mikrokristalldispersionen von Hydrazinen enthalten

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EP (1) EP0326433B1 (de)
JP (1) JPH023033A (de)
DE (1) DE68926127T2 (de)
GB (1) GB8802024D0 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0663611A1 (de) * 1993-12-17 1995-07-19 Konica Corporation Lichtempfindliches, photographisches Silberhalogenidmaterial

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2803196A1 (de) * 1977-02-01 1978-08-03 Konishiroku Photo Ind Lichtempfindliches photographisches silberhalogenid-aufzeichnungsmaterial
DE3246826A1 (de) * 1981-12-17 1983-06-30 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur herstellung einer photographischen emulsion
EP0253665B1 (de) * 1986-07-16 1992-01-02 Minnesota Mining And Manufacturing Company Lichtempfindliche photographische Silberhalogenidsysteme

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5722089A (en) * 1980-07-10 1982-02-04 Serabisu Sa Pageant indicator for typewriter
JPS589410A (ja) * 1981-07-09 1983-01-19 Toshiba Corp 演算増幅器
JPS5830568A (ja) * 1981-08-19 1983-02-23 Oval Eng Co Ltd 定流量弁
JPS5952817A (ja) * 1982-09-20 1984-03-27 Hitachi Ltd 変圧器
CA1232068A (en) * 1984-06-08 1988-01-26 National Research Council Of Canada Form depicting, optical interference authenticating device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2803196A1 (de) * 1977-02-01 1978-08-03 Konishiroku Photo Ind Lichtempfindliches photographisches silberhalogenid-aufzeichnungsmaterial
DE3246826A1 (de) * 1981-12-17 1983-06-30 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur herstellung einer photographischen emulsion
EP0253665B1 (de) * 1986-07-16 1992-01-02 Minnesota Mining And Manufacturing Company Lichtempfindliche photographische Silberhalogenidsysteme

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0663611A1 (de) * 1993-12-17 1995-07-19 Konica Corporation Lichtempfindliches, photographisches Silberhalogenidmaterial
US5478696A (en) * 1993-12-17 1995-12-26 Konica Corporation Silver halide photographic light-sensitive material

Also Published As

Publication number Publication date
EP0326433B1 (de) 1996-04-03
JPH023033A (ja) 1990-01-08
DE68926127T2 (de) 1996-08-29
GB8802024D0 (en) 1988-02-24
EP0326433A3 (de) 1991-01-16
DE68926127D1 (de) 1996-05-09

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