EP0088581B1 - White light handleable photographic materials - Google Patents

White light handleable photographic materials Download PDF

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Publication number
EP0088581B1
EP0088581B1 EP83301090A EP83301090A EP0088581B1 EP 0088581 B1 EP0088581 B1 EP 0088581B1 EP 83301090 A EP83301090 A EP 83301090A EP 83301090 A EP83301090 A EP 83301090A EP 0088581 B1 EP0088581 B1 EP 0088581B1
Authority
EP
European Patent Office
Prior art keywords
photographic element
compound
carbon atoms
carbon
atoms
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
Application number
EP83301090A
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German (de)
English (en)
French (fr)
Other versions
EP0088581A1 (en
Inventor
Jonathan P. Minnesota Mining And Man. Co. Kitchin
Robert F. Minnesota Mining And Man. Co. Coles
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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Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0088581A1 publication Critical patent/EP0088581A1/en
Application granted granted Critical
Publication of EP0088581B1 publication Critical patent/EP0088581B1/en
Expired 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
    • G03C1/36—Desensitisers
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes

Definitions

  • This invention relates to silver halide photographic materials which may be handled under normal lighting conditions without fogging and which are capable of recording images of high intensity light or other actinic radiation.
  • photographic recording materials require specially filtered and subdued light in order to be handled safely without fogging. This applies particularly to silver halide photographic recording materials which are, in general, more light sensitive than non-silver materials.
  • Silver halide recording materials which have not been spectrally sensitized by the addition of sensitizing dye are normally only highly sensitive to ultraviolet and blue light. Such materials may be safely handled in subdued yellow or red light. It is very desirable to produce a silver halide photographic recording film which may be safely handled in bright white light. The benefits of this include ease of working and inspection of the material during exposure and processing, and generally more pleasant working conditions for the operators.
  • white light used herein is defined as the emission of a typical commercially available “white” or “warm white” fluorescent tube which has relatively little emission shorter than 400 nm wavelength, or longer than 700 nm. Various techniques have been employed in order to achieve some degree of white light handleability.
  • Silver halide materials which are intended for exposure to wavelengths outside the above range; e.g., direct X-ray recording materials or ultraviolet recording materials, may be afforded some degree of "white light handleability" by overcoating the radiation sensitive layer with a layer containing a filter dye.
  • the dye will absorb visible light, particularly blue light, and prevent exposure of the radiation sensitive layer by this light.
  • the filter dye is chosen such that it does not greatly interfere with intentional exposure of the material to U.V. or X-rays. Examples of constructions incorporating such filter layers are disclosed in United States Patent Nos. 4,140,531 and 4,232,116 which employ blue absorbing dyes which are bleached during processing.
  • An alternative method for achieving handleability in white light is to add a substance to the radiation sensitive layer which causes desensitization to radiation of all wavelengths. Materials desensitized in this way must then be exposed to a very powerful light source, much brighter than the room light in which they can be handled. Silver halide materials desensitized by the addition of rhodium salts are disclosed, for example, in Japanese Patent Specification No. J5 6125-734. The white light handleability of materials desensitized in this way is not very great unless impractically high levels of desensitization are effected.
  • Materials for direct X-ray recording may be rendered handleable by the addition, to the silver halide layer, of compounds which desensitize the silver halide to visible (white) light, but not to X-rays.
  • United States Patent Nos. 3,671,254; 3,237,008 and 3,658,547 disclose examples of such components.
  • L.I.R.F. low intensity reciprocity failure
  • L.I.R.F. inducers Compounds which promote this effect will hereafter be referred to as "L.I.R.F. inducers".
  • the application of L.I.R.F. inducers to white light handleable photographic film has been described in Professional Printer, 1981, Vol. 25(2), page 9.
  • classes or organic compounds which act as desensitizers towards silver halide emulsions see, for example, P. Glafkides, Photographic Chemistry, Chapter XLII, Fountain Press, 1960.
  • Classes of organic compounds which are known to form derivatives which may act as desensitizers include: phenazines, tetrazines, quinoxalines, aromatic nitro compounds, azo dyes, anthraquinones, diphenyl methanes, triphenylmethanes, cyanines, nitrated cyanines, styryl derivatives, styryl vinyl derivatives, benzopyrilium derivatives, furyl vinyl quinolines, methine-anthraquinone derivatives, anils, aza cyanines, triazoles, dipyridine derivatives and phenazine N-oxides.
  • United States Patent Specification No. 4030932 discloses spectral sensitizers for silver halide emulsions which are compounds containing an isoindole nucleus having a substituent in the 2-position which is an alkyl or substituted alkyl group.
  • the patent also discloses that the compounds: and are desensitizers for negative silver halide emulsions. There is no indication that these two compounds are L.I.R.F. inducers.
  • a photographic element which exhibits safe handling characteristics under white light (as defined herein) and is capable of recording images of higher intensity visible light or other actinic radiations, the element comprising one or more layers of silver halide emulsion at least one or of said layers containing an effective amount in the range 0.01 to 10 g per mol of silver of a compound of the formula: in which:
  • the compounds of formula (I) act as L.I.R.F. inducers and do not cause latent image fading in silver halide emulsions and are therefore useful in the production of photographic elements which may be handled without fogging under white light; e.g. normal lighting conditions.
  • the compounds may be incorporated into the emulsion before or after imagewise exposure.
  • Certain compounds within the scope of formula (I) are known and have been used as dyestuffs and colorants; see, for example, United States Patent Nos. 3,646,033; 3,994,921 and 4,217,309 and British Patent No. 1,219,041.
  • compounds of formula (I) possess suitable properties for use in white light handleable films. These properties include the ability to desensitize silver halide to normal lighting conditions while allowing the silver halide to remain sensitive to intense visible or ultraviolet exposing devices or X-ray exposing devices.
  • L.I.R.F. inducers for use in our invention must be capable of accepting an electron which has been excited to the conduction band of the silver halide crystal.
  • L.I.R.F. inducers of this invention are those having a cathodic half wave potential less negative than -1.0 volts measured versus a normal calomel electrode.
  • the nucleus: in formula (I) does not appear to have a significant effect on the desensitizing properties.
  • the ring R is preferably an optionally substituted aromatic ring.
  • other ring systems are suitable as defined above, an example of which includes dithiacyclohexenylene.
  • the substituent(s) R 1 may be selected from a wide range of groups including halogen; e.g., chlorine, hydroxy, alkyl or alkenyl, containing 1 to 8 carbon atoms, cycloalkyl; e.g., cyclohexyl, alkoxy containing 1 to 8 carbon atoms, aryl containing up to 8 carbon atoms; e.g., phenyl, substituted phenyl, acylamine, etc.
  • the above aliphatic substituents may themselves be substituted with, for example, phenyl, hydroxyl or halogen, carboxyl, esterified carboxyl, carbamoyl, sulpho or esterified sulpho group.
  • the nucleus of formula (2) has the formula: in which each of R 3 to R 6 are independently selected from hydrogen, halogen, alkyl or alkoxy containing up to 8 carbon atoms, aryl containing up to 8 carbon atoms and acylamine, any two adjacent R 3 to R 6 groups optionally forming the necessary atoms selected from carbon, nitrogen, oxygen and sulphur to complete one or more fused rings having up to 12 carbon atoms in the skeletal ring structure.
  • substituents X and Y which have a significant effect upon the desensitizing properties of the compound of formula (I) may be selected from a wide range of groups within the above definitions.
  • suitable substituents for X and Y include those of the following formulae (4) to (8): in which:
  • Q represents oxime, hydrazone or aryl hydrazone in which the aryl group contains up to 8 carbon atoms.
  • An example of a group of formula (8) is para-nitrophenylhydrazone.
  • At least one of X and Y represents a divalent group linked via a carbon atom or nitrogen atom, which atom is separated by one carbon atom from a quaternized nitrogen atom.
  • 3-imino isoindolines may exist in equilibrium with the tautomeric 3-aminoisoindolenine.
  • many of the compounds of formula (I) may be capable of existing in protonated or un- protonated forms depending on the pH of the environment.
  • the compounds of formula (I) may be added at any stage during the preparation of the silver halide emulsion. Additionally, it is possible to apply the compounds to the photographic element in the form of a solution, which solution may be applied subsequent to exposure but prior to development in order that development may be carried out in lighting sufficiently bright to permit inspection of the photographic element. Preferably, the compound is incorporated during the emulsion preparation.
  • the compounds of the formula (I) preferably have a solubility which is greater than 10- 4 molar in one or more water miscible solvent at 40°C.
  • Typical solvents include one or any combination of methanol, ethanol, water, acetone, pyridine, 2-methoxyethanol, dimethylformamide, dimethyl sulfoxide, 0.1 N aqueous sodium hydroxide and 0.1 N aqueous nitric acid.
  • the amount of compound employed varies with the degree of desensitization required and the L.I.R.F. inducing properties of the particular compound employed. Generally concentrations within the range 0.01 to 10 g per mole of silver are used and usually within the range 0.1 to 5 g per mole of silver.
  • Suitable silver halide emulsions for use in the invention include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochlorobromide and silver iodochloride emulsions.
  • the emulsions preferably employ gelatin as a binder.
  • the gelatin may be wholly or partly replaced by other polymers including chemically modified gelatin, albumin, agar-agar, arabic acid, alginic acid and derivatives thereof, starch and derivatives thereof, cellulose derivatives; e.g., cellulose ethers, partially hydrolyzed cellulose acetate, carboxymethyl cellulose, etc., polyvinyl alcohol, polyvinylpyrrolidone, methacrylic acid, or derivatives thereof; e.g., esters, amides and nitriles, vinyl polymers; e.g., vinyl ethers and vinyl esters.
  • the silver halide emulsion employed in this invention may be chemically sensitized. Chemical sensitization may be carried out by heating the emulsion in the presence of active gelatin or sulfur sensitizers such as dodium thiosulphate or selenium, and noble metal sensitizers. Alternatively, or in addition, the emulsion may be reduction sensitized, for example, by treating at low pAg (less than 5) and high pH (greater than 8) or through the use of reducing agents such as stannous chloride, thiourea dioxide and amine boranes.
  • the silver halide elements may contain any of the conventional emulsion additives which are known in the art including: development accelerating compounds; e.g., polyalkylene glycols, cationic surfactive compounds of the ammonium, sulfonium and phosphonium types and thioethers; antifoggants and stabilizers; e.g., thiazolium salts, azaindenes; e.g., hydroxytetraazaindenes, nitroindazoles, nitro- benzimidazoles, mercaptotetrazoles, divalent salts of cadmium, cobalt, mercury, zinc or manganese and benzene thiosulfonates.
  • development accelerating compounds e.g., polyalkylene glycols, cationic surfactive compounds of the ammonium, sulfonium and phosphonium types and thioethers
  • antifoggants and stabilizers e.g.,
  • the silver halide elements may also contain conventional additives such as coating aids, hardeners, plasticizers and antistatic agents.
  • the silver halide elements of this invention may additionally contain any of the conventional desensitizers known in the art.
  • a fine-grained silver halide emulsion consisting of 98% silver chloride and 2% silver bromide was prepared by a conventional double jetting technique.
  • the emulsion was coagulated with sodium sulfate and washed normally.
  • the coagulum was reconstituted with gelatin solution to give a final gelatin content of 80 g per mole of silver.
  • the emulsion was divided into 0.1 mole portions and each additive, as indicated in Table 2, was added to a respective portion of the emulsion in methanol solution prior to addition of wetting agent and hardener.
  • the pH of the emulsions was adjusted to pH 5 and the emulsions were coated on polyester base.
  • the coatings were exposed under two conditions:
  • the compounds which are most useful for imparting white light handleability to a silver halide material are those which have a small effect on the sensitivity towards high intensity exposure and a large effect in reducing the sensitivity of the emulsion to low intensity (room light exposure).
  • the most effective L.I.R.F. inducers should have a low value in both Columns A and C in Table 2. It will be noted from Table 2 that the compounds used in accordance with the invention compare favorably with those of the prior art and in many cases are significantly superior as L.I.R.F. inducers.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)
EP83301090A 1982-03-08 1983-03-01 White light handleable photographic materials Expired EP0088581B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8206716 1982-03-08
GB8206716 1982-03-08

Publications (2)

Publication Number Publication Date
EP0088581A1 EP0088581A1 (en) 1983-09-14
EP0088581B1 true EP0088581B1 (en) 1987-05-13

Family

ID=10528855

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83301090A Expired EP0088581B1 (en) 1982-03-08 1983-03-01 White light handleable photographic materials

Country Status (10)

Country Link
EP (1) EP0088581B1 (enrdf_load_stackoverflow)
JP (1) JPH0629944B2 (enrdf_load_stackoverflow)
AR (1) AR244893A1 (enrdf_load_stackoverflow)
AU (1) AU561406B2 (enrdf_load_stackoverflow)
BR (1) BR8301100A (enrdf_load_stackoverflow)
CA (1) CA1246377A (enrdf_load_stackoverflow)
DE (1) DE3371572D1 (enrdf_load_stackoverflow)
ES (1) ES8407214A1 (enrdf_load_stackoverflow)
GR (1) GR78071B (enrdf_load_stackoverflow)
MX (1) MX161970A (enrdf_load_stackoverflow)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0536434Y2 (enrdf_load_stackoverflow) * 1990-08-01 1993-09-14
DE4119505A1 (de) * 1991-06-13 1992-12-17 Du Pont Deutschland Verfahren zur herstellung eines radiographischen aufzeichnungsmaterials mit geringer lichtempfindlichkeit
DE69528640D1 (de) * 1995-07-18 2002-11-28 Agfa Gevaert Nv Photographisches Silberhalogenidröntgenmaterial das zur Verwendung in hellem Dunkelkammerlicht geeignet ist

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4030932A (en) * 1975-05-28 1977-06-21 Eastman Kodak Company Silver halide sensitized with dyes containing an isoindole nucleus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
T.H. JAMES: "The theory of the photographic process", 4th edition 1977, Macmillan, page 265 *

Also Published As

Publication number Publication date
ES520324A0 (es) 1984-08-16
AU1209683A (en) 1983-09-15
DE3371572D1 (en) 1987-06-19
AU561406B2 (en) 1987-05-07
GR78071B (enrdf_load_stackoverflow) 1984-09-26
EP0088581A1 (en) 1983-09-14
ES8407214A1 (es) 1984-08-16
CA1246377A (en) 1988-12-13
JPH0629944B2 (ja) 1994-04-20
MX161970A (es) 1991-03-13
BR8301100A (pt) 1983-11-22
JPS58166342A (ja) 1983-10-01
AR244893A1 (es) 1993-11-30

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