US3779764A - Silver halide emulsions for the production of reversal colorphotographic images - Google Patents

Silver halide emulsions for the production of reversal colorphotographic images Download PDF

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Publication number
US3779764A
US3779764A US00197480A US3779764DA US3779764A US 3779764 A US3779764 A US 3779764A US 00197480 A US00197480 A US 00197480A US 3779764D A US3779764D A US 3779764DA US 3779764 A US3779764 A US 3779764A
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Prior art keywords
emulsion
silver halide
reversal
colorphotographic
emulsions
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Expired - Lifetime
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US00197480A
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English (en)
Inventor
F Moll
B Morcher
E Reckziegel
W Saleck
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer

Definitions

  • ABSTRACT [22] Filed: Nov. 10, I971 i 1 A s
  • This invention relates to a process for the production of silver halide gelatine emulsions for use in colorphotographic reversal films which yield a positive colorphotographic image upon exposure and development in developers which contain thiocyanates.
  • mixtures of different silver halide emulsions are generally employed in colorphotographic reversal materials. These may, for example, consist of a high speed emulsion, an emulsion of medium speed and a low speed emulsion.
  • the proportions of the individual emulsions which are used can be varied within wide limits depending on the photographic properties of the individual emulsions and on the effects desired.
  • the average grain size of the less sensitive or low speed silver halide emulsion should be at least 50 percent and preferably 50 to percent of that of the high speed emulsion. This measure is not confined to mixtures of two emulsions but also applied to mixtures of several emulsions.
  • the effect of the invention is extremely unexpected since it has previously been assumed that the grain granularity of the image dye can only be improved by using finer grained silver halide emulsions. For this reason, the average grain size of the less sensitive emulsions used in the previously known silver halide emulsion mixtures for color reversal materials was generally only about 20 to 30 percent of that of the more sensitive emulsion. For the same reasons, there was a tendency to use even smaller average grain sizes.
  • a silver nitrate solution is added over a given time at a predetermined temperature to a gelatine solution which contains potassium iodide and potassium bromide.
  • Potassium bromide is used in excess so that the so-called physical ripening i. e. the increase in the large silver halide crystals at the expense of the smaller grains, can take place by complex formation with the silver halide already formed.
  • the physical ripening starts as soon as silver nitrate is added -to the aqueous alkali metal halide solution. It can be assisted by occasionally interrupting the addition of silver nitrate solution into the precipitation mixture.
  • the physical ripening is carried out at temperatures of between 45 to 70C.
  • the physical ripening can be controlled by varying the temperature. A higher temperature produces increased physical ripening due to greater complex formation and hence results in a coarser grain and higher speed.
  • a coarser grain structure consist, for example, in the addition of a silver halide solvent, e. g. ammonia or by using a more concentrated reaction mixture, which is equivalent to increasing the bromine ion concentration, or by using an increased quantity of gelatine when preparing the mixture.
  • a silver halide solvent e. g. ammonia
  • a more concentrated reaction mixture which is equivalent to increasing the bromine ion concentration, or by using an increased quantity of gelatine when preparing the mixture.
  • Silver halide emulsions of this type yield a finer dye grain if processed in accordance with a color reversal process including black-white development in a thiocyanate-containing developer than silver halide emulsions which have been ripened at lower temperatures under otherwise the same conditions and which have a smaller average grain size.
  • the sensitivity of the coarser silver halide emulsion prepared according to the invention is higher. This can be corrected by modifying the chemical ripening, or by using certain kinds of gelatine or by changing the pH or pAg value. Further more it is possible to add certain ingredients which decrease the the sensitivity.
  • Stabilizers may also be added to the emulsion in such quantities that the sensitivity is reduced by the required amount.
  • Stabilizers of this type are, for example, mercury compounds, palladium compounds, rhodium compounds and osmium compounds.
  • the usual sulfur compounds, gold salts and if desired onium salts for chemical sensitization are added to the emulsion.
  • the quantity of gold salt added may also be varied to reduce the sensitivity or the gold may even be omitted completely.
  • the gold sensitization we refer to the book by R. Koslowski, Z. wiss. Phot. 46, 65 72 (1959).
  • the emulsions may also be optically sensitized, e. g. with the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonoles and the like.
  • polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonoles and the like.
  • Such sensitizers have been described in F. M. Hamer The Cyanine Dyes and related Compounds (1964).
  • For suitable color couplers. reference may be made to the chapter dealing with this subject in the book mentioned above by Glafltides.
  • the emulsions which have been after-ripened are mixed with other silver halide emulsions to obtain the desired gamma-value and speed. Thereafter the usual casting additives such as stabilizers against fogging on storage, hardening agents, plasticizers, bactericidal agents and wetting agents are also added.
  • a silver halide gelatine emulsion mixture for the red sensitive emulsion layer of a three-layered colorphotographic reversal material, which emulsion layer contains a cyan color coupler, is prepared as follows:
  • the more sensitive emulsion is a silver iodobromide gelatine emulsion which has been prepared in the usual manner and which has an iodine content of 6 mols per cent
  • This emulsion has a relatively coarse grain owing to its sensitivity.
  • the result of a sedimentation analysis which is representative for the grain size distribution is shown by curve I in FIG. 1.
  • the axis of ordinates represents the grain size in am and the axis of abscissas the residue in percent.
  • the average grain size of this emulsion is about 0.76
  • the grain distribution was determined by means of the known sedimentation analysis (see e. g. VDI Zeitschrift, Volume 109, No. 17 pages 757 et seq.).
  • Part A 40 parts by weight of a less sensitive silver halide gelatine emulsion 3 (curve 3 of FIG. 1) was added to 60 parts by weight of the above high-speed emulsion 1.
  • Emulsion 3 is a silver iodobromide gelatine emulsion which has an iodide content of 8 mols per cent, which was prepared in the usual manner.
  • emulsion 3 has the grain distribution represented by curve 3 in FIG. 1, 50 percent of the grains being larger than 0.32 p. up to a maximum of 0.8 p. and 50 percent of the grains being smaller than 0.32 a down to a minimum of 0.95 1,.
  • Part B 40 parts by weight of the less sensitive silver iodobromide gelatine emulsion 2 (curve 2 of FIG. 1) are also added to parts by weight of the above high-speed 60 sented by curve 2 in FIG. 1. It is found that 50 percent of the grains are large 1111.50.44 p. up to a maximum of 0.95 ,u. and 50 percent of the grains were smaller than 0.4 4 ,u. down to a minimum of 0.09 a.
  • Emulsion mixtures A and B are processed in the same mannersThe following additives are first added per litre to the emulsions:
  • the emulsions are then applied on to a support of cellulose acetate and dried.
  • a cyan step wedge is obtained in both cases.
  • the dye grain of the cyan image is then measured for both samples by determining the Wiener spectrum.
  • the wiener spectrum W gives information on the noise energy and its frequency distribution of statistically distributed events.
  • W indicates the magnitude of the noise energy (fluctuations in density) and how these grain sizes (lines per mm) are distributed.
  • the curves obtained with the emulsion are shown in FIG. 2.
  • the local frequency spectrum of the grain is plotted along the abscissa and the square root of the noise energy along the ordinate.
  • the steep rise w of sample A indicates a high proportion of coarse dye grains.
  • the flatness of the curve of the emulsion mixture B indicates a much finer grain of the image dye. It is found that the noise energy of emulsion mixture B is only about one-fourth of that of emulsion
  • the comparison test proves that a much finer grained dye image is obtained although a coarser grained silver halide emulsion mixture is used as the starting material.
  • EXAMPLE 2 A high-speed silver iodobromide gelatine emulsion which has anieisl sgnt n Q ..4.PQFSQH. isate i9 the usual manner. This emulsion is relatively coarse grained.
  • the grain size distribution as the result of a sedimentation analysis as described in Example 1 is shown by curve 4 of FIG. 3. In the diagram the grain size in pm is plotted along the axis of abscissa against the residue in percent along the axis of ordinates.
  • This emulsion serves as the more sensitive component for the preparation of an emulsion mixture for the green sensitive layer, which contains a magenta color coupler, of a color reversal material.
  • Part C 60 parts by weight of a less sensitive silver iodobromide gelatine emulsion 6 (silver iodide content 4 mol.-%) are added to 40 parts by weight of the above emulsion 4.
  • the total time for the physical ripening of the emulsion 6 was minutes.
  • the temperature was 50C.
  • the grain size distribution of emulsion 6 is represented by curve 6 in FIG. 3. 50 percent of the silver halide grains of this emulsion have a'grain diameter of more than 0.18 p..
  • This emulsion is then chemically ripened by the addition of sulfur ripening accelerators and gold salts.
  • Emulsion 5 has the same silver halide composition as emulsion 6 but has been longer physically ripened. The time of physical ripening was 24 minutes at the same temperature. The grain size distribution of this emulsion is represented by curve 5 of FIG. 3. 50 percent of the grains have a diameter of more than 0.3 11..
  • the emulsion is chemically ripened in the same way as emulsion 6 but without the addition of gold salts. The same sensitivity as in emulsion 6 is thereby obtained in spite of the coarser grain.
  • Parts C and D are further treated in the same manner, employing substantially the same procedure as in Example 1. Instead of the red sens itizer, mg. of the green sensitizer of the following formula:
  • a process for the preparation of color photographic reversal images in a multi-layered color photographic reversal material which comprises:
  • a red sensitive silver halide emulsion layer with a cyan color coupler capable of reacting with the oxidation product of a color-forming developer to yield a cyan dye
  • the improvement comprises at least one of the silver halide emulsion layers consisting of a mixture of at least two silver halide emulsions each containing regular silver halide grains and having different sensitivities wherein the average grain size of the less sensitive silver halide emulsion is at least 50 percent of that of the more highly sensitive emulsion and the spectral sensitivity of the two mixed emulsions being substantially the same.
  • the average grain size of the less sensitive silver halide emulsion is 50 to percent of that of the more highly sensitive silver halide emulsion.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00197480A 1967-12-15 1971-11-10 Silver halide emulsions for the production of reversal colorphotographic images Expired - Lifetime US3779764A (en)

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DE1597506A DE1597506C3 (de) 1967-12-15 1967-12-15 Verfahren zur Herstellung farbiger, positiver Bilder

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BE (1) BE725315A (de)
DE (1) DE1597506C3 (de)
FR (1) FR1597840A (de)
GB (1) GB1242708A (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4148647A (en) * 1975-12-12 1979-04-10 Agfa-Gevaert N.V. Reversal processing of exposed Lippman-emulsions
US4194911A (en) * 1973-01-22 1980-03-25 Minnesota Mining And Manufacturing Company Inhibitor removing bath for direct positive color photographic development
US4276372A (en) * 1977-04-26 1981-06-30 Agfa-Gevaert, A.G. Photographic material with interimage effect
US4332885A (en) * 1980-04-07 1982-06-01 Fuji Photo Film Co., Ltd. Photographic sensitive materials for color diffusion transfer process
US4554245A (en) * 1983-01-28 1985-11-19 Fuji Photo Film Co., Ltd. Color reversal light-sensitive materials
US4659646A (en) * 1984-06-18 1987-04-21 Fuji Photo Film Co., Ltd. Silver salt diffusion transfer photographic material
US5378591A (en) * 1990-07-04 1995-01-03 Eastman Kodak Company Reversal color photographic material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840866A (en) * 1988-03-24 1989-06-20 The Mead Corporation Microcapsule imaging system having improved dynamic range
EP0365348A3 (en) * 1988-10-20 1990-11-14 Konica Corporation A silver halide color photographic light-sensitive material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600180A (en) * 1968-11-04 1971-08-17 Eastman Kodak Co Method of making a blend of fogged,direct positive silver halide emulsions of different grain sizes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600180A (en) * 1968-11-04 1971-08-17 Eastman Kodak Co Method of making a blend of fogged,direct positive silver halide emulsions of different grain sizes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4194911A (en) * 1973-01-22 1980-03-25 Minnesota Mining And Manufacturing Company Inhibitor removing bath for direct positive color photographic development
US4148647A (en) * 1975-12-12 1979-04-10 Agfa-Gevaert N.V. Reversal processing of exposed Lippman-emulsions
US4276372A (en) * 1977-04-26 1981-06-30 Agfa-Gevaert, A.G. Photographic material with interimage effect
US4332885A (en) * 1980-04-07 1982-06-01 Fuji Photo Film Co., Ltd. Photographic sensitive materials for color diffusion transfer process
US4554245A (en) * 1983-01-28 1985-11-19 Fuji Photo Film Co., Ltd. Color reversal light-sensitive materials
US4659646A (en) * 1984-06-18 1987-04-21 Fuji Photo Film Co., Ltd. Silver salt diffusion transfer photographic material
US4677052A (en) * 1984-06-18 1987-06-30 Fuji Photo Film Co., Ltd. Silver salt diffusion transfer photographic material comprising fine and coarse grain silver halide
US5378591A (en) * 1990-07-04 1995-01-03 Eastman Kodak Company Reversal color photographic material

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Publication number Publication date
DE1597506A1 (de) 1970-06-18
BE725315A (de) 1969-06-12
DE1597506B2 (de) 1975-04-10
GB1242708A (en) 1971-08-11
DE1597506C3 (de) 1975-11-20
FR1597840A (de) 1970-06-29

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