EP0023670B1 - Emulsion photographique, procédé de production et matériaux photographiques - Google Patents

Emulsion photographique, procédé de production et matériaux photographiques Download PDF

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Publication number
EP0023670B1
EP0023670B1 EP80104328A EP80104328A EP0023670B1 EP 0023670 B1 EP0023670 B1 EP 0023670B1 EP 80104328 A EP80104328 A EP 80104328A EP 80104328 A EP80104328 A EP 80104328A EP 0023670 B1 EP0023670 B1 EP 0023670B1
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EP
European Patent Office
Prior art keywords
silver halide
alkyl
represents hydrogen
photographic
acyl group
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
EP80104328A
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German (de)
English (en)
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EP0023670A1 (fr
Inventor
Herbert Dr. Gernert
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • the invention relates to a photographic emulsion which is stabilized by the addition of certain amino carboxylic acids and whose sensitivity is improved.
  • the invention further relates to a process for the preparation of photographic emulsions and photographic materials.
  • these stabilizers have the disadvantage that they generally reduce the sensitivity of the stabilized emulsion in effective concentrations, thereby impairing their applicability.
  • the gradation of the emulsion can also be adversely affected by these stabilizers.
  • Stabilizing agents have various requirements, particularly with regard to the interaction with other photographic additives and with regard to the diversity of photographic reproduction processes and the photographic materials used for this, which the known stabilizing agents do not meet.
  • Substances which increase the sensitivity usually show in the best case the property that when the stability of the photographic material is tested at an elevated temperature the fog is also increased somewhat in accordance with the increase in sensitivity.
  • the invention was u. a. based on the task of finding substances which improve the stability in the sense described and at the same time unchanged or increased sensitivity.
  • Compound I can optionally be present in the emulsion as a disulfide. It can also be present as a salt, and both the carboxyl and the amino group can be included in the salt formation.
  • the invention further relates to a process for the preparation of photographic emulsions by precipitation in the presence of a protective colloid and addition of the compounds to be used according to the invention to the emulsion.
  • the invention furthermore relates to a photographic material with a support, at least one silver halide emulsion layer and optionally further layers, at least one layer containing a compound to be used according to the invention.
  • the compound to be used according to the invention is preferably contained in a silver halide emulsion layer. However, it can optionally also be contained in another colloid layer which does not contain silver halide, but is in a water-permeable relationship to at least one silver halide emulsion layer.
  • the compounds to be used according to the invention are generally added to the emulsion in amounts of not more than 9 mg per mole of silver halide.
  • the emulsions thus contain no more than 9 mg of the compound to be used according to the invention per mole of silver halide.
  • a preferred amount range is from 0.1-8 mg per mole of silver halide, in particular from 0.2-4 mg per mole of silver halide.
  • alkyl, aryl and acyl groups mentioned can also be substituted with substituents which have no adverse effect in photographic materials.
  • Preferred alkyl radicals (R 1 , R 4 and R 2 ) have 1-4 C atoms, for example methyl, butyl. Methyl and ethyl are particularly preferred.
  • Preferred aryl groups can be those with 6-12 C atoms, especially phenyl.
  • Preferred aralkyl groups (R 1 and R 2 ) have 1-2 C atoms in the aliphatic and 6-12 C atoms in the aromatic part, for example benzyl.
  • compound 1.1 penicillamine
  • Penicmamm is described in DE-A-2335093 as an additive to photographic silver halide emulsions in an amount of 10 -5000 mg per mole of AgX to stabilize the latent image. It is therefore surprising that this compound in the amount range of ⁇ 9 mg per mole of AgX added to the emulsion has a fog-reducing and density-stabilizing effect with significantly increased sensitivity.
  • the compounds which can be used according to the invention can be introduced into at least one layer or intermediate layer of a photographic material.
  • they can be added to the light-sensitive silver halide emulsion or the finished casting solution, or they can be applied to the photographic material together with the last protective layer.
  • the compounds which can be used according to the invention can be added to light-sensitive silver halide emulsions at any time during the preparation or further processing of the emulsion.
  • the stabilizing agents which can be used according to the invention are added after chemical ripening, preferably to the finished casting solution.
  • the compounds to be used according to the invention can be used in the usual light-sensitive photographic materials which are suitable for the production of black and white images, e.g. B. black and white recording or copying materials or reversal materials. Furthermore, color couplers can be contained in the material without affecting the stabilization.
  • the usual silver halide emulsions which can consist of pure silver halides or mixtures thereof, are suitable for the present invention.
  • the silver halide grains can consist of silver chloride, silver bromide, silver iodide, silver chloride bromide, silver chloride iodide, silver bromide iodide and silver chloride bromide iodide.
  • the present invention is suitable for silver bromide iodide emulsions with an iodide content of up to 8 mol%.
  • the emulsions can be chemically sensitized, e.g. B. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like.
  • Reducing agents e.g. B. the tin compounds described in Belgian patents 493 464 and 568 687, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. B. according to Belgian patent 547 323 used.
  • polyalkylene oxide derivatives e.g. B. with polyethylene oxide of a molecular weight between 1000 and 20,000, further with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have a molecular weight of at least 700, preferably more than 1000.
  • these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.
  • the emulsions are preferably not optically sensitized or orthosensitized with the usual dyes.
  • the emulsions can be hardened in the usual manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type. Examples of such hardeners are e.g. B. described in German Offenlegungsschrift 2,263,602 or British Patent 1,266,655.
  • hardeners of the diazine, triazine or 1,2-dihydroquinoline series are alkyl or arylsulfonyl group-containing diazine derivatives, derivatives of hydrogenated diazines or triazines such as.
  • the present invention can be applied to both black and white and color photographic images.
  • Colored photographic images can e.g. B. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of coloring p-phenylenediamine developers to form dyes.
  • the color couplers can contain at least one layer of the photographic material, e.g. B. at least one silver halide layer itself. Examples of color couplers that can be used are the publication “Color Couplers” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff”, Volume III (1961) and K. Venkataraman in “The Chemistry of Synthetic Dyes”, Vol. 4 , Pp. 341-387, Academic Press (1971).
  • the emulsions can be applied to the usual substrates, e.g. B. on carriers of cellulose esters such as cellulose acetate or cellulose acetobutyrate, further polyester, especially polyethylene terephthalate or polycarbonates, especially based on bis-phenylolpropane.
  • cellulose esters such as cellulose acetate or cellulose acetobutyrate
  • polyester especially polyethylene terephthalate or polycarbonates, especially based on bis-phenylolpropane.
  • paper supports which are optionally impermeable polyolefin layers, e.g. B. of polyethylene or polypropylene, can also contain supports made of glass or metal.
  • black / white developer compounds are suitable, such as. B. hydroxybenzenes and 3-pyrazolidones.
  • the usual color developer substances can be used to generate color images.
  • a silver bromide iodide emulsion sensitized with gold and thiosulfate with an iodide content of 2.5 mol% and an average sensitivity is added after the maturation has ended to 1.2 g of triazaindolizine per mole of silver halide.
  • This emulsion which was adjusted to a silver content of 170 g AgN0 3 per liter and a gelatin content of 15%, was 0, 0.25, 0.5, 1.0, 2.0 and 4.0 mg per mole of silver halide Penicillamine added and the emulsion stirred at 40 ° C for 10 minutes. Then 20 ml of a 5% saponin solution was added to the emulsion. For hardening, 35 ml of a 2% formalin solution per mole of silver halide were added to the emulsion shortly before pouring.
  • the protective layer contained 5% of a suitable protective layer gelatin as well as 40 ml of a 5% saponin solution and 40 ml of a 5% sucrose monolaurate solution per liter of protective layer solution. From the cast-ready emulsion a web with a silver coating of 9.5 g AgN0 3 / m 2 and a protective layer thickness of 1.8 11 m was poured onto a polyester base with anti-halo and dried. The total layer thickness of this film was 12 ⁇ m.
  • Sensitometer strips of the fresh film and of the film stored at 60 ° C. for 72 hours were then exposed on a short-term sensitometer at 1/1000 seconds and processed as usual.
  • the developer contained: posed.
  • the development time at 26 ° C was 2 minutes 30 seconds.
  • Table 1 shows the haze values, sensitivities, gradients and increases in sensitivity after storing the fresh samples and the samples stored in the heating cabinet.
  • the test series shows that with an addition of 0.25 mg penicillamine per mole of silver halide, the haze and sensitivity increase after storage in the heating cabinet is already reduced.
  • the optimal result is achieved with an amount of 2.0 mg penicillamine per mole of silver halide, with a sensitivity increase of 50% being observed.

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  • 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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

1. Emulsion photographique d'halogénure d'argent, caractérisée en ce qu'elle contient au plus 9 mg par mole d'halogénure d'argent d'au moins un composé de formule générale 1
Figure imgb0011
dans laquelle:
R' représente H ou un groupe alkyle, aryle, arylalkyle ou acyle,
R2 représente un groupe alkyle, arylalkyle ou acyle,
R3 représente H ou un cation,
R4 représente H ou un groupe alkyle ou acyle,
n est égal à 0 ou à un nombre entier,

et/ou
R1 et R2, pris ensemble, représentent le reste pour compléter un noyau,

et/ou du disulfure correspondant.
2. Procédé pour la préparation d'une émulsion photographique d'halogénure d'argent par précipitation d'un halogénure d'argent en présence d'un colloide protecteur, caractérisé en ce que l'on ajoute à l'émulsion par mole d'halogénure d'argent au moins un composé de formule
Figure imgb0012
dans laquelle:
R1 représente H ou un groupe alkyle, aryle, arylalkyle ou acyle,
R2 représente un groupe alkyle, aryle, arylalkyle ou acyle,
R3 représente H ou un cation,
R4 représente H ou un groupe alkyle ou acyle,
n est égal à 0 ou à un nombre entier,

et/ou
R1 et R2, pris ensemble, représentent le reste pour compléter un noyau,

et/ou du disulfure correspondant,
en quantité telle que l'émulsion d'halogénure d'argent finale contienne au plus 9 mg du composé par mole d'halogénure d'argent.
3. Matériau photographique comportant un support de couche et au moins une couche d'émulsion d'halogénure d'argent sensible à la lumière et éventuellement d'autres couches, caractérisé en ce qu'il contient au plus 9 mg par mole d'halogénure d'argent d'au moins un composé de formule générale
Figure imgb0013
dans laquelle:
R1 représente H ou un groupe alkyle, aryle, arylalkyle ou acyle,
R2 représente un groupe alkyle, aryle, arylalkyle ou acyle,
R3 représente H ou un cation,
R4 représente H ou un groupe alkyle ou acyle,
n est égal à 0 ou à un nombre entier,

et/ou
R1 et R2, pris ensemble, représentent le reste pour compléter un noyau,

et/ou du disulfure correspondant.
4. Matériau photographique selon la revendication 3, caractérisé en ce que le composé est contenu dans une couche d'émulsion d'halogénure d'argent en quantité de 9 mg au plus par mole d'halogénure d'argent.
5. Matériau photographique selon la revendication 3, caractérisé en ce que
R1 représente H ou un alkyle en C1― C4,
R2 représente un alkyle en C1―C4,
R3 représente H ou un cation,
R4 représente H,
n est égal à 0, 1 ou 2.
6. Matériau photographique selon la revendication 5, caractérisé en ce que
R1 représente CH3,
R2 représente CH3,
R3 représente H,
R4 représente H,
n est égal à 0
EP80104328A 1979-08-04 1980-07-23 Emulsion photographique, procédé de production et matériaux photographiques Expired EP0023670B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2931690 1979-08-04
DE19792931690 DE2931690A1 (de) 1979-08-04 1979-08-04 Photographische emulsion, verfahren zur herstellung sowie photographische materialien

Publications (2)

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EP0023670A1 EP0023670A1 (fr) 1981-02-11
EP0023670B1 true EP0023670B1 (fr) 1982-06-02

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US (1) US4314024A (fr)
EP (1) EP0023670B1 (fr)
JP (1) JPS5629228A (fr)
DE (2) DE2931690A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0743518B2 (ja) * 1987-07-06 1995-05-15 コニカ株式会社 ハロゲン化銀写真乳剤
JP2627149B2 (ja) * 1987-07-08 1997-07-02 コニカ株式会社 返し特性の改良された画像形成方法
DE3838467C2 (de) * 1988-11-12 1998-12-10 Agfa Gevaert Ag Fotografisches Aufzeichnungsmaterial
EP0373339B1 (fr) * 1988-11-15 1994-05-04 Agfa-Gevaert AG Matériau d'enregistrement photosensible à l'halogénure d'argent
US5035989A (en) * 1988-11-28 1991-07-30 Fuji Photo Film Co., Ltd. Silver halide photographic material for reversal processing
JPH03215844A (ja) * 1990-01-19 1991-09-20 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2438716A (en) * 1944-10-06 1948-03-30 Gen Aniline & Film Corp Stabilized silver halide emulsions
BE594454A (fr) * 1959-09-04
FR89467E (fr) * 1961-12-08
DE1816571A1 (de) * 1968-12-23 1970-07-09 Agfa Gevaert Ag Photographische Halogensilberemulsion mit erhoehter Empfindlichkeit und vermindertemSchleier
US3708302A (en) * 1971-01-07 1973-01-02 Eastman Kodak Co Silver halide emulsion sensitized with thioamine-glutaraldehyde or acrylic aldehyde adduct
GB1386630A (en) 1972-07-12 1975-03-12 Ilford Ltd Sulphur-containing amino acids and their use in photographic materials
GB1387654A (en) * 1972-07-12 1975-03-19 Ilford Ltd Photographic silver halide materials

Also Published As

Publication number Publication date
US4314024A (en) 1982-02-02
EP0023670A1 (fr) 1981-02-11
JPS5629228A (en) 1981-03-24
DE2931690A1 (de) 1981-02-19
DE3060503D1 (en) 1982-07-22

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