EP0364280B1 - Photographisches Silberhalogenidelement - Google Patents

Photographisches Silberhalogenidelement Download PDF

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Publication number
EP0364280B1
EP0364280B1 EP89310492A EP89310492A EP0364280B1 EP 0364280 B1 EP0364280 B1 EP 0364280B1 EP 89310492 A EP89310492 A EP 89310492A EP 89310492 A EP89310492 A EP 89310492A EP 0364280 B1 EP0364280 B1 EP 0364280B1
Authority
EP
European Patent Office
Prior art keywords
emulsion
grains
silver halide
developable
speed
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
Application number
EP89310492A
Other languages
English (en)
French (fr)
Other versions
EP0364280A2 (de
EP0364280A3 (de
Inventor
Peter J. Twist
John R. Jarvis
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.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Publication of EP0364280A2 publication Critical patent/EP0364280A2/de
Publication of EP0364280A3 publication Critical patent/EP0364280A3/de
Application granted granted Critical
Publication of EP0364280B1 publication Critical patent/EP0364280B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

Definitions

  • the invention relates to photographic silver halide elements and, in particular to such elements having increased photographic speed.
  • Couplers which release a development accelerator or fogging agent have been described in US Patent 3,214,377. They are added to silver halide emulsions in order to achieve an increase in speed brought about by the increased image development caused by the imagewise release of the development accelerator. Too much DARC will cause fogging and this limits the extent to which speed can be increased.
  • the present invention relates to a silver halide element containing a DARC showing improved speed increase without undue fog formation.
  • a photographic colour element comprising a support bearing a photosensitive silver halide emulsion layer containing a coupler capable of releasing a development accelerator or fogging agent on colour development (DARC) characterised in that the emulsion has added thereto photosensitive silver halide grains which are more developable than the grains of said silver halide layer whereby the speed of the emulsion is increased without unduly increasing fog.
  • DARC colour development
  • the elements of the present invention show higher photographic speeds and improved mid-scale granularity compared to elements without the added slow emulsion without undue increase in fog levels.
  • silver halide grains can be made more developable in a number of ways.
  • the halide content is significant and the rate of development reduces as the halide changes, ie. Cl > Br > I.
  • Another way to increase developability is to increase the surface area of the grains and this can be achieved by using smaller sized grains which, of course, will usually be of slower photographic speed.
  • a comparison of developability can be made by determining the time taken for comparable imagewise exposed coatings of different emulsions to reach a particular density in the same developer solution.
  • the more developable silver chloride emulsion will develop to completion in 45 secs while the less developable bromoiodide emulsion takes 2.5 mins to only partially develop.
  • the more developable grains have a speed of at least 0.15, preferably at least 0.3, logE slower than that of the emulsion layer.
  • the added grains are preferably of small size and high specific surface area, preferably their size is from 0.01 to 1.0, especially from 0.125 to 0.15, of the mean grain size of the original emulsion layer.
  • the emulsion layer itself (before addition of the slower grains) may contain grains of a different size and indeed usually will. Its speed is to be taken as the speed of the emulsion when coated and tested. Typically a plot of the size distribution of grains in the original emulsion layer will show a single peak whereas after addition of the slower/smaller grains there will be two peaks.
  • size in connection with grains means diameter if circular, or the diameter of a circle having the same area if not.
  • Granularity although improved in the mid-scale, is increased in the toe region.
  • Granularity can be improved by the inclusion of a DIR (developer inhibitor releasing) coupler or an anti-foggant.
  • DIR developer inhibitor releasing
  • the emulsion layer may also have, associated therewith, an image-dye providing coupler in addition to the DARC.
  • the element will have two or usually three emulsion layer units each sensitised to a different region of the visible spectrum.
  • the DARC compounds can be any of the types known in the art. These include the compounds described in US Patents 3,124,377; 3,253,924; 4,390,618; 4,656,123; in Japanese published, unexamined application 17,437/76, or in British patent specification 2,097,140.
  • A is a coupler residue
  • X is a divalent linking group
  • R1 is formyl, sulphonyl, alkoxycarbonyl, carbamoyl or sulphamoyl group
  • R2 is hydrogen, or an acetyl, ethoxycarbonyl or a methanesulphonyl group
  • R3 and R4 are hydrogen, halogen or an alkyl or alkoxy group having from 1 to 4 carbon atoms.
  • the term "associated with” signifies that the coupler is incorporated in the silver halide emulsion layer or in a layer adjacent thereto where, during processing, it is capable of reacting with silver halide development products.
  • Such multicolour elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum.
  • Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element including the layers of the image-forming units, can be arranged in various orders as known in the art.
  • a typical multicolour photographic element comprises a support bearing yellow, magenta and cyan dye image-forming units comprising at least one blue-, green- or red-sensitive silver halide emulsion layer having associated therewith at least one yellow, magenta or cyan dye-forming coupler respectively.
  • the element can contain additional layers, such as filter and barrier layers.
  • the silver halide emulsion employed in the elements of this invention can be either negative-working or positive-working. They may contain grains of any shape, eg. cubic, octahedral or tubular or mixtures thereof. Suitable emulsions and their preparation are described in the literature, eg. in Research Disclosure Sections I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited therein.
  • the elements of the invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein.
  • the DAR-couplers useful in this invention and any additional couplers can be incorporated in the elements and emulsions as described in Research Disclosures of Section VII, paragraph C and the publications cited therein.
  • the photographic elements of this invention or individual layers thereof can contain brighteners (see Research Disclosure Section V), antifoggants and stabilisers (see Research Disclosure Section VI), antistain agents and image dye stabiliser (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardeners (see Research Disclosure Section XI), plasticisers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research Disclosure Section XIII), matting agents (see Research Disclosure Section XVI) and development modifiers (see Research Disclosure Section XXI).
  • brighteners see Research Disclosure Section V
  • antifoggants and stabilisers see Research Disclosure Section VI
  • antistain agents and image dye stabiliser see Research Disclosure Section VII, paragraphs I and J
  • light absorbing and scattering materials see Research Disclosure Section VIII
  • hardeners see Research Disclosure Section XI
  • plasticisers and lubricants see Research Disclosure Section XII
  • antistatic agents see Research Disclosure Section XIII
  • matting agents see Research Disclosure
  • the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
  • Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX.
  • Processing to form a visible dye image includes the step of contacting the element with a colour developing agent to reduce developable silver halide and oxidise the colour developing agent. Oxidized colour developing agent in turn reacts with the coupler to yield a dye.
  • Preferred colour developing agents are p-phenylene diamines.
  • 4-amino-3-methyl-N,N-diethylaniline hydrochloride 4-amino-3-methyl-N-ethyl-N- ⁇ -(methanesulphonamido)-ethylaniline sulphate hydrate, 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulphate, 4-amino-3- ⁇ -(methanesulphonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxy-ethyl)-m-toluidine di-p-toluene sulphonate.
  • this processing step leads to a negative image.
  • this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
  • a direct positive emulsion can be employed to obtain a positive image.
  • a set of coatings of the structure described below was made with a range of blends of fast and slow emulsions in which the total silver coating weight was 1.0 g/m2. All units are in g/m2.
  • a yellow image coupler of the formula: was included and three levels of the DARC of the formula: in each emulsion combination.
  • the fast emulsion was an ISO400 speed bromo-iodide (6% iodide) T-grain emulsion of 1.14 »m grain size and the slow was IS0 100 speed bromoiodide (4.8% iodide) three dimensional grain emulsion of 0.32 »m grain size. Both emulsions were chemically sensitised. All figures are coating weights in g/m2. Details of coatings are as follows: All emulsion layers contained gelatin (2.2) and coupler (0.6) and had a supercoat of gelatin (1.0) above.
  • the developer and fixer were standard C-41 solutions at 37.8°C.
  • the customary bleach bath was omitted in order to leave the silver image in place for diagnostic purposes.
  • Exposures were made on a graduated 21-step test object with a 0.2 logE exposure increment for 0.01 seconds to simulated daylight.
  • the sensitometric response curves showing dye + silver density are shown in Figure 1. It can be seen that the DARC increases the speed of the fast emulsion by about 0.15 logE whereas with 25% of slow emulsion blended in the speed increase is about 0.3 logE with increased contrast.
  • the slow emulsion by itself is approximately 0.8 logE slower than the fast emulsion.
  • Example II To illustrate the general nature of this phenomomeon, a second set of coatings was made as described in Example I but now with a chemically sensitised silver chloride 0.44 »m cubic grain paper emulsion as slow component.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (4)

  1. Photographisches Farbelement mit einem Träger, auf dem sich eine photosensitive Silberhalogenidemulsionsschicht befindet, die einen Kuppler enthält, der bei der Farbentwicklung (DARC) einen Entwicklungsbeschleuniger oder ein Schleiermittel freizusetzen vermag, dadurch gekennzeichnet, daß die Emulsion zugesetzte photosensitive Silberhalogenidkörner aufweist, die entwickelbarer sind als die Körner der Silberhalogenidschicht, wodurch die Empfindlichkeit der Emulsion, ohne den Schleier unangemessen zu erhöhen, erhöht wird.
  2. Photographisches Element nach Anspruch 1, in dem die mehr entwickelbaren Körner eine Größe aufweisen, die bei 0,01 bis 1,0, vorzugsweise 0,125 bis 0,15, bezogen auf die mittlere Korngröße der Emulsionsschicht liegt.
  3. Photographisches Element nach Anspruch 1 oder 2, in dem die mehr entwickelbaren Körner eine Empfindlichkeit aufweisen, die mindestens 0,15, vorzugsweise mindestens 0,3 logE kleiner ist als die der Emulsionsschicht.
  4. Photographisches Element nach einem der Ansprüche 1 bis 3, in dem die mehr entwickelbaren Körner einen höheren Anteil an Silberchlorid und/oder einen niedrigeren Anteil an Silberiodid aufweisen als in den weniger entwickelbaren Körnern.
EP89310492A 1988-10-13 1989-10-12 Photographisches Silberhalogenidelement Expired - Lifetime EP0364280B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8824061 1988-10-13
GB888824061A GB8824061D0 (en) 1988-10-13 1988-10-13 Photographic silver halide element

Publications (3)

Publication Number Publication Date
EP0364280A2 EP0364280A2 (de) 1990-04-18
EP0364280A3 EP0364280A3 (de) 1991-06-12
EP0364280B1 true EP0364280B1 (de) 1995-04-19

Family

ID=10645163

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89310492A Expired - Lifetime EP0364280B1 (de) 1988-10-13 1989-10-12 Photographisches Silberhalogenidelement

Country Status (5)

Country Link
EP (1) EP0364280B1 (de)
JP (1) JPH02222941A (de)
AT (1) ATE121550T1 (de)
DE (1) DE68922268T2 (de)
GB (1) GB8824061D0 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9716555D0 (en) * 1997-08-06 1997-10-08 Eastman Kodak Co New coupler capable of releasing a development accelerator

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60156059A (ja) * 1984-01-25 1985-08-16 Fuji Photo Film Co Ltd ハロゲン化銀感光材料
JPS60162252A (ja) * 1984-02-02 1985-08-24 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
JPS625234A (ja) * 1985-07-01 1987-01-12 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料

Also Published As

Publication number Publication date
DE68922268T2 (de) 1995-12-07
JPH02222941A (ja) 1990-09-05
DE68922268D1 (de) 1995-05-24
EP0364280A2 (de) 1990-04-18
GB8824061D0 (en) 1988-11-23
EP0364280A3 (de) 1991-06-12
ATE121550T1 (de) 1995-05-15

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