EP0193826B1 - Matériau d'enregistrement photographique couleur pourvu d'une émulsion à l'halogénure d'argent et son procédé de préparation - Google Patents

Matériau d'enregistrement photographique couleur pourvu d'une émulsion à l'halogénure d'argent et son procédé de préparation Download PDF

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Publication number
EP0193826B1
EP0193826B1 EP86102369A EP86102369A EP0193826B1 EP 0193826 B1 EP0193826 B1 EP 0193826B1 EP 86102369 A EP86102369 A EP 86102369A EP 86102369 A EP86102369 A EP 86102369A EP 0193826 B1 EP0193826 B1 EP 0193826B1
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EP
European Patent Office
Prior art keywords
imidazole
silver halide
recording material
photographic recording
color photographic
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
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EP86102369A
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German (de)
English (en)
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EP0193826A3 (en
EP0193826A2 (fr
Inventor
Sieghart Dipl.-Ing. Klötzer
Bruno Dr. Mücke
Günther Dr. Mahlberg
Manfred Dr. Becker
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0193826A3 publication Critical patent/EP0193826A3/de
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    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C2200/00—Details
    • G03C2200/06—Additive

Definitions

  • the invention relates to a color photographic recording material with a silver halide emulsion and a method for producing this silver halide emulsion.
  • the recording materials according to the invention are notable for improved properties, in particular with regard to sensitivity, fog and susceptibility to pressure.
  • iridium salts it is also known to add iridium salts to the emulsions to improve the reciprocity error. In this case, the sensitivity is generally increased only with short exposure, see DE-A-2 611 037.
  • the iridium salts are either added when the halogen silver is precipitated, so that iridium ions are incorporated into the crystal lattice of the silver halide, or the iridium salts are added during chemical ripening.
  • DE-A-2 063 669 and 2 165 764 describe optical sensitizers in addition to the use of iridium salts.
  • Neither the iridium-doped emulsions nor the thioether-based emulsions can meet the requirements for constancy of gradation and sensitivity with maximum sensitivity over a wide exposure time range (between 20 / thousandths of a second and 150 seconds) compared to today's emulsions in color materials, especially colored paper.
  • Other disadvantages of these emulsions are pressure sensitivity and changes in gradation depending on the processing. In certain cases, this leads to undesirable color casts in the color images.
  • US Pat. No. 4,469,783 also discloses silver halide emulsions which have been prepared in the presence of a water-soluble iridium compound and additionally in the presence of a thiourea or an organic thioether. This is intended to improve sensitivity, gradation and fog.
  • the emulsions described are used to produce dot images. None is said about their applicability in color photographic recording materials.
  • An object of the present invention is to provide new color photographic recording materials with improved sensitometric properties.
  • a color photographic recording material which contains at least one light-sensitive silver halide emulsion layer and optionally further layers on a layer support, in which the silver halide emulsion of the silver halide emulsion layer contains silver halide grains, the grain formation and / or grain growth of which was carried out at least partially in the presence of an imidazole. According to the invention, grain formation and / or grain growth of the silver halide grains were additionally carried out at least partially in the presence of an iridium compound.
  • the recording materials according to the invention surprisingly show a high sensitivity, a steep gradation and an excellent constancy of the sensitivity and gradation over an exposure period of at least 20/1000 sec to 150 s and insensitivity to pressure at low fog. This is surprising because emulsions containing iridium alone do not have the properties described above. Also the presence of imidazoles, but in the absence of iridium compounds
  • Emulsions do not reach the values achievable according to the invention.
  • Preferred alkyl groups have 1 to 8 carbon atoms, especially 1 to 4 carbon atoms, e.g. Methyl and ethyl.
  • Alkenyl radicals can be those with 3 to 8 carbon atoms, for example allyl, butenyl, hexenyl or octenyl. Alkenyl radicals having 3 to 4 carbon atoms are preferred; the allyl radical is particularly preferred.
  • Aryl substituents can be those having 6 to 12 carbon atoms, for example phenyl, biphenyl or naphthyl.
  • the preferred aryl substituent is the phenyl radical.
  • Araliphatic substituents can be those having 1 to 2 carbon atoms in the aliphatic part and 6 to 12 carbon atoms in the aromatic part, for example benzyl and phenylethyl.
  • Suitable substituted alkyl groups are, for example, hydroxyl, cyano, alkoxy, free or esterified carboxy and / or sulfoalkyl groups.
  • the substances to be used according to the invention are preferably water-soluble.
  • the protective colloid in particular the gelatin
  • the protective colloid can be present not only in the initial charge, but also in the incoming halide solution.
  • the imidazoles to be used according to the invention can be used in a very wide concentration range.
  • concentration to be used depends on the desired final size of the silver halide crystals and can range from 10 ⁇ 4 molar solution to the saturation limit of the compound. They are preferably used in 0.003 molar to 1 molar solution.
  • Suitable iridium compounds are, in particular, water-soluble iridium salts and complex compounds.
  • iridium trichloride, iridium tetrachloride and tri- and tetravalent hexachloroiridates of sodium, potassium and ammonium are particularly preferred.
  • the iridium compounds to be used according to the invention can be added to the emulsion at any time during their preparation, regardless of the addition of the imidazole or together with it. Amounts of 10 ⁇ 10 to 10 ⁇ 4 mol per mol of silver are particularly preferred
  • the pH in the preparation of the emulsion is generally> 4, preferably pH values between 5.5 and 6.5 are chosen, but alkaline pH values are also possible.
  • the pH can also be changed during the precipitation.
  • the silver halide nuclei can be precipitated at pH> 5 and then allowed to grow further to larger silver halide crystals at pH ⁇ 5.
  • the pAg in the preparation of the emulsions can be varied within a wide range.
  • the emulsion precipitation can be carried out at pAg values at which cubic or octahedral area growth is preferred.
  • the pAg value can also be varied during the precipitation.
  • Substances that are usually used as ripening agents can also be present during the precipitation: e.g. Compounds of sulfur, selenium, tellurium, gold, palladium, platinum, thiourea derivatives, formamidine sulfinic acid, tin (II) chloride.
  • divalent and / or polyvalent cations such as La3 + , Zn2 + , Pb2 + , T13 + , Co2 + , Rh3 + , etc. can be present during the precipitation.
  • the precipitation temperature is advantageously between 30 and 90 ° C. It is also possible to keep the temperature during change the precipitation, eg form the nuclei at high temperature and then allow the rest of the crystal growth process to proceed at a lower temperature, as described, for example, in US Pat. No. 3,790,387.
  • Silver halide emulsions can contain any of the silver halides commonly used in silver halide photography, e.g. Silver chloride, silver bromide, silver chloride bromide, silver chloride bromide iodide, silver chloride iodide and silver bromide iodide.
  • the silver halide emulsions to be used according to the invention contain at least 20 mol% of silver chloride, less than 80 mol% of silver bromide and at most 5 mol% of silver iodide.
  • the crystals are predominantly compact, for example cubic or octahedral or have transition forms. They can be characterized in that they essentially have a thickness of more than 0.2 ⁇ m.
  • the average ratio of diameter to thickness is preferably less than 8; 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
  • the emulsion has a narrow grain size distribution.
  • at least 95% by weight of the grains have a diameter which does not deviate from the average grain diameter by more than 40%.
  • the emulsions can also have a broad grain size distribution.
  • at least 10%, preferably 20%, of the silver halide grains have a diameter which deviates from the average grain diameter by at least 40%.
  • the silver halide emulsions can be prepared using the usual procedures (e.g. single inlet, double inlet, with constant or variable material flow). It is particularly preferred to use the double-inlet process under control of the pAg value.
  • the silver halide grains can have a layered grain structure consisting of a core and at least one shell, as is known, for example, from British Patent 1,027,146.
  • the core and shell can have different or the same halide composition.
  • the core can be 100% AgCl, 100% AgBr or consist of intermediate mixtures and corresponding proportions of AgJ.
  • the emulsions are preferably chemically sensitized on the grain surface to a high surface sensitivity. They can be chemically sensitized using known methods, e.g. with active gelatin or with compounds of sulfur, selenium, tellurium, gold, palladium, platinum, iridium, the pAg values between 4 and 10, the pH values between 3.5 and 9 and the temperatures between 30 ° C and 90 ° C can fluctuate; chemical sensitization can be carried out in the presence of heterocyclic nitrogen compounds such as imidazoles, azaindenes, azapyridazines and azapyrimidines and thiocyanate derivatives, thioethers and other silver halide solvents.
  • heterocyclic nitrogen compounds such as imidazoles, azaindenes, azapyridazines and azapyrimidines and thiocyanate derivatives, thioethers and other silver halide solvents.
  • the emulsions according to the invention can be subjected to a reduction sensitization, e.g. by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8), by reducing agents such as tin (II) chloride, thiourea dioxide and aminoborane.
  • a reduction sensitization e.g. by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8), by reducing agents such as tin (II) chloride, thiourea dioxide and aminoborane.
  • the surface ripening nuclei can also be present as troglodyte nuclei (sub-surface nuclei) according to DE-OS 2 306 447 and US Pat. No. 3,966,476. If necessary, the grains can also be matured inside. Other methods are described in the above. Research Disclosure No. 17643 in Section 111.
  • the emulsions can be optically sensitized in a manner known per se, for example using the customary polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • the customary polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • Such sensitizers are described by FM Hamer in "The Cyanine Dyes and related Compounds', (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to the research disclosure given above No. 17643, Section IV.
  • antifoggants and stabilizers can be used.
  • Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
  • Such connections are, for example, in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58.
  • Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17643 above in Section IV.
  • Color couplers which react with color developer oxidation products to form a non-diffusing dye are preferably assigned to the light-sensitive silver halide emulsion layers.
  • the color couplers are expediently housed non-diffusively in the light-sensitive layer itself or in close proximity to it.
  • the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
  • the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone type usually being used.
  • the blue-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • the color couplers can be, for example, 6, 4 and 2 equivalent couplers. Suitable couplers are known, for example, from the publications "Color Coupler" by W.
  • the recording material can also contain DIR compounds and white couplers which do not give any dye on reaction with color developer erosion ion products.
  • the inhibitors which can be split off from the DIR compounds can be split off directly or via non-inhibiting intermediate compounds.
  • the components of the photographic material can be incorporated in the usual way.
  • the usual substrates can be used for the materials according to the invention, e.g. Cellulose ester supports, e.g. Cellulose acetate and polyester.
  • paper supports which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene.
  • polyolefins especially with polyethylene or polypropylene.
  • hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin.
  • the layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Further suitable hardening agents are from the German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from the above Research Disclosure 17643, Section XI.
  • Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine. Further useful color developers are described, for example, in J.Amer.Chem.Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and
  • the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
  • the conventional compounds can be used, such as Fe + salts and Fe + complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
  • ferric complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic , Alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulphates are also suitable as bleaching agents.
  • solution E-1 is heated to 55 ° C and adjusted to pH 6.0.
  • solution E-2 likewise heated to 55 ° C., is metered in at a feed rate of 600 ml per minute.
  • Solutions E-3, E-4, E-5 and E-6 are added in succession at a constant dosing rate of 600 ml per minute. After a digestion time of 30 minutes at 55 ° C., the emulsion is cooled and then freed from the soluble salts by flocculation and washing in the usual way. The washed flocculate is then redispersed in solution E-7 by stirring at 40 ° C. for 30 minutes.
  • This emulsion is called EM-1 and has an average grain diameter of 0.48 ⁇ m.
  • the comparative emulsion EM-2 is prepared similarly to EM-1; the following solutions are required:
  • the comparison emulsion EM-2 is precipitated as described for emulsion EM-1, but the initial charge F-1 and the solutions F-2 to F-6 were heated to 60.degree.
  • Emulsion EM-3 according to the invention
  • the emulsion EM-3 according to the invention was produced according to the recipe described under EM-1. Only the solution E-S was added 10.1 mg Na2IrCl6 * 6 H2O.
  • the emulsions EM-1 to EM-3 are each mixed with 38 ⁇ mol sodium thiosulfate, based on 1 mol silver halide, and digested at 50 ° C. for 120 minutes.
  • the emulsions are poured onto a paper base together with a conventional magenta coupler and, after exposure behind a gray wedge, processed in the process specified in DE-A-3 107 173, page 23 ff.
  • the emulsion EM-3 according to the invention is characterized by steeper gradation with significantly higher sensitivity.
  • the template - solution K-1 is heated to 55 ° C and adjusted to pH 6.0. With intensive mixing, the solution K-2, which is also heated to 55 ° C., is added to the solution K-1 in 10 seconds. After a digestion time of 40 minutes at 55 ° C., the emulsion is cooled and then freed from the soluble salts by flocculation and washing in the usual way.
  • the washed flocculate is then redispersed in solution K-3 at 30 ° C. for 30 minutes.
  • the emulsion produced in this way is designated EM-4 and has an average grain diameter of 0.26 ⁇ m; the halide composition is 75 mol% AgCl and 25 mol% AgBr.
  • the comparison emulsion EM-5 is precipitated as described under EM-4, but the initial solution L-1 and solution L-2 are heated to 60 ° C. in order to obtain a comparable grain size even without a silver halide solvent.
  • Emulsion EM-6 according to the invention
  • the emulsion EM-6 according to the invention was produced according to the recipe described for the emulsion EM-4. Only the solution K-1 was changed in such a way that 10.1 mg Na2IrCl6 * H2O were added to it.
  • the emulsions EM-4 to EM-6 were each mixed with 25 ⁇ mol sodium thiosulfate, based on 1 mol silver halide, and digested at 55 ° C. for 90 minutes.
  • the emulsion EM-6 according to the invention has the highest sensitivity with steep gradation; the veil is at the level of the comparison emulsions.

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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)

Claims (9)

  1. Matériau de reproduction photographique couleur qui contient sur un support de couches au moins une couche d'émulsion d'halogénure d'argent sensible à la lumière et éventuellement d'autres couches, dans lequel l'émulsion d'halogénure d'argent de la couche d'émulsion d'halogénure d'argent contient des grains d'halogénure d'argent dont la formation de grain et/ou la croissance de grain ont été effectuées au moins partiellement en présence d'un imidazole, caractérisé en ce que la formation de grain et/ou la croissance de grain ont été effectuées en outre au moins partiellement en présence d'un composé d'iridium.
  2. Matériau de reproduction photographique couleur selon la revendication 1, caractérisé en ce que le composé d'iridium et l'imidazole ont été utilisés pendant la précipitation.
  3. Matériau de reproduction photographique couleur selon la revendication 1, caractérisé en ce que le composé d'iridium est un composé soluble dans l'eau.
  4. Matériau de reproduction photographique couleur selon la revendication 1, caractérisé en ce que le composé d'iridium est un hexachloroiridate.
  5. Matériau de reproduction photographique couleur selon la revendication 1, caractérisé en ce que l'imidazole répond à la formule suivante :
    Figure imgb0014
     dans laquelle
    R¹ , R² , R³ et R⁴ sont identiques ou différents et représentent l'hydrogène et/ou un groupe alkyle, alcényle, aryle et/ou aryl-alkyle éventuellement substitué.
  6. Matériau de reproduction photographique couleur selon la revendication 1, caractérisé en ce que l'imidazole est choisi dans le groupe suivant : imidazole, 1-méthylimidazole, 2-méthylimidazole, 1,2-diméthylimidazole, 1-allylimidazole, 1-méthoxyméthylimidazole, 1-(2-carboxyéthyl)-imidazole, 4-(ou 5-)méthylimidazole et 2-éthyl-4-méthylimidazole.
  7. Matériau de reproduction photographique couleur selon la revendication 1, caractérisé en ce que le matériau contient des coupleurs chromogènes.
  8. Matériau de reproduction photographique couleur selon la revendication 1, caractérisé en ce que la couche d'émulsion d'halogénure d'argent contient au moins 20 mol % de chlorure d'argent et au maxiumum 80 mol % de bromure d'argent.
  9. Procédé pour la fabrication d'une émulsion d'halogénure d'argent photographique, dans lequel les grains d'halogénure d'argent ont été fabriqués au moins temporairement en présence d'un imidazole avant la fin de la croissance de grain, caractérisé en ce qu'ils ont en outre été fabriqués au moins temporairement en présence d'un composé d'iridium.
EP86102369A 1985-03-06 1986-02-24 Matériau d'enregistrement photographique couleur pourvu d'une émulsion à l'halogénure d'argent et son procédé de préparation Expired - Lifetime EP0193826B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853507830 DE3507830A1 (de) 1985-03-06 1985-03-06 Farbfotografisches aufzeichnungsmaterial mit einer silberhalogenidemulsion und verfahren zu deren herstellung
DE3507830 1985-03-06

Publications (3)

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EP0193826A2 EP0193826A2 (fr) 1986-09-10
EP0193826A3 EP0193826A3 (en) 1989-02-08
EP0193826B1 true EP0193826B1 (fr) 1991-03-13

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EP86102369A Expired - Lifetime EP0193826B1 (fr) 1985-03-06 1986-02-24 Matériau d'enregistrement photographique couleur pourvu d'une émulsion à l'halogénure d'argent et son procédé de préparation

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US (1) US4705747A (fr)
EP (1) EP0193826B1 (fr)
JP (1) JPS61205930A (fr)
DE (2) DE3507830A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6461751A (en) * 1987-09-01 1989-03-08 Konishiroku Photo Ind Silver halide photographic sensitive material
JP2565766B2 (ja) * 1988-02-09 1996-12-18 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH0299716U (fr) * 1989-01-25 1990-08-08
US5362619A (en) * 1989-06-27 1994-11-08 Konica Corporation High-speed halide photographic light-sensitive material
JP2670885B2 (ja) * 1990-05-15 1997-10-29 富士写真フイルム株式会社 ハロゲン化銀写真感光材料及びその現像処理方法
DE19507913C2 (de) * 1995-03-07 1998-04-16 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial
JPH08314037A (ja) * 1995-05-17 1996-11-29 Fuji Photo Film Co Ltd 微粒子ハロゲン化銀乳剤の製造方法
US6451520B1 (en) * 2000-07-29 2002-09-17 Agfa-Gevaert Color photographic silver halide material
US7159717B2 (en) * 2004-05-11 2007-01-09 Cadbury Adams Usa, Llc Packaging design with separate compartments

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3574625A (en) * 1967-04-07 1971-04-13 Eastman Kodak Co Photographic systems with polyvalent metal ions contiguous to the silver halide grains
JPS53134430A (en) * 1977-04-27 1978-11-24 Mitsubishi Paper Mills Ltd Silver halide photosensitive materials for multiilayer color photograph
DE2758711A1 (de) * 1977-12-29 1979-07-19 Agfa Gevaert Ag Lichtempfindliches photographisches material
JPS6054662B2 (ja) * 1981-09-28 1985-11-30 富士写真フイルム株式会社 ハロゲン化銀乳剤
JPS58211753A (ja) * 1982-06-04 1983-12-09 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤

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US4705747A (en) 1987-11-10
DE3678013D1 (de) 1991-04-18
EP0193826A3 (en) 1989-02-08
DE3507830A1 (de) 1986-09-11
EP0193826A2 (fr) 1986-09-10
JPS61205930A (ja) 1986-09-12

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